μ-Biphenyl-3,3′,4,4′-tetra­carboxyl­ato-κ2O3:O3′-bis­[triaqua­(2,2′-bipyridyl-κ2N,N′)nickel(II)] hexa­hydrate

Zhou, D.; Shao, M.; He, X.; Zhao, Y.; Zhu, S.

doi:10.1107/S1600536809014639

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 5| May 2009| Pages m562-m563

doi:10.1107/S1600536809014639

Open

access

μ-Biphenyl-3,3′,4,4′-tetracarboxylato-κ²O³:O^3′-bis[triaqua(2,2′-bipyridyl-κ²N,N′)nickel(II)] hexahydrate

Dong Zhou,^a Min Shao,^b Xiang He,^b Yongmei Zhao ^b and Shourong Zhu ^a ^*

^aDepartment of Chemistry, Shanghai University, Shanghai 200444, People's Republic of China, and ^bInstrumental Analysis Center, Shanghai University, Shanghai 200444, People's Republic of China
^*Correspondence e-mail: shourongzhu@shu.edu.cn

(Received 13 March 2009; accepted 20 April 2009; online 25 April 2009)

The asymmetric unit of the title complex, [Ni₂(C₁₆H₆O₈)(C₁₀H₈N₂)₂(H₂O)₆]·6H₂O, contains one Ni^II atom, one 2,2′-bipyridine ligand, three coordinated water molecules, one-half of a fully deprotonated biphenyl-3,3′,4,4′-tetracarboxylate anion and three lattice water molecules. The Ni^II atom displays a distorted NiN₂O₄ octahedral coordination formed by one carboxylate O atom, three water O atoms and two N atoms of the chelating ligand. The complete biphenyl-3,3′,4,4′-tetracarboxylate ligand displays inversion symmetry and links two symmetry-related Ni^II atoms into a binuclear complex. Neighbouring complex molecules are linked through O—H⋯O hydrogen bonds into a three-dimensional structure. Additional O—H⋯O hydrogen bonds between the lattice water molecules help to consolidate the crystal packing.

Related literature

For other metal complexes with biphenyl-3,3′,4,4′-tetracarboxylate as ligand, see: Hao et al. (2005 ); Wang et al. (2005 , 2006 , 2007 ). For related structures containing biphenyl-3,3′,4,4′-tetracarboxylate and neutral chelating ligands, see: Zhu et al. (2008a ,b ).

Experimental

Crystal data

[Ni₂(C₁₆H₆O₈)(C₁₀H₈N₂)₂(H₂O)₆]·6H₂O
M_r = 972.19
Triclinic, $[P \overline 1]$
a = 7.5126 (14) Å
b = 12.088 (2) Å
c = 12.285 (2) Å
α = 105.445 (2)°
β = 98.075 (2)°
γ = 92.162 (3)°
V = 1061.4 (3) Å³
Z = 1
Mo Kα radiation
μ = 0.97 mm⁻¹
T = 296 K
0.20 × 0.20 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.829, T_max = 0.868
5556 measured reflections
3698 independent reflections
2526 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.062
wR(F²) = 0.172
S = 1.05
3698 reflections
280 parameters
H-atom parameters constrained
Δρ_max = 0.61 e Å⁻³
Δρ_min = −0.53 e Å⁻³

Table 1
Selected bond lengths (Å)

Ni1—N2	2.063 (4)
Ni1—N1	2.064 (4)
Ni1—O2W	2.067 (3)
Ni1—O1	2.069 (3)
Ni1—O3W	2.075 (3)
Ni1—O1W	2.076 (4)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O4ⁱ	0.82	1.91	2.720 (5)	168
O1W—H1WB⋯O3	0.85	2.04	2.889 (5)	176
O2W—H2WA⋯O2	0.82	1.99	2.708 (5)	146
O2W—H2WB⋯O3ⁱⁱ	0.84	2.06	2.715 (5)	135
O3W—H3WA⋯O3ⁱ	0.85	1.88	2.723 (5)	168
O3W—H3WB⋯O4W	0.82	1.97	2.793 (6)	178
O4W—H4WA⋯O2ⁱⁱⁱ	0.87	1.87	2.715 (6)	164
O4W—H4WB⋯O5W	0.85	2.22	2.803 (8)	125
O5W—H5WB⋯O6W^iv	0.83	2.18	2.770 (15)	128
O6W—H6WA⋯O2	0.85	2.44	3.091 (11)	134
O6W—H6WA⋯O2	0.85	2.44	3.091 (11)	134
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x+2, -y+1, -z+1; (iii) x-1, y, z; (iv) -x+1, -y, -z.

