CEJC 4 (2003) 477490

Synthesis and crystal structure of1-ethyl-3-(phenyl)-123-triazolium perchlorate

Beeranahally H Doreswamy1 Madegowda Mahendra1 Sridhar MAnandalwar1 Javaregowda S Prasad1curren Kempegowda Mantelingu2

Basappa2 Kanchugarakoppal S Rangappa2y

1 Department of Studies in PhysicsUniversity of Mysore

Manasagangotri Mysore 570 006 India2 Department of Studies in Chemistry

University of MysoreManasagangotri Mysore 570 006 India

Received 11 July 2003 accepted 22 September 2003

Abstract The isolation of stable carbenes of the Arduengo (la) and Wanzlick (2a) type

has prompted us to look for stable nitrenium ions of the related structural type 1-ethyl-3-

(phenyl)-123-triazolium perchlorate (6+) The title compound C10H14Cl N3O4 was isolated

and structure was investigated by X-ray crystallography It crystallizes in the monoclinic space

group P 21=c with cell parameters a = 6697(4) A b = 9724(9) A c = 19844(2) A and Z = 4

The shy nal residual factor is R1 = 00471 for 1545 reregections with I gt 2 frac14 (I) The structure

exhibits intermolecular hydrogen bonds

creg Central European Science Journals All rights reserved

Keywords Nitrenium ions Carbenes Triazolium perchlorates Crystal structure

1 Introduction

The chemistry of aromatic amines amides have been receiving a lot of interest due to

the carcinogenic activity and their synthetic utility [1] The carcinogenic activities of

all aromatic amines and amides are due to their metabolites like N-aryl hydroxy N-

aryl sulfoxy derivatives and nitrenium ions [2] Nitrenium ions are involved as highly

reactive intermediates in a wide variety of organic reactions [3] For example aromatic

curren E-mail jspuomphysicsnet TelFax+91-821-2516133y Email rangappaksyahoocom Tel +91-821-2412191

478 BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490

nitrenium ion (Fig 1) with R1= aryl R2=H or C(O) CH3 or SO3 are considered to be

the ultimate carcinogens in carcinogenesis initiated by aromatic amines [4] Nitrenium

ions are isoeletronic with carbenes R2C containing a cationic [5] divalent nitrogen atom

R2N+ Recent time resolved studies allowed the UV and IR spectra of some short-lived

aryl nitrenium ions to be measured and provided important results on their structure

and reactivity [6] Although electronically demacrcient molecules of the types mentioned

above are extremely short-lived Arduengo [7a] and Wanzlick [7b] et al recently isolated

and structurally characterized stable crystalline carbenes (Fig 1) concomitantly Stable

crystals of nitrenium ions more precisely ion pair of nitrenium ions were synthesized

and their X-ray crystal structures obtained [8] From experimental data and theoretical

calculations it emerged that these molecules are stabilized by electronic delocalization

[9] Intramolecular rearrangement reaction of nitrenium ions have been reported and

established as useful intermediates in wide variety of biological applications [10] In our

previous work we described the synthesis of some stable nitrenium ions [8] and their

comparison study with structurally related carbenes and found that stable nitrenium

ions (as their carbene analogues) are electronically diregerent from non stable ones To get

further insight into their exact nature and role of nitrenium ions the title compound 6+

was synthesized as per scheme 1 and characterized by proton and carbon NMR elemental

analyses and its structure is conformed by X-ray studies

2 Experimental

21 Synthesis and Characterization

3-(2-Hydroxyethyl)-3-ethyl-1-(phenyl)-triazene (5)

5 was synthesized by diazotisation of aniline (931 gm 100 mmol) Aniline was dissolved

in 25 ml of 37 concentrated hydrochloric acid 50 ml of water and cooled to 0 plusmnC in ice

bath and added sodium nitrite (76 gm 110 mmol) to this cold solution The diazonium

salt solution 4 was mixed with a cold solution of 2-ethylamino-ethanol (980 gm 110

mmol in 20 Na2CO3) The mixture was stirred for 30 minutes at 0 plusmnC extracted

with ether washed with water dried with MgSO4 and the solvent was evaporated The

product was distilled under reduced pressure at 125-130plusmnC to yield yellow oil (58) mp

10-12plusmnC bp 135-137 plusmnC1H NMR (CDCl3 400 MHz) plusmn 145 (t 3H CH3-CH2) 336 (s 1H OH) 352 (q

2H CH2-CH3) 383-391 (m 4H CH2-CH2) 757 (s 5H Ar-H) 13C NMR (CDCl3 100

MHz) plusmn(ppm) 283 396 488 5121 1173 1278 1296 1356 IR (Nujol) ordmmax (cmiexcl1)

3435 (OH) 1622 (C=C) 1548 (C-N) ( Ana Cacld for C10H15N3O C 6217 H 777

N 2176 Found C 6232 H 781 N 2163)

1-ethyl-3-(phenyl)-123-triazolium perchlorate (6+)

To a solution of triazene 5 (0177 gm 10 mmol) and triethylamine (0153 ml 110 mmol)

were added to 10 ml of dichloromethane at -15-10 plusmnC Added drop wise quickly a solution

BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490 479

of methanelsulfonyl chloride (084 ml 10 mmol) in 07 ml of dry dichloromethane without

raising the temperature above 5 plusmnC The reaction mixture was stirred for 40-50 minutes

the reaction mass was rotary evaporated oreg and the residue was washed with benzene

The crude compound was dissolved in ethanol to make a solution and an aqueous solution

of NaClO4 in 40 ml of water was added The product was stirred for half an hour macrltered

oreg and followed by recrystallization with ethanolwater (11) to yield as yellow crystalline

solid Yield 72 mp 128-132 plusmnC

IR (KBr) ordmmax (cmiexcl1) 1623 (C=C) 1506 1489 (C-N) 1095 (ClO4)1H NMR

(DMSO-d6 400 MHz) plusmn(ppm) 148 (t 3H CH3-CH2) 394 (q 2H CH2-CH3) 459

(t 2H CH2-CH2) 473 (t 2H CH2-CH2) 762 (s 5H Ar-H) 13C NMR (DMSO-d6

100 MHz) plusmn(ppm) 285 397 493 514 1175 1282 1301 1364 Ana Calcd for

C10H14N3O4Cl C 4355 H 508 N 1524 Found C 4349 H 512 N 1527

3 X-ray Crystallography

Single crystal of 6+ of dimensions 025 pound 02 pound 02 mm was chosen for X-ray diregrac-

tion studies The measurements were made on a DIPLabo Imaging Plate system with

graphite monochromated MoKreg radiation Thirty six frames of data were collected us-

ing oscillation method Image processing and data reduction were done by using Denzo

[13] The structure was solved and remacrned using maXus [11 14 15] program All the

non-hydrogen atoms were revealed in the macrrst map Full-matrix least-squares remacrnement

based on 1545 observed redegections (I gt 2frac34(I)) with isotropic temperature factors for all

the atoms converged residual to R = 01600 Remacrnement of non-hydrogen atoms with

anisotropic thermal parameters was started at this stage After eight cycles of remacrne-

ment the residuals saturated to R = 00471 for 1545 observed redegections with I gt 2frac34(I)

The hydrogen atoms were placed at geometrically calculated positions Table 1 gives the

details of crystal data data collection and remacrnement The macrnal positional coordinates

with equivalent isotropic temperature factors for all the non-hydrogen atoms are listed

in Table 3

Results and discussion

The bond distances and bond angles are in good agreement with the standard values

(Table 4) Figure 2 represents the ORTEP [12] diagram of the molecule with thermal

ellipsoids at 50 probability The structure of 6+ exhibits interionic hydrogen bonds of

the type CHO The lengths and angles along with the symmetry codes are given in

Table 2 The crystal structure shows that the anion ClO4iexcl is not directly connected to

the positively charged part of the respective nitrenium ion ClO4iexcl holds cation by means

of CHClO4iexcl hydrogen bonds [16 17] and their interionic interactions appeared to be

responsible for molecular cohesion in the unit cell The packing of the molecules in the

unit cell shows stacking (Fig 2) when viewed down a-axis The molecular packing along

b axis (Fig 3) shows that ions are linked continuously by hydrogen bonds to form a linear

polymer structure

480 BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490

Acknowledgements

The authors would like to express their thanks to DST and AICTE Government of

India for macrnancial assistance under the projects SPI2FOO93 and 8017RDMON-

Sw653RampD98-992000

References

[1] (a) H Bartsch M Dworkin JA Miller EC Miller Electrophilic N-acetoxyamino-arenes derived from carcinogenic N-hydroxy-N-acetylaminoarenes by enzymaticdeacetylation and transacetylation in liver Biochem Biophys Acta Vol 286(1972) pp 272-298(b) Y Berwald L Sachs In vitro cell transformation with chemical carcinogensNature Vol 200 (1963) pp 1182-1184

