Bis(μ-3-hydroxy-benzoato)-κO:O;κO:O-bis-[bis-(1H-benzimidazole-κN)(3-hydroxy-benzoato-κO)nickel(II)] bis-(1H-benzimidazole-κN)bis-(3-hy-droxy-benzoato-κO)nickel(II) hexa-hydrate.

The title compound, [Ni(2)(C(7)H(5)O(3))(4)(C(7)H(6)N(2))(4)][Ni(C(7)H(5)O(3))(2)(C(7)H(6)N(2))(2)]·6H(2)O, is a mononuclear/dinuclear nickel(II) cocrystal, the two mol-ecular species inter-acting through hydrogen bonds that involve the uncoordinated water mol-ecules. In the mononuclear species, the Ni(II) ion, located on an inversion center, is coordinated by two 1H-benzimidazole (bzim) ligands and two 3-hydroxy-benzoate (hba) anions in a square-planar geometry. In the centrosymmetric dinuclear species, the Ni(II) ion is coordinated by two bzim ligands and three hba anions in a square-pyramidal geometry; of the two independent hba anions, one bridges two Ni(II) ions with both carboxylate and hydroxyl groups whereas the other coordin-ates in a unidentate manner to the Ni(II) ion. The apical Ni-O(hydrox-yl) bond is 0.39 Å longer than the basal Ni-O(carbox-yl) bonds. The face-to-face separation of 3.326 (9) Å indicates the existence of π-π stacking between parallel bzim ligands of adjacent dinuclear entities. Extensive N-H⋯O and O-H⋯O hydrogen bonds help to stabilize the crystal structure.

Related literature

For general background, see: Deisenhofer & Michel (1989 ▶); Wu et al. (2003 ▶); Luo et al. (2004 ▶). For a related structure, see: Li et al. (2005 ▶).

Experimental

Crystal data

[Ni2(C7H5O3)4(C7H6N2)4][Ni(C7H5O3)2(C7H6N2)2]·6H2O

M = 1815.65

Triclinic,

a = 9.9926 (12) Å

b = 12.9504 (15) Å

c = 17.069 (2) Å

α = 100.05 (2)°

β = 104.88 (3)°

γ = 101.75 (2)°

V = 2029.1 (6) Å3

Z = 1

Mo Kα radiation

μ = 0.78 mm−1

T = 291 (2) K

0.36 × 0.30 × 0.22 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.728, T max = 0.840

17583 measured reflections

7894 independent reflections

5818 reflections with I > 2σ(I)

R int = 0.043

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.151

S = 1.10

7894 reflections

556 parameters

H-atom parameters constrained

Δρmax = 0.77 e Å−3

Δρmin = −0.49 e Å−3

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680800216X/ng2421sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680800216X/ng2421Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Ni2(C7H5O3)4(C7H6N2)4][Ni(C7H5O3)2(C7H6N2)2]·6H2O	Z = 1
Mr = 1815.65	F000 = 942
Triclinic, P1	Dx = 1.486 Mg m−3
Hall symbol: -P 1	Mo Kα radiation λ = 0.71073 Å
a = 9.9926 (12) Å	Cell parameters from 8706 reflections
b = 12.9504 (15) Å	θ = 3.2–25.5º
c = 17.069 (2) Å	µ = 0.78 mm−1
α = 100.05 (2)º	T = 291 (2) K
β = 104.88 (3)º	Prism, green
γ = 101.75 (2)º	0.36 × 0.30 × 0.22 mm
V = 2029.1 (6) Å3

Rigaku R-AXIS RAPID IP diffractometer	7894 independent reflections
Radiation source: fine-focus sealed tube	5818 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.043
Detector resolution: 10.00 pixels mm-1	θmax = 26.0º
T = 291(2) K	θmin = 3.1º
ω scans	h = −12→10
Absorption correction: multi-scan(ABSCOR; Higashi, 1995)	k = −15→15
Tmin = 0.728, Tmax = 0.840	l = −20→20
17583 measured reflections

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)] = 0.052	H-atom parameters constrained
wR(F2) = 0.151	w = 1/[σ2(Fo2) + (0.0807P)2 + 0.2523P] where P = (Fo2 + 2Fc2)/3
S = 1.10	(Δ/σ)max = 0.001
7894 reflections	Δρmax = 0.77 e Å−3
556 parameters	Δρmin = −0.49 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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.