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2006 ) and ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809014639/wm2225sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809014639/wm2225Isup2.hkl

checkCIF report

Comment top

Coordination compounds of biphenyl-3,3',4,4'-tetracarboxylic acid have been investigated previously. As expected, the deprotonated ligand coordinates to metal ions in a versatile mode due to its multidentate character (Hao et al., 2005; Wang et al., 2005; 2006; 2007). Upon adding chelating ligands, such as 2,2'-bipyridine or 1,10-phenanthroline, ternary coordination polymers can be formed (Zhu et al., 2008a). In all these complexes, biphenyl-3,3',4,4'-tetracarboxylate acts as counter ion and/or multidentate ligand. Here we present the crystal structure of the dinuclear complex [Ni₂(C₁₀H₈N₂)₂(C₁₆H₆O₈)(H₂O)₆]^.6H₂O, (I).

The unique Ni atom in the structure of complex (I) (Fig. 1) is in a distorted octahedral coordination sphere formed by one carboxylate O, three water O and two N atoms with Ni—O and Ni—N bond lengths in the range 2.063 (4) Å - 2.076 (4) Å with σ=0.87 (Zhu et al., 2008b). The fully deprotonated biphenyl-3,3',4,4'-tetracarboxylate ligand displays inversion symmetry and links two symmetry-related Ni^II atoms. Due to symmetric reason, the two benzene rings of the biphenyl ligand are coplanar. The two pyridine rings in the 2,2'-bipyridine molecule have a torsion angle of 4.7 (8)°. The carboxylate group that coordinate to nickel is almost coplanar with the benzene ring (torsion angle 8.6 (8)°), while the free carboxylate has a torsion angle of 72.2 (7)° with the benzene ring which is almost perpendicular each other. The intramolecular distance between the two nickel(II) ions is 14.788 (11) Å.

As expected, there are considerable hydrogen bonds in the structure. Table 2 lists bond distances and angles. These H-bonds link dinuclear complex together to a three-dimensional structure (Fig 2.). The uncoordinated crystal lattice water molecules interact through additional hydrogen bonds, as shown in Fig. 3, and thus help to consolidate the crystal packing.

Related literature top

For other metal complexes with biphenyl-3,3',4,4'-tetracarboxylate as ligand, see: Hao et al. (2005); Wang et al. (2005, 2006, 2007). For related structures containing biphenyl-3,3',4,4'-tetracarboxylate and neutral chelating ligands, see: Zhu et al. (2008a,b).

Experimental top

A mixture of biphenyl-3,3',4,4'-tetracarboxylic acid dianhydride (0.5 mmol), 2,2'-bipyridine (0.5 mmol), NaOH (2 mmol) and Ni(NO₃)₂ (1 mmol) in 8 ml H₂O was placed in a 25 ml Teflon reactor, which was sealed and heated in a oven at 433 K for 72 h. Then the autoclave was cooled to room temperature at the rate of 10 K to get light-blue flat crystals of the title compound (in ca 85% yield based on biphenyltetracarboxylic dianhydride). The crystals were isolated by filtration and washed with water.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2006) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit in the structure of complex (I), displayed with ellipsoids at the 50% probability level. Dashed lines represent hydrogen bonds.
	Fig. 2. Crystal packing in the crystal structure of compound (I) viewed down the a axis with ellipsoids ath the 30% probability level.
	Fig. 3. (a) The π—π interaction between adjacent 2, 2'-bipyridine molecules. (b) The crystal lattice water molecules arranged in chains via H -bonds; other atoms are omitted for clarity.

µ-Biphenyl-3,3',4,4'-tetracarboxylato-κ²O³:O^3'- bis[triaqua(2,2'-bipyridyl-κ²N,N')nickel(II)] hexahydrate top

Crystal data top

[Ni₂(C₁₆H₆O₈)(C₁₀H₈N₂)₂(H₂O)₆]·6H₂O	Z = 1
M_r = 972.19	F(000) = 506
Triclinic, P1	D_x = 1.521 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5126 (14) Å	Cell parameters from 1042 reflections
b = 12.088 (2) Å	θ = 2.8–21.2°
c = 12.285 (2) Å	µ = 0.97 mm⁻¹
α = 105.445 (2)°	T = 296 K
β = 98.075 (2)°	Flat, light-blue
γ = 92.162 (3)°	0.20 × 0.20 × 0.15 mm
V = 1061.4 (3) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	3698 independent reflections
Radiation source: fine-focus sealed tube	2526 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ϕ and ω scans	θ_max = 25.1°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −8→8
T_min = 0.829, T_max = 0.868	k = −11→14
5556 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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.172	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0835P)² + 0.0076P]
3698 reflections	(Δ/σ)_max < 0.001
280 parameters	Δρ_max = 0.61 e Å⁻³
0 restraints	Δρ_min = −0.53 e Å⁻³

Crystal data top

[Ni₂(C₁₆H₆O₈)(C₁₀H₈N₂)₂(H₂O)₆]·6H₂O	γ = 92.162 (3)°
M_r = 972.19	V = 1061.4 (3) Å³
Triclinic, P1	Z = 1
a = 7.5126 (14) Å	Mo Kα radiation
b = 12.088 (2) Å	µ = 0.97 mm⁻¹
c = 12.285 (2) Å	T = 296 K
α = 105.445 (2)°	0.20 × 0.20 × 0.15 mm
β = 98.075 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3698 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	2526 reflections with I > 2σ(I)
T_min = 0.829, T_max = 0.868	R_int = 0.037
5556 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	0 restraints
wR(F²) = 0.172	H-atom parameters constrained
S = 1.05	Δρ_max = 0.61 e Å⁻³
3698 reflections	Δρ_min = −0.53 e Å⁻³
280 parameters

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 F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > σ(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ 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	0.76324 (9)	0.27456 (6)	0.46907 (5)	0.0292 (2)
C1	0.8729 (8)	0.3451 (5)	0.2678 (4)	0.0353 (13)
C2	0.8455 (7)	0.4289 (4)	0.1965 (4)	0.0279 (12)
C3	0.7072 (7)	0.5022 (4)	0.2062 (4)	0.0271 (11)
C4	0.6778 (8)	0.5682 (5)	0.1309 (5)	0.0390 (14)
H4	0.5816	0.6146	0.1345	0.047*
C5	0.7894 (8)	0.5668 (5)	0.0497 (5)	0.0439 (16)
H5	0.7662	0.6122	−0.0002	0.053*
C6	0.9365 (7)	0.4985 (4)	0.0411 (4)	0.0294 (12)
C7	0.9582 (7)	0.4283 (4)	0.1148 (4)	0.0325 (13)
H7	1.0511	0.3793	0.1095	0.039*
C8	0.5935 (8)	0.5223 (4)	0.3010 (5)	0.0319 (13)
C9	0.7786 (9)	0.2720 (6)	0.7187 (5)	0.0498 (16)
H9	0.7915	0.3519	0.7363	0.060*
C10	0.7713 (11)	0.2212 (7)	0.8067 (6)	0.071 (2)
H10	0.7805	0.2658	0.8820	0.086*
C11	0.7506 (12)	0.1055 (7)	0.7801 (7)	0.078 (2)
H11	0.7430	0.0692	0.8374	0.093*
C12	0.7407 (10)	0.0414 (6)	0.6699 (6)	0.064 (2)
H12	0.7271	−0.0385	0.6516	0.077*
C13	0.7509 (7)	0.0962 (5)	0.5854 (5)	0.0384 (14)
C14	0.7468 (7)	0.0348 (5)	0.4639 (5)	0.0362 (13)
C15	0.7461 (9)	−0.0842 (5)	0.4239 (6)	0.0596 (19)
H15	0.7454	−0.1292	0.4745	0.072*
C16	0.7463 (11)	−0.1351 (6)	0.3104 (7)	0.075 (2)
H16	0.7468	−0.2147	0.2837	0.091*
C17	0.7460 (10)	−0.0692 (6)	0.2371 (6)	0.070 (2)
H17	0.7472	−0.1023	0.1597	0.084*
C18	0.7437 (8)	0.0492 (5)	0.2803 (5)	0.0490 (16)
H18	0.7395	0.0946	0.2297	0.059*
N1	0.7680 (6)	0.2112 (4)	0.6097 (4)	0.0375 (11)
N2	0.7472 (6)	0.1002 (4)	0.3901 (4)	0.0333 (10)
O1	0.7508 (5)	0.3349 (3)	0.3258 (3)	0.0327 (9)
O2	1.0074 (6)	0.2870 (4)	0.2630 (4)	0.0519 (12)
O3	0.6703 (5)	0.5796 (3)	0.3995 (3)	0.0357 (9)
O4	0.4305 (5)	0.4876 (3)	0.2757 (3)	0.0414 (10)
O1W	0.7793 (5)	0.4475 (3)	0.5584 (3)	0.0378 (9)
H1WA	0.7075	0.4576	0.6039	0.045*
H1WB	0.7528	0.4864	0.5108	0.045*
O2W	1.0407 (5)	0.2754 (3)	0.4820 (3)	0.0366 (9)
H2WA	1.0698	0.2647	0.4183	0.044*
H2WB	1.0810	0.3312	0.5383	0.044*
O3W	0.4835 (5)	0.2653 (3)	0.4440 (3)	0.0372 (9)
H3WA	0.4238	0.3141	0.4852	0.045*
H3WB	0.4455	0.2638	0.3776	0.045*
O4W	0.3480 (6)	0.2550 (4)	0.2175 (4)	0.0662 (13)
H4WA	0.2365	0.2698	0.2201	0.079*
H4WB	0.3472	0.2363	0.1454	0.079*
O5W	0.3527 (11)	0.0578 (6)	0.0358 (6)	0.141 (3)
H5WA	0.4255	0.1162	0.0371	0.169*
H5WB	0.3141	−0.0088	−0.0025	0.169*
O6W	0.9624 (19)	0.0848 (9)	0.0429 (9)	0.288 (7)
H6WA	0.9844	0.1042	0.1156	0.345*
H6WB	0.9808	0.1578	0.0631	0.345*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0322 (4)	0.0294 (4)	0.0321 (4)	0.0051 (3)	0.0127 (3)	0.0145 (3)
C1	0.038 (3)	0.042 (3)	0.033 (3)	0.006 (3)	0.016 (3)	0.015 (3)
C2	0.028 (3)	0.033 (3)	0.027 (3)	0.006 (2)	0.012 (2)	0.012 (2)
C3	0.030 (3)	0.028 (3)	0.026 (3)	0.004 (2)	0.014 (2)	0.008 (2)
C4	0.038 (3)	0.048 (4)	0.041 (3)	0.019 (3)	0.023 (3)	0.019 (3)
C5	0.047 (4)	0.056 (4)	0.047 (4)	0.016 (3)	0.022 (3)	0.036 (3)
C6	0.034 (3)	0.036 (3)	0.023 (3)	0.007 (2)	0.015 (2)	0.012 (2)
C7	0.038 (3)	0.037 (3)	0.032 (3)	0.013 (3)	0.017 (2)	0.019 (2)
C8	0.038 (3)	0.027 (3)	0.038 (3)	0.009 (2)	0.018 (3)	0.015 (2)
C9	0.061 (4)	0.049 (4)	0.042 (4)	0.002 (3)	0.011 (3)	0.017 (3)
C10	0.098 (6)	0.083 (6)	0.038 (4)	0.000 (5)	0.012 (4)	0.025 (4)
C11	0.118 (7)	0.074 (6)	0.056 (5)	−0.004 (5)	0.015 (5)	0.044 (4)
C12	0.091 (6)	0.059 (5)	0.055 (5)	0.005 (4)	0.014 (4)	0.038 (4)
C13	0.034 (3)	0.039 (3)	0.046 (4)	0.000 (3)	0.004 (3)	0.018 (3)
C14	0.029 (3)	0.029 (3)	0.053 (4)	0.002 (2)	0.007 (3)	0.016 (3)
C15	0.066 (5)	0.041 (4)	0.077 (5)	0.003 (3)	−0.003 (4)	0.031 (4)
C16	0.111 (7)	0.037 (4)	0.069 (5)	0.010 (4)	0.000 (5)	0.005 (4)
C17	0.086 (6)	0.057 (5)	0.058 (5)	0.007 (4)	0.017 (4)	−0.003 (4)
C18	0.063 (4)	0.046 (4)	0.038 (4)	0.009 (3)	0.012 (3)	0.009 (3)
N1	0.038 (3)	0.043 (3)	0.038 (3)	0.011 (2)	0.012 (2)	0.017 (2)
N2	0.031 (3)	0.034 (3)	0.037 (3)	0.004 (2)	0.008 (2)	0.013 (2)
O1	0.037 (2)	0.038 (2)	0.032 (2)	0.0107 (17)	0.0208 (17)	0.0162 (17)
O2	0.051 (3)	0.065 (3)	0.065 (3)	0.036 (2)	0.039 (2)	0.042 (2)
O3	0.038 (2)	0.039 (2)	0.029 (2)	0.0016 (18)	0.0134 (17)	0.0021 (17)
O4	0.031 (2)	0.054 (3)	0.039 (2)	0.0020 (19)	0.0156 (18)	0.0096 (19)
O1W	0.043 (2)	0.039 (2)	0.040 (2)	0.0053 (18)	0.0209 (18)	0.0157 (18)
O2W	0.033 (2)	0.044 (2)	0.036 (2)	0.0058 (18)	0.0107 (17)	0.0136 (18)
O3W	0.033 (2)	0.045 (2)	0.039 (2)	0.0084 (18)	0.0172 (18)	0.0134 (18)
O4W	0.048 (3)	0.075 (3)	0.071 (3)	0.005 (2)	0.015 (2)	0.009 (3)
O5W	0.189 (8)	0.116 (6)	0.113 (6)	0.008 (5)	0.038 (5)	0.019 (5)
O6W	0.42 (2)	0.237 (14)	0.165 (11)	−0.049 (13)	0.054 (12)	−0.011 (9)

