Diaqua­bis(2,2′-bi-1H-imidazole-κ2N3,N3′)nickel(II) bis­(3-methyl­benzoate) 3-methyl­benzoic acid disolvate

Hui, Z.

doi:10.1107/S1600536809044705

metal-organic compounds

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Volume 65| Part 12| December 2009| Page m1497

doi:10.1107/S1600536809044705

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Diaquabis(2,2′-bi-1H-imidazole-κ²N³,N^3′)nickel(II) bis(3-methylbenzoate) 3-methylbenzoic acid disolvate

Zhou Hui ^a ^*

^aCollege of Chemistry and Chemical Engineering, Henan University, Kaifeng 475001, People's Republic of China
^*Correspondence e-mail: hedazhouhui@163.com

(Received 14 October 2009; accepted 27 October 2009; online 4 November 2009)

In the title compound, [Ni(C₆H₆N₄)₂(H₂O)₂](C₈H₇O₂)₂·2C₈H₈O₂, the Ni^II atom (site symmetry $[\overline{1}]$ ) is coordinated by two N,N′-bidentate 2,2′-biimidazole ligands and two water molecules, resulting in a slightly distorted trans-NiO₂N₄ geometry for the metal ion. In the crystal, the components are linked by N—H⋯O and O—H⋯O hydrogen bonds, generating an infinite two-dimensional network running parallel to (100). The methyl group of the benzoic acid molecule is disordered over two sites in a 0.563 (17):0.437 (17) ratio.

Related literature

For a related structure, see: Yang et al. (2009 ).

Experimental

Crystal data

[Ni(C₆H₆N₄)₂(H₂O)₂](C₈H₇O₂)₂·2C₈H₈O₂
M_r = 905.60
Monoclinic, C 2/c
a = 34.747 (15) Å
b = 9.237 (4) Å
c = 14.099 (6) Å
β = 93.564 (8)°
V = 4516 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.50 mm⁻¹
T = 296 K
0.25 × 0.19 × 0.13 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.886, T_max = 0.939
12088 measured reflections
4417 independent reflections
2926 reflections with I > 2σ(I)
R_int = 0.057

Refinement

R[F² > 2σ(F²)] = 0.091
wR(F²) = 0.269
S = 1.00
4417 reflections
287 parameters
12 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 2.27 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Selected bond lengths (Å)

Ni1—N1	2.092 (3)
Ni1—N4	2.097 (3)
Ni1—O1W	2.105 (3)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4⋯O2ⁱ	0.852 (8)	1.759 (9)	2.606 (4)	172 (3)
O1W—H1WB⋯O3	0.849 (7)	2.094 (10)	2.897 (4)	158 (2)
O1W—H1WA⋯O1	0.847 (7)	1.819 (8)	2.649 (3)	166 (2)
N3—H3A⋯O2ⁱⁱ	0.890 (9)	1.920 (12)	2.763 (3)	157 (2)
N2—H2A⋯O1ⁱⁱ	0.889 (8)	1.854 (9)	2.732 (3)	169.4 (19)
Symmetry codes: (i) x, y-1, z; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809044705/hb5141sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809044705/hb5141Isup2.hkl

checkCIF report

Comment top

2,2'-Biimidazole is an interesting ligand because it has two N sites and two –NH donors. Both N-donors having the stronger coordination ability and flexible coordination modes. Moreover, two –NH donors can interact with other hydrogen bonding acceptors via hydrogen bonds (Yang et al., 2009). Herein, we report the title compound, (I).

In the symmetric unit of (I), Ni²⁺ having an inversion centre is coordinated by two water molecules occupied the axial sites and two 2,2'-biimidazole ligands through respective two N atoms occupied the equatorial plane, which results in a more regular octahedron (Ni1—N1 2.092 (3) Å; Ni1—N4 2.097 (3) Å; Ni1—O1W 2.105 (3) Å). Each water molecule interacts with 3-methyl-benzenecarboxylate and 3-methyl-benzenecarboxylic acid through O1W—H1WA···O1 and O1W—H1WA···O3 hydrogen bonds (Fig. 1). Adjacent units are linked together by two pairs of N2—H2A···O1 and N3—H3A···O1, and one O4—H4···O2 hydrogen bonds into an infinite two-dimensional network along the (100) direction (Fig. 2).

