Bis(μ-3,5-dinitro-2-oxidobenzoato)-κ3O1,O2:O1;κ3O1:O1,O2-bis[aqua­(2-phenyl-1,3,7,8-tetra­azacyclo­penta­[l]phenanthrene-κ2N7,N8)cobalt(II)]

Wang, X.-C.; Chen, J.; Wang, C.-J.; Li, C.-X.

doi:10.1107/S1600536810017629

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Pages m751-m752

doi:10.1107/S1600536810017629

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Bis(μ-3,5-dinitro-2-oxidobenzoato)-κ³O¹,O²:O¹;κ³O¹:O¹,O²-bis[aqua(2-phenyl-1,3,7,8-tetraazacyclopenta[l]phenanthrene-κ²N⁷,N⁸)cobalt(II)]

Xiang-Cheng Wang,^a Jing Chen,^a Chun-Jie Wang ^a and Chun-Xiang Li ^a ^*

^aSchool of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, People's Republic of China
^*Correspondence e-mail: yys@ujs.edu.cn

(Received 27 April 2010; accepted 13 May 2010; online 5 June 2010)

In the title compound, [Co₂(C₇H₂N₂O₇)₂(C₁₉H₁₂N₄)₂(H₂O)₂], the Co^II atom is six-coordinated by two N atoms from a 2-phenyl-1H-1,3,7,8,-tetraazacyclopenta[l]phenanthrene (L) ligand, three O atoms from two 3,5-dinitro-2-oxidobenzoate (3,5-dinitrosalicylate or DNSA) ligands and one O atom from a water molecule in a distorted octahedral geometry. The Co^II atoms are bridged by two carboxylate O atoms from two DNSA ligands, forming a centrosymmetric dinuclear structure. Neighbouring dinuclear units interact with each other through two types of π–π interactions between the L ligands [shortest centroid–centroid distance = 3.646 (3) Å] and between the L and DNSA ligands [shortest atom-to-centroid distance = 3.794 (3) Å]. N—H⋯O, O—H⋯N and O—H⋯O hydrogen bonds are observed, which lead to a three-dimensional structure.

Related literature

For general background to metal–organic coordination polymers, see: Che et al. (2008 ). For a related structure, see: Liu et al. (2009 ). For the ligand synthesis, see: Steck & Day (1943 ).

Experimental

Crystal data

[Co₂(C₇H₂N₂O₇)₂(C₁₉H₁₂N₄)₂(H₂O)₂]
M_r = 1198.76
Triclinic, $[P \overline 1]$
a = 8.2943 (4) Å
b = 11.0232 (5) Å
c = 13.6139 (7) Å
α = 102.690 (4)°
β = 107.282 (4)°
γ = 90.459 (4)°
V = 1155.9 (1) Å³
Z = 1
Mo Kα radiation
μ = 0.81 mm⁻¹
T = 292 K
0.32 × 0.27 × 0.23 mm

Data collection

Oxford Diffraction Gemini R Ultra CCD diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ) T_min = 0.771, T_max = 0.829
7153 measured reflections
4041 independent reflections
2933 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.111
S = 1.00
4041 reflections
378 parameters
168 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.97 e Å⁻³
Δρ_min = −1.00 e Å⁻³

Table 1
Selected bond lengths (Å)

Co—N1	2.102 (3)
Co—N2	2.095 (3)
Co—O1	2.050 (2)
Co—O1ⁱ	2.216 (3)
Co—O3	1.991 (3)
Co—OW1	2.139 (3)
Symmetry code: (i) -x, -y, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4⋯O6ⁱⁱ	0.86	2.17	2.948 (5)	150
OW1—H1WA⋯N3ⁱⁱⁱ	0.81 (6)	2.03 (6)	2.831 (5)	172 (5)
OW1—H1WB⋯O2^iv	0.80 (5)	1.88 (5)	2.662 (4)	165 (5)
Symmetry codes: (ii) x-1, y, z-1; (iii) -x, -y+1, -z+1; (iv) -x+1, -y, -z+1.

