catena-Poly[[[diaqua­(1,10-phenanthroline-κ2N,N′)cobalt(II)]-μ-1H-benzimidazole-5,6-dicarboxyl­ato-κ2N3:O6] sesquihydrate}

Xu, D.-B.; Fang, Y.; Jiang, D.-L.; Zhu, Y.; Chen, M.

doi:10.1107/S1600536812043760

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 12| December 2012| Pages m1440-m1441

doi:10.1107/S1600536812043760

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catena-Poly[[[diaqua(1,10-phenanthroline-κ²N,N′)cobalt(II)]-μ-1H-benzimidazole-5,6-dicarboxylato-κ²N³:O⁶] sesquihydrate}

Dong-Bo Xu,^a Yu Fang,^a De-Li Jiang,^a Yu Zhu ^a and Min Chen ^a ^*

^aSchool of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, People's Republic of China
^*Correspondence e-mail: chenmin3226@sina.com

(Received 17 September 2012; accepted 22 October 2012; online 3 November 2012)

In the title compound, {[Co(C₉H₄N₂O₄)(C₁₂H₈N₂)(H₂O)₂]·1.5H₂O}_n, the Co^II atom is hexacoordinated by one N atom and one O atom from two symmetry-related 1H-benzimidazole-5,6-dicarboxylate ligands, two N atoms from one 1,10-phenanthroline ligand (phen) and two water molecules. The dihedral angle between the 1H-benzimidazole-5,6-dicarboxylate and 1,10-phenanthroline ligands is 74.41 (4)°. The crystal packing is governed by intermolecular O—H⋯O and N—H⋯O hydrogen-bonding interactions. All water (coordinating and lattice) molecules take part in the hydrogen-bonding interactions. In addition, there are π–π stacking interactions between inversion-related phen ligands, the shortest centroid–centroid distance being 3.7536 (16) Å. One of the two lattice water molecules shows half-occupancy.

Related literature

For general background to 1H-benzoimidazole-5,6-dicarboxylate complexes, see: Lo et al. (2007 ); Gao et al. (2008 ); Yao et al. (2008 ). For 1,10-phenanthroline as a bridging ligand, see: Chesnut et al. (1999 ). For a similar structure with Ni^II, see: Song et al. (2009 ).

Experimental

Crystal data

[Co(C₉H₄N₂O₄)(C₁₂H₈N₂)(H₂O)₂]·1.5H₂O
M_r = 506.33
Monoclinic, P 2₁ /c
a = 9.7250 (11) Å
b = 11.3956 (13) Å
c = 19.296 (2) Å
β = 103.109 (2)°
V = 2082.7 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.88 mm⁻¹
T = 173 K
0.30 × 0.24 × 0.20 mm

Data collection

Rigaku Saturn724+ diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008 ) T_min = 0.776, T_max = 0.838
17888 measured reflections
4797 independent reflections
3761 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.090
S = 1.05
4796 reflections
331 parameters
12 restraints
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.49 e Å⁻³

Table 1
Selected bond lengths (Å)

N2—Co1ⁱ	2.1304 (17)
N3—Co1	2.1412 (18)
N4—Co1	2.1478 (18)
O4—Co1	2.0582 (14)
OW1—Co1	2.1859 (15)
OW2—Co1	2.0689 (16)
Symmetry codes: (i) $[-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
OW1—H1C⋯O3	0.85	1.83	2.650 (2)	160
OW2—H2D⋯OW3	0.83	1.88	2.693 (2)	164
N1—H1A⋯OW1ⁱⁱⁱ	0.86	2.05	2.837 (2)	151
OW1—H1D⋯O2^iv	0.85	1.82	2.654 (2)	168
OW2—H2C⋯O1^iv	0.86	1.77	2.619 (2)	172 (3)
OW3—H3C⋯O3^v	0.87	1.92	2.726 (3)	155 (3)
OW3—H3D⋯OW4^vi	0.84	2.38	2.940 (5)	125
OW4—H4C⋯OW3^vii	0.85	2.10	2.891 (4)	154 (5)
OW4—H4C⋯OW2^vii	0.85	2.54	3.166 (4)	131 (5)
OW4—H4D⋯O1ⁱⁱ	0.86	2.06	2.837 (4)	151
Symmetry codes: (ii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) x+1, y, z; (iv) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (v) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (vi) x-1, y, z; (vii) -x+2, -y, -z+2.