	x	y	z	Uiso*/Ueq
Ni1	1.0000	0.5000	0.0000	0.03773 (18)
Ni2	0.56466 (4)	0.17869 (3)	0.34773 (2)	0.03137 (14)
N11	0.5837 (4)	0.3399 (3)	−0.1408 (2)	0.0653 (10)
H11	0.5046	0.3413	−0.1750	0.078*
N13	0.8089 (3)	0.3954 (3)	−0.05883 (17)	0.0467 (8)
N21	0.3270 (4)	0.3388 (3)	0.4636 (2)	0.0572 (9)
H21	0.2738	0.3397	0.4960	0.069*
N23	0.4653 (3)	0.2811 (2)	0.39320 (17)	0.0412 (7)
N31	0.8151 (4)	0.0406 (3)	0.2271 (2)	0.0600 (9)
H31	0.8558	0.0370	0.1883	0.072*
N33	0.6783 (3)	0.0884 (2)	0.30243 (18)	0.0417 (7)
O1	1.0141 (3)	0.4464 (2)	0.09861 (15)	0.0502 (7)
O2	0.8657 (3)	0.5328 (2)	0.14279 (15)	0.0513 (7)
O3	0.8177 (3)	0.3899 (2)	0.39189 (16)	0.0544 (7)
H3O	0.8298	0.3590	0.4328	0.082*
O4	0.5044 (3)	0.2087 (2)	0.23718 (13)	0.0414 (6)
O5	0.2715 (3)	0.1264 (2)	0.18550 (16)	0.0552 (7)
O6	0.1196 (3)	0.3096 (3)	−0.0511 (2)	0.0861 (12)
H6O	0.1298	0.3644	−0.0841	0.129*
O7	0.6324 (3)	0.1567 (2)	0.46053 (14)	0.0464 (6)
O8	0.8407 (3)	0.2847 (2)	0.50983 (16)	0.0505 (7)
O9	0.6492 (3)	−0.0408 (2)	0.68827 (16)	0.0584 (8)
H9O	0.6882	−0.0609	0.7382	0.088*
O1W	0.1500 (3)	0.3747 (2)	0.5685 (2)	0.0683 (8)
H1A	0.1355	0.4444	0.5641	0.102*
H1B	0.0564	0.3550	0.5663	0.102*
O2W	0.9835 (4)	0.0153 (4)	0.1156 (2)	0.0996 (12)
H2A	1.0817	0.0434	0.1317	0.149*
H2B	0.9734	−0.0446	0.0800	0.149*
O3W	0.3024 (4)	0.3628 (4)	−0.2241 (3)	0.1175 (15)
H3A	0.2405	0.3351	−0.2713	0.176*
H3B	0.2619	0.3958	−0.1932	0.176*
C12	0.7043 (4)	0.4195 (4)	−0.1113 (2)	0.0549 (10)
H12	0.7140	0.4857	−0.1263	0.066*
C14	0.8112 (5)	0.2222 (3)	−0.0099 (3)	0.0597 (11)
H14	0.9056	0.2439	0.0246	0.072*
C15	0.7215 (7)	0.1191 (4)	−0.0204 (3)	0.0834 (16)
H15	0.7572	0.0709	0.0083	0.100*
C16	0.5819 (6)	0.0870 (5)	−0.0721 (4)	0.0939 (19)
H16	0.5267	0.0175	−0.0776	0.113*
C17	0.5222 (6)	0.1540 (5)	−0.1155 (3)	0.0863 (17)
H17	0.4275	0.1323	−0.1495	0.104*
C18	0.6092 (4)	0.2549 (4)	−0.1061 (3)	0.0593 (11)
C19	0.7499 (4)	0.2898 (3)	−0.0543 (2)	0.0510 (10)
C22	0.3921 (4)	0.2620 (3)	0.4456 (2)	0.0506 (9)
H22	0.3865	0.2010	0.4677	0.061*
C24	0.5023 (4)	0.4399 (3)	0.3268 (2)	0.0511 (9)
H24	0.5606	0.4164	0.2968	0.061*
C25	0.4651 (6)	0.5373 (4)	0.3246 (3)	0.0720 (13)
H25	0.5003	0.5807	0.2925	0.086*
