Reactivity of 1,2,4,5-tetracarboxylatebenzene with Cobalt(II) Matthias Zeller2, Andrew R. Chema1, Paul S. Szalay1*, Allen D. Hunter2 Paul S. Szalay

Assistant Professor, Department of Chemistry

Muskingum College

163 Stormont St.

New Concord, OH 43762

pszalay@muskingum.edu

phone: (740) 826-8231

fax: (740) 826-8229

Reactivity of 1,2,4,5-tetracarboxylatebenzene with Cobalt(II) Matthias Zeller2, Andrew R. Chema1, Paul S. Szalay1*, Allen D. Hunter2

The reactivity of the tetraanionic ligand 1,2,4,5-tetracarboxylatebenzene with cobalt(II) is described.

Reactivity of 1,2,4,5-tetracarboxylatebenzene with Cobalt(II) Matthias Zeller2, Andrew R. Chema1, Paul S. Szalay1*, Allen D. Hunter2

1) Department of Chemistry, Muskingum College, 163 Stormont Street, New Concord, OH 43762 2) Department of Chemistry, Youngstown State University, One University Plaza, Youngstown, OH 44555-3663 Abstract

The complexes [Co(H2O)6][Co(BTCA)(H2O)4]•7.2H2O (1) and [Na2Co(H2O)4(µ-

H2O)2(µ-BTCA)] (2) (BTCA = 1,2,4,5-tetracarboxylatebenzene) have been synthesized

and characterized by single crystal X-ray diffraction. Compound (1) crystallizes in the

triclinic space group P -1 with a = 6.8591(9) Å, b = 9.9691(13) Å, c = 10.9231(11) Å, α =

93.021(2)°, β = 104.883(2)°, and γ = 103.702° with Z = 1. This compound exhibits a 1-

dimensional structure of two alternating layers. A chain of cobalt ions and BTCA

constitute one layer. Cobalt complex ions and solvent water molecules occupy the other.

Compound (2) crystallizes in the monoclinic space group C 2/m with a = 8.8647(6) Å, b

= 10.5247(7) Å, c = 21.2265(14) Å, and β = 92.525(2)°, with Z = 2. This compound

consists of a 3-dimensional network of cobalt and sodium ions linked by BTCA. The

sodium complex moiety is disordered around a center of inversion.

Keywords: X-ray Crystallography, Cobalt Complexes, O-ligands

Introduction

An especially active research area in recent years has involved the preparation of both

molecular and solid state metal-organic hybrid compounds through the metal ion directed

assembly of organic molecular building blocks. Distinct molecular entities have

increasingly been employed as building blocks in the solution assembly of new solid state

materials.1 This approach is better enabling researchers to exploit the relationship

between the structure of a compound and its properties.

Potential properties of specific interest include magnetism and electrical conductivity.2

The choice of rigid building blocks have also lead to the preparation of robust three

dimensional porous lattices that maintain structural integrity with the loss of solvent

and/or guest molecules.3 Materials of this type have attracted attention as candidates for

exploring selective sorption, host-guest chemistry, and catalytic properties.4 Polar

molecular building blocks have been used to prepare materials that display non-linear

optical properties.5 Tri- and tetracarboxylates as ligands bridging multiple metal ions

have proven to be excellent candidates for the synthesis of metal-organic hybrid

compounds,6 and several compounds involving transition metals and anions of BTCAH4

have been reported.7

One avenue of our present investigations involves the use of benzene-1,2,4,5-

tetracarboxylic acid (BTCAH4) and its fully deprotonated form 1,2,4,5-

tetracarboxylatebenzene (BTCA) as rigid building blocks in the synthesis of metal-

organic hybrid compounds. Herein we report the room temperature solution phase

synthesis of two compounds, one composed of Co(II) and BTCA and the other composed

of Na(I), Co(II), and BTCA.

Experimental

Materials

The starting materials benzene-1,2,4,5-tetracarboxylic acid (BTCAH4), KOH, and

NaOH were all purchased from Aldrich. The salt Co(ClO4)2•6H2O was purchased from

Strem Chemicals. All reagents were used as received without further purification.

Acetonitrile was dried over anhydrous CaSO4 and distilled prior to use. All water was

distilled prior to its use.

X-Ray Crystallography

Diffraction data of both compounds have been collected with a 'Bruker AXS SMART

APEX CCD' diffractometer. The data for (1) and (2) were collected at 298 K and 100 K,

respectively using monochromatographed Mo Kα radiation with omega scan technique.

The unit cell was determined using SAINT+ and the structure was solved by direct

methods and refined by full matrix least squares against F2 with all reflections using the

SHELXTL programs.8

The interstitial water molecules of O12, O13 and O14 of compound (1) have been

found to have a large freedom of movement and are only partially occupied. Their

anisotropic displacement parameters have been restrained to be isotropic within a

standard deviation of 0.04, and the site occupancies refined to 68, 24 and 92%,

respectively. The cobalt coordinated water molecules defined by O7, O8, and O9 were

disordered over two positions with a ratio of 87:13. The anisotropic displacement

parameters of the minor component oxygen atoms have been restrained to be equal to that

of its major component counterpart.