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810017629/hy2303sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810017629/hy2303Isup2.hkl

checkCIF report

Comment top

Metal-organic coordination polymers have attracted increasing interest over the past decade because of their intriguing structures and tremendous potential applications in catalysis, molecular adsorption, nonlinear optics, magnetism, and so on (Che et al., 2008). 1,10-Phenanthroline (phen) has been widely used to build supramolecular architectures owing to its excellent coordinating ability and large conjugated system. However, building blocks derived from the appropriate modification of phen, such as 2-phenyl-1H-1,3,7,8-tetra-azacyclopenta[l]phenanthrene (L) have received considerably less attention (Liu et al., 2009). Hereby, we have prepared the title compound based on L and 3,5-dinitrosalicylic acid (H₂DNSA) ligands.

In the title compound, the Co^II atom is six-coordinated by two N atoms from one L ligand, four O atoms from two DNSA ligands and one water molecule (Fig. 1). The Co—O distances range from 1.991 (3) to 2.216 (3) Å and the Co—N lengths are 2.095 (3) and 2.102 (3) Å (Table 1). The N1, N2, O1, O3 atoms comprise the equatorial plane, while the O1ⁱ and OW1 atoms occupy the axial position [symmetry code: (i) -x, -y, 1-z]. A carboxylate O atom and the hydroxy O atom of the DNSA ligand coordinate to one Co atom, and this carboxylate O atom bridges the other Co atom, forming a dinuclear structure. The two nitro groups are uncoordinated.

It is noteworthy that various hydrogen bonds interactions are observed in the title compound. (a) An N—H···O hydrogen bond between the imidazole ring donor and the nitro group of the DNSA ligand (Table 2). (b) O—H···N or O—H···O hydrogen bonds involving the coordinated water molecule OW1 and the imidazole N3 and carboxylate O2 atoms (Table 2). In addition, two types of π–π stacking interactions further intensify the architectures. One is the offset face-to-face π–π interactions between the L ligands with the shortest centroid–centroid distance of 3.646 (3) Å, while the other exists between the L and DNSA ligands [shortest atom-to-centroid distance = 3.794 (3) Å] (Fig. 2), which lead to a three-dimensional supramolecular structure (Fig. 3).

Related literature top

For general background to metal–organic coordination polymers, see: Che et al. (2008). For a related structure, see: Liu et al. (2009). For the ligand synthesis, see: Steck & Day (1943).

Experimental top

The L ligand was synthesized according to the literature method (Steck & Day, 1943). The title compound was synthesized under hydrothermal conditions. A mixture of L (0.06 g, 0.2 mmol), H₂DNSA (0.048 g, 0.2 mmol), Co(NO₃)₂ (0.036 g, 0.2 mmol) and water (10 ml) in a mole ratio 1:1:1:5000 was placed in a 25 ml Teflon-lined autoclave and heated for 3 d at 433 K under autogenous pressure. Upon cooling and opening the bomb, yellow block-shaped crystals were obtained, washed with H₂O and dried in air (yield 45% based on Co).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. [Symmetry code: (A) -x, -y, -z+1.]
	Fig. 2. View of the one-dimensional supramolecular chain generated by π–π interactions (dashed lines). H atoms except those of water molecules have been omitted for clarity.
	Fig. 3. View of a three-dimensional supramolecular structure with hydrogen bonds indicated by dotted lines. Most H atoms have been omitted.

Bis(µ-3,5-dinitro-2-oxidobenzoato)-κ³O¹,O²:O¹;κ³O¹:O¹,O²- bis[aqua(2-phenyl-1,3,7,8-tetraazacyclopenta[l]phenanthrene- κ²N⁷,N⁸)cobalt(II)] top

Crystal data top

[Co₂(C₇H₂N₂O₇)₂(C₁₉H₁₂N₄)₂(H₂O)₂]	Z = 1
M_r = 1198.76	F(000) = 610
Triclinic, P1	D_x = 1.722 Mg m⁻³ D_m = 1.722 Mg m⁻³ D_m measured by not measured
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.2943 (4) Å	Cell parameters from 3653 reflections
b = 11.0232 (5) Å	θ = 4.4–25°
c = 13.6139 (7) Å	µ = 0.81 mm⁻¹
α = 102.690 (4)°	T = 292 K
β = 107.282 (4)°	Block, yellow
γ = 90.459 (4)°	0.32 × 0.27 × 0.23 mm
V = 1155.9 (1) Å³

Data collection top

Oxford Diffraction Gemini R Ultra CCD diffractometer	4041 independent reflections
Radiation source: fine-focus sealed tube	2933 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ω scans	θ_max = 25.0°, θ_min = 4.4°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	h = −9→9
T_min = 0.771, T_max = 0.829	k = −13→11
7153 measured reflections	l = −14→16

