Bis{1-[(1H-benzimidazol-1-yl)meth­yl]-1H-imidazole-κN3}bis­(3,5-dicarb­oxy­benzoato-κ2O1,O1′)nickel(II) octa­hydrate

Jia, Y.-Y.; Fan, J.-J.; Yin, X.-G.; Zhao, W.-L.

doi:10.1107/S1600536813003322

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 4| April 2013| Page m184

doi:10.1107/S1600536813003322

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Bis{1-[(1H-benzimidazol-1-yl)methyl]-1H-imidazole-κN³}bis(3,5-dicarboxybenzoato-κ²O¹,O^1′)nickel(II) octahydrate

Yong-Yan Jia,^a ^* Jing-Jing Fan,^a Xiang-Ge Yin ^a and Wen-Long Zhao ^a

^aPharmacy College, Henan University of Traditional Chinese Medicine, Zhengzhou 450008, People's Republic of China
^*Correspondence e-mail: hnzyjyy@126.com

(Received 28 January 2013; accepted 1 February 2013; online 2 March 2013)

In the title complex, [Ni(C₉H₅O₆)₂(C₁₁H₁₀N₄)₂]·8H₂O, the Ni^II ion exhibits site symmetry 2. It has a distorted octahedral coordination defined by two N atoms from two symmetry-related 1-[(1H-benzimidazol-1-yl)methyl]-1H-imidazole ligands and four O atoms from two symmetry-related 3,5-dicarboxybenzoate anions. In the crystal, the complex molecules and solvent water molecules are linked via O—H⋯O, O—H⋯N and N—H⋯O hydrogen bonds, forming a three-dimensional structure. There are also a number of C—H⋯O interactions present.

Related literature

For background information to Ni^II complexes constructed from both aromatic carboxylates and N-heterocyclic ligands, see: Hu et al. (2011 ); Xu et al. (2010 ).

Experimental

Crystal data

[Ni(C₉H₅O₆)₂(C₁₁H₁₀N₄)₂]·8H₂O
M_r = 1017.56
Monoclinic, C 2/c
a = 20.623 (4) Å
b = 14.626 (3) Å
c = 15.471 (3) Å
β = 104.03 (3)°
V = 4527.2 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.52 mm⁻¹
T = 293 K
0.19 × 0.17 × 0.12 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2004 ) T_min = 0.908, T_max = 0.940
16185 measured reflections
4215 independent reflections
3719 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.172
S = 1.13
4215 reflections
314 parameters
H-atom parameters constrained
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H1W⋯O10	0.85	2.09	2.936 (7)	170
O7—H2W⋯O6ⁱⁱ	0.85	1.96	2.802 (4)	172
O3—H3⋯O7ⁱⁱⁱ	0.82	2.04	2.782 (5)	150
N3—H3B⋯O8^iv	0.86	1.95	2.780 (5)	162
O8—H3W⋯O1^v	0.85	2.05	2.866 (4)	161
O8—H4W⋯O7	0.85	2.14	2.915 (5)	151
O5—H5⋯N4^vi	0.82	1.77	2.586 (4)	172
O9—H5W⋯O3^vii	0.85	2.28	3.133 (5)	180
O9—H6W⋯O6ⁱ	0.85	2.05	2.791 (5)	146
O10—H7W⋯O4	0.85	1.73	2.579 (7)	173
C1—H1A⋯O5^vii	0.93	2.56	3.320 (4)	139
C3—H3A⋯O4^v	0.93	2.46	3.078 (5)	124
C4—H4A⋯O1^viii	0.97	2.55	3.479 (4)	160
Symmetry codes: (i) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (iii) $[-x, y, -z+{\script{1\over 2}}]$ ; (iv) $[-x+{\script{1\over 2}}, -y-{\script{1\over 2}}, -z+1]$ ; (v) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (vi) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (vii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (viii) $[x, -y, z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku/MSC, 2004); 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: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813003322/su2557sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813003322/su2557Isup2.hkl

checkCIF report

Comment top

Since Ni^II ions are able to coordinate simultaneously to both oxygen and nitrogen containing ligands the final products can exhibit attractive structures and useful functional properties. A great number of Ni^II complexes containing both aromatic carboxylates and N-heterocyclic ligands have been reported (Hu et al., 2011; Xu et al., 2010). In order to further explore such compounds with possibly new structures, we selected 1-((1H-benzimidazol-1-yl)methyl)-1H-imidazole and 1,3,5-benzenetricarboxylic acid as ligands to self-assemble with Ni(NO₃)₂ and obtained the title complex. The crystal structure of which is reported on herein.