[2] G Boche RH Sommerlade Oxidation of amines with bis-(diphenylphosphinyl)peroxide to give o-phosphinylated aminating reagents Tetrahedron Vol 42 (1986)pp 2703-2706

[3] RA Abramovitch and Jeyaraman Reactivity and Utility In (Ed) Azides andnitrenes Academic Orlando 1984 pp 297-357

[4] PG Gassman Nitrenium ions Acc Chem Res Vol 3 (1970) pp 26-33

[5] (a) F Bosold G Boche W Kleemissmall Formation of acceptor substitutedphenylnitrenes via small alpha Greek-elimination under mild conditionsTetrahedron Lett Vol 29 (1988) pp 1780-1781b) R Uldrich M Famulok F Bosold G Boche SN2 at nitrogen The reactionof N-(4-cyanophenyl)-O-diphenylphosphinoylhydroxylamine with NMethylaniline Amodel for the reactions of ultimate carcinogens of aromatic amines with (bio)nucleophiles Tetrahedron Lett Vol 31 (1990) pp 1689-1692

[6] GB Anderson and DE Falvey Photogenerated arylnitrenium ions absorptionspectra and absolute rate constants for tert-butyl(4-halo-2-acetylphenyl)nitreniumions measured by time-resolved laser spectroscopy J Am Chem Soc Vol 115(1993) pp 9870-9871

[7] (a) AJ Arduengo RL Harlow M Kline A stable crystalline carbene J AmChem Soc Vol 113 (1991) pp 361-363(b) HW Wanzlick Aspects of nucleophilic carbene chemistry Angew Chem IntEd Engl Vol 1 (1962) pp 75-80

[8] (a) G Boche P Andrews K Harms M Marsch K S Rangappa M Schimeczek CWilleke Crystal and Electronic Structure of Stable Nitrenium ions A Comparisonwith Structurally Related Carbenes J Am ChemSoc Vol 118 (1996) pp 4925-4930(b) G Boche KS Rangappa K Harms M Marsch Crystal structure of 1-benzyl-3-methyl-123-triazolinium perchlorate (C6H5)(N3C3H7)+(ClO4)

iexcl Z KristallogrVol 211 (1996) pp 581-582(c) MA Sridhar NK Lokanath J Shashidhara Prasad DG Bhadregowda KSRangappa Crystal structure of 1-methyl-3-phenyl-123-triazolinium perchlorateC9H12N3(ClO4) Z Kristallogr Vol 212 (1997) pp 33-34

[9] (a) R Marc N Andreas G Boche KS Rangappa P Andrews Electron transferchemistry of some unusal nitrogen compounds from stable nitrenium ions to the

478 BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490

nitrenium ion (Fig 1) with R1= aryl R2=H or C(O) CH3 or SO3 are considered to be

the ultimate carcinogens in carcinogenesis initiated by aromatic amines [4] Nitrenium

ions are isoeletronic with carbenes R2C containing a cationic [5] divalent nitrogen atom

R2N+ Recent time resolved studies allowed the UV and IR spectra of some short-lived

aryl nitrenium ions to be measured and provided important results on their structure

and reactivity [6] Although electronically demacrcient molecules of the types mentioned

above are extremely short-lived Arduengo [7a] and Wanzlick [7b] et al recently isolated

and structurally characterized stable crystalline carbenes (Fig 1) concomitantly Stable

crystals of nitrenium ions more precisely ion pair of nitrenium ions were synthesized

and their X-ray crystal structures obtained [8] From experimental data and theoretical

calculations it emerged that these molecules are stabilized by electronic delocalization

[9] Intramolecular rearrangement reaction of nitrenium ions have been reported and

established as useful intermediates in wide variety of biological applications [10] In our

previous work we described the synthesis of some stable nitrenium ions [8] and their

comparison study with structurally related carbenes and found that stable nitrenium

ions (as their carbene analogues) are electronically diregerent from non stable ones To get

further insight into their exact nature and role of nitrenium ions the title compound 6+

was synthesized as per scheme 1 and characterized by proton and carbon NMR elemental

analyses and its structure is conformed by X-ray studies

2 Experimental

21 Synthesis and Characterization

3-(2-Hydroxyethyl)-3-ethyl-1-(phenyl)-triazene (5)

5 was synthesized by diazotisation of aniline (931 gm 100 mmol) Aniline was dissolved

in 25 ml of 37 concentrated hydrochloric acid 50 ml of water and cooled to 0 plusmnC in ice

bath and added sodium nitrite (76 gm 110 mmol) to this cold solution The diazonium

salt solution 4 was mixed with a cold solution of 2-ethylamino-ethanol (980 gm 110

mmol in 20 Na2CO3) The mixture was stirred for 30 minutes at 0 plusmnC extracted

with ether washed with water dried with MgSO4 and the solvent was evaporated The

product was distilled under reduced pressure at 125-130plusmnC to yield yellow oil (58) mp

10-12plusmnC bp 135-137 plusmnC1H NMR (CDCl3 400 MHz) plusmn 145 (t 3H CH3-CH2) 336 (s 1H OH) 352 (q

2H CH2-CH3) 383-391 (m 4H CH2-CH2) 757 (s 5H Ar-H) 13C NMR (CDCl3 100

MHz) plusmn(ppm) 283 396 488 5121 1173 1278 1296 1356 IR (Nujol) ordmmax (cmiexcl1)

3435 (OH) 1622 (C=C) 1548 (C-N) ( Ana Cacld for C10H15N3O C 6217 H 777

N 2176 Found C 6232 H 781 N 2163)

1-ethyl-3-(phenyl)-123-triazolium perchlorate (6+)

To a solution of triazene 5 (0177 gm 10 mmol) and triethylamine (0153 ml 110 mmol)

were added to 10 ml of dichloromethane at -15-10 plusmnC Added drop wise quickly a solution

BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490 479

of methanelsulfonyl chloride (084 ml 10 mmol) in 07 ml of dry dichloromethane without

raising the temperature above 5 plusmnC The reaction mixture was stirred for 40-50 minutes

the reaction mass was rotary evaporated oreg and the residue was washed with benzene

The crude compound was dissolved in ethanol to make a solution and an aqueous solution

of NaClO4 in 40 ml of water was added The product was stirred for half an hour macrltered

oreg and followed by recrystallization with ethanolwater (11) to yield as yellow crystalline

solid Yield 72 mp 128-132 plusmnC

IR (KBr) ordmmax (cmiexcl1) 1623 (C=C) 1506 1489 (C-N) 1095 (ClO4)1H NMR

(DMSO-d6 400 MHz) plusmn(ppm) 148 (t 3H CH3-CH2) 394 (q 2H CH2-CH3) 459

(t 2H CH2-CH2) 473 (t 2H CH2-CH2) 762 (s 5H Ar-H) 13C NMR (DMSO-d6

100 MHz) plusmn(ppm) 285 397 493 514 1175 1282 1301 1364 Ana Calcd for

C10H14N3O4Cl C 4355 H 508 N 1524 Found C 4349 H 512 N 1527

3 X-ray Crystallography

Single crystal of 6+ of dimensions 025 pound 02 pound 02 mm was chosen for X-ray diregrac-

tion studies The measurements were made on a DIPLabo Imaging Plate system with

graphite monochromated MoKreg radiation Thirty six frames of data were collected us-

ing oscillation method Image processing and data reduction were done by using Denzo

[13] The structure was solved and remacrned using maXus [11 14 15] program All the

non-hydrogen atoms were revealed in the macrrst map Full-matrix least-squares remacrnement

based on 1545 observed redegections (I gt 2frac34(I)) with isotropic temperature factors for all

the atoms converged residual to R = 01600 Remacrnement of non-hydrogen atoms with

anisotropic thermal parameters was started at this stage After eight cycles of remacrne-

ment the residuals saturated to R = 00471 for 1545 observed redegections with I gt 2frac34(I)

The hydrogen atoms were placed at geometrically calculated positions Table 1 gives the

details of crystal data data collection and remacrnement The macrnal positional coordinates

with equivalent isotropic temperature factors for all the non-hydrogen atoms are listed

in Table 3

Results and discussion

The bond distances and bond angles are in good agreement with the standard values