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear; data reduction: CrystalClear; 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 global, I. DOI: 10.1107/S1600536812043760/zq2183sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812043760/zq2183Isup2.hkl

checkCIF report

Comment top

The design and construction of supramolecular architectures have received considerable attention in recent years, in the structural investigation of 1H-benzimidazole-5,6-dicarboxylate complexes, it has been found that 1H-benzimidazole-5,6-dicarboxylate acid can function as a multidentate ligand (Lo et al., 2007; Gao et al., 2008; Yao et al., 2008), with versatile binding and coordination modes. 1,10-phenanthroline is also a good example for a bridging ligand that can link metal centers into extended networks, and a number of one-, two- and three- dimensional metal-1,10-phenanthroline frameworks have been generated (Chesnut et al., 1999). According to the procedure by Song et al. (Song et al., 2009), the reaction of 1H-benzimidazole-5,6-dicarboxylate acid with cobalt chloride in an alkaline aqueous solution yielded the Co^II coordination polymer whose the crystal structure is reported here.

As illustrated in Fig. 1, the Co^II atom exhibits a slightly distorted octahedral coordination sphere, defined by one N atom and one O atom [Co1ⁱ—N2 = 2.1304 (17) Å, Co1—O4 = 2.0582 (14) Å] from two different 1H-benzimidazole-5,6-dicarboxylate ligands, two N atoms [Co1—N3 = 2.1412 (18) Å, Co1—N4 = 2.1478 (18) Å] from one 1,10-phenanthroline ligand and two water molecules [Co1—OW1 = 2.1859 (15) Å, Co1—OW2 = 2.0689 (16) Å]. The metal atoms are linked by bidentate 1H-benzimidazole-5,6-dicarboxylate groups into one dimensional chain. Inter/intramolecular O—H···O and N—H···O hydrogen bonds between the carboxylate O atoms of 1H-benzimidazole-5,6-dicarboxylate and the coordinated water and solvent water molecules lead to a two-dimensional layer (Fig. 2). The layers are further self-assembled into a three-dimensional supramolecular network by intermolecular N-H···O hydrogen bonds between the imidazole units and carboxylate groups (Table 1). In the crystal structure, π-π stacking interactions between inversion-related phen ligands are also observed with a shortest centroid-centroid distance of 3.7536 (16) Å [between (N4/C16/C18/C19/C20/C21) and (N4/C16/C18/C19/C20/C21)^viii with (viii) = 1-x, 1-y, 2-z)].

Related literature top

For general background to 1H-benzoimidazole-5,6-dicarboxylate complexes, see: Lo et al. (2007); Gao et al. (2008); Yao et al. (2008). For 1,10-phenanthroline as a bridging ligand, see: Chesnut et al. (1999). For a similar structure with Ni^II, see: Song et al. (2009).

Experimental top

According to the procedure by Song et al. (2009), a mixture of cobalt chloride (0.2 mmol), 1H-benzimidazole-5,6-dicarboxylate acid (0.2 mmol), 1,10-phenanthroline (0.2 mmol), NaOH (0.1 mmol) and H₂O (15 mL) was placed in a 25 mL Teflon reactor, which was heated to 413 K for four days and then cooled to room temperature at a rate of 10 K h^-1. The crystals obtained were washed with water and dryed in air.