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0638P)²] where P = (F_o² + 2F_c²)/3
4041 reflections	(Δ/σ)_max = 0.002
378 parameters	Δρ_max = 0.97 e Å⁻³
168 restraints	Δρ_min = −1.00 e Å⁻³

Crystal data top

[Co₂(C₇H₂N₂O₇)₂(C₁₉H₁₂N₄)₂(H₂O)₂]	γ = 90.459 (4)°
M_r = 1198.76	V = 1155.9 (1) Å³
Triclinic, P1	Z = 1
a = 8.2943 (4) Å	Mo Kα radiation
b = 11.0232 (5) Å	µ = 0.81 mm⁻¹
c = 13.6139 (7) Å	T = 292 K
α = 102.690 (4)°	0.32 × 0.27 × 0.23 mm
β = 107.282 (4)°

Data collection top

Oxford Diffraction Gemini R Ultra CCD diffractometer	4041 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	2933 reflections with I > 2σ(I)
T_min = 0.771, T_max = 0.829	R_int = 0.028
7153 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	168 restraints
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.97 e Å⁻³
4041 reflections	Δρ_min = −1.00 e Å⁻³
378 parameters

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

	x	y	z	U_iso*/U_eq
C1	−0.0231 (5)	0.3815 (4)	0.6428 (3)	0.0304 (9)
H1	0.0452	0.3635	0.7049	0.037*
C2	−0.1233 (6)	0.4828 (4)	0.6499 (3)	0.0346 (10)
H2	−0.1214	0.5307	0.7157	0.041*
C3	−0.2237 (5)	0.5105 (4)	0.5595 (3)	0.0336 (9)
H3	−0.2911	0.5774	0.5631	0.040*
C4	−0.2245 (5)	0.4375 (4)	0.4614 (3)	0.0286 (8)
C5	−0.3250 (5)	0.4543 (4)	0.3592 (3)	0.0299 (8)
C6	−0.3182 (5)	0.3757 (4)	0.2679 (3)	0.0311 (9)
C7	−0.2138 (5)	0.2745 (4)	0.2631 (3)	0.0277 (8)
C8	−0.1991 (5)	0.1923 (4)	0.1726 (3)	0.0344 (9)
H8	−0.2600	0.2020	0.1058	0.041*
C9	−0.0946 (6)	0.0974 (4)	0.1829 (3)	0.0369 (10)
H9	−0.0838	0.0422	0.1233	0.044*
C10	−0.0049 (5)	0.0841 (4)	0.2834 (3)	0.0325 (9)
H10	0.0650	0.0189	0.2895	0.039*
C11	−0.1165 (5)	0.2559 (4)	0.3627 (3)	0.0247 (8)
C12	−0.1215 (5)	0.3373 (3)	0.4607 (3)	0.0249 (8)
C13	−0.4998 (5)	0.5157 (4)	0.2329 (3)	0.0322 (9)
C14	−0.6334 (5)	0.5801 (4)	0.1703 (3)	0.0356 (9)
C15	−0.6963 (6)	0.6831 (4)	0.2208 (4)	0.0438 (11)
H15	−0.6518	0.7137	0.2935	0.053*
C16	−0.8264 (7)	0.7403 (5)	0.1618 (4)	0.0546 (13)
H16	−0.8696	0.8091	0.1957	0.066*
C17	−0.8916 (7)	0.6973 (5)	0.0553 (4)	0.0606 (14)
H17	−0.9787	0.7365	0.0167	0.073*
C18	−0.8286 (7)	0.5960 (6)	0.0052 (4)	0.0619 (15)
H18	−0.8723	0.5671	−0.0677	0.074*