The positions of the hydrogen atoms on the interstitial water molecule of O13 could

not reliably be determined from the diffraction data and have been omitted. The

hydrogen atoms of the water molecules of O10, O11, O12, and O14 were all located from

the electron density map and refined using different types of riding models. The positions

of the hydrogen atoms attached to O14 were not refined at all and were set to ride on the

oxygen atom. The hydrogen-oxygen distances of O10, O11 and O12 were restrained to

0.9 Å with a standard deviation of 0.02 and the respective hydrogen-hydrogen distances

within the water molecules were restrained to be the same within a standard deviation of

0.02.

The hydrogen atoms of the disordered water molecules defined by O7, O8, and O9

were tentatively found in the density Fourier map, but were all eventually added in

calculated positions. For each water molecule the first hydrogen atom was added as an

ideal OH group with respect to the cobalt core using an “AFIX 83” command. For the

second hydrogen atoms the hydrogen-oxygen distances were set to be equal to the first

within a standard deviation of 0.02 for the major disordered component and 0.01 for the

minor component. The hydrogen-hydrogen distances within all six coordinated water

molecules were set to be equal with a standard deviation of 0.02.

All hydrogen atoms discussed thus far were set to have an isotropic displacement

parameter of 1.5 times that of the adjacent oxygen atom. All other hydrogen atoms were

located from the electron difference map and refined isotropically.

The sodium ion Na1 and the oxygen atoms O4, O6 and O7 in compound (2) are

forming a moiety disordered over two positions. The two components are symmetry

dependent and the second component is created by an inversion center near the sodium

atom at ¾, ¾, ½. Due to the proximity of the two sodium ions and significant overlap,

they had to be refined isotropically. All other nonhydrogen atoms were refined

anisotropically. The bond lengths of Na1 to the terminal water ligands of O4 and O6

were restrained to be the same as were the anisotropic displacement parameters for O4

and O6. The sodium carboxylate interactions of Na1, O3, and O7 were treated in the

same fashion. The geometries of the water molecules defined by O4, O5, and O6 were

restrained to be equivalent. Crystal data and experimental details for both compounds are

listed in Table 1.

Syntheses

The compound [Co(H2O)6][Co(BTCA)(H2O)4]•7.2H2O (1) was prepared using a thin

tube slow diffusion reaction. Solid BTCAH4 (10.0 mg, 0.039 mmol) was dissolved in 8

mL of deionized water containing 4.0 mL of 0.05 M KOH (0.2 mmol). Solid

Co(ClO4)2•6H2O (10.4 mg, 0.039 mmol) was dissolved in 8 mL of acetonitrile. The

BTCA containing solution was added to a thin glass tube, 4 mm ID. The Co(ClO4)2

solution was added slowly on top of the BTCA containing solution such that the solutions

remained layered. The tube was allowed to stand for a week during which time pale

yellow crystals appeared. These crystals were harvested and analyzed by single crystal

X-ray diffraction. Yield 0.009g (67.0%).

The compound [Na2Co(H2O)4(µ-H2O)2(µ-BTCA)] (2) was prepared as follows. Solid

Co(ClO4)2•6H2O (10.4 mg, 0.039 mmol) and BTCAH4 (10.0 mg, 0.039 mmol ) were

dissolved separately in 8 mL quantities of deionized water. These solutions were then

mixed in a test tube. A 5.0 mL volume of 0.05 M (0.25 mmol) NaOH was added to this

solution over a period of 1 hour. The resulting mixture was capped and allowed to stand

for two weeks during which time pale pink crystals appeared. These crystals were

harvested and analyzed by single crystal X-ray diffraction. Yield 0.012g (61.7%).

Results and Discussion

The molecule benzenetetracarboxylic acid (BTCAH4) has structural features that make

it desirable as a precursor in reactions with metal ions to prepare metal-organic hybrid

compounds. The molecule possesses four divergent carboxylic acid groups with the

potential to act as binding sites for metal ions. The ten carbon backbone of the molecule

is rigid due to its aromatic nature. The carboxylic acid groups can be selectively

deprotonated to form the 1-, 2-, and 4- anions though the later two are by far the most

common.9 This deprotonation greatly increases the Lewis basic character of the molecule

and the resulting salts have very high aqueous solubility. The compound BTCAH4 is

noteworthy as a ligand because the carboxylate anion has nine known coordination

modes with metal ions.9 This variety of coordination capabilities makes single crystal X-

ray structure determination an especially important characterization tool for compounds

containing the anions of BTCAH4.

Since the fully protonated BTCAH4 is a poor nucleophile the process of deprotonating

the carboxylic acid groups can be used to slow the rate of the eventual reaction between

BTCA and metal ions. Slowing reactions can, of course, enhance crystal growing

conditions. In the synthesis of (1), BTCAH4 was deprotonated prior to the introduction

of an acetonitrile solution of Co(II) ions. Deprotonation prior to metal ion introduction

should lead to a more rapid initial reaction because BTCA is a much stronger nucleophile

than BTCAH4, however, the solutions of BTCA and Co(II) were layered in a thin tube

slowing down the bulk reaction. In the preparation of (2), aqueous solutions of BTCAH4

and Co(II) ions were mixed and then a solution of NaOH was added to the mixture. The

gradual introduction of base into the BTCAH and Co(II) mixture in the preparation of (2)

served to slow the reaction in that synthesis.

The structure of compound (1) (Figures 1-3) as determined by single crystal X-ray

diffraction consists of alternating layers. One layer consists of 1-dimensional chains of

Co(II) ions linked by trans carboxylate groups of BTCA. The inner coordination sphere

of these cobalt ions consists of two axial oxygen atoms from the BTCA carboxylate

groups and four equatorial water molecules, with the cobalt atom itself residing on an

inversion center.

Octahedral [Co(H2O)6]+2 ions occupy the second layer, taking up about half of its

volume with the other half being filled by interstitial water molecules. The complex ions

are offset from the cobalt-BTCA chains in the layers above and below them. They reside

between the centers of the cobalt-BTCA chains in the adjacent layers (Figure 2). The

cobalt atom of the complex ions is located on an inversion center and the water ligands

are disordered over two positions with a ratio of 87:13.

The cobalt ions in the BTCA chains consist of a slightly distorted octahedron. The

unique bond angles range from 87.01(8)° (O1-Co1-O6) to 91.12(9)° (O2-Co1-O6). As

expected, the lengths of the cobalt-oxygen bonds for the interaction of cobalt with the

anionic BTCA (Co1-O1) with a distance of 2.0777(18) Ǻ is shorter than the distances

between the cobalt center and the neutral water molecules Co1-O2 and Co1-O6 with

respective distances of to 2.130(2) and 2.101(2) Ǻ.

Numerous hydrogen bonding interactions are found within the structure of (1), which

will be briefly described in the following paragraph. A detailed summary of all the

hydrogen bonding interactions is listed in Table 6, and a representation of the hydrogen

bonding network is shown in Figure 3. Two types of hydrogen bonding interactions can

be distinguished within the structure of compound (1). The first type consists of strong

interactions between the carboxylate groups of the BTCA and the aquo ligands

coordinated to Co1 and Co2. These highly directional hydrogen bonds are formed

between the oxygen atoms O3, O4, and O5 of BTCA and the oxygen atoms O2, O6, O7,

O8 and O9 of the cobalt ions. These interactions are in part direct hydrogen bonds

between these atoms and partially they are bridged by the interstitial water molecules of

O10 and O11. (See Figure 3). The second type consists of hydrogen bonds towards the

remaining interstitial water molecules of O12, O13 and O14, which seem to be much

weaker and less directional. These water molecules are only partially occupied and

exhibit a large degree of thermal motion, thus their role seems to be that of mere

spacefillers without any contribution towards the structural features of the molecular

assembly. Do you think we should include the figure currently labeled Figure 3 as

well as one of the two you have at the end of this file. There is a good deal of

hydrogen bonding in this compound and that might help people understand it or it

might be overkill? What do you think?

Let’s keep Fig 1 to Fig 3, but that is enough, I think

The structure of (2) (Figure 4 & 5 Let’s add another figure showing the Na-chains

without disorder, the title picture should easily do) as determined by single crystal X-ray

diffraction consists of a three dimensional network of Co(II) and Na(I) sites linked by

BTCA. All of the cobalt and sodium ion sites are octahedrally coordinated. Each

monoanionic carboxylate group of BTCA is bridging a Co(II) ion and a Na(I) ion.

Therefore each tetraanionic BTCA is connected to a total of four Co(II) ions and four

Na(I) ions. The inner coordination sphere of Co(II) consists of two axial water molecules

and four equatorial oxygen atoms from separate carboxylate groups of BTCA. The inner

coordination sphere of the sodium ions consists of two trans terminal water molecules,

two trans bridging water molecules, and two trans oxygen atoms from the carboxylate

groups of separate BTCA ligands. The µ-aquo ligands bridge nearest neighbor sodium

ions. The cobalt ions reside on two-fold rotation axes. Mirror planes bisect the water

molecules that bridge the sodium ions.

We should mention that the sodiums are forming infinite chains etc

The sodium atoms and the surrounding oxygen atoms O4, O6 and O7 are disordered

over two positions. The two components are symmetry dependent and the second

component is created by an inversion center at ¾, ¾, ½. The coordination geometry of

Na1 is a distorted octahedron. The O5-Na1-O3, O5-Na1-O4A, and O3A-Na1-O4 angles

are 92.84(4)°, 89.01(4)° and 99.91(6)° respectively. The bond lengths of the sodium ion

to the two trans terminal water molecules of O4 and O6 average 2.404(6) Ǻ. The bond

length of the two disorderd sodium ions to the bridging water molecule of O5 is

expectedly longer with lengths of 2.436(11) and 2.691(12) Ǻ to Na1 and Na1A

respectively. The bond lengths of the sodium ion to the two trans carboxylate oxygens of

BTCA ligands, O3 and O4, average 2.342(5) Ǻ.

