Tris(1,10-phenanthroline-κN,N')nickel(II) dinitrate tetra-hydrate.

In the title complex, [Ni(C(12)H(8)N(2))(3)](NO(3))(2)·4H(2)O, the Ni(II) ion is octa-hedrally coordinated by three bidentate 1,10-phenanthroline ligands, each forming a five-membered chelate ring. In the crystal, O-H⋯O and C-H⋯O hydrogen bonds are present between the complex cations, nitrate anions and water mol-ecules. O-H⋯O hydrogen bonds between the uncoord-inated water mol-ecules lead to the formation of a four-membered ring water cluster, with a planar configuration. There were an additional five grossly disordered water mol-ecules in the asymmetric unit, which were removed by the subroutine SQUEEZE; these were were excluded in the calculation of the molecular weight, etc. π-π stacking inter-actions between the aromatic rings are also observed [centroid-centroid distances = 3.697 (2), 3.728 (2) and 3.761 (2) Å].

Related literature

For background information on Ni–phenanthroline complexes and related structures, see: Qiua et al. (2011 ▶). For water clusters, see: Rodríguez-Cuamatzi et al. (2004 ▶); Sharif et al. (2010 ▶). For FTIR spectra of phenanthroline complexes, see: Schilt & Taylor (1959 ▶). For the synthesis of 4-amino-5-methyl-2H-1,2,4-triazole-3(4H)-thione, see: Beyer & Kröger (1960 ▶).

Experimental

Crystal data

[Ni(C12H8N2)3](NO3)2·4H2O

M = 795.41

Triclinic,

a = 13.0463 (6) Å

b = 13.1785 (5) Å

c = 13.4093 (4) Å

α = 82.688 (2)°

β = 72.147 (2)°

γ = 67.402 (2)°

V = 2025.85 (14) Å3

Z = 2

Mo Kα radiation

μ = 0.54 mm−1

T = 173 K

0.14 × 0.12 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer with APEXII CCD

Absorption correction: multi-scan (SORTAV; Blessing, 1997 ▶) T min = 0.928, T max = 0.948

13391 measured reflections

7100 independent reflections

5845 reflections with I > 2σ(I)

R int = 0.037

Refinement

R[F 2 > 2σ(F 2)] = 0.057

wR(F 2) = 0.160

S = 1.08

7100 reflections

496 parameters

H-atom parameters constrained

Δρmax = 0.42 e Å−3

Δρmin = −0.39 e Å−3

Data collection: COLLECT (Hooft, 1998 ▶); cell refinement: DENZO (Otwinowski & Minor, 1997 ▶); data reduction: SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681104880X/hy2480sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681104880X/hy2480Isup2.hkl

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

[Ni(C12H8N2)3](NO3)2·4H2O	Z = 2
Mr = 795.41	F(000) = 824
Triclinic, P1	Dx = 1.304 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 13.0463 (6) Å	Cell parameters from 8521 reflections
b = 13.1785 (5) Å	θ = 1.0–27.5°
c = 13.4093 (4) Å	µ = 0.54 mm−1
α = 82.688 (2)°	T = 173 K
β = 72.147 (2)°	Prism, pink
γ = 67.402 (2)°	0.14 × 0.12 × 0.10 mm
V = 2025.85 (14) Å3

Nonius KappaCCD diffractometer with APEXII CCD	7100 independent reflections
Radiation source: fine-focus sealed tube	5845 reflections with I > 2σ(I)
graphite	Rint = 0.037
ω and φ scans	θmax = 25.0°, θmin = 2.8°
Absorption correction: multi-scan (SORTAV; Blessing, 1997)	h = −15→15
Tmin = 0.928, Tmax = 0.948	k = −15→15
13391 measured reflections	l = −15→15

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.160	H-atom parameters constrained
S = 1.08	w = 1/[σ2(Fo2) + (0.0795P)2 + 1.9793P] where P = (Fo2 + 2Fc2)/3
7100 reflections	(Δ/σ)max = 0.001
496 parameters	Δρmax = 0.42 e Å−3
0 restraints	Δρmin = −0.39 e Å−3

Experimental. IR Spectra IR spectra were recorded using FTIR Spectra Bruker Tensor 27 spectrometer (KBr pellets, 4000–400 cm-1). TGA-DTA measurements were performed at heating rate of 10 K min-1 in the temperature range of 298–1273 K, under nitrogen flow of 20 ml min-1 on instrument Perkin Elmer Pyris Diamond Thermogravimetric/Differential Thermal Analyzer. Elemental analyses were performed using a Costech ECS 4010 CHNS analyzer.The FTIR spectrum of the crystals shows broad strong bands at the region 3000–3500 cm-1. In the spectra of the phenanthroline complexes strong bands are observed in three frequency regions, between 700 - 900 cm-1, 1125 - 1250 cm-1, and 1400 - 1650 cm-1 (Schilt & Taylor 1959). In the title complex, these bonds were observed in the regions 721–869 cm -1, 1138- 1225 cm -1 and 1429–1573 in the IR spectra.Thermal Analyses The thermogravimetric analysis curve for compound shows that the weight loss from at 635 K corresponds to the loss of H2O (experimental value 18.76% and calculated value 18.29%). The further decomposition began at 801 K and finished at 803 K indicating the complete removal of organic part of the compound (experimental value 93.34% and calculated value 91.5%).