Computing details top

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); 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. The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level [H-atoms are shown as spheres of arbitrary size; symmetry code: (i) = x+2, y-0.5, -z+1.5].
	Fig. 2. A view of the two-dimensional layer constructed by O-H···O and N-H···O hydrogen bonding interactions.

catena-Poly[[[diaqua(1,10-phenanthroline- κ²N,N')cobalt(II)]-µ-1H-benzimidazole-5,6- dicarboxylato-κ²N³:O⁶] sesquihydrate} top

Crystal data top

[Co(C₉H₄N₂O₄)(C₁₂H₈N₂)(H₂O)₂]·1.5H₂O	F(000) = 1040
M_r = 506.33	D_x = 1.615 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4850 reflections
a = 9.7250 (11) Å	θ = 2.1–27.5°
b = 11.3956 (13) Å	µ = 0.88 mm⁻¹
c = 19.296 (2) Å	T = 173 K
β = 103.109 (2)°	Prism, red
V = 2082.7 (4) Å³	0.30 × 0.24 × 0.20 mm
Z = 4

Data collection top

Rigaku Saturn724+ diffractometer	4797 independent reflections
Radiation source: fine-focus sealed tube	3761 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
ω scans	θ_max = 27.5°, θ_min = 2.1°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008)	h = −11→12
T_min = 0.776, T_max = 0.838	k = −14→14
17888 measured reflections	l = −25→25

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.090	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0355P)² + 1.1164P] where P = (F_o² + 2F_c²)/3
4796 reflections	(Δ/σ)_max = 0.002
331 parameters	Δρ_max = 0.42 e Å⁻³
12 restraints	Δρ_min = −0.49 e Å⁻³

Crystal data top

[Co(C₉H₄N₂O₄)(C₁₂H₈N₂)(H₂O)₂]·1.5H₂O	V = 2082.7 (4) Å³
M_r = 506.33	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.7250 (11) Å	µ = 0.88 mm⁻¹
b = 11.3956 (13) Å	T = 173 K
c = 19.296 (2) Å	0.30 × 0.24 × 0.20 mm
β = 103.109 (2)°