Geometric parameters (Å, º) top

Ni1—N2	2.063 (4)	C11—H11	0.9300
Ni1—N1	2.064 (4)	C12—C13	1.380 (8)
Ni1—O2W	2.067 (3)	C12—H12	0.9300
Ni1—O1	2.069 (3)	C13—N1	1.340 (7)
Ni1—O3W	2.075 (3)	C13—C14	1.475 (8)
Ni1—O1W	2.076 (4)	C14—N2	1.352 (7)
C1—O2	1.252 (6)	C14—C15	1.390 (8)
C1—O1	1.259 (6)	C15—C16	1.366 (9)
C1—C2	1.508 (7)	C15—H15	0.9300
C2—C3	1.388 (7)	C16—C17	1.351 (10)
C2—C7	1.400 (6)	C16—H16	0.9300
C3—C4	1.375 (7)	C17—C18	1.390 (8)
C3—C8	1.513 (7)	C17—H17	0.9300
C4—C5	1.387 (7)	C18—N2	1.322 (7)
C4—H4	0.9300	C18—H18	0.9300
C5—C6	1.403 (7)	O1W—H1WA	0.8201
C5—H5	0.9300	O1W—H1WB	0.8498
C6—C7	1.394 (7)	O2W—H2WA	0.8201
C6—C6ⁱ	1.489 (9)	O2W—H2WB	0.8379
C7—H7	0.9300	O3W—H3WA	0.8542
C8—O4	1.248 (6)	O3W—H3WB	0.8200
C8—O3	1.266 (6)	O4W—H4WA	0.8664
C9—N1	1.334 (7)	O4W—H4WB	0.8528
C9—C10	1.384 (8)	O5W—H5WA	0.8722
C9—H9	0.9300	O5W—H5WB	0.8339
C10—C11	1.347 (9)	O6W—H6WA	0.8500
C10—H10	0.9300	O6W—H6WB	0.8500
C11—C12	1.359 (10)

