research papers

Acta Cryst. (2016). C72, 917–922 http://dx.doi.org/10.1107/S2053229616016430 917

Received 10 September 2016

Accepted 14 October 2016

Edited by A. L. Spek, Utrecht University, The

Netherlands

Keywords: zinc(II); crystal structure; 1-[(benzo-

triazol-1-yl)methyl]-1H-imidazole; spectro-

scopic properties; PXRD patterns; fluorescence

properties; bromide; iodide.

CCDC references: 1510011; 1510010

Supporting information: this article has

supporting information at journals.iucr.org/c

Syntheses, structures and properties of twonew isostructural zinc(II) complexes based on1-[(benzotriazol-1-yl)methyl]-1H-imidazole

Chun-Li Liu,a Xu Wei,a Qiu-Ying Huanga* and Xiang-Ru Mengb

aDepartment of Chemical Engineering, Henan Polytechnic Institute, 473009 Nanyang, Henan, People’s Republic of

China, and bThe College of Chemistry and Molecular Engineering, Zhengzhou University, 450001 Zhengzhou, Henan,

People’s Republic of China. *Correspondence e-mail: huangqy72@163.com

Due to their strong coordination ability and the diversities of their coordination

modes, N-heterocyclic organic compounds are used extensively as ligands for

the construction of complexes with fascinating structures and potential appli-

cations in many fields. Two new complexes, namely bis{1-[(benzotriazol-1-yl)-

methyl]-1H-imidazole-�N3}dibromidozinc(II), [ZnBr2(C10H9N5)2], (I), and bis-

{1-[(benzotriazol-1-yl)methyl]-1H-imidazole-�N3}diiodidozinc(II), [ZnI2(C10H9-

N5)2], (II), have been synthesized by reaction of the unsymmetrical N-hetero-

cyclic ligand 1-[(benzotriazol-1-yl)methyl]-1H-imidazole (bmi) with Zn(ace-

tate)2 in the presence of KBr or KI. Single-crystal X-ray diffraction analysis

shows that both complexes exhibit a mononuclear structure, in which the bmi

ligands coordinate to the central metal ion in a monodentate mode. In the solid

state, both complexes possess a three-dimensional network formed by hydrogen

bonds and �–� interactions. In addition, the IR spectroscopic properties, PXRD

patterns and fluorescence properties of both complexes have been investigated.

1. Introduction

Owing to the strong coordination ability and diversities of

their coordination modes, N-heterocyclic organic compounds,

such as imidazole, triazole, benzimidazole, benzotriazole and

their derivatives, have been used extensively as ligands for the

construction of complexes with intriguing structures and

potential applications in fluorescent materials, nonlinear

optical (NLO) and ferroelectric materials, dielectric materials

and the pharmaceutical industry (Wang et al., 2010; Dou et al.,

2016; Castillo et al., 2016; Brede et al., 2016). In recent years,

many researchers, including our group, have focused their

attention on the design and synthesis of metal–organic

complexes based on 1-[(benzotriazol-1-yl)methyl]-1H-imida-

zole (bmi), since it has three potential N-atom donors and can

coordinate to metal ions in monodentate or bridging coordi-

nation modes in the construction of complexes (An et al., 2008;

Zhang et al., 2015). Up to now, more than 20 complexes

constructed from the bmi ligand have been reported, ranging

from zero-dimensional complexes to two-dimensional

networks with a rich structural diversity. In previous work,

through the self-assembly of the unsymmetrical bmi ligand

with ZnCl2, Zn(NO3)2, ZnSO4 and Zn(Ac)2 (Ac is acetate), in

the presence or absence of benzene-1,4-dicarboxylic acid

(H2bdc) or NaN3, a series of complexes, namely [ZnCl2-

(bmi)2], [Zn(NO3)2(bmi)2]n, [Zn(SO4)(bmi)(H2O)4]�2H2O,

[Zn(bdc)(bmi)2]n and [Zn(N3)2(bmi)2] (Duan et al., 2010b;

Meng et al., 2009; Zhang et al., 2015), have been synthesized.

In order to enrich the variety and number of complexes

ISSN 2053-2296

# 2016 International Union of Crystallography

involving the bmi ligand, in this paper, we have reacted bmi

with Zn(Ac)2 in the presence of KBr or KI and obtained two

new complexes, viz. [ZnBr2(bmi)2], (I), and [ZnI2(bmi)2], (II).

In addition, the elemental analysis, IR spectra, PXRD patterns

and fluorescence properties of both complexes have been

investigated.

2. Experimental

All chemicals were of AR grade and were used without

purification. Elemental analyses (C, H and N) were carried out

on a FLASH EA 1112 elemental analyzer. IR data were

recorded on a Bruker TENSOR 27 spectrophotometer with

KBr pellets in the 4000–400 cm�1 region. PXRD patterns were

recorded using Cu K� radiation on a PANalytical X’Pert PRO

diffractometer. Steady-state fluorescence measurements were

performed using an F-7000 fluorescence spectrophotometer

operating at 700 V at room temperature in the solid state. The

excitation slit was 5 nm, the emission slit was also 5 nm and the

scan speed was 240 nm min�1.

2.1. Synthesis and crystallization

1-[(Benzotriazol-1-yl)methyl]-1H-imidazole (bmi) was syn-

thesized according to the literature method of Katritzky et al.