(Table 4) Figure 2 represents the ORTEP [12] diagram of the molecule with thermal

ellipsoids at 50 probability The structure of 6+ exhibits interionic hydrogen bonds of

the type CHO The lengths and angles along with the symmetry codes are given in

Table 2 The crystal structure shows that the anion ClO4iexcl is not directly connected to

the positively charged part of the respective nitrenium ion ClO4iexcl holds cation by means

of CHClO4iexcl hydrogen bonds [16 17] and their interionic interactions appeared to be

responsible for molecular cohesion in the unit cell The packing of the molecules in the

unit cell shows stacking (Fig 2) when viewed down a-axis The molecular packing along

b axis (Fig 3) shows that ions are linked continuously by hydrogen bonds to form a linear

polymer structure

480 BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490

Acknowledgements

The authors would like to express their thanks to DST and AICTE Government of

India for macrnancial assistance under the projects SPI2FOO93 and 8017RDMON-

Sw653RampD98-992000

References

[1] (a) H Bartsch M Dworkin JA Miller EC Miller Electrophilic N-acetoxyamino-arenes derived from carcinogenic N-hydroxy-N-acetylaminoarenes by enzymaticdeacetylation and transacetylation in liver Biochem Biophys Acta Vol 286(1972) pp 272-298(b) Y Berwald L Sachs In vitro cell transformation with chemical carcinogensNature Vol 200 (1963) pp 1182-1184

[2] G Boche RH Sommerlade Oxidation of amines with bis-(diphenylphosphinyl)peroxide to give o-phosphinylated aminating reagents Tetrahedron Vol 42 (1986)pp 2703-2706

[3] RA Abramovitch and Jeyaraman Reactivity and Utility In (Ed) Azides andnitrenes Academic Orlando 1984 pp 297-357

[4] PG Gassman Nitrenium ions Acc Chem Res Vol 3 (1970) pp 26-33

[5] (a) F Bosold G Boche W Kleemissmall Formation of acceptor substitutedphenylnitrenes via small alpha Greek-elimination under mild conditionsTetrahedron Lett Vol 29 (1988) pp 1780-1781b) R Uldrich M Famulok F Bosold G Boche SN2 at nitrogen The reactionof N-(4-cyanophenyl)-O-diphenylphosphinoylhydroxylamine with NMethylaniline Amodel for the reactions of ultimate carcinogens of aromatic amines with (bio)nucleophiles Tetrahedron Lett Vol 31 (1990) pp 1689-1692

[6] GB Anderson and DE Falvey Photogenerated arylnitrenium ions absorptionspectra and absolute rate constants for tert-butyl(4-halo-2-acetylphenyl)nitreniumions measured by time-resolved laser spectroscopy J Am Chem Soc Vol 115(1993) pp 9870-9871

[7] (a) AJ Arduengo RL Harlow M Kline A stable crystalline carbene J AmChem Soc Vol 113 (1991) pp 361-363(b) HW Wanzlick Aspects of nucleophilic carbene chemistry Angew Chem IntEd Engl Vol 1 (1962) pp 75-80

[8] (a) G Boche P Andrews K Harms M Marsch K S Rangappa M Schimeczek CWilleke Crystal and Electronic Structure of Stable Nitrenium ions A Comparisonwith Structurally Related Carbenes J Am ChemSoc Vol 118 (1996) pp 4925-4930(b) G Boche KS Rangappa K Harms M Marsch Crystal structure of 1-benzyl-3-methyl-123-triazolinium perchlorate (C6H5)(N3C3H7)+(ClO4)

iexcl Z KristallogrVol 211 (1996) pp 581-582(c) MA Sridhar NK Lokanath J Shashidhara Prasad DG Bhadregowda KSRangappa Crystal structure of 1-methyl-3-phenyl-123-triazolinium perchlorateC9H12N3(ClO4) Z Kristallogr Vol 212 (1997) pp 33-34

[9] (a) R Marc N Andreas G Boche KS Rangappa P Andrews Electron transferchemistry of some unusal nitrogen compounds from stable nitrenium ions to the

BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490 479

of methanelsulfonyl chloride (084 ml 10 mmol) in 07 ml of dry dichloromethane without

raising the temperature above 5 plusmnC The reaction mixture was stirred for 40-50 minutes

the reaction mass was rotary evaporated oreg and the residue was washed with benzene

The crude compound was dissolved in ethanol to make a solution and an aqueous solution

of NaClO4 in 40 ml of water was added The product was stirred for half an hour macrltered

oreg and followed by recrystallization with ethanolwater (11) to yield as yellow crystalline

solid Yield 72 mp 128-132 plusmnC

IR (KBr) ordmmax (cmiexcl1) 1623 (C=C) 1506 1489 (C-N) 1095 (ClO4)1H NMR

(DMSO-d6 400 MHz) plusmn(ppm) 148 (t 3H CH3-CH2) 394 (q 2H CH2-CH3) 459

(t 2H CH2-CH2) 473 (t 2H CH2-CH2) 762 (s 5H Ar-H) 13C NMR (DMSO-d6

100 MHz) plusmn(ppm) 285 397 493 514 1175 1282 1301 1364 Ana Calcd for

C10H14N3O4Cl C 4355 H 508 N 1524 Found C 4349 H 512 N 1527

3 X-ray Crystallography

Single crystal of 6+ of dimensions 025 pound 02 pound 02 mm was chosen for X-ray diregrac-

tion studies The measurements were made on a DIPLabo Imaging Plate system with

graphite monochromated MoKreg radiation Thirty six frames of data were collected us-

ing oscillation method Image processing and data reduction were done by using Denzo

[13] The structure was solved and remacrned using maXus [11 14 15] program All the

non-hydrogen atoms were revealed in the macrrst map Full-matrix least-squares remacrnement

based on 1545 observed redegections (I gt 2frac34(I)) with isotropic temperature factors for all

the atoms converged residual to R = 01600 Remacrnement of non-hydrogen atoms with

anisotropic thermal parameters was started at this stage After eight cycles of remacrne-

ment the residuals saturated to R = 00471 for 1545 observed redegections with I gt 2frac34(I)

The hydrogen atoms were placed at geometrically calculated positions Table 1 gives the

details of crystal data data collection and remacrnement The macrnal positional coordinates

with equivalent isotropic temperature factors for all the non-hydrogen atoms are listed

in Table 3

Results and discussion

The bond distances and bond angles are in good agreement with the standard values

(Table 4) Figure 2 represents the ORTEP [12] diagram of the molecule with thermal

ellipsoids at 50 probability The structure of 6+ exhibits interionic hydrogen bonds of

the type CHO The lengths and angles along with the symmetry codes are given in

Table 2 The crystal structure shows that the anion ClO4iexcl is not directly connected to

the positively charged part of the respective nitrenium ion ClO4iexcl holds cation by means

of CHClO4iexcl hydrogen bonds [16 17] and their interionic interactions appeared to be

responsible for molecular cohesion in the unit cell The packing of the molecules in the

unit cell shows stacking (Fig 2) when viewed down a-axis The molecular packing along

b axis (Fig 3) shows that ions are linked continuously by hydrogen bonds to form a linear

polymer structure

480 BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490

Acknowledgements

The authors would like to express their thanks to DST and AICTE Government of

India for macrnancial assistance under the projects SPI2FOO93 and 8017RDMON-

Sw653RampD98-992000

References

[1] (a) H Bartsch M Dworkin JA Miller EC Miller Electrophilic N-acetoxyamino-arenes derived from carcinogenic N-hydroxy-N-acetylaminoarenes by enzymaticdeacetylation and transacetylation in liver Biochem Biophys Acta Vol 286(1972) pp 272-298(b) Y Berwald L Sachs In vitro cell transformation with chemical carcinogensNature Vol 200 (1963) pp 1182-1184

[2] G Boche RH Sommerlade Oxidation of amines with bis-(diphenylphosphinyl)peroxide to give o-phosphinylated aminating reagents Tetrahedron Vol 42 (1986)pp 2703-2706

[3] RA Abramovitch and Jeyaraman Reactivity and Utility In (Ed) Azides andnitrenes Academic Orlando 1984 pp 297-357

[4] PG Gassman Nitrenium ions Acc Chem Res Vol 3 (1970) pp 26-33

[5] (a) F Bosold G Boche W Kleemissmall Formation of acceptor substitutedphenylnitrenes via small alpha Greek-elimination under mild conditionsTetrahedron Lett Vol 29 (1988) pp 1780-1781b) R Uldrich M Famulok F Bosold G Boche SN2 at nitrogen The reactionof N-(4-cyanophenyl)-O-diphenylphosphinoylhydroxylamine with NMethylaniline Amodel for the reactions of ultimate carcinogens of aromatic amines with (bio)nucleophiles Tetrahedron Lett Vol 31 (1990) pp 1689-1692

[6] GB Anderson and DE Falvey Photogenerated arylnitrenium ions absorptionspectra and absolute rate constants for tert-butyl(4-halo-2-acetylphenyl)nitreniumions measured by time-resolved laser spectroscopy J Am Chem Soc Vol 115(1993) pp 9870-9871

[7] (a) AJ Arduengo RL Harlow M Kline A stable crystalline carbene J AmChem Soc Vol 113 (1991) pp 361-363(b) HW Wanzlick Aspects of nucleophilic carbene chemistry Angew Chem IntEd Engl Vol 1 (1962) pp 75-80