As shown in Fig. 1, the Ni^II ion is located on a two-fold rotation axis. Each Ni^II ion features a distorted octahedral geometry and is hexacoordinated by four O atoms from two symmetry related 1,3,5-dicarboxybenzoate anions, in which carboxylate groups coordinate to the Ni^II ion in the chelating mode, and by two N atoms from two symmetry related 1-((1H-benzimidazol-1-yl)methyl)- 1H-imidazole ligands, which coordinate to Ni^II ion in a monodentate mode. Atoms O2, O2A, O1A, N1A, and Ni1 are nearly co-planar (the mean deviation from the plane is 0.0726 (12) Å), while atom O1 and N1 are located in the apical positions.

In the crystal, a series of O—H···O, O—H···N, and N—H···O hydrogen bonds linking, solvent water to water molecules, solvent water molecules and carboxylate O atoms, carboxyl groups and benzimidazole N atoms, and benzimidazole units and solvent water molecules, consolidate the crystal packing forming a three-dimensional structure (Table 1). There are also a number of C-H···O interactions present (Table 1).

Related literature top

For background information to Ni^II complexes constructed from both aromatic carboxylates and N-heterocyclic ligands, see: Hu et al. (2011); Xu et al. (2010).

Experimental top

A mixture of Ni(NO₃)₂ (0.1 mmol), 1-((1H-benzimidazol-1-yl)methyl)-1H-imidazole (0.1 mmol), 1,3,5-benzenetricarboxylic acid (0.1 mmol) and water (10 ml) was placed in a 25 ml Teflon-lined stainless steel vessel and heated at 373 K for 72 h, then cooled to room temperature. Green crystals were obtained from the filtrate and dried in air.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2004); cell refinement: CrystalClear (Rigaku/MSC, 2004); data reduction: CrystalClear (Rigaku/MSC, 2004); 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: publCIF (Westrip, 2010).

Figures top

Fig. 1. View of the molecular structure of the title complex, showing the atom labelling. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity [symmetry code: A = -x + 1, y, -z + 1/2.].

Bis{1-[(1H-benzimidazol-1-yl)methyl]-1H-imidazole-κN³}bis(3,5-dicarboxybenzoato-κ²O¹,O^1')nickel(II) octahydrate top

Crystal data top

[Ni(C₉H₅O₆)₂(C₁₁H₁₀N₄)₂]·8H₂O	F(000) = 2120
M_r = 1017.56	D_x = 1.493 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 20.623 (4) Å	Cell parameters from 5823 reflections
b = 14.626 (3) Å	θ = 1.7–27.9°
c = 15.471 (3) Å	µ = 0.52 mm⁻¹
β = 104.03 (3)°	T = 293 K
V = 4527.2 (16) Å³	Prism, green
Z = 4	0.19 × 0.17 × 0.12 mm

Data collection top

Rigaku Saturn diffractometer	4215 independent reflections
Radiation source: fine-focus sealed tube	3719 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
Detector resolution: 28.5714 pixels mm^-1	θ_max = 25.5°, θ_min = 2.0°
ω scans	h = −24→24
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2004)	k = −14→17
T_min = 0.908, T_max = 0.940	l = −18→15
16185 measured reflections

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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.172	H-atom parameters constrained
S = 1.13	w = 1/[σ²(F_o²) + (0.0894P)² + 4.146P] where P = (F_o² + 2F_c²)/3
4215 reflections	(Δ/σ)_max < 0.001
314 parameters	Δρ_max = 0.67 e Å⁻³
0 restraints	Δρ_min = −0.47 e Å⁻³

