cyclo-Tetra-μ-malato-κO,O',O'':O'''-tetra-kis[bis-(1H-benzimidazole-κN)cobalt(II)] eicosa-hydrate.

The title compound, [Co(4)(C(4)H(4)O(5))(4)(C(7)H(6)N(2))(8)]·20H(2)O, consists of tetra-nuclear Co(II) complexes and disordered uncoordinated water mol-ecules. The tetra-meric complex mol-ecule has symmetry. While two benzimidazole mol-ecules and a tridentate malate dianion coordinate a Co(II) ion, the carboxylate O atom from an adjacent malate dianion bridges the Co(II) ions to complete a distorted octa-hedral coordination geometry. The tridentate malate dianion chelates the Co(II) ion, and the chelate six- and five-membered rings show half-chair and envelope configurations, respectively. A face-to-face separation of 3.494 (9) Å between parallel benzimidazole ligands indicates the existence of π-π stacking between adjacent complexes. The crystal structure also involves N-H⋯O and O-H⋯O hydrogen bonds.

Related literature

For general background, see: Deisenhofer & Michel (1989 ▶); Su & Xu (2004 ▶); Liu et al. (2004 ▶); Li et al. (2005 ▶). For related structures, see: Nie et al. (2002 ▶);

Experimental

Crystal data

[Co4(C4H4O5)4(C7H6N2)8]·20H2O

M = 2069.43

Tetragonal,

a = 20.230 (2) Å

c = 11.6203 (12) Å

V = 4755.6 (8) Å3

Z = 2

Mo Kα radiation

μ = 0.78 mm−1

T = 295 (2) K

0.35 × 0.30 × 0.22 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.748, T max = 0.840

29983 measured reflections

4053 independent reflections

3191 reflections with I > 2σ(I)

R int = 0.075

Refinement

R[F 2 > 2σ(F 2)] = 0.076

wR(F 2) = 0.190

S = 1.15

4053 reflections

294 parameters

H-atom parameters constrained

Δρmax = 0.43 e Å−3

Δρmin = −0.31 e Å−3

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808006715/ng2434sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808006715/ng2434Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Co4(C4H4O5)4(C7H6N2)8]·20H2O	Z = 2
Mr = 2069.43	F000 = 2152
Tetragonal, P4/n	Dx = 1.445 Mg m−3
Hall symbol: -P 4a	Mo Kα radiation λ = 0.71069 Å
a = 20.230 (2) Å	Cell parameters from 8672 reflections
b = 20.230 Å	θ = 2.0–24.0º
c = 11.6203 (12) Å	µ = 0.78 mm−1
α = 90º	T = 295 (2) K
β = 90º	Prism, pink
γ = 90º	0.35 × 0.30 × 0.22 mm
V = 4755.6 (8) Å3

Rigaku R-AXIS RAPID IP diffractometer	4053 independent reflections
Radiation source: fine-focus sealed tube	3191 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.075
Detector resolution: 10.00 pixels mm-1	θmax = 25.0º
T = 295(2) K	θmin = 1.4º
ω scans	h = −22→24
Absorption correction: multi-scan(ABSCOR; Higashi, 1995)	k = −23→21
Tmin = 0.748, Tmax = 0.840	l = −12→12
29983 measured reflections

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.076	w = 1/[σ2(Fo2) + (0.0761P)2 + 7.4753P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.190	(Δ/σ)max = 0.001
S = 1.15	Δρmax = 0.43 e Å−3
4053 reflections	Δρmin = −0.31 e Å−3
294 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0022 (4)
Secondary atom site location: difference Fourier map

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

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Co	0.43554 (3)	0.71743 (3)	0.55558 (6)	0.0519 (3)
N11	0.5316 (3)	0.8011 (3)	0.8403 (6)	0.106 (2)
H11	0.5680	0.8134	0.8721	0.128*
N13	0.4649 (2)	0.7567 (2)	0.7126 (4)	0.0602 (11)
N21	0.5804 (3)	0.5747 (3)	0.4877 (6)	0.0909 (18)
H21	0.6114	0.5610	0.4429	0.109*
N23	0.5019 (2)	0.6392 (2)	0.5566 (4)	0.0667 (12)
O1	0.50329 (18)	0.7760 (2)	0.4621 (4)	0.0691 (11)
O2	0.5563 (2)	0.8172 (3)	0.3159 (4)	0.1038 (16)
O3	0.39943 (17)	0.69288 (15)	0.3869 (3)	0.0571 (9)
H3A	0.3602	0.6703	0.3976	0.068*
O4	0.36459 (17)	0.79509 (16)	0.5193 (3)	0.0556 (9)
O5	0.33611 (16)	0.85780 (16)	0.3690 (3)	0.0562 (9)
C1	0.5066 (3)	0.7899 (3)	0.3585 (6)	0.0628 (14)
C2	0.4512 (3)	0.7765 (3)	0.2754 (5)	0.0712 (16)
H2A	0.4652	0.7422	0.2225	0.085*
H2B	0.4434	0.8162	0.2306	0.085*
C3	0.3868 (2)	0.7556 (2)	0.3297 (5)	0.0570 (13)
H3	0.3541	0.7486	0.2688	0.068*
C4	0.3602 (2)	0.8070 (2)	0.4135 (5)	0.0506 (12)
C12	0.5260 (3)	0.7690 (4)	0.7395 (7)	0.093 (2)
H12	0.5619	0.7569	0.6941	0.111*
C14	0.3604 (3)	0.7854 (3)	0.8185 (5)	0.0652 (15)
H14	0.3313	0.7661	0.7663	0.078*
C15	0.3380 (4)	0.8176 (4)	0.9149 (6)	0.088 (2)
H15	0.2927	0.8205	0.9272	0.106*
C16	0.3800 (6)	0.8455 (4)	0.9937 (7)	0.104 (2)
H16	0.3624	0.8663	1.0581	0.125*
C17	0.4469 (6)	0.8436 (4)	0.9804 (6)	0.110 (3)
H17	0.4756	0.8629	1.0331	0.132*
C18	0.4696 (4)	0.8110 (3)	0.8834 (6)	0.0838 (18)
C19	0.4273 (3)	0.7829 (2)	0.8026 (5)	0.0584 (13)
C22	0.5461 (3)	0.6295 (3)	0.4751 (7)	0.086 (2)
H22	0.5526	0.6587	0.4144	0.103*
C24	0.4745 (3)	0.5679 (3)	0.7273 (6)	0.086 (2)
H24	0.4417	0.5951	0.7572	0.104*
C25	0.4908 (4)	0.5093 (4)	0.7806 (7)	0.109 (3)
H25	0.4695	0.4967	0.8480	0.131*
C26	0.5408 (4)	0.4680 (4)	0.7312 (9)	0.108 (3)
H26	0.5506	0.4280	0.7669	0.130*
C27	0.5738 (3)	0.4843 (4)	0.6366 (8)	0.097 (2)
H27	0.6064	0.4568	0.6065	0.116*
C28	0.5580 (3)	0.5432 (3)	0.5846 (6)	0.0707 (17)
C29	0.5082 (2)	0.5850 (3)	0.6283 (6)	0.0637 (15)
O1WA	0.6498 (6)	0.7660 (6)	0.5347 (11)	0.111 (4)*	0.50
O1WB	0.6657 (13)	0.7678 (12)	0.450 (2)	0.232 (10)*	0.50
O2WA	0.612 (2)	0.656 (2)	0.164 (4)	0.382 (18)*	0.50
O2WB	0.724 (5)	0.683 (3)	0.306 (5)	0.55 (4)*	0.50
O3WA	0.6433 (16)	0.8792 (19)	0.941 (3)	0.294 (13)*	0.50
O3WB	0.656 (2)	0.954 (2)	1.036 (3)	0.358 (17)*	0.50
O4WA	0.6559 (16)	0.7823 (16)	1.177 (3)	0.306 (14)*	0.50
O4WB	0.6030 (17)	0.8444 (17)	1.094 (3)	0.305 (13)*	0.50
O5WA	0.6861 (19)	0.6634 (15)	0.943 (2)	0.294 (13)*	0.50
O5WB	0.688 (3)	0.692 (3)	0.719 (4)	0.49 (3)*	0.50

	U11	U22	U33	U12	U13	U23
Co	0.0465 (4)	0.0514 (4)	0.0579 (5)	0.0028 (3)	−0.0040 (3)	−0.0070 (3)
N11	0.092 (5)	0.139 (6)	0.088 (5)	−0.022 (4)	−0.033 (4)	−0.028 (4)
N13	0.053 (3)	0.066 (3)	0.061 (3)	0.003 (2)	−0.011 (2)	−0.006 (2)
N21	0.065 (3)	0.085 (4)	0.122 (5)	0.016 (3)	0.020 (3)	−0.020 (4)
N23	0.050 (3)	0.068 (3)	0.082 (3)	0.013 (2)	0.002 (2)	−0.009 (3)
O1	0.059 (2)	0.080 (3)	0.068 (3)	−0.0198 (18)	−0.0013 (19)	−0.005 (2)
O2	0.085 (3)	0.119 (4)	0.108 (4)	−0.038 (3)	0.019 (3)	−0.004 (3)
O3	0.061 (2)	0.0489 (19)	0.061 (2)	−0.0063 (15)	−0.0033 (17)	−0.0063 (16)
O4	0.060 (2)	0.0530 (19)	0.054 (2)	0.0098 (15)	−0.0076 (17)	−0.0001 (16)
O5	0.055 (2)	0.057 (2)	0.056 (2)	−0.0009 (15)	−0.0015 (17)	0.0061 (17)
C1	0.053 (3)	0.063 (3)	0.072 (4)	−0.003 (2)	0.006 (3)	−0.017 (3)
C2	0.077 (4)	0.074 (4)	0.062 (4)	−0.008 (3)	0.010 (3)	−0.010 (3)
C3	0.056 (3)	0.060 (3)	0.055 (3)	−0.006 (2)	−0.009 (2)	−0.009 (3)
C4	0.037 (2)	0.052 (3)	0.063 (4)	−0.005 (2)	−0.007 (2)	−0.003 (2)
C12	0.064 (4)	0.122 (6)	0.093 (6)	0.000 (4)	−0.014 (4)	−0.022 (5)
C14	0.073 (4)	0.071 (4)	0.052 (4)	0.014 (3)	−0.004 (3)	0.003 (3)
C15	0.104 (5)	0.099 (5)	0.062 (5)	0.024 (4)	0.007 (4)	0.011 (4)
C16	0.154 (8)	0.108 (6)	0.050 (4)	0.008 (5)	0.006 (5)	−0.008 (4)
C17	0.158 (8)	0.116 (6)	0.056 (5)	−0.033 (6)	−0.008 (5)	−0.023 (4)
C18	0.091 (5)	0.090 (5)	0.071 (5)	−0.014 (4)	−0.011 (4)	−0.006 (4)
C19	0.076 (4)	0.052 (3)	0.047 (3)	0.002 (2)	−0.012 (3)	0.004 (2)
C22	0.073 (4)	0.079 (4)	0.105 (6)	0.011 (3)	0.022 (4)	−0.011 (4)
C24	0.075 (4)	0.095 (5)	0.089 (5)	0.030 (3)	−0.007 (4)	0.008 (4)
C25	0.102 (6)	0.114 (6)	0.111 (6)	0.034 (5)	−0.001 (5)	0.030 (5)
C26	0.093 (6)	0.092 (5)	0.140 (8)	0.028 (4)	−0.024 (5)	0.027 (5)
C27	0.064 (4)	0.081 (5)	0.144 (8)	0.020 (3)	−0.020 (5)	−0.019 (5)
C28	0.056 (3)	0.059 (3)	0.098 (5)	0.016 (3)	−0.016 (3)	−0.017 (3)
C29	0.046 (3)	0.073 (4)	0.072 (4)	0.011 (2)	−0.012 (3)	−0.013 (3)

Co—N13	2.078 (4)	C2—H2B	0.9700
Co—N23	2.075 (4)	C3—C4	1.523 (7)
Co—O1	2.112 (4)	C3—H3	0.9800
Co—O3	2.150 (4)	C12—H12	0.9300
Co—O4	2.169 (3)	C14—C19	1.367 (8)
Co—O5i	2.101 (4)	C14—C15	1.373 (8)
N11—C12	1.344 (9)	C14—H14	0.9300
N11—C18	1.366 (9)	C15—C16	1.371 (11)
N11—H11	0.8600	C15—H15	0.9300
N13—C12	1.298 (7)	C16—C17	1.363 (12)
N13—C19	1.396 (7)	C16—H16	0.9300
N21—C22	1.316 (8)	C17—C18	1.382 (11)
N21—C28	1.370 (9)	C17—H17	0.9300
N21—H21	0.8600	C18—C19	1.392 (8)
N23—C22	1.318 (8)	C22—H22	0.9300
N23—C29	1.382 (7)	C24—C25	1.377 (9)
O1—C1	1.239 (7)	C24—C29	1.382 (9)
O2—C1	1.250 (7)	C24—H24	0.9300
O3—C3	1.454 (6)	C25—C26	1.432 (11)
O3—H3A	0.9247	C25—H25	0.9300
O4—C4	1.256 (6)	C26—C27	1.328 (11)
O5—C4	1.250 (6)	C26—H26	0.9300
C1—C2	1.504 (8)	C27—C28	1.375 (10)
C2—C3	1.507 (7)	C27—H27	0.9300
C2—H2A	0.9700	C28—C29	1.409 (7)
N23—Co—N13	95.85 (18)	C4—C3—H3	108.8
N23—Co—O5i	95.05 (16)	O5—C4—O4	126.1 (5)
N13—Co—O5i	92.60 (16)	O5—C4—C3	115.8 (5)
N23—Co—O1	90.65 (18)	O4—C4—C3	118.1 (4)
N13—Co—O1	92.93 (17)	N13—C12—N11	112.5 (6)
O5i—Co—O1	171.61 (15)	N13—C12—H12	123.8
N23—Co—O3	92.79 (16)	N11—C12—H12	123.8
N13—Co—O3	170.57 (15)	C19—C14—C15	117.0 (6)
O5i—Co—O3	90.39 (13)	C19—C14—H14	121.5
O1—Co—O3	83.18 (14)	C15—C14—H14	121.5
N23—Co—O4	168.94 (18)	C16—C15—C14	122.4 (7)
N13—Co—O4	94.74 (15)	C16—C15—H15	118.8
O5i—Co—O4	87.65 (13)	C14—C15—H15	118.8
O1—Co—O4	85.61 (15)	C17—C16—C15	121.9 (8)
O3—Co—O4	76.44 (13)	C17—C16—H16	119.0
C12—N11—C18	108.2 (6)	C15—C16—H16	119.0
C12—N11—H11	125.9	C16—C17—C18	115.8 (7)
C18—N11—H11	125.9	C16—C17—H17	122.1
C12—N13—C19	105.4 (5)	C18—C17—H17	122.1
C12—N13—Co	123.8 (5)	N11—C18—C17	132.3 (7)
C19—N13—Co	130.3 (3)	N11—C18—C19	104.8 (6)
C22—N21—C28	107.9 (5)	C17—C18—C19	122.8 (7)
C22—N21—H21	126.1	C14—C19—C18	120.1 (6)
C28—N21—H21	126.1	C14—C19—N13	130.9 (5)
C22—N23—C29	104.6 (5)	C18—C19—N13	109.0 (5)
C22—N23—Co	123.3 (5)	N21—C22—N23	113.8 (7)
C29—N23—Co	132.0 (4)	N21—C22—H22	123.1
C1—O1—Co	131.5 (3)	N23—C22—H22	123.1
C3—O3—Co	105.9 (3)	C25—C24—C29	118.1 (6)
C3—O3—H3A	110.0	C25—C24—H24	120.9
Co—O3—H3A	106.4	C29—C24—H24	120.9
C4—O4—Co	112.0 (3)	C24—C25—C26	119.5 (8)
C4—O5—Coii	130.1 (3)	C24—C25—H25	120.3
O1—C1—O2	121.9 (6)	C26—C25—H25	120.3
O1—C1—C2	122.9 (5)	C27—C26—C25	122.8 (7)
O2—C1—C2	115.2 (6)	C27—C26—H26	118.6
C1—C2—C3	115.2 (5)	C25—C26—H26	118.6
C1—C2—H2A	108.5	C26—C27—C28	117.6 (7)
C3—C2—H2A	108.5	C26—C27—H27	121.2
C1—C2—H2B	108.5	C28—C27—H27	121.2
C3—C2—H2B	108.5	N21—C28—C27	133.4 (6)
H2A—C2—H2B	107.5	N21—C28—C29	104.8 (5)
O3—C3—C2	106.6 (4)	C27—C28—C29	121.9 (7)
O3—C3—C4	111.5 (4)	C24—C29—N23	130.9 (5)
C2—C3—C4	112.4 (4)	C24—C29—C28	120.2 (6)
O3—C3—H3	108.8	N23—C29—C28	108.9 (6)
C2—C3—H3	108.8
N23—Co—N13—C12	50.3 (6)	C2—C3—C4—O5	73.8 (6)
O5i—Co—N13—C12	145.7 (5)	O3—C3—C4—O4	13.6 (6)
O1—Co—N13—C12	−40.6 (5)	C2—C3—C4—O4	−105.9 (5)
O4—Co—N13—C12	−126.5 (5)	C19—N13—C12—N11	0.1 (8)
N23—Co—N13—C19	−138.7 (5)	Co—N13—C12—N11	172.9 (5)
O5i—Co—N13—C19	−43.4 (5)	C18—N11—C12—N13	−0.1 (9)
O1—Co—N13—C19	130.3 (5)	C19—C14—C15—C16	−0.9 (10)
O4—Co—N13—C19	44.5 (5)	C14—C15—C16—C17	0.7 (12)
N13—Co—N23—C22	−121.7 (5)	C15—C16—C17—C18	−0.8 (13)
O5i—Co—N23—C22	145.1 (5)	C12—N11—C18—C17	−176.7 (8)
O1—Co—N23—C22	−28.7 (5)	C12—N11—C18—C19	0.1 (8)
O3—Co—N23—C22	54.5 (5)	C16—C17—C18—N11	177.6 (8)
O4—Co—N23—C22	41.4 (11)	C16—C17—C18—C19	1.2 (12)
N13—Co—N23—C29	64.3 (5)	C15—C14—C19—C18	1.3 (8)
O5i—Co—N23—C29	−28.9 (5)	C15—C14—C19—N13	−177.0 (6)
O1—Co—N23—C29	157.3 (5)	N11—C18—C19—C14	−178.7 (5)
O3—Co—N23—C29	−119.5 (5)	C17—C18—C19—C14	−1.5 (10)
O4—Co—N23—C29	−132.6 (8)	N11—C18—C19—N13	0.0 (7)
N23—Co—O1—C1	100.5 (5)	C17—C18—C19—N13	177.2 (7)
N13—Co—O1—C1	−163.6 (5)	C12—N13—C19—C14	178.5 (6)
O3—Co—O1—C1	7.7 (5)	Co—N13—C19—C14	6.3 (9)
O4—Co—O1—C1	−69.1 (5)	C12—N13—C19—C18	0.0 (7)
N23—Co—O3—C3	−143.1 (3)	Co—N13—C19—C18	−172.2 (4)
O5i—Co—O3—C3	121.8 (3)	C28—N21—C22—N23	0.6 (8)
O1—Co—O3—C3	−52.8 (3)	C29—N23—C22—N21	−0.2 (8)
O4—Co—O3—C3	34.3 (3)	Co—N23—C22—N21	−175.6 (4)
N23—Co—O4—C4	−16.0 (10)	C29—C24—C25—C26	−1.1 (11)
N13—Co—O4—C4	147.1 (3)	C24—C25—C26—C27	1.6 (13)
O5i—Co—O4—C4	−120.5 (3)	C25—C26—C27—C28	−0.7 (12)
O1—Co—O4—C4	54.5 (3)	C22—N21—C28—C27	177.6 (7)
O3—Co—O4—C4	−29.5 (3)	C22—N21—C28—C29	−0.8 (7)
Co—O1—C1—O2	−168.7 (4)	C26—C27—C28—N21	−178.9 (7)
Co—O1—C1—C2	12.5 (8)	C26—C27—C28—C29	−0.7 (10)
O1—C1—C2—C3	9.8 (8)	C25—C24—C29—N23	178.7 (6)
O2—C1—C2—C3	−169.0 (5)	C25—C24—C29—C28	−0.2 (10)
Co—O3—C3—C2	86.6 (4)	C22—N23—C29—C24	−179.3 (7)
Co—O3—C3—C4	−36.3 (4)	Co—N23—C29—C24	−4.5 (9)
C1—C2—C3—O3	−63.4 (6)	C22—N23—C29—C28	−0.3 (6)
C1—C2—C3—C4	58.9 (6)	Co—N23—C29—C28	174.5 (4)
Coii—O5—C4—O4	−9.6 (7)	N21—C28—C29—C24	179.8 (6)
Coii—O5—C4—C3	170.8 (3)	C27—C28—C29—C24	1.2 (9)
Co—O4—C4—O5	−162.3 (4)	N21—C28—C29—N23	0.7 (6)
Co—O4—C4—C3	17.4 (5)	C27—C28—C29—N23	−178.0 (6)
O3—C3—C4—O5	−166.7 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···O3WA	0.86	2.18	3.00 (4)	159
N11—H11···O5WAiii	0.86	2.10	2.93 (4)	163
N21—H21···O1iv	0.86	2.57	3.258 (7)	138
N21—H21···O2iv	0.86	2.07	2.901 (8)	163
O3—H3A···O4i	0.92	1.78	2.645 (5)	155

Table 1

Selected bond lengths (Å)

Co—N13	2.078 (4)
Co—N23	2.075 (4)
Co—O1	2.112 (4)
Co—O3	2.150 (4)
Co—O4	2.169 (3)
Co—O5i	2.101 (4)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N11—H11⋯O3WA	0.86	2.18	3.00 (4)	159
N11—H11⋯O5WAii	0.86	2.10	2.93 (4)	163
N21—H21⋯O1iii	0.86	2.57	3.258 (7)	138
N21—H21⋯O2iii	0.86	2.07	2.901 (8)	163
O3—H3A⋯O4i	0.92	1.78	2.645 (5)	155

Symmetry codes: (i) ; (ii) ; (iii) .