[8] (a) G Boche P Andrews K Harms M Marsch K S Rangappa M Schimeczek CWilleke Crystal and Electronic Structure of Stable Nitrenium ions A Comparisonwith Structurally Related Carbenes J Am ChemSoc Vol 118 (1996) pp 4925-4930(b) G Boche KS Rangappa K Harms M Marsch Crystal structure of 1-benzyl-3-methyl-123-triazolinium perchlorate (C6H5)(N3C3H7)+(ClO4)

iexcl Z KristallogrVol 211 (1996) pp 581-582(c) MA Sridhar NK Lokanath J Shashidhara Prasad DG Bhadregowda KSRangappa Crystal structure of 1-methyl-3-phenyl-123-triazolinium perchlorateC9H12N3(ClO4) Z Kristallogr Vol 212 (1997) pp 33-34

[9] (a) R Marc N Andreas G Boche KS Rangappa P Andrews Electron transferchemistry of some unusal nitrogen compounds from stable nitrenium ions to the

480 BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490

Acknowledgements

The authors would like to express their thanks to DST and AICTE Government of

India for macrnancial assistance under the projects SPI2FOO93 and 8017RDMON-

Sw653RampD98-992000

References

[1] (a) H Bartsch M Dworkin JA Miller EC Miller Electrophilic N-acetoxyamino-arenes derived from carcinogenic N-hydroxy-N-acetylaminoarenes by enzymaticdeacetylation and transacetylation in liver Biochem Biophys Acta Vol 286(1972) pp 272-298(b) Y Berwald L Sachs In vitro cell transformation with chemical carcinogensNature Vol 200 (1963) pp 1182-1184

[2] G Boche RH Sommerlade Oxidation of amines with bis-(diphenylphosphinyl)peroxide to give o-phosphinylated aminating reagents Tetrahedron Vol 42 (1986)pp 2703-2706

[3] RA Abramovitch and Jeyaraman Reactivity and Utility In (Ed) Azides andnitrenes Academic Orlando 1984 pp 297-357

[4] PG Gassman Nitrenium ions Acc Chem Res Vol 3 (1970) pp 26-33

[5] (a) F Bosold G Boche W Kleemissmall Formation of acceptor substitutedphenylnitrenes via small alpha Greek-elimination under mild conditionsTetrahedron Lett Vol 29 (1988) pp 1780-1781b) R Uldrich M Famulok F Bosold G Boche SN2 at nitrogen The reactionof N-(4-cyanophenyl)-O-diphenylphosphinoylhydroxylamine with NMethylaniline Amodel for the reactions of ultimate carcinogens of aromatic amines with (bio)nucleophiles Tetrahedron Lett Vol 31 (1990) pp 1689-1692

[6] GB Anderson and DE Falvey Photogenerated arylnitrenium ions absorptionspectra and absolute rate constants for tert-butyl(4-halo-2-acetylphenyl)nitreniumions measured by time-resolved laser spectroscopy J Am Chem Soc Vol 115(1993) pp 9870-9871

[7] (a) AJ Arduengo RL Harlow M Kline A stable crystalline carbene J AmChem Soc Vol 113 (1991) pp 361-363(b) HW Wanzlick Aspects of nucleophilic carbene chemistry Angew Chem IntEd Engl Vol 1 (1962) pp 75-80

[8] (a) G Boche P Andrews K Harms M Marsch K S Rangappa M Schimeczek CWilleke Crystal and Electronic Structure of Stable Nitrenium ions A Comparisonwith Structurally Related Carbenes J Am ChemSoc Vol 118 (1996) pp 4925-4930(b) G Boche KS Rangappa K Harms M Marsch Crystal structure of 1-benzyl-3-methyl-123-triazolinium perchlorate (C6H5)(N3C3H7)+(ClO4)

iexcl Z KristallogrVol 211 (1996) pp 581-582(c) MA Sridhar NK Lokanath J Shashidhara Prasad DG Bhadregowda KSRangappa Crystal structure of 1-methyl-3-phenyl-123-triazolinium perchlorateC9H12N3(ClO4) Z Kristallogr Vol 212 (1997) pp 33-34

[9] (a) R Marc N Andreas G Boche KS Rangappa P Andrews Electron transferchemistry of some unusal nitrogen compounds from stable nitrenium ions to the

BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490 481

corresponding nitrogen centered radicals New J Chem Vol XyX (1998) pp1437-1444(b) KS Rangappa H Mallesha NV AnilKumar NK Lokanath MASridhar J Shashidhara Prasad Synthesis and crystal structure of 13-dimethylbenzotriazolium trideguoromethane sulfonate Mol Cryst LiqCryst Vol 357 (2001)pp 291-298

[10] RJ Moran C Cramer DE Falvey Reactions of Diarylnitrenium Ions withElectron Rich Alkenes An Experimental and Theoretical Study J Org ChemVol 62 (1997) pp 2742-2751

[11] S Mackay CJ Gilmore C Edwards N Stewart K Shankland maXus ComputerProgram for the Solution and Remacrnement of Crystal Structures Bruker Nonius TheNetherlands MacScience Japan and The University of Glasgow 1999

[12] CK Johnson ORTEPII A Fortran ThermalEllipsoid Plot Program ReportORNL-5138 Oak Ridge National Laboratory Oak Ridge Tennessee USA 1976

[13] Z Otwinowski W Minor In Methods in Enzymology Vol 276 edited by CWCarter Jr RM Sweet Academic Press New York 1997 pp 307326

[14] GM Sheldrick SHELXS-97 Program for Crystal Structure Solution Universityof GAumlottingen Germany 1997

[15] GM Sheldrick SHELXL-97 Program for the Remacrnement of Crystal StructuresUniversity of GAumlottingen Germany 1997

[16] (a) Z Berkovitch-Yellin L Leiserowitz The role played by C-HO and C-HNinteractions in determining molecular packing and conformation Acta Cryst VolB40 (1984) pp 159-165(b) G A Jeregrey H Maluszynska J Mitra Hydrogen bonding in nucleosides andnucleotides Int J Biol Macromol Vol 7 (1985) pp 3336-348

[17] Bondi A van der Waals Volumes and Radii JPhysChem Vol 64 (1964) pp441-451

482 BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490

NH2Na NO2

N2Cl+ shy

CH2shy CH3

HCl 0 o C

43

Hshy Nshy CH2shy CH2shy OH

i ) ( Et ) 3N

i i ) CH3SO2Cl

56 +

CH2shy CH3 N

N

CH2shy CH3

N= Nshy Nshy CH2shy CH2shy OH N Cl O4

+ shy

2 0 Na 2CO3

shy 1 5 t 0 shy 2 0 o C

i i i ) Na Cl O4

Scheme 1

BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490 483

R

R

1+ 1a 2a

R

R

R

N

CN

R2N

R1X_+

H

H

R

R

R

N

CN

Fig 1 Stable carbene of the Arduengo (1a) and Wanzlick (2a) type

484 BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490

Fig 2 ORTEP of the molecule at 50 probability

BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490 485

Fig 3 Packing of the molecules down a axis and dashed lines represent the hydrogen bonds

486 BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490

Fig 4 Packing of the molecules down b axis

BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490 487

Empirical formula C10H14 Cl N3O4

Formula weight 27569

Temperature 293(2)K

Wavelength 071073A

Crystal system Monoclinic

Space group P 21=c

Cell dimensions a = 6697(4) A

b = 9724(9) A

c = 19844(2) A

shy = 10972plusmn

Volume 121646(17)A3

Z 4

Density(calculated) 1505 Mgm3

Absorption coemacr cient 0326 mmiexcl1

F000 576

Crystal size 025 pound 02 pound 02 mm

Theta range for data collection 385plusmn to 3246plusmn

Index ranges iexcl 8 micro h micro 8

iexcl 14 micro k micro 14

iexcl 29 micro l micro 29

Reregections collected 3582

Independent reregections 2049 [R(int) = 00223]

Reshy nement method Full-matrix least-squares on F 2

Data restraints parameters 2049 0 164

Goodness-of-shy t on F 2 1066

Final R indices [I gt 2frac14 (I)] R1 = 00471

R indices (all data) R1 = 00635

Largest dinot peak and hole 0212 and -0187 eAiexcl3

Table 1 Experimental crystallographic details of 6 +

488 BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490

Atoms Length(A) Angle(plusmn) Symmetry Code

C8H1O1 3414 14969 iexcl x iexcl y iexcl z

C9H6O4 3499 16500 x 1=2 iexcl y iexcl 1=2 + z

C13H10AO2 3383 14938

C13H10BO3 3359 14893 1 + x y z

C12H11AO2 3317 16177 1 iexcl x iexcl 1=2 + y 1=2 iexcl z

C12H11BO3 3303 16201 iexcl x iexcl 1=2 + y 1=2 iexcl z

Table 2 Hydrogen Bonds

BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490 489

Atom x y z Ueq

N15 -06754(5) 015238(19) 007575(12) 00466(8)