Crystal data top

[Ni(C₉H₅O₆)₂(C₁₁H₁₀N₄)₂]·8H₂O	V = 4527.2 (16) Å³
M_r = 1017.56	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 20.623 (4) Å	µ = 0.52 mm⁻¹
b = 14.626 (3) Å	T = 293 K
c = 15.471 (3) Å	0.19 × 0.17 × 0.12 mm
β = 104.03 (3)°

Data collection top

Rigaku Saturn diffractometer	4215 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2004)	3719 reflections with I > 2σ(I)
T_min = 0.908, T_max = 0.940	R_int = 0.045
16185 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	0 restraints
wR(F²) = 0.172	H-atom parameters constrained
S = 1.13	Δρ_max = 0.67 e Å⁻³
4215 reflections	Δρ_min = −0.47 e Å⁻³
314 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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
Ni1	0.50000	0.05398 (4)	0.25000	0.0263 (2)
O1	0.44973 (11)	0.17115 (16)	0.15907 (16)	0.0365 (8)
O2	0.40111 (11)	0.07735 (16)	0.23391 (16)	0.0338 (8)
O3	0.15958 (15)	0.0697 (2)	0.1857 (2)	0.0608 (13)
O4	0.09844 (14)	0.1905 (2)	0.1294 (3)	0.0686 (13)
O5	0.20784 (14)	0.46292 (18)	0.0447 (2)	0.0522 (10)
O6	0.31803 (15)	0.46684 (19)	0.0667 (2)	0.0568 (10)
N1	0.51386 (13)	−0.03683 (19)	0.35162 (18)	0.0300 (9)
N2	0.54931 (13)	−0.09621 (19)	0.48450 (18)	0.0293 (8)
N3	0.65040 (14)	−0.2528 (2)	0.61442 (19)	0.0340 (9)
N4	0.70616 (14)	−0.13469 (19)	0.58371 (19)	0.0327 (9)
C1	0.55815 (16)	−0.0300 (2)	0.4289 (2)	0.0277 (10)
C2	0.47484 (17)	−0.1117 (2)	0.3587 (2)	0.0377 (11)
C3	0.49601 (18)	−0.1488 (3)	0.4409 (2)	0.0390 (12)
C4	0.58605 (17)	−0.1066 (2)	0.5776 (2)	0.0335 (11)
C5	0.64692 (16)	−0.1648 (2)	0.5901 (2)	0.0292 (10)
C6	0.75139 (17)	−0.2070 (2)	0.6066 (2)	0.0326 (10)
C7	0.81932 (18)	−0.2116 (3)	0.6135 (2)	0.0413 (11)
C8	0.8498 (2)	−0.2936 (3)	0.6411 (3)	0.0488 (14)
C9	0.8142 (2)	−0.3693 (3)	0.6597 (3)	0.0491 (14)
C10	0.7470 (2)	−0.3652 (3)	0.6525 (3)	0.0473 (14)
C11	0.71606 (17)	−0.2822 (2)	0.6260 (2)	0.0329 (11)
C12	0.39819 (16)	0.1458 (2)	0.1831 (2)	0.0305 (10)
C13	0.33326 (16)	0.1947 (2)	0.1540 (2)	0.0298 (10)
C14	0.27601 (17)	0.1527 (2)	0.1660 (2)	0.0338 (11)
C15	0.21442 (16)	0.1966 (2)	0.1419 (2)	0.0330 (11)
C16	0.21099 (17)	0.2849 (2)	0.1080 (2)	0.0352 (11)
C17	0.26850 (17)	0.3292 (2)	0.0971 (2)	0.0331 (11)
C18	0.32924 (17)	0.2827 (2)	0.1189 (2)	0.0325 (10)
C19	0.15416 (19)	0.1473 (3)	0.1539 (3)	0.0441 (14)
C20	0.26497 (19)	0.4268 (2)	0.0666 (3)	0.0403 (11)
O7	−0.07964 (17)	−0.0247 (2)	0.2232 (2)	0.0719 (11)
O8	−0.03597 (17)	−0.1763 (2)	0.3458 (3)	0.0795 (14)
O9	0.5992 (2)	0.5579 (3)	0.5235 (3)	0.107 (2)
O10	−0.0070 (3)	0.0946 (5)	0.1264 (4)	0.183 (3)
H1A	0.59100	0.01480	0.44280	0.0330*
H2A	0.43950	−0.13330	0.31400	0.0450*
H3	0.12890	0.06020	0.20980	0.0730*
H3A	0.47820	−0.19940	0.46330	0.0470*
H3B	0.61750	−0.28560	0.62170	0.0410*
H4A	0.55640	−0.13310	0.61090	0.0400*
H4B	0.59910	−0.04650	0.60230	0.0400*
H5	0.21090	0.51760	0.05690	0.0630*
H7A	0.84320	−0.16180	0.60010	0.0500*
H8A	0.89570	−0.29890	0.64760	0.0580*
H9A	0.83670	−0.42380	0.67730	0.0590*
H10A	0.72310	−0.41550	0.66490	0.0570*
H14A	0.27870	0.09430	0.19040	0.0410*