Related literature top

For a related structure, see: Yang et al. (2009).

Experimental top

NiSO₄.6H₂O(0.18 g, 0.70 mmol) was added into the aqueous solution (15 ml) including 3-methyl-benzenecarboxylic acid (0.14 g, 1.0 mmol) and NaOH (0.04 g, 1.0 mmol) and refluxed for 30 min. Then an ethanol solution (10 ml) containing 2,2'-biimidazole (0.08 g, 0.60 mmol) was slowly added with continuous stirring. The resulting solution was refluxed for 3 h, filtered and kept for crystallization. After nine days, green blocks of (I) were obtained.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. Molecular structure of (I), showing displacement ellipsoids drawn at the 30% probability level. H-bonds are shown as dashed lines. Disordered part of C22' and H atoms not involved in the hydrogen bonds have been omitted for the clarity. Unlabeled atoms are related to labeled atoms by the symmetry transformation 1/2 - x, 1/2 - y, -z.
	Fig. 2. Part of the crystal structure of (I), showing the formation of the two-dimensional network along the (100) direction. Hydrogen bonds are shown as dashed lines. Disordered part of C22' and H atoms not involved in the hydrogen bonds have been omitted for the clarity.

Diaquabis(2,2'-bi-1H-imidazole-κ²N³,N^3')nickel(II) bis(3-methylbenzoate) 3-methylbenzoic acid disolvate top

Crystal data top

[Ni(C₆H₆N₄)₂(H₂O)₂](C₈H₇O₂)₂·2C₈H₈O₂	F(000) = 1896
M_r = 905.60	D_x = 1.332 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2285 reflections
a = 34.747 (15) Å	θ = 2.3–22.7°
b = 9.237 (4) Å	µ = 0.50 mm⁻¹
c = 14.099 (6) Å	T = 296 K
β = 93.564 (8)°	Block, green
V = 4516 (3) Å³	0.25 × 0.19 × 0.13 mm
Z = 4

Data collection top

Bruker SMART APEX CCD diffractometer	4417 independent reflections
Radiation source: fine-focus sealed tube	2926 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.057
0.3° wide ω exposures scans	θ_max = 26.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −41→42
T_min = 0.886, T_max = 0.939	k = −11→10
12088 measured reflections	l = −12→17

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.091	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.269	w = 1/[σ²(F_o²) + (0.1377P)² + 26.2495P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
4417 reflections	Δρ_max = 2.27 e Å⁻³
287 parameters	Δρ_min = −0.39 e Å⁻³
12 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0013 (2)

Crystal data top

[Ni(C₆H₆N₄)₂(H₂O)₂](C₈H₇O₂)₂·2C₈H₈O₂	V = 4516 (3) Å³
M_r = 905.60	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 34.747 (15) Å	µ = 0.50 mm⁻¹
b = 9.237 (4) Å	T = 296 K
c = 14.099 (6) Å	0.25 × 0.19 × 0.13 mm
β = 93.564 (8)°

Data collection top

Bruker SMART APEX CCD diffractometer	4417 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	2926 reflections with I > 2σ(I)
T_min = 0.886, T_max = 0.939	R_int = 0.057
12088 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.091	12 restraints
wR(F²) = 0.269	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.1377P)² + 26.2495P] where P = (F_o² + 2F_c²)/3
4417 reflections	Δρ_max = 2.27 e Å⁻³
287 parameters	Δρ_min = −0.39 e Å⁻³