C26	0.3773 (6)	0.5716 (4)	0.3687 (4)	0.0809 (15)
H26	0.3548	0.6371	0.3647	0.097*
C27	0.3222 (5)	0.5128 (4)	0.4182 (3)	0.0701 (13)
H27	0.2632	0.5363	0.4477	0.084*
C28	0.3603 (4)	0.4164 (3)	0.4210 (2)	0.0493 (9)
C29	0.4475 (4)	0.3799 (3)	0.3763 (2)	0.0407 (8)
C32	0.7295 (4)	0.1028 (3)	0.2400 (2)	0.0457 (8)
H32	0.7075	0.1520	0.2083	0.055*
C34	0.7195 (7)	−0.0391 (5)	0.3972 (4)	0.103 (2)
H34	0.6549	−0.0245	0.4256	0.124*
C35	0.8018 (8)	−0.1100 (6)	0.4176 (6)	0.142 (3)
H35	0.7935	−0.1427	0.4611	0.171*
C36	0.8963 (8)	−0.1337 (6)	0.3744 (6)	0.146 (4)
H36	0.9526	−0.1798	0.3908	0.175*
C37	0.9083 (7)	−0.0899 (5)	0.3076 (5)	0.116 (3)
H37	0.9683	−0.1079	0.2769	0.140*
C38	0.8265 (5)	−0.0178 (4)	0.2884 (4)	0.0749 (15)
C39	0.7371 (5)	0.0096 (4)	0.3329 (3)	0.0616 (12)
C41	0.9422 (4)	0.4681 (3)	0.1481 (2)	0.0423 (8)
C42	0.9567 (4)	0.4094 (3)	0.21743 (19)	0.0380 (8)
C43	0.8825 (4)	0.4256 (3)	0.2744 (2)	0.0395 (8)
H43	0.8238	0.4729	0.2703	0.047*
C44	0.8957 (4)	0.3709 (3)	0.3382 (2)	0.0391 (8)
C45	0.9817 (4)	0.3006 (3)	0.3451 (2)	0.0399 (8)
H45	0.9901	0.2642	0.3879	0.048*
C46	1.0561 (4)	0.2843 (3)	0.2872 (2)	0.0464 (9)
H46	1.1141	0.2365	0.2913	0.056*
C47	1.0445 (4)	0.3386 (3)	0.2237 (2)	0.0436 (8)
H47	1.0951	0.3279	0.1855	0.052*
C51	0.3826 (4)	0.1894 (3)	0.1838 (2)	0.0374 (8)
C52	0.3786 (3)	0.2490 (3)	0.11543 (19)	0.0357 (7)
C53	0.2499 (4)	0.2489 (3)	0.0608 (2)	0.0479 (9)
H53	0.1640	0.2093	0.0645	0.058*
C54	0.2486 (4)	0.3080 (3)	0.0001 (2)	0.0494 (10)
C55	0.3752 (4)	0.3648 (3)	−0.0060 (2)	0.0529 (10)
H55	0.3746	0.4029	−0.0475	0.064*
C56	0.5029 (4)	0.3659 (3)	0.0484 (2)	0.0522 (10)
H56	0.5886	0.4056	0.0443	0.063*
C57	0.5053 (4)	0.3083 (3)	0.1096 (2)	0.0455 (9)
H57	0.5923	0.3096	0.1467	0.055*
C61	0.7452 (4)	0.2114 (3)	0.5177 (2)	0.0374 (8)
C62	0.7627 (3)	0.1868 (3)	0.6019 (2)	0.0342 (7)
C63	0.6919 (4)	0.0856 (3)	0.6079 (2)	0.0391 (8)
H63	0.6324	0.0339	0.5601	0.047*
C64	0.7111 (4)	0.0623 (3)	0.6861 (2)	0.0399 (8)
C65	0.7907 (4)	0.1410 (3)	0.7573 (2)	0.0434 (8)
H65	0.7984	0.1263	0.8095	0.052*
C66	0.8591 (4)	0.2421 (3)	0.7513 (2)	0.0468 (9)
H66	0.9121	0.2955	0.7995	0.056*
C67	0.8492 (4)	0.2641 (3)	0.6740 (2)	0.0405 (8)
H67	0.9003	0.3306	0.6702	0.049*