H16A	0.17000	0.31480	0.09230	0.0420*
H18A	0.36750	0.31080	0.11000	0.0390*
H1W	−0.06060	0.01530	0.19800	0.0860*
H2W	−0.11320	−0.02630	0.17870	0.0860*
H3W	−0.00440	−0.21200	0.34160	0.0950*
H4W	−0.04180	−0.14410	0.29870	0.0950*
H5W	0.61540	0.52330	0.56760	0.1280*
H6W	0.63240	0.55220	0.50050	0.1280*
H7W	0.02720	0.12840	0.13100	0.2200*
H8W	−0.03660	0.09890	0.07760	0.2200*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0205 (3)	0.0263 (4)	0.0307 (4)	0.0000	0.0033 (2)	0.0000
O1	0.0243 (12)	0.0331 (14)	0.0513 (15)	0.0031 (10)	0.0077 (11)	0.0034 (11)
O2	0.0270 (12)	0.0347 (14)	0.0377 (13)	0.0067 (10)	0.0042 (10)	0.0067 (11)
O3	0.0446 (18)	0.0437 (18)	0.102 (3)	0.0041 (13)	0.0330 (17)	0.0223 (16)
O4	0.0281 (15)	0.0512 (19)	0.124 (3)	0.0069 (13)	0.0135 (16)	0.0257 (18)
O5	0.0395 (16)	0.0236 (13)	0.087 (2)	0.0071 (11)	0.0026 (14)	0.0013 (14)
O6	0.0411 (17)	0.0366 (16)	0.091 (2)	−0.0024 (13)	0.0129 (15)	0.0155 (15)
N1	0.0242 (14)	0.0300 (15)	0.0347 (16)	0.0026 (11)	0.0048 (12)	0.0012 (12)
N2	0.0243 (14)	0.0289 (15)	0.0332 (15)	0.0024 (11)	0.0039 (11)	0.0034 (12)
N3	0.0287 (15)	0.0293 (16)	0.0445 (17)	−0.0005 (12)	0.0101 (13)	0.0083 (13)
N4	0.0280 (15)	0.0285 (15)	0.0395 (16)	0.0000 (12)	0.0044 (12)	0.0006 (12)
C1	0.0224 (15)	0.0256 (17)	0.0349 (18)	0.0017 (13)	0.0067 (13)	0.0007 (13)
C2	0.0286 (18)	0.037 (2)	0.043 (2)	−0.0081 (15)	0.0002 (15)	0.0003 (16)
C3	0.036 (2)	0.032 (2)	0.047 (2)	−0.0066 (15)	0.0064 (16)	0.0048 (16)
C4	0.0305 (18)	0.037 (2)	0.0316 (18)	0.0079 (15)	0.0049 (14)	0.0020 (15)
C5	0.0297 (17)	0.0279 (18)	0.0280 (17)	0.0025 (13)	0.0029 (13)	0.0005 (13)
C6	0.0335 (18)	0.0285 (18)	0.0341 (18)	0.0037 (14)	0.0048 (14)	−0.0005 (14)
C7	0.0310 (19)	0.045 (2)	0.047 (2)	0.0018 (16)	0.0079 (16)	−0.0029 (17)
C8	0.034 (2)	0.056 (3)	0.055 (2)	0.0137 (18)	0.0083 (17)	−0.003 (2)
C9	0.044 (2)	0.040 (2)	0.060 (3)	0.0183 (18)	0.0065 (19)	0.0026 (19)
C10	0.045 (2)	0.035 (2)	0.061 (3)	0.0074 (17)	0.0112 (19)	0.0092 (19)
C11	0.0298 (18)	0.0283 (18)	0.0387 (19)	0.0059 (14)	0.0044 (14)	0.0016 (14)
C12	0.0264 (17)	0.0296 (18)	0.0324 (18)	0.0049 (14)	0.0012 (13)	−0.0053 (14)
C13	0.0272 (17)	0.0275 (18)	0.0325 (18)	0.0050 (13)	0.0030 (13)	−0.0008 (14)
C14	0.0286 (17)	0.0263 (18)	0.045 (2)	0.0036 (14)	0.0061 (15)	0.0034 (15)
C15	0.0262 (17)	0.0280 (18)	0.044 (2)	0.0009 (14)	0.0067 (15)	0.0008 (15)
C16	0.0262 (17)	0.0310 (19)	0.047 (2)	0.0073 (14)	0.0062 (15)	0.0017 (15)
C17	0.0269 (17)	0.0274 (18)	0.042 (2)	0.0052 (13)	0.0023 (14)	−0.0004 (14)
C18	0.0278 (17)	0.0298 (18)	0.0400 (19)	0.0018 (13)	0.0082 (14)	−0.0026 (15)
C19	0.034 (2)	0.036 (2)	0.061 (3)	0.0022 (16)	0.0092 (17)	0.0035 (18)
C20	0.038 (2)	0.0285 (19)	0.053 (2)	0.0036 (15)	0.0081 (17)	0.0001 (16)
O7	0.0484 (19)	0.075 (2)	0.090 (2)	−0.0035 (17)	0.0122 (17)	−0.0016 (19)
O8	0.074 (2)	0.059 (2)	0.125 (3)	0.0071 (18)	0.062 (2)	0.008 (2)
O9	0.114 (4)	0.104 (4)	0.106 (3)	0.019 (3)	0.034 (3)	0.002 (3)
O10	0.087 (4)	0.270 (8)	0.165 (5)	−0.095 (5)	−0.024 (4)	0.106 (5)