(1989). A methanol solution (3 ml) of bmi (0.1 mmol) was

added dropwise to an aqueous solution (2 ml) of Zn(Ac)2 (Ac

is acetate; 0.05 mmol) and KBr (0.1 mmol) to give a clear

solution at room temperature. Colourless crystals of (I)

suitable for X-ray analysis were obtained after four weeks by

slow crystallization in a closed container (yield 42%, based on

Zn). Analysis calculated for C20H18Br2N10Zn: C 38.52, H 2.91,

N 22.46%; found: C 37.99, H 2.79, N 22.81%. IR (KBr disc, �,

cm�1): 3127 (s), 3007 (s), 1617 (m), 1520 (s), 1496 (s), 1454 (s),

1388 (s), 1310 (s), 1280 (s), 1226 (s), 1160 (s), 1104 (s), 1080 (s),

753 (s), 653 (m). The preparation of (II) was similar to that of

(I), except that KBr was replaced with KI. Crystals of (II)

suitable for X-ray analysis were obtained by slow crystal-

lization in a closed container (yield 41%, based on Zn).

Analysis calculated for C20H18I2N10Zn: C 33.47, H 2.53, N

19.52%; found: C 33.79, H 2.34, N 20.31%. IR (KBr disc, �,

cm�1): 3125 (s), 3004 (s), 1617 (m), 1520 (s), 1495 (s), 1453 (s),

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918 Liu et al. � [ZnBr2(C10H9N5)2] and [ZnI2(C10H9N5)2] Acta Cryst. (2016). C72, 917–922

Table 1Experimental details.

(I) (II)

Crystal dataChemical formula [ZnBr2(C10H9N5)2] [ZnI2(C10H9N5)2]Mr 623.63 717.61Crystal system, space group Orthorhombic, Pbcn Orthorhombic, PbcnTemperature (K) 293 293a, b, c (A) 11.498 (2), 11.715 (2), 17.071 (3) 11.729 (2), 11.853 (2), 17.563 (4)V (A3) 2299.4 (8) 2441.7 (8)Z 4 4Radiation type Mo K� Mo K�� (mm�1) 4.58 3.56Crystal size (mm) 0.17 � 0.16 � 0.12 0.16 � 0.13 � 0.08

Data collectionDiffractometer Rigaku Saturn Rigaku SaturnAbsorption correction Multi-scan (CrystalClear; Rigaku/MSC, 2004) Multi-scan (CrystalClear; Rigaku/MSC, 2004)Tmin, Tmax 0.742, 1.000 0.813, 1.000No. of measured, independent and observed

[I > 2�(I)] reflections14163, 2271, 1977 14216, 2400, 2235

Rint 0.044 0.033(sin �/)max (A�1) 0.617 0.617

RefinementR[F 2 > 2�(F 2)], wR(F 2), S 0.042, 0.082, 1.12 0.032, 0.064, 1.14No. of reflections 2271 2400No. of parameters 150 150H-atom treatment H-atom parameters constrained H-atom parameters constrained�max, �min (e A�3) 0.45, �0.42 0.48, �0.62

Computer programs: CrystalClear (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), DIAMOND (Brandenburg & Putz, 2005) and publCIF (Westrip,2010).

1390 (s), 1309 (s), 1279 (m), 1225 (s), 1159 (s), 1103 (s),

1080 (s), 750 (s), 652 (s).

2.2. Refinement

Crystal data, data collection and structure refinement

details are summarized in Table 1. H atoms were positioned

geometrically and refined as riding atoms, with C—H = 0.93

(aromatic) and 0.97 A (CH2). All H atoms were refined with

Uiso(H) = 1.2Ueq(C).

3. Results and discussion

3.1. IR spectroscopy

The IR spectra of complexes (I) and (II) show that the

absorption bands at 3127 cm�1 for (I) and 3125 cm�1 for (II)

can be attributed to the stretching vibrations of aromatic H

atoms. The absorption bands at 3007 cm�1 for (I) and

3004 cm�1 for (II) originate from CH2 stretching vibrations.

The four sharp absorption bands observed at 1617, 1520, 1496

and 1454 cm�1 for (I), and at 1617, 1520, 1495 and 1453 cm�1

for (II) could be associated with the stretching vibrations of

C C, N N and C N. The absorption bands at 1280 cm�1

for (I) and 1279 cm�1 for (II) are due to the stretching

vibrations of C—N. The absorption bands at 753 cm�1 for (I)

and 750 cm�1 for (II) belong to the characteristic C—H

deformation vibration of a 1,2-disubstituted benzene ring.

These findings are confirmed by the results of the X-ray

diffraction analysis.

3.2. Structures of (I) and (II)

The crystal and molecular structures of complexes (I) and

(II) closely resemble each other, the similarity extending to

crystallizing in the same orthorhombic Pbcn space group.

Complexes (I) and (II) are isostructural, with only slight

differences in their bond lengths and angles (Tables 2 and 3).

Therefore, only the structure of (I) will be discussed in detail

here. The asymmetric unit of (I) contains a ZnII ion, located on

a centre of inversion, one bmi ligand and one bromide ligand.

As shown in Fig. 1(a), each ZnII ion is four-coordinated by two

symmetry-related bromide anions and two N atoms from two

symmetry-related bmi ligands. The Zn—N and Zn—Br bond

lengths are 2.026 (3) and 2.3698 (6) A, respectively. The

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Acta Cryst. (2016). C72, 917–922 Liu et al. � [ZnBr2(C10H9N5)2] and [ZnI2(C10H9N5)2] 919

Figure 1The coordination environments of the ZnII ions in complexes (I) and (II),with displacement ellipsoids drawn at the 30% probability level.[Symmetry code: (i) �x, y, �z + 1

2.]

Table 2Selected geometric parameters (A, �) for (I).

Zn1—N1 2.026 (3) Zn1—Br1 2.3698 (6)

N1—Zn1—N1i 109.71 (16) N1i—Zn1—Br1 104.74 (8)N1—Zn1—Br1 110.10 (8) Br1—Zn1—Br1i 117.41 (3)

Symmetry code: (i) �x; y;�zþ 12.

Table 3Selected geometric parameters (A, �) for (II).

Zn1—N1 2.028 (3) Zn1—I1 2.5611 (5)

N1i—Zn1—N1 110.27 (16) N1—Zn1—I1 109.45 (8)N1i—Zn1—I1 104.87 (8) I1i—Zn1—I1 117.91 (3)

Symmetry code: (i) �x; y;�zþ 12.

Figure 2A view of the two-dimensional structure of complex (I) supported byhydrogen bonds (dash lines). Molecules are shown in two colours forclarity and some of the H atoms have been omitted.

Zn—N bond length is almost equal to the Zn—N bond lengths

observed in [Zn(N3)2(bmi)2], [Zn(NO3)2(bmi)2]n, [Zn(SO4)-

(bmi)(H2O)4]�2H2O and [Zn(Me-Alt-NNO)Cl] {Me-Alt-

NNO is methyl 4,6-O-benzylidene-3-deoxy-3-[2-(salicylidene-

amino)ethylamino]-�-d-altropyranoside; Duan et al., 2010b;

Meng et al., 2009; Liu et al., 2009}. The Zn—Br bond length is

close to those observed in [ZnBr2(L2)] [L2 is bis(2H-indazol-2-

yl)methane; Claudio et al., 2010], but longer than the Zn—Cl

bond length [2.2363 (8) A] in [ZnCl2(bmi)2] (Duan et al.,

2010b). The angles around the ZnII ion range from 104.74 (8)

to 117.41 (3)�. Thus, the the ZnII ion is located in a distorted

tetrahedral coordination environment.

As shown in Table 4, there are two kinds of intermolecular

hydrogen bonds in (I) [the hydrogen bonds for (II) are listed

in Table 5]. One is a C(CH2)—H� � �Br hydrogen bond and the

other is a C(CH2)—H� � �N(benzotriazole) hydrogen bond.

The [ZnBr2(bmi)2] units are connected by these two kinds of

hydrogen bonds, leading to an infinite two-dimensional

layered structure parallel to the ab plane (Fig. 2). In addition,

benzotriazole rings from adjacent layers are parallel to each

other, with the distance between the centroids of the N3/N4/

N5/C5/C10 and C5–C10 rings being 3.745 (2) A, which is in the

range for common �–� interactions (Zhang et al., 2014).

Therefore, adjacent layers are further linked by the �–�interactions, resulting in a three-dimensional supramolecular

architecture in the solid state (Fig. 3).

In complex (II), the Zn—N bond length (Table 3) is similar

to that in (I). The Zn—I bond length is identical to those

found in [ZnI2(L1)] [L1 is bis(1H-indazol-1-yl)methane;

Claudio et al., 2010] and longer than the Zn—Br bond length

in (I). Thus, including the reported [ZnCl2(bmi)2] complex

[Zn—Cl = 2.2363 (8) A; Duan et al., 2010b], the

bond lengths increase in the order Zn—Cl < Zn—Br < Zn—I.

Among the 27 reported bmi-based complexes, the bmi

ligands coordinate to the metal ions in a monodentate mode in

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920 Liu et al. � [ZnBr2(C10H9N5)2] and [ZnI2(C10H9N5)2] Acta Cryst. (2016). C72, 917–922

Figure 3The three-dimensional structure of complex (I) in the solid statesupported by hydrogen bonds and �–� interactions. Adjacent layersare shown in different colours. Some of the H atoms have been omittedfor clarity.

Table 4Hydrogen-bond geometry (A, �) for (I).

D—H� � �A D—H H� � �A D� � �A D—H� � �A

C4—H4A� � �Br1ii 0.97 3.01 3.951 (4) 163C4—H4B� � �N5iii 0.97 2.50 3.449 (5) 167

Symmetry codes: (ii) xþ 12; y� 1

2;�zþ 12; (iii) �xþ 1

2; y þ 12; z.

Table 5Hydrogen-bond geometry (A, �) for (II).

D—H� � �A D—H H� � �A D� � �A D—H� � �A

C4—H4A� � �I1ii 0.97 3.17 4.112 (4) 165C4—H4B� � �N5iii 0.97 2.47 3.424 (5) 167

Symmetry codes: (ii) xþ 12; yþ 1

2;�zþ 12; (iii) �xþ 1

2; y � 12; z.