Special details top

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	Occ. (<1)
Ni1	0.2500	0.2500	0.0000	0.03434 (15)
N1	0.23426 (8)	0.0763 (3)	0.08464 (19)	0.0378 (7)
N2	0.20745 (8)	0.0135 (3)	0.2167 (2)	0.0439 (8)
H2A	0.1934 (3)	0.014 (4)	0.2673 (7)	0.052 (11)*
N3	0.18763 (9)	0.3465 (3)	0.2311 (2)	0.0497 (8)
H3A	0.1819 (7)	0.2986 (18)	0.2832 (8)	0.052 (4)*
N4	0.21821 (9)	0.3628 (3)	0.0979 (2)	0.0428 (8)
O3	0.37232 (9)	0.1134 (4)	0.1108 (3)	0.0818 (11)
O4	0.40602 (10)	−0.0866 (4)	0.1032 (3)	0.0912 (13)
H4	0.3851 (3)	−0.1337 (17)	0.108 (2)	0.040 (10)*
O1W	0.29960 (7)	0.2675 (2)	0.09288 (19)	0.0485 (7)
H1WA	0.3112 (4)	0.3481 (6)	0.094 (2)	0.024 (8)*
H1WB	0.3173 (3)	0.2048 (8)	0.090 (3)	0.065 (13)*
C1	0.23884 (11)	−0.0697 (4)	0.0987 (3)	0.0453 (10)
H1	0.2515	−0.1321	0.0593	0.054*
C2	0.22193 (11)	−0.1089 (4)	0.1793 (2)	0.0455 (10)
H2	0.2206	−0.2019	0.2041	0.055*
C3	0.21533 (10)	0.1215 (4)	0.1581 (2)	0.0370 (8)
C4	0.20634 (10)	0.2754 (4)	0.1646 (3)	0.0406 (9)
C5	0.18747 (12)	0.4897 (4)	0.2047 (3)	0.0561 (11)
H5	0.1767	0.5661	0.2368	0.067*
C6	0.20573 (12)	0.4988 (4)	0.1241 (3)	0.0563 (11)
H6	0.2095	0.5839	0.0906	0.068*
C15	0.40297 (13)	0.0524 (5)	0.1077 (3)	0.0600 (12)
C16	0.44042 (13)	0.1300 (6)	0.1130 (3)	0.0694 (14)
C17	0.44083 (15)	0.2790 (6)	0.1168 (3)	0.0726 (15)
H17	0.4175	0.3279	0.1184	0.087*
C18	0.47472 (17)	0.3594 (7)	0.1183 (4)	0.1015 (19)
C19	0.5081 (2)	0.2839 (10)	0.1168 (6)	0.144 (3)
H19	0.5312	0.3347	0.1164	0.173*
C20	0.50918 (19)	0.1346 (10)	0.1159 (6)	0.138 (3)
H20	0.5328	0.0868	0.1188	0.166*
C21	0.47463 (5)	0.05430 (17)	0.11043 (11)	0.116 (3)
H21	0.4748	−0.0461	0.1053	0.140*
C22	0.47839 (5)	0.50541 (17)	0.12443 (11)	0.102 (5)*	0.437 (17)
C22'	0.46819 (5)	0.54041 (17)	0.12053 (11)	0.117 (4)*	0.563 (17)
O1	0.32801 (5)	0.53214 (17)	0.11606 (11)	0.0665 (9)
O2	0.34258 (5)	0.76257 (17)	0.10071 (11)	0.0758 (10)
C7	0.34256 (5)	0.63145 (17)	0.07347 (11)	0.0528 (11)
C8	0.36146 (5)	0.59948 (17)	−0.01813 (11)	0.0536 (11)
C9	0.37173 (5)	0.45833 (17)	−0.04007 (11)	0.0560 (11)
H9	0.3662	0.3844	0.0017	0.067*
C10	0.38992 (13)	0.4239 (6)	−0.1220 (3)	0.0663 (14)
C11	0.39556 (13)	0.5355 (7)	−0.1846 (3)	0.0798 (17)
H11	0.4069	0.5150	−0.2411	0.096*
C12	0.38518 (13)	0.6747 (7)	−0.1668 (3)	0.0777 (15)
H12	0.3887	0.7467	−0.2116	0.093*
C13	0.36927 (13)	0.7085 (5)	−0.0815 (3)	0.0660 (13)
H13	0.3639	0.8043	−0.0670	0.079*