C19	−0.7008 (7)	0.5364 (5)	0.0621 (4)	0.0511 (13)
H19	−0.6599	0.4668	0.0276	0.061*
C20	0.3815 (5)	−0.0284 (4)	0.6442 (3)	0.0269 (8)
C21	0.5087 (5)	−0.0973 (4)	0.6896 (3)	0.0328 (9)
H21	0.5419	−0.1637	0.6466	0.039*
C22	0.5884 (5)	−0.0697 (4)	0.7980 (3)	0.0368 (9)
C23	0.5475 (5)	0.0299 (4)	0.8637 (3)	0.0360 (9)
H23	0.6050	0.0499	0.9358	0.043*
C24	0.4202 (5)	0.0997 (4)	0.8213 (3)	0.0323 (9)
C25	0.3257 (5)	0.0739 (4)	0.7106 (3)	0.0265 (8)
C26	0.2996 (5)	−0.0712 (4)	0.5268 (3)	0.0271 (8)
N1	−0.0218 (4)	0.3109 (3)	0.5517 (2)	0.0254 (7)
N2	−0.0149 (4)	0.1606 (3)	0.3706 (2)	0.0250 (6)
N3	−0.4378 (4)	0.5429 (3)	0.3369 (3)	0.0324 (8)
N4	−0.4312 (4)	0.4167 (3)	0.1875 (3)	0.0321 (8)
H4	−0.4538	0.3850	0.1209	0.039*
N5	0.7161 (5)	−0.1487 (4)	0.8424 (3)	0.0484 (9)
N6	0.3854 (5)	0.2056 (4)	0.8942 (3)	0.0446 (9)
O1	0.1485 (3)	−0.0397 (2)	0.4865 (2)	0.0305 (5)
O2	0.3743 (4)	−0.1379 (3)	0.4735 (2)	0.0459 (8)
O3	0.2036 (4)	0.1369 (3)	0.6762 (2)	0.0339 (5)
O4	0.7338 (5)	−0.2469 (4)	0.7867 (3)	0.0650 (9)
O5	0.8033 (5)	−0.1117 (4)	0.9352 (3)	0.0691 (10)
O6	0.4661 (6)	0.2254 (4)	0.9869 (3)	0.0813 (11)
O7	0.2851 (6)	0.2779 (4)	0.8644 (3)	0.0857 (10)
OW1	0.3241 (4)	0.2215 (3)	0.5222 (3)	0.0345 (5)
Co	0.09090 (7)	0.14151 (5)	0.52610 (4)	0.0264 (2)
H1WA	0.362 (7)	0.285 (6)	0.566 (5)	0.064 (18)*
H1WB	0.407 (7)	0.184 (5)	0.523 (4)	0.058 (16)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.034 (2)	0.031 (2)	0.0251 (15)	0.0072 (17)	0.0071 (17)	0.0072 (14)
C2	0.041 (3)	0.031 (2)	0.0312 (16)	0.0091 (18)	0.0129 (18)	0.0042 (17)
C3	0.032 (2)	0.031 (2)	0.0381 (15)	0.0114 (19)	0.0118 (18)	0.0079 (15)
C4	0.027 (2)	0.0249 (19)	0.0326 (12)	0.0062 (16)	0.0055 (16)	0.0089 (14)
C5	0.026 (2)	0.027 (2)	0.0351 (13)	0.0054 (16)	0.0042 (16)	0.0115 (14)
C6	0.027 (2)	0.035 (2)	0.0308 (14)	0.0071 (17)	0.0025 (16)	0.0133 (14)
C7	0.024 (2)	0.0286 (19)	0.0279 (13)	0.0026 (15)	0.0021 (15)	0.0094 (14)
C8	0.036 (3)	0.040 (2)	0.0254 (16)	0.0039 (18)	0.0045 (18)	0.0088 (15)
C9	0.040 (3)	0.041 (2)	0.0267 (14)	0.0078 (19)	0.0101 (18)	0.0022 (17)
C10	0.029 (2)	0.037 (2)	0.0295 (13)	0.0080 (19)	0.0082 (17)	0.0038 (15)
C11	0.020 (2)	0.0269 (19)	0.0264 (12)	0.0036 (15)	0.0042 (15)	0.0091 (13)
