[1-(2-Oxidobenzyl­idene)-4-phenyl­thio­semicarbazonato-κ³S,N¹,O](pyridine-κN)nickel(II)

In the title complex, [Ni(C₁₄H₁₁N₃OS)(C₅H₅N)], the Ni^II atom is N,O,S-chelated by the deprotonated salicylaldimine-4-phenyl­thio­semicarbazide dianion and is also coordinated by a pyridine mol­ecule, the coordinating atoms giving rise to a square-planar geometry for the Ni atom. The asymmetric unit contains two molecules. The mononuclear units are linked into a chain structure along the b axis by inter­molecular N—H...S hydrogen bonds and weak π–π stacking inter­actions between the pyridine rings [centroid–centroid = 3.758 (3) Å].

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.011 Å
• R factor = 0.037
• wR factor = 0.089
• Data-to-parameter ratio = 15.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...         11

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.47
           From the CIF: _reflns_number_total               7370
           Count of symmetry unique reflns         4015
           Completeness (_total/calc)            183.56%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      3355
           Fraction of Friedel pairs measured     0.836
           Are heavy atom types Z>Si present        yes
PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni1         (3)       2.82
PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni2         (3)       2.82
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          4

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   4 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

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S1. Comment

Up to now, a number of metal complexes of N-salicyldimine-4-phenylthiosemicarbazide have been synthesized, and most of them are mononuclear (Milanesio et al., 2000; Prabhakaran et al., 2005; Soriano-García et al., 1985; Naik et al., 2003; Thomas et al., 2004). Recently, a dinuclear complex has been reported (Deng et al., 2007). In these complexs, the hydrazone ligand chelates in a terdentate manner. In the title mononuclear complex, [Ni(C₁₄H₁₁N₃OS)(C₅H₅N)], the ligand binds in a similar mode. As shown in Fig. 1, the Ni^II atom is N,O,S-chelated by deprotonated salicylaldimine-4-phenylthiosemicarbazide dianion. It is also coordinated by pyridine molecule, and a square planar geometry results. The mononuclear units are linked into a chain structure along b axis by N—H···S intermolecular hydrogen bonds and weak π-π stacking interactions between the pyridine rings [centroid···centroid = 3.758 (3) Å] (Fig. 2).

Related literature

For other metal derivatives of N-salicylaldimine-4-phenylthiosemicarbazide, see: Milanesio et al. (2000) for vanadium, Prabhakaran et al. (2005) and Soriano-García et al. (1985) for nickel, Naik et al. (2003) and Thomas et al. (2004) for copper, Deng et al. (2007) for zinc.

S2. Experimental

N-salicldimine-4-phenylthiosemicarbazone ligand was synthesized by condensing salicylaldehyde with 4-phenylthiosemicarbazide in ethonal for 2.5 h, and the hydrazone ligand was isolated as yellow crystals from the resulting solution. The title compound was prepared by the addition of nickel(II) acetate tetrahydrate (1 mmol) and pyridine (1 ml) to a methanol solution (15 ml) of the ligand (1 mmol). The mixture was refluxed for 1 h, cooled slowly to room temperature and filtered. Red-brown crystals were isolated from the solution after three days. Analysis calculated for C₁₉H₁₆N₄OSNi: C 56.06, H 3.96, N 13.76%; found: C 56.01, H 3.94, N 13.79%.

S3. Refinement

C-bound H atoms were placed in calculated positions, with C—H = 0.93 and U_iso(H) = 1.2U_eq(C), and were included in the refinement in the riding-model approximation. H atoms on the N atoms were located in Fourier difference maps and refined with the restraints N—H = 0.86 (1) Å, and with U_iso(H) = 1.2U_eq(N). The Flack parameter was refined from 3366 Friedel paris.

Computing details

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. A view of complex (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The chain structure of (I), viewed along the b axis. Green dashed lines indicate N–H···S hydrogen bonds. H atoms not involved in hydrogen bonding have been omitted. Cg1 and Cg2 represent the centroids of adjacent pyridine rings, as defined in the comment.

[1-(2-Oxidobenzylidene)-4-phenylthiosemicarbazonato- κ³S,N¹,O](pyridine-κN)nickel(II)

Crystal data

[Ni(C14H11N3OS)(C5H5N)]	F(000) = 840
Mr = 407.13	Dx = 1.550 Mg m^−3
Monoclinic, Pc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P -2yc	Cell parameters from 11939 reflections
a = 5.7294 (11) Å	θ = 3.0–27.5°
b = 12.924 (3) Å	µ = 1.25 mm^−1
c = 23.683 (5) Å	T = 295 K
β = 95.64 (3)°	Prism, colorless
V = 1745.2 (6) Å^3	0.35 × 0.24 × 0.17 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID diffractometer	7370 independent reflections
Radiation source: fine-focus sealed tube	4892 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.044
Detector resolution: 10.000 pixels mm^-1	θmax = 27.5°, θmin = 3.0°
ω scans	h = −6→7
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −16→16
Tmin = 0.669, Tmax = 0.816	l = −30→30
16815 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.089	w = 1/[σ^2(Fo^2) + (0.022P)^2 + 0.9787P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
7370 reflections	Δρmax = 0.60 e Å^−3
475 parameters	Δρmin = −0.57 e Å^−3
4 restraints	Absolute structure: Flack (1983), with 3366 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.029 (17)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ni1	0.42415 (9)	0.92246 (4)	0.75792 (3)	0.03968 (16)
Ni2	0.30864 (10)	0.32924 (4)	0.63710 (3)	0.03927 (16)
S1	0.1296 (2)	1.01932 (11)	0.72961 (6)	0.0479 (4)
S2	0.6011 (3)	0.23095 (11)	0.66440 (6)	0.0486 (4)
O1	0.6638 (8)	0.8306 (2)	0.78157 (17)	0.0491 (11)
O2	0.0683 (7)	0.4217 (2)	0.61431 (17)	0.0479 (11)
N1	0.5015 (8)	1.0198 (3)	0.81387 (19)	0.0399 (10)
N2	0.3641 (8)	1.1071 (3)	0.8204 (2)	0.0444 (11)
N3	0.0183 (8)	1.1876 (4)	0.78621 (19)	0.0464 (11)
H3N	−0.096 (6)	1.185 (4)	0.7596 (16)	0.056*
N4	0.3432 (8)	0.8267 (3)	0.69777 (19)	0.0372 (11)
N5	0.2299 (7)	0.2349 (3)	0.57989 (19)	0.0381 (10)
N6	0.3675 (8)	0.1466 (3)	0.57220 (19)	0.0451 (11)
N7	0.7084 (8)	0.0632 (4)	0.60734 (18)	0.0464 (11)
H7N	0.825 (6)	0.066 (4)	0.6330 (17)	0.056*
N8	0.3873 (8)	0.4238 (3)	0.69807 (19)	0.0380 (11)
C1	0.8281 (16)	0.8445 (6)	0.8244 (4)	0.0414 (19)
C2	0.995 (2)	0.7658 (7)	0.8368 (4)	0.057 (3)
H2	0.9801	0.7038	0.8169	0.069*
C3	1.176 (2)	0.7786 (8)	0.8771 (4)	0.062 (3)
H3	1.2856	0.7256	0.8826	0.075*
C4	1.2076 (16)	0.8661 (7)	0.9108 (4)	0.054 (2)
H4	1.3329	0.8726	0.9387	0.065*
C5	1.0409 (13)	0.9432 (6)	0.9004 (3)	0.053 (2)
H5	1.0548	1.0034	0.9220	0.064*
C6	0.8511 (12)	0.9335 (5)	0.8582 (3)	0.0424 (16)
C7	0.6850 (9)	1.0158 (4)	0.8509 (2)	0.0404 (12)
H7	0.7103	1.0723	0.8750	0.049*
C8	0.1818 (9)	1.1111 (4)	0.7833 (2)	0.0390 (12)
C9	0.0002 (17)	1.2640 (6)	0.8284 (4)	0.041 (2)
C10	−0.2062 (17)	1.3186 (6)	0.8283 (5)	0.051 (2)
H10	−0.3307	1.3035	0.8014	0.062*
C11	−0.2306 (14)	1.3955 (5)	0.8679 (3)	0.0557 (19)
H11	−0.3713	1.4315	0.8670	0.067*
C12	−0.0527 (15)	1.4192 (6)	0.9080 (4)	0.057 (2)
H12	−0.0701	1.4715	0.9342	0.068*
C13	0.1552 (17)	1.3640 (7)	0.9090 (5)	0.061 (3)
H13	0.2778	1.3783	0.9366	0.074*
C14	0.1808 (17)	1.2872 (6)	0.8688 (4)	0.047 (2)
H14	0.3217	1.2513	0.8694	0.056*
C15	0.4957 (11)	0.8095 (4)	0.6593 (3)	0.0456 (14)
H15	0.6289	0.8508	0.6602	0.055*
C16	0.4640 (11)	0.7341 (4)	0.6189 (2)	0.0508 (15)
H16	0.5721	0.7253	0.5925	0.061*
C17	0.2700 (11)	0.6712 (5)	0.6180 (2)	0.0537 (14)
H17	0.2463	0.6180	0.5916	0.064*
C18	0.1127 (10)	0.6887 (4)	0.6568 (2)	0.0484 (14)
H18	−0.0200	0.6473	0.6571	0.058*
C19	0.1518 (10)	0.7674 (4)	0.6951 (2)	0.0459 (13)
H19	0.0405	0.7802	0.7202	0.055*
C20	−0.0943 (17)	0.4123 (6)	0.5718 (4)	0.0416 (19)
C21	−0.2597 (18)	0.4920 (7)	0.5611 (4)	0.050 (2)
H21	−0.2470	0.5516	0.5832	0.059*
C22	−0.4421 (19)	0.4834 (7)	0.5179 (4)	0.059 (3)
H22	−0.5520	0.5361	0.5115	0.071*
C23	−0.4570 (17)	0.3963 (8)	0.4851 (5)	0.061 (3)
H23	−0.5804	0.3898	0.4567	0.074*
C24	−0.2986 (14)	0.3196 (6)	0.4926 (3)	0.052 (2)
H24	−0.3117	0.2624	0.4687	0.062*
C25	−0.1122 (12)	0.3246 (5)	0.5364 (3)	0.0417 (17)
C26	0.0501 (9)	0.2410 (4)	0.5421 (2)	0.0439 (13)
H26	0.0254	0.1862	0.5168	0.053*
C27	0.5462 (10)	0.1413 (4)	0.6101 (2)	0.0403 (13)
C28	0.7199 (17)	−0.0134 (6)	0.5662 (4)	0.0381 (19)
C29	0.9279 (18)	−0.0694 (6)	0.5667 (4)	0.047 (2)
H29	1.0531	−0.0532	0.5933	0.057*
C30	0.9513 (14)	−0.1482 (6)	0.5287 (3)	0.057 (2)
