Hexakis­(imidazole-N)­cobalt(II) 1,4-benzene­di­carboxyl­ate tetrahydrate

In the crystal structure of the title compound, [Co(C₃H₄N₂)₆](C₈H₄O₄)·4H₂O, the hexakis­(imidazole-N)­co­balt(II) cation and 1,4-benzene­di­carboxyl­ate anion occupy special positions on inversion centres; two independent water mol­ecules are in general positions. The Co^II atom has almost ideal octahedral coordination formed by the N atoms of six imidazole ligands. Seven independent hydrogen bonds involving cations, anions and water mol­ecules link all the residues in the crystal into a complex three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.058
• wR factor = 0.179
• Data-to-parameter ratio = 18.2

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level B:



PLAT_731  Alert B Bond    Calc     0.84(6), Rep   0.850(10) ....       6.00 s.u-Ratio
                     O1W  -H1W2    1.555   1.555

PLAT_735  Alert B D-H     Calc     0.84(6), Rep   0.850(10) ....       6.00 s.u-Ratio
                     O1W  -H1W2    1.555   1.555

PLAT_736  Alert B H...A   Calc     2.04(6), Rep   2.030(10) ....       6.00 s.u-Ratio
                     H1W2 -O2      1.555   2.465


 Alert Level C:



PLAT_369  Alert C Long   C(sp2)-C(sp2) Bond  C(10)  -   C(11)  =       1.53 Ang.

PLAT_731  Alert C Bond    Calc     0.85(4), Rep   0.850(10) ....       4.00 s.u-Ratio
                     O1W  -H1W1    1.555   1.555

PLAT_731  Alert C Bond    Calc     0.85(3), Rep   0.850(10) ....       3.00 s.u-Ratio
                     O2W  -H2W1    1.555   1.555

PLAT_731  Alert C Bond    Calc     0.85(4), Rep   0.850(10) ....       4.00 s.u-Ratio
                     O2W  -H2W2    1.555   1.555

PLAT_732  Alert C Angle   Calc      111(5), Rep      111(2) ....       2.50 s.u-Ratio
                     H1W1 -O1W  -H1W2    1.555   1.555   1.555

PLAT_735  Alert C D-H     Calc     0.85(4), Rep   0.850(10) ....       4.00 s.u-Ratio
                     O1W  -H1W1    1.555   1.555

PLAT_735  Alert C D-H     Calc     0.85(4), Rep   0.850(10) ....       4.00 s.u-Ratio
                     O2W  -H2W2    1.555   1.555

PLAT_735  Alert C D-H     Calc     0.85(3), Rep   0.850(10) ....       3.00 s.u-Ratio
                     O2W  -H2W1    1.555   1.555

PLAT_736  Alert C H...A   Calc     2.20(4), Rep   2.200(10) ....       4.00 s.u-Ratio
                     H2W2 -O2      1.555   1.555

PLAT_736  Alert C H...A   Calc     1.91(4), Rep   1.910(10) ....       4.00 s.u-Ratio
                     H2W1 -O2      1.555   2.465


 0 Alert Level A = Potentially serious problem

 3 Alert Level B = Potential problem

 10 Alert Level C = Please check

---

S1. Comment

Pronounced interest has recently been focused on the crystal engineering of supramolecular architectures organized by coordination covalent or supramolecular contacts (such as hydrogen bonding, π–π interaction etc.) (Aakeroy, 1997; Beatty, 2001; Braga et al., 1998; Desiraju, 1996; Janiak, 2000; Moulton & Zaworotko, 2001). Currently, the most prevalent strategy for engineering the structures of crystals takes advantage of directional intermolecular interactions between molecules as the principal means of controlling molecular assembly during crystallization. We report here the synthesis and structure of hexakis(imidazole-N)cobalt(II) 1,4-benzenedicarboxylate tetrahydrate, [Co(Him)₆](tp)·4H₂O, (I) (Him = imidazole and tp = 1,4-benzenedicarboxylate).

The crystal structure of (I) is built of mononuclear [Co(Him)₆]²⁺ dications, tp^2- dianions and lattice water molecules. As shown in Fig. 1, the Co^II ion has an almost ideal octahedral environment formed by six imidazole N atoms. The Co—N bond distances vary from 2.180 (2) to 2.207 (2) Å, and the cis-N—Co—N bond angles are in the range from 89.1 (1) to 90.9 (1)°. The Co—N(Him) bond distances are similar to the corresponding values reported previously in the range 2.140–2.188 Å in [Co(Him)₆](MeCO₂)₂·H₂O (Gadet & Lefebvre-Soubeyran, 1974), [Co(Him)₆](NO₃)₂ (Prince et al., 1972), [Co(Him)₆](CO₃)·5H₂O (Strandberg & Lundberg, 1971), [Co(Him)₆](PhCO₂)₂ (Wang et al., 1999) and [Co(Him)₆](ClO₄)₂ (Suresh & Venkatasubramanian, 1997).

In the crystal of the title compound, there is an extensive hydrogen-bonding system, involving all types of species, viz. the [Co(Him)₆]²⁺ cations, tp^2- anions, and lattice water molecules. Each Him unit of [Co(Him)₆]²⁺ forms one donor hydrogen bond with adjacent water molecule or tp^2- anion, and each tp^2- anion forms eight acceptor hydrogen bonds with water molecules and/or cations. Each water molecule forms one acceptor hydrogen bond with a Him unit and two donor hydrogen bonds with tp^2- anions. Thus, the structure of the title compound provides an interesting three-dimensional supramolecular architecture driven by the extensive hydrogen-bonding system (Fig. 2).

S2. Experimental

To a solution of CoCl₂ (0.5 mmol) in 1:1 (v/v) MeOH/H₂O (10 ml), a solution of imidazole (4.0 mmol) and 1,4-benzenedicarboxylic acid (0.5 mmol) in MeOH (10 ml) was added slowly with stirring for 30 min at 323 K. Light-red polyhedral crystals precipitated within ten days (75% yield).

S3. Refinement

The C-bound H atoms were generated geometrically, and they ride on their parent C atoms; U_iso(H) = 1.2U_eq(C). The water and the N-bound H atoms were located and refined. For water H atoms, the O—H distance was restrained to 0.85±0.01 Å and the H···H to 1.39±0.01 Å; the N—H bonds are in the range 0.83—0.86 Å.

Computing details

Data collection: XSCANS (Siemens, 1990); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The structure of the dication and dianion in the crystal of (I) with 50% probability displacement displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. Perspective view of the three-dimensional hydrogen-bonded network of (I).

Hexakis(imidazole-N)cobalt(II) 1,4-benzenedicarboxylate tetrahydrate

Crystal data

[Co(C3H4N2)6](C8H4O4)·4H2O	F(000) = 734
Mr = 703.60	Dx = 1.400 Mg m^−3
Monoclinic, P21/a	Mo Kα radiation, λ = 0.71073 Å
a = 8.219 (4) Å	Cell parameters from 25 reflections
b = 16.203 (7) Å	θ = 7–15°
c = 12.991 (6) Å	µ = 0.58 mm^−1
β = 105.19 (1)°	T = 298 K
V = 1670 (1) Å^3	Block, red
Z = 2	0.52 × 0.40 × 0.32 mm

Data collection

Siemens R3m four-circle diffractometer	3159 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.051
Graphite monochromator	θmax = 29.0°, θmin = 2.0°
ω scans	h = 0→11
Absorption correction: ψ scan (North et al., 1968)	k = 0→22
Tmin = 0.753, Tmax = 0.837	l = −17→17
4723 measured reflections	2 standard reflections every 150 reflections
4433 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.058	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.179	w = 1/[σ^2(Fo^2) + (0.098P)^2 + 0.6325P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
4433 reflections	Δρmax = 0.34 e Å^−3
243 parameters	Δρmin = −0.73 e Å^−3
6 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.073 (6)

Special details

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Co1	0.5000	0.5000	0.5000	0.0375 (2)
O1	1.0719 (3)	0.9141 (1)	0.9645 (2)	0.055 (1)
O2	1.2513 (3)	0.8110 (1)	1.0213 (2)	0.057 (1)
O1w	0.8129 (4)	0.8034 (2)	0.8659 (2)	0.064 (1)
O2w	1.0021 (4)	0.7819 (2)	1.1541 (2)	0.065 (1)
N1	0.6927 (3)	0.5814 (2)	0.6006 (2)	0.045 (1)
N2	0.8122 (4)	0.6783 (2)	0.7164 (2)	0.063 (1)
N3	0.3311 (3)	0.6060 (2)	0.4468 (2)	0.045 (1)
N4	0.1718 (4)	0.6990 (2)	0.3407 (2)	0.058 (1)
N5	0.6059 (3)	0.5193 (2)	0.3646 (2)	0.043 (1)
N6	0.6334 (4)	0.5203 (2)	0.1995 (2)	0.050 (1)
C1	0.6698 (4)	0.6523 (2)	0.6465 (2)	0.053 (1)
C2	0.9351 (5)	0.6214 (3)	0.7165 (3)	0.067 (1)
C3	0.8609 (4)	0.5622 (2)	0.6448 (3)	0.058 (1)
C4	0.5422 (4)	0.4943 (2)	0.2648 (2)	0.051 (1)
C5	0.7649 (4)	0.5663 (2)	0.2598 (3)	0.059 (1)
C6	0.7471 (4)	0.5653 (2)	0.3612 (2)	0.050 (1)
C7	0.2936 (4)	0.6415 (2)	0.3507 (2)	0.051 (1)
C8	0.1270 (5)	0.7014 (2)	0.4357 (3)	0.068 (1)
C9	0.2258 (4)	0.6444 (2)	0.5004 (3)	0.059 (1)
C10	1.2190 (3)	0.8852 (2)	0.9925 (2)	0.040 (1)
C11	1.3655 (3)	0.9441 (2)	0.9957 (2)	0.039 (1)
C12	1.3342 (4)	1.0293 (2)	0.9803 (2)	0.046 (1)
C13	1.5318 (4)	0.9155 (2)	1.0151 (2)	0.047 (1)
H1	0.5678	0.6805	0.6321	0.063*
H2	1.0466	0.6228	0.7571	0.081*
H3	0.9152	0.5158	0.6280	0.069*
H4	0.4453	0.4623	0.2428	0.061*
H5	0.8489	0.5928	0.2362	0.071*
H6	0.8188	0.5915	0.4194	0.060*
H7	0.3452	0.6282	0.2972	0.061*
H8	0.0458	0.7350	0.4523	0.081*
H9	0.2232	0.6329	0.5701	0.071*
H12	1.2245	1.0492	0.9671	0.055*
H13	1.5538	0.8594	1.0252	0.056*
H1w1	0.903 (4)	0.830 (3)	0.892 (4)	0.11 (2)*
H1w2	0.793 (7)	0.770 (4)	0.911 (4)	0.20 (4)*
H2w1	0.925 (4)	0.751 (2)	1.117 (3)	0.09 (1)*
H2w2	1.067 (5)	0.797 (3)	1.116 (3)	0.12 (2)*
H2n	0.819 (5)	0.721 (3)	0.753 (3)	0.08 (1)*
H4n	0.127 (5)	0.727 (2)	0.286 (3)	0.07 (1)*
H6n	0.607 (6)	0.508 (2)	0.133 (4)	0.08 (1)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0382 (3)	0.0423 (3)	0.0308 (3)	−0.0014 (2)	0.0067 (2)	−0.0029 (2)
O1	0.039 (1)	0.047 (1)	0.076 (2)	0.001 (1)	0.010 (1)	0.001 (1)
O2	0.049 (1)	0.041 (1)	0.076 (2)	0.000 (1)	0.010 (1)	0.011 (1)
O1w	0.068 (2)	0.056 (1)	0.058 (1)	−0.010 (1)	−0.002 (1)	−0.006 (1)
O2w	0.072 (2)	0.066 (2)	0.050 (1)	−0.022 (1)	0.002 (1)	0.002 (1)
N1	0.042 (1)	0.051 (1)	0.039 (1)	−0.007 (1)	0.006 (1)	−0.005 (1)
N2	0.076 (2)	0.058 (2)	0.048 (2)	−0.019 (2)	0.008 (1)	−0.013 (1)
N3	0.045 (1)	0.045 (1)	0.043 (1)	0.003 (1)	0.006 (1)	−0.001 (1)
N4	0.061 (2)	0.050 (2)	0.055 (2)	0.006 (1)	0.000 (1)	0.005 (1)
N5	0.044 (1)	0.051 (1)	0.035 (1)	0.001 (1)	0.011 (1)	0.001 (1)
N6	0.059 (2)	0.057 (2)	0.035 (1)	0.000 (1)	0.014 (1)	0.002 (1)
C1	0.058 (2)	0.050 (2)	0.046 (2)	−0.007 (1)	0.008 (1)	−0.004 (1)
C2	0.058 (2)	0.080 (3)	0.054 (2)	−0.019 (2)	−0.003 (2)	−0.007 (2)
C3	0.045 (2)	0.071 (2)	0.051 (2)	−0.002 (2)	0.004 (1)	−0.008 (2)
C4	0.061 (2)	0.053 (2)	0.037 (1)	−0.008 (1)	0.010 (1)	−0.004 (1)
C5	0.056 (2)	0.075 (2)	0.048 (2)	−0.006 (2)	0.018 (1)	0.011 (2)
C6	0.045 (2)	0.062 (2)	0.040 (1)	−0.003 (1)	0.005 (1)	0.004 (1)
C7	0.053 (2)	0.049 (2)	0.047 (2)	0.002 (1)	0.007 (1)	0.003 (1)
C8	0.070 (2)	0.064 (2)	0.065 (2)	0.021 (2)	0.010 (2)	−0.005 (2)
C9	0.067 (2)	0.061 (2)	0.047 (2)	0.014 (2)	0.011 (1)	−0.002 (1)
C10	0.042 (1)	0.041 (1)	0.036 (1)	0.002 (1)	0.011 (1)	0.000 (1)
C11	0.041 (1)	0.040 (1)	0.037 (1)	0.002 (1)	0.012 (1)	−0.001 (1)
C12	0.040 (1)	0.043 (1)	0.057 (2)	0.006 (1)	0.014 (1)	0.002 (1)
C13	0.045 (2)	0.036 (1)	0.059 (2)	0.004 (1)	0.014 (1)	0.003 (1)

Geometric parameters (Å, º)

Co1—N1	2.207 (2)	C10—C11	1.528 (4)
Co1—N1^i	2.207 (2)	C11—C13	1.402 (4)
Co1—N3	2.203 (2)	C11—C12	1.408 (4)
Co1—N3^i	2.203 (2)	C12—C13^ii	1.408 (4)
Co1—N5	2.180 (2)	C13—C12^ii	1.408 (4)
Co1—N5^i	2.180 (2)	O1w—H1w1	0.85 (1)
O1—C10	1.258 (3)	O1w—H1w2	0.85 (1)
O2—C10	1.266 (3)	O2w—H2w1	0.85 (1)
N1—C1	1.330 (4)	O2w—H2w2	0.85 (1)
N1—C3	1.386 (4)	N2—H2n	0.83 (4)
N2—C1	1.347 (4)	N4—H4n	0.84 (4)
N2—C2	1.367 (5)	N6—H6n	0.86 (5)
N3—C7	1.336 (4)	C1—H1	0.9300
N3—C9	1.392 (4)	C2—H2	0.9300
N4—C7	1.348 (4)	C3—H3	0.9300
N4—C8	1.377 (5)	C4—H4	0.9300
N5—C4	1.328 (4)	C5—H5	0.9300
N5—C6	1.390 (4)	C6—H6	0.9300
N6—C4	1.339 (4)	C7—H7	0.9300
N6—C5	1.377 (4)	C8—H8	0.9300
C2—C3	1.365 (5)	C9—H9	0.9300
C5—C6	1.363 (4)	C12—H12	0.9300
C8—C9	1.364 (5)	C13—H13	0.9300
N1—Co1—N1^i	180.0 (1)	O1—C10—C11	117.7 (2)
N1—Co1—N3	90.9 (1)	O2—C10—C11	118.9 (2)
N1—Co1—N3^i	89.1 (1)	C13—C11—C12	118.8 (2)
N1—Co1—N5	90.9 (1)	C13—C11—C10	121.5 (2)
N1—Co1—N5^i	89.1 (1)	C12—C11—C10	119.7 (2)
N1^i—Co1—N3	89.1 (1)	C13^ii—C12—C11	120.3 (3)
N1^i—Co1—N3^i	90.9 (1)	C11—C13—C12^ii	120.9 (3)
N1^i—Co1—N5	89.1 (1)	H1w1—O1w—H1w2	111 (2)
N1^i—Co1—N5^i	90.9 (1)	H2w1—O2w—H2w2	109 (2)
N3—Co1—N3^i	180.000 (1)	C1—N2—H2n	124 (3)
N3—Co1—N5	89.3 (1)	C2—N2—H2n	128 (3)
N3—Co1—N5^i	90.7 (1)	C7—N4—H4n	127 (3)
N3^i—Co1—N5	90.7 (1)	C8—N4—H4n	125 (3)
N3^i—Co1—N5^i	89.3 (1)	C4—N6—H6n	122 (3)
N5—Co1—N5^i	180.000 (1)	C5—N6—H6n	131 (3)
C1—N1—C3	104.5 (3)	N1—C1—H1	124.1
C1—N1—Co1	128.1 (2)	N2—C1—H1	124.1
C3—N1—Co1	126.5 (2)	C3—C2—H2	127.0
C1—N2—C2	107.5 (3)	N2—C2—H2	127.0
C7—N3—C9	104.7 (3)	C2—C3—H3	124.9
C7—N3—Co1	127.0 (2)	N1—C3—H3	124.9
C9—N3—Co1	128.0 (2)	N5—C4—H4	123.9
C7—N4—C8	107.4 (3)	N6—C4—H4	123.9
C4—N5—C6	104.6 (2)	C6—C5—H5	127.0
C4—N5—Co1	127.2 (2)	N6—C5—H5	127.0
C6—N5—Co1	128.0 (2)	C5—C6—H6	125.1
C4—N6—C5	107.3 (3)	N5—C6—H6	125.1
N1—C1—N2	111.9 (3)	N3—C7—H7	124.1
C3—C2—N2	106.0 (3)	N4—C7—H7	124.1
C2—C3—N1	110.1 (3)	C9—C8—H8	126.9
N5—C4—N6	112.3 (3)	N4—C8—H8	126.9
C6—C5—N6	106.0 (3)	C8—C9—H9	125.0
C5—C6—N5	109.9 (3)	N3—C9—H9	125.0
N3—C7—N4	111.8 (3)	C13^ii—C12—H12	119.9
C9—C8—N4	106.1 (3)	C11—C12—H12	119.9
C8—C9—N3	110.0 (3)	C11—C13—H13	119.6
O1—C10—O2	123.4 (3)	C12^ii—C13—H13	119.6
N5—Co1—N1—C1	117.3 (3)	C1—N2—C2—C3	0.3 (4)
N5^i—Co1—N1—C1	−62.7 (3)	N2—C2—C3—N1	−0.4 (4)
N3—Co1—N1—C1	28.1 (3)	C1—N1—C3—C2	0.4 (4)
N3^i—Co1—N1—C1	−151.9 (3)	Co1—N1—C3—C2	−169.7 (2)
N5—Co1—N1—C3	−74.9 (3)	C6—N5—C4—N6	0.6 (4)
N5^i—Co1—N1—C3	105.1 (3)	Co1—N5—C4—N6	176.4 (2)
N3—Co1—N1—C3	−164.2 (3)	C5—N6—C4—N5	−0.7 (4)
N3^i—Co1—N1—C3	15.8 (3)	C4—N6—C5—C6	0.5 (4)
N5—Co1—N3—C7	16.7 (3)	N6—C5—C6—N5	−0.1 (4)
N5^i—Co1—N3—C7	−163.3 (3)	C4—N5—C6—C5	−0.3 (4)
N1^i—Co1—N3—C7	−72.4 (3)	Co1—N5—C6—C5	−176.0 (2)
N1—Co1—N3—C7	107.6 (3)	C9—N3—C7—N4	−0.3 (4)
N5—Co1—N3—C9	−171.5 (3)	Co1—N3—C7—N4	173.1 (2)
N5^i—Co1—N3—C9	8.5 (3)	C8—N4—C7—N3	0.0 (4)
N1^i—Co1—N3—C9	99.4 (3)	C7—N4—C8—C9	0.2 (4)
N1—Co1—N3—C9	−80.6 (3)	N4—C8—C9—N3	−0.4 (4)
N3—Co1—N5—C4	−81.7 (3)	C7—N3—C9—C8	0.4 (4)
N3^i—Co1—N5—C4	98.3 (3)	Co1—N3—C9—C8	−172.8 (2)
N1^i—Co1—N5—C4	7.4 (3)	O1—C10—C11—C13	−173.3 (3)
N1—Co1—N5—C4	−172.6 (3)	O2—C10—C11—C13	9.1 (4)
N3—Co1—N5—C6	93.1 (3)	O1—C10—C11—C12	7.5 (4)
N3^i—Co1—N5—C6	−86.9 (3)	O2—C10—C11—C12	−170.0 (3)
N1^i—Co1—N5—C6	−177.8 (3)	C13—C11—C12—C13^ii	−0.2 (5)
N1—Co1—N5—C6	2.2 (3)	C10—C11—C12—C13^ii	179.0 (3)
C3—N1—C1—N2	−0.2 (4)	C12—C11—C13—C12^ii	0.2 (5)
Co1—N1—C1—N2	169.6 (2)	C10—C11—C13—C12^ii	−179.0 (3)
C2—N2—C1—N1	0.0 (4)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+3, −y+2, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2n···O1w	0.83 (4)	2.00 (4)	2.806 (4)	165 (4)
N4—H4n···O2w^iii	0.84 (4)	1.97 (4)	2.802 (4)	173 (4)
N6—H6n···O1^iv	0.86 (5)	2.25 (5)	2.909 (4)	133 (4)
O1w—H1w1···O1	0.85 (1)	2.00 (2)	2.821 (3)	164 (5)
O1w—H1w2···O2^v	0.85 (1)	2.03 (1)	2.880 (4)	178 (5)
O2w—H2w2···O2	0.85 (1)	2.20 (1)	3.041 (4)	169 (5)
O2w—H2w1···O2^v	0.85 (1)	1.91 (1)	2.761 (3)	174 (4)

Symmetry codes: (iii) x−1, y, z−1; (iv) −x+3/2, y−1/2, −z+1; (v) x−1/2, −y+3/2, z.