C12	0.021 (2)	0.0230 (18)	0.0279 (12)	0.0032 (15)	0.0026 (15)	0.0069 (13)
C13	0.031 (2)	0.030 (2)	0.0349 (14)	0.0058 (16)	0.0057 (16)	0.0121 (16)
C14	0.030 (2)	0.036 (2)	0.0398 (16)	0.0072 (17)	0.0048 (16)	0.0158 (16)
C15	0.044 (3)	0.036 (2)	0.049 (2)	0.011 (2)	0.008 (2)	0.0137 (18)
C16	0.048 (3)	0.047 (3)	0.072 (2)	0.021 (2)	0.014 (2)	0.025 (2)
C17	0.046 (3)	0.070 (3)	0.069 (2)	0.023 (3)	0.005 (2)	0.041 (2)
C18	0.058 (4)	0.074 (4)	0.045 (2)	0.015 (3)	−0.005 (2)	0.024 (2)
C19	0.050 (3)	0.059 (3)	0.0401 (16)	0.018 (2)	0.005 (2)	0.0139 (19)
C20	0.019 (2)	0.029 (2)	0.0318 (13)	0.0034 (15)	0.0040 (13)	0.0095 (14)
C21	0.025 (2)	0.035 (2)	0.0384 (15)	0.0094 (17)	0.0063 (16)	0.0134 (16)
C22	0.024 (2)	0.047 (2)	0.0400 (16)	0.0079 (18)	0.0040 (16)	0.0203 (16)
C23	0.027 (2)	0.051 (2)	0.0278 (19)	0.0026 (18)	−0.0005 (17)	0.0160 (16)
C24	0.025 (2)	0.042 (2)	0.0263 (13)	0.0014 (17)	0.0010 (14)	0.0089 (14)
C25	0.022 (2)	0.031 (2)	0.0252 (13)	0.0047 (15)	0.0029 (14)	0.0104 (13)
C26	0.0219 (17)	0.0223 (19)	0.0328 (14)	0.0051 (15)	0.0040 (12)	0.0035 (14)
N1	0.0257 (17)	0.0237 (14)	0.0258 (11)	0.0052 (13)	0.0052 (13)	0.0070 (11)
N2	0.0223 (16)	0.0260 (15)	0.0258 (10)	0.0044 (12)	0.0052 (12)	0.0071 (11)
N3	0.032 (2)	0.0288 (17)	0.0350 (13)	0.0090 (15)	0.0051 (15)	0.0109 (13)
N4	0.033 (2)	0.0336 (18)	0.0272 (14)	0.0092 (15)	0.0014 (14)	0.0112 (13)
N5	0.034 (2)	0.062 (2)	0.0523 (18)	0.0166 (19)	0.0058 (15)	0.0300 (15)
N6	0.041 (2)	0.057 (2)	0.0267 (13)	0.0099 (17)	0.0015 (15)	0.0037 (14)
O1	0.0280 (10)	0.0323 (9)	0.0278 (9)	0.0142 (9)	0.0037 (8)	0.0059 (8)
O2	0.0315 (15)	0.0534 (16)	0.0404 (14)	0.0173 (13)	0.0048 (12)	−0.0062 (12)
O3	0.0321 (11)	0.0361 (11)	0.0274 (8)	0.0156 (9)	0.0014 (8)	0.0050 (8)
O4	0.055 (2)	0.0667 (19)	0.0686 (19)	0.0307 (17)	0.0039 (16)	0.0270 (15)
O5	0.059 (2)	0.084 (2)	0.0569 (17)	0.0309 (18)	−0.0046 (14)	0.0289 (16)
O6	0.092 (2)	0.092 (2)	0.0308 (12)	0.0423 (19)	−0.0108 (15)	−0.0076 (15)
O7	0.0906 (19)	0.0901 (18)	0.0420 (14)	0.0503 (15)	−0.0127 (14)	−0.0113 (14)
OW1	0.0268 (11)	0.0354 (13)	0.0367 (13)	0.0091 (10)	0.0058 (10)	0.0039 (11)
Co	0.0251 (3)	0.0267 (3)	0.0236 (3)	0.0104 (2)	0.0015 (2)	0.0059 (2)