Geometric parameters (Å, º) top

Ni1—O1	2.299 (2)	N3—H3B	0.8600
Ni1—O2	2.023 (2)	C2—C3	1.354 (4)
Ni1—N1	2.025 (3)	C4—C5	1.490 (5)
Ni1—O1ⁱ	2.299 (2)	C6—C11	1.392 (4)
Ni1—O2ⁱ	2.023 (2)	C6—C7	1.381 (5)
Ni1—N1ⁱ	2.025 (3)	C7—C8	1.373 (6)
O1—C12	1.264 (4)	C8—C9	1.397 (6)
O2—C12	1.265 (4)	C9—C10	1.365 (6)
O3—C19	1.231 (5)	C10—C11	1.386 (5)
O4—C19	1.285 (5)	C12—C13	1.488 (5)
O5—C20	1.260 (5)	C13—C18	1.392 (4)
O6—C20	1.241 (5)	C13—C14	1.383 (5)
O3—H3	0.8200	C14—C15	1.391 (5)
O5—H5	0.8200	C15—C16	1.389 (4)
O7—H1W	0.8500	C15—C19	1.487 (5)
O7—H2W	0.8500	C16—C17	1.397 (5)
O8—H3W	0.8500	C17—C18	1.393 (5)
O8—H4W	0.8500	C17—C20	1.500 (4)
O9—H5W	0.8500	C1—H1A	0.9300
O9—H6W	0.8500	C2—H2A	0.9300
O10—H8W	0.8500	C3—H3A	0.9300
O10—H7W	0.8500	C4—H4A	0.9700
N1—C1	1.321 (4)	C4—H4B	0.9700
N1—C2	1.379 (4)	C7—H7A	0.9300
N2—C4	1.464 (4)	C8—H8A	0.9300
N2—C3	1.377 (5)	C9—H9A	0.9300
N2—C1	1.337 (4)	C10—H10A	0.9300
N3—C5	1.338 (4)	C14—H14A	0.9300
N3—C11	1.390 (5)	C16—H16A	0.9300
N4—C6	1.398 (4)	C18—H18A	0.9300
N4—C5	1.325 (4)