Data collection top

Rigaku Saturn724+ diffractometer	4797 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008)	3761 reflections with I > 2σ(I)
T_min = 0.776, T_max = 0.838	R_int = 0.043
17888 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	12 restraints
wR(F²) = 0.090	H-atom parameters constrained
S = 1.05	Δρ_max = 0.42 e Å⁻³
4796 reflections	Δρ_min = −0.49 e Å⁻³
331 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	Occ. (<1)
C1	1.3426 (2)	0.48546 (18)	0.68601 (11)	0.0196 (4)
H1	1.4358	0.4878	0.6816	0.023*
C2	1.1479 (2)	0.42156 (18)	0.71347 (10)	0.0162 (4)
C3	1.1260 (2)	0.53227 (18)	0.68112 (10)	0.0158 (4)
C4	1.0404 (2)	0.36045 (18)	0.73494 (11)	0.0184 (4)
H4	1.0562	0.2867	0.7559	0.022*
C5	0.9938 (2)	0.58516 (18)	0.66973 (10)	0.0166 (4)
H5	0.9779	0.6581	0.6478	0.020*
C6	0.8856 (2)	0.52623 (18)	0.69192 (10)	0.0155 (4)
C7	0.9086 (2)	0.41394 (18)	0.72378 (10)	0.0162 (4)
C8	0.7474 (2)	0.59071 (19)	0.68525 (11)	0.0202 (4)
C9	0.7931 (2)	0.34525 (17)	0.74648 (11)	0.0173 (4)
C10	0.9568 (2)	0.1841 (2)	0.99354 (12)	0.0285 (5)
H10	0.9609	0.1120	0.9715	0.034*
C11	1.0612 (3)	0.2105 (3)	1.05439 (13)	0.0372 (6)
H11	1.1333	0.1573	1.0717	0.045*
C12	1.0563 (3)	0.3156 (3)	1.08825 (13)	0.0393 (7)
H12	1.1254	0.3346	1.1285	0.047*
C13	0.9455 (3)	0.3945 (2)	1.06151 (12)	0.0327 (6)
C14	0.8459 (2)	0.3620 (2)	0.99951 (11)	0.0243 (5)
C15	0.9306 (3)	0.5065 (3)	1.09338 (13)	0.0416 (7)
H15	0.9968	0.5290	1.1340	0.050*
C16	0.7329 (2)	0.4407 (2)	0.96903 (11)	0.0242 (5)
C17	0.8237 (3)	0.5794 (3)	1.06611 (14)	0.0420 (7)
H17	0.8160	0.6504	1.0887	0.050*
C18	0.7208 (3)	0.5495 (2)	1.00241 (13)	0.0310 (6)
C19	0.6081 (3)	0.6230 (2)	0.96966 (15)	0.0392 (6)
H19	0.5964	0.6958	0.9894	0.047*
C20	0.5165 (3)	0.5876 (2)	0.90918 (15)	0.0380 (6)
H20	0.4416	0.6354	0.8875	0.046*
C21	0.5363 (3)	0.4778 (2)	0.87982 (13)	0.0321 (6)
H21	0.4731	0.4545	0.8384	0.039*
N1	1.28761 (18)	0.39420 (15)	0.71539 (9)	0.0195 (4)
H1A	1.3311	0.3310	0.7321	0.023*
N2	1.25154 (17)	0.57083 (15)	0.66427 (9)	0.0172 (4)
N3	0.85195 (19)	0.25700 (17)	0.96580 (9)	0.0220 (4)
N4	0.64096 (19)	0.40575 (16)	0.90847 (9)	0.0237 (4)
O1	0.71519 (16)	0.66394 (16)	0.63497 (9)	0.0359 (4)
O2	0.67695 (16)	0.57174 (14)	0.73083 (8)	0.0279 (4)
O3	0.68891 (16)	0.31022 (14)	0.69976 (8)	0.0250 (4)
O4	0.81500 (15)	0.32296 (12)	0.81218 (7)	0.0191 (3)
OW1	0.51234 (15)	0.24220 (13)	0.77827 (8)	0.0184 (3)
H1C	0.5615	0.2496	0.7472	0.028*
H1D	0.4589	0.1824	0.7723	0.028*
OW2	0.55560 (16)	0.15584 (16)	0.92303 (8)	0.0280 (4)
H2C	0.4677	0.1657	0.9039	0.042*
H2D	0.5734	0.1556	0.9673	0.042*
OW3	0.5829 (3)	0.1182 (2)	1.06327 (10)	0.0635 (7)
H3C	0.6403	0.1383	1.1027	0.095*
H3D	0.5210	0.0701	1.0688	0.095*
OW4	1.2843 (5)	0.0672 (3)	1.0004 (2)	0.0451 (10)	0.50
H4C	1.3167	0.0004	0.9924	0.068*	0.50
H4D	1.2609	0.1116	0.9637	0.068*	0.50
Co1	0.69156 (3)	0.23795 (2)	0.870080 (14)	0.01613 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0132 (10)	0.0213 (11)	0.0250 (11)	0.0005 (8)	0.0060 (8)	−0.0015 (9)
C2	0.0125 (10)	0.0178 (11)	0.0182 (10)	0.0033 (8)	0.0030 (8)	−0.0001 (8)
C3	0.0138 (10)	0.0170 (10)	0.0175 (10)	−0.0015 (8)	0.0052 (8)	−0.0020 (8)
C4	0.0180 (10)	0.0161 (10)	0.0210 (10)	0.0003 (8)	0.0046 (8)	0.0028 (8)
C5	0.0161 (10)	0.0153 (10)	0.0185 (10)	0.0020 (8)	0.0039 (8)	0.0007 (8)
C6	0.0119 (10)	0.0168 (10)	0.0174 (10)	0.0010 (8)	0.0024 (8)	−0.0010 (8)
C7	0.0142 (10)	0.0184 (10)	0.0171 (10)	−0.0038 (8)	0.0057 (8)	−0.0022 (8)
C8	0.0133 (10)	0.0188 (11)	0.0284 (11)	−0.0023 (9)	0.0044 (9)	−0.0007 (9)
C9	0.0152 (10)	0.0137 (10)	0.0234 (10)	0.0012 (8)	0.0056 (8)	−0.0010 (8)
C10	0.0252 (12)	0.0360 (14)	0.0239 (11)	0.0017 (10)	0.0049 (10)	0.0073 (10)
C11	0.0267 (13)	0.0548 (18)	0.0270 (13)	0.0008 (12)	0.0000 (10)	0.0131 (12)
C12	0.0298 (14)	0.0624 (19)	0.0221 (12)	−0.0170 (13)	−0.0018 (10)	0.0036 (12)
C13	0.0300 (13)	0.0483 (16)	0.0196 (11)	−0.0168 (12)	0.0056 (10)	−0.0046 (11)
C14	0.0245 (12)	0.0306 (13)	0.0188 (11)	−0.0090 (10)	0.0070 (9)	−0.0028 (9)
C15	0.0444 (17)	0.0558 (18)	0.0243 (12)	−0.0224 (15)	0.0071 (12)	−0.0168 (12)
C16	0.0269 (12)	0.0262 (12)	0.0219 (11)	−0.0056 (10)	0.0107 (9)	−0.0048 (9)
C17	0.0540 (18)	0.0423 (17)	0.0350 (14)	−0.0205 (14)	0.0213 (13)	−0.0217 (12)
C18	0.0363 (14)	0.0304 (13)	0.0315 (13)	−0.0106 (11)	0.0185 (11)	−0.0100 (10)
C19	0.0492 (17)	0.0260 (13)	0.0501 (16)	−0.0004 (12)	0.0273 (14)	−0.0116 (12)
C20	0.0418 (15)	0.0285 (14)	0.0464 (16)	0.0112 (12)	0.0157 (13)	−0.0016 (12)
C21	0.0322 (14)	0.0299 (14)	0.0337 (13)	0.0068 (11)	0.0062 (11)	−0.0038 (11)
N1	0.0151 (9)	0.0175 (9)	0.0266 (9)	0.0037 (7)	0.0058 (7)	0.0038 (7)
N2	0.0122 (8)	0.0169 (9)	0.0230 (9)	−0.0003 (7)	0.0052 (7)	−0.0012 (7)
N3	0.0179 (9)	0.0298 (11)	0.0179 (9)	−0.0026 (8)	0.0030 (7)	0.0025 (8)
N4	0.0235 (10)	0.0254 (10)	0.0234 (9)	0.0014 (8)	0.0080 (8)	−0.0030 (8)
O1	0.0180 (8)	0.0454 (11)	0.0462 (11)	0.0108 (8)	0.0115 (8)	0.0256 (9)
O2	0.0198 (8)	0.0337 (9)	0.0343 (9)	0.0079 (7)	0.0149 (7)	0.0098 (7)
O3	0.0210 (8)	0.0329 (9)	0.0204 (8)	−0.0104 (7)	0.0030 (6)	0.0012 (7)
O4	0.0172 (7)	0.0199 (8)	0.0198 (7)	−0.0028 (6)	0.0036 (6)	0.0014 (6)
OW1	0.0139 (7)	0.0203 (8)	0.0216 (7)	−0.0007 (6)	0.0055 (6)	0.0004 (6)
OW2	0.0193 (8)	0.0442 (11)	0.0215 (8)	0.0020 (8)	0.0066 (7)	0.0014 (8)
OW3	0.101 (2)	0.0582 (16)	0.0250 (10)	0.0048 (13)	0.0016 (11)	−0.0050 (10)
OW4	0.057 (3)	0.031 (2)	0.053 (2)	0.0131 (19)	0.027 (2)	0.0075 (18)
Co1	0.01335 (15)	0.01823 (16)	0.01708 (14)	0.00037 (11)	0.00402 (10)	−0.00106 (11)

Geometric parameters (Å, º) top

C1—N2	1.318 (3)	C15—C17	1.342 (4)
C1—N1	1.352 (3)	C15—H15	0.9300
C1—H1	0.9300	C16—N4	1.360 (3)
C2—N1	1.387 (2)	C16—C18	1.414 (3)
C2—C4	1.395 (3)	C17—C18	1.439 (4)
C2—C3	1.402 (3)	C17—H17	0.9300
C3—C5	1.392 (3)	C18—C19	1.411 (4)
C3—N2	1.403 (2)	C19—C20	1.359 (4)
C4—C7	1.391 (3)	C19—H19	0.9300
C4—H4	0.9300	C20—C21	1.405 (3)
C5—C6	1.395 (3)	C20—H20	0.9300
C5—H5	0.9300	C21—N4	1.327 (3)
C6—C7	1.415 (3)	C21—H21	0.9300
C6—C8	1.512 (3)	N1—H1A	0.8600
C7—C9	1.513 (3)	N2—Co1ⁱ	2.1304 (17)
C8—O2	1.250 (3)	N3—Co1	2.1412 (18)
C8—O1	1.264 (3)	N4—Co1	2.1478 (18)
C9—O3	1.259 (2)	O4—Co1	2.0582 (14)
C9—O4	1.263 (2)	OW1—Co1	2.1859 (15)
C10—N3	1.330 (3)	OW1—H1C	0.85
C10—C11	1.400 (3)	OW1—H1D	0.85
C10—H10	0.9300	OW2—Co1	2.0689 (16)
C11—C12	1.370 (4)	OW2—H2C	0.86
C11—H11	0.9300	OW2—H2D	0.83
C12—C13	1.409 (4)	OW3—H3C	0.87
C12—H12	0.9300	OW3—H3D	0.84
C13—C14	1.408 (3)	OW4—H4C	0.85
C13—C15	1.438 (4)	OW4—H4D	0.86
C14—N3	1.369 (3)	Co1—N2ⁱⁱ	2.1304 (17)
C14—C16	1.437 (3)

N2—C1—N1	113.57 (18)	C18—C17—H17	119.5
N2—C1—H1	123.2	C19—C18—C16	116.9 (2)
N1—C1—H1	123.2	C19—C18—C17	124.1 (2)
N1—C2—C4	132.52 (19)	C16—C18—C17	118.9 (2)
N1—C2—C3	105.23 (17)	C20—C19—C18	120.0 (2)
C4—C2—C3	122.24 (18)	C20—C19—H19	120.0
C5—C3—C2	120.06 (18)	C18—C19—H19	120.0
C5—C3—N2	130.47 (19)	C19—C20—C21	119.2 (2)
C2—C3—N2	109.46 (17)	C19—C20—H20	120.4
C7—C4—C2	117.49 (19)	C21—C20—H20	120.4
C7—C4—H4	121.3	N4—C21—C20	123.0 (2)
C2—C4—H4	121.3	N4—C21—H21	118.5
C3—C5—C6	118.51 (19)	C20—C21—H21	118.5
C3—C5—H5	120.7	C1—N1—C2	107.13 (17)
C6—C5—H5	120.7	C1—N1—H1A	126.4
C5—C6—C7	120.88 (18)	C2—N1—H1A	126.4
C5—C6—C8	117.26 (18)	C1—N2—C3	104.61 (17)
C7—C6—C8	121.72 (17)	C1—N2—Co1ⁱ	123.74 (14)
C4—C7—C6	120.81 (18)	C3—N2—Co1ⁱ	130.77 (13)
C4—C7—C9	116.55 (18)	C10—N3—C14	117.8 (2)
C6—C7—C9	122.64 (18)	C10—N3—Co1	128.73 (16)
O2—C8—O1	125.1 (2)	C14—N3—Co1	113.40 (14)
O2—C8—C6	118.34 (19)	C21—N4—C16	118.0 (2)
O1—C8—C6	116.54 (18)	C21—N4—Co1	128.41 (16)
O3—C9—O4	125.49 (19)	C16—N4—Co1	113.55 (15)
O3—C9—C7	119.11 (18)	C9—O4—Co1	130.78 (13)
O4—C9—C7	115.30 (18)	Co1—OW1—H1C	96
N3—C10—C11	123.2 (2)	Co1—OW1—H1D	116.4
N3—C10—H10	118.4	H1C—OW1—H1D	114.1
C11—C10—H10	118.4	Co1—OW2—H2C	114
C12—C11—C10	119.4 (2)	Co1—OW2—H2D	120.0
C12—C11—H11	120.3	H2C—OW2—H2D	113.4
C10—C11—H11	120.3	H3C—OW3—H3D	113.6
C11—C12—C13	119.3 (2)	H4C—OW4—H4D	114.7
C11—C12—H12	120.3	O4—Co1—OW2	176.10 (6)
C13—C12—H12	120.3	O4—Co1—N2ⁱⁱ	91.56 (6)
C14—C13—C12	117.7 (2)	OW2—Co1—N2ⁱⁱ	89.40 (7)
C14—C13—C15	118.7 (2)	O4—Co1—N3	91.15 (6)
C12—C13—C15	123.6 (2)	OW2—Co1—N3	92.41 (7)
N3—C14—C13	122.6 (2)	N2ⁱⁱ—Co1—N3	99.75 (7)
N3—C14—C16	117.51 (19)	O4—Co1—N4	88.60 (6)
C13—C14—C16	119.9 (2)	OW2—Co1—N4	90.59 (7)
C17—C15—C13	121.7 (2)	N2ⁱⁱ—Co1—N4	177.70 (7)
C17—C15—H15	119.1	N3—Co1—N4	77.95 (7)
C13—C15—H15	119.1	O4—Co1—OW1	90.32 (6)
N4—C16—C18	122.8 (2)	OW2—Co1—OW1	85.92 (6)
N4—C16—C14	117.5 (2)	N2ⁱⁱ—Co1—OW1	89.04 (6)
C18—C16—C14	119.7 (2)	N3—Co1—OW1	171.05 (6)
C15—C17—C18	121.0 (2)	N4—Co1—OW1	93.26 (6)
C15—C17—H17	119.5