Geometric parameters (Å, º) top

C1—N1	1.314 (5)	C17—C18	1.369 (8)
C1—C2	1.401 (5)	C17—H17	0.9300
C1—H1	0.9300	C18—C19	1.379 (6)
C2—C3	1.365 (6)	C18—H18	0.9300
C2—H2	0.9300	C19—H19	0.9300
C3—C4	1.398 (6)	C20—C21	1.379 (5)
C3—H3	0.9300	C20—C25	1.453 (5)
C4—C12	1.402 (5)	C20—C26	1.503 (6)
C4—C5	1.446 (5)	C21—C22	1.389 (6)
C5—C6	1.366 (6)	C21—H21	0.9300
C5—N3	1.377 (5)	C22—C23	1.368 (6)
C6—N4	1.376 (5)	C22—N5	1.454 (5)
C6—C7	1.420 (5)	C23—C24	1.373 (5)
C7—C8	1.398 (6)	C23—H23	0.9300
C7—C11	1.416 (5)	C24—C25	1.440 (5)
C8—C9	1.368 (6)	C24—N6	1.448 (5)
C8—H8	0.9300	C25—O3	1.265 (4)
C9—C10	1.389 (6)	C26—O2	1.220 (5)
C9—H9	0.9300	C26—O1	1.294 (4)
C10—N2	1.322 (5)	N4—H4	0.8600
C10—H10	0.9300	N5—O4	1.215 (5)
C11—N2	1.356 (5)	N5—O5	1.229 (5)
C11—C12	1.447 (5)	N6—O7	1.202 (5)
C12—N1	1.363 (5)	N6—O6	1.209 (5)
C13—N3	1.319 (5)	OW1—H1WA	0.81 (6)
C13—N4	1.349 (5)	OW1—H1WB	0.80 (5)
C13—C14	1.475 (5)	Co—N1	2.102 (3)
C14—C19	1.383 (6)	Co—N2	2.095 (3)
C14—C15	1.383 (6)	Co—O1	2.050 (2)
C15—C16	1.388 (6)	Co—O1ⁱ	2.216 (3)
C15—H15	0.9300	Co—O3	1.991 (3)
C16—C17	1.359 (8)	Co—OW1	2.139 (3)
C16—H16	0.9300

N1—C1—C2	122.5 (4)	C21—C20—C26	116.4 (3)
N1—C1—H1	118.8	C25—C20—C26	123.5 (3)
C2—C1—H1	118.8	C20—C21—C22	121.5 (4)
C3—C2—C1	119.4 (4)	C20—C21—H21	119.3
C3—C2—H2	120.3	C22—C21—H21	119.3
C1—C2—H2	120.3	C23—C22—C21	121.1 (4)
C2—C3—C4	119.4 (4)	C23—C22—N5	119.6 (4)
C2—C3—H3	120.3	C21—C22—N5	119.3 (4)
C4—C3—H3	120.3	C22—C23—C24	118.9 (4)
C3—C4—C12	117.8 (3)	C22—C23—H23	120.6
C3—C4—C5	125.9 (3)	C24—C23—H23	120.6
C12—C4—C5	116.3 (3)	C23—C24—C25	123.5 (4)
C6—C5—N3	110.5 (3)	C23—C24—N6	116.4 (4)
C6—C5—C4	121.0 (3)	C25—C24—N6	120.0 (3)
N3—C5—C4	128.5 (4)	O3—C25—C24	121.1 (3)
C5—C6—N4	105.3 (3)	O3—C25—C20	124.0 (3)
C5—C6—C7	124.8 (3)	C24—C25—C20	114.9 (3)
N4—C6—C7	129.9 (4)	O2—C26—O1	122.3 (4)
C8—C7—C11	117.7 (3)	O2—C26—C20	119.4 (3)
C8—C7—C6	127.5 (4)	O1—C26—C20	118.2 (3)
C11—C7—C6	114.8 (3)	C1—N1—C12	118.8 (3)
C9—C8—C7	119.6 (4)	C1—N1—Co	127.4 (2)
C9—C8—H8	120.2	C12—N1—Co	113.2 (2)
C7—C8—H8	120.2	C10—N2—C11	119.2 (3)
C8—C9—C10	119.4 (4)	C10—N2—Co	127.0 (2)
C8—C9—H9	120.3	C11—N2—Co	113.5 (2)
C10—C9—H9	120.3	C13—N3—C5	104.8 (3)
N2—C10—C9	122.7 (4)	C13—N4—C6	107.2 (3)
N2—C10—H10	118.7	C13—N4—H4	126.4
C9—C10—H10	118.7	C6—N4—H4	126.4
N2—C11—C7	121.5 (3)	O4—N5—O5	123.0 (4)
N2—C11—C12	116.9 (3)	O4—N5—C22	119.2 (4)
C7—C11—C12	121.7 (3)	O5—N5—C22	117.9 (4)
N1—C12—C4	122.0 (3)	O7—N6—O6	119.1 (4)
N1—C12—C11	116.5 (3)	O7—N6—C24	121.8 (4)
C4—C12—C11	121.5 (3)	O6—N6—C24	118.9 (3)
N3—C13—N4	112.1 (3)	C26—O1—Co	120.4 (3)
N3—C13—C14	125.6 (4)	C26—O1—Coⁱ	125.8 (2)
N4—C13—C14	122.2 (4)	Co—O1—Coⁱ	100.87 (10)
C19—C14—C15	119.4 (4)	C25—O3—Co	127.0 (2)
C19—C14—C13	120.8 (4)	Co—OW1—H1WA	116 (4)
C15—C14—C13	119.8 (4)	Co—OW1—H1WB	124 (4)
C14—C15—C16	119.4 (5)	H1WA—OW1—H1WB	102 (5)
C14—C15—H15	120.3	O3—Co—O1	87.05 (10)
C16—C15—H15	120.3	O3—Co—N2	175.08 (14)
C17—C16—C15	120.9 (5)	O1—Co—N2	96.09 (11)
C17—C16—H16	119.5	O3—Co—N1	98.70 (11)
C15—C16—H16	119.5	O1—Co—N1	167.77 (12)
C16—C17—C18	119.7 (4)	N2—Co—N1	78.95 (12)
C16—C17—H17	120.1	O3—Co—OW1	88.76 (12)
C18—C17—H17	120.1	O1—Co—OW1	95.00 (13)
C17—C18—C19	120.5 (5)	N2—Co—OW1	87.20 (12)
C17—C18—H18	119.7	N1—Co—OW1	95.91 (13)
C19—C18—H18	119.7	O3—Co—O1ⁱ	95.02 (11)
C18—C19—C14	120.0 (5)	O1—Co—O1ⁱ	79.13 (10)
C18—C19—H19	120.0	N2—Co—O1ⁱ	89.30 (11)
C14—C19—H19	120.0	N1—Co—O1ⁱ	89.56 (11)
C21—C20—C25	119.9 (4)	OW1—Co—O1ⁱ	172.82 (12)