O1—Ni1—O2	60.46 (9)	C6—C11—C10	121.9 (3)
O1—Ni1—N1	157.24 (10)	N3—C11—C10	132.3 (3)
O1—Ni1—O1ⁱ	83.59 (9)	O1—C12—O2	119.9 (3)
O1—Ni1—O2ⁱ	103.95 (10)	O1—C12—C13	122.0 (3)
O1—Ni1—N1ⁱ	93.21 (10)	O2—C12—C13	118.2 (3)
O2—Ni1—N1	98.90 (11)	C12—C13—C14	118.7 (3)
O1ⁱ—Ni1—O2	103.95 (10)	C14—C13—C18	119.4 (3)
O2—Ni1—O2ⁱ	160.54 (10)	C12—C13—C18	121.8 (3)
O2—Ni1—N1ⁱ	93.84 (11)	C13—C14—C15	120.9 (3)
O1ⁱ—Ni1—N1	93.21 (10)	C14—C15—C19	118.6 (3)
O2ⁱ—Ni1—N1	93.84 (11)	C16—C15—C19	122.0 (3)
N1—Ni1—N1ⁱ	98.01 (12)	C14—C15—C16	119.3 (3)
O1ⁱ—Ni1—O2ⁱ	60.46 (9)	C15—C16—C17	120.6 (3)
O1ⁱ—Ni1—N1ⁱ	157.24 (10)	C16—C17—C20	120.1 (3)
O2ⁱ—Ni1—N1ⁱ	98.90 (11)	C16—C17—C18	119.0 (3)
Ni1—O1—C12	83.57 (18)	C18—C17—C20	120.9 (3)
Ni1—O2—C12	96.0 (2)	C13—C18—C17	120.7 (3)
C19—O3—H3	109.00	O3—C19—O4	124.0 (4)
C20—O5—H5	109.00	O3—C19—C15	120.0 (4)
H1W—O7—H2W	91.00	O4—C19—C15	116.1 (4)
H3W—O8—H4W	103.00	O6—C20—C17	118.3 (3)
H5W—O9—H6W	94.00	O5—C20—O6	124.7 (3)
H7W—O10—H8W	116.00	O5—C20—C17	117.0 (3)
Ni1—N1—C2	127.4 (2)	N2—C1—H1A	125.00
Ni1—N1—C1	126.1 (2)	N1—C1—H1A	125.00
C1—N1—C2	106.1 (3)	N1—C2—H2A	125.00
C1—N2—C4	126.1 (3)	C3—C2—H2A	125.00
C1—N2—C3	107.9 (3)	N2—C3—H3A	127.00
C3—N2—C4	125.8 (3)	C2—C3—H3A	127.00
C5—N3—C11	108.5 (3)	N2—C4—H4B	109.00
C5—N4—C6	107.5 (3)	C5—C4—H4A	109.00
C11—N3—H3B	126.00	C5—C4—H4B	109.00
C5—N3—H3B	126.00	N2—C4—H4A	109.00
N1—C1—N2	110.8 (3)	H4A—C4—H4B	108.00
N1—C2—C3	109.4 (3)	C8—C7—H7A	122.00
N2—C3—C2	105.9 (3)	C6—C7—H7A	122.00
N2—C4—C5	113.9 (3)	C9—C8—H8A	119.00
N3—C5—N4	110.7 (3)	C7—C8—H8A	119.00
N3—C5—C4	124.9 (3)	C10—C9—H9A	119.00
N4—C5—C4	124.3 (3)	C8—C9—H9A	119.00
N4—C6—C7	131.2 (3)	C9—C10—H10A	122.00
C7—C6—C11	121.3 (3)	C11—C10—H10A	122.00
N4—C6—C11	107.5 (3)	C13—C14—H14A	120.00
C6—C7—C8	116.5 (4)	C15—C14—H14A	120.00
C7—C8—C9	122.2 (4)	C17—C16—H16A	120.00
C8—C9—C10	121.5 (4)	C15—C16—H16A	120.00
C9—C10—C11	116.6 (4)	C13—C18—H18A	120.00
N3—C11—C6	105.8 (3)	C17—C18—H18A	120.00