The coordination geometry of Co1 is also a distorted octahedron. The O1-Co1-O2

bond angle is 86.21(4)°. The bond from the cobalt ion to the terminal water ligand (Co1-

O2) is as expected longer than that of the cobalt center to the oxygen of the anionic

BTCA ligand (Co1-O1) with distances of 2.125(16) and 2.100(12) Ǻ respectively.

Several types of hydrogen bonding interactions are found within the network structure

of (2), which will be briefly described in the following paragraph. A detailed summary

of all the hydrogen bonding interactions is listed in Table 11. The first type are hydrogen

bonds between water molecules and carboxylate oxygen atoms (O2-H2···O3a, O4-

H4B···O1c and O6-H6A···O3g). These interactions are bridging each sodium and cobalt

moieties. There are also hydrogen bonding interactions between water molecules

coordinated to nearest neighbor sodium ions (O4-H4A···O6d) and coordinated to sodium

on one side and cobalt on the other (O2-H2···O7b). The water molecules bridging the

sodium atoms are forming hydrogen bonds with both carboxylate groups (O5-H5A···O7

and O5-H5A···O7f) as well as water molecules coordinated to cobalt ions (O5-

H5B···O2e). All hydrogen bonds in compound (2) are highly directional and no weak

interactions as in compound (1) are found here.

Summary

Despite using equivalent amounts of the starting materials Co(ClO4)2•6H2O and

BTCAH4 in the preparation of (1) and (2) relatively minor changes in the reaction

conditions produced significantly different structural results. Compound (1) exhibits an

alternating layered structure of cobalt-BTCA chains and cobalt complex ions. In

contrast, compound (2) consists of a three dimensional network of BTCA ligands, cobalt

(II) ions, and sodium ions. The incorporation of sodium ions in (2), but not potassium

ions in (1) was likely influenced by the presence of a greater excess of base in the

synthesis of (2). Additionally, in the synthesis of (2) all three reagents were combined in

a test tube (with the NaOH being added dropwise to the Co(II) and BTCAH4 solution)

and allowed to react. In the synthesis of (1), deprotonation of the BTCAH4 took place

prior to the introduction of the Co(II), which was subsequently added via thin tube slow

diffusion.

Acknowledgements

MZ was supported by NSF grant 0111511, CLP by ACS PRF grant 37228-B3, JCW by

ACS PRF grant 37228-B3-SRF, and the diffractometer was funded by NSF grant

0087210, by Ohio Board of Regents grant CAP-491, and by YSU.

Supplementary Material

CCDC-XXXXXX and CCDC-XXXXXX contain the supplementary crystallographic

data for this paper. These data can be obtained free of charge at

www.ccdc.cam.uk/conts/retrieving.html [or from the Cambridge Crystallographic Data

Centre (CCDC), 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44(0)1223-336033;

email: deposit@ccdc.cam.ac.uk]

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Gutschke, S. O. H.; Price, D. J.; Powell, A. K.; Wood, P. T. Eur. J. Inorg. Chem. 2001,

2739. (s) Chu, D.-Q.; Xu, J.-Q.; Duan, L.-M.; Wang, T.-G.; Tang, A.-Q.; Ye, L. Eur. J.

Inorg. Chem. 2001, 1135. (t) Kumagai, H.; Kepert, C. J.; and Kurmoo, M. Inorg. Chem.

2002, 41, 3410.

8. Bruker (1997). SAINT (Version 6.02), SMART for WNT/2000 (Version 5.625) and

SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.

9. Kumagai, H.; Kepert, C. J.; and Kurmoo, M. Inorg. Chem. 2002, 41, 3410.

Table 1. X-ray crystal data and details of data collections and structure refinements. Compound (1) (2) CCDC deposit no. CCDC XXXXX CCDC XXXXX Color/shape yellow/plate pink/needle Formula C10H36.44Co2O25.70 C10H18CoNa2O16 Formula Weight 685.59 499.15 Temperature (K) 298(2) 100(2) Crystal System triclinic monoclinic Space group P -1 C 2/m a (Å) 6.8591(9) 8.8647(6) b (Å) 9.9691(13) 10.5247(7) c (Å) 10.9231(11) 21.2265(14) α 93.021(2)° 90° β 104.883(2)° 92.525(2)° γ 103.702(2)° 90° V (Å3) 696.16(16) 899.07(18) Z 1 2 Dcalc (Mg m-3) 1.636 1.844 Absorption coefficient, mm-1 1.292 1.087 F(000) 356.1 510.0 Crystal Size (mm) 0.38 × 0.21 × 0.17 0.41 × 0.15 × 0.17 θ range for data collection 0.860-28.29° 0.996-28.37° Reflections collected 5166 4732 Unique reflections 3450 1196 Parameters 253 109 Goodness-of-fit 1.197 1.098 Ra [I > 2σ(I )] 0.0386 0.0342 wRb (all data) 0.1072 0.0873 ___________________________________________________________________________________

a R = Σ( ‌‌‌‌‌‌‌|‌Fo ‌| – |Fc|)/Σ|Fo| b wR = (Σ[w( ‌‌‌‌‌‌F ‌o2 – Fc

2)2] /Σ[w(Fo2)2])1/2

Table 2. Atomic coordinates ( × 104) and equivalent isotropic displacement

parameters (Ǻ2 × 103) for (1). U(eq) is defined as one third of the trace of the

orthogonalized Uij tensor.

