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Acta Cryst. (2007). E63, m1961-m1962    [ doi:10.1107/S1600536807029698 ]

[1-(2-Oxidobenzylidene)-4-phenylthiosemicarbazonato-[kappa]3S,N1,O](pyridine-[kappa]N)nickel(II)

Z.-Y. Cao, Z.-P. Deng and S. Gao

Abstract top

In the title complex, [Ni(C14H11N3OS)(C5H5N)], the NiII 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 [pi]-[pi] stacking interactions between the pyridine rings [centroid-centroid = 3.758 (3) Å].

Comment top

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 NiII 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 top

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.

Experimental top

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%.

Refinement top

C-bound H atoms were placed in calculated positions, with C—H = 0.93 and Uiso(H) = 1.2Ueq(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 Uiso(H) = 1.2Ueq(N). The Flack parameter was refined from 3366 Friedel paris.

Computing details top

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 top
[Figure 1] Fig. 1. A view of complex (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] 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) top
Crystal data top
[Ni(C14H11N3OS)(C5H5N)]F(000) = 840
Mr = 407.13Dx = 1.550 Mg m−3
Monoclinic, PcMo Kα radiation, λ = 0.71073 Å
Hall symbol: P -2ycCell parameters from 11939 reflections
a = 5.7294 (11) Åθ = 3.0–27.5°
b = 12.924 (3) ŵ = 1.25 mm−1
c = 23.683 (5) ÅT = 295 K
β = 95.64 (3)°Prism, colorless
V = 1745.2 (6) Å30.35 × 0.24 × 0.17 mm
Z = 4
Data collection top
Rigaku R-AXIS RAPID
diffractometer		7370 independent reflections
Radiation source: fine-focus sealed tube4892 reflections with I > 2σ(I)
graphiteRint = 0.044
Detector resolution: 10.000 pixels mm-1θmax = 27.5°, θmin = 3.0°
ω scansh = −6→7
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		k = −16→16
Tmin = 0.669, Tmax = 0.816l = −30→30
16815 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.089 w = 1/[σ2(Fo2) + (0.022P)2 + 0.9787P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
7370 reflectionsΔρmax = 0.60 e Å−3
475 parametersΔρmin = −0.57 e Å−3
4 restraintsAbsolute structure: Flack (1983), with 3366 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.029 (17)
Crystal data top
[Ni(C14H11N3OS)(C5H5N)]V = 1745.2 (6) Å3
Mr = 407.13Z = 4
Monoclinic, PcMo Kα radiation
a = 5.7294 (11) ŵ = 1.25 mm−1
b = 12.924 (3) ÅT = 295 K
