Poly[[bis­{μ2-1,2-bis­[(1H-imidazol-1-yl)meth­yl]benzene}(μ4-9,10-dioxo-9,10-dihydro­anthracene-1,4,5,8-tetra­carbox­yl­ato)dicobalt(II)] dihydrate]

Sheng, X.-L.; Xu, D.-H.; Cai, B.; Liu, J.-L.

doi:10.1107/S160053681202716X

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 3| March 2013| Page m136

doi:10.1107/S160053681202716X

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Poly[[bis{μ₂-1,2-bis[(1H-imidazol-1-yl)methyl]benzene}(μ₄-9,10-dioxo-9,10-dihydroanthracene-1,4,5,8-tetracarboxylato)dicobalt(II)] dihydrate]

Xiao-Li Sheng,^a Duo-Hui Xu,^a Bin Cai ^a and Jian-Lan Liu ^a ^*

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: njutljl@163.com

(Received 19 May 2012; accepted 15 June 2012; online 6 February 2013)

The title complex, {[Co₂(C₁₈H₄O₁₀)(C₁₄H₁₄N₄)₂]·2H₂O}_n was synthesized from CoCl₂·6H₂O, 9,10-dioxo-9,10-dihydroanthracene-1,4,5,8-tetracarboxylic acid (H₄AQTC) and 1,2-bis[(1H-imidazol-1-yl)methyl]benzene (o-bix) in water. The anthraquinone unit is located about a crystallographic center of inversion. Each asymmetric unit therefore contains one Co^II atom and one o-bix ligand, as well as half an AQTC⁴⁻ ligand and an additional solvent water molecule. The Co^II ions are tetrahedrally surrounded by two O atoms from two AQTC⁴⁻ anions and by two N atoms from two o-bix ligands, forming a two-dimensional coordination polymer. The solvent water molecules are connected to the carboxylate groups by O—H⋯O hydrogen bonds. Additional weak C—H⋯O hydrogen bonds are observed in the crystal structure.

Related literature

For general background to metal organic frameworks, see: Li et al. (1999 , 2012 ); Cheng et al. (2010 ); Hong et al. (2009 ); Miller & Gatteschi (2011 ); Liu et al. (2010 ).

Experimental

Crystal data

[Co₂(C₁₈H₄O₁₀)(C₁₄H₁₄N₄)₂]·2H₂O
M_r = 1010.68
Triclinic, $[P \overline 1]$
a = 9.561 (4) Å
b = 10.594 (5) Å
c = 12.436 (5) Å
α = 107.095 (7)°
β = 102.454 (6)°
γ = 106.551 (6)°
V = 1090.7 (8) Å³
Z = 1
Mo Kα radiation
μ = 0.83 mm⁻¹
T = 296 K
0.43 × 0.36 × 0.28 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.717, T_max = 0.801
10020 measured reflections
3787 independent reflections
3411 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.091
S = 1.04
3787 reflections
315 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O6—H24⋯O4ⁱ	0.83 (5)	2.10 (5)	2.911 (4)	166 (5)
O6—H25⋯O2ⁱⁱ	0.99 (6)	1.92 (6)	2.883 (4)	164 (5)
C11—H11⋯O6ⁱⁱⁱ	0.93	2.37	3.192 (4)	148
C12—H12⋯O5ⁱⁱ	0.93	2.39	3.268 (4)	157
C13—H13A⋯O1ⁱⁱ	0.97	2.58	3.389 (4)	141
C13—H13B⋯O3^iv	0.97	2.54	3.278 (3)	133
C20—H20A⋯O2ⁱⁱ	0.97	2.58	3.301 (3)	131
C21—H21⋯O6^v	0.93	2.52	3.302 (4)	143
Symmetry codes: (i) x+1, y, z; (ii) -x+1, -y, -z; (iii) x-1, y, z; (iv) -x, -y, -z; (v) -x+2, -y, -z+1.