________________________________________________________________

x y z U(eq)

________________________________________________________________

Co(1) 10000 0 10000 20(1) Co(2) 0 5000 5000 33(1) C(1) 7051(4) 473(3) 4958(3) 25(1) C(2) 6611(4) 382(3) 6131(2) 23(1) C(3) 4542(4) -83(3) 6170(2) 23(1) C(5) 3994(4) -107(3) 7426(2) 25(1) O(1) 8407(3) -214(2) 8077(2) 25(1) O(2) 7634(4) -1690(2) 10255(2) 32(1) O(3) 2749(4) -1173(2) 7573(2) 41(1) O(4) 4782(3) 973(2) 8220(2) 30(1) O(5) 9682(4) 1867(2) 7533(2) 42(1) O(6) 8290(3) 1419(2) 10295(2) 29(1) O(7) -1697(5) 6483(3) 4989(3) 54(1) O(8) 2467(5) 6342(3) 6352(4) 64(1) O(9) 1033(6) 5838(3) 3476(3) 58(1) O(7B) 3030(30) 6050(20) 4990(20) 55(1) O(8B) -190(30) 6680(20) 6100(20) 64(1) O(9B) 1190(30) 5850(20) 3330(19) 58(1) O(10) 4990(5) 6503(3) 2919(3) 66(1) O(11) 6869(5) 6969(3) 7086(3) 66(1) O(12) 5260(20) 4518(12) 1043(11) 167(6) O(13) 7580(90) 5410(30) 9390(40) 220(30) O(14) 318(17) 5695(5) 9021(5) 197(6) ________________________________________________________________

Table 3. Selected bond lengths [Å] and angles [°] for (1).

_____________________________________________________________

Co(1)-O(1) 2.0778(18) Co(1)-O(6) 2.101(2) Co(1)-O(2) 2.130(2) Co(2)-O(8B) 2.062(19) Co(2)-O(8) 2.067(3) Co(2)-O(7) 2.086(3) Co(2)-O(7B) 2.10(2) Co(2)-O(9) 2.108(3) Co(2)-O(9B) 2.108(19) C(1)-H(1) 0.90(4) C(2)-C(1) 1.392(4) C(3)-C(2) 1.397(4) C(4)-O(5) 1.242(3) C(4)-C(2) 1.501(4) C(5)-O(3) 1.242(3) C(5)-O(4) 1.261(3) C(5)-C(3) 1.513(3) O(1)-C(4) 1.268(3) O(2)-H(2A) 0.74(4) O(2)-H(2B) 0.80(6) O(6)-H(6B) 0.77(5) O(6)-H(6A) 0.91(5) O(7)-H(7A) 0.8200 O(7)-H(7B) 0.827(19) O(7)-H(8D) 1.40(8) O(7B)-H(7C) 0.8200 O(7B)-H(7D) 0.819(10) O(8)-H(8A) 0.8200 O(8)-H(8B) 0.829(18) O(8B)-H(8C) 0.8200 O(8B)-H(8D) 0.821(11) O(9)-H(9A) 0.8200 O(9)-H(9B) 0.843(19) O(9B)-H(9C) 0.8200 O(9B)-H(9D) 0.820(11) O(10)-H(10A) 0.893(19) O(10)-H(10B) 0.900(19) O(11)-H(11A) 0.886(19) O(11)-H(11B) 0.891(19) O(12)-H(12A) 0.91(2) O(12)-H(12B) 0.91(2) O(14)-H(14A) 0.9030 O(14)-H(14B) 0.9013

C(2)-C(3)-C(5) 121.1(2) O(1)-Co(1)-O(6) 87.01(8) O(1)-Co(1)-O(2) 89.40(8) O(6)-Co(1)-O(2) 91.12(9) O(8B)-Co(2)-O(8) 54.4(6) O(8B)-Co(2)-O(7) 38.0(6) O(8)-Co(2)-O(7) 88.69(13) O(8B)-Co(2)-O(7B) 90.6(7) O(8)-Co(2)-O(7B) 47.2(6) O(7)-Co(2)-O(7B) 107.4(5) O(8B)-Co(2)-O(9) 105.3(7) O(8)-Co(2)-O(9) 92.55(15) O(7)-Co(2)-O(9) 89.62(13) O(7B)-Co(2)-O(9) 51.0(6) O(8B)-Co(2)-O(9B) 90.9(8) O(8)-Co(2)-O(9B) 115.4(6) O(7)-Co(2)-O(9B) 58.4(6) O(7B)-Co(2)-O(9B) 88.7(7) O(9)-Co(2)-O(9B) 41.3(6) C(2)-C(1)-H(1) 123(2) C(1)-C(2)-C(3) 119.7(2) C(1)-C(2)-C(4) 119.5(2) C(3)-C(2)-C(4) 120.8(2) O(5)-C(4)-O(1) 125.1(2) O(5)-C(4)-C(2) 119.0(2) O(1)-C(4)-C(2) 115.9(2) O(3)-C(5)-O(4) 125.3(2) O(3)-C(5)-C(3) 117.3(2) O(4)-C(5)-C(3) 117.4(2) C(4)-O(1)-Co(1) 127.97(17) Co(1)-O(2)-H(2A) 114(3) Co(1)-O(2)-H(2B) 108(4) H(2A)-O(2)-H(2B) 106(5) Co(1)-O(6)-H(6B) 116(4) Co(1)-O(6)-H(6A) 111(3) H(6B)-O(6)-H(6A) 106(5) Co(2)-O(7)-H(7A) 109.5 Co(2)-O(7)-H(7B) 113(4) H(7A)-O(7)-H(7B) 129.6 Co(2)-O(7)-H(8D) 78(10) H(7A)-O(7)-H(8D) 84.5 H(7B)-O(7)-H(8D) 130(5) Co(2)-O(8)-H(8A) 109.5 Co(2)-O(8)-H(8B) 121(4) H(8A)-O(8)-H(8B) 128.5 Co(2)-O(9)-H(9A) 109.5