	U11	U22	U33	U12	U13	U23
Ni1	0.0354 (3)	0.0542 (4)	0.0231 (3)	0.0028 (3)	0.0126 (2)	0.0128 (3)
Ni2	0.0360 (2)	0.0384 (2)	0.0247 (2)	0.01420 (18)	0.00910 (17)	0.01509 (18)
N11	0.048 (2)	0.087 (3)	0.0465 (19)	−0.0023 (19)	0.0037 (16)	0.0199 (19)
N13	0.0425 (17)	0.062 (2)	0.0317 (15)	0.0035 (15)	0.0123 (13)	0.0121 (15)
N21	0.048 (2)	0.074 (2)	0.0505 (19)	0.0172 (18)	0.0222 (16)	0.0049 (18)
N23	0.0461 (17)	0.0462 (17)	0.0391 (15)	0.0189 (14)	0.0174 (13)	0.0158 (14)
N31	0.055 (2)	0.060 (2)	0.078 (2)	0.0166 (17)	0.0405 (19)	0.018 (2)
N33	0.0388 (16)	0.0455 (17)	0.0457 (16)	0.0165 (13)	0.0135 (14)	0.0159 (14)
O1	0.0484 (15)	0.0724 (18)	0.0347 (12)	0.0080 (13)	0.0205 (12)	0.0223 (13)
O2	0.0550 (16)	0.0641 (17)	0.0412 (13)	0.0153 (14)	0.0145 (12)	0.0296 (13)
O3	0.0700 (18)	0.0728 (19)	0.0500 (15)	0.0362 (15)	0.0388 (14)	0.0387 (15)
O4	0.0441 (14)	0.0541 (15)	0.0317 (11)	0.0168 (11)	0.0113 (11)	0.0206 (11)
O5	0.0471 (15)	0.0693 (18)	0.0507 (15)	0.0053 (13)	0.0101 (12)	0.0373 (14)
O6	0.0464 (17)	0.154 (3)	0.075 (2)	0.0245 (19)	0.0118 (16)	0.082 (2)
O7	0.0498 (15)	0.0560 (16)	0.0345 (12)	0.0127 (12)	0.0074 (12)	0.0226 (12)
O8	0.0555 (16)	0.0570 (16)	0.0480 (14)	0.0102 (13)	0.0212 (13)	0.0320 (13)
O9	0.0612 (17)	0.0551 (17)	0.0469 (15)	−0.0095 (13)	0.0011 (13)	0.0334 (14)
O1W	0.0643 (19)	0.0645 (19)	0.086 (2)	0.0204 (15)	0.0396 (17)	0.0140 (17)
O2W	0.057 (2)	0.135 (4)	0.092 (3)	0.016 (2)	0.023 (2)	0.000 (2)
O3W	0.086 (3)	0.174 (5)	0.090 (3)	0.054 (3)	0.011 (2)	0.027 (3)
C12	0.048 (2)	0.073 (3)	0.0360 (19)	0.003 (2)	0.0079 (17)	0.017 (2)
C14	0.069 (3)	0.057 (3)	0.056 (2)	0.013 (2)	0.027 (2)	0.015 (2)
C15	0.114 (5)	0.068 (3)	0.078 (3)	0.021 (3)	0.042 (3)	0.029 (3)
C16	0.086 (4)	0.075 (4)	0.088 (4)	−0.027 (3)	0.015 (3)	0.009 (3)
C17	0.077 (4)	0.087 (4)	0.069 (3)	−0.019 (3)	0.014 (3)	0.011 (3)
C18	0.049 (2)	0.069 (3)	0.048 (2)	−0.005 (2)	0.0139 (19)	0.006 (2)
C19	0.056 (2)	0.055 (2)	0.042 (2)	0.0028 (19)	0.0238 (18)	0.0131 (19)
C22	0.053 (2)	0.062 (3)	0.042 (2)	0.016 (2)	0.0216 (18)	0.0132 (19)
C24	0.054 (2)	0.050 (2)	0.050 (2)	0.0159 (18)	0.0106 (19)	0.0198 (19)
C25	0.079 (3)	0.057 (3)	0.079 (3)	0.024 (2)	0.006 (3)	0.031 (3)
C26	0.075 (3)	0.056 (3)	0.101 (4)	0.037 (3)	0.003 (3)	0.004 (3)