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681202716X/im2380sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681202716X/im2380Isup2.hkl

checkCIF report

Comment top

Porous solid materials, such as MOFs (metal-organic frameworks) have been widely studied for their potential applications in gas absorption, separation, catalysis and magnetic materials. explorations of advanced porous materials for these applications are an intense subject of scientific research. (Li et al., 1999; Li et al., 2012; Cheng et al., 2010; Hong et al., 2009; Miller et al., 2011; Liu et al., 2010.) Herein we report the crystal structure of the title compound.

The molecular structure of (I) is illustrated in Fig. 1., a summary of the observed hydrogen bonds and the corresponding angles are given in Table 1.

The center of the anthraquinone moiety is a crystallographic center of inversion. Each asymmetric unit therefore contains one cobalt atom and one o-bix ligand as well as one half AQTC^4- ligand and an additional solvent water molecule. Cobalt(II) ions are tetrahedrally surrounded by two O atoms from two AQTC^4- and two N atoms from two o-bix ligands forming a 2D-coordination polymer.

Related literature top

For general background to metal organic frameworks, see: Li et al. (1999, 2012); Cheng et al. (2010); Hong et al. (2009); Miller & Gatteschi (2011); Liu et al. (2010).

Experimental top

A mixture of H₄AQTC (0.025 mmol, 9.8 mg) and o-bix (0.025 mmol, 6.0 mg) were added to distilled water (4 ml) and ultra-sounded for 10 min. The pH value of the mixture was then adjusted to 8.0 with NaOH (0.5 mol.L^-1). Then CoCl₂ × 6 H₂O (0.05 mmol, 12 mg) was added. The reactants were placed in a Teflon-lined stainless steel vessel, heated for 3 days, and then cooled to ambient temperature over 12 h. Red block shaped crystals of (I) were obtained in 30% yield.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. State of an asymmetric unit of compound (I), showing the atom-numbering scheme and displacement ellipsoids at the 30% probability level(Symmetry code: #1 - x,-y,-z; #2 x,y - 1,z; #3 x,y + 1,z; #4 x + 1,y,z; #5 x - 1,y,z).
	Fig. 2. : A view of stacking structure of the title compound (H atom omited for clear except solvent water).

Poly[[bis{µ₂-1,2-bis[(1H-imidazol-1-yl)methyl]benzene}(µ₄- 9,10-dioxo-9,10-dihydroanthracene-1,4,5,8-tetracarboxylato)dicobalt(II)] monohydrate] top

Crystal data top

[Co₂(C₁₈H₄O₁₀)(C₁₄H₁₄N₄)₂]·H₂O	Z = 1
M_r = 1010.68	F(000) = 518
Triclinic, P1	D_x = 1.539 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.561 (4) Å	Cell parameters from 5133 reflections
b = 10.594 (5) Å	θ = 2.2–27.6°
c = 12.436 (5) Å	µ = 0.83 mm⁻¹
α = 107.095 (7)°	T = 296 K
β = 102.454 (6)°	Block, red
γ = 106.551 (6)°	0.43 × 0.36 × 0.28 mm
V = 1090.7 (8) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	3787 independent reflections
Radiation source: sealed tube	3411 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
phi and ω scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −11→11
T_min = 0.717, T_max = 0.801	k = −12→12
10020 measured reflections	l = −14→14

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.091	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0366P)² + 0.4627P] where P = (F_o² + 2F_c²)/3
3787 reflections	(Δ/σ)_max = 0.001
315 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

[Co₂(C₁₈H₄O₁₀)(C₁₄H₁₄N₄)₂]·H₂O	γ = 106.551 (6)°
M_r = 1010.68	V = 1090.7 (8) Å³
Triclinic, P1	Z = 1
a = 9.561 (4) Å	Mo Kα radiation
b = 10.594 (5) Å	µ = 0.83 mm⁻¹
c = 12.436 (5) Å	T = 296 K
α = 107.095 (7)°	0.43 × 0.36 × 0.28 mm
β = 102.454 (6)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3787 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	3411 reflections with I > 2σ(I)
T_min = 0.717, T_max = 0.801	R_int = 0.045
10020 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.091	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.39 e Å⁻³
3787 reflections	Δρ_min = −0.32 e Å⁻³
315 parameters

Special details top

Experimental. Anal. Calcd. for C₂₃H₁₈Co₁N₄O₆: C, 54.66; H, 3.59; N, 11.09%. Found: C, 54.34; H, 3.37; N, 10.86%. FT—IR data (KBr pellets, cm^-1): 3359(m), 3140(w), 3111(m), 15109(m), 1455(w), 1078(m), 754(m), 732(w), 685(m).

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.

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

	x	y	z	U_iso*/U_eq
C1	0.3229 (3)	0.2312 (2)	−0.08418 (19)	0.0307 (5)
C2	−0.1263 (3)	0.3036 (2)	0.1570 (2)	0.0329 (5)
C3	−0.0113 (3)	0.2767 (2)	0.09487 (18)	0.0301 (5)
C4	0.0924 (3)	0.3922 (2)	0.0854 (2)	0.0377 (5)
H4	0.0902	0.4823	0.1182	0.045*
C5	0.1986 (3)	0.3753 (2)	0.0281 (2)	0.0362 (5)
H5	0.2643	0.4533	0.0203	0.043*
C6	0.2080 (3)	0.2425 (2)	−0.01795 (18)	0.0286 (5)
C7	0.1067 (2)	0.1253 (2)	−0.00744 (17)	0.0258 (4)
C8	−0.0065 (2)	0.1415 (2)	0.04555 (17)	0.0262 (4)
C9	0.1271 (2)	−0.0137 (2)	−0.04162 (17)	0.0263 (4)
C10	0.3621 (3)	0.1884 (2)	0.23544 (18)	0.0307 (5)
H10	0.3323	0.2661	0.2552	0.037*
C11	0.2936 (3)	0.0631 (2)	0.24410 (18)	0.0295 (5)
H11	0.2085	0.0380	0.2692	0.035*
C12	0.4870 (3)	0.0555 (2)	0.17763 (18)	0.0302 (5)
H12	0.5576	0.0225	0.1495	0.036*
C13	0.3365 (3)	−0.1710 (2)	0.19313 (19)	0.0345 (5)
H13A	0.4237	−0.1977	0.1848	0.041*
H13B	0.2499	−0.2302	0.1207	0.041*
C14	0.2956 (3)	−0.1986 (2)	0.29720 (19)	0.0319 (5)
C15	0.1425 (3)	−0.2315 (3)	0.2937 (3)	0.0468 (6)
H15	0.0691	−0.2373	0.2279	0.056*
C16	0.0982 (4)	−0.2559 (3)	0.3875 (3)	0.0635 (9)
H16	−0.0041	−0.2765	0.3847	0.076*
C17	0.2054 (4)	−0.2496 (3)	0.4845 (3)	0.0601 (9)
H17	0.1758	−0.2662	0.5471	0.072*
C18	0.3566 (3)	−0.2188 (3)	0.4884 (2)	0.0442 (6)
H18	0.4283	−0.2161	0.5536	0.053*
C19	0.4047 (3)	−0.1913 (2)	0.39615 (19)	0.0305 (5)
C20	0.5728 (3)	−0.1577 (2)	0.4074 (2)	0.0344 (5)
H20A	0.5976	−0.1098	0.3545	0.041*
H20B	0.6361	−0.0934	0.4882	0.041*
C21	0.6999 (3)	−0.3245 (3)	0.4543 (2)	0.0467 (6)
H21	0.7494	−0.2738	0.5356	0.056*
C22	0.5629 (3)	0.6109 (2)	0.26958 (19)	0.0337 (5)
H22	0.5005	0.6117	0.2013	0.040*
C23	0.7029 (3)	0.5502 (3)	0.3882 (2)	0.0494 (7)
H23	0.7557	0.4994	0.4172	0.059*
Co1	0.58835 (3)	0.33412 (3)	0.13769 (2)	0.02845 (12)
N1	0.4836 (2)	0.18355 (19)	0.19274 (15)	0.0304 (4)
N2	0.3755 (2)	−0.02007 (18)	0.20818 (15)	0.0281 (4)
N3	0.6159 (2)	0.50944 (18)	0.27147 (16)	0.0315 (4)
N4	0.6099 (2)	−0.28740 (18)	0.37783 (15)	0.0299 (4)
O1	0.46596 (18)	0.30258 (17)	−0.02288 (13)	0.0351 (4)
O2	0.2749 (2)	0.16438 (19)	−0.19247 (14)	0.0458 (4)
O3	−0.22850 (19)	0.33483 (18)	0.09643 (15)	0.0395 (4)
O4	−0.1135 (2)	0.29987 (19)	0.25620 (15)	0.0463 (4)
O5	0.24715 (17)	−0.02029 (16)	−0.05752 (13)	0.0331 (4)
O6	0.9984 (3)	0.0915 (3)	0.3137 (2)	0.0614 (6)
H25	0.912 (6)	−0.001 (6)	0.285 (5)	0.15 (2)*
H24	0.982 (5)	0.161 (5)	0.304 (4)	0.108 (17)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0325 (14)	0.0336 (11)	0.0336 (11)	0.0138 (10)	0.0166 (10)	0.0177 (9)
C2	0.0306 (13)	0.0294 (10)	0.0355 (12)	0.0101 (10)	0.0150 (10)	0.0060 (9)
C3	0.0253 (12)	0.0362 (11)	0.0287 (10)	0.0134 (9)	0.0093 (9)	0.0100 (9)
C4	0.0377 (15)	0.0327 (11)	0.0452 (13)	0.0163 (10)	0.0185 (11)	0.0115 (10)
C5	0.0343 (14)	0.0347 (11)	0.0417 (12)	0.0115 (10)	0.0169 (11)	0.0156 (10)
C6	0.0246 (12)	0.0375 (11)	0.0260 (10)	0.0129 (9)	0.0095 (9)	0.0131 (9)
C7	0.0227 (12)	0.0346 (10)	0.0226 (9)	0.0123 (9)	0.0096 (8)	0.0109 (8)
C8	0.0236 (12)	0.0342 (11)	0.0235 (10)	0.0129 (9)	0.0097 (8)	0.0111 (8)
C9	0.0239 (12)	0.0368 (11)	0.0198 (9)	0.0123 (9)	0.0098 (8)	0.0099 (8)
C10	0.0369 (13)	0.0357 (11)	0.0288 (10)	0.0204 (10)	0.0158 (10)	0.0147 (9)
C11	0.0325 (13)	0.0379 (11)	0.0277 (10)	0.0183 (10)	0.0164 (9)	0.0157 (9)
C12	0.0330 (13)	0.0370 (11)	0.0299 (11)	0.0175 (10)	0.0166 (10)	0.0164 (9)
C13	0.0487 (15)	0.0312 (11)	0.0289 (11)	0.0174 (10)	0.0166 (10)	0.0135 (9)
C14	0.0412 (14)	0.0271 (10)	0.0342 (11)	0.0156 (10)	0.0180 (10)	0.0144 (9)
C15	0.0380 (16)	0.0479 (14)	0.0630 (16)	0.0172 (12)	0.0190 (13)	0.0297 (13)
C16	0.052 (2)	0.074 (2)	0.100 (2)	0.0316 (16)	0.0545 (19)	0.0523 (19)
C17	0.082 (2)	0.0705 (19)	0.0719 (19)	0.0419 (18)	0.0586 (19)	0.0506 (16)
C18	0.0666 (19)	0.0486 (14)	0.0380 (13)	0.0318 (13)	0.0300 (13)	0.0252 (11)
C19	0.0419 (14)	0.0270 (10)	0.0304 (11)	0.0170 (10)	0.0189 (10)	0.0125 (8)
C20	0.0415 (15)	0.0262 (10)	0.0347 (11)	0.0146 (10)	0.0132 (10)	0.0081 (9)
C21	0.0584 (18)	0.0495 (14)	0.0289 (12)	0.0294 (14)	0.0056 (11)	0.0077 (10)
C22	0.0423 (15)	0.0307 (11)	0.0283 (11)	0.0150 (10)	0.0114 (10)	0.0105 (9)
C23	0.0604 (19)	0.0484 (15)	0.0432 (14)	0.0346 (14)	0.0079 (13)	0.0150 (12)
Co1	0.0323 (2)	0.02908 (17)	0.03102 (17)	0.01470 (14)	0.01786 (14)	0.01245 (13)
N1	0.0347 (11)	0.0334 (9)	0.0308 (9)	0.0162 (8)	0.0165 (8)	0.0152 (8)
N2	0.0346 (11)	0.0326 (9)	0.0261 (8)	0.0169 (8)	0.0153 (8)	0.0150 (7)
N3	0.0356 (11)	0.0304 (9)	0.0335 (9)	0.0159 (8)	0.0167 (8)	0.0119 (8)
N4	0.0353 (11)	0.0284 (9)	0.0274 (9)	0.0147 (8)	0.0118 (8)	0.0088 (7)
O1	0.0277 (10)	0.0480 (9)	0.0394 (8)	0.0151 (8)	0.0176 (7)	0.0243 (7)
O2	0.0449 (11)	0.0543 (10)	0.0340 (9)	0.0097 (9)	0.0214 (8)	0.0136 (8)
O3	0.0338 (10)	0.0504 (10)	0.0462 (9)	0.0245 (8)	0.0216 (8)	0.0201 (8)
O4	0.0502 (12)	0.0581 (11)	0.0356 (9)	0.0248 (9)	0.0224 (8)	0.0143 (8)
O5	0.0267 (9)	0.0384 (8)	0.0385 (8)	0.0149 (7)	0.0185 (7)	0.0122 (7)
O6	0.0451 (14)	0.0713 (15)	0.0586 (13)	0.0237 (12)	0.0117 (10)	0.0142 (11)

Geometric parameters (Å, º) top

C1—O2	1.230 (3)	C14—C19	1.398 (3)
C1—O1	1.283 (3)	C15—C16	1.392 (4)
C1—C6	1.519 (3)	C15—H15	0.9300
C2—O4	1.226 (3)	C16—C17	1.374 (5)
C2—O3	1.283 (3)	C16—H16	0.9300
C2—C3	1.517 (3)	C17—C18	1.374 (4)
C3—C4	1.392 (3)	C17—H17	0.9300
C3—C8	1.401 (3)	C18—C19	1.400 (3)
C4—C5	1.382 (3)	C18—H18	0.9300
C4—H4	0.9300	C19—C20	1.509 (3)
C5—C6	1.391 (3)	C20—N4	1.478 (3)
C5—H5	0.9300	C20—H20A	0.9700
C6—C7	1.401 (3)	C20—H20B	0.9700
C7—C8	1.408 (3)	C21—C23ⁱⁱ	1.352 (3)
C7—C9	1.489 (3)	C21—N4	1.364 (3)
C8—C9ⁱ	1.488 (3)	C21—H21	0.9300
C9—O5	1.223 (3)	C22—N3	1.316 (3)
C9—C8ⁱ	1.488 (3)	C22—N4ⁱⁱⁱ	1.336 (3)
C10—C11	1.349 (3)	C22—H22	0.9300
C10—N1	1.384 (3)	C23—C21ⁱⁱⁱ	1.352 (3)
C10—H10	0.9300	C23—N3	1.376 (3)
C11—N2	1.380 (3)	C23—H23	0.9300
C11—H11	0.9300	Co1—O3^iv	1.9267 (17)
C12—N1	1.325 (3)	Co1—O1	1.9610 (17)
C12—N2	1.337 (3)	Co1—N3	2.0008 (18)
C12—H12	0.9300	Co1—N1	2.0110 (18)
C13—N2	1.479 (3)	N4—C22ⁱⁱ	1.336 (3)
C13—C14	1.513 (3)	O3—Co1^v	1.9267 (17)
C13—H13A	0.9700	O6—H25	0.99 (6)
C13—H13B	0.9700	O6—H24	0.83 (5)
C14—C15	1.392 (4)

O2—C1—O1	124.1 (2)	C17—C16—C15	120.1 (3)
O2—C1—C6	119.3 (2)	C17—C16—H16	119.9
O1—C1—C6	116.41 (18)	C15—C16—H16	119.9
O4—C2—O3	126.4 (2)	C16—C17—C18	119.7 (2)
O4—C2—C3	121.2 (2)	C16—C17—H17	120.2
O3—C2—C3	112.36 (19)	C18—C17—H17	120.2
C4—C3—C8	118.88 (19)	C17—C18—C19	121.3 (3)
C4—C3—C2	118.03 (19)	C17—C18—H18	119.3
C8—C3—C2	123.08 (19)	C19—C18—H18	119.3
C5—C4—C3	121.2 (2)	C14—C19—C18	119.0 (2)
C5—C4—H4	119.4	C14—C19—C20	122.88 (19)
C3—C4—H4	119.4	C18—C19—C20	118.1 (2)
C4—C5—C6	120.5 (2)	N4—C20—C19	111.96 (18)
C4—C5—H5	119.8	N4—C20—H20A	109.2
C6—C5—H5	119.8	C19—C20—H20A	109.2
C5—C6—C7	119.27 (19)	N4—C20—H20B	109.2
C5—C6—C1	117.40 (19)	C19—C20—H20B	109.2
C7—C6—C1	123.23 (19)	H20A—C20—H20B	107.9
C6—C7—C8	120.01 (19)	C23ⁱⁱ—C21—N4	106.3 (2)
C6—C7—C9	120.37 (18)	C23ⁱⁱ—C21—H21	126.9
C8—C7—C9	119.38 (18)	N4—C21—H21	126.9
C3—C8—C7	119.98 (19)	N3—C22—N4ⁱⁱⁱ	111.6 (2)
C3—C8—C9ⁱ	120.16 (18)	N3—C22—H22	124.2
C7—C8—C9ⁱ	119.73 (18)	N4ⁱⁱⁱ—C22—H22	124.2
O5—C9—C8ⁱ	120.24 (19)	C21ⁱⁱⁱ—C23—N3	109.5 (2)
O5—C9—C7	120.15 (19)	C21ⁱⁱⁱ—C23—H23	125.2
C8ⁱ—C9—C7	119.39 (18)	N3—C23—H23	125.2
C11—C10—N1	109.68 (19)	O3^iv—Co1—O1	94.24 (7)
C11—C10—H10	125.2	O3^iv—Co1—N3	115.00 (8)
N1—C10—H10	125.2	O1—Co1—N3	117.63 (8)
C10—C11—N2	105.96 (19)	O3^iv—Co1—N1	119.89 (8)
C10—C11—H11	127.0	O1—Co1—N1	111.05 (7)
N2—C11—H11	127.0	N3—Co1—N1	100.17 (8)
N1—C12—N2	111.04 (19)	C12—N1—C10	105.58 (17)
N1—C12—H12	124.5	C12—N1—Co1	131.62 (14)
N2—C12—H12	124.5	C10—N1—Co1	121.56 (14)
N2—C13—C14	112.12 (16)	C12—N2—C11	107.74 (18)
N2—C13—H13A	109.2	C12—N2—C13	125.85 (18)
C14—C13—H13A	109.2	C11—N2—C13	126.09 (18)
N2—C13—H13B	109.2	C22—N3—C23	105.27 (18)
C14—C13—H13B	109.2	C22—N3—Co1	129.70 (16)
H13A—C13—H13B	107.9	C23—N3—Co1	125.00 (16)
C15—C14—C19	119.1 (2)	C22ⁱⁱ—N4—C21	107.31 (18)
C15—C14—C13	118.1 (2)	C22ⁱⁱ—N4—C20	125.81 (19)
C19—C14—C13	122.8 (2)	C21—N4—C20	126.87 (18)
C14—C15—C16	120.7 (3)	C1—O1—Co1	132.29 (13)
C14—C15—H15	119.6	C2—O3—Co1^v	120.57 (14)
C16—C15—H15	119.6	H25—O6—H24	120 (4)

O4—C2—C3—C4	−107.8 (3)	C17—C18—C19—C14	−1.4 (4)
O3—C2—C3—C4	69.5 (3)	C17—C18—C19—C20	179.8 (2)
O4—C2—C3—C8	73.1 (3)	C14—C19—C20—N4	−100.3 (2)
O3—C2—C3—C8	−109.6 (2)	C18—C19—C20—N4	78.5 (2)
C8—C3—C4—C5	0.3 (4)	N2—C12—N1—C10	0.0 (2)
C2—C3—C4—C5	−178.9 (2)	N2—C12—N1—Co1	−167.10 (15)
C3—C4—C5—C6	−2.3 (4)	C11—C10—N1—C12	−0.7 (2)
C4—C5—C6—C7	1.1 (3)	C11—C10—N1—Co1	168.03 (15)
C4—C5—C6—C1	177.5 (2)	O3^iv—Co1—N1—C12	−21.8 (2)
O2—C1—C6—C5	−110.7 (2)	O1—Co1—N1—C12	86.4 (2)
O1—C1—C6—C5	64.2 (3)	N3—Co1—N1—C12	−148.5 (2)
O2—C1—C6—C7	65.6 (3)	O3^iv—Co1—N1—C10	172.85 (15)
O1—C1—C6—C7	−119.5 (2)	O1—Co1—N1—C10	−78.94 (17)
C5—C6—C7—C8	2.2 (3)	N3—Co1—N1—C10	46.09 (18)
C1—C6—C7—C8	−174.02 (19)	N1—C12—N2—C11	0.7 (2)
C5—C6—C7—C9	−172.1 (2)	N1—C12—N2—C13	174.39 (19)
C1—C6—C7—C9	11.7 (3)	C10—C11—N2—C12	−1.0 (2)
C4—C3—C8—C7	3.0 (3)	C10—C11—N2—C13	−174.75 (19)
C2—C3—C8—C7	−177.9 (2)	C14—C13—N2—C12	141.3 (2)
C4—C3—C8—C9ⁱ	−172.8 (2)	C14—C13—N2—C11	−46.2 (3)
C2—C3—C8—C9ⁱ	6.2 (3)	N4ⁱⁱⁱ—C22—N3—C23	−0.5 (3)
C6—C7—C8—C3	−4.3 (3)	N4ⁱⁱⁱ—C22—N3—Co1	−178.48 (14)
C9—C7—C8—C3	170.09 (19)	C21ⁱⁱⁱ—C23—N3—C22	0.2 (3)
C6—C7—C8—C9ⁱ	171.61 (19)	C21ⁱⁱⁱ—C23—N3—Co1	178.31 (18)
C9—C7—C8—C9ⁱ	−14.0 (3)	O3^iv—Co1—N3—C22	109.9 (2)
C6—C7—C9—O5	13.8 (3)	O1—Co1—N3—C22	0.3 (2)
C8—C7—C9—O5	−160.54 (19)	N1—Co1—N3—C22	−120.1 (2)
C6—C7—C9—C8ⁱ	−171.68 (18)	O3^iv—Co1—N3—C23	−67.7 (2)
C8—C7—C9—C8ⁱ	14.0 (3)	O1—Co1—N3—C23	−177.34 (19)
N1—C10—C11—N2	1.1 (2)	N1—Co1—N3—C23	62.3 (2)
N2—C13—C14—C15	88.0 (3)	C23ⁱⁱ—C21—N4—C22ⁱⁱ	−0.4 (3)
N2—C13—C14—C19	−91.5 (3)	C23ⁱⁱ—C21—N4—C20	−179.3 (2)
C19—C14—C15—C16	0.5 (4)	C19—C20—N4—C22ⁱⁱ	69.5 (3)
C13—C14—C15—C16	−179.1 (2)	C19—C20—N4—C21	−111.9 (3)
C14—C15—C16—C17	−0.9 (4)	O2—C1—O1—Co1	−143.51 (19)
C15—C16—C17—C18	0.2 (5)	C6—C1—O1—Co1	41.9 (3)
C16—C17—C18—C19	1.0 (4)	O3^iv—Co1—O1—C1	144.39 (19)
C15—C14—C19—C18	0.6 (3)	N3—Co1—O1—C1	−94.5 (2)
C13—C14—C19—C18	−179.8 (2)	N1—Co1—O1—C1	20.1 (2)
C15—C14—C19—C20	179.4 (2)	O4—C2—O3—Co1^v	−16.1 (3)
C13—C14—C19—C20	−1.1 (3)	C3—C2—O3—Co1^v	166.74 (14)

Symmetry codes: (i) −x, −y, −z; (ii) x, y−1, z; (iii) x, y+1, z; (iv) x+1, y, z; (v) x−1, y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O6—H24···O4^iv	0.83 (5)	2.10 (5)	2.911 (4)	166 (5)
O6—H25···O2^vi	0.99 (6)	1.92 (6)	2.883 (4)	164 (5)
C11—H11···O6^v	0.93	2.37	3.192 (4)	148
C12—H12···O5^vi	0.93	2.39	3.268 (4)	157
C13—H13A···O1^vi	0.97	2.58	3.389 (4)	141
C13—H13B···O3ⁱ	0.97	2.54	3.278 (3)	133
C20—H20A···O2^vi	0.97	2.58	3.301 (3)	131
C21—H21···O6^vii	0.93	2.52	3.302 (4)	143

Symmetry codes: (i) −x, −y, −z; (iv) x+1, y, z; (v) x−1, y, z; (vi) −x+1, −y, −z; (vii) −x+2, −y, −z+1.

Experimental details

Crystal data
Chemical formula	[Co₂(C₁₈H₄O₁₀)(C₁₄H₁₄N₄)₂]·H₂O
M_r	1010.68
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	9.561 (4), 10.594 (5), 12.436 (5)
α, β, γ (°)	107.095 (7), 102.454 (6), 106.551 (6)
V (Å³)	1090.7 (8)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.83
Crystal size (mm)	0.43 × 0.36 × 0.28

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.717, 0.801
No. of measured, independent and observed [I > 2σ(I)] reflections	10020, 3787, 3411
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.091, 1.04
No. of reflections	3787
No. of parameters	315
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.32

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O6—H24···O4ⁱ	0.83 (5)	2.10 (5)	2.911 (4)	166 (5)
O6—H25···O2ⁱⁱ	0.99 (6)	1.92 (6)	2.883 (4)	164 (5)
C11—H11···O6ⁱⁱⁱ	0.9300	2.3700	3.192 (4)	148.00
C12—H12···O5ⁱⁱ	0.9300	2.3900	3.268 (4)	157.00
C13—H13A···O1ⁱⁱ	0.9700	2.5800	3.389 (4)	141.00
C13—H13B···O3^iv	0.9700	2.5400	3.278 (3)	133.00
C20—H20A···O2ⁱⁱ	0.9700	2.5800	3.301 (3)	131.00
C21—H21···O6^v	0.9300	2.5200	3.302 (4)	143.00

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

Acknowledgements

The authors thank the Center of Test and Analysis, Nanjing University, for the support.

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