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
OW1—H1C···O3	0.85	1.83	2.650 (2)	160
OW2—H2D···OW3	0.83	1.88	2.693 (2)	164
N1—H1A···OW1ⁱⁱⁱ	0.86	2.05	2.837 (2)	151
OW1—H1D···O2^iv	0.85	1.82	2.654 (2)	168
OW2—H2C···O1^iv	0.86	1.77	2.619 (2)	172 (3)
OW3—H3C···O3^v	0.87	1.92	2.726 (3)	155 (3)
OW3—H3D···OW4^vi	0.84	2.38	2.940 (5)	125
OW4—H4C···OW3^vii	0.85	2.10	2.891 (4)	154 (5)
OW4—H4C···OW2^vii	0.85	2.54	3.166 (4)	131 (5)
OW4—H4D···O1ⁱⁱ	0.86	2.06	2.837 (4)	151

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

Experimental details

Crystal data
Chemical formula	[Co(C₉H₄N₂O₄)(C₁₂H₈N₂)(H₂O)₂]·1.5H₂O
M_r	506.33
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	9.7250 (11), 11.3956 (13), 19.296 (2)
β (°)	103.109 (2)
V (Å³)	2082.7 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.88
Crystal size (mm)	0.30 × 0.24 × 0.20

Data collection
Diffractometer	Rigaku Saturn724+ diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2008)
T_min, T_max	0.776, 0.838
No. of measured, independent and observed [I > 2σ(I)] reflections	17888, 4797, 3761
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.090, 1.05
No. of reflections	4796
No. of parameters	331
No. of restraints	12
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.49

Computer programs: CrystalClear (Rigaku, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

N2—Co1ⁱ	2.1304 (17)	OW1—Co1	2.1859 (15)
N3—Co1	2.1412 (18)	OW2—Co1	2.0689 (16)
N4—Co1	2.1478 (18)	Co1—N2ⁱⁱ	2.1304 (17)
O4—Co1	2.0582 (14)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
OW1—H1C···O3	0.85	1.83	2.650 (2)	160
OW2—H2D···OW3	0.83	1.88	2.693 (2)	164.3
N1—H1A···OW1ⁱⁱⁱ	0.86	2.05	2.837 (2)	151.2
OW1—H1D···O2^iv	0.85	1.82	2.654 (2)	168.4
OW2—H2C···O1^iv	0.86	1.77	2.619 (2)	172 (3)
OW3—H3C···O3^v	0.87	1.92	2.726 (3)	155 (3)
OW3—H3D···OW4^vi	0.84	2.38	2.940 (5)	124.8
OW4—H4C···OW3^vii	0.85	2.10	2.891 (4)	154 (5)
OW4—H4C···OW2^vii	0.85	2.54	3.166 (4)	131 (5)
OW4—H4D···O1ⁱⁱ	0.86	2.06	2.837 (4)	150.5

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

Acknowledgements

The authors thank Jiangsu University for supporting this work.

References

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