C27	0.056 (3)	0.062 (3)	0.083 (3)	0.026 (2)	0.012 (2)	−0.006 (3)
C28	0.036 (2)	0.053 (2)	0.047 (2)	0.0132 (17)	0.0039 (17)	−0.0057 (18)
C29	0.0387 (19)	0.0411 (19)	0.0385 (18)	0.0133 (15)	0.0055 (15)	0.0053 (16)
C32	0.043 (2)	0.047 (2)	0.045 (2)	0.0112 (17)	0.0123 (17)	0.0086 (17)
C34	0.127 (5)	0.109 (5)	0.155 (6)	0.087 (4)	0.099 (5)	0.093 (5)
C35	0.162 (7)	0.153 (7)	0.230 (9)	0.121 (6)	0.134 (7)	0.145 (7)
C36	0.140 (6)	0.141 (6)	0.267 (10)	0.106 (5)	0.136 (7)	0.139 (7)
C37	0.115 (5)	0.110 (5)	0.206 (8)	0.079 (4)	0.116 (5)	0.090 (5)
C38	0.063 (3)	0.067 (3)	0.125 (4)	0.034 (2)	0.054 (3)	0.044 (3)
C39	0.058 (3)	0.062 (3)	0.094 (3)	0.034 (2)	0.044 (3)	0.041 (3)
C41	0.0377 (19)	0.052 (2)	0.0285 (16)	−0.0037 (16)	0.0040 (15)	0.0133 (16)
C42	0.0417 (19)	0.0433 (19)	0.0261 (15)	0.0002 (15)	0.0109 (14)	0.0125 (15)
C43	0.045 (2)	0.046 (2)	0.0326 (17)	0.0125 (16)	0.0151 (15)	0.0185 (16)
C44	0.0402 (19)	0.047 (2)	0.0324 (17)	0.0070 (16)	0.0135 (15)	0.0163 (16)
C45	0.044 (2)	0.0407 (19)	0.0369 (17)	0.0079 (15)	0.0117 (15)	0.0177 (16)
C46	0.046 (2)	0.048 (2)	0.047 (2)	0.0162 (17)	0.0143 (17)	0.0150 (18)
C47	0.043 (2)	0.055 (2)	0.0328 (17)	0.0098 (17)	0.0157 (16)	0.0096 (17)
C51	0.042 (2)	0.044 (2)	0.0322 (16)	0.0172 (16)	0.0134 (15)	0.0152 (15)
C52	0.0392 (18)	0.0443 (19)	0.0274 (15)	0.0121 (15)	0.0122 (14)	0.0140 (15)
C53	0.043 (2)	0.069 (3)	0.0393 (19)	0.0121 (18)	0.0160 (16)	0.0290 (19)
C54	0.042 (2)	0.075 (3)	0.0387 (19)	0.0176 (19)	0.0114 (16)	0.032 (2)
C55	0.058 (2)	0.070 (3)	0.046 (2)	0.020 (2)	0.0233 (19)	0.038 (2)
C56	0.046 (2)	0.064 (3)	0.048 (2)	0.0034 (18)	0.0153 (18)	0.030 (2)
C57	0.041 (2)	0.059 (2)	0.0414 (19)	0.0148 (17)	0.0109 (16)	0.0235 (18)
C61	0.0410 (19)	0.046 (2)	0.0369 (18)	0.0182 (16)	0.0167 (16)	0.0230 (16)
C62	0.0337 (17)	0.0386 (18)	0.0365 (17)	0.0126 (14)	0.0123 (14)	0.0191 (15)
C63	0.0396 (19)	0.0419 (19)	0.0280 (16)	0.0005 (15)	0.0010 (14)	0.0141 (15)
C64	0.0353 (18)	0.048 (2)	0.0390 (18)	0.0066 (15)	0.0094 (15)	0.0242 (17)
C65	0.053 (2)	0.052 (2)	0.0296 (16)	0.0156 (18)	0.0120 (16)	0.0180 (17)
C66	0.057 (2)	0.045 (2)	0.0319 (17)	0.0113 (18)	0.0063 (17)	0.0070 (16)
C67	0.042 (2)	0.0381 (19)	0.0420 (19)	0.0092 (15)	0.0109 (16)	0.0163 (16)