c = 23.683 (5) Å0.35 × 0.24 × 0.17 mm
β = 95.64 (3)°
Data collection top
Rigaku R-AXIS RAPID
diffractometer		7370 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		4892 reflections with I > 2σ(I)
Tmin = 0.669, Tmax = 0.816Rint = 0.044
16815 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.037H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.089Δρmax = 0.60 e Å−3
S = 1.06Δρmin = −0.57 e Å−3
7370 reflectionsAbsolute structure: Flack (1983), with 3366 Friedel pairs
475 parametersFlack parameter: 0.029 (17)
4 restraints
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ni10.42415 (9)0.92246 (4)0.75792 (3)0.03968 (16)
Ni20.30864 (10)0.32924 (4)0.63710 (3)0.03927 (16)
S10.1296 (2)1.01932 (11)0.72961 (6)0.0479 (4)
S20.6011 (3)0.23095 (11)0.66440 (6)0.0486 (4)
O10.6638 (8)0.8306 (2)0.78157 (17)0.0491 (11)
O20.0683 (7)0.4217 (2)0.61431 (17)0.0479 (11)
N10.5015 (8)1.0198 (3)0.81387 (19)0.0399 (10)
N20.3641 (8)1.1071 (3)0.8204 (2)0.0444 (11)
N30.0183 (8)1.1876 (4)0.78621 (19)0.0464 (11)
H3N−0.096 (6)1.185 (4)0.7596 (16)0.056*
N40.3432 (8)0.8267 (3)0.69777 (19)0.0372 (11)
N50.2299 (7)0.2349 (3)0.57989 (19)0.0381 (10)
N60.3675 (8)0.1466 (3)0.57220 (19)0.0451 (11)
N70.7084 (8)0.0632 (4)0.60734 (18)0.0464 (11)
H7N0.825 (6)0.066 (4)0.6330 (17)0.056*
N80.3873 (8)0.4238 (3)0.69807 (19)0.0380 (11)
C10.8281 (16)0.8445 (6)0.8244 (4)0.0414 (19)
C20.995 (2)0.7658 (7)0.8368 (4)0.057 (3)
H20.98010.70380.81690.069*
C31.176 (2)0.7786 (8)0.8771 (4)0.062 (3)
H31.28560.72560.88260.075*
C41.2076 (16)0.8661 (7)0.9108 (4)0.054 (2)
H41.33290.87260.93870.065*
C51.0409 (13)0.9432 (6)0.9004 (3)0.053 (2)
H51.05481.00340.92200.064*
C60.8511 (12)0.9335 (5)0.8582 (3)0.0424 (16)
C70.6850 (9)1.0158 (4)0.8509 (2)0.0404 (12)
H70.71031.07230.87500.049*
C80.1818 (9)1.1111 (4)0.7833 (2)0.0390 (12)
C90.0002 (17)1.2640 (6)0.8284 (4)0.041 (2)
C10−0.2062 (17)1.3186 (6)0.8283 (5)0.051 (2)
H10−0.33071.30350.80140.062*
C11−0.2306 (14)1.3955 (5)0.8679 (3)0.0557 (19)
H11−0.37131.43150.86700.067*
C12−0.0527 (15)1.4192 (6)0.9080 (4)0.057 (2)
H12−0.07011.47150.93420.068*
C130.1552 (17)1.3640 (7)0.9090 (5)0.061 (3)
H130.27781.37830.93660.074*
C140.1808 (17)1.2872 (6)0.8688 (4)0.047 (2)
H140.32171.25130.86940.056*
C150.4957 (11)0.8095 (4)0.6593 (3)0.0456 (14)
H150.62890.85080.66020.055*
C160.4640 (11)0.7341 (4)0.6189 (2)0.0508 (15)
H160.57210.72530.59250.061*
C170.2700 (11)0.6712 (5)0.6180 (2)0.0537 (14)
H170.24630.61800.59160.064*
C180.1127 (10)0.6887 (4)0.6568 (2)0.0484 (14)
H18−0.02000.64730.65710.058*
C190.1518 (10)0.7674 (4)0.6951 (2)0.0459 (13)
H190.04050.78020.72020.055*
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)
H21−0.24700.55160.58320.059*
C22−0.4421 (19)0.4834 (7)0.5179 (4)0.059 (3)
H22−0.55200.53610.51150.071*
C23−0.4570 (17)0.3963 (8)0.4851 (5)0.061 (3)
H23−0.58040.38980.45670.074*
C24−0.2986 (14)0.3196 (6)0.4926 (3)0.052 (2)
H24−0.31170.26240.46870.062*
C25−0.1122 (12)0.3246 (5)0.5364 (3)0.0417 (17)
C260.0501 (9)0.2410 (4)0.5421 (2)0.0439 (13)
H260.02540.18620.51680.053*
C270.5462 (10)0.1413 (4)0.6101 (2)0.0403 (13)
C280.7199 (17)−0.0134 (6)0.5662 (4)0.0381 (19)
C290.9279 (18)−0.0694 (6)0.5667 (4)0.047 (2)
H291.0531−0.05320.59330.057*
C300.9513 (14)−0.1482 (6)0.5287 (3)0.057 (2)
H301.0917−0.18450.52980.069*
C310.7675 (15)−0.1739 (6)0.4886 (4)0.052 (2)
H310.7825−0.22720.46280.062*
C320.5649 (16)−0.1191 (6)0.4881 (4)0.051 (2)
H320.4408−0.13660.46160.061*
C330.5341 (17)−0.0390 (6)0.5250 (4)0.045 (2)
H330.3936−0.00260.52290.054*
C340.5814 (9)0.4822 (4)0.7015 (2)0.0435 (13)
H340.69530.46910.67700.052*
C350.6158 (11)0.5614 (5)0.7404 (2)0.0534 (15)
H350.74760.60350.74070.064*
C360.4544 (11)0.5779 (5)0.7788 (2)0.0548 (14)
H360.47540.63110.80530.066*
C370.2619 (11)0.5145 (4)0.7774 (2)0.0509 (15)
H370.15310.52230.80380.061*
C380.2330 (11)0.4391 (4)0.7362 (2)0.0443 (14)
H380.10080.39710.73490.053*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0444 (4)0.0343 (3)0.0392 (4)0.0006 (3)−0.0018 (3)−0.0047 (3)
Ni20.0437 (4)0.0347 (3)0.0380 (4)0.0012 (3)−0.0026 (3)−0.0043 (3)
S10.0541 (9)0.0433 (7)0.0433 (8)0.0063 (7)−0.0103 (7)−0.0090 (6)
S20.0550 (9)0.0426 (7)0.0452 (9)0.0087 (7)−0.0105 (7)−0.0087 (7)
O10.057 (3)0.043 (2)0.044 (3)0.0073 (17)−0.007 (2)−0.0095 (16)
O20.053 (3)0.040 (2)0.048 (3)0.0083 (17)−0.010 (2)−0.0123 (16)
N10.043 (3)0.036 (2)0.041 (3)0.002 (2)0.000 (2)0.000 (2)
N20.044 (3)0.033 (2)0.054 (3)0.011 (2)−0.009 (2)−0.007 (2)
N30.048 (3)0.043 (3)0.045 (3)0.009 (2)−0.012 (2)−0.005 (2)
N40.038 (3)0.034 (2)0.039 (3)0.0015 (19)0.001 (2)−0.0015 (19)
N50.038 (3)0.031 (2)0.044 (3)0.0033 (19)−0.001 (2)−0.0020 (19)
N60.049 (3)0.037 (2)0.048 (3)0.008 (2)−0.001 (2)−0.008 (2)
N70.046 (3)0.046 (3)0.043 (3)0.009 (2)−0.014 (2)−0.009 (2)
N80.043 (3)0.035 (2)0.036 (3)0.002 (2)0.002 (2)−0.0005 (19)
C10.039 (4)0.044 (4)0.041 (4)0.009 (3)−0.001 (3)0.009 (3)
C20.075 (7)0.051 (5)0.044 (5)0.019 (4)−0.004 (4)−0.013 (4)
C30.072 (6)0.068 (5)0.045 (5)0.034 (4)−0.004 (4)0.005 (4)
C40.047 (4)0.071 (5)0.042 (5)0.014 (4)−0.008 (4)−0.006 (4)
C50.048 (4)0.060 (4)0.049 (4)0.004 (3)−0.009 (4)−0.005 (3)
C60.044 (4)0.042 (3)0.040 (4)0.002 (3)0.001 (3)−0.003 (3)
C70.038 (3)0.041 (3)0.041 (3)0.000 (2)−0.005 (2)−0.007 (2)
C80.045 (3)0.032 (3)0.039 (3)0.006 (2)−0.002 (2)0.003 (2)
C90.049 (5)0.036 (4)0.036 (4)−0.001 (3)0.001 (3)0.000 (3)
C100.037 (4)0.053 (4)0.061 (5)0.012 (3)−0.007 (4)0.003 (4)
C110.053 (5)0.056 (4)0.060 (5)0.015 (4)0.011 (4)0.003 (4)
C120.062 (6)0.052 (4)0.059 (5)0.007 (4)0.017 (4)−0.008 (3)
C130.063 (6)0.062 (5)0.058 (6)−0.005 (4)0.002 (5)−0.022 (4)
C140.046 (4)0.046 (4)0.047 (5)0.013 (3)−0.002 (3)−0.005 (3)
C150.043 (4)0.045 (3)0.049 (4)0.002 (3)0.005 (3)0.003 (3)
C160.062 (4)0.048 (3)0.042 (3)0.015 (3)0.007 (3)−0.004 (3)
C170.068 (4)0.042 (3)0.049 (3)0.006 (3)−0.007 (3)−0.008 (3)
C180.054 (3)0.044 (3)0.047 (3)−0.010 (3)0.003 (3)−0.009 (3)
C190.049 (3)0.046 (3)0.042 (3)−0.001 (3)0.004 (3)−0.005 (3)
C200.054 (5)0.043 (3)0.027 (3)0.000 (3)0.000 (3)−0.003 (3)
C210.059 (6)0.045 (4)0.043 (4)0.020 (4)−0.005 (4)0.000 (3)
C220.066 (6)0.064 (5)0.045 (5)0.025 (4)−0.009 (4)−0.002 (4)
C230.052 (4)0.076 (6)0.052 (5)0.018 (4)−0.018 (4)−0.009 (4)
C240.052 (5)0.057 (4)0.044 (4)0.009 (3)−0.013 (3)−0.015 (3)
C250.043 (4)0.043 (3)0.038 (4)0.007 (3)0.001 (3)0.000 (3)
C260.046 (3)0.040 (3)0.043 (3)−0.002 (2)−0.006 (3)−0.007 (2)
C270.046 (3)0.036 (3)0.037 (3)0.003 (2)−0.004 (2)0.000 (2)
C280.045 (4)0.030 (3)0.040 (4)0.005 (3)0.007 (3)0.006 (3)
C290.049 (4)0.049 (4)0.044 (4)0.003 (3)0.003 (3)−0.007 (4)
C300.056 (5)0.059 (5)0.057 (5)0.020 (4)0.005 (4)0.001 (4)
C310.070 (6)0.044 (4)0.043 (4)0.010 (3)0.010 (4)−0.006 (3)
C320.052 (5)0.054 (5)0.043 (5)0.012 (4)−0.009 (4)−0.010 (4)
C330.037 (4)0.045 (4)0.052 (5)0.002 (3)−0.004 (3)−0.008 (4)
C340.044 (3)0.048 (3)0.038 (3)−0.003 (3)0.002 (2)−0.004 (3)
C350.055 (4)0.053 (4)0.051 (3)−0.005 (3)−0.002 (3)−0.003 (3)
C360.067 (4)0.044 (3)0.051 (4)0.009 (3)−0.004 (3)−0.014 (3)
C370.057 (4)0.053 (3)0.044 (3)0.008 (3)0.012 (3)0.002 (3)
C380.045 (4)0.045 (3)0.042 (3)−0.003 (3)0.000 (3)0.002 (3)
Geometric parameters (Å, °) top
Ni1—N11.849 (4)C12—C131.387 (12)
Ni1—O11.859 (4)C12—H120.9300
Ni1—N41.909 (4)C13—C141.394 (12)
Ni1—S12.1547 (15)C13—H130.9300
Ni2—N51.845 (4)C14—H140.9300
Ni2—O21.863 (4)C15—C161.366 (8)
Ni2—N81.911 (4)C15—H150.9300
Ni2—S22.1507 (15)C16—C171.375 (8)
S1—C81.744 (5)C16—H160.9300
S2—C271.736 (5)C17—C181.367 (8)
O1—C11.327 (10)C17—H170.9300
O2—C201.308 (10)C18—C191.367 (7)
N1—C71.302 (6)C18—H180.9300
N1—N21.393 (6)C19—H190.9300
N2—C81.297 (6)C20—C211.406 (12)
N3—C81.368 (7)C20—C251.407 (11)
N3—C91.415 (10)C21—C221.392 (11)
N3—H3N0.86 (4)C21—H210.9300
N4—C191.334 (6)C22—C231.366 (13)
N4—C151.341 (7)C22—H220.9300
N5—C261.298 (6)C23—C241.343 (12)
N5—N61.410 (5)C23—H230.9300
N6—C271.295 (6)C24—C251.415 (10)
N7—C271.378 (7)C24—H240.9300
N7—C281.397 (10)C25—C261.424 (8)
N7—H7N0.86 (4)C26—H260.9300
N8—C381.340 (7)C28—C291.393 (13)
N8—C341.340 (6)C28—C331.410 (11)
C1—C61.400 (11)C29—C301.375 (12)
C1—C21.406 (12)C29—H290.9300
C2—C31.348 (12)C30—C311.386 (11)
C2—H20.9300C30—H300.9300
C3—C41.386 (13)C31—C321.359 (12)
C3—H30.9300C31—H310.9300
C4—C51.386 (12)C32—C331.377 (12)
C4—H40.9300C32—H320.9300
C5—C61.409 (10)C33—H330.9300
C5—H50.9300C34—C351.379 (7)
C6—C71.426 (8)C34—H340.9300
C7—H70.9300C35—C361.376 (8)
C9—C141.372 (11)C35—H350.9300
C9—C101.377 (13)C36—C371.371 (8)
C10—C111.382 (12)C36—H360.9300
C10—H100.9300C37—C381.378 (8)
C11—C121.358 (11)C37—H370.9300
C11—H110.9300C38—H380.9300
N1—Ni1—O195.77 (17)C9—C14—C13120.6 (10)
N1—Ni1—N4177.51 (19)C9—C14—H14119.7
O1—Ni1—N485.93 (17)C13—C14—H14119.7
N1—Ni1—S187.31 (14)N4—C15—C16122.9 (5)
O1—Ni1—S1175.83 (13)N4—C15—H15118.5
N4—Ni1—S191.08 (13)C16—C15—H15118.5
N5—Ni2—O295.19 (17)C15—C16—C17119.0 (6)
N5—Ni2—N8178.16 (19)C15—C16—H16120.5
O2—Ni2—N885.50 (17)C17—C16—H16120.5
N5—Ni2—S287.57 (13)C18—C17—C16118.5 (5)
O2—Ni2—S2176.29 (13)C18—C17—H17120.8
N8—Ni2—S291.81 (14)C16—C17—H17120.8
C8—S1—Ni195.46 (18)C19—C18—C17119.5 (6)
C27—S2—Ni295.30 (18)C19—C18—H18120.2
C1—O1—Ni1126.3 (4)C17—C18—H18120.2
C20—O2—Ni2127.8 (4)N4—C19—C18122.7 (5)
C7—N1—N2112.7 (4)N4—C19—H19118.7
C7—N1—Ni1125.2 (4)C18—C19—H19118.7
N2—N1—Ni1122.1 (3)O2—C20—C21119.2 (7)
C8—N2—N1112.6 (4)O2—C20—C25122.6 (8)
C8—N3—C9129.6 (5)C21—C20—C25118.3 (8)
C8—N3—H3N114 (4)C22—C21—C20121.2 (9)
C9—N3—H3N116 (4)C22—C21—H21119.4
C19—N4—C15117.4 (5)C20—C21—H21119.4
C19—N4—Ni1123.1 (4)C23—C22—C21118.9 (9)
C15—N4—Ni1119.1 (4)C23—C22—H22120.5
C26—N5—N6112.1 (4)C21—C22—H22120.5
C26—N5—Ni2125.9 (4)C24—C23—C22121.9 (10)
N6—N5—Ni2122.0 (3)C24—C23—H23119.0
C27—N6—N5111.5 (4)C22—C23—H23119.0
C27—N7—C28129.1 (5)C23—C24—C25121.0 (8)
C27—N7—H7N115 (4)C23—C24—H24119.5
C28—N7—H7N116 (4)C25—C24—H24119.5
C38—N8—C34118.3 (5)C20—C25—C24118.6 (7)
C38—N8—Ni2118.8 (4)C20—C25—C26123.1 (7)
C34—N8—Ni2122.6 (4)C24—C25—C26118.3 (6)
O1—C1—C6124.6 (7)N5—C26—C25125.3 (5)
O1—C1—C2118.6 (8)N5—C26—H26117.4
C6—C1—C2116.8 (8)C25—C26—H26117.4
C3—C2—C1121.2 (9)N6—C27—N7119.8 (5)
C3—C2—H2119.4N6—C27—S2123.5 (4)
C1—C2—H2119.4N7—C27—S2116.7 (4)
C2—C3—C4123.8 (10)C29—C28—N7117.4 (8)
C2—C3—H3118.1C29—C28—C33118.2 (9)
C4—C3—H3118.1N7—C28—C33124.4 (8)
C5—C4—C3115.8 (9)C30—C29—C28121.1 (9)
C5—C4—H4122.1C30—C29—H29119.5
C3—C4—H4122.1C28—C29—H29119.5
C4—C5—C6122.2 (8)C29—C30—C31120.7 (8)
C4—C5—H5118.9C29—C30—H30119.7
C6—C5—H5118.9C31—C30—H30119.7
C1—C6—C5120.1 (7)C32—C31—C30118.1 (8)
C1—C6—C7121.3 (7)C32—C31—H31121.0
C5—C6—C7118.6 (6)C30—C31—H31121.0
N1—C7—C6126.6 (5)C31—C32—C33123.3 (9)
N1—C7—H7116.7C31—C32—H32118.3
C6—C7—H7116.7C33—C32—H32118.3
N2—C8—N3120.3 (5)C32—C33—C28118.7 (9)
N2—C8—S1122.4 (4)C32—C33—H33120.7
N3—C8—S1117.3 (4)C28—C33—H33120.7
C14—C9—C10118.5 (9)N8—C34—C35121.4 (5)
C14—C9—N3122.8 (9)N8—C34—H34119.3
C10—C9—N3118.7 (8)C35—C34—H34119.3
C9—C10—C11120.8 (9)C36—C35—C34119.7 (6)
C9—C10—H10119.6C36—C35—H35120.1
C11—C10—H10119.6C34—C35—H35120.1
C12—C11—C10121.2 (8)C37—C36—C35118.9 (5)
C12—C11—H11119.4C37—C36—H36120.6
C10—C11—H11119.4C35—C36—H36120.6
C11—C12—C13118.7 (8)C36—C37—C38118.7 (6)
C11—C12—H12120.7C36—C37—H37120.7
C13—C12—H12120.7C38—C37—H37120.7
C12—C13—C14120.2 (10)N8—C38—C37122.8 (5)
C12—C13—H13119.9N8—C38—H38118.6
C14—C13—H13119.9C37—C38—H38118.6
N1—Ni1—S1—C8−3.0 (2)C9—C10—C11—C12−0.3 (13)
N4—Ni1—S1—C8178.9 (2)C10—C11—C12—C13−0.6 (13)
N5—Ni2—S2—C272.4 (2)C11—C12—C13—C141.2 (14)
N8—Ni2—S2—C27−179.4 (2)C10—C9—C14—C130.2 (15)
N1—Ni1—O1—C1−2.1 (6)N3—C9—C14—C13179.3 (8)
N4—Ni1—O1—C1176.1 (6)C12—C13—C14—C9−1.1 (15)
N5—Ni2—O2—C201.4 (6)C19—N4—C15—C16−1.0 (8)
N8—Ni2—O2—C20−176.9 (6)Ni1—N4—C15—C16172.3 (4)
O1—Ni1—N1—C75.3 (5)N4—C15—C16—C17−1.3 (8)
S1—Ni1—N1—C7−177.5 (5)C15—C16—C17—C181.7 (8)
O1—Ni1—N1—N2−174.8 (4)C16—C17—C18—C190.0 (9)
S1—Ni1—N1—N22.3 (4)C15—N4—C19—C182.9 (8)
C7—N1—N2—C8179.8 (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—C19108.6 (4)Ni2—O2—C20—C21−179.2 (7)
S1—Ni1—N4—C19−68.5 (4)Ni2—O2—C20—C251.4 (12)
O1—Ni1—N4—C15−64.3 (4)O2—C20—C21—C22−177.1 (9)
S1—Ni1—N4—C15118.6 (4)C25—C20—C21—C222.4 (15)
O2—Ni2—N5—C26−3.7 (5)C20—C21—C22—C23−1.0 (17)
S2—Ni2—N5—C26178.8 (5)C21—C22—C23—C24−1.2 (17)
O2—Ni2—N5—N6175.2 (4)C22—C23—C24—C252.0 (16)
S2—Ni2—N5—N6−2.4 (4)O2—C20—C25—C24177.9 (8)
C26—N5—N6—C27180.0 (5)C21—C20—C25—C24−1.6 (12)
Ni2—N5—N6—C271.0 (6)O2—C20—C25—C26−2.8 (12)
O2—Ni2—N8—C3864.2 (4)C21—C20—C25—C26177.8 (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—C3467.8 (4)N6—N5—C26—C25−175.6 (5)
Ni1—O1—C1—C6−2.1 (12)Ni2—N5—C26—C253.4 (9)
Ni1—O1—C1—C2179.2 (7)C20—C25—C26—N50.3 (11)
O1—C1—C2—C3175.1 (10)C24—C25—C26—N5179.6 (6)
C6—C1—C2—C3−3.8 (16)N5—N6—C27—N7−176.3 (4)
C1—C2—C3—C42.9 (19)N5—N6—C27—S21.7 (7)
C2—C3—C4—C5−0.9 (17)C28—N7—C27—N63.9 (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—C52.8 (12)Ni2—S2—C27—N7175.1 (4)
O1—C1—C6—C74.2 (12)C27—N7—C28—C29166.5 (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—C30178.1 (7)
C4—C5—C6—C7178.9 (7)C33—C28—C29—C30−0.6 (13)
N2—N1—C7—C6175.4 (5)C28—C29—C30—C310.0 (13)
Ni1—N1—C7—C6−4.7 (9)C29—C30—C31—C320.1 (12)
C1—C6—C7—N1−0.6 (11)C30—C31—C32—C330.5 (14)
C5—C6—C7—N1179.5 (6)C31—C32—C33—C28−1.2 (15)
N1—N2—C8—N3175.1 (4)C29—C28—C33—C321.2 (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—S1171.9 (6)Ni2—N8—C34—C35169.4 (4)
Ni1—S1—C8—N24.3 (5)N8—C34—C35—C363.5 (8)
Ni1—S1—C8—N3−174.1 (4)C34—C35—C36—C370.1 (9)
C8—N3—C9—C1414.8 (13)C35—C36—C37—C38−2.4 (9)
C8—N3—C9—C10−166.2 (7)C34—N8—C38—C372.2 (8)
C14—C9—C10—C110.4 (14)Ni2—N8—C38—C37−172.0 (4)
N3—C9—C10—C11−178.6 (7)C36—C37—C38—N81.3 (8)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3N···S2i0.86 (4)2.77 (4)3.605 (4)163 (5)
N7—H7N···S1ii0.86 (4)2.80 (2)3.627 (4)161 (5)
Symmetry codes: (i) x−1, y+1, z; (ii) x+1, y−1, z.
Table 1
Selected geometric parameters (Å, °) top
Ni1—N11.849 (4)Ni2—N51.845 (4)
Ni1—O11.859 (4)Ni2—O21.863 (4)
Ni1—N41.909 (4)Ni2—N81.911 (4)
Ni1—S12.1547 (15)Ni2—S22.1507 (15)
N1—Ni1—O195.77 (17)N5—Ni2—O295.19 (17)
N1—Ni1—N4177.51 (19)N5—Ni2—N8178.16 (19)
O1—Ni1—N485.93 (17)O2—Ni2—N885.50 (17)
N1—Ni1—S187.31 (14)N5—Ni2—S287.57 (13)
O1—Ni1—S1175.83 (13)O2—Ni2—S2176.29 (13)
N4—Ni1—S191.08 (13)N8—Ni2—S291.81 (14)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3N···S2i0.86 (4)2.77 (4)3.605 (4)163 (5)
N7—H7N···S1ii0.86 (4)2.80 (2)3.627 (4)161 (5)
Symmetry codes: (i) x−1, y+1, z; (ii) x+1, y−1, z.
Acknowledgements top

We thank the Heilongjiang Province Natural Science Foundation (No. B200501), the Scientific Fund for Remarkable Teachers of Heilongjiang Province (No. 1054 G036), the Scientific Research Fund of Heilongjiang Provincial Education Department (No. 11515140), Heilongjiang University and Mudanjiang University for supporting this work.

references
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