N11 -06756(4) 001959(18) 007455(11) 00426(8)

C9 -08053(6) 00188(2) -005552(15) 00455(9)

N14 -06089(5) 01946(2) 014060(13) 00505(9)

C10 -07422(5) -00530(2) 000843(14) 00422(9)

C8 -08699(6) -00544(3) -011917(15) 00529(10)

C13 -05553(7) 00834(3) 019408(16) 00591(11)

C12 -06022(6) -00437(3) 014707(15) 00519(10)

C7 -08691(6) -01970(3) -011884(18) 00601(12)

C5 -07399(6) -01948(3) 000981(17) 00578(12)

C6 -08032(7) -02659(3) -00544(2) 00642(13)

C17 -06557(9) 04344(3) 00952(2) 00752(17)

C16 -05897(7) 03398(3) 015933(19) 00673(14)

Cl1 -091661(15) 035832(6) -016632(4) 00501(3)

O1 -09493(7) 04885(2) -019944(14) 00997(17)

O3 -11103(7) 02837(4) -01887(2) 01098(19)

O2 -07721(6) 02834(3) -01890(2) 01072(17)

O4 -08499(8) 03717(3) -009211(14) 0118(2)

Table 3 Atomic coordinates and equivalent thermal parameters

490 BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490

Atoms Length Atoms Length

N15-N14 1279(3) C8-C7 1387(4)

N15-N11 1291(3) C13-C12 1516(4)

N11-C10 1423(3) C7-C6 1378(5)

N11-C12 1488(3) C5-C6 1384(5)

C9-C10 1384(4) C17-C16 1510(5)

C9-C8 1386(4) Cl1-O4 1393(3)

N14-C16 1455(3) Cl1-O2 1401(2)

N14-C13 1472(3) Cl1-O1 1409(2)

C10-C5 1379(4) Cl1-O3 1420(4)

Atoms Angle Atoms Angle

N14-N15-N11 1097(2) N14-C13-C12 1019(2)

N15-N11-C10 1207(2) N11-C12-C13 1010(2)

N15-N11-C12 1134(2) C6-C7-C8 1194(3)

C10-N11-C12 1258(2) C10-C5-C6 1189(3)

C10-C9-C8 1188(2) C7-C6-C5 1209(2)

N15-N14-C16 1226(2) N14-C16-C17 1136(3)

N15-N14-C13 1140(2) O4-Cl1-O2 1122(3)

C16-N14-C13 1233(2) O4-Cl1-O1 1107(2)

C5-C10-C9 1214(2) O2-Cl1-O1 1094(2)

C5-C10-N11 1187(2) O4-Cl1-O3 1082(2)

C9-C10-N11 1199(2) O2-Cl1-O3 1069(2)

C9-C8-C7 1206(3) O1-Cl1-O3 1093(3)

Table 4 Bond Lengths (A) and Bond Angles (macr)

BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490 483

R

R

1+ 1a 2a

R

R

R

N

CN

R2N

R1X_+

H

H

R

R

R

N

CN

Fig 1 Stable carbene of the Arduengo (1a) and Wanzlick (2a) type

484 BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490

Fig 2 ORTEP of the molecule at 50 probability

BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490 485

Fig 3 Packing of the molecules down a axis and dashed lines represent the hydrogen bonds

486 BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490

Fig 4 Packing of the molecules down b axis

BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490 487

Empirical formula C10H14 Cl N3O4

Formula weight 27569

Temperature 293(2)K

Wavelength 071073A

Crystal system Monoclinic

Space group P 21=c

Cell dimensions a = 6697(4) A

b = 9724(9) A

c = 19844(2) A

shy = 10972plusmn

Volume 121646(17)A3

Z 4

Density(calculated) 1505 Mgm3

Absorption coemacr cient 0326 mmiexcl1

F000 576

Crystal size 025 pound 02 pound 02 mm

Theta range for data collection 385plusmn to 3246plusmn

Index ranges iexcl 8 micro h micro 8

iexcl 14 micro k micro 14

iexcl 29 micro l micro 29

Reregections collected 3582

Independent reregections 2049 [R(int) = 00223]

Reshy nement method Full-matrix least-squares on F 2

Data restraints parameters 2049 0 164

Goodness-of-shy t on F 2 1066

Final R indices [I gt 2frac14 (I)] R1 = 00471

R indices (all data) R1 = 00635

Largest dinot peak and hole 0212 and -0187 eAiexcl3

Table 1 Experimental crystallographic details of 6 +

488 BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490

Atoms Length(A) Angle(plusmn) Symmetry Code

C8H1O1 3414 14969 iexcl x iexcl y iexcl z

C9H6O4 3499 16500 x 1=2 iexcl y iexcl 1=2 + z

C13H10AO2 3383 14938

C13H10BO3 3359 14893 1 + x y z

C12H11AO2 3317 16177 1 iexcl x iexcl 1=2 + y 1=2 iexcl z

C12H11BO3 3303 16201 iexcl x iexcl 1=2 + y 1=2 iexcl z

Table 2 Hydrogen Bonds

BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490 489

Atom x y z Ueq

N15 -06754(5) 015238(19) 007575(12) 00466(8)

N11 -06756(4) 001959(18) 007455(11) 00426(8)

C9 -08053(6) 00188(2) -005552(15) 00455(9)

N14 -06089(5) 01946(2) 014060(13) 00505(9)

C10 -07422(5) -00530(2) 000843(14) 00422(9)

C8 -08699(6) -00544(3) -011917(15) 00529(10)

C13 -05553(7) 00834(3) 019408(16) 00591(11)

C12 -06022(6) -00437(3) 014707(15) 00519(10)

C7 -08691(6) -01970(3) -011884(18) 00601(12)

C5 -07399(6) -01948(3) 000981(17) 00578(12)

C6 -08032(7) -02659(3) -00544(2) 00642(13)

C17 -06557(9) 04344(3) 00952(2) 00752(17)

C16 -05897(7) 03398(3) 015933(19) 00673(14)

Cl1 -091661(15) 035832(6) -016632(4) 00501(3)

O1 -09493(7) 04885(2) -019944(14) 00997(17)

O3 -11103(7) 02837(4) -01887(2) 01098(19)

O2 -07721(6) 02834(3) -01890(2) 01072(17)

O4 -08499(8) 03717(3) -009211(14) 0118(2)

Table 3 Atomic coordinates and equivalent thermal parameters

490 BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490

Atoms Length Atoms Length

N15-N14 1279(3) C8-C7 1387(4)

N15-N11 1291(3) C13-C12 1516(4)

N11-C10 1423(3) C7-C6 1378(5)

N11-C12 1488(3) C5-C6 1384(5)

C9-C10 1384(4) C17-C16 1510(5)

C9-C8 1386(4) Cl1-O4 1393(3)

N14-C16 1455(3) Cl1-O2 1401(2)

N14-C13 1472(3) Cl1-O1 1409(2)

C10-C5 1379(4) Cl1-O3 1420(4)

Atoms Angle Atoms Angle

N14-N15-N11 1097(2) N14-C13-C12 1019(2)

N15-N11-C10 1207(2) N11-C12-C13 1010(2)

N15-N11-C12 1134(2) C6-C7-C8 1194(3)

C10-N11-C12 1258(2) C10-C5-C6 1189(3)

C10-C9-C8 1188(2) C7-C6-C5 1209(2)

N15-N14-C16 1226(2) N14-C16-C17 1136(3)

N15-N14-C13 1140(2) O4-Cl1-O2 1122(3)

C16-N14-C13 1233(2) O4-Cl1-O1 1107(2)

C5-C10-C9 1214(2) O2-Cl1-O1 1094(2)

C5-C10-N11 1187(2) O4-Cl1-O3 1082(2)

C9-C10-N11 1199(2) O2-Cl1-O3 1069(2)

C9-C8-C7 1206(3) O1-Cl1-O3 1093(3)

Table 4 Bond Lengths (A) and Bond Angles (macr)

484 BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490

Fig 2 ORTEP of the molecule at 50 probability

BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490 485

Fig 3 Packing of the molecules down a axis and dashed lines represent the hydrogen bonds

486 BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490

Fig 4 Packing of the molecules down b axis

BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490 487

Empirical formula C10H14 Cl N3O4

Formula weight 27569

Temperature 293(2)K

Wavelength 071073A

Crystal system Monoclinic

Space group P 21=c

Cell dimensions a = 6697(4) A

b = 9724(9) A

c = 19844(2) A

shy = 10972plusmn

Volume 121646(17)A3

Z 4

Density(calculated) 1505 Mgm3

Absorption coemacr cient 0326 mmiexcl1

F000 576

Crystal size 025 pound 02 pound 02 mm

Theta range for data collection 385plusmn to 3246plusmn

Index ranges iexcl 8 micro h micro 8

iexcl 14 micro k micro 14

iexcl 29 micro l micro 29

Reregections collected 3582

Independent reregections 2049 [R(int) = 00223]