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···O6ⁱⁱ	0.86	2.17	2.948 (5)	150
OW1—H1WA···N3ⁱⁱⁱ	0.81 (6)	2.03 (6)	2.831 (5)	172 (5)
OW1—H1WB···O2^iv	0.80 (5)	1.88 (5)	2.662 (4)	165 (5)

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

Experimental details

Crystal data
Chemical formula	[Co₂(C₇H₂N₂O₇)₂(C₁₉H₁₂N₄)₂(H₂O)₂]
M_r	1198.76
Crystal system, space group	Triclinic, P1
Temperature (K)	292
a, b, c (Å)	8.2943 (4), 11.0232 (5), 13.6139 (7)
α, β, γ (°)	102.690 (4), 107.282 (4), 90.459 (4)
V (Å³)	1155.9 (1)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.81
Crystal size (mm)	0.32 × 0.27 × 0.23

Data collection
Diffractometer	Oxford Diffraction Gemini R Ultra CCD diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2006)
T_min, T_max	0.771, 0.829
No. of measured, independent and observed [I > 2σ(I)] reflections	7153, 4041, 2933
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.111, 1.00
No. of reflections	4041
No. of parameters	378
No. of restraints	168
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.97, −1.00

Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999).

Selected bond lengths (Å) top

Co—N1	2.102 (3)	Co—O1ⁱ	2.216 (3)
Co—N2	2.095 (3)	Co—O3	1.991 (3)
Co—O1	2.050 (2)	Co—OW1	2.139 (3)

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···O6ⁱⁱ	0.86	2.17	2.948 (5)	150
OW1—H1WA···N3ⁱⁱⁱ	0.81 (6)	2.03 (6)	2.831 (5)	172 (5)
OW1—H1WB···O2^iv	0.80 (5)	1.88 (5)	2.662 (4)	165 (5)

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

Acknowledgements

The authors thank Jiangsu University for supporting this work.

References

Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Che, G.-B., Liu, C.-B., Liu, B., Wang, Q.-W. & Xu, Z.-L. (2008). CrystEngComm, 10, 184–191. Web of Science CSD CrossRef CAS Google Scholar
Liu, D.-M., Li, X.-Y., Wang, X.-C., Li, C.-X. & Liu, C.-B. (2009). Acta Cryst. E65, o1308. Web of Science CSD CrossRef IUCr Journals Google Scholar
Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Steck, E. A. & Day, A. R. (1943). J. Am. Chem. Soc. 65, 452–456. CrossRef CAS Google Scholar

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