Figure 4The measured and simulated PXRD patterns of complexes (I) and (II).

17 complexes and in a bridging mode in ten complexes (Duan

et al., 2010a,b; Meng et al., 2009; Zhou et al., 2011; Wang & Sun,

2011; An et al., 2008; Hu et al., 2012; Huang et al., 2014; Zhang

et al., 2015). In this work, the bmi ligands coordinate to the

ZnII ion only via imidazole atom N1 in a monodentate mode,

even though there are three potential N-atom donors in bmi.

The origin of this behaviour can be traced back to the

differences in the Mulliken atomic charge distributions of the

N atoms in free bmi; the Mulliken charges are�0.237 for atom

N1, �0.049 for atom N4 and �0.155 for atom N5 (Duan et al.,

2010a). Thus, there is an obvious advantage in atom N1

coordinating to metal atoms and bmi can be used as a

monodentate ligand. Under the appropriate reaction condi-

tions, bmi can act as a bridging ligand (with atoms N1 and N5

as donors), forming one-, two- and three-dimensional struc-

tures (Zhang et al., 2015; Zhou et al., 2011).

3.3. PXRD analysis

To confirm that the crystal structures of (I) and (II) are truly

representative of the bulk materials, powder X-ray diffraction

(PXRD) experiments were carried out. As shown in Figs. 4(a)

and 4(b), the major peak positions of the PXRD patterns of

the bulk solids match well with those of the corresponding

simulated ones obtained from the single-crystal data, indi-

cating, in each case, the presence of mainly one crystalline

phase and that the synthesized bulk material is the same as the

single crystal.

3.4. Fluorescence properties

It is well known that a number of d10 transition-metal

complexes exhibit interesting fluorescence properties if the

ligands incorporated in the complexes display a fluorescence

emission (Wang et al., 2014). Therefore, the fluorescence

properties of free bmi and complexes (I) and (II) were

examined in the solid state at room temperature. As illustrated

in Fig. 5, free bmi displays an emission band with a maximum

at 391 nm when excited at 334 nm, complex (I) displays an

emission band at 375 nm when excited at 334 nm and complex

(II) shows an emission band at 402 nm when excited at

332 nm. Apparently, the emission spectra of both complexes

(I) and (II) are similar to that of bmi in terms of the position

and the band shape, indicating that the emission bands of

complexes (I) and (II) may be attributed to the emission of an

intraligand �–�* transition. Compared with the emission

spectrum of bmi, a slight blue shift of 16 nm is observed for (I)

and a slight red shift of 11 nm is observed for (II), both of

which are considered to arise mainly from the different

coordination environments of the metal ions. The fluorescence

emission of complex (II) is weaker than that of (I). This may

be due to the fluorescence quenching effect of iodide anions

(Mu et al., 2009; Jin et al., 2012).

Acknowledgements

The authors gratefully acknowledge financial support by

Henan Province Foundation and Advanced Technology

Research Project (grant No. 162300410206) and the Founda-

tion of Henan Educational Committee (grant No. 16B150002).

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922 Liu et al. � [ZnBr2(C10H9N5)2] and [ZnI2(C10H9N5)2] Acta Cryst. (2016). C72, 917–922

supporting information

sup-1Acta Cryst. (2016). C72, 917-922

supporting information

Acta Cryst. (2016). C72, 917-922 [https://doi.org/10.1107/S2053229616016430]

Syntheses, structures and properties of two new isostructural zinc(II) complexes

based on 1-[(benzotriazol-1-yl)methyl]-1H-imidazole

Chun-Li Liu, Xu Wei, Qiu-Ying Huang and Xiang-Ru Meng

Computing details

For both compounds, data collection: CrystalClear (Rigaku/MSC, 2004); cell refinement: CrystalClear (Rigaku/MSC,

2004); data reduction: CrystalClear (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick,

2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND

(Brandenburg & Putz, 2005); software used to prepare material for publication: publCIF (Westrip, 2010).

(I) Bis{1-[(benzotriazol-1-yl)methyl]-1H-imidazole-κN3}dibromidozinc(II)

Crystal data

[ZnBr2(C10H9N5)2]Mr = 623.63Orthorhombic, Pbcna = 11.498 (2) Åb = 11.715 (2) Åc = 17.071 (3) ÅV = 2299.4 (8) Å3

Z = 4F(000) = 1232

Dx = 1.801 Mg m−3

Mo Kα radiation, λ = 0.71073 ÅCell parameters from 5172 reflectionsθ = 2.1–27.8°µ = 4.58 mm−1

T = 293 KPrism, colourless0.17 × 0.16 × 0.12 mm

Data collection

Rigaku Saturn diffractometer

Radiation source: fine-focus sealed tubeDetector resolution: 28.5714 pixels mm-1

ω scansAbsorption correction: multi-scan

(CrystalClear; Rigaku/MSC, 2004)Tmin = 0.742, Tmax = 1.000

14163 measured reflections2271 independent reflections1977 reflections with I > 2σ(I)Rint = 0.044θmax = 26.0°, θmin = 2.4°h = −13→14k = −10→14l = −16→21

Refinement

Refinement on F2

Least-squares matrix: fullR[F2 > 2σ(F2)] = 0.042wR(F2) = 0.082S = 1.122271 reflections150 parameters0 restraints