C14	0.40365 (16)	0.2721 (6)	−0.1383 (4)	0.0880 (17)
H14A	0.4071	0.2582	−0.2047	0.132*
H14B	0.3849	0.2044	−0.1179	0.132*
H14C	0.4277	0.2566	−0.1027	0.132*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0416 (3)	0.0285 (3)	0.0337 (3)	0.0008 (3)	0.0086 (2)	0.0003 (2)
N1	0.0382 (15)	0.0335 (14)	0.0427 (15)	−0.0014 (12)	0.0097 (12)	−0.0007 (12)
N2	0.0453 (16)	0.0449 (16)	0.0422 (15)	−0.0005 (13)	0.0087 (13)	0.0048 (13)
N3	0.0542 (17)	0.0502 (16)	0.0464 (16)	0.0046 (14)	0.0160 (13)	0.0003 (14)
N4	0.0506 (16)	0.0339 (14)	0.0457 (15)	−0.0016 (13)	0.0165 (13)	−0.0025 (12)
O3	0.0574 (18)	0.069 (2)	0.120 (3)	−0.0004 (16)	0.0135 (18)	−0.0039 (19)
O4	0.070 (2)	0.069 (2)	0.135 (3)	0.0079 (18)	0.016 (2)	−0.008 (2)
O1W	0.0504 (14)	0.0431 (14)	0.0523 (14)	−0.0011 (12)	0.0068 (11)	0.0002 (11)
C1	0.054 (2)	0.0344 (17)	0.0485 (19)	0.0021 (16)	0.0121 (16)	−0.0034 (15)
C2	0.060 (2)	0.0359 (17)	0.0407 (18)	−0.0001 (16)	0.0068 (16)	0.0080 (15)
C3	0.0375 (17)	0.0382 (17)	0.0353 (16)	−0.0004 (14)	0.0028 (13)	0.0007 (14)
C4	0.0418 (18)	0.0376 (18)	0.0432 (18)	0.0012 (14)	0.0074 (14)	−0.0022 (14)
C5	0.067 (2)	0.045 (2)	0.058 (2)	0.0105 (19)	0.0118 (19)	−0.0050 (18)
C6	0.077 (3)	0.0348 (18)	0.059 (2)	0.0029 (18)	0.025 (2)	−0.0019 (17)
C15	0.058 (2)	0.068 (3)	0.055 (2)	0.001 (2)	0.0119 (19)	0.001 (2)
C16	0.050 (2)	0.105 (4)	0.054 (2)	−0.007 (2)	0.0080 (19)	−0.012 (2)
C17	0.068 (3)	0.092 (3)	0.057 (3)	−0.022 (3)	0.005 (2)	−0.006 (2)
C18	0.095 (4)	0.146 (5)	0.065 (3)	−0.057 (3)	0.020 (3)	−0.025 (3)
C19	0.076 (4)	0.233 (8)	0.126 (6)	−0.068 (5)	0.022 (4)	−0.042 (5)
C20	0.053 (3)	0.207 (8)	0.153 (7)	0.003 (5)	−0.001 (4)	−0.027 (7)
C21	0.077 (4)	0.145 (6)	0.128 (5)	0.009 (4)	0.010 (4)	−0.038 (5)
O1	0.0949 (19)	0.0607 (16)	0.0472 (14)	−0.0204 (15)	0.0307 (14)	−0.0076 (13)
O2	0.101 (2)	0.0515 (16)	0.0805 (19)	−0.0076 (16)	0.0458 (16)	−0.0024 (14)
C7	0.056 (2)	0.054 (2)	0.049 (2)	−0.0049 (19)	0.0106 (17)	−0.0028 (18)
C8	0.054 (2)	0.070 (2)	0.0381 (18)	−0.005 (2)	0.0124 (16)	0.0022 (18)
C9	0.052 (2)	0.068 (2)	0.048 (2)	−0.003 (2)	0.0063 (18)	−0.0046 (19)
C10	0.051 (2)	0.094 (3)	0.053 (2)	0.000 (2)	0.0013 (19)	−0.015 (2)
C11	0.057 (2)	0.135 (4)	0.049 (2)	0.009 (3)	0.0175 (19)	0.006 (3)
C12	0.060 (3)	0.118 (4)	0.057 (2)	0.003 (3)	0.018 (2)	0.027 (3)
C13	0.055 (2)	0.081 (3)	0.063 (2)	−0.001 (2)	0.015 (2)	0.020 (2)
C14	0.083 (3)	0.102 (4)	0.080 (3)	0.015 (3)	0.015 (3)	−0.038 (3)

Geometric parameters (Å, º) top

Ni1—N1ⁱ	2.092 (3)	C16—C21	1.381 (5)
Ni1—N1	2.092 (3)	C16—C17	1.378 (7)
Ni1—N4ⁱ	2.097 (3)	C17—C18	1.391 (7)
Ni1—N4	2.097 (3)	C17—H17	0.9300
Ni1—O1Wⁱ	2.105 (3)	C18—C19	1.354 (10)
Ni1—O1W	2.105 (3)	C18—C22	1.357 (7)
N1—C3	1.328 (4)	C18—C22'	1.688 (7)
N1—C1	1.371 (4)	C19—C20	1.380 (12)
N2—C3	1.335 (4)	C19—H19	0.9300
N2—C2	1.357 (5)	C20—C21	1.409 (8)
N2—H2A	0.889 (8)	C20—H20	0.9300
N3—C4	1.345 (5)	C21—H21	0.9300
N3—C5	1.374 (5)	O1—C7	1.2229
N3—H3A	0.890 (9)	O2—C7	1.2706
N4—C4	1.325 (4)	C7—C8	1.5138
N4—C6	1.387 (5)	C8—C13	1.384 (5)
O3—C15	1.208 (5)	C8—C9	1.3917
O4—C15	1.290 (6)	C9—C10	1.388 (5)
O4—H4	0.852 (8)	C9—H9	0.9300
O1W—H1WA	0.847 (7)	C10—C11	1.379 (7)
O1W—H1WB	0.849 (7)	C10—C14	1.503 (7)
C1—C2	1.362 (5)	C11—C12	1.362 (8)
C1—H1	0.9300	C11—H11	0.9300
C2—H2	0.9300	C12—C13	1.391 (7)
C3—C4	1.460 (5)	C12—H12	0.9300
C5—C6	1.338 (6)	C13—H13	0.9300
C5—H5	0.9300	C14—H14A	0.9600
C6—H6	0.9300	C14—H14B	0.9600
C15—C16	1.483 (6)	C14—H14C	0.9600

N1ⁱ—Ni1—N1	180.0	O3—C15—C16	123.0 (4)
N1ⁱ—Ni1—N4ⁱ	80.71 (11)	O4—C15—C16	114.2 (4)
N1—Ni1—N4ⁱ	99.29 (11)	C21—C16—C17	120.0 (4)
N1ⁱ—Ni1—N4	99.29 (11)	C21—C16—C15	120.5 (4)
N1—Ni1—N4	80.71 (11)	C17—C16—C15	119.5 (4)
N4ⁱ—Ni1—N4	180.0	C16—C17—C18	122.7 (5)
N1ⁱ—Ni1—O1Wⁱ	86.39 (10)	C16—C17—H17	118.6
N1—Ni1—O1Wⁱ	93.61 (10)	C18—C17—H17	118.6
N4ⁱ—Ni1—O1Wⁱ	89.82 (11)	C19—C18—C22	115.8 (5)
N4—Ni1—O1Wⁱ	90.18 (11)	C19—C18—C17	116.7 (7)
N1ⁱ—Ni1—O1W	93.61 (10)	C22—C18—C17	127.4 (5)
N1—Ni1—O1W	86.39 (10)	C19—C18—C22'	128.8 (5)
N4ⁱ—Ni1—O1W	90.18 (11)	C22—C18—C22'	13.21 (8)
N4—Ni1—O1W	89.82 (11)	C17—C18—C22'	114.5 (5)
O1Wⁱ—Ni1—O1W	180.0	C18—C19—C20	122.6 (7)
C3—N1—C1	104.8 (3)	C18—C19—H19	118.7
C3—N1—Ni1	111.3 (2)	C20—C19—H19	118.7
C1—N1—Ni1	143.6 (2)	C19—C20—C21	120.1 (6)
C3—N2—C2	106.7 (3)	C19—C20—H20	119.9
C3—N2—H2A	129 (2)	C21—C20—H20	119.9
C2—N2—H2A	124 (2)	C16—C21—C20	117.6 (4)
C4—N3—C5	106.0 (3)	C16—C21—H21	121.2
C4—N3—H3A	118.4 (13)	C20—C21—H21	121.2
C5—N3—H3A	134.8 (12)	O1—C7—O2	124.0
C4—N4—C6	104.3 (3)	O1—C7—C8	119.1
C4—N4—Ni1	111.4 (2)	O2—C7—C8	116.9
C6—N4—Ni1	144.3 (2)	C13—C8—C9	118.4 (2)
C15—O4—H4	115.6 (12)	C13—C8—C7	121.4 (2)
Ni1—O1W—H1WA	116.6 (14)	C9—C8—C7	120.2
Ni1—O1W—H1WB	119 (2)	C10—C9—C8	122.4 (2)
H1WA—O1W—H1WB	104.7 (10)	C10—C9—H9	118.8
C2—C1—N1	109.3 (3)	C8—C9—H9	118.8
C2—C1—H1	125.4	C11—C10—C9	116.8 (4)
N1—C1—H1	125.4	C11—C10—C14	122.7 (4)
N2—C2—C1	107.0 (3)	C9—C10—C14	120.4 (4)
N2—C2—H2	126.5	C12—C11—C10	122.6 (4)
C1—C2—H2	126.5	C12—C11—H11	118.7
N1—C3—N2	112.3 (3)	C10—C11—H11	118.7
N1—C3—C4	118.2 (3)	C11—C12—C13	119.6 (5)
N2—C3—C4	129.5 (3)	C11—C12—H12	120.2
N4—C4—N3	112.5 (3)	C13—C12—H12	120.2
N4—C4—C3	118.1 (3)	C8—C13—C12	120.0 (4)
N3—C4—C3	129.4 (3)	C8—C13—H13	120.0
C6—C5—N3	107.3 (3)	C12—C13—H13	120.0
C6—C5—H5	126.4	C10—C14—H14A	109.5
N3—C5—H5	126.4	C10—C14—H14B	109.5
C5—C6—N4	110.0 (3)	H14A—C14—H14B	109.5
C5—C6—H6	125.0	C10—C14—H14C	109.5
N4—C6—H6	125.0	H14A—C14—H14C	109.5
O3—C15—O4	122.8 (4)	H14B—C14—H14C	109.5

Symmetry code: (i) −x+1/2, −y+1/2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O2ⁱⁱ	0.85 (1)	1.76 (1)	2.606 (4)	172 (3)
O1W—H1WB···O3	0.85 (1)	2.09 (1)	2.897 (4)	158 (2)
O1W—H1WA···O1	0.85 (1)	1.82 (1)	2.649 (3)	166 (2)
N3—H3A···O2ⁱⁱⁱ	0.89 (1)	1.92 (1)	2.763 (3)	157 (2)
N2—H2A···O1ⁱⁱⁱ	0.89 (1)	1.85 (1)	2.732 (3)	169 (2)

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

Experimental details

Crystal data
Chemical formula	[Ni(C₆H₆N₄)₂(H₂O)₂](C₈H₇O₂)₂·2C₈H₈O₂
M_r	905.60
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	34.747 (15), 9.237 (4), 14.099 (6)
β (°)	93.564 (8)
V (Å³)	4516 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.50
Crystal size (mm)	0.25 × 0.19 × 0.13

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.886, 0.939
No. of measured, independent and observed [I > 2σ(I)] reflections	12088, 4417, 2926
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.091, 0.269, 1.00
No. of reflections	4417
No. of parameters	287
No. of restraints	12
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
	w = 1/[σ²(F_o²) + (0.1377P)² + 26.2495P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	2.27, −0.39

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Selected bond lengths (Å) top

Ni1—N1	2.092 (3)	Ni1—O1W	2.105 (3)
Ni1—N4	2.097 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O2ⁱ	0.852 (8)	1.759 (9)	2.606 (4)	172 (3)
O1W—H1WB···O3	0.849 (7)	2.094 (10)	2.897 (4)	158 (2)
O1W—H1WA···O1	0.847 (7)	1.819 (8)	2.649 (3)	166 (2)
N3—H3A···O2ⁱⁱ	0.890 (9)	1.920 (12)	2.763 (3)	157 (2)
N2—H2A···O1ⁱⁱ	0.889 (8)	1.854 (9)	2.732 (3)	169.4 (19)

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

References

Bruker (2001). SMART, SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yang, L. F., Cao, M. L., Mo, H. J., Hao, H. G., Wu, J. J., Zhang, J. P. & Ye, B. H. (2009). CrystEngComm, 11, 1114–1121. Web of Science CSD CrossRef CAS Google Scholar

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