Reshy nement method Full-matrix least-squares on F 2

Data restraints parameters 2049 0 164

Goodness-of-shy t on F 2 1066

Final R indices [I gt 2frac14 (I)] R1 = 00471

R indices (all data) R1 = 00635

Largest dinot peak and hole 0212 and -0187 eAiexcl3

Table 1 Experimental crystallographic details of 6 +

488 BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490

Atoms Length(A) Angle(plusmn) Symmetry Code

C8H1O1 3414 14969 iexcl x iexcl y iexcl z

C9H6O4 3499 16500 x 1=2 iexcl y iexcl 1=2 + z

C13H10AO2 3383 14938

C13H10BO3 3359 14893 1 + x y z

C12H11AO2 3317 16177 1 iexcl x iexcl 1=2 + y 1=2 iexcl z

C12H11BO3 3303 16201 iexcl x iexcl 1=2 + y 1=2 iexcl z

Table 2 Hydrogen Bonds

BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490 489

Atom x y z Ueq

N15 -06754(5) 015238(19) 007575(12) 00466(8)

N11 -06756(4) 001959(18) 007455(11) 00426(8)

C9 -08053(6) 00188(2) -005552(15) 00455(9)

N14 -06089(5) 01946(2) 014060(13) 00505(9)

C10 -07422(5) -00530(2) 000843(14) 00422(9)

C8 -08699(6) -00544(3) -011917(15) 00529(10)

C13 -05553(7) 00834(3) 019408(16) 00591(11)

C12 -06022(6) -00437(3) 014707(15) 00519(10)

C7 -08691(6) -01970(3) -011884(18) 00601(12)

C5 -07399(6) -01948(3) 000981(17) 00578(12)

C6 -08032(7) -02659(3) -00544(2) 00642(13)

C17 -06557(9) 04344(3) 00952(2) 00752(17)

C16 -05897(7) 03398(3) 015933(19) 00673(14)

Cl1 -091661(15) 035832(6) -016632(4) 00501(3)

O1 -09493(7) 04885(2) -019944(14) 00997(17)

O3 -11103(7) 02837(4) -01887(2) 01098(19)

O2 -07721(6) 02834(3) -01890(2) 01072(17)

O4 -08499(8) 03717(3) -009211(14) 0118(2)

Table 3 Atomic coordinates and equivalent thermal parameters

490 BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490

Atoms Length Atoms Length

N15-N14 1279(3) C8-C7 1387(4)

N15-N11 1291(3) C13-C12 1516(4)

N11-C10 1423(3) C7-C6 1378(5)

N11-C12 1488(3) C5-C6 1384(5)

C9-C10 1384(4) C17-C16 1510(5)

C9-C8 1386(4) Cl1-O4 1393(3)

N14-C16 1455(3) Cl1-O2 1401(2)

N14-C13 1472(3) Cl1-O1 1409(2)

C10-C5 1379(4) Cl1-O3 1420(4)

Atoms Angle Atoms Angle

N14-N15-N11 1097(2) N14-C13-C12 1019(2)

N15-N11-C10 1207(2) N11-C12-C13 1010(2)

N15-N11-C12 1134(2) C6-C7-C8 1194(3)

C10-N11-C12 1258(2) C10-C5-C6 1189(3)

C10-C9-C8 1188(2) C7-C6-C5 1209(2)

N15-N14-C16 1226(2) N14-C16-C17 1136(3)

N15-N14-C13 1140(2) O4-Cl1-O2 1122(3)

C16-N14-C13 1233(2) O4-Cl1-O1 1107(2)

C5-C10-C9 1214(2) O2-Cl1-O1 1094(2)

C5-C10-N11 1187(2) O4-Cl1-O3 1082(2)

C9-C10-N11 1199(2) O2-Cl1-O3 1069(2)

C9-C8-C7 1206(3) O1-Cl1-O3 1093(3)

Table 4 Bond Lengths (A) and Bond Angles (macr)

BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490 485

Fig 3 Packing of the molecules down a axis and dashed lines represent the hydrogen bonds

486 BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490

Fig 4 Packing of the molecules down b axis

BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490 487

Empirical formula C10H14 Cl N3O4

Formula weight 27569

Temperature 293(2)K

Wavelength 071073A

Crystal system Monoclinic

Space group P 21=c

Cell dimensions a = 6697(4) A

b = 9724(9) A

c = 19844(2) A

shy = 10972plusmn

Volume 121646(17)A3

Z 4

Density(calculated) 1505 Mgm3

Absorption coemacr cient 0326 mmiexcl1

F000 576

Crystal size 025 pound 02 pound 02 mm

Theta range for data collection 385plusmn to 3246plusmn

Index ranges iexcl 8 micro h micro 8

iexcl 14 micro k micro 14

iexcl 29 micro l micro 29

Reregections collected 3582

Independent reregections 2049 [R(int) = 00223]

Reshy nement method Full-matrix least-squares on F 2

Data restraints parameters 2049 0 164

Goodness-of-shy t on F 2 1066

Final R indices [I gt 2frac14 (I)] R1 = 00471

R indices (all data) R1 = 00635

Largest dinot peak and hole 0212 and -0187 eAiexcl3

Table 1 Experimental crystallographic details of 6 +

488 BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490

Atoms Length(A) Angle(plusmn) Symmetry Code

C8H1O1 3414 14969 iexcl x iexcl y iexcl z

C9H6O4 3499 16500 x 1=2 iexcl y iexcl 1=2 + z

C13H10AO2 3383 14938

C13H10BO3 3359 14893 1 + x y z

C12H11AO2 3317 16177 1 iexcl x iexcl 1=2 + y 1=2 iexcl z

C12H11BO3 3303 16201 iexcl x iexcl 1=2 + y 1=2 iexcl z

Table 2 Hydrogen Bonds

BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490 489

Atom x y z Ueq

N15 -06754(5) 015238(19) 007575(12) 00466(8)

N11 -06756(4) 001959(18) 007455(11) 00426(8)

C9 -08053(6) 00188(2) -005552(15) 00455(9)

N14 -06089(5) 01946(2) 014060(13) 00505(9)

C10 -07422(5) -00530(2) 000843(14) 00422(9)

C8 -08699(6) -00544(3) -011917(15) 00529(10)

C13 -05553(7) 00834(3) 019408(16) 00591(11)

C12 -06022(6) -00437(3) 014707(15) 00519(10)

C7 -08691(6) -01970(3) -011884(18) 00601(12)

C5 -07399(6) -01948(3) 000981(17) 00578(12)

C6 -08032(7) -02659(3) -00544(2) 00642(13)

C17 -06557(9) 04344(3) 00952(2) 00752(17)

C16 -05897(7) 03398(3) 015933(19) 00673(14)

Cl1 -091661(15) 035832(6) -016632(4) 00501(3)

O1 -09493(7) 04885(2) -019944(14) 00997(17)

O3 -11103(7) 02837(4) -01887(2) 01098(19)

O2 -07721(6) 02834(3) -01890(2) 01072(17)

O4 -08499(8) 03717(3) -009211(14) 0118(2)

Table 3 Atomic coordinates and equivalent thermal parameters

490 BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490

Atoms Length Atoms Length

N15-N14 1279(3) C8-C7 1387(4)

N15-N11 1291(3) C13-C12 1516(4)

N11-C10 1423(3) C7-C6 1378(5)

N11-C12 1488(3) C5-C6 1384(5)

C9-C10 1384(4) C17-C16 1510(5)

C9-C8 1386(4) Cl1-O4 1393(3)

N14-C16 1455(3) Cl1-O2 1401(2)

N14-C13 1472(3) Cl1-O1 1409(2)

C10-C5 1379(4) Cl1-O3 1420(4)

Atoms Angle Atoms Angle

N14-N15-N11 1097(2) N14-C13-C12 1019(2)

N15-N11-C10 1207(2) N11-C12-C13 1010(2)

N15-N11-C12 1134(2) C6-C7-C8 1194(3)

C10-N11-C12 1258(2) C10-C5-C6 1189(3)

C10-C9-C8 1188(2) C7-C6-C5 1209(2)

N15-N14-C16 1226(2) N14-C16-C17 1136(3)

N15-N14-C13 1140(2) O4-Cl1-O2 1122(3)

C16-N14-C13 1233(2) O4-Cl1-O1 1107(2)

C5-C10-C9 1214(2) O2-Cl1-O1 1094(2)

C5-C10-N11 1187(2) O4-Cl1-O3 1082(2)

C9-C10-N11 1199(2) O2-Cl1-O3 1069(2)

C9-C8-C7 1206(3) O1-Cl1-O3 1093(3)

Table 4 Bond Lengths (A) and Bond Angles (macr)

486 BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490

Fig 4 Packing of the molecules down b axis

BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490 487

Empirical formula C10H14 Cl N3O4

Formula weight 27569

Temperature 293(2)K

Wavelength 071073A

Crystal system Monoclinic

Space group P 21=c

Cell dimensions a = 6697(4) A

b = 9724(9) A

c = 19844(2) A

shy = 10972plusmn

Volume 121646(17)A3

Z 4

Density(calculated) 1505 Mgm3

Absorption coemacr cient 0326 mmiexcl1

F000 576

Crystal size 025 pound 02 pound 02 mm

Theta range for data collection 385plusmn to 3246plusmn

Index ranges iexcl 8 micro h micro 8

iexcl 14 micro k micro 14

iexcl 29 micro l micro 29

Reregections collected 3582

Independent reregections 2049 [R(int) = 00223]

Reshy nement method Full-matrix least-squares on F 2

Data restraints parameters 2049 0 164

Goodness-of-shy t on F 2 1066

Final R indices [I gt 2frac14 (I)] R1 = 00471

R indices (all data) R1 = 00635

Largest dinot peak and hole 0212 and -0187 eAiexcl3

Table 1 Experimental crystallographic details of 6 +

488 BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490

Atoms Length(A) Angle(plusmn) Symmetry Code

C8H1O1 3414 14969 iexcl x iexcl y iexcl z

C9H6O4 3499 16500 x 1=2 iexcl y iexcl 1=2 + z

C13H10AO2 3383 14938

C13H10BO3 3359 14893 1 + x y z

C12H11AO2 3317 16177 1 iexcl x iexcl 1=2 + y 1=2 iexcl z

C12H11BO3 3303 16201 iexcl x iexcl 1=2 + y 1=2 iexcl z

Table 2 Hydrogen Bonds

BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490 489

Atom x y z Ueq

N15 -06754(5) 015238(19) 007575(12) 00466(8)

N11 -06756(4) 001959(18) 007455(11) 00426(8)

C9 -08053(6) 00188(2) -005552(15) 00455(9)

N14 -06089(5) 01946(2) 014060(13) 00505(9)

C10 -07422(5) -00530(2) 000843(14) 00422(9)

C8 -08699(6) -00544(3) -011917(15) 00529(10)

C13 -05553(7) 00834(3) 019408(16) 00591(11)

C12 -06022(6) -00437(3) 014707(15) 00519(10)

C7 -08691(6) -01970(3) -011884(18) 00601(12)

C5 -07399(6) -01948(3) 000981(17) 00578(12)

C6 -08032(7) -02659(3) -00544(2) 00642(13)

C17 -06557(9) 04344(3) 00952(2) 00752(17)

C16 -05897(7) 03398(3) 015933(19) 00673(14)

Cl1 -091661(15) 035832(6) -016632(4) 00501(3)

O1 -09493(7) 04885(2) -019944(14) 00997(17)

O3 -11103(7) 02837(4) -01887(2) 01098(19)

O2 -07721(6) 02834(3) -01890(2) 01072(17)

O4 -08499(8) 03717(3) -009211(14) 0118(2)

Table 3 Atomic coordinates and equivalent thermal parameters

490 BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490

Atoms Length Atoms Length

N15-N14 1279(3) C8-C7 1387(4)

N15-N11 1291(3) C13-C12 1516(4)

N11-C10 1423(3) C7-C6 1378(5)

N11-C12 1488(3) C5-C6 1384(5)

C9-C10 1384(4) C17-C16 1510(5)

C9-C8 1386(4) Cl1-O4 1393(3)

N14-C16 1455(3) Cl1-O2 1401(2)

N14-C13 1472(3) Cl1-O1 1409(2)

C10-C5 1379(4) Cl1-O3 1420(4)

Atoms Angle Atoms Angle

N14-N15-N11 1097(2) N14-C13-C12 1019(2)

N15-N11-C10 1207(2) N11-C12-C13 1010(2)

N15-N11-C12 1134(2) C6-C7-C8 1194(3)

C10-N11-C12 1258(2) C10-C5-C6 1189(3)

C10-C9-C8 1188(2) C7-C6-C5 1209(2)

N15-N14-C16 1226(2) N14-C16-C17 1136(3)

N15-N14-C13 1140(2) O4-Cl1-O2 1122(3)

C16-N14-C13 1233(2) O4-Cl1-O1 1107(2)

C5-C10-C9 1214(2) O2-Cl1-O1 1094(2)

C5-C10-N11 1187(2) O4-Cl1-O3 1082(2)

C9-C10-N11 1199(2) O2-Cl1-O3 1069(2)

C9-C8-C7 1206(3) O1-Cl1-O3 1093(3)

Table 4 Bond Lengths (A) and Bond Angles (macr)

BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490 487

Empirical formula C10H14 Cl N3O4

Formula weight 27569

Temperature 293(2)K

Wavelength 071073A

Crystal system Monoclinic

Space group P 21=c

Cell dimensions a = 6697(4) A

b = 9724(9) A

c = 19844(2) A

shy = 10972plusmn

Volume 121646(17)A3

Z 4

Density(calculated) 1505 Mgm3

Absorption coemacr cient 0326 mmiexcl1

F000 576

Crystal size 025 pound 02 pound 02 mm

Theta range for data collection 385plusmn to 3246plusmn

Index ranges iexcl 8 micro h micro 8

iexcl 14 micro k micro 14

iexcl 29 micro l micro 29

Reregections collected 3582

Independent reregections 2049 [R(int) = 00223]

Reshy nement method Full-matrix least-squares on F 2

Data restraints parameters 2049 0 164

Goodness-of-shy t on F 2 1066

Final R indices [I gt 2frac14 (I)] R1 = 00471

R indices (all data) R1 = 00635

Largest dinot peak and hole 0212 and -0187 eAiexcl3

Table 1 Experimental crystallographic details of 6 +

488 BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490

Atoms Length(A) Angle(plusmn) Symmetry Code

C8H1O1 3414 14969 iexcl x iexcl y iexcl z

C9H6O4 3499 16500 x 1=2 iexcl y iexcl 1=2 + z

C13H10AO2 3383 14938

C13H10BO3 3359 14893 1 + x y z

C12H11AO2 3317 16177 1 iexcl x iexcl 1=2 + y 1=2 iexcl z

C12H11BO3 3303 16201 iexcl x iexcl 1=2 + y 1=2 iexcl z

Table 2 Hydrogen Bonds

BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490 489

Atom x y z Ueq

N15 -06754(5) 015238(19) 007575(12) 00466(8)

N11 -06756(4) 001959(18) 007455(11) 00426(8)

C9 -08053(6) 00188(2) -005552(15) 00455(9)

N14 -06089(5) 01946(2) 014060(13) 00505(9)

C10 -07422(5) -00530(2) 000843(14) 00422(9)

C8 -08699(6) -00544(3) -011917(15) 00529(10)

C13 -05553(7) 00834(3) 019408(16) 00591(11)

C12 -06022(6) -00437(3) 014707(15) 00519(10)

C7 -08691(6) -01970(3) -011884(18) 00601(12)

C5 -07399(6) -01948(3) 000981(17) 00578(12)

C6 -08032(7) -02659(3) -00544(2) 00642(13)

C17 -06557(9) 04344(3) 00952(2) 00752(17)

C16 -05897(7) 03398(3) 015933(19) 00673(14)

Cl1 -091661(15) 035832(6) -016632(4) 00501(3)

O1 -09493(7) 04885(2) -019944(14) 00997(17)

O3 -11103(7) 02837(4) -01887(2) 01098(19)

O2 -07721(6) 02834(3) -01890(2) 01072(17)

O4 -08499(8) 03717(3) -009211(14) 0118(2)

Table 3 Atomic coordinates and equivalent thermal parameters

490 BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490

Atoms Length Atoms Length

N15-N14 1279(3) C8-C7 1387(4)

N15-N11 1291(3) C13-C12 1516(4)

N11-C10 1423(3) C7-C6 1378(5)

N11-C12 1488(3) C5-C6 1384(5)

C9-C10 1384(4) C17-C16 1510(5)

C9-C8 1386(4) Cl1-O4 1393(3)

N14-C16 1455(3) Cl1-O2 1401(2)

N14-C13 1472(3) Cl1-O1 1409(2)

C10-C5 1379(4) Cl1-O3 1420(4)

Atoms Angle Atoms Angle

N14-N15-N11 1097(2) N14-C13-C12 1019(2)

N15-N11-C10 1207(2) N11-C12-C13 1010(2)

N15-N11-C12 1134(2) C6-C7-C8 1194(3)

C10-N11-C12 1258(2) C10-C5-C6 1189(3)

C10-C9-C8 1188(2) C7-C6-C5 1209(2)

N15-N14-C16 1226(2) N14-C16-C17 1136(3)

N15-N14-C13 1140(2) O4-Cl1-O2 1122(3)

C16-N14-C13 1233(2) O4-Cl1-O1 1107(2)

C5-C10-C9 1214(2) O2-Cl1-O1 1094(2)

C5-C10-N11 1187(2) O4-Cl1-O3 1082(2)

C9-C10-N11 1199(2) O2-Cl1-O3 1069(2)

C9-C8-C7 1206(3) O1-Cl1-O3 1093(3)

Table 4 Bond Lengths (A) and Bond Angles (macr)

488 BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490

Atoms Length(A) Angle(plusmn) Symmetry Code

C8H1O1 3414 14969 iexcl x iexcl y iexcl z

C9H6O4 3499 16500 x 1=2 iexcl y iexcl 1=2 + z

C13H10AO2 3383 14938

C13H10BO3 3359 14893 1 + x y z

C12H11AO2 3317 16177 1 iexcl x iexcl 1=2 + y 1=2 iexcl z

C12H11BO3 3303 16201 iexcl x iexcl 1=2 + y 1=2 iexcl z

Table 2 Hydrogen Bonds

BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490 489

Atom x y z Ueq

N15 -06754(5) 015238(19) 007575(12) 00466(8)

N11 -06756(4) 001959(18) 007455(11) 00426(8)

C9 -08053(6) 00188(2) -005552(15) 00455(9)

N14 -06089(5) 01946(2) 014060(13) 00505(9)

C10 -07422(5) -00530(2) 000843(14) 00422(9)

C8 -08699(6) -00544(3) -011917(15) 00529(10)

C13 -05553(7) 00834(3) 019408(16) 00591(11)

C12 -06022(6) -00437(3) 014707(15) 00519(10)

C7 -08691(6) -01970(3) -011884(18) 00601(12)

C5 -07399(6) -01948(3) 000981(17) 00578(12)

C6 -08032(7) -02659(3) -00544(2) 00642(13)

C17 -06557(9) 04344(3) 00952(2) 00752(17)

C16 -05897(7) 03398(3) 015933(19) 00673(14)

Cl1 -091661(15) 035832(6) -016632(4) 00501(3)

O1 -09493(7) 04885(2) -019944(14) 00997(17)

O3 -11103(7) 02837(4) -01887(2) 01098(19)

O2 -07721(6) 02834(3) -01890(2) 01072(17)

O4 -08499(8) 03717(3) -009211(14) 0118(2)

Table 3 Atomic coordinates and equivalent thermal parameters

490 BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490

Atoms Length Atoms Length

N15-N14 1279(3) C8-C7 1387(4)

N15-N11 1291(3) C13-C12 1516(4)

N11-C10 1423(3) C7-C6 1378(5)

N11-C12 1488(3) C5-C6 1384(5)

C9-C10 1384(4) C17-C16 1510(5)

C9-C8 1386(4) Cl1-O4 1393(3)

N14-C16 1455(3) Cl1-O2 1401(2)

N14-C13 1472(3) Cl1-O1 1409(2)

C10-C5 1379(4) Cl1-O3 1420(4)

Atoms Angle Atoms Angle

N14-N15-N11 1097(2) N14-C13-C12 1019(2)

N15-N11-C10 1207(2) N11-C12-C13 1010(2)

N15-N11-C12 1134(2) C6-C7-C8 1194(3)

C10-N11-C12 1258(2) C10-C5-C6 1189(3)

C10-C9-C8 1188(2) C7-C6-C5 1209(2)

N15-N14-C16 1226(2) N14-C16-C17 1136(3)

N15-N14-C13 1140(2) O4-Cl1-O2 1122(3)

C16-N14-C13 1233(2) O4-Cl1-O1 1107(2)

C5-C10-C9 1214(2) O2-Cl1-O1 1094(2)

C5-C10-N11 1187(2) O4-Cl1-O3 1082(2)

C9-C10-N11 1199(2) O2-Cl1-O3 1069(2)

C9-C8-C7 1206(3) O1-Cl1-O3 1093(3)

Table 4 Bond Lengths (A) and Bond Angles (macr)

BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490 489

Atom x y z Ueq

N15 -06754(5) 015238(19) 007575(12) 00466(8)

N11 -06756(4) 001959(18) 007455(11) 00426(8)

C9 -08053(6) 00188(2) -005552(15) 00455(9)

N14 -06089(5) 01946(2) 014060(13) 00505(9)

C10 -07422(5) -00530(2) 000843(14) 00422(9)

C8 -08699(6) -00544(3) -011917(15) 00529(10)

C13 -05553(7) 00834(3) 019408(16) 00591(11)

C12 -06022(6) -00437(3) 014707(15) 00519(10)

C7 -08691(6) -01970(3) -011884(18) 00601(12)

C5 -07399(6) -01948(3) 000981(17) 00578(12)

C6 -08032(7) -02659(3) -00544(2) 00642(13)

C17 -06557(9) 04344(3) 00952(2) 00752(17)

C16 -05897(7) 03398(3) 015933(19) 00673(14)

Cl1 -091661(15) 035832(6) -016632(4) 00501(3)

O1 -09493(7) 04885(2) -019944(14) 00997(17)

O3 -11103(7) 02837(4) -01887(2) 01098(19)

O2 -07721(6) 02834(3) -01890(2) 01072(17)

O4 -08499(8) 03717(3) -009211(14) 0118(2)

Table 3 Atomic coordinates and equivalent thermal parameters

490 BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490

Atoms Length Atoms Length

N15-N14 1279(3) C8-C7 1387(4)

N15-N11 1291(3) C13-C12 1516(4)

N11-C10 1423(3) C7-C6 1378(5)

N11-C12 1488(3) C5-C6 1384(5)

C9-C10 1384(4) C17-C16 1510(5)

C9-C8 1386(4) Cl1-O4 1393(3)

N14-C16 1455(3) Cl1-O2 1401(2)

N14-C13 1472(3) Cl1-O1 1409(2)

C10-C5 1379(4) Cl1-O3 1420(4)

Atoms Angle Atoms Angle

N14-N15-N11 1097(2) N14-C13-C12 1019(2)

N15-N11-C10 1207(2) N11-C12-C13 1010(2)

N15-N11-C12 1134(2) C6-C7-C8 1194(3)

C10-N11-C12 1258(2) C10-C5-C6 1189(3)

C10-C9-C8 1188(2) C7-C6-C5 1209(2)

N15-N14-C16 1226(2) N14-C16-C17 1136(3)

N15-N14-C13 1140(2) O4-Cl1-O2 1122(3)

C16-N14-C13 1233(2) O4-Cl1-O1 1107(2)

C5-C10-C9 1214(2) O2-Cl1-O1 1094(2)

C5-C10-N11 1187(2) O4-Cl1-O3 1082(2)

C9-C10-N11 1199(2) O2-Cl1-O3 1069(2)

C9-C8-C7 1206(3) O1-Cl1-O3 1093(3)

Table 4 Bond Lengths (A) and Bond Angles (macr)

490 BH Doreswamy et al Central European Journal of Chemistry 4 (2003) 477490

Atoms Length Atoms Length

N15-N14 1279(3) C8-C7 1387(4)

N15-N11 1291(3) C13-C12 1516(4)

N11-C10 1423(3) C7-C6 1378(5)

N11-C12 1488(3) C5-C6 1384(5)

C9-C10 1384(4) C17-C16 1510(5)

C9-C8 1386(4) Cl1-O4 1393(3)

N14-C16 1455(3) Cl1-O2 1401(2)

N14-C13 1472(3) Cl1-O1 1409(2)

C10-C5 1379(4) Cl1-O3 1420(4)

Atoms Angle Atoms Angle

N14-N15-N11 1097(2) N14-C13-C12 1019(2)

N15-N11-C10 1207(2) N11-C12-C13 1010(2)

N15-N11-C12 1134(2) C6-C7-C8 1194(3)

C10-N11-C12 1258(2) C10-C5-C6 1189(3)

C10-C9-C8 1188(2) C7-C6-C5 1209(2)

N15-N14-C16 1226(2) N14-C16-C17 1136(3)

N15-N14-C13 1140(2) O4-Cl1-O2 1122(3)

C16-N14-C13 1233(2) O4-Cl1-O1 1107(2)

C5-C10-C9 1214(2) O2-Cl1-O1 1094(2)

C5-C10-N11 1187(2) O4-Cl1-O3 1082(2)

C9-C10-N11 1199(2) O2-Cl1-O3 1069(2)

C9-C8-C7 1206(3) O1-Cl1-O3 1093(3)

Table 4 Bond Lengths (A) and Bond Angles (macr)