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrainedw = 1/[σ2(Fo

2) + (0.0336P)2 + 1.2668P] where P = (Fo

2 + 2Fc2)/3

(Δ/σ)max < 0.001Δρmax = 0.45 e Å−3

Δρmin = −0.42 e Å−3

supporting information

sup-2Acta Cryst. (2016). C72, 917-922

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

x y z Uiso*/Ueq

Zn1 0.0000 0.36417 (5) 0.2500 0.03343 (17)Br1 0.06408 (4) 0.46925 (3) 0.13951 (2) 0.04817 (15)N1 0.1306 (3) 0.2646 (2) 0.29102 (15) 0.0345 (7)N2 0.2490 (3) 0.1814 (2) 0.37410 (14) 0.0324 (6)N3 0.2304 (3) 0.0759 (2) 0.49422 (15) 0.0338 (7)N4 0.2355 (3) −0.0394 (2) 0.48559 (18) 0.0458 (8)N5 0.1587 (3) −0.0850 (2) 0.53165 (19) 0.0471 (8)C1 0.1668 (3) 0.2613 (3) 0.36456 (19) 0.0341 (8)H1A 0.1390 0.3082 0.4043 0.041*C2 0.1949 (3) 0.1836 (3) 0.2520 (2) 0.0403 (9)H2A 0.1896 0.1676 0.1988 0.048*C3 0.2663 (3) 0.1314 (3) 0.3027 (2) 0.0417 (9)H3A 0.3178 0.0725 0.2915 0.050*C4 0.3044 (3) 0.1492 (3) 0.44837 (19) 0.0366 (8)H4A 0.3771 0.1102 0.4376 0.044*H4B 0.3221 0.2176 0.4781 0.044*C5 0.1482 (3) 0.1042 (3) 0.54808 (18) 0.0331 (8)C6 0.1113 (3) 0.2074 (3) 0.58013 (19) 0.0378 (8)H6A 0.1434 0.2768 0.5649 0.045*C7 0.0256 (4) 0.2008 (4) 0.6349 (2) 0.0475 (10)H7A 0.0002 0.2677 0.6588 0.057*C8 −0.0260 (4) 0.0971 (4) 0.6568 (2) 0.0537 (11)H8A −0.0870 0.0972 0.6925 0.064*C9 0.0119 (4) −0.0037 (4) 0.6266 (2) 0.0515 (11)H9A −0.0209 −0.0727 0.6420 0.062*C10 0.1019 (3) 0.0002 (3) 0.5716 (2) 0.0376 (9)

Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23

Zn1 0.0363 (4) 0.0307 (3) 0.0333 (3) 0.000 −0.0025 (2) 0.000Br1 0.0489 (3) 0.0499 (3) 0.0458 (3) −0.00021 (19) 0.00781 (18) 0.01271 (18)N1 0.0373 (18) 0.0321 (16) 0.0340 (16) −0.0024 (13) −0.0031 (13) −0.0019 (12)N2 0.0313 (17) 0.0323 (15) 0.0337 (16) 0.0021 (13) −0.0015 (12) −0.0018 (13)N3 0.0394 (19) 0.0254 (14) 0.0367 (16) 0.0033 (13) −0.0054 (13) 0.0008 (12)N4 0.058 (2) 0.0309 (17) 0.0489 (19) 0.0090 (16) −0.0114 (17) −0.0016 (14)N5 0.058 (2) 0.0282 (16) 0.055 (2) −0.0007 (16) −0.0144 (17) 0.0021 (15)C1 0.036 (2) 0.0305 (18) 0.0360 (19) 0.0001 (15) 0.0006 (15) −0.0019 (15)C2 0.041 (2) 0.046 (2) 0.0340 (19) 0.0018 (18) 0.0025 (17) −0.0060 (17)

supporting information

sup-3Acta Cryst. (2016). C72, 917-922

C3 0.041 (2) 0.042 (2) 0.042 (2) 0.0104 (18) 0.0038 (17) −0.0080 (17)C4 0.033 (2) 0.039 (2) 0.039 (2) 0.0039 (16) −0.0045 (15) 0.0000 (16)C5 0.033 (2) 0.0332 (19) 0.0334 (18) −0.0017 (15) −0.0082 (15) 0.0043 (15)C6 0.042 (2) 0.0301 (18) 0.042 (2) 0.0027 (16) −0.0018 (17) 0.0022 (15)C7 0.051 (3) 0.049 (2) 0.042 (2) 0.010 (2) −0.0014 (18) 0.0007 (18)C8 0.041 (3) 0.075 (3) 0.045 (2) 0.001 (2) −0.0017 (18) 0.007 (2)C9 0.047 (3) 0.058 (3) 0.050 (2) −0.018 (2) −0.014 (2) 0.023 (2)C10 0.040 (2) 0.0327 (19) 0.041 (2) −0.0030 (16) −0.0141 (17) 0.0056 (16)

Geometric parameters (Å, º)

Zn1—N1 2.026 (3) C2—C3 1.341 (5)Zn1—N1i 2.026 (3) C2—H2A 0.9300Zn1—Br1 2.3698 (6) C3—H3A 0.9300Zn1—Br1i 2.3699 (6) C4—H4A 0.9700N1—C1 1.323 (4) C4—H4B 0.9700N1—C2 1.374 (4) C5—C10 1.389 (5)N2—C1 1.340 (4) C5—C6 1.393 (5)N2—C3 1.366 (4) C6—C7 1.361 (5)N2—C4 1.469 (4) C6—H6A 0.9300N3—N4 1.360 (4) C7—C8 1.403 (6)N3—C5 1.360 (4) C7—H7A 0.9300N3—C4 1.440 (4) C8—C9 1.359 (6)N4—N5 1.298 (4) C8—H8A 0.9300N5—C10 1.374 (5) C9—C10 1.398 (6)C1—H1A 0.9300 C9—H9A 0.9300

N1—Zn1—N1i 109.71 (16) N2—C3—H3A 126.5N1—Zn1—Br1 110.10 (8) N3—C4—N2 111.4 (3)N1i—Zn1—Br1 104.74 (8) N3—C4—H4A 109.3N1—Zn1—Br1i 104.74 (8) N2—C4—H4A 109.3N1i—Zn1—Br1i 110.10 (8) N3—C4—H4B 109.3Br1—Zn1—Br1i 117.41 (3) N2—C4—H4B 109.3C1—N1—C2 105.7 (3) H4A—C4—H4B 108.0C1—N1—Zn1 125.3 (2) N3—C5—C10 104.4 (3)C2—N1—Zn1 128.9 (2) N3—C5—C6 133.5 (3)C1—N2—C3 107.1 (3) C10—C5—C6 122.0 (3)C1—N2—C4 126.2 (3) C7—C6—C5 116.2 (3)C3—N2—C4 126.6 (3) C7—C6—H6A 121.9N4—N3—C5 110.2 (3) C5—C6—H6A 121.9N4—N3—C4 120.5 (3) C6—C7—C8 122.5 (4)C5—N3—C4 129.3 (3) C6—C7—H7A 118.7N5—N4—N3 108.3 (3) C8—C7—H7A 118.7N4—N5—C10 109.0 (3) C9—C8—C7 121.1 (4)N1—C1—N2 111.0 (3) C9—C8—H8A 119.5N1—C1—H1A 124.5 C7—C8—H8A 119.5N2—C1—H1A 124.5 C8—C9—C10 117.6 (4)C3—C2—N1 109.3 (3) C8—C9—H9A 121.2

supporting information

sup-4Acta Cryst. (2016). C72, 917-922

C3—C2—H2A 125.3 C10—C9—H9A 121.2N1—C2—H2A 125.3 N5—C10—C5 108.1 (3)C2—C3—N2 106.9 (3) N5—C10—C9 131.5 (4)C2—C3—H3A 126.5 C5—C10—C9 120.4 (4)

C5—N3—N4—N5 0.5 (4) C4—N3—C5—C10 178.1 (3)C4—N3—N4—N5 −178.4 (3) N4—N3—C5—C6 177.4 (4)N3—N4—N5—C10 −0.2 (4) C4—N3—C5—C6 −3.8 (6)C2—N1—C1—N2 −1.0 (4) N3—C5—C6—C7 −178.9 (4)Zn1—N1—C1—N2 175.7 (2) C10—C5—C6—C7 −1.1 (5)C3—N2—C1—N1 0.2 (4) C5—C6—C7—C8 −1.9 (6)C4—N2—C1—N1 −176.4 (3) C6—C7—C8—C9 3.3 (6)C1—N1—C2—C3 1.4 (4) C7—C8—C9—C10 −1.6 (6)Zn1—N1—C2—C3 −175.2 (3) N4—N5—C10—C5 −0.2 (4)N1—C2—C3—N2 −1.3 (4) N4—N5—C10—C9 179.0 (4)C1—N2—C3—C2 0.6 (4) N3—C5—C10—N5 0.5 (4)C4—N2—C3—C2 177.3 (3) C6—C5—C10—N5 −177.8 (3)N4—N3—C4—N2 89.6 (4) N3—C5—C10—C9 −178.8 (3)C5—N3—C4—N2 −89.0 (4) C6—C5—C10—C9 2.8 (5)C1—N2—C4—N3 78.5 (4) C8—C9—C10—N5 179.4 (4)C3—N2—C4—N3 −97.5 (4) C8—C9—C10—C5 −1.4 (6)N4—N3—C5—C10 −0.6 (4)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

C4—H4A···Br1ii 0.97 3.01 3.951 (4) 163C4—H4B···N5iii 0.97 2.50 3.449 (5) 167

Symmetry codes: (ii) x+1/2, y−1/2, −z+1/2; (iii) −x+1/2, y+1/2, z.

(II) Bis{1-[(benzotriazol-1-yl)methyl]-1H-imidazole-κN3}diiodidozinc(II)

Crystal data

[ZnI2(C10H9N5)2]Mr = 717.61Orthorhombic, Pbcna = 11.729 (2) Åb = 11.853 (2) Åc = 17.563 (4) ÅV = 2441.7 (8) Å3

Z = 4F(000) = 1376

Dx = 1.952 Mg m−3

Mo Kα radiation, λ = 0.71073 ÅCell parameters from 6875 reflectionsθ = 1.7–28.0°µ = 3.56 mm−1

T = 293 KPrism, colourless0.16 × 0.13 × 0.08 mm

Data collection

Rigaku Saturn diffractometer

Radiation source: fine-focus sealed tubeDetector resolution: 28.5714 pixels mm-1

ω scans

Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2004)

Tmin = 0.813, Tmax = 1.00014216 measured reflections2400 independent reflections

supporting information

sup-5Acta Cryst. (2016). C72, 917-922

2235 reflections with I > 2σ(I)Rint = 0.033θmax = 26.0°, θmin = 2.3°

h = −14→14k = −12→14l = −13→21

Refinement

Refinement on F2

Least-squares matrix: fullR[F2 > 2σ(F2)] = 0.032wR(F2) = 0.064S = 1.142400 reflections150 parameters0 restraints

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrainedw = 1/[σ2(Fo

2) + (0.0216P)2 + 3.1101P] where P = (Fo

2 + 2Fc2)/3

(Δ/σ)max = 0.001Δρmax = 0.48 e Å−3

Δρmin = −0.62 e Å−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

x y z Uiso*/Ueq

Zn1 0.0000 0.13958 (5) 0.2500 0.03295 (14)I1 0.07239 (2) 0.02815 (2) 0.36520 (2) 0.04549 (10)N1 0.1276 (2) 0.2374 (2) 0.20866 (16) 0.0351 (6)N2 0.2447 (3) 0.3164 (2) 0.12729 (15) 0.0343 (6)N3 0.2266 (3) 0.4231 (2) 0.01187 (16) 0.0361 (7)N4 0.2339 (3) 0.5370 (3) 0.02233 (19) 0.0506 (9)N5 0.1625 (3) 0.5859 (3) −0.0232 (2) 0.0565 (10)C1 0.1626 (3) 0.2395 (3) 0.13763 (19) 0.0369 (8)H1A 0.1339 0.1933 0.0993 0.044*C2 0.1920 (3) 0.3170 (3) 0.2461 (2) 0.0467 (9)H2A 0.1869 0.3337 0.2977 0.056*C3 0.2636 (4) 0.3670 (3) 0.1966 (2) 0.0478 (10)H3A 0.3154 0.4243 0.2071 0.057*C4 0.2979 (3) 0.3478 (3) 0.0548 (2) 0.0400 (8)H4A 0.3706 0.3839 0.0647 0.048*H4B 0.3122 0.2802 0.0251 0.048*C5 0.1478 (3) 0.3994 (3) −0.04272 (19) 0.0359 (8)C6 0.1064 (4) 0.5050 (3) −0.0647 (2) 0.0452 (10)C7 0.0211 (4) 0.5127 (4) −0.1207 (2) 0.0611 (14)H7A −0.0089 0.5819 −0.1353 0.073*C8 −0.0156 (4) 0.4150 (5) −0.1524 (3) 0.0633 (13)H8A −0.0724 0.4177 −0.1892 0.076*C9 0.0293 (4) 0.3101 (4) −0.1314 (2) 0.0574 (11)H9A 0.0031 0.2455 −0.1558 0.069*C10 0.1101 (3) 0.3002 (3) −0.0764 (2) 0.0450 (9)H10A 0.1389 0.2303 −0.0620 0.054*

supporting information

sup-6Acta Cryst. (2016). C72, 917-922

Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23

Zn1 0.0337 (3) 0.0335 (3) 0.0317 (3) 0.000 0.0007 (2) 0.000I1 0.04298 (16) 0.05144 (18) 0.04206 (15) 0.00149 (12) −0.00946 (11) 0.01041 (11)N1 0.0351 (16) 0.0359 (16) 0.0343 (15) −0.0035 (13) 0.0021 (12) −0.0005 (13)N2 0.0355 (16) 0.0330 (15) 0.0344 (15) −0.0068 (13) 0.0040 (12) −0.0018 (13)N3 0.0437 (18) 0.0248 (14) 0.0399 (16) −0.0059 (13) 0.0101 (14) −0.0014 (13)N4 0.066 (2) 0.0301 (17) 0.056 (2) −0.0105 (16) 0.0207 (18) −0.0060 (15)N5 0.071 (3) 0.0332 (19) 0.065 (2) 0.0056 (18) 0.026 (2) 0.0072 (18)C1 0.041 (2) 0.0325 (19) 0.0366 (18) −0.0052 (16) 0.0020 (16) −0.0028 (16)C2 0.048 (2) 0.056 (2) 0.0353 (19) −0.0120 (19) 0.0009 (17) −0.0099 (18)C3 0.048 (2) 0.052 (2) 0.044 (2) −0.0146 (19) −0.0017 (18) −0.0121 (19)C4 0.034 (2) 0.042 (2) 0.044 (2) −0.0075 (16) 0.0074 (16) −0.0032 (17)C5 0.037 (2) 0.033 (2) 0.0381 (18) 0.0008 (15) 0.0106 (15) 0.0047 (15)C6 0.046 (2) 0.039 (2) 0.051 (2) 0.0071 (18) 0.0232 (19) 0.0119 (19)C7 0.058 (3) 0.066 (3) 0.060 (3) 0.028 (2) 0.022 (2) 0.028 (2)C8 0.049 (3) 0.091 (4) 0.049 (2) 0.010 (3) 0.001 (2) 0.011 (3)C9 0.056 (3) 0.065 (3) 0.051 (2) −0.008 (2) −0.002 (2) 0.001 (2)C10 0.046 (2) 0.040 (2) 0.048 (2) −0.0040 (18) 0.0015 (18) 0.0004 (18)

Geometric parameters (Å, º)

Zn1—N1i 2.028 (3) C2—C3 1.346 (5)Zn1—N1 2.028 (3) C2—H2A 0.9300Zn1—I1i 2.5610 (5) C3—H3A 0.9300Zn1—I1 2.5611 (5) C4—H4A 0.9700N1—C1 1.313 (4) C4—H4B 0.9700N1—C2 1.377 (4) C5—C10 1.389 (5)N2—C1 1.339 (4) C5—C6 1.396 (5)N2—C3 1.375 (4) C6—C7 1.405 (7)N2—C4 1.465 (4) C7—C8 1.355 (7)N3—C5 1.361 (5) C7—H7A 0.9300N3—N4 1.365 (4) C8—C9 1.399 (7)N3—C4 1.438 (5) C8—H8A 0.9300N4—N5 1.295 (5) C9—C10 1.359 (6)N5—C6 1.374 (6) C9—H9A 0.9300C1—H1A 0.9300 C10—H10A 0.9300

N1i—Zn1—N1 110.27 (16) N2—C3—H3A 126.9N1i—Zn1—I1i 109.45 (8) N3—C4—N2 111.5 (3)N1—Zn1—I1i 104.87 (8) N3—C4—H4A 109.3N1i—Zn1—I1 104.87 (8) N2—C4—H4A 109.3N1—Zn1—I1 109.45 (8) N3—C4—H4B 109.3I1i—Zn1—I1 117.91 (3) N2—C4—H4B 109.3C1—N1—C2 105.7 (3) H4A—C4—H4B 108.0C1—N1—Zn1 125.5 (2) N3—C5—C10 133.7 (3)C2—N1—Zn1 128.8 (2) N3—C5—C6 104.3 (3)

supporting information

sup-7Acta Cryst. (2016). C72, 917-922

C1—N2—C3 107.0 (3) C10—C5—C6 122.0 (4)C1—N2—C4 126.7 (3) N5—C6—C5 108.2 (4)C3—N2—C4 126.1 (3) N5—C6—C7 131.8 (4)C5—N3—N4 110.0 (3) C5—C6—C7 120.0 (4)C5—N3—C4 129.5 (3) C8—C7—C6 117.2 (4)N4—N3—C4 120.5 (3) C8—C7—H7A 121.4N5—N4—N3 108.6 (3) C6—C7—H7A 121.4N4—N5—C6 108.9 (3) C7—C8—C9 122.1 (4)N1—C1—N2 111.5 (3) C7—C8—H8A 118.9N1—C1—H1A 124.3 C9—C8—H8A 118.9N2—C1—H1A 124.3 C10—C9—C8 121.7 (5)C3—C2—N1 109.6 (3) C10—C9—H9A 119.1C3—C2—H2A 125.2 C8—C9—H9A 119.1N1—C2—H2A 125.2 C9—C10—C5 116.9 (4)C2—C3—N2 106.2 (3) C9—C10—H10A 121.6C2—C3—H3A 126.9 C5—C10—H10A 121.6

C5—N3—N4—N5 0.4 (4) C4—N3—C5—C10 −1.3 (6)C4—N3—N4—N5 179.3 (3) N4—N3—C5—C6 −0.5 (4)N3—N4—N5—C6 0.0 (4) C4—N3—C5—C6 −179.4 (3)C2—N1—C1—N2 −0.6 (4) N4—N5—C6—C5 −0.3 (4)Zn1—N1—C1—N2 177.1 (2) N4—N5—C6—C7 179.4 (4)C3—N2—C1—N1 0.0 (4) N3—C5—C6—N5 0.5 (4)C4—N2—C1—N1 −175.3 (3) C10—C5—C6—N5 −177.9 (3)C1—N1—C2—C3 0.9 (5) N3—C5—C6—C7 −179.3 (3)Zn1—N1—C2—C3 −176.7 (3) C10—C5—C6—C7 2.3 (5)N1—C2—C3—N2 −0.9 (5) N5—C6—C7—C8 178.8 (4)C1—N2—C3—C2 0.6 (4) C5—C6—C7—C8 −1.5 (6)C4—N2—C3—C2 175.9 (4) C6—C7—C8—C9 −0.5 (6)C5—N3—C4—N2 −93.0 (4) C7—C8—C9—C10 1.9 (7)N4—N3—C4—N2 88.3 (4) C8—C9—C10—C5 −1.1 (6)C1—N2—C4—N3 78.9 (4) N3—C5—C10—C9 −178.9 (4)C3—N2—C4—N3 −95.4 (4) C6—C5—C10—C9 −1.0 (6)N4—N3—C5—C10 177.6 (4)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

C4—H4A···I1ii 0.97 3.17 4.112 (4) 165C4—H4B···N5iii 0.97 2.47 3.424 (5) 167

Symmetry codes: (ii) x+1/2, y+1/2, −z+1/2; (iii) −x+1/2, y−1/2, z.