H30	1.0917	−0.1845	0.5298	0.069*
C31	0.7675 (15)	−0.1739 (6)	0.4886 (4)	0.052 (2)
H31	0.7825	−0.2272	0.4628	0.062*
C32	0.5649 (16)	−0.1191 (6)	0.4881 (4)	0.051 (2)
H32	0.4408	−0.1366	0.4616	0.061*
C33	0.5341 (17)	−0.0390 (6)	0.5250 (4)	0.045 (2)
H33	0.3936	−0.0026	0.5229	0.054*
C34	0.5814 (9)	0.4822 (4)	0.7015 (2)	0.0435 (13)
H34	0.6953	0.4691	0.6770	0.052*
C35	0.6158 (11)	0.5614 (5)	0.7404 (2)	0.0534 (15)
H35	0.7476	0.6035	0.7407	0.064*
C36	0.4544 (11)	0.5779 (5)	0.7788 (2)	0.0548 (14)
H36	0.4754	0.6311	0.8053	0.066*
C37	0.2619 (11)	0.5145 (4)	0.7774 (2)	0.0509 (15)
H37	0.1531	0.5223	0.8038	0.061*
C38	0.2330 (11)	0.4391 (4)	0.7362 (2)	0.0443 (14)
H38	0.1008	0.3971	0.7349	0.053*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0444 (4)	0.0343 (3)	0.0392 (4)	0.0006 (3)	−0.0018 (3)	−0.0047 (3)
Ni2	0.0437 (4)	0.0347 (3)	0.0380 (4)	0.0012 (3)	−0.0026 (3)	−0.0043 (3)
S1	0.0541 (9)	0.0433 (7)	0.0433 (8)	0.0063 (7)	−0.0103 (7)	−0.0090 (6)
S2	0.0550 (9)	0.0426 (7)	0.0452 (9)	0.0087 (7)	−0.0105 (7)	−0.0087 (7)
O1	0.057 (3)	0.043 (2)	0.044 (3)	0.0073 (17)	−0.007 (2)	−0.0095 (16)
O2	0.053 (3)	0.040 (2)	0.048 (3)	0.0083 (17)	−0.010 (2)	−0.0123 (16)
N1	0.043 (3)	0.036 (2)	0.041 (3)	0.002 (2)	0.000 (2)	0.000 (2)
N2	0.044 (3)	0.033 (2)	0.054 (3)	0.011 (2)	−0.009 (2)	−0.007 (2)
N3	0.048 (3)	0.043 (3)	0.045 (3)	0.009 (2)	−0.012 (2)	−0.005 (2)
N4	0.038 (3)	0.034 (2)	0.039 (3)	0.0015 (19)	0.001 (2)	−0.0015 (19)
N5	0.038 (3)	0.031 (2)	0.044 (3)	0.0033 (19)	−0.001 (2)	−0.0020 (19)
N6	0.049 (3)	0.037 (2)	0.048 (3)	0.008 (2)	−0.001 (2)	−0.008 (2)
N7	0.046 (3)	0.046 (3)	0.043 (3)	0.009 (2)	−0.014 (2)	−0.009 (2)
N8	0.043 (3)	0.035 (2)	0.036 (3)	0.002 (2)	0.002 (2)	−0.0005 (19)
C1	0.039 (4)	0.044 (4)	0.041 (4)	0.009 (3)	−0.001 (3)	0.009 (3)
C2	0.075 (7)	0.051 (5)	0.044 (5)	0.019 (4)	−0.004 (4)	−0.013 (4)
C3	0.072 (6)	0.068 (5)	0.045 (5)	0.034 (4)	−0.004 (4)	0.005 (4)
C4	0.047 (4)	0.071 (5)	0.042 (5)	0.014 (4)	−0.008 (4)	−0.006 (4)
C5	0.048 (4)	0.060 (4)	0.049 (4)	0.004 (3)	−0.009 (4)	−0.005 (3)
C6	0.044 (4)	0.042 (3)	0.040 (4)	0.002 (3)	0.001 (3)	−0.003 (3)
C7	0.038 (3)	0.041 (3)	0.041 (3)	0.000 (2)	−0.005 (2)	−0.007 (2)
C8	0.045 (3)	0.032 (3)	0.039 (3)	0.006 (2)	−0.002 (2)	0.003 (2)
C9	0.049 (5)	0.036 (4)	0.036 (4)	−0.001 (3)	0.001 (3)	0.000 (3)
C10	0.037 (4)	0.053 (4)	0.061 (5)	0.012 (3)	−0.007 (4)	0.003 (4)
C11	0.053 (5)	0.056 (4)	0.060 (5)	0.015 (4)	0.011 (4)	0.003 (4)
C12	0.062 (6)	0.052 (4)	0.059 (5)	0.007 (4)	0.017 (4)	−0.008 (3)
C13	0.063 (6)	0.062 (5)	0.058 (6)	−0.005 (4)	0.002 (5)	−0.022 (4)
C14	0.046 (4)	0.046 (4)	0.047 (5)	0.013 (3)	−0.002 (3)	−0.005 (3)
C15	0.043 (4)	0.045 (3)	0.049 (4)	0.002 (3)	0.005 (3)	0.003 (3)
C16	0.062 (4)	0.048 (3)	0.042 (3)	0.015 (3)	0.007 (3)	−0.004 (3)
C17	0.068 (4)	0.042 (3)	0.049 (3)	0.006 (3)	−0.007 (3)	−0.008 (3)
C18	0.054 (3)	0.044 (3)	0.047 (3)	−0.010 (3)	0.003 (3)	−0.009 (3)
C19	0.049 (3)	0.046 (3)	0.042 (3)	−0.001 (3)	0.004 (3)	−0.005 (3)
C20	0.054 (5)	0.043 (3)	0.027 (3)	0.000 (3)	0.000 (3)	−0.003 (3)
C21	0.059 (6)	0.045 (4)	0.043 (4)	0.020 (4)	−0.005 (4)	0.000 (3)
C22	0.066 (6)	0.064 (5)	0.045 (5)	0.025 (4)	−0.009 (4)	−0.002 (4)
C23	0.052 (4)	0.076 (6)	0.052 (5)	0.018 (4)	−0.018 (4)	−0.009 (4)
C24	0.052 (5)	0.057 (4)	0.044 (4)	0.009 (3)	−0.013 (3)	−0.015 (3)
C25	0.043 (4)	0.043 (3)	0.038 (4)	0.007 (3)	0.001 (3)	0.000 (3)
C26	0.046 (3)	0.040 (3)	0.043 (3)	−0.002 (2)	−0.006 (3)	−0.007 (2)
C27	0.046 (3)	0.036 (3)	0.037 (3)	0.003 (2)	−0.004 (2)	0.000 (2)
C28	0.045 (4)	0.030 (3)	0.040 (4)	0.005 (3)	0.007 (3)	0.006 (3)
C29	0.049 (4)	0.049 (4)	0.044 (4)	0.003 (3)	0.003 (3)	−0.007 (4)
C30	0.056 (5)	0.059 (5)	0.057 (5)	0.020 (4)	0.005 (4)	0.001 (4)
C31	0.070 (6)	0.044 (4)	0.043 (4)	0.010 (3)	0.010 (4)	−0.006 (3)
C32	0.052 (5)	0.054 (5)	0.043 (5)	0.012 (4)	−0.009 (4)	−0.010 (4)
C33	0.037 (4)	0.045 (4)	0.052 (5)	0.002 (3)	−0.004 (3)	−0.008 (4)
C34	0.044 (3)	0.048 (3)	0.038 (3)	−0.003 (3)	0.002 (2)	−0.004 (3)
C35	0.055 (4)	0.053 (4)	0.051 (3)	−0.005 (3)	−0.002 (3)	−0.003 (3)
C36	0.067 (4)	0.044 (3)	0.051 (4)	0.009 (3)	−0.004 (3)	−0.014 (3)
C37	0.057 (4)	0.053 (3)	0.044 (3)	0.008 (3)	0.012 (3)	0.002 (3)
C38	0.045 (4)	0.045 (3)	0.042 (3)	−0.003 (3)	0.000 (3)	0.002 (3)

Geometric parameters (Å, º)

Ni1—N1	1.849 (4)	C12—C13	1.387 (12)
Ni1—O1	1.859 (4)	C12—H12	0.9300
Ni1—N4	1.909 (4)	C13—C14	1.394 (12)
Ni1—S1	2.1547 (15)	C13—H13	0.9300
Ni2—N5	1.845 (4)	C14—H14	0.9300
Ni2—O2	1.863 (4)	C15—C16	1.366 (8)
Ni2—N8	1.911 (4)	C15—H15	0.9300
Ni2—S2	2.1507 (15)	C16—C17	1.375 (8)
S1—C8	1.744 (5)	C16—H16	0.9300
S2—C27	1.736 (5)	C17—C18	1.367 (8)
O1—C1	1.327 (10)	C17—H17	0.9300
O2—C20	1.308 (10)	C18—C19	1.367 (7)
N1—C7	1.302 (6)	C18—H18	0.9300
N1—N2	1.393 (6)	C19—H19	0.9300
N2—C8	1.297 (6)	C20—C21	1.406 (12)
N3—C8	1.368 (7)	C20—C25	1.407 (11)
N3—C9	1.415 (10)	C21—C22	1.392 (11)
N3—H3N	0.86 (4)	C21—H21	0.9300
N4—C19	1.334 (6)	C22—C23	1.366 (13)
N4—C15	1.341 (7)	C22—H22	0.9300
N5—C26	1.298 (6)	C23—C24	1.343 (12)
N5—N6	1.410 (5)	C23—H23	0.9300
N6—C27	1.295 (6)	C24—C25	1.415 (10)
N7—C27	1.378 (7)	C24—H24	0.9300
N7—C28	1.397 (10)	C25—C26	1.424 (8)
N7—H7N	0.86 (4)	C26—H26	0.9300
N8—C38	1.340 (7)	C28—C29	1.393 (13)
N8—C34	1.340 (6)	C28—C33	1.410 (11)
C1—C6	1.400 (11)	C29—C30	1.375 (12)
C1—C2	1.406 (12)	C29—H29	0.9300
C2—C3	1.348 (12)	C30—C31	1.386 (11)
C2—H2	0.9300	C30—H30	0.9300
C3—C4	1.386 (13)	C31—C32	1.359 (12)
C3—H3	0.9300	C31—H31	0.9300
C4—C5	1.386 (12)	C32—C33	1.377 (12)
C4—H4	0.9300	C32—H32	0.9300
C5—C6	1.409 (10)	C33—H33	0.9300
C5—H5	0.9300	C34—C35	1.379 (7)
C6—C7	1.426 (8)	C34—H34	0.9300
C7—H7	0.9300	C35—C36	1.376 (8)
C9—C14	1.372 (11)	C35—H35	0.9300
C9—C10	1.377 (13)	C36—C37	1.371 (8)
C10—C11	1.382 (12)	C36—H36	0.9300
C10—H10	0.9300	C37—C38	1.378 (8)
C11—C12	1.358 (11)	C37—H37	0.9300
C11—H11	0.9300	C38—H38	0.9300
N1—Ni1—O1	95.77 (17)	C9—C14—C13	120.6 (10)
N1—Ni1—N4	177.51 (19)	C9—C14—H14	119.7
O1—Ni1—N4	85.93 (17)	C13—C14—H14	119.7
N1—Ni1—S1	87.31 (14)	N4—C15—C16	122.9 (5)
O1—Ni1—S1	175.83 (13)	N4—C15—H15	118.5
N4—Ni1—S1	91.08 (13)	C16—C15—H15	118.5
N5—Ni2—O2	95.19 (17)	C15—C16—C17	119.0 (6)
N5—Ni2—N8	178.16 (19)	C15—C16—H16	120.5
O2—Ni2—N8	85.50 (17)	C17—C16—H16	120.5
N5—Ni2—S2	87.57 (13)	C18—C17—C16	118.5 (5)
O2—Ni2—S2	176.29 (13)	C18—C17—H17	120.8
N8—Ni2—S2	91.81 (14)	C16—C17—H17	120.8
C8—S1—Ni1	95.46 (18)	C19—C18—C17	119.5 (6)
C27—S2—Ni2	95.30 (18)	C19—C18—H18	120.2
C1—O1—Ni1	126.3 (4)	C17—C18—H18	120.2
C20—O2—Ni2	127.8 (4)	N4—C19—C18	122.7 (5)
C7—N1—N2	112.7 (4)	N4—C19—H19	118.7
C7—N1—Ni1	125.2 (4)	C18—C19—H19	118.7
N2—N1—Ni1	122.1 (3)	O2—C20—C21	119.2 (7)
C8—N2—N1	112.6 (4)	O2—C20—C25	122.6 (8)
C8—N3—C9	129.6 (5)	C21—C20—C25	118.3 (8)
C8—N3—H3N	114 (4)	C22—C21—C20	121.2 (9)
C9—N3—H3N	116 (4)	C22—C21—H21	119.4
C19—N4—C15	117.4 (5)	C20—C21—H21	119.4
C19—N4—Ni1	123.1 (4)	C23—C22—C21	118.9 (9)
C15—N4—Ni1	119.1 (4)	C23—C22—H22	120.5
C26—N5—N6	112.1 (4)	C21—C22—H22	120.5
C26—N5—Ni2	125.9 (4)	C24—C23—C22	121.9 (10)
N6—N5—Ni2	122.0 (3)	C24—C23—H23	119.0
C27—N6—N5	111.5 (4)	C22—C23—H23	119.0
C27—N7—C28	129.1 (5)	C23—C24—C25	121.0 (8)
C27—N7—H7N	115 (4)	C23—C24—H24	119.5
C28—N7—H7N	116 (4)	C25—C24—H24	119.5
C38—N8—C34	118.3 (5)	C20—C25—C24	118.6 (7)
C38—N8—Ni2	118.8 (4)	C20—C25—C26	123.1 (7)
C34—N8—Ni2	122.6 (4)	C24—C25—C26	118.3 (6)
O1—C1—C6	124.6 (7)	N5—C26—C25	125.3 (5)
O1—C1—C2	118.6 (8)	N5—C26—H26	117.4
C6—C1—C2	116.8 (8)	C25—C26—H26	117.4
C3—C2—C1	121.2 (9)	N6—C27—N7	119.8 (5)
C3—C2—H2	119.4	N6—C27—S2	123.5 (4)
C1—C2—H2	119.4	N7—C27—S2	116.7 (4)
C2—C3—C4	123.8 (10)	C29—C28—N7	117.4 (8)
C2—C3—H3	118.1	C29—C28—C33	118.2 (9)
C4—C3—H3	118.1	N7—C28—C33	124.4 (8)
C5—C4—C3	115.8 (9)	C30—C29—C28	121.1 (9)
C5—C4—H4	122.1	C30—C29—H29	119.5
C3—C4—H4	122.1	C28—C29—H29	119.5
C4—C5—C6	122.2 (8)	C29—C30—C31	120.7 (8)
C4—C5—H5	118.9	C29—C30—H30	119.7
C6—C5—H5	118.9	C31—C30—H30	119.7
C1—C6—C5	120.1 (7)	C32—C31—C30	118.1 (8)
C1—C6—C7	121.3 (7)	C32—C31—H31	121.0
C5—C6—C7	118.6 (6)	C30—C31—H31	121.0
N1—C7—C6	126.6 (5)	C31—C32—C33	123.3 (9)
N1—C7—H7	116.7	C31—C32—H32	118.3
C6—C7—H7	116.7	C33—C32—H32	118.3
N2—C8—N3	120.3 (5)	C32—C33—C28	118.7 (9)
N2—C8—S1	122.4 (4)	C32—C33—H33	120.7
N3—C8—S1	117.3 (4)	C28—C33—H33	120.7
C14—C9—C10	118.5 (9)	N8—C34—C35	121.4 (5)
C14—C9—N3	122.8 (9)	N8—C34—H34	119.3
C10—C9—N3	118.7 (8)	C35—C34—H34	119.3
C9—C10—C11	120.8 (9)	C36—C35—C34	119.7 (6)
C9—C10—H10	119.6	C36—C35—H35	120.1
C11—C10—H10	119.6	C34—C35—H35	120.1
C12—C11—C10	121.2 (8)	C37—C36—C35	118.9 (5)
C12—C11—H11	119.4	C37—C36—H36	120.6
C10—C11—H11	119.4	C35—C36—H36	120.6
C11—C12—C13	118.7 (8)	C36—C37—C38	118.7 (6)
C11—C12—H12	120.7	C36—C37—H37	120.7
C13—C12—H12	120.7	C38—C37—H37	120.7
C12—C13—C14	120.2 (10)	N8—C38—C37	122.8 (5)
C12—C13—H13	119.9	N8—C38—H38	118.6
C14—C13—H13	119.9	C37—C38—H38	118.6
N1—Ni1—S1—C8	−3.0 (2)	C9—C10—C11—C12	−0.3 (13)
N4—Ni1—S1—C8	178.9 (2)	C10—C11—C12—C13	−0.6 (13)
N5—Ni2—S2—C27	2.4 (2)	C11—C12—C13—C14	1.2 (14)
N8—Ni2—S2—C27	−179.4 (2)	C10—C9—C14—C13	0.2 (15)
N1—Ni1—O1—C1	−2.1 (6)	N3—C9—C14—C13	179.3 (8)
N4—Ni1—O1—C1	176.1 (6)	C12—C13—C14—C9	−1.1 (15)
N5—Ni2—O2—C20	1.4 (6)	C19—N4—C15—C16	−1.0 (8)
N8—Ni2—O2—C20	−176.9 (6)	Ni1—N4—C15—C16	172.3 (4)
O1—Ni1—N1—C7	5.3 (5)	N4—C15—C16—C17	−1.3 (8)
S1—Ni1—N1—C7	−177.5 (5)	C15—C16—C17—C18	1.7 (8)
O1—Ni1—N1—N2	−174.8 (4)	C16—C17—C18—C19	0.0 (9)
S1—Ni1—N1—N2	2.3 (4)	C15—N4—C19—C18	2.9 (8)
C7—N1—N2—C8	179.8 (5)	Ni1—N4—C19—C18	−170.1 (4)
Ni1—N1—N2—C8	−0.1 (6)	C17—C18—C19—N4	−2.4 (8)
O1—Ni1—N4—C19	108.6 (4)	Ni2—O2—C20—C21	−179.2 (7)
S1—Ni1—N4—C19	−68.5 (4)	Ni2—O2—C20—C25	1.4 (12)
O1—Ni1—N4—C15	−64.3 (4)	O2—C20—C21—C22	−177.1 (9)
S1—Ni1—N4—C15	118.6 (4)	C25—C20—C21—C22	2.4 (15)
O2—Ni2—N5—C26	−3.7 (5)	C20—C21—C22—C23	−1.0 (17)
S2—Ni2—N5—C26	178.8 (5)	C21—C22—C23—C24	−1.2 (17)
O2—Ni2—N5—N6	175.2 (4)	C22—C23—C24—C25	2.0 (16)
S2—Ni2—N5—N6	−2.4 (4)	O2—C20—C25—C24	177.9 (8)
C26—N5—N6—C27	180.0 (5)	C21—C20—C25—C24	−1.6 (12)
Ni2—N5—N6—C27	1.0 (6)	O2—C20—C25—C26	−2.8 (12)
O2—Ni2—N8—C38	64.2 (4)	C21—C20—C25—C26	177.8 (8)
S2—Ni2—N8—C38	−118.3 (4)	C23—C24—C25—C20	−0.6 (13)
O2—Ni2—N8—C34	−109.7 (4)	C23—C24—C25—C26	−179.9 (8)
S2—Ni2—N8—C34	67.8 (4)	N6—N5—C26—C25	−175.6 (5)
Ni1—O1—C1—C6	−2.1 (12)	Ni2—N5—C26—C25	3.4 (9)
Ni1—O1—C1—C2	179.2 (7)	C20—C25—C26—N5	0.3 (11)
O1—C1—C2—C3	175.1 (10)	C24—C25—C26—N5	179.6 (6)
C6—C1—C2—C3	−3.8 (16)	N5—N6—C27—N7	−176.3 (4)
C1—C2—C3—C4	2.9 (19)	N5—N6—C27—S2	1.7 (7)
C2—C3—C4—C5	−0.9 (17)	C28—N7—C27—N6	3.9 (10)
C3—C4—C5—C6	−0.1 (14)	C28—N7—C27—S2	−174.2 (6)
O1—C1—C6—C5	−175.9 (8)	Ni2—S2—C27—N6	−3.0 (5)
C2—C1—C6—C5	2.8 (12)	Ni2—S2—C27—N7	175.1 (4)
O1—C1—C6—C7	4.2 (12)	C27—N7—C28—C29	166.5 (7)
C2—C1—C6—C7	−177.0 (8)	C27—N7—C28—C33	−14.8 (13)
C4—C5—C6—C1	−1.0 (13)	N7—C28—C29—C30	178.1 (7)
C4—C5—C6—C7	178.9 (7)	C33—C28—C29—C30	−0.6 (13)
N2—N1—C7—C6	175.4 (5)	C28—C29—C30—C31	0.0 (13)
Ni1—N1—C7—C6	−4.7 (9)	C29—C30—C31—C32	0.1 (12)
C1—C6—C7—N1	−0.6 (11)	C30—C31—C32—C33	0.5 (14)
C5—C6—C7—N1	179.5 (6)	C31—C32—C33—C28	−1.2 (15)
N1—N2—C8—N3	175.1 (4)	C29—C28—C33—C32	1.2 (14)
N1—N2—C8—S1	−3.3 (7)	N7—C28—C33—C32	−177.5 (8)
C9—N3—C8—N2	−6.5 (10)	C38—N8—C34—C35	−4.6 (7)
C9—N3—C8—S1	171.9 (6)	Ni2—N8—C34—C35	169.4 (4)
Ni1—S1—C8—N2	4.3 (5)	N8—C34—C35—C36	3.5 (8)
Ni1—S1—C8—N3	−174.1 (4)	C34—C35—C36—C37	0.1 (9)
C8—N3—C9—C14	14.8 (13)	C35—C36—C37—C38	−2.4 (9)
C8—N3—C9—C10	−166.2 (7)	C34—N8—C38—C37	2.2 (8)
C14—C9—C10—C11	0.4 (14)	Ni2—N8—C38—C37	−172.0 (4)
N3—C9—C10—C11	−178.6 (7)	C36—C37—C38—N8	1.3 (8)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···S2^i	0.86 (4)	2.77 (4)	3.605 (4)	163 (5)
N7—H7N···S1^ii	0.86 (4)	2.80 (2)	3.627 (4)	161 (5)

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