N2—Ni1—N1	80.00 (17)	C9—C10—H10	120.9
N2—Ni1—O2W	88.41 (16)	C10—C11—C12	120.3 (6)
N1—Ni1—O2W	91.05 (16)	C10—C11—H11	119.9
N2—Ni1—O1	98.95 (15)	C12—C11—H11	119.9
N1—Ni1—O1	178.17 (17)	C11—C12—C13	119.4 (7)
O2W—Ni1—O1	90.43 (14)	C11—C12—H12	120.3
N2—Ni1—O3W	88.32 (16)	C13—C12—H12	120.3
N1—Ni1—O3W	91.12 (16)	N1—C13—C12	121.3 (6)
O2W—Ni1—O3W	175.71 (14)	N1—C13—C14	115.0 (5)
O1—Ni1—O3W	87.34 (14)	C12—C13—C14	123.7 (6)
N2—Ni1—O1W	176.34 (15)	N2—C14—C15	119.8 (6)
N1—Ni1—O1W	96.33 (16)	N2—C14—C13	116.8 (5)
O2W—Ni1—O1W	91.76 (15)	C15—C14—C13	123.4 (5)
O1—Ni1—O1W	84.71 (14)	C16—C15—C14	120.2 (6)
O3W—Ni1—O1W	91.67 (14)	C16—C15—H15	119.9
O2—C1—O1	123.8 (5)	C14—C15—H15	119.9
O2—C1—C2	119.8 (4)	C17—C16—C15	119.6 (7)
O1—C1—C2	116.3 (5)	C17—C16—H16	120.2
C3—C2—C7	119.6 (4)	C15—C16—H16	120.2
C3—C2—C1	121.8 (4)	C16—C17—C18	118.4 (7)
C7—C2—C1	118.6 (4)	C16—C17—H17	120.8
C4—C3—C2	119.0 (4)	C18—C17—H17	120.8
C4—C3—C8	116.6 (4)	N2—C18—C17	122.8 (6)
C2—C3—C8	124.2 (4)	N2—C18—H18	118.6
C3—C4—C5	121.1 (5)	C17—C18—H18	118.6
C3—C4—H4	119.5	C9—N1—C13	118.1 (5)
C5—C4—H4	119.5	C9—N1—Ni1	127.2 (4)
C4—C5—C6	121.6 (5)	C13—N1—Ni1	114.7 (4)
C4—C5—H5	119.2	C18—N2—C14	119.1 (5)
C6—C5—H5	119.2	C18—N2—Ni1	127.5 (4)
C7—C6—C5	116.1 (4)	C14—N2—Ni1	113.3 (4)
C7—C6—C6ⁱ	121.8 (6)	C1—O1—Ni1	129.2 (3)
C5—C6—C6ⁱ	122.1 (6)	Ni1—O1W—H1WA	109.6
C6—C7—C2	122.5 (5)	Ni1—O1W—H1WB	108.5
C6—C7—H7	118.8	H1WA—O1W—H1WB	109.4
C2—C7—H7	118.8	Ni1—O2W—H2WA	109.7
O4—C8—O3	125.0 (5)	Ni1—O2W—H2WB	105.3
O4—C8—C3	118.2 (5)	H2WA—O2W—H2WB	124.6
O3—C8—C3	116.7 (5)	Ni1—O3W—H3WA	122.7
N1—C9—C10	122.8 (6)	Ni1—O3W—H3WB	109.6
N1—C9—H9	118.6	H3WA—O3W—H3WB	105.8
C10—C9—H9	118.6	H4WA—O4W—H4WB	100.3
C11—C10—C9	118.1 (7)	H5WA—O5W—H5WB	143.0
C11—C10—H10	120.9	H6WA—O6W—H6WB	74.3

Symmetry code: (i) −x+2, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O4ⁱⁱ	0.82	1.91	2.720 (5)	168
O1W—H1WB···O3	0.85	2.04	2.889 (5)	176
O2W—H2WA···O2	0.82	1.99	2.708 (5)	146
O2W—H2WB···O3ⁱⁱⁱ	0.84	2.06	2.715 (5)	135
O3W—H3WA···O3ⁱⁱ	0.85	1.88	2.723 (5)	168
O3W—H3WB···O4W	0.82	1.97	2.793 (6)	178
O4W—H4WA···O2^iv	0.87	1.87	2.715 (6)	164
O4W—H4WB···O5W	0.85	2.22	2.803 (8)	125
O5W—H5WB···O6W^v	0.83	2.18	2.770 (15)	128
O6W—H6WA···O2	0.85	2.44	3.091 (11)	134
O6W—H6WA···O2	0.85	2.44	3.091 (11)	134

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

Experimental details

Crystal data
Chemical formula	[Ni₂(C₁₆H₆O₈)(C₁₀H₈N₂)₂(H₂O)₆]·6H₂O
M_r	972.19
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	7.5126 (14), 12.088 (2), 12.285 (2)
α, β, γ (°)	105.445 (2), 98.075 (2), 92.162 (3)
V (Å³)	1061.4 (3)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.97
Crystal size (mm)	0.20 × 0.20 × 0.15

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.829, 0.868
No. of measured, independent and observed [I > 2σ(I)] reflections	5556, 3698, 2526
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.172, 1.05
No. of reflections	3698
No. of parameters	280
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.61, −0.53

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2006) and ORTEP-3 for Windows (Farrugia, 1997), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Ni1—N2	2.063 (4)	Ni1—O1	2.069 (3)
Ni1—N1	2.064 (4)	Ni1—O3W	2.075 (3)
Ni1—O2W	2.067 (3)	Ni1—O1W	2.076 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O4ⁱ	0.82	1.91	2.720 (5)	167.6
O1W—H1WB···O3	0.85	2.04	2.889 (5)	175.8
O2W—H2WA···O2	0.82	1.99	2.708 (5)	145.6
O2W—H2WB···O3ⁱⁱ	0.84	2.06	2.715 (5)	134.6
O3W—H3WA···O3ⁱ	0.85	1.88	2.723 (5)	168.2
O3W—H3WB···O4W	0.82	1.97	2.793 (6)	177.9
O4W—H4WA···O2ⁱⁱⁱ	0.87	1.87	2.715 (6)	163.7
O4W—H4WB···O5W	0.85	2.22	2.803 (8)	125.2
O5W—H5WB···O6W^iv	0.83	2.18	2.770 (15)	128.3
O6W—H6WA···O2	0.85	2.44	3.091 (11)	134.2
O6W—H6WA···O2	0.85	2.44	3.091 (11)	134.2

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

Acknowledgements

The authors thank Shanghai University for financial support.

References

Brandenburg, K. & Putz, H. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2002). SADABS, SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Hao, X.-R., Su, Z.-M., Zhao, Y.-H., Shao, K.-Z. & Wang, Y. (2005). Acta Cryst. C61, m469–m471. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, X. L., Cao, Q. & Wang, E. B. (2005). Eur. J. Inorg. Chem. pp 3418–3421. Google Scholar
Wang, X. L., Cao, Q. & Wang, E. B. (2006). Cryst. Growth Des. 6, 439–433. Web of Science CSD CrossRef CAS Google Scholar
Wang, J. J., Yang, M. L. & Hu, H. M. (2007). Z. Anorg. Allg. Chem. 633, 341–345. Web of Science CSD CrossRef CAS Google Scholar
Zhu, S., Zhang, H. & Shao, M. (2008a). Transition Met. Chem. 33, 669–680. Web of Science CSD CrossRef CAS Google Scholar
Zhu, S., Zhang, H. & Zhao, Y. (2008b). J. Mol. Struct. 892, 420–426. Web of Science CSD CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.