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 > 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	0.63475 (4)	0.15916 (3)	0.69156 (3)	0.02848 (15)
N1	0.4993 (3)	0.2563 (2)	0.8096 (2)	0.0325 (6)
N2	0.5688 (2)	0.0406 (2)	0.77467 (19)	0.0290 (6)
N3	0.7612 (2)	0.1153 (2)	0.77055 (19)	0.0311 (6)
N4	0.7707 (2)	0.0408 (2)	0.5899 (2)	0.0324 (6)
N5	0.6785 (2)	0.2890 (2)	0.6102 (2)	0.0301 (6)
N6	0.5324 (2)	0.2015 (2)	0.5887 (2)	0.0312 (6)
C1	0.4656 (4)	0.3632 (3)	0.8248 (3)	0.0434 (9)
H1	0.5112	0.4022	0.7816	0.052*
C2	0.3655 (4)	0.4211 (3)	0.9020 (3)	0.0510 (10)
H2	0.3432	0.4980	0.9093	0.061*
C3	0.3003 (4)	0.3658 (3)	0.9667 (3)	0.0458 (9)
H3	0.2327	0.4039	1.0198	0.055*
C4	0.3341 (3)	0.2526 (3)	0.9540 (2)	0.0356 (8)
C5	0.2720 (3)	0.1873 (3)	1.0187 (3)	0.0408 (9)
H5	0.2043	0.2209	1.0736	0.049*
C6	0.3093 (3)	0.0789 (3)	1.0020 (3)	0.0408 (8)
H6	0.2670	0.0374	1.0461	0.049*
C7	0.4095 (3)	0.0241 (3)	0.9210 (2)	0.0338 (7)
C8	0.4522 (3)	−0.0897 (3)	0.8999 (3)	0.0380 (8)
H8	0.4134	−0.1351	0.9417	0.046*
C9	0.5486 (3)	−0.1334 (3)	0.8200 (3)	0.0385 (8)
H9	0.5778	−0.2097	0.8061	0.046*
C10	0.6051 (3)	−0.0662 (3)	0.7581 (3)	0.0349 (8)
H10	0.6720	−0.0983	0.7019	0.042*
C11	0.4337 (3)	0.2018 (3)	0.8734 (2)	0.0305 (7)
C12	0.4717 (3)	0.0857 (3)	0.8554 (2)	0.0298 (7)
C13	0.7583 (3)	0.1566 (3)	0.8574 (2)	0.0359 (8)
H13	0.6927	0.2187	0.8881	0.043*
C14	0.8470 (4)	0.1129 (3)	0.9051 (3)	0.0439 (9)
H14	0.8424	0.1459	0.9661	0.053*
C15	0.9405 (4)	0.0228 (3)	0.8640 (3)	0.0449 (9)
H15	1.0004	−0.0089	0.8974	0.054*
C16	0.9484 (3)	−0.0236 (3)	0.7721 (3)	0.0376 (8)
C17	1.0444 (4)	−0.1179 (3)	0.7218 (3)	0.0504 (10)
H17	1.1066	−0.1532	0.7521	0.060*
C18	1.0475 (3)	−0.1572 (3)	0.6320 (3)	0.0475 (9)
H18	1.1113	−0.2203	0.6008	0.057*
C19	0.9565 (3)	−0.1053 (3)	0.5835 (3)	0.0393 (8)
C20	0.9564 (3)	−0.1402 (3)	0.4882 (3)	0.0440 (9)
H20	1.0187	−0.2022	0.4532	0.053*
C21	0.8667 (3)	−0.0848 (3)	0.4469 (3)	0.0423 (9)
H21	0.8663	−0.1075	0.3826	0.051*
C22	0.7751 (3)	0.0058 (3)	0.4994 (2)	0.0368 (8)
H22	0.7134	0.0441	0.4691	0.044*
C23	0.8561 (3)	0.0273 (3)	0.7274 (2)	0.0322 (7)
C24	0.8607 (3)	−0.0132 (3)	0.6311 (2)	0.0326 (7)
C25	0.7471 (3)	0.3352 (3)	0.6247 (3)	0.0359 (8)
H25	0.7780	0.3117	0.6829	0.043*
C26	0.7760 (3)	0.4173 (3)	0.5578 (3)	0.0399 (8)
H26	0.8239	0.4496	0.5717	0.048*
C27	0.7346 (3)	0.4498 (3)	0.4731 (3)	0.0396 (8)
H27	0.7558	0.5030	0.4257	0.047*
C28	0.6603 (3)	0.4045 (3)	0.4557 (2)	0.0335 (8)
C29	0.6100 (3)	0.4353 (3)	0.3700 (3)	0.0407 (9)
H29	0.6297	0.4870	0.3194	0.049*
C30	0.5352 (3)	0.3921 (3)	0.3601 (3)	0.0412 (9)
H30	0.5029	0.4142	0.3026	0.049*
C31	0.5035 (3)	0.3138 (3)	0.4343 (2)	0.0340 (7)
C32	0.4228 (3)	0.2689 (3)	0.4297 (3)	0.0422 (9)
H32	0.3850	0.2913	0.3760	0.051*
C33	0.3996 (3)	0.1932 (3)	0.5033 (3)	0.0431 (9)
H33	0.3450	0.1628	0.5015	0.052*
C34	0.4568 (3)	0.1606 (3)	0.5812 (3)	0.0376 (8)
H34	0.4408	0.1067	0.6310	0.045*
C35	0.6342 (3)	0.3242 (3)	0.5274 (2)	0.0278 (7)
C36	0.5545 (3)	0.2786 (2)	0.5166 (2)	0.0286 (7)
N7	0.7221 (3)	0.0523 (3)	0.2402 (3)	0.0523 (9)
O1	0.6907 (3)	−0.0150 (3)	0.2998 (2)	0.0791 (11)
O2	0.7909 (2)	0.0240 (2)	0.1500 (2)	0.0519 (7)
O3	0.6849 (3)	0.1498 (3)	0.2673 (3)	0.0939 (13)
N8	0.1200 (4)	0.3433 (4)	0.3285 (4)	0.0794 (12)
O4	0.1898 (4)	0.3125 (5)	0.3753 (4)	0.1248 (19)
O5	0.1483 (6)	0.3317 (8)	0.2355 (4)	0.198 (4)
O6	0.0122 (4)	0.3875 (4)	0.3707 (5)	0.133 (2)
O7	0.0438 (3)	0.7131 (3)	0.2656 (2)	0.0672 (9)
H71	0.0963	0.6673	0.2233	0.081*
H72	0.0004	0.6814	0.2998	0.081*
O8	0.1078 (3)	0.2081 (3)	0.8549 (3)	0.0772 (10)
H81	0.0596	0.2280	0.8225	0.093*
H82	0.1271	0.1419	0.8650	0.093*
O9	0.0897 (3)	0.3860 (3)	0.5860 (3)	0.0781 (10)
H91	0.0999	0.3794	0.5230	0.094*
H92	0.0559	0.4519	0.5987	0.094*
O10	0.2177 (3)	0.3503 (3)	0.7381 (3)	0.0862 (11)
H101	0.1943	0.3028	0.7709	0.103*
H102	0.1700	0.3890	0.7071	0.103*