Ni1—O1i	1.914 (2)	C24—C29	1.382 (5)
Ni1—O1	1.914 (2)	C24—C25	1.390 (6)
Ni1—N13i	1.994 (3)	C24—H24	0.9300
Ni1—N13	1.994 (3)	C25—C26	1.384 (7)
Ni2—O4	1.960 (2)	C25—H25	0.9300
Ni2—O7	1.961 (2)	C26—C27	1.374 (7)
Ni2—N23	1.980 (3)	C26—H26	0.9300
Ni2—N33	1.983 (3)	C27—C28	1.382 (6)
Ni2—O9ii	2.349 (3)	C27—H27	0.9300
N11—C12	1.330 (5)	C28—C29	1.396 (5)
N11—C18	1.375 (6)	C32—H32	0.9300
N11—H11	0.8600	C34—C35	1.383 (7)
N13—C12	1.320 (5)	C34—C39	1.388 (6)
N13—C19	1.398 (5)	C34—H34	0.9300
N21—C22	1.329 (5)	C35—C36	1.388 (9)
N21—C28	1.376 (5)	C35—H35	0.9300
N21—H21	0.8600	C36—C37	1.379 (8)
N23—C22	1.318 (4)	C36—H36	0.9300
N23—C29	1.395 (4)	C37—C38	1.388 (7)
N31—C32	1.321 (5)	C37—H37	0.9300
N31—C38	1.390 (6)	C38—C39	1.373 (6)
N31—H31	0.8600	C41—C42	1.507 (4)
N33—C32	1.320 (4)	C42—C43	1.379 (5)
N33—C39	1.389 (5)	C42—C47	1.391 (5)
O1—C41	1.273 (4)	C43—C44	1.392 (4)
O2—C41	1.244 (4)	C43—H43	0.9300
O3—C44	1.369 (4)	C44—C45	1.373 (5)
O3—H3O	0.8583	C45—C46	1.394 (5)
O4—C51	1.265 (4)	C45—H45	0.9300
O5—C51	1.247 (4)	C46—C47	1.385 (5)
O6—C54	1.365 (4)	C46—H46	0.9300
O6—H6O	0.9838	C47—H47	0.9300
O7—C61	1.262 (4)	C51—C52	1.504 (4)
O8—C61	1.254 (4)	C52—C57	1.378 (5)
O9—C64	1.364 (4)	C52—C53	1.381 (5)
O9—H9O	0.9450	C53—C54	1.390 (4)
O1W—H1A	0.9556	C53—H53	0.9300
O1W—H1B	0.9067	C54—C55	1.367 (5)
O2W—H2A	0.9226	C55—C56	1.368 (5)
O2W—H2B	0.8684	C55—H55	0.9300
O3W—H3A	0.8443	C56—C57	1.382 (4)
O3W—H3B	0.8519	C56—H56	0.9300
C12—H12	0.9300	C57—H57	0.9300
C14—C19	1.388 (6)	C61—C62	1.501 (4)
C14—C15	1.402 (6)	C62—C63	1.391 (4)
C14—H14	0.9300	C62—C67	1.391 (5)
C15—C16	1.378 (8)	C63—C64	1.394 (4)
C15—H15	0.9300	C63—H63	0.9300
C16—C17	1.365 (8)	C64—C65	1.374 (5)
C16—H16	0.9300	C65—C66	1.382 (5)
C17—C18	1.373 (6)	C65—H65	0.9300
C17—H17	0.9300	C66—C67	1.380 (5)
C18—C19	1.388 (6)	C66—H66	0.9300
C22—H22	0.9300	C67—H67	0.9300
O1i—Ni1—O1	180.0	N23—C29—C28	108.3 (3)
O1i—Ni1—N13i	91.67 (11)	N33—C32—N31	113.5 (3)
O1—Ni1—N13i	88.33 (11)	N33—C32—H32	123.3
O1i—Ni1—N13	88.33 (11)	N31—C32—H32	123.3
O1—Ni1—N13	91.67 (11)	C35—C34—C39	117.5 (5)
N13i—Ni1—N13	180.0	C35—C34—H34	121.2
O4—Ni2—O7	176.81 (10)	C39—C34—H34	121.2
O4—Ni2—N23	91.29 (11)	C34—C35—C36	121.4 (6)
O7—Ni2—N23	87.74 (11)	C34—C35—H35	119.3
O4—Ni2—N33	87.26 (11)	C36—C35—H35	119.3
O7—Ni2—N33	93.42 (11)	C37—C36—C35	121.1 (5)
N23—Ni2—N33	174.55 (12)	C37—C36—H36	119.4
O4—Ni2—O9ii	89.67 (9)	C35—C36—H36	119.4
O7—Ni2—O9ii	93.33 (10)	C36—C37—C38	116.8 (5)
N23—Ni2—O9ii	88.21 (12)	C36—C37—H37	121.6
N33—Ni2—O9ii	97.04 (12)	C38—C37—H37	121.6
C12—N11—C18	107.1 (3)	C39—C38—C37	122.4 (5)
C12—N11—H11	126.4	C39—C38—N31	106.2 (4)
C18—N11—H11	126.4	C37—C38—N31	131.3 (5)
C12—N13—C19	104.6 (3)	C38—C39—C34	120.5 (4)
C12—N13—Ni1	123.2 (3)	C38—C39—N33	108.7 (4)
C19—N13—Ni1	132.1 (3)	C34—C39—N33	130.8 (4)
C22—N21—C28	107.6 (3)	O2—C41—O1	124.9 (3)
C22—N21—H21	126.2	O2—C41—C42	120.4 (3)
C28—N21—H21	126.2	O1—C41—C42	114.7 (3)
C22—N23—C29	105.4 (3)	C43—C42—C47	120.1 (3)
C22—N23—Ni2	123.5 (3)	C43—C42—C41	120.0 (3)
C29—N23—Ni2	131.0 (2)	C47—C42—C41	119.9 (3)
C32—N31—C38	106.5 (3)	C42—C43—C44	119.8 (3)
C32—N31—H31	126.8	C42—C43—H43	120.1
C38—N31—H31	126.8	C44—C43—H43	120.1
C32—N33—C39	105.0 (3)	O3—C44—C45	122.6 (3)
C32—N33—Ni2	124.6 (2)	O3—C44—C43	116.6 (3)
C39—N33—Ni2	129.9 (3)	C45—C44—C43	120.8 (3)
C41—O1—Ni1	122.7 (2)	C44—C45—C46	119.1 (3)
C44—O3—H3O	116.4	C44—C45—H45	120.4
C51—O4—Ni2	132.3 (2)	C46—C45—H45	120.4
C54—O6—H6O	112.3	C47—C46—C45	120.7 (3)
C61—O7—Ni2	127.1 (2)	C47—C46—H46	119.6
C64—O9—Ni2ii	146.4 (2)	C45—C46—H46	119.6
C64—O9—H9O	114.9	C46—C47—C42	119.4 (3)
Ni2ii—O9—H9O	92.5	C46—C47—H47	120.3
H1A—O1W—H1B	86.3	C42—C47—H47	120.3
H2A—O2W—H2B	100.9	O5—C51—O4	124.4 (3)
H3A—O3W—H3B	107.0	O5—C51—C52	120.6 (3)
N13—C12—N11	113.5 (4)	O4—C51—C52	115.1 (3)
N13—C12—H12	123.3	C57—C52—C53	119.5 (3)
N11—C12—H12	123.3	C57—C52—C51	119.3 (3)
C19—C14—C15	115.6 (5)	C53—C52—C51	121.1 (3)
C19—C14—H14	122.2	C52—C53—C54	120.1 (3)
C15—C14—H14	122.2	C52—C53—H53	120.0
C16—C15—C14	121.9 (5)	C54—C53—H53	120.0
C16—C15—H15	119.0	O6—C54—C55	121.5 (3)
C14—C15—H15	119.0	O6—C54—C53	118.8 (3)
C17—C16—C15	122.1 (5)	C55—C54—C53	119.7 (3)
C17—C16—H16	118.9	C54—C55—C56	120.4 (3)
C15—C16—H16	118.9	C54—C55—H55	119.8
C16—C17—C18	116.5 (5)	C56—C55—H55	119.8
C16—C17—H17	121.8	C55—C56—C57	120.3 (3)
C18—C17—H17	121.8	C55—C56—H56	119.9
C17—C18—N11	131.2 (4)	C57—C56—H56	119.9
C17—C18—C19	122.8 (5)	C52—C57—C56	119.9 (3)
N11—C18—C19	106.1 (3)	C52—C57—H57	120.0
C18—C19—C14	121.0 (4)	C56—C57—H57	120.0
C18—C19—N13	108.7 (4)	O8—C61—O7	125.4 (3)
C14—C19—N13	130.3 (4)	O8—C61—C62	118.3 (3)
N23—C22—N21	113.0 (3)	O7—C61—C62	116.3 (3)
N23—C22—H22	123.5	C63—C62—C67	119.7 (3)
N21—C22—H22	123.5	C63—C62—C61	119.6 (3)
C29—C24—C25	116.0 (4)	C67—C62—C61	120.7 (3)
C29—C24—H24	122.0	C62—C63—C64	119.4 (3)
C25—C24—H24	122.0	C62—C63—H63	120.3
C26—C25—C24	121.9 (5)	C64—C63—H63	120.3
C26—C25—H25	119.0	O9—C64—C65	122.3 (3)
C24—C25—H25	119.0	O9—C64—C63	117.3 (3)
C27—C26—C25	122.7 (4)	C65—C64—C63	120.4 (3)
C27—C26—H26	118.7	C64—C65—C66	119.9 (3)
C25—C26—H26	118.7	C64—C65—H65	120.0
C26—C27—C28	115.4 (4)	C66—C65—H65	120.0
C26—C27—H27	122.3	C67—C66—C65	120.3 (3)
C28—C27—H27	122.3	C67—C66—H66	119.8
N21—C28—C27	131.4 (4)	C65—C66—H66	119.8
N21—C28—C29	105.8 (3)	C66—C67—C62	120.0 (3)
C27—C28—C29	122.8 (4)	C66—C67—H67	120.0
C24—C29—N23	130.5 (3)	C62—C67—H67	120.0
C24—C29—C28	121.2 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···O3W	0.86	2.07	2.906 (6)	163
N21—H21···O1W	0.86	2.02	2.867 (5)	168
N31—H31···O2W	0.86	2.02	2.866 (5)	167
O3—H3O···O8	0.86	1.75	2.609 (4)	174
O6—H6O···O2iii	0.99	1.80	2.783 (5)	175
O9—H9O···O5ii	0.95	1.68	2.610 (4)	166
O1W—H1A···O3iv	0.96	2.06	2.936 (4)	152
O1W—H1B···O8v	0.91	2.06	2.907 (4)	156
O2W—H2A···O5vi	0.92	1.88	2.780 (5)	165
O3W—H3B···O2iii	0.85	2.00	2.836 (5)	168

Table 1

Selected bond lengths (Å)

Ni1—O1	1.914 (2)
Ni1—N13	1.994 (3)
Ni2—O4	1.960 (2)
Ni2—O7	1.961 (2)
Ni2—N23	1.980 (3)
Ni2—N33	1.983 (3)
Ni2—O9i	2.349 (3)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N11—H11⋯O3W	0.86	2.07	2.906 (6)	163
N21—H21⋯O1W	0.86	2.02	2.867 (5)	168
N31—H31⋯O2W	0.86	2.02	2.866 (5)	167
O3—H3O⋯O8	0.86	1.75	2.609 (4)	174
O6—H6O⋯O2ii	0.99	1.80	2.783 (5)	175
O9—H9O⋯O5i	0.95	1.68	2.610 (4)	166
O1W—H1A⋯O3iii	0.96	2.06	2.936 (4)	152
O1W—H1B⋯O8iv	0.91	2.06	2.907 (4)	156
O2W—H2A⋯O5v	0.92	1.88	2.780 (5)	165
O3W—H3B⋯O2ii	0.85	2.00	2.836 (5)	168

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .