(3-Acetyl-4-methyl-1H-pyrazol-1-ide-5-carboxyl-ato)bis-(1,10-phenanthroline)nickel(II) 3.5-hydrate.

The title compound, [Ni(C7H6N2O3)(C12H8N2)2]·3.5H2O, crystallizes as a neutral mononuclear complex with 3.5 solvent water mol-ecules. One of the water mol-ecules lies on an inversion centre, so that its H atoms are disordered over two sites. The coordination environment of Ni(II) has a slightly distorted octa-hedral geometry, which is formed by one O and five N atoms belonging to the N,O-chelating pyrazol-1-ide-5-carboxyl-ate and two N,N'-chelating phenanthroline mol-ecules. In the crystal, O-H⋯O, N-H⋯O and O-H⋯N hydrogen bonds involving the solvent water mol-ecules and pyrazole-5-carboxyl-ate ligands form layers parallel to the ab plane. These layers are linked further via weak π-π inter-actions between two adjacent phenanthroline mol-ecules, with centroid-to-centroid distances in the range 3.886 (2)-4.018 (1) Å, together with C-H⋯π contacts, forming a three-dimensional network.

Related literature

The work presented here continues studies of complexes based on pyrazolate ligands with transition metals, see: Klingele et al. (2009 ▶); Malinkin et al. (2009 ▶, 2012a ▶,b ▶,c ▶); Ng et al. (2011 ▶); Penkova et al. (2008 ▶, 2009 ▶); Meyer & Pritzkow (2000 ▶); Bauer-Siebenlist et al. (2005 ▶); Świątek-Kozłowska et al. (2000 ▶). For related structures, see: Zhong et al. (2009 ▶); Zheng et al. (2009 ▶); Bouchene et al. (2013 ▶); Fang & Wang (2010 ▶); Fritsky et al. (2004 ▶, 2006 ▶); Kanderal et al. (2005 ▶); Moroz et al. (2010 ▶). For the starting material, see: Sachse et al. (2008 ▶).

Experimental

Crystal data

[Ni(C7n class="Species">H6N2O3)(C12H8N2)2]·3.5H2O

M = 648.29

Triclinic,

a = 9.865 (3) Å

b = 11.659 (4) Å

c = 13.561 (5) Å

α = 91.91 (3)°

β = 98.85 (3)°

γ = 105.20 (4)°

V = 1482.8 (9) Å3

Z = 2

Mo Kα radiation

μ = 0.71 mm−1

T = 170 K

0.23 × 0.18 × 0.11 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: numerical (DENZO/SCALEPACK; Otwinowski & Minor, 1997 ▶) T min = 0.857, T max = 0.929

12624 measured reflections

6830 independent reflections

3040 reflections with I > 2σ(I)

R int = 0.070

Refinement

R[F 2 > 2σ(F 2)] = 0.062

wR(F 2) = 0.153

S = 0.85

6830 reflections

405 parameters

13 restraints

H-atom parameters constrained

Δρmax = 1.12 e Å−3

Δρmin = −0.59 e Å−3

Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: WinGX (Farrugia, 2012 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 2012 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813017194/sj5334sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813017194/sj5334Isup2.hkl

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

[Ni(C7H6N2O3)(C12H8N2)2]·3.5H2O	Z = 2
Mr = 648.29	F(000) = 674
Triclinic, P1	Dx = 1.452 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.865 (3) Å	Cell parameters from 11133 reflections
b = 11.659 (4) Å	θ = 3.4–36.5°
c = 13.561 (5) Å	µ = 0.71 mm−1
α = 91.91 (3)°	T = 170 K
β = 98.85 (3)°	Block, light green
γ = 105.20 (4)°	0.23 × 0.18 × 0.11 mm
V = 1482.8 (9) Å3

Nonius KappaCCD diffractometer	6830 independent reflections
Radiation source: fine-focus sealed tube	3040 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	Rint = 0.070
Detector resolution: 9 pixels mm-1	θmax = 28.6°, θmin = 3.0°
φ scans and ω scans with κ offset	h = −12→12
Absorption correction: numerical (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	k = −15→15
Tmin = 0.857, Tmax = 0.929	l = −18→18
12624 measured reflections

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) = 0.153	H-atom parameters constrained
S = 0.85	w = 1/[σ2(Fo2) + (0.0675P)2] where P = (Fo2 + 2Fc2)/3
6830 reflections	(Δ/σ)max = 0.001
405 parameters	Δρmax = 1.12 e Å−3
13 restraints	Δρmin = −0.59 e Å−3

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	Occ. (<1)
N1	0.6503 (4)	0.6632 (3)	0.7897 (2)	0.0294 (9)
N2	0.5838 (4)	0.5594 (3)	0.8208 (2)	0.0322 (10)
N3	0.7221 (4)	0.6920 (3)	0.5843 (3)	0.0331 (10)
N4	0.8913 (4)	0.5870 (3)	0.6988 (2)	0.0303 (9)
N5	0.9485 (4)	0.7889 (3)	0.8732 (2)	0.0293 (9)
N6	1.0125 (4)	0.8544 (3)	0.6950 (2)	0.0299 (9)
O1	0.5691 (4)	0.9471 (3)	0.7919 (2)	0.0416 (9)
O2	0.7478 (3)	0.8848 (3)	0.7411 (2)	0.0318 (8)
O3	0.2663 (4)	0.4867 (3)	0.9303 (3)	0.0518 (10)
Ni1	0.82850 (7)	0.73904 (5)	0.73104 (4)	0.0312 (2)
C1	0.6312 (6)	0.8686 (4)	0.7797 (3)	0.0316 (12)
C2	0.5759 (5)	0.7458 (4)	0.8088 (3)	0.0315 (11)
C3	0.4603 (5)	0.6920 (4)	0.8544 (3)	0.0332 (12)
C4	0.4690 (5)	0.5759 (4)	0.8588 (3)	0.0287 (11)
C5	0.3683 (6)	0.4731 (4)	0.8924 (3)	0.0365 (13)
C6	0.3883 (6)	0.3506 (4)	0.8784 (4)	0.0508 (15)
H6A	0.4691	0.3442	0.9250	0.076*
H6B	0.4038	0.3372	0.8113	0.076*
H6C	0.3045	0.2922	0.8898	0.076*
C7	0.3526 (5)	0.7476 (4)	0.8889 (4)	0.0431 (13)
H7A	0.3621	0.7487	0.9605	0.065*
H7B	0.2584	0.7018	0.8592	0.065*
H7C	0.3686	0.8277	0.8691	0.065*
C8	0.6363 (5)	0.7446 (4)	0.5314 (3)	0.0383 (13)
H8	0.6268	0.8159	0.5584	0.046*
C9	0.5574 (5)	0.6988 (5)	0.4354 (3)	0.0458 (14)
H9	0.4957	0.7376	0.4009	0.055*
C10	0.5754 (6)	0.5954 (5)	0.3951 (3)	0.0482 (16)
H10	0.5254	0.5635	0.3321	0.058*
C11	0.6679 (5)	0.5375 (4)	0.4475 (3)	0.0382 (13)
C12	0.6942 (6)	0.4303 (5)	0.4122 (4)	0.0501 (16)
H12	0.6486	0.3956	0.3489	0.060*
C13	0.7818 (6)	0.3779 (4)	0.4666 (4)	0.0483 (15)
H13	0.7965	0.3083	0.4404	0.058*
C14	0.8553 (6)	0.4280 (4)	0.5668 (3)	0.0404 (14)
C15	0.9472 (6)	0.3781 (4)	0.6280 (4)	0.0462 (14)
H15	0.9663	0.3088	0.6052	0.055*
C16	1.0106 (5)	0.4308 (4)	0.7228 (4)	0.0425 (13)
H16	1.0728	0.3985	0.7644	0.051*
C17	0.9775 (5)	0.5347 (4)	0.7536 (4)	0.0382 (13)
H17	1.0194	0.5697	0.8174	0.046*
C18	0.7407 (5)	0.5897 (4)	0.5443 (3)	0.0318 (12)
C19	0.8312 (5)	0.5333 (4)	0.6038 (3)	0.0329 (12)
C20	0.9158 (5)	0.7544 (4)	0.9607 (3)	0.0348 (12)
H20	0.8343	0.6925	0.9614	0.042*
C21	1.0000 (5)	0.8078 (4)	1.0528 (3)	0.0360 (12)
H21	0.9734	0.7815	1.1128	0.043*
C22	1.1195 (5)	0.8975 (4)	1.0534 (3)	0.0331 (12)
H22	1.1747	0.9339	1.1138	0.040*
C23	1.1596 (5)	0.9353 (4)	0.9623 (3)	0.0299 (11)
C24	1.2904 (5)	1.0252 (4)	0.9547 (3)	0.0367 (12)
H24	1.3502	1.0638	1.0128	0.044*
C25	1.3267 (5)	1.0535 (4)	0.8642 (3)	0.0390 (13)
H25	1.4124	1.1094	0.8612	0.047*
C26	1.2346 (5)	0.9984 (4)	0.7734 (3)	0.0333 (12)
C27	1.2673 (6)	1.0234 (4)	0.6772 (3)	0.0456 (14)
H27	1.3521	1.0784	0.6704	0.055*
C28	1.1733 (6)	0.9662 (4)	0.5937 (4)	0.0477 (15)
H28	1.1940	0.9816	0.5300	0.057*
C29	1.0464 (5)	0.8846 (4)	0.6058 (3)	0.0373 (12)
H29	0.9819	0.8492	0.5487	0.045*
C30	1.0704 (5)	0.8775 (3)	0.8739 (3)	0.0240 (10)
C31	1.1071 (5)	0.9121 (4)	0.7786 (3)	0.0284 (11)
O4	0.2548 (5)	0.6130 (4)	1.1314 (3)	0.0849 (15)
H4A	0.3056	0.6009	1.0797	0.127*
H4B	0.2955	0.5559	1.1627	0.127*
O5	0.6423 (4)	1.1780 (3)	0.7310 (3)	0.0707 (13)
H5A	0.6793	1.2428	0.7689	0.106*
H5B	0.5979	1.1190	0.7654	0.106*
O6	0.8621 (6)	1.0978 (3)	0.6534 (3)	0.1067 (19)
H6D	0.8036	1.1361	0.6718	0.160*
H6E	0.8406	1.0267	0.6755	0.160*
O7	0.0000	0.5000	1.0000	0.383 (10)
H7D	0.0556	0.4810	0.9600	0.575*	0.50
H7E	0.0563	0.5411	1.0543	0.575*	0.50

	U11	U22	U33	U12	U13	U23
N1	0.040 (2)	0.0185 (19)	0.0159 (17)	−0.0093 (18)	−0.0078 (16)	−0.0005 (14)
N2	0.046 (3)	0.020 (2)	0.0188 (18)	−0.0036 (19)	−0.0079 (18)	0.0005 (15)
N3	0.043 (3)	0.023 (2)	0.027 (2)	−0.0004 (19)	0.0018 (19)	0.0016 (16)
N4	0.041 (3)	0.021 (2)	0.0210 (18)	−0.0037 (18)	0.0042 (17)	0.0008 (15)
N5	0.040 (3)	0.0186 (19)	0.0217 (18)	−0.0043 (17)	0.0037 (17)	−0.0003 (15)
N6	0.040 (2)	0.023 (2)	0.0198 (18)	0.0001 (18)	−0.0009 (17)	−0.0015 (15)
O1	0.054 (2)	0.0216 (18)	0.045 (2)	0.0063 (17)	0.0017 (17)	0.0011 (14)
O2	0.035 (2)	0.0276 (18)	0.0281 (17)	0.0016 (15)	0.0052 (15)	0.0003 (13)
O3	0.054 (3)	0.043 (2)	0.053 (2)	−0.0003 (19)	0.015 (2)	0.0153 (17)
Ni1	0.0433 (4)	0.0227 (3)	0.0173 (3)	−0.0043 (3)	−0.0027 (2)	−0.0026 (2)
C1	0.045 (3)	0.023 (3)	0.021 (2)	0.005 (2)	−0.004 (2)	0.0005 (19)
C2	0.042 (3)	0.023 (2)	0.023 (2)	0.003 (2)	−0.004 (2)	−0.0050 (18)
C3	0.043 (3)	0.025 (3)	0.022 (2)	0.001 (2)	−0.009 (2)	0.0006 (19)
C4	0.032 (3)	0.024 (2)	0.026 (2)	0.004 (2)	−0.002 (2)	−0.0038 (18)
C5	0.044 (3)	0.032 (3)	0.026 (2)	0.001 (2)	0.001 (2)	0.007 (2)
C6	0.068 (4)	0.026 (3)	0.044 (3)	−0.012 (3)	0.008 (3)	0.003 (2)
C7	0.048 (3)	0.029 (3)	0.051 (3)	0.007 (3)	0.008 (3)	0.007 (2)
C8	0.046 (3)	0.034 (3)	0.027 (2)	−0.004 (2)	0.007 (2)	0.003 (2)
C9	0.047 (3)	0.048 (3)	0.028 (2)	−0.007 (3)	−0.004 (2)	0.005 (2)
C10	0.053 (4)	0.053 (3)	0.018 (2)	−0.018 (3)	−0.002 (2)	0.001 (2)
C11	0.045 (3)	0.036 (3)	0.022 (2)	−0.010 (2)	0.007 (2)	−0.005 (2)
C12	0.060 (4)	0.043 (3)	0.031 (3)	−0.016 (3)	0.010 (3)	−0.012 (2)
C13	0.062 (4)	0.031 (3)	0.041 (3)	−0.014 (3)	0.023 (3)	−0.011 (2)
C14	0.054 (4)	0.029 (3)	0.032 (3)	−0.004 (3)	0.016 (3)	−0.002 (2)
C15	0.051 (4)	0.027 (3)	0.056 (3)	−0.004 (3)	0.025 (3)	−0.004 (2)
C16	0.046 (3)	0.033 (3)	0.051 (3)	0.011 (3)	0.014 (3)	0.009 (2)
C17	0.042 (3)	0.030 (3)	0.036 (3)	0.000 (2)	0.005 (2)	0.002 (2)
C18	0.040 (3)	0.025 (2)	0.022 (2)	−0.008 (2)	0.005 (2)	−0.0001 (19)
C19	0.039 (3)	0.025 (2)	0.028 (2)	−0.008 (2)	0.014 (2)	−0.0038 (19)
C20	0.041 (3)	0.030 (3)	0.023 (2)	−0.006 (2)	−0.003 (2)	0.0000 (19)
C21	0.047 (3)	0.029 (3)	0.024 (2)	0.000 (2)	0.001 (2)	−0.0022 (19)
C22	0.042 (3)	0.028 (3)	0.022 (2)	0.005 (2)	−0.006 (2)	−0.0061 (19)
C23	0.037 (3)	0.020 (2)	0.027 (2)	0.004 (2)	−0.001 (2)	−0.0056 (18)
C24	0.040 (3)	0.024 (2)	0.036 (3)	−0.005 (2)	−0.001 (2)	−0.006 (2)
C25	0.043 (3)	0.021 (2)	0.044 (3)	−0.003 (2)	0.002 (2)	−0.002 (2)
C26	0.041 (3)	0.023 (2)	0.030 (2)	−0.002 (2)	0.005 (2)	0.0035 (19)
C27	0.051 (4)	0.035 (3)	0.042 (3)	−0.006 (3)	0.010 (3)	0.004 (2)
C28	0.059 (4)	0.046 (3)	0.030 (3)	−0.002 (3)	0.010 (3)	0.010 (2)
C29	0.045 (3)	0.037 (3)	0.025 (2)	0.002 (2)	0.007 (2)	0.006 (2)
C30	0.031 (3)	0.015 (2)	0.023 (2)	0.0038 (19)	0.0004 (19)	−0.0037 (17)
C31	0.036 (3)	0.018 (2)	0.024 (2)	−0.001 (2)	0.001 (2)	0.0013 (17)
O4	0.101 (4)	0.065 (3)	0.118 (4)	0.042 (3)	0.065 (3)	0.054 (3)
O5	0.067 (3)	0.044 (2)	0.093 (3)	0.008 (2)	−0.002 (2)	0.030 (2)
O6	0.205 (6)	0.043 (3)	0.097 (3)	0.033 (3)	0.098 (4)	0.027 (2)
O7	0.51 (2)	0.397 (17)	0.303 (16)	0.246 (16)	0.044 (14)	0.047 (13)

N1—N2	1.333 (4)	C12—H12	0.9300
N1—Ni1	2.041 (4)	C12—C13	1.333 (7)
N1—C2	1.394 (6)	C13—H13	0.9300
N2—C4	1.368 (6)	C13—C14	1.461 (6)
N3—Ni1	2.085 (4)	C14—C15	1.387 (7)
N3—C8	1.312 (6)	C14—C19	1.401 (6)
N3—C18	1.361 (5)	C15—H15	0.9300
N4—Ni1	2.080 (4)	C15—C16	1.386 (7)
N4—C17	1.324 (6)	C16—H16	0.9300
N4—C19	1.386 (5)	C16—C17	1.401 (6)
N5—Ni1	2.078 (3)	C17—H17	0.9300
N5—C20	1.324 (5)	C18—C19	1.415 (7)
N5—C30	1.363 (5)	C20—H20	0.9300
N6—Ni1	2.093 (4)	C20—C21	1.413 (5)
N6—C29	1.337 (5)	C21—H21	0.9300
N6—C31	1.379 (5)	C21—C22	1.355 (6)
O1—C1	1.247 (5)	C22—H22	0.9300
O2—Ni1	2.066 (3)	C22—C23	1.404 (6)
O2—C1	1.308 (6)	C23—C24	1.453 (6)
O3—C5	1.240 (6)	C23—C30	1.406 (5)
C1—C2	1.482 (6)	C24—H24	0.9300
C2—C3	1.395 (6)	C24—C25	1.358 (6)
C3—C4	1.382 (6)	C25—H25	0.9300
C3—C7	1.503 (7)	C25—C26	1.433 (6)
C4—C5	1.477 (6)	C26—C27	1.413 (6)
C5—C6	1.502 (7)	C26—C31	1.403 (6)
C6—H6A	0.9600	C27—H27	0.9300
C6—H6B	0.9600	C27—C28	1.374 (6)
C6—H6C	0.9600	C28—H28	0.9300
C7—H7A	0.9600	C28—C29	1.396 (6)
C7—H7B	0.9600	C29—H29	0.9300
C7—H7C	0.9600	C30—C31	1.438 (6)
C8—H8	0.9300	O4—H4A	0.9495
C8—C9	1.418 (6)	O4—H4B	0.9445
C9—H9	0.9300	O5—H5A	0.8599
C9—C10	1.371 (7)	O5—H5B	0.9001
C10—H10	0.9300	O6—H6D	0.8749
C10—C11	1.396 (7)	O6—H6E	0.8751
C11—C12	1.424 (7)	O7—H7D	0.8900
C11—C18	1.427 (5)	O7—H7E	0.8900
N2—N1—Ni1	140.1 (3)	C10—C11—C12	125.1 (5)
N2—N1—C2	107.9 (4)	C10—C11—C18	117.2 (5)
C2—N1—Ni1	111.9 (3)	C12—C11—C18	117.7 (5)
N1—N2—C4	107.4 (4)	C11—C12—H12	118.8
C8—N3—Ni1	127.8 (3)	C13—C12—C11	122.3 (5)
C8—N3—C18	118.8 (4)	C13—C12—H12	118.8
C18—N3—Ni1	113.2 (3)	C12—C13—H13	119.4
C17—N4—Ni1	130.8 (3)	C12—C13—C14	121.2 (5)
C17—N4—C19	116.1 (4)	C14—C13—H13	119.4
C19—N4—Ni1	113.1 (3)	C15—C14—C13	124.4 (5)
C20—N5—Ni1	128.9 (3)	C15—C14—C19	117.7 (4)
C20—N5—C30	117.7 (4)	C19—C14—C13	117.9 (5)
C30—N5—Ni1	113.1 (3)	C14—C15—H15	119.8
C29—N6—Ni1	130.3 (3)	C16—C15—C14	120.4 (5)
C29—N6—C31	117.0 (4)	C16—C15—H15	119.8
C31—N6—Ni1	112.6 (3)	C15—C16—H16	121.3
C1—O2—Ni1	116.3 (3)	C15—C16—C17	117.4 (5)
N1—Ni1—N3	92.73 (14)	C17—C16—H16	121.3
N1—Ni1—N4	99.54 (15)	N4—C17—C16	125.1 (4)
N1—Ni1—N5	91.36 (14)	N4—C17—H17	117.4
N1—Ni1—N6	165.31 (14)	C16—C17—H17	117.4
N1—Ni1—O2	80.47 (15)	N3—C18—C11	121.8 (5)
N3—Ni1—N6	96.35 (14)	N3—C18—C19	117.6 (4)
N4—Ni1—N3	79.56 (15)	C19—C18—C11	120.5 (4)
N4—Ni1—N6	93.46 (15)	N4—C19—C14	123.1 (5)
N5—Ni1—N3	175.80 (16)	N4—C19—C18	116.5 (4)
N5—Ni1—N4	98.84 (15)	C14—C19—C18	120.4 (4)
N5—Ni1—N6	79.83 (14)	N5—C20—H20	118.7
O2—Ni1—N3	91.62 (14)	N5—C20—C21	122.5 (4)
O2—Ni1—N4	171.18 (13)	C21—C20—H20	118.7
O2—Ni1—N5	89.97 (13)	C20—C21—H21	120.1
O2—Ni1—N6	87.73 (14)	C22—C21—C20	119.7 (4)
O1—C1—O2	124.6 (4)	C22—C21—H21	120.1
O1—C1—C2	121.4 (5)	C21—C22—H22	120.2
O2—C1—C2	114.0 (5)	C21—C22—C23	119.6 (4)
N1—C2—C1	117.3 (4)	C23—C22—H22	120.2
N1—C2—C3	109.9 (4)	C22—C23—C24	123.8 (4)
C3—C2—C1	132.8 (5)	C22—C23—C30	117.2 (4)
C2—C3—C7	128.1 (4)	C30—C23—C24	118.8 (4)
C4—C3—C2	102.8 (4)	C23—C24—H24	119.5
C4—C3—C7	129.1 (4)	C25—C24—C23	121.0 (4)
N2—C4—C3	112.0 (4)	C25—C24—H24	119.5
N2—C4—C5	119.7 (4)	C24—C25—H25	119.6
C3—C4—C5	128.2 (5)	C24—C25—C26	120.9 (4)
O3—C5—C4	120.8 (5)	C26—C25—H25	119.6
O3—C5—C6	119.8 (5)	C27—C26—C25	123.4 (4)
C4—C5—C6	119.4 (5)	C31—C26—C25	119.3 (4)
C5—C6—H6A	109.5	C31—C26—C27	117.3 (4)
C5—C6—H6B	109.5	C26—C27—H27	120.1
C5—C6—H6C	109.5	C28—C27—C26	119.7 (5)
H6A—C6—H6B	109.5	C28—C27—H27	120.1
H6A—C6—H6C	109.5	C27—C28—H28	120.5
H6B—C6—H6C	109.5	C27—C28—C29	119.1 (4)
C3—C7—H7A	109.5	C29—C28—H28	120.5
C3—C7—H7B	109.5	N6—C29—C28	123.7 (4)
C3—C7—H7C	109.5	N6—C29—H29	118.2
H7A—C7—H7B	109.5	C28—C29—H29	118.2
H7A—C7—H7C	109.5	N5—C30—C23	123.2 (4)
H7B—C7—H7C	109.5	N5—C30—C31	117.3 (3)
N3—C8—H8	118.2	C23—C30—C31	119.5 (4)
N3—C8—C9	123.6 (5)	N6—C31—C26	123.1 (4)
C9—C8—H8	118.2	N6—C31—C30	116.4 (4)
C8—C9—H9	121.2	C26—C31—C30	120.5 (4)
C10—C9—C8	117.7 (5)	H4A—O4—H4B	83.7
C10—C9—H9	121.2	H5A—O5—H5B	111.0
C9—C10—H10	119.6	H6D—O6—H6E	107.9
C9—C10—C11	120.8 (4)	H7D—O7—H7E	107.6
C11—C10—H10	119.6

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O3	0.95	2.31	3.088 (6)	139
O4—H4B···N2i	0.94	2.01	2.906 (6)	157
O5—H5A···O4ii	0.86	2.02	2.875 (6)	172
O5—H5B···O1	0.90	2.00	2.787 (5)	145
O6—H6D···O5	0.87	2.05	2.895 (6)	163
O6—H6E···O2	0.88	1.98	2.827 (5)	163
O7—H7D···O3	0.89	2.16	2.964 (4)	150
O7—H7E···O4	0.89	2.02	2.821 (5)	149
C12—H12···Cg1iii	0.93	2.77	3.646 (6)	158

Table 1

Selected bond lengths (Å)

N1—Ni1	2.041 (4)
N3—Ni1	2.085 (4)
N4—Ni1	2.080 (4)
N5—Ni1	2.078 (3)
N6—Ni1	2.093 (4)
O2—Ni1	2.066 (3)

Table 2

Hydrogen-bond geometry (Å, °)

Cg is the centroid of the N1/N2/C2/C3/C4 pyrazole ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4A⋯O3	0.95	2.31	3.088 (6)	139
O4—H4B⋯N2i	0.94	2.01	2.906 (6)	157
O5—H5A⋯O4ii	0.86	2.02	2.875 (6)	172
O5—H5B⋯O1	0.90	2.00	2.787 (5)	145
O6—H6D⋯O5	0.87	2.05	2.895 (6)	163
O6—H6E⋯O2	0.88	1.98	2.827 (5)	163
O7—H7D⋯O3	0.89	2.16	2.964 (4)	150
O7—H7E⋯O4	0.89	2.02	2.821 (5)	149
C12—H12⋯Cg1iii	0.93	2.77	3.646 (6)	158

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