O2—Ni1—O1—C12	1.55 (17)	C5—N4—C6—C11	0.7 (3)
N1—Ni1—O1—C12	−25.5 (3)	N1—C2—C3—N2	−0.6 (4)
O1ⁱ—Ni1—O1—C12	−108.47 (18)	N2—C4—C5—N3	−99.5 (4)
O2ⁱ—Ni1—O1—C12	−165.85 (18)	N2—C4—C5—N4	84.7 (4)
N1ⁱ—Ni1—O1—C12	94.15 (19)	N4—C6—C7—C8	177.7 (4)
O1—Ni1—O2—C12	−1.55 (17)	C11—C6—C7—C8	−0.6 (5)
N1—Ni1—O2—C12	168.19 (19)	N4—C6—C11—N3	−0.2 (3)
O1ⁱ—Ni1—O2—C12	72.61 (19)	N4—C6—C11—C10	−179.1 (3)
N1ⁱ—Ni1—O2—C12	−93.1 (2)	C7—C6—C11—N3	178.5 (3)
O1—Ni1—N1—C1	−101.9 (3)	C7—C6—C11—C10	−0.4 (5)
O1—Ni1—N1—C2	70.1 (4)	C6—C7—C8—C9	1.2 (6)
O2—Ni1—N1—C1	−125.5 (3)	C7—C8—C9—C10	−0.9 (7)
O2—Ni1—N1—C2	46.5 (3)	C8—C9—C10—C11	−0.1 (6)
O1ⁱ—Ni1—N1—C1	−20.8 (3)	C9—C10—C11—N3	−177.8 (4)
O1ⁱ—Ni1—N1—C2	151.2 (3)	C9—C10—C11—C6	0.8 (6)
O2ⁱ—Ni1—N1—C1	39.8 (3)	O1—C12—C13—C14	166.0 (3)
O2ⁱ—Ni1—N1—C2	−148.3 (3)	O1—C12—C13—C18	−16.9 (5)
N1ⁱ—Ni1—N1—C1	139.4 (3)	O2—C12—C13—C14	−14.5 (4)
N1ⁱ—Ni1—N1—C2	−48.7 (3)	O2—C12—C13—C18	162.6 (3)
Ni1—O1—C12—O2	−2.5 (3)	C12—C13—C14—C15	178.4 (3)
Ni1—O1—C12—C13	177.0 (3)	C18—C13—C14—C15	1.2 (5)
Ni1—O2—C12—O1	2.8 (3)	C12—C13—C18—C17	−176.1 (3)
Ni1—O2—C12—C13	−176.7 (2)	C14—C13—C18—C17	1.0 (5)
Ni1—N1—C1—N2	173.3 (2)	C13—C14—C15—C16	−2.1 (5)
C2—N1—C1—N2	−0.1 (4)	C13—C14—C15—C19	178.3 (3)
Ni1—N1—C2—C3	−172.8 (2)	C14—C15—C16—C17	0.7 (5)
C1—N1—C2—C3	0.4 (4)	C19—C15—C16—C17	−179.7 (3)
C3—N2—C1—N1	−0.3 (4)	C14—C15—C19—O3	0.9 (6)
C4—N2—C1—N1	−175.6 (3)	C14—C15—C19—O4	−179.1 (4)
C1—N2—C3—C2	0.5 (4)	C16—C15—C19—O3	−178.7 (4)
C4—N2—C3—C2	175.9 (3)	C16—C15—C19—O4	1.3 (6)
C1—N2—C4—C5	−91.3 (4)	C15—C16—C17—C18	1.4 (4)
C3—N2—C4—C5	94.2 (4)	C15—C16—C17—C20	−175.7 (3)
C11—N3—C5—N4	0.9 (4)	C16—C17—C18—C13	−2.3 (4)
C11—N3—C5—C4	−175.4 (3)	C20—C17—C18—C13	174.8 (3)
C5—N3—C11—C6	−0.4 (3)	C16—C17—C20—O5	−5.8 (5)
C5—N3—C11—C10	178.3 (4)	C16—C17—C20—O6	172.5 (3)
C6—N4—C5—N3	−1.0 (4)	C18—C17—C20—O5	177.2 (3)
C6—N4—C5—C4	175.3 (3)	C18—C17—C20—O6	−4.5 (5)
C5—N4—C6—C7	−177.7 (3)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H1W···O10	0.85	2.09	2.936 (7)	170
O7—H2W···O6ⁱⁱ	0.85	1.96	2.802 (4)	172
O3—H3···O7ⁱⁱⁱ	0.82	2.04	2.782 (5)	150
N3—H3B···O8^iv	0.86	1.95	2.780 (5)	162
O8—H3W···O1^v	0.85	2.05	2.866 (4)	161
O8—H4W···O7	0.85	2.14	2.915 (5)	151
O5—H5···N4^vi	0.82	1.77	2.586 (4)	172
O9—H5W···O3^vii	0.85	2.28	3.133 (5)	180
O9—H6W···O6ⁱ	0.85	2.05	2.791 (5)	146
O10—H7W···O4	0.85	1.73	2.579 (7)	173
C1—H1A···O5^vii	0.93	2.56	3.320 (4)	139
C3—H3A···O4^v	0.93	2.46	3.078 (5)	124
C4—H4A···O2^viii	0.97	2.49	2.895 (4)	105
C4—H4A···O1^ix	0.97	2.55	3.479 (4)	160

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

Experimental details

Crystal data
Chemical formula	[Ni(C₉H₅O₆)₂(C₁₁H₁₀N₄)₂]·8H₂O
M_r	1017.56
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	20.623 (4), 14.626 (3), 15.471 (3)
β (°)	104.03 (3)
V (Å³)	4527.2 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.52
Crystal size (mm)	0.19 × 0.17 × 0.12

Data collection
Diffractometer	Rigaku Saturn diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2004)
T_min, T_max	0.908, 0.940
No. of measured, independent and observed [I > 2σ(I)] reflections	16185, 4215, 3719
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.172, 1.13
No. of reflections	4215
No. of parameters	314
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.67, −0.47

Computer programs: CrystalClear (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010).

Selected bond lengths (Å) top

Ni1—O1	2.299 (2)	O1—C12	1.264 (4)
Ni1—O2	2.023 (2)	O2—C12	1.265 (4)
Ni1—N1	2.025 (3)	O3—C19	1.231 (5)
Ni1—O1ⁱ	2.299 (2)	O4—C19	1.285 (5)
Ni1—O2ⁱ	2.023 (2)	O5—C20	1.260 (5)
Ni1—N1ⁱ	2.025 (3)	O6—C20	1.241 (5)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H1W···O10	0.85	2.09	2.936 (7)	170
O7—H2W···O6ⁱⁱ	0.85	1.96	2.802 (4)	172
O3—H3···O7ⁱⁱⁱ	0.82	2.04	2.782 (5)	150
N3—H3B···O8^iv	0.86	1.95	2.780 (5)	162
O8—H3W···O1^v	0.85	2.05	2.866 (4)	161
O8—H4W···O7	0.85	2.14	2.915 (5)	151
O5—H5···N4^vi	0.82	1.77	2.586 (4)	172
O9—H5W···O3^vii	0.85	2.28	3.133 (5)	180
O9—H6W···O6ⁱ	0.85	2.05	2.791 (5)	146
O10—H7W···O4	0.85	1.73	2.579 (7)	173
C1—H1A···O5^vii	0.93	2.56	3.320 (4)	139
C3—H3A···O4^v	0.93	2.46	3.078 (5)	124
C4—H4A···O1^viii	0.97	2.55	3.479 (4)	160

Acknowledgements

This study was supported by the Science and Technology Department of Henan Province (082102330003).

References

Hu, J.-S., Huang, L.-F., Yao, X.-Q., Qin, L., Li, Y.-Z., Guo, Z.-J., Zheng, H.-G. & Xue, Z.-L. (2011). Inorg. Chem. 50, 2404–2414. Web of Science CSD CrossRef CAS PubMed Google Scholar
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