Co(2)-O(7B)-H(7C) 109.5 Co(2)-O(7B)-H(7D) 111(10) H(7C)-O(7B)-H(7D) 130.3 Co(2)-O(8B)-H(8C) 109.4 Co(2)-O(8B)-H(8D) 92(10) H(8C)-O(8B)-H(8D) 129.9 Co(2)-O(9B)-H(9C) 109.5 H(10A)-O(10)-H(10B) 101(3) H(11A)-O(11)-H(11B) 103(3) H(12A)-O(12)-H(12B) 99(3) H(14A)-O(14)-H(14B) 100.9 _____________________________________________________________

Table 4. Anisotropic displacement parameters [Å2 × 103] for (1). The anisotropic

displacement factor exponent takes the form: -2 π2 [(h a*)2 U11 + ... + 2 h k a* b* U12]

_______________________________________________________________________

U11 U22 U33 U23 U13 U12

_______________________________________________________________________

Co(1) 22(1) 26(1) 12(1) 4(1) 3(1) 7(1) Co(2) 38(1) 27(1) 32(1) 6(1) 8(1) 8(1) O(1) 29(1) 30(1) 14(1) 6(1) 2(1) 9(1) O(2) 30(1) 38(1) 27(1) 6(1) 10(1) 6(1) O(3) 53(1) 43(1) 24(1) 1(1) 22(1) -4(1) O(4) 32(1) 38(1) 20(1) 0(1) 8(1) 11(1) O(5) 39(1) 40(1) 30(1 15(1) -7(1) -5(1) O(6) 34(1) 40(1) 18(1) 6(1) 10(1) 15(1) C(1) 23(1) 35(1) 17(1) 5(1) 5(1) 6(1) C(2) 25(1) 29(1) 14(1) 5(1) 4(1) 8(1) C(3) 27(1) 31(1) 13(1) 6(1) 7(1) 9(1) C(4) 25(1) 33(1) 14(1) 4(1) 4(1) 8(1) C(5) 25(1) 37(1) 14(1) 4(1) 5(1) 11(1) O(7) 61(2) 55(2) 54(2) 9(1) 11(2) 32(2) O(8) 48(2) 47(2) 80(2) -17(2) -3(2) 10(1) O(9) 73(2) 50(2) 67(2) 28(2) 36(2) 27(2) O(7B) 61(2) 55(2) 54(2) 9(1) 11(2) 32(2) O(8B) 48(2) 47(2) 80(2) -17(2) -3(2) 10(1) O(9B) 73(2) 50(2) 67(2) 28(2) 36(2) 27(2) O(10) 72(2) 57(2) 71(2) 23(2) 19(2) 23(2) O(11) 73(2) 44(2) 73(2) -7(1) 8(2) 15(1) O(12) 202(13) 128(8) 146(9) -21(6) 60(8) -9(7) O(13) 310(50) 150(30) 190(30) 30(20) 80(30) 40(20) O(14) 397(15) 64(3) 81(4) -2(3) 65(6) -30(5) _______________________________________________________________________

Table 5. Hydrogen coordinates (× 104) and isotropic displacement parameters

(Å2 × 103) for (1).

________________________________________________________________

x y z U(eq)

________________________________________________________________

H(1) 8360(60) 670(40) 4880(30) 36(9) H(2A) 6800(70) -1470(40) 10470(40) 41(11) H(2B) 8210(100) -2040(60) 10840(60) 100(20) H(6A) 7090(70) 1280(40) 9660(50) 55(12) H(6B) 7960(80) 1390(50) 10910(50) 74(16) H(7A) -1962 6562 5675 82 H(7B) -2470(70) 6530(70) 4300(20) 82 H(7C) 3824 5554 5223 82 H(7D) 3400(200) 6890(60) 5200(300) 82 H(8A) 2032 6904 6711 95 H(8B) 3710(40) 6370(60) 6480(60) 95 H(8C) 233 6592 6861 95 H(8D) 400(400) 7300(300) 5770(110) 95 H(9A) 764 6592 3389 87 H(9B) 2150(60) 5730(50) 3340(60) 87 H(9C) -1832 6406 3492 87 H(9D) -100(300) 6090(70) 3200(400) 87 H(10A) 5040(100) 6070(50) 2200(30) 98 H(10B) 4940(90) 7350(30) 2690(50) 98 H(11A) 7960(60) 6740(50) 7580(50) 99 H(11B) 7100(80) 7860(30) 7360(50) 99 H(12A) 5200(300) 4000(170) 330(110) 250 H(12B) 6600(120) 5040(180) 1250(170) 250 H(14A) 1553 5503 9059 296 H(14B) 753 6566 9432 296 ________________________________________________________________

Table 6. Hydrogen Bonding Geometry Parameters in the structure of (1). Specified

hydrogen bonds with H..A < r(A) + 2.000 Angstroms (with esds except for fixed and

riding H). Hydrogen bonds to the minor occupied cobalt-hexaaqua complex are omitted.

D-H···A D-H (Å) H···A (Å) D···A (Å) D-H···A (deg) O2-H2A···O4a O2-H2B···O5h O6-H6B···O3a O6-H6A···O4 O7m-H7Am···O11 O7m-H7Bm···O10 O8-H8B···O11 O8-H8A···O3e O9-H9A···O5j O10-H10A···O12 O10-H10B···O4f O11-H11A···O14m O11-H11B···O1b O12-H12A···O2k O12-H12A···O12i O14-H14B···O6c

0.74(4) 0.80(6) 0.77 0.91 0.82 0.83(2) 0.83(2) 0.82 0.82 0.89 0.90(2) 0.89(2) 0.89(2) 0.91(2) 0.91(2) 0.90

2.11(4) 1.95(6) 1.85(5) 1.87(5) 1.98 1.20(3) 2.04(3) 1.98 1.92 2.00 1.98(3) 2.42(2) 1.94(3) 2.58(15) 2.2(2) 1.94

2.807(3) 2.677(3) 2.612(3) 2.777(3) 2.777(5) 2.769(5) 2.822(5) 2.691(4) 2.685(4) 2.846(11) 2.854(4) 3.289(10) 2.803(3) 3.063(10) 2.49(3) 2.803(5)

157(4) 150(6) 175(6) 173(4) 165 162(5) 164(5) 144 154 157 162(5) 166(1) 164(5) 114(12) 99(14) 159

Note: Symmetry codes: (a) -x+1, -y,-z+2; (b) x, y+1, z; (c) -x+1, -y+1, -z+2; (d) x+1, y, z; (e) x, y+1, z; (f) -x+1, -y+1, -z+1; (g) -x+2, -y+1, -z+1; (h) -x+2, -y, -z+2; (i) -x+1, -y+1, -z; (j) -x+1, -y+1, -z+1; (k) -x+1, -y, -z+1; (l) -x+1, -y+1, -z+1; (m) x+1, -y+1, -z+1

Table 7. Atomic coordinates (× 104) and equivalent isotropic displacement

parameters (Ǻ2 × 103) for (2). U(eq) is defined as one third of the trace of the

orthogonalized Uij tensor.

________________________________________________________________ x y z U(eq) ________________________________________________________________ Co(1) 10000 10000 10000 8(1) Na(1A) 7496(2) 7673(120) 5163(4) 16(1) C(1) 9731(1) 6264(2) 5893(3) 11(1) C(2) 9460(1) 5000 6760(4) 12(1) C(4) 9482(1) 7596(2) 7021(3) 16(1) O(1) 10084(1) 8394(1) 7652(2) 16(1) O(2) 11369(1) 10000 10135(3) 11(1) O(3) 8679(2) 7608(3) 7738(5) 14(1) O(4) 8190(4) 6887(4) 1892(9) 26(1) O(5) 7058(1) 5000 5979(3) 18(1) O(6) 6749(4) 8660(5) 8150(11) 26(1) O(7) 6271(3) 7048(4) 3060(6) 14(1)

Table 8. Selected bond lengths [Å] and angles [°] for (2).

_____________________________________________________________

Co(1)-O(1) 2.1003(12) Co(1)-O(2) 2.126(2) O(1)-C(4) 1.254(3) O(2)-H(2) 0.87(3) C(1)-C(4) 1.502(3) C(2)-C(1) 1.388(2) C(2)-H(2B) 0.95(5) C(4)-O(3) 1.340(5) Na(1)-O(3) 2.361(5) Na(1)-O(4) 2.419(6) Na(1)-O(5) 2.691(2) Na(1)-O(6) 2.388(6) Na(1)-O(7) 2.323(5) O(4)-H(4A) 0.90(3) O(4)-H(4B) 0.87(3) O(5)-H(5B) 0.83(3) O(5)-H(5A) 0.87(3) O(6)-H(6A) 0.89(3) O(6)-H(6B) 0.88(3) O(1)-Co(1)-O(2) 86.21(6) C(4)-O(1)-Co(1) 125.61(14) C(2)-C(1)-C(4) 118.31(18) C(1)-C(2)-H(2B) 119.69(13) O(1)-C(4)-O(3) 126.1(2) O(1)-C(4)-C(1) 116.71(18) O(3)-C(4)-C(1) 114.7(2) O(7)-Na(1)-O(3) 162.30(17) O(7)-Na(1)-O(6) 96.0(2) O(3)-Na(1)-O(6) 84.2(2) O(7)-Na(1)-O(4) 81.6(2) O(3)-Na(1)-O(4) 99.9(2) O(6)-Na(1)-O(4) 173.6(3) O(7)-Na(1)-O(5) 69.51(12) O(3)-Na(1)-O(5) 92.84(13) O(6)-Na(1)-O(5) 95.68(17) O(4)-Na(1)-O(5) 89.01(16) Co(1)-O(2)-H(2) 102(2) C(4)-O(3)-Na(1) 119.7(2) Na(1)-O(4)-H(4A) 115(2) Na(1)-O(4)-H(4B) 118(2) H(4A)-O(4)-H(4B) 101(4) Na(1)-O(5)-H(5B) 104.1(6)

Na(1)-O(5)-H(5A) 97.2(8) H(5B)-O(5)-H(5A) 107(4) Na(1)-O(6)-H(6A) 120(2) Na(1)-O(6)-H(6B) 120(2) H(6A)-O(6)-H(6B) 101(3) _____________________________________________________________

Table 9. Anisotropic displacement parameters [Å2 × 103] for (2). The anisotropic

displacement factor exponent takes the form: -2 π2 [(h a*)2 U11 + ... + 2 h k a* b* U12]

_______________________________________________________________________

U11 U22 U33 U23 U13 U12

_______________________________________________________________________

Co(1) 9(1) 7(1) 8(1) 0 1(1) 0 C(1) 11(1) 11(1) 13(1) -2(1) -1(1) 1(1) C(2) 11(1) 16(1) 10(1) 0 2(1) 0 C(4) 15(1) 13(1) 19(1) -6(1) -4(1) 4(1) O(1) 18(1) 16(1) 14(1) -6(1) 4(1) -5(1) O(2) 13(1) 8(1) 11(1) 0 0(1) 0 O(3) 11(1) 12(1) 18(2) -3(1) 2(1) -1(1) O(4) 26(1) 32(2) 20(1) -7(2) 1(1) 12(2) O(5) 20(1) 20(1) 13(1) 0 3(1) 0 O(6) 26(1) 32(3) 20(1) -7(2) 1(1) 12(2) O(7) 11(1) 12(2) 18(2) -3(1) 2(1) -1(1) _______________________________________________________________________

Table 10. Hydrogen coordinates (× 104) and isotropic displacement parameters (Å2 ×

103) for (2).

________________________________________________________________

x y z U(eq)

________________________________________________________________

H(2) 11490(20) 10730(30) 10950(50) 27 H(2B) 9080(30) 5000 7940(80) 27 H(4A) 8130(40) 5960(40) 1590(90) 39 H(4B) 8750(20) 6980(70) 1860(70) 39 H(5A) 6570(20) 5000 5230(60) 27 H(5B) 6950(30) 5000 7310(40) 27 H(6A) 6770(40) 8230(60) 9450(50) 39 H(6B) 6200(20) 8860(70) 7990(60) 39

Table 11. Hydrogen Bonding Geometry Parameters in the structure of (2). Specified

hydrogen bonds with H..A < r(A) + 2.000 Angstroms (with esds except for riding H).

D-H···A D-H (Å) H···A (Å) D···A (Å) D-H···A (deg) O2-H2···O3a O2-H2···O7b O4-H4A···O6d O4-H4B···O1c

O5-H5A···O7 O5-H5A···O7f O5-H5B···O2e O6-H6A···O3g O6-H6A···O7h

0.87 0.87 0.90 0.87 0.87 0.87 0.83 0.83 0.89

1.80 1.84 2.21 2.27 2.390 2.390 1.97 2.04 2.61

2.624(4) 2.648(4) 3.081(7) 3.045(7) 2.875(4) 2.875(4) 2.783(3) 2.877(7) 3.462(7)

158 155 161 148 115.8 115.8 165 158 161

Note: Symmetry codes: (a) -x+2, -y+2, -z+2; (b) x+1/2, y+1/2, z+1; (c) -x+2, y, -z+1;

(d) -x+3/2, y-1/2, -z+1; (e) x-1/2, y-1/2, z; (f) x, -y+1, z; (g) -x+3/2, -y+3/2, -z+2; (h) x,

y, z+1

Figure 1. A thermal ellipsoid plot of the structure of

[Co(OH)2(H2O)4][Co(BTCA)(H2O)4]•7.2H2O (1). Solvent water molecules were omitted

for the sake of clarity and only one set of disordered ligands around Co2 are shown.

Atoms are shown at the 50% probability level.

Figure 2. A packing diagram illustrating the unit cell of (1) as well as the extended

structure of as viewed down the a axis. Solvent water molecules were omitted for clarity.

Figure 3. A representation of the hydrogen bonding interactions in (1).

Figure 4. A thermal ellipsoid plot of the structure of [Na2Co(H2O)4(µ-H2O)2(µ-BTCA)]

(2). Atoms are shown at the 50% probability level.

Two more pictures to choose from: