mer-(3,5-Dichloro-2-oxidobenzaldehyde thio­semicarbazonato-κ3S,N1,O)(methanol-κO)(1,10-phenanthroline-κ2N,N′)nickel(II)

Gao, J.Y.; Liu, Z.; Wang, Y.

doi:10.1107/S1600536809013208

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Pages m523-m524

doi:10.1107/S1600536809013208

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mer-(3,5-Dichloro-2-oxidobenzaldehyde thiosemicarbazonato-κ³S,N¹,O)(methanol-κO)(1,10-phenanthroline-κ²N,N′)nickel(II)

J. Y. Gao,^a Z. Liu ^a ^* and Y. Wang ^a

^aKey Laboratory of Non-ferrous Metal Materials and Processing Technology, Department of Material and Chemical Engineering, Guilin University of Technology, Ministry of Education, Guilin 541004, People's Republic of China
^*Correspondence e-mail: lisa4.6@163.com

(Received 19 March 2009; accepted 7 April 2009; online 18 April 2009)

In the title compound, [Ni(C₈H₅Cl₂N₃OS)(C₁₂H₈N₂)(CH₃OH)], the Ni^II atom is octahedrally coordinated by one N, one O and one S atom from a 3,5-dichloro-2-oxidobenzaldehyde thiosemicarbazonate ligand, another O atom from methanol and another two N atoms from 1,10-phenanthroline. The crystal structure is constructed by N—H⋯Cl, N—H⋯N, C—H⋯S and O—H⋯S hydrogen bonds.

Related literature

For nickel complexes with salicylic aldehyde thiosemicarbazone ligands, see: Dapporto et al. (1984 ); Schulte et al. (1991 ); García-Reynaldos et al. (2007 ); Kolotilov et al. (2007 ); Qiu & Wu (2004 ). For related Cu(II) compounds with a distorted octahedral coordination as a result of the Jahn–Teller effect, see: García-Orozco et al. (2002 ). For bond-length data, see: Orpen et al. (1989 ). For related structures, see: Seena & Kurup (2007 ); Wang et al. (2008 ); Zhang et al. (2007 ).

Experimental

Crystal data

[Ni(C₈H₅Cl₂N₃OS)(C₁₂H₈N₂)(CH₄O)]
M_r = 533.07
Monoclinic, P 2₁ /n
a = 12.058 (1) Å
b = 12.946 (1) Å
c = 14.973 (2) Å
β = 105.918 (1)°
V = 2247.6 (4) Å³
Z = 4
Mo Kα radiation
μ = 1.22 mm⁻¹
T = 298 K
0.30 × 0.28 × 0.13 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.710, T_max = 0.857
10910 measured reflections
3951 independent reflections
2708 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.119
S = 1.06
3951 reflections
289 parameters
H-atom parameters constrained
Δρ_max = 0.64 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯S1ⁱ	0.82	2.49	3.310 (3)	174
N3—H3A⋯N2ⁱⁱ	0.86	2.24	3.087 (4)	170
N3—H3B⋯Cl1ⁱⁱⁱ	0.86	2.86	3.573 (2)	142
C11—H11⋯S1^iv	0.93	2.81	3.593 (5)	142
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x+2, -y+2, -z+1; (iii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) -x+1, -y+2, -z.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809013208/im2109sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809013208/im2109Isup2.hkl

checkCIF report

Comment top

As a special kind of Schiff bases, thiosemicarbazones and their metal complexes have become the subjects of intensive study because of their wide ranging biological activities, analytical applications and interesting chemical and structural properties. By now there are not many nickel complexes with salicylic aldehyde thiosemicarbazone ligands [Dapporto et al. (1984); Schulte et al. (1991); García-Reynaldos et al. (2007); Kolotilov et al. (2007); Qiu et al. (2004)]. The additional use of 1,10-phenanthroline as the third ligand depicts another structural type.

In (I), the Ni^II atom is coordinated by one N, one O and one S atom from the tridentate dianionic 3,5-dichlorosalicylaldehyde thiosemicarbazonato ligand, one O atom from methanol and two N atoms from phen. The six atoms form a distorted octahedral coordination sphere around the metal because of Jahn-Teller effect (García-Orozco et al., 2002). The Ni—S bond length is 2.358 (1) Å, which is very close to 2.295Å (Orpen et al. 1989). The three-dimensional network of (I) is established by N–H···Cl, N–H···N, C–H···S and O–H···S hydrogen bonds (Fig.2).

Related literature top

For nickel complexes with salicylic aldehyde thiosemicarbazone ligands, see: Dapporto et al. (1984); Schulte et al. (1991); García-Reynaldos et al. (2007); Kolotilov et al. (2007); Qiu & Wu (2004). The six atoms form a distorted octahedral coordination environment around the metal as a result of the Jahn–Teller effect, see: García-Orozco et al. (2002);. For bond-length data, see: Orpen et al. (1989). For related structures, see: Seena & Kurup (2007); Wang & Gao (2008); Zhang et al. (2007).

Experimental top

A solution of 3,5-dichlorosalicylaldehyde (10 mmol) in EtOH (30 ml) was added dropwise to an aqueous solution (25 ml) of thiosemicarbazide (10 mmol) and 1.5 ml acetic anhydride with stirring at ca 70° C for 4.5 h. The light brown precipitate was removed by filtration and recrystallized from 1:1 (v/v) MeOH/EtOH. Then a mixture of the ligand (1 mmol) and nickel nitrate (1 mmol) in MeOH (35 ml) was stirred at ca 65° C for 2 h. After 1,10-phenanthroline (1 mmol) was added to the mixture heating was continued for another 2 h. The Ni complex was dissolved in DMF and the resulting red solution was filtrated. After 4 days, red block crystals were obtained by slow evaporation of the solvent from the filtrate.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids. Carbon-bound H atoms have been omitted.
	Fig. 2. Three-dimensional network of (I), broken lines show N–H···Cl, N–H···N, C–H···S and O–H···S hydrogen bonds.

mer-(3,5-Dichloro-2-oxidobenzaldehyde thiosemicarbazonato-κ³S,N¹,O)(methanol- κO)(1,10-phenanthroline-κ²N,N')nickel(II) top

Crystal data top

[Ni(C₈H₅Cl₂N₃OS)(C₁₂H₈N₂)(CH₄O)]	F(000) = 1088
M_r = 533.07	D_x = 1.575 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 12.058 (1) Å	Cell parameters from 3309 reflections
b = 12.946 (1) Å	θ = 3.6–25.3°
c = 14.973 (2) Å	µ = 1.22 mm⁻¹
β = 105.918 (1)°	T = 298 K
V = 2247.6 (4) Å³	Block, red
Z = 4	0.30 × 0.28 × 0.13 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	3951 independent reflections
Radiation source: fine-focus sealed tube	2708 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→14
T_min = 0.710, T_max = 0.857	k = −15→14
10910 measured reflections	l = −17→17

Refinement top

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.119	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0487P)² + 1.8417P] where P = (F_o² + 2F_c²)/3
3951 reflections	(Δ/σ)_max = 0.001
289 parameters	Δρ_max = 0.64 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

[Ni(C₈H₅Cl₂N₃OS)(C₁₂H₈N₂)(CH₄O)]	V = 2247.6 (4) Å³
M_r = 533.07	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 12.058 (1) Å	µ = 1.22 mm⁻¹
b = 12.946 (1) Å	T = 298 K
c = 14.973 (2) Å	0.30 × 0.28 × 0.13 mm
β = 105.918 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3951 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2708 reflections with I > 2σ(I)
T_min = 0.710, T_max = 0.857	R_int = 0.040
10910 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.119	H-atom parameters constrained
S = 1.06	Δρ_max = 0.64 e Å⁻³
3951 reflections	Δρ_min = −0.37 e Å⁻³
289 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Ni1	0.79152 (4)	0.87614 (4)	0.19294 (3)	0.03473 (17)
S1	0.73435 (9)	1.01246 (8)	0.27489 (7)	0.0455 (3)
Cl1	0.88829 (11)	0.63336 (11)	−0.01564 (9)	0.0725 (4)
Cl2	1.32931 (13)	0.62176 (14)	0.18947 (12)	0.0989 (6)
N1	0.9387 (3)	0.8831 (2)	0.2981 (2)	0.0352 (7)
N2	0.9476 (3)	0.9456 (3)	0.3753 (2)	0.0431 (8)
N3	0.8598 (3)	1.0689 (3)	0.4404 (2)	0.0646 (12)
H3A	0.9190	1.0694	0.4881	0.077*
H3B	0.8024	1.1090	0.4385	0.077*
N4	0.6453 (3)	0.8694 (2)	0.0803 (2)	0.0362 (7)
N5	0.8398 (3)	0.9774 (2)	0.1016 (2)	0.0400 (8)
O1	0.8512 (2)	0.7563 (2)	0.13516 (18)	0.0420 (7)
O2	0.7231 (3)	0.7590 (2)	0.2641 (2)	0.0538 (8)
H2	0.7287	0.6980	0.2512	0.081*
C1	1.0316 (3)	0.8325 (3)	0.3000 (3)	0.0394 (10)
H1	1.0940	0.8421	0.3519	0.047*
C2	1.0484 (3)	0.7622 (3)	0.2296 (3)	0.0382 (9)
C3	0.9579 (3)	0.7308 (3)	0.1505 (3)	0.0378 (9)
C4	0.9926 (4)	0.6668 (3)	0.0864 (3)	0.0483 (11)
C5	1.1037 (4)	0.6326 (4)	0.0978 (3)	0.0584 (12)
H5	1.1217	0.5898	0.0539	0.070*
C6	1.1881 (4)	0.6634 (4)	0.1761 (3)	0.0579 (12)
C7	1.1614 (4)	0.7264 (3)	0.2404 (3)	0.0503 (11)
H7	1.2194	0.7461	0.2926	0.060*
C8	0.8571 (3)	1.0056 (3)	0.3689 (3)	0.0418 (10)
C9	0.5507 (4)	0.8126 (3)	0.0704 (3)	0.0480 (11)
H9	0.5425	0.7747	0.1209	0.058*
C10	0.4635 (4)	0.8078 (4)	−0.0128 (3)	0.0587 (13)
H10	0.3990	0.7665	−0.0175	0.070*
C11	0.4735 (4)	0.8640 (3)	−0.0866 (3)	0.0560 (13)
H11	0.4154	0.8615	−0.1423	0.067*
C12	0.5710 (4)	0.9260 (3)	−0.0794 (3)	0.0460 (11)
C13	0.6555 (3)	0.9246 (3)	0.0063 (3)	0.0371 (9)
C14	0.7589 (3)	0.9836 (3)	0.0181 (3)	0.0385 (9)
C15	0.7722 (4)	1.0463 (3)	−0.0550 (3)	0.0501 (11)
C16	0.8737 (5)	1.1054 (4)	−0.0371 (3)	0.0611 (13)
H16	0.8860	1.1489	−0.0829	0.073*
C17	0.9543 (4)	1.0995 (4)	0.0467 (4)	0.0631 (14)
H17	1.0213	1.1387	0.0588	0.076*
C18	0.9340 (4)	1.0331 (4)	0.1140 (3)	0.0532 (12)
H18	0.9900	1.0281	0.1706	0.064*
C19	0.5891 (4)	0.9883 (4)	−0.1528 (3)	0.0591 (13)
H19	0.5339	0.9884	−0.2101	0.071*
C20	0.6836 (5)	1.0465 (4)	−0.1410 (3)	0.0614 (13)
H20	0.6918	1.0879	−0.1896	0.074*
C21	0.6611 (6)	0.7670 (5)	0.3301 (5)	0.108 (2)
H21A	0.7122	0.7870	0.3888	0.162*
H21B	0.6267	0.7015	0.3365	0.162*
H21C	0.6017	0.8181	0.3105	0.162*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0340 (3)	0.0319 (3)	0.0326 (3)	0.0002 (2)	−0.0005 (2)	−0.0013 (2)
S1	0.0426 (6)	0.0409 (6)	0.0424 (6)	0.0096 (5)	−0.0065 (5)	−0.0087 (5)
Cl1	0.0662 (8)	0.0739 (9)	0.0733 (9)	−0.0054 (7)	0.0119 (6)	−0.0356 (7)
Cl2	0.0624 (9)	0.1247 (14)	0.1059 (12)	0.0483 (9)	0.0165 (8)	−0.0035 (10)
N1	0.0361 (18)	0.0347 (18)	0.0302 (16)	0.0029 (15)	0.0015 (13)	0.0019 (14)
N2	0.043 (2)	0.044 (2)	0.0340 (18)	0.0084 (16)	−0.0028 (15)	−0.0093 (15)
N3	0.060 (2)	0.074 (3)	0.047 (2)	0.022 (2)	−0.0076 (18)	−0.026 (2)
N4	0.0354 (18)	0.0324 (18)	0.0366 (18)	0.0010 (15)	0.0028 (14)	−0.0042 (15)
N5	0.0381 (18)	0.0372 (19)	0.0400 (19)	−0.0003 (15)	0.0025 (15)	0.0009 (15)
O1	0.0351 (16)	0.0375 (16)	0.0496 (16)	−0.0010 (12)	0.0051 (12)	−0.0068 (13)
O2	0.071 (2)	0.0428 (18)	0.0553 (19)	−0.0042 (16)	0.0301 (16)	0.0033 (15)
C1	0.034 (2)	0.045 (2)	0.031 (2)	0.0009 (19)	−0.0040 (17)	0.0041 (18)
C2	0.041 (2)	0.033 (2)	0.039 (2)	0.0036 (18)	0.0088 (18)	0.0083 (17)
C3	0.044 (2)	0.027 (2)	0.044 (2)	−0.0016 (18)	0.0137 (19)	0.0038 (17)
C4	0.053 (3)	0.035 (2)	0.056 (3)	−0.001 (2)	0.012 (2)	−0.007 (2)
C5	0.064 (3)	0.047 (3)	0.070 (3)	0.011 (2)	0.028 (3)	−0.007 (2)
C6	0.047 (3)	0.058 (3)	0.069 (3)	0.018 (2)	0.016 (2)	0.009 (3)
C7	0.046 (3)	0.051 (3)	0.050 (3)	0.011 (2)	0.006 (2)	0.010 (2)
C8	0.040 (2)	0.041 (2)	0.037 (2)	0.0004 (19)	−0.0015 (18)	−0.0050 (18)
C9	0.043 (3)	0.042 (3)	0.056 (3)	−0.003 (2)	0.008 (2)	−0.006 (2)
C10	0.038 (3)	0.054 (3)	0.070 (3)	−0.003 (2)	−0.009 (2)	−0.013 (3)
C11	0.047 (3)	0.050 (3)	0.053 (3)	0.011 (2)	−0.017 (2)	−0.016 (2)
C12	0.049 (3)	0.045 (3)	0.035 (2)	0.010 (2)	−0.0034 (19)	−0.0093 (19)
C13	0.043 (2)	0.030 (2)	0.034 (2)	0.0076 (18)	0.0038 (18)	−0.0036 (17)
C14	0.046 (2)	0.033 (2)	0.035 (2)	0.0056 (18)	0.0080 (18)	−0.0007 (17)
C15	0.058 (3)	0.044 (3)	0.049 (3)	0.008 (2)	0.016 (2)	0.007 (2)
C16	0.076 (4)	0.052 (3)	0.063 (3)	0.004 (3)	0.031 (3)	0.018 (2)
C17	0.060 (3)	0.051 (3)	0.077 (4)	−0.013 (2)	0.017 (3)	0.009 (3)
C18	0.045 (3)	0.054 (3)	0.054 (3)	−0.009 (2)	0.003 (2)	0.002 (2)
C19	0.070 (3)	0.061 (3)	0.036 (2)	0.015 (3)	−0.004 (2)	−0.002 (2)
C20	0.080 (4)	0.064 (3)	0.037 (3)	0.019 (3)	0.012 (2)	0.012 (2)
C21	0.132 (6)	0.090 (5)	0.108 (5)	−0.016 (4)	0.043 (5)	0.021 (4)

Geometric parameters (Å, º) top

Ni1—O1	2.004 (3)	C5—C6	1.383 (6)
Ni1—N1	2.026 (3)	C5—H5	0.9300
Ni1—N4	2.081 (3)	C6—C7	1.366 (6)
Ni1—N5	2.089 (3)	C7—H7	0.9300
Ni1—O2	2.145 (3)	C9—C10	1.393 (6)
Ni1—S1	2.3578 (11)	C9—H9	0.9300
S1—C8	1.743 (4)	C10—C11	1.357 (7)
Cl1—C4	1.746 (4)	C10—H10	0.9300
Cl2—C6	1.745 (5)	C11—C12	1.403 (6)
N1—C1	1.290 (5)	C11—H11	0.9300
N1—N2	1.391 (4)	C12—C13	1.403 (5)
N2—C8	1.321 (5)	C12—C19	1.427 (6)
N3—C8	1.342 (5)	C13—C14	1.430 (5)
N3—H3A	0.8600	C14—C15	1.406 (6)
N3—H3B	0.8600	C15—C16	1.405 (6)
N4—C9	1.331 (5)	C15—C20	1.430 (6)
N4—C13	1.353 (5)	C16—C17	1.362 (6)
N5—C18	1.314 (5)	C16—H16	0.9300
N5—C14	1.362 (5)	C17—C18	1.396 (6)
O1—C3	1.286 (4)	C17—H17	0.9300
O2—C21	1.398 (7)	C18—H18	0.9300
O2—H2	0.8200	C19—C20	1.338 (7)
C1—C2	1.448 (5)	C19—H19	0.9300
C1—H1	0.9300	C20—H20	0.9300
C2—C7	1.407 (5)	C21—H21A	0.9600
C2—C3	1.433 (5)	C21—H21B	0.9600
C3—C4	1.415 (6)	C21—H21C	0.9600
C4—C5	1.376 (6)

O1—Ni1—N1	91.59 (11)	C5—C6—Cl2	118.4 (4)
O1—Ni1—N4	86.69 (11)	C6—C7—C2	121.6 (4)
N1—Ni1—N4	177.11 (12)	C6—C7—H7	119.2
O1—Ni1—N5	90.32 (12)	C2—C7—H7	119.2
N1—Ni1—N5	97.97 (12)	N2—C8—N3	117.6 (3)
N4—Ni1—N5	79.74 (12)	N2—C8—S1	126.2 (3)
O1—Ni1—O2	84.23 (11)	N3—C8—S1	116.3 (3)
N1—Ni1—O2	91.15 (12)	N4—C9—C10	122.5 (4)
N4—Ni1—O2	90.98 (12)	N4—C9—H9	118.7
N5—Ni1—O2	169.51 (12)	C10—C9—H9	118.7
O1—Ni1—S1	174.34 (8)	C11—C10—C9	119.4 (4)
N1—Ni1—S1	83.20 (9)	C11—C10—H10	120.3
N4—Ni1—S1	98.62 (9)	C9—C10—H10	120.3
N5—Ni1—S1	92.58 (10)	C10—C11—C12	120.2 (4)
O2—Ni1—S1	93.65 (9)	C10—C11—H11	119.9
C8—S1—Ni1	94.43 (14)	C12—C11—H11	119.9
C1—N1—N2	114.1 (3)	C13—C12—C11	116.5 (4)
C1—N1—Ni1	124.4 (3)	C13—C12—C19	119.0 (4)
N2—N1—Ni1	121.5 (2)	C11—C12—C19	124.4 (4)
C8—N2—N1	114.1 (3)	N4—C13—C12	123.3 (4)
C8—N3—H3A	120.0	N4—C13—C14	116.9 (3)
C8—N3—H3B	120.0	C12—C13—C14	119.7 (4)
H3A—N3—H3B	120.0	N5—C14—C15	122.9 (4)
C9—N4—C13	118.0 (3)	N5—C14—C13	117.5 (3)
C9—N4—Ni1	128.5 (3)	C15—C14—C13	119.6 (4)
C13—N4—Ni1	113.3 (2)	C16—C15—C14	116.4 (4)
C18—N5—C14	118.1 (4)	C16—C15—C20	124.5 (4)
C18—N5—Ni1	129.5 (3)	C14—C15—C20	119.0 (4)
C14—N5—Ni1	112.3 (3)	C17—C16—C15	120.6 (4)
C3—O1—Ni1	125.6 (2)	C17—C16—H16	119.7
C21—O2—Ni1	130.7 (3)	C15—C16—H16	119.7
C21—O2—H2	109.5	C16—C17—C18	118.5 (4)
Ni1—O2—H2	119.7	C16—C17—H17	120.7
N1—C1—C2	126.6 (3)	C18—C17—H17	120.7
N1—C1—H1	116.7	N5—C18—C17	123.4 (4)
C2—C1—H1	116.7	N5—C18—H18	118.3
C7—C2—C3	119.7 (4)	C17—C18—H18	118.3
C7—C2—C1	116.6 (4)	C20—C19—C12	121.5 (4)
C3—C2—C1	123.6 (4)	C20—C19—H19	119.3
O1—C3—C4	119.8 (4)	C12—C19—H19	119.3
O1—C3—C2	124.9 (4)	C19—C20—C15	121.1 (4)
C4—C3—C2	115.3 (4)	C19—C20—H20	119.5
C5—C4—C3	124.2 (4)	C15—C20—H20	119.5
C5—C4—Cl1	118.2 (3)	O2—C21—H21A	109.5
C3—C4—Cl1	117.5 (3)	O2—C21—H21B	109.5
C4—C5—C6	118.5 (4)	H21A—C21—H21B	109.5
C4—C5—H5	120.7	O2—C21—H21C	109.5
C6—C5—H5	120.7	H21A—C21—H21C	109.5
C7—C6—C5	120.6 (4)	H21B—C21—H21C	109.5
C7—C6—Cl2	121.0 (4)

O1—Ni1—S1—C8	17.3 (9)	C7—C2—C3—C4	−2.1 (5)
N1—Ni1—S1—C8	−5.61 (16)	C1—C2—C3—C4	176.2 (4)
N4—Ni1—S1—C8	176.66 (17)	O1—C3—C4—C5	−177.9 (4)
N5—Ni1—S1—C8	−103.33 (16)	C2—C3—C4—C5	2.0 (6)
O2—Ni1—S1—C8	85.12 (16)	O1—C3—C4—Cl1	4.5 (5)
O1—Ni1—N1—C1	10.5 (3)	C2—C3—C4—Cl1	−175.6 (3)
N4—Ni1—N1—C1	−43 (3)	C3—C4—C5—C6	−1.0 (7)
N5—Ni1—N1—C1	−80.1 (3)	Cl1—C4—C5—C6	176.6 (4)
O2—Ni1—N1—C1	94.7 (3)	C4—C5—C6—C7	−0.1 (7)
S1—Ni1—N1—C1	−171.7 (3)	C4—C5—C6—Cl2	−178.9 (4)
O1—Ni1—N1—N2	−170.2 (3)	C5—C6—C7—C2	−0.1 (7)
N4—Ni1—N1—N2	137 (2)	Cl2—C6—C7—C2	178.7 (3)
N5—Ni1—N1—N2	99.2 (3)	C3—C2—C7—C6	1.3 (6)
O2—Ni1—N1—N2	−86.0 (3)	C1—C2—C7—C6	−177.1 (4)
S1—Ni1—N1—N2	7.6 (3)	N1—N2—C8—N3	−179.3 (4)
C1—N1—N2—C8	173.2 (3)	N1—N2—C8—S1	−0.6 (5)
Ni1—N1—N2—C8	−6.2 (4)	Ni1—S1—C8—N2	5.3 (4)
O1—Ni1—N4—C9	87.0 (3)	Ni1—S1—C8—N3	−175.9 (3)
N1—Ni1—N4—C9	140 (2)	C13—N4—C9—C10	0.4 (6)
N5—Ni1—N4—C9	177.9 (4)	Ni1—N4—C9—C10	−173.5 (3)
O2—Ni1—N4—C9	2.8 (3)	N4—C9—C10—C11	−1.0 (7)
S1—Ni1—N4—C9	−91.0 (3)	C9—C10—C11—C12	0.3 (7)
O1—Ni1—N4—C13	−87.1 (3)	C10—C11—C12—C13	0.9 (6)
N1—Ni1—N4—C13	−34 (3)	C10—C11—C12—C19	−179.6 (4)
N5—Ni1—N4—C13	3.8 (3)	C9—N4—C13—C12	0.9 (6)
O2—Ni1—N4—C13	−171.3 (3)	Ni1—N4—C13—C12	175.7 (3)
S1—Ni1—N4—C13	94.8 (2)	C9—N4—C13—C14	−179.0 (3)
O1—Ni1—N5—C18	−96.3 (4)	Ni1—N4—C13—C14	−4.1 (4)
N1—Ni1—N5—C18	−4.6 (4)	C11—C12—C13—N4	−1.6 (6)
N4—Ni1—N5—C18	177.2 (4)	C19—C12—C13—N4	178.9 (4)
O2—Ni1—N5—C18	−154.8 (6)	C11—C12—C13—C14	178.3 (4)
S1—Ni1—N5—C18	78.9 (4)	C19—C12—C13—C14	−1.2 (6)
O1—Ni1—N5—C14	83.7 (3)	C18—N5—C14—C15	0.4 (6)
N1—Ni1—N5—C14	175.4 (3)	Ni1—N5—C14—C15	−179.6 (3)
N4—Ni1—N5—C14	−2.8 (3)	C18—N5—C14—C13	−178.5 (4)
O2—Ni1—N5—C14	25.2 (8)	Ni1—N5—C14—C13	1.5 (4)
S1—Ni1—N5—C14	−101.1 (3)	N4—C13—C14—N5	1.8 (5)
N1—Ni1—O1—C3	−20.1 (3)	C12—C13—C14—N5	−178.1 (4)
N4—Ni1—O1—C3	157.6 (3)	N4—C13—C14—C15	−177.2 (4)
N5—Ni1—O1—C3	77.9 (3)	C12—C13—C14—C15	3.0 (6)
O2—Ni1—O1—C3	−111.1 (3)	N5—C14—C15—C16	−1.5 (6)
S1—Ni1—O1—C3	−42.8 (10)	C13—C14—C15—C16	177.4 (4)
O1—Ni1—O2—C21	178.3 (5)	N5—C14—C15—C20	178.8 (4)
N1—Ni1—O2—C21	86.9 (5)	C13—C14—C15—C20	−2.3 (6)
N4—Ni1—O2—C21	−95.1 (5)	C14—C15—C16—C17	1.0 (7)
N5—Ni1—O2—C21	−122.7 (7)	C20—C15—C16—C17	−179.3 (5)
S1—Ni1—O2—C21	3.6 (5)	C15—C16—C17—C18	0.3 (7)
N2—N1—C1—C2	−179.7 (4)	C14—N5—C18—C17	1.1 (7)
Ni1—N1—C1—C2	−0.3 (6)	Ni1—N5—C18—C17	−178.9 (3)
N1—C1—C2—C7	171.7 (4)	C16—C17—C18—N5	−1.5 (8)
N1—C1—C2—C3	−6.6 (6)	C13—C12—C19—C20	−1.2 (7)
Ni1—O1—C3—C4	−160.4 (3)	C11—C12—C19—C20	179.3 (4)
Ni1—O1—C3—C2	19.7 (5)	C12—C19—C20—C15	1.9 (7)
C7—C2—C3—O1	177.8 (4)	C16—C15—C20—C19	−179.8 (5)
C1—C2—C3—O1	−3.9 (6)	C14—C15—C20—C19	−0.1 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···S1ⁱ	0.82	2.49	3.310 (3)	174
N3—H3A···N2ⁱⁱ	0.86	2.24	3.087 (4)	170
N3—H3B···Cl1ⁱⁱⁱ	0.86	2.86	3.573 (2)	142
C11—H11···S1^iv	0.93	2.81	3.593 (5)	142

Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) −x+2, −y+2, −z+1; (iii) −x+3/2, y+1/2, −z+1/2; (iv) −x+1, −y+2, −z.

Experimental details

Crystal data
Chemical formula	[Ni(C₈H₅Cl₂N₃OS)(C₁₂H₈N₂)(CH₄O)]
M_r	533.07
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	12.058 (1), 12.946 (1), 14.973 (2)
β (°)	105.918 (1)
V (Å³)	2247.6 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.22
Crystal size (mm)	0.30 × 0.28 × 0.13

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.710, 0.857
No. of measured, independent and observed [I > 2σ(I)] reflections	10910, 3951, 2708
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.119, 1.06
No. of reflections	3951
No. of parameters	289
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.64, −0.37

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···S1ⁱ	0.820	2.493	3.310 (3)	173.9
N3—H3A···N2ⁱⁱ	0.860	2.237	3.087 (4)	169.5
N3—H3B···Cl1ⁱⁱⁱ	0.860	2.859	3.573 (2)	141.5
C11—H11···S1^iv	0.931	2.810	3.593 (5)	142.4

Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) −x+2, −y+2, −z+1; (iii) −x+3/2, y+1/2, −z+1/2; (iv) −x+1, −y+2, −z.

Acknowledgements

We acknowledge financial support by the Key Laboratory of Non-ferrous Metal Materials and New Processing Technology, Ministry of Education, P. R. China.

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