	U11	U22	U33	U12	U13	U23
Ni1	0.0334 (3)	0.0289 (2)	0.0266 (2)	−0.01518 (19)	−0.01072 (17)	0.00554 (16)
N1	0.0399 (17)	0.0291 (15)	0.0298 (14)	−0.0134 (13)	−0.0128 (12)	0.0056 (11)
N2	0.0303 (15)	0.0294 (14)	0.0287 (13)	−0.0124 (12)	−0.0104 (11)	0.0049 (11)
N3	0.0377 (16)	0.0354 (15)	0.0265 (13)	−0.0198 (13)	−0.0124 (12)	0.0075 (11)
N4	0.0354 (16)	0.0366 (15)	0.0306 (14)	−0.0199 (13)	−0.0095 (12)	0.0034 (11)
N5	0.0309 (15)	0.0307 (14)	0.0304 (13)	−0.0147 (12)	−0.0079 (11)	0.0031 (11)
N6	0.0328 (16)	0.0334 (15)	0.0299 (13)	−0.0153 (13)	−0.0103 (12)	0.0051 (11)
C1	0.053 (2)	0.0336 (19)	0.0410 (19)	−0.0179 (18)	−0.0103 (17)	0.0055 (15)
C2	0.064 (3)	0.036 (2)	0.046 (2)	−0.011 (2)	−0.015 (2)	−0.0028 (17)
C3	0.048 (2)	0.043 (2)	0.040 (2)	−0.0115 (19)	−0.0085 (17)	−0.0057 (16)
C4	0.0347 (19)	0.041 (2)	0.0307 (16)	−0.0105 (16)	−0.0139 (14)	0.0007 (14)
C5	0.032 (2)	0.055 (2)	0.0324 (17)	−0.0166 (18)	−0.0060 (15)	0.0022 (16)
C6	0.039 (2)	0.051 (2)	0.0377 (18)	−0.0256 (18)	−0.0092 (16)	0.0062 (16)
C7	0.0348 (19)	0.0380 (19)	0.0340 (17)	−0.0180 (16)	−0.0153 (15)	0.0094 (14)
C8	0.045 (2)	0.043 (2)	0.0382 (18)	−0.0282 (18)	−0.0181 (16)	0.0126 (15)
C9	0.051 (2)	0.0301 (18)	0.0426 (19)	−0.0200 (17)	−0.0195 (17)	0.0057 (15)
C10	0.038 (2)	0.0327 (18)	0.0378 (18)	−0.0156 (16)	−0.0137 (15)	0.0039 (14)
C11	0.0327 (18)	0.0319 (17)	0.0289 (16)	−0.0118 (15)	−0.0144 (14)	0.0070 (13)
C12	0.0307 (18)	0.0363 (18)	0.0284 (15)	−0.0167 (15)	−0.0136 (13)	0.0069 (13)
C13	0.046 (2)	0.044 (2)	0.0267 (16)	−0.0265 (17)	−0.0114 (15)	0.0066 (14)
C14	0.053 (2)	0.062 (3)	0.0330 (18)	−0.035 (2)	−0.0191 (17)	0.0083 (17)
C15	0.045 (2)	0.065 (3)	0.041 (2)	−0.034 (2)	−0.0245 (17)	0.0165 (18)
C16	0.036 (2)	0.042 (2)	0.0420 (19)	−0.0214 (17)	−0.0164 (15)	0.0137 (15)
C17	0.038 (2)	0.056 (2)	0.062 (3)	−0.020 (2)	−0.0227 (19)	0.015 (2)
C18	0.033 (2)	0.040 (2)	0.065 (3)	−0.0083 (17)	−0.0145 (18)	0.0019 (18)
C19	0.0330 (19)	0.0363 (19)	0.048 (2)	−0.0170 (16)	−0.0064 (16)	0.0028 (15)
C20	0.038 (2)	0.035 (2)	0.055 (2)	−0.0116 (17)	−0.0053 (17)	−0.0088 (17)
C21	0.049 (2)	0.043 (2)	0.0358 (18)	−0.0214 (19)	−0.0062 (17)	−0.0043 (16)
C22	0.044 (2)	0.042 (2)	0.0277 (16)	−0.0199 (17)	−0.0104 (15)	0.0029 (14)
C23	0.0328 (18)	0.0389 (19)	0.0326 (16)	−0.0232 (16)	−0.0106 (14)	0.0092 (14)
C24	0.0357 (19)	0.0366 (18)	0.0307 (16)	−0.0211 (16)	−0.0097 (14)	0.0079 (14)
C25	0.0359 (19)	0.0400 (19)	0.0383 (18)	−0.0209 (16)	−0.0126 (15)	0.0055 (15)
C26	0.039 (2)	0.038 (2)	0.045 (2)	−0.0216 (17)	−0.0085 (16)	0.0032 (16)
C27	0.040 (2)	0.0344 (19)	0.0402 (19)	−0.0176 (17)	−0.0038 (16)	0.0064 (15)
C28	0.0317 (18)	0.0293 (17)	0.0284 (16)	−0.0070 (14)	0.0010 (13)	0.0008 (13)
C29	0.049 (2)	0.0376 (19)	0.0295 (17)	−0.0140 (17)	−0.0084 (15)	0.0091 (14)
C30	0.049 (2)	0.038 (2)	0.0274 (17)	−0.0034 (17)	−0.0139 (15)	0.0023 (14)
C31	0.0328 (19)	0.0327 (18)	0.0306 (16)	−0.0026 (15)	−0.0116 (14)	−0.0027 (13)
C32	0.041 (2)	0.044 (2)	0.0418 (19)	−0.0068 (17)	−0.0212 (17)	−0.0035 (16)
C33	0.041 (2)	0.046 (2)	0.053 (2)	−0.0189 (18)	−0.0206 (17)	−0.0048 (17)
C34	0.036 (2)	0.040 (2)	0.0420 (19)	−0.0177 (16)	−0.0136 (15)	0.0016 (15)
C35	0.0294 (17)	0.0278 (16)	0.0227 (14)	−0.0092 (14)	−0.0058 (13)	0.0042 (12)
C36	0.0323 (18)	0.0266 (16)	0.0239 (15)	−0.0087 (14)	−0.0061 (13)	−0.0012 (12)
N7	0.043 (2)	0.075 (3)	0.051 (2)	−0.0298 (19)	−0.0183 (16)	−0.0039 (18)
O1	0.083 (3)	0.123 (3)	0.0530 (18)	−0.064 (2)	−0.0270 (17)	0.0274 (19)
O2	0.0473 (17)	0.0572 (17)	0.0486 (16)	−0.0220 (14)	−0.0046 (13)	−0.0042 (13)
O3	0.069 (2)	0.088 (3)	0.121 (3)	−0.028 (2)	0.000 (2)	−0.057 (2)
N8	0.066 (3)	0.092 (3)	0.078 (3)	−0.029 (3)	−0.013 (3)	−0.013 (3)
O4	0.056 (3)	0.201 (6)	0.117 (4)	−0.030 (3)	−0.038 (3)	−0.021 (3)
O5	0.134 (5)	0.359 (11)	0.085 (4)	−0.056 (6)	−0.018 (3)	−0.084 (5)
O6	0.067 (3)	0.093 (3)	0.182 (5)	−0.010 (2)	0.017 (3)	−0.001 (3)
O7	0.0550 (19)	0.098 (3)	0.0602 (18)	−0.0392 (19)	−0.0137 (15)	−0.0114 (17)
O8	0.095 (3)	0.058 (2)	0.091 (2)	−0.0182 (19)	−0.057 (2)	0.0015 (17)
O9	0.089 (3)	0.063 (2)	0.079 (2)	−0.032 (2)	−0.0155 (19)	0.0027 (17)
O10	0.078 (3)	0.093 (3)	0.095 (3)	−0.039 (2)	−0.022 (2)	−0.006 (2)

Ni1—N1	2.080 (3)	C17—C18	1.353 (6)
Ni1—N5	2.083 (3)	C17—H17	0.9500
Ni1—N6	2.087 (3)	C18—C19	1.428 (5)
Ni1—N3	2.088 (3)	C18—H18	0.9500
Ni1—N4	2.090 (3)	C19—C24	1.408 (5)
Ni1—N2	2.103 (2)	C19—C20	1.412 (5)
N1—C1	1.328 (4)	C20—C21	1.360 (6)
N1—C11	1.358 (4)	C20—H20	0.9500
N2—C10	1.326 (4)	C21—C22	1.396 (5)
N2—C12	1.369 (4)	C21—H21	0.9500
N3—C13	1.332 (4)	C22—H22	0.9500
N3—C23	1.356 (4)	C23—C24	1.435 (5)
N4—C22	1.330 (4)	C25—C26	1.407 (5)
N4—C24	1.359 (4)	C25—H25	0.9500
N5—C25	1.329 (4)	C26—C27	1.356 (5)
N5—C35	1.356 (4)	C26—H26	0.9500
N6—C34	1.325 (4)	C27—C28	1.402 (5)
N6—C36	1.361 (4)	C27—H27	0.9500
C1—C2	1.402 (6)	C28—C35	1.407 (4)
C1—H1	0.9500	C28—C29	1.434 (5)
C2—C3	1.367 (6)	C29—C30	1.350 (5)
C2—H2	0.9500	C29—H29	0.9500
C3—C4	1.402 (5)	C30—C31	1.429 (5)
C3—H3	0.9500	C30—H30	0.9500
C4—C11	1.400 (5)	C31—C36	1.399 (4)
C4—C5	1.436 (5)	C31—C32	1.410 (5)
C5—C6	1.346 (5)	C32—C33	1.363 (5)
C5—H5	0.9500	C32—H32	0.9500
C6—C7	1.420 (5)	C33—C34	1.397 (5)
C6—H6	0.9500	C33—H33	0.9500
C7—C12	1.407 (4)	C34—H34	0.9500
C7—C8	1.417 (5)	C35—C36	1.434 (5)
C8—C9	1.354 (5)	N7—O1	1.221 (5)
C8—H8	0.9500	N7—O3	1.245 (5)
C9—C10	1.399 (5)	N7—O2	1.265 (4)
C9—H9	0.9500	N8—O4	1.179 (6)
C10—H10	0.9500	N8—O5	1.199 (6)
C11—C12	1.443 (5)	N8—O6	1.266 (6)
C13—C14	1.388 (5)	O7—H71	0.8200
C13—H13	0.9500	O7—H72	0.8200
C14—C15	1.358 (6)	O8—H81	0.8200
C14—H14	0.9500	O8—H82	0.8200
C15—C16	1.403 (5)	O9—H91	0.8248
C15—H15	0.9500	O9—H92	0.8200
C16—C23	1.407 (5)	O10—H101	0.8200
C16—C17	1.437 (6)	O10—H102	0.8200
N1—Ni1—N5	95.20 (10)	C14—C15—H15	120.1
N1—Ni1—N6	92.06 (11)	C16—C15—H15	120.1
N5—Ni1—N6	79.80 (10)	C15—C16—C23	116.8 (4)
N1—Ni1—N3	96.51 (11)	C15—C16—C17	124.0 (3)
N5—Ni1—N3	93.96 (10)	C23—C16—C17	119.2 (3)
N6—Ni1—N3	169.85 (10)	C18—C17—C16	121.0 (4)
N1—Ni1—N4	170.85 (10)	C18—C17—H17	119.5
N5—Ni1—N4	93.40 (10)	C16—C17—H17	119.5
N6—Ni1—N4	92.55 (11)	C17—C18—C19	121.0 (4)
N3—Ni1—N4	79.75 (11)	C17—C18—H18	119.5
N1—Ni1—N2	79.88 (10)	C19—C18—H18	119.5
N5—Ni1—N2	172.77 (11)	C24—C19—C20	116.8 (3)
N6—Ni1—N2	95.00 (10)	C24—C19—C18	119.5 (3)
N3—Ni1—N2	91.88 (10)	C20—C19—C18	123.7 (4)
N4—Ni1—N2	91.84 (10)	C21—C20—C19	119.7 (3)
C1—N1—C11	117.6 (3)	C21—C20—H20	120.1
C1—N1—Ni1	128.6 (2)	C19—C20—H20	120.1
C11—N1—Ni1	113.6 (2)	C20—C21—C22	119.7 (3)
C10—N2—C12	117.9 (3)	C20—C21—H21	120.2
C10—N2—Ni1	129.9 (2)	C22—C21—H21	120.2
C12—N2—Ni1	112.1 (2)	N4—C22—C21	122.7 (3)
C13—N3—C23	117.7 (3)	N4—C22—H22	118.6
C13—N3—Ni1	129.7 (3)	C21—C22—H22	118.6
C23—N3—Ni1	112.5 (2)	N3—C23—C16	123.1 (3)
C22—N4—C24	118.0 (3)	N3—C23—C24	117.2 (3)
C22—N4—Ni1	129.4 (3)	C16—C23—C24	119.7 (3)
C24—N4—Ni1	112.2 (2)	N4—C24—C19	123.0 (3)
C25—N5—C35	117.9 (3)	N4—C24—C23	117.3 (3)
C25—N5—Ni1	129.3 (2)	C19—C24—C23	119.7 (3)
C35—N5—Ni1	112.7 (2)	N5—C25—C26	122.9 (3)
C34—N6—C36	117.8 (3)	N5—C25—H25	118.6
C34—N6—Ni1	129.7 (2)	C26—C25—H25	118.6
C36—N6—Ni1	112.4 (2)	C27—C26—C25	119.1 (3)
N1—C1—C2	122.8 (3)	C27—C26—H26	120.5
N1—C1—H1	118.6	C25—C26—H26	120.5
C2—C1—H1	118.6	C26—C27—C28	119.9 (3)
C3—C2—C1	119.4 (4)	C26—C27—H27	120.1
C3—C2—H2	120.3	C28—C27—H27	120.1
C1—C2—H2	120.3	C27—C28—C35	117.4 (3)
C2—C3—C4	119.4 (4)	C27—C28—C29	124.0 (3)
C2—C3—H3	120.3	C35—C28—C29	118.6 (3)
C4—C3—H3	120.3	C30—C29—C28	121.2 (3)
C11—C4—C3	117.4 (3)	C30—C29—H29	119.4
C11—C4—C5	119.1 (3)	C28—C29—H29	119.4
C3—C4—C5	123.5 (3)	C29—C30—C31	121.2 (3)
C6—C5—C4	120.4 (3)	C29—C30—H30	119.4
C6—C5—H5	119.8	C31—C30—H30	119.4
C4—C5—H5	119.8	C36—C31—C32	117.3 (3)
C5—C6—C7	122.4 (3)	C36—C31—C30	119.1 (3)
C5—C6—H6	118.8	C32—C31—C30	123.6 (3)
C7—C6—H6	118.8	C33—C32—C31	119.3 (3)
C12—C7—C8	116.6 (3)	C33—C32—H32	120.3
C12—C7—C6	118.7 (3)	C31—C32—H32	120.3
C8—C7—C6	124.7 (3)	C32—C33—C34	119.6 (3)
C9—C8—C7	119.8 (3)	C32—C33—H33	120.2
C9—C8—H8	120.1	C34—C33—H33	120.2
C7—C8—H8	120.1	N6—C34—C33	122.9 (3)
C8—C9—C10	120.0 (3)	N6—C34—H34	118.5
C8—C9—H9	120.0	C33—C34—H34	118.5
C10—C9—H9	120.0	N5—C35—C28	122.8 (3)
N2—C10—C9	122.5 (3)	N5—C35—C36	117.2 (3)
N2—C10—H10	118.7	C28—C35—C36	120.0 (3)
C9—C10—H10	118.7	N6—C36—C31	123.0 (3)
N1—C11—C4	123.3 (3)	N6—C36—C35	117.2 (3)
N1—C11—C12	116.8 (3)	C31—C36—C35	119.8 (3)
C4—C11—C12	119.9 (3)	O1—N7—O3	120.1 (4)
N2—C12—C7	123.1 (3)	O1—N7—O2	120.3 (4)
N2—C12—C11	117.4 (3)	O3—N7—O2	119.6 (4)
C7—C12—C11	119.5 (3)	O4—N8—O5	120.6 (6)
N3—C13—C14	122.8 (4)	O4—N8—O6	124.0 (6)
N3—C13—H13	118.6	O5—N8—O6	115.3 (6)
C14—C13—H13	118.6	H71—O7—H72	105.6
C15—C14—C13	119.7 (3)	H81—O8—H82	109.1
C15—C14—H14	120.2	H91—O9—H92	106.6
C13—C14—H14	120.2	H101—O10—H102	107.6
C14—C15—C16	119.9 (3)
N5—Ni1—N1—C1	−4.6 (3)	C6—C7—C12—N2	−179.5 (3)
N6—Ni1—N1—C1	−84.5 (3)	C8—C7—C12—C11	−179.2 (3)
N3—Ni1—N1—C1	90.0 (3)	C6—C7—C12—C11	1.3 (5)
N2—Ni1—N1—C1	−179.2 (3)	N1—C11—C12—N2	−1.3 (4)
N5—Ni1—N1—C11	170.3 (2)	C4—C11—C12—N2	179.2 (3)
N6—Ni1—N1—C11	90.3 (2)	N1—C11—C12—C7	178.0 (3)
N3—Ni1—N1—C11	−95.2 (2)	C4—C11—C12—C7	−1.5 (5)
N2—Ni1—N1—C11	−4.4 (2)	C23—N3—C13—C14	−0.6 (5)
N1—Ni1—N2—C10	−178.5 (3)	Ni1—N3—C13—C14	175.1 (2)
N6—Ni1—N2—C10	90.3 (3)	N3—C13—C14—C15	−1.5 (5)
N3—Ni1—N2—C10	−82.2 (3)	C13—C14—C15—C16	1.9 (5)
N4—Ni1—N2—C10	−2.4 (3)	C14—C15—C16—C23	−0.3 (5)
N1—Ni1—N2—C12	3.7 (2)	C14—C15—C16—C17	179.1 (3)
N6—Ni1—N2—C12	−87.5 (2)	C15—C16—C17—C18	−178.7 (4)
N3—Ni1—N2—C12	99.9 (2)	C23—C16—C17—C18	0.7 (5)
N4—Ni1—N2—C12	179.7 (2)	C16—C17—C18—C19	1.0 (6)
N1—Ni1—N3—C13	−12.4 (3)	C17—C18—C19—C24	−1.5 (5)
N5—Ni1—N3—C13	83.3 (3)	C17—C18—C19—C20	178.0 (4)
N6—Ni1—N3—C13	134.9 (5)	C24—C19—C20—C21	0.4 (5)
N4—Ni1—N3—C13	176.0 (3)	C18—C19—C20—C21	−179.0 (3)
N2—Ni1—N3—C13	−92.5 (3)	C19—C20—C21—C22	−0.4 (5)
N1—Ni1—N3—C23	163.4 (2)	C24—N4—C22—C21	1.4 (5)
N5—Ni1—N3—C23	−100.9 (2)	Ni1—N4—C22—C21	−171.0 (2)
N6—Ni1—N3—C23	−49.3 (7)	C20—C21—C22—N4	−0.6 (5)
N4—Ni1—N3—C23	−8.1 (2)	C13—N3—C23—C16	2.2 (4)
N2—Ni1—N3—C23	83.4 (2)	Ni1—N3—C23—C16	−174.2 (2)
N5—Ni1—N4—C22	−85.2 (3)	C13—N3—C23—C24	−177.1 (3)
N6—Ni1—N4—C22	−5.2 (3)	Ni1—N3—C23—C24	6.5 (3)
N3—Ni1—N4—C22	−178.6 (3)	C15—C16—C23—N3	−1.8 (5)
N2—Ni1—N4—C22	89.8 (3)	C17—C16—C23—N3	178.8 (3)
N5—Ni1—N4—C24	102.1 (2)	C15—C16—C23—C24	177.6 (3)
N6—Ni1—N4—C24	−178.0 (2)	C17—C16—C23—C24	−1.9 (5)
N3—Ni1—N4—C24	8.7 (2)	C22—N4—C24—C19	−1.4 (4)
N2—Ni1—N4—C24	−82.9 (2)	Ni1—N4—C24—C19	172.3 (2)
N1—Ni1—N5—C25	85.3 (3)	C22—N4—C24—C23	178.3 (3)
N6—Ni1—N5—C25	176.5 (3)	Ni1—N4—C24—C23	−8.0 (3)
N3—Ni1—N5—C25	−11.6 (3)	C20—C19—C24—N4	0.5 (5)
N4—Ni1—N5—C25	−91.6 (3)	C18—C19—C24—N4	180.0 (3)
N1—Ni1—N5—C35	−99.1 (2)	C20—C19—C24—C23	−179.2 (3)
N6—Ni1—N5—C35	−7.9 (2)	C18—C19—C24—C23	0.3 (5)
N3—Ni1—N5—C35	164.0 (2)	N3—C23—C24—N4	1.1 (4)
N4—Ni1—N5—C35	84.1 (2)	C16—C23—C24—N4	−178.3 (3)
N1—Ni1—N6—C34	−82.2 (3)	N3—C23—C24—C19	−179.2 (3)
N5—Ni1—N6—C34	−177.1 (3)	C16—C23—C24—C19	1.4 (4)
N3—Ni1—N6—C34	130.3 (6)	C35—N5—C25—C26	−0.7 (5)
N4—Ni1—N6—C34	89.9 (3)	Ni1—N5—C25—C26	174.8 (3)
N2—Ni1—N6—C34	−2.2 (3)	N5—C25—C26—C27	−1.5 (6)
N1—Ni1—N6—C36	101.9 (2)	C25—C26—C27—C28	2.5 (5)
N5—Ni1—N6—C36	7.0 (2)	C26—C27—C28—C35	−1.4 (5)
N3—Ni1—N6—C36	−45.6 (7)	C26—C27—C28—C29	178.5 (3)
N4—Ni1—N6—C36	−86.0 (2)	C27—C28—C29—C30	−177.1 (3)
N2—Ni1—N6—C36	−178.1 (2)	C35—C28—C29—C30	2.8 (5)
C11—N1—C1—C2	−1.0 (5)	C28—C29—C30—C31	−0.2 (6)
Ni1—N1—C1—C2	173.7 (3)	C29—C30—C31—C36	−2.3 (5)
N1—C1—C2—C3	1.6 (6)	C29—C30—C31—C32	177.7 (3)
C1—C2—C3—C4	−0.6 (6)	C36—C31—C32—C33	−1.0 (5)
C2—C3—C4—C11	−0.9 (5)	C30—C31—C32—C33	178.9 (3)
C2—C3—C4—C5	179.4 (4)	C31—C32—C33—C34	−0.6 (6)
C11—C4—C5—C6	0.1 (5)	C36—N6—C34—C33	−0.1 (5)
C3—C4—C5—C6	179.9 (4)	Ni1—N6—C34—C33	−175.8 (3)
C4—C5—C6—C7	−0.3 (6)	C32—C33—C34—N6	1.2 (6)
C5—C6—C7—C12	−0.3 (5)	C25—N5—C35—C28	1.8 (5)
C5—C6—C7—C8	−179.9 (3)	Ni1—N5—C35—C28	−174.4 (2)
C12—C7—C8—C9	0.2 (5)	C25—N5—C35—C36	−176.1 (3)
C6—C7—C8—C9	179.7 (3)	Ni1—N5—C35—C36	7.7 (4)
C7—C8—C9—C10	−0.5 (5)	C27—C28—C35—N5	−0.8 (5)
C12—N2—C10—C9	−0.5 (5)	C29—C28—C35—N5	179.3 (3)
Ni1—N2—C10—C9	−178.2 (2)	C27—C28—C35—C36	177.1 (3)
C8—C9—C10—N2	0.7 (5)	C29—C28—C35—C36	−2.8 (5)
C1—N1—C11—C4	−0.6 (5)	C34—N6—C36—C31	−1.6 (5)
Ni1—N1—C11—C4	−176.1 (2)	Ni1—N6—C36—C31	174.8 (2)
C1—N1—C11—C12	179.9 (3)	C34—N6—C36—C35	178.4 (3)
Ni1—N1—C11—C12	4.4 (4)	Ni1—N6—C36—C35	−5.2 (4)
C3—C4—C11—N1	1.6 (5)	C32—C31—C36—N6	2.2 (5)
C5—C4—C11—N1	−178.7 (3)	C30—C31—C36—N6	−177.7 (3)
C3—C4—C11—C12	−179.0 (3)	C32—C31—C36—C35	−177.8 (3)
C5—C4—C11—C12	0.8 (5)	C30—C31—C36—C35	2.2 (5)
C10—N2—C12—C7	0.1 (5)	N5—C35—C36—N6	−1.7 (4)
Ni1—N2—C12—C7	178.2 (2)	C28—C35—C36—N6	−179.7 (3)
C10—N2—C12—C11	179.4 (3)	N5—C35—C36—C31	178.3 (3)
Ni1—N2—C12—C11	−2.5 (3)	C28—C35—C36—C31	0.4 (5)
C8—C7—C12—N2	0.0 (5)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H72···O9i	0.82	1.97	2.768 (5)	164
O8—H81···O7i	0.82	1.94	2.749 (5)	172
O8—H82···O2ii	0.82	2.04	2.827 (4)	164
O9—H91···O4	0.82	2.07	2.845 (6)	155
O9—H92···O6i	0.82	2.00	2.817 (6)	175
O10—H101···O8	0.82	2.01	2.822 (5)	169
O10—H102···O9	0.82	2.20	2.900 (6)	143
C5—H5···O5iii	0.95	2.53	3.293 (7)	138
C15—H15···O2iv	0.95	2.53	3.265 (5)	134
C25—H25···O7v	0.95	2.52	3.300 (5)	140
C32—H32···O4	0.95	2.46	3.165 (6)	131
C34—H34···O1ii	0.95	2.37	3.180 (5)	143

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H72⋯O9i	0.82	1.97	2.768 (5)	164
O8—H81⋯O7i	0.82	1.94	2.749 (5)	172
O8—H82⋯O2ii	0.82	2.04	2.827 (4)	164
O9—H91⋯O4	0.82	2.07	2.845 (6)	155
O9—H92⋯O6i	0.82	2.00	2.817 (6)	175
O10—H101⋯O8	0.82	2.01	2.822 (5)	169
O10—H102⋯O9	0.82	2.20	2.900 (6)	143
C5—H5⋯O5iii	0.95	2.53	3.293 (7)	138
C15—H15⋯O2iv	0.95	2.53	3.265 (5)	134
C25—H25⋯O7v	0.95	2.52	3.300 (5)	140
C32—H32⋯O4	0.95	2.46	3.165 (6)	131
C34—H34⋯O1ii	0.95	2.37	3.180 (5)	143

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