Bis{N-ethyl-2-[3-(hy­droxy­imino-κN)butan-2-yl­idene]hydrazinecarbothio­amide-κ2N2,S}nickel(II) dichloride

Abduelftah, H.S.; Ali, A.Q.; Eltayeb, N.E.; Teoh, S.G.; Fun, H.-K.

doi:10.1107/S1600536811055383

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Pages m183-m184

doi:10.1107/S1600536811055383

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Bis{N-ethyl-2-[3-(hydroxyimino-κN)butan-2-ylidene]hydrazinecarbothioamide-κ²N²,S}nickel(II) dichloride

Halema Shaban Abduelftah,^a,^b Amna Qasem Ali,^a,^b Naser Eltaher Eltayeb,^a,^c ‡ Siang Guan Teoh ^a ^* and Hoong-Kun Fun ^d §

^aSchool of Chemical Sciences, Universiti Sains Malaysia, Minden, Penang, Malaysia, ^bFaculty of Science, Sabha University, Libya, ^cDepartment of Chemistry, International University of Africa, Sudan, and ^dX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: sgteoh@usm.my

(Received 29 November 2011; accepted 23 December 2011; online 21 January 2012)

In the title complex, [Ni(C₇H₁₄N₄OS)₂]Cl₂, the Ni^II ion is six-coordinated in a distorted octahedral geometry by four N atoms from the two imine and two oxime groups, and two S atoms from the thione groups. Two chloride ions complete the asymmetric unit. In the crystal, molecules are linked through N—H⋯Cl and O—H⋯Cl hydrogen bonds into an infinite chain propagating along [101].

Related literature

For bond-length data, see: Allen et al. (1987 ). For a related structure, see: Choi et al. (2008 ). For the biological activity, pharmacological properties and analytical applications of thiosemicarbazones and their metal complexes, see: Cowley et al. (2002 ); Ming (2003 ); Lobana et al. (2004 , 2007 ).

Experimental

Crystal data

[Ni(C₇H₁₄N₄OS)₂]Cl₂
M_r = 534.17
Monoclinic, P 2₁ /c
a = 18.4990 (11) Å
b = 14.2097 (9) Å
c = 9.2422 (6) Å
β = 98.542 (1)°
V = 2402.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 1.23 mm⁻¹
T = 293 K
0.42 × 0.20 × 0.12 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.625, T_max = 0.869
30693 measured reflections
8190 independent reflections
6071 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.089
S = 1.03
8190 reflections
292 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.66 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Selected bond lengths (Å)

Ni1—N1	2.1247 (14)
Ni1—N2	2.0120 (12)
Ni1—N5	2.1258 (13)
Ni1—N6	2.0086 (12)
Ni1—S1	2.4089 (5)
Ni1—S2	2.4126 (5)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H1N4⋯Cl1ⁱ	0.730 (19)	2.47 (2)	3.1689 (17)	161 (2)
O2—H1O2⋯Cl1	0.84 (3)	2.20 (3)	3.0062 (14)	161 (2)
N7—H1N7⋯Cl2ⁱⁱ	0.87 (2)	2.34 (2)	3.1488 (16)	153.9 (17)
N3—H1N3⋯Cl1ⁱ	0.76 (2)	2.50 (2)	3.2015 (16)	154 (2)
O1—H1O1⋯Cl2	0.79 (3)	2.20 (3)	2.9396 (16)	157 (2)
N8—H1N8⋯Cl2ⁱⁱ	0.85 (2)	2.349 (19)	3.1567 (19)	159 (2)
Symmetry codes: (i) -x, -y+1, -z+1; (ii) -x+1, -y+1, -z+2.

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); 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 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811055383/is5020sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811055383/is5020Isup2.hkl

checkCIF report

Comment top

Thiosemicarbazones and their metal complexes have attracted significant attention because of their wide-ranging biological and pharmacological properties, analytical applications, specific structures, and chemical properties (Cowley et al., 2002; Ming, 2003; Lobana et al., 2007; Lobana et al., 2004). In this paper we report the crystal structure of bis{N-ethyl-2-[2-(hydroxyimino-κN)butan-2-ylidene]hydrazinecarbothioamide-κ²N²,S}nickle(II)dichloride.

In the mononuclear title complex (Fig. 1), [Ni(C₇H₁₄N₄OS)₂]Cl₂, the nickel(II) ion is six-coordinated in a distorted octahedral geometry by four N atoms from two imine groups and two oxime groups and two S atoms from two thione groups. The Ni—N and Ni—S bond distances (Table 1) and the bond angles around Ni1 are in agreement with the values found for related Ni(II) complex (Choi et al., 2008). Bond lengths and angles observed in the structure are normal (Allen et al., 1987). Ni1 is a meeting-point of four five-membered rings, namely: A (Ni1/S1/N2/N3/C9), B ((Ni1/S2/N6/N7/C12), C ((Ni1/N1/N2/C1/C2) and D ((Ni1/N5/N6/C5/C6).The dihedral angles between these four rings as follows: A/B = 87.11 (5)°, A/C = 4.37 (6)°, A/D = 88.83 (6)°, B/C = 88.55 (6)°, B/D = 4.26 (6)° and C/D = 86.88 (7)°. In the crystal, molecules are linked through intermolecular N4—H1N4···Cl1, O2—H1O2···Cl1, N7—H1N7···Cl2, N3—H1N3···Cl1, O1—H1O1···Cl2 and N8—H1N8···Cl2 hydrogen bonds (Table 2) into infinite chains propagating along [101] (Fig. 2).

Related literature top

For bond-length data, see: Allen et al. (1987). For a related structure, see: Choi et al. (2008). For the biological activity, pharmacological properties and analytical applications of thiosemicarbazones and their metal complexes, see: Cowley et al. (2002); Ming (2003); Lobana et al. (2004, 2007).

Experimental top

The ligand was prepared by the mixing of 2,3-butanedione monoxime (1.01 g) dissolved in 20 ml of EtOH with 4-ethyl-3-thiosemicarbazide (1.19 g) dissolved in 20 ml of EtOH and a few drops of acetic acid. The mixture was boiled under reflux with stirring for 3 h. The mixture was filtered and left to cool and evaporate the solvent at room temperature and the resulting white solid formed was collected by suction filtration and washed with cold EtOH (yield 66%, m.p. 475.2 - 477.2 K). To a solution of the ligand (0.2021 g) in EtOH (20 ml) was added a solution of (NiCl₂.6H₂O) (0.2377 g) in EtOH (20 ml). The mixture was boiled under reflux for 2 h with stirring. The mixture was filtered and left to cool accompanied by slow evaporation of the solvent at room temperature. The brown crystals were grown in DMF-acetone (1:4) mixture by slow evaporation at room temperature for 2 weeks (yield 45%, m.p. 513.9 K).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, with 50% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. The crystal packing of the title compound viewed down the a axis. Hydrogen bonds are shown as dashed lines.

Bis{N-ethyl-2-[3-(hydroxyimino-κN)butan-2- ylidene]hydrazinecarbothioamide-κ²N²,S}nickel(II) dichloride top

Crystal data top

[Ni(C₇H₁₄N₄OS)₂]Cl₂	F(000) = 1112
M_r = 534.17	D_x = 1.477 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7955 reflections
a = 18.4990 (11) Å	θ = 2.7–31.5°
b = 14.2097 (9) Å	µ = 1.23 mm⁻¹
c = 9.2422 (6) Å	T = 293 K
β = 98.542 (1)°	Block, purple
V = 2402.5 (3) Å³	0.42 × 0.20 × 0.12 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	8190 independent reflections
Radiation source: fine-focus sealed tube	6071 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ϕ and ω scans	θ_max = 31.8°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −27→24
T_min = 0.625, T_max = 0.869	k = −21→19
30693 measured reflections	l = −12→13

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0413P)² + 0.4822P] where P = (F_o² + 2F_c²)/3
8190 reflections	(Δ/σ)_max = 0.001
292 parameters	Δρ_max = 0.66 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

[Ni(C₇H₁₄N₄OS)₂]Cl₂	V = 2402.5 (3) Å³
M_r = 534.17	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 18.4990 (11) Å	µ = 1.23 mm⁻¹
b = 14.2097 (9) Å	T = 293 K
c = 9.2422 (6) Å	0.42 × 0.20 × 0.12 mm
β = 98.542 (1)°

Data collection top

Bruker APEXII CCD diffractometer	8190 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	6071 reflections with I > 2σ(I)
T_min = 0.625, T_max = 0.869	R_int = 0.030
30693 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.66 e Å⁻³
8190 reflections	Δρ_min = −0.36 e Å⁻³
292 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	0.254705 (10)	0.544056 (14)	0.720936 (19)	0.03000 (6)
S1	0.19095 (2)	0.69236 (3)	0.69747 (5)	0.04214 (10)
S2	0.33886 (2)	0.59247 (4)	0.55926 (4)	0.04259 (11)
O1	0.32326 (8)	0.33683 (10)	0.76904 (16)	0.0528 (3)
O2	0.15128 (7)	0.47332 (11)	0.94881 (14)	0.0493 (3)
N1	0.27241 (7)	0.39758 (10)	0.69614 (14)	0.0355 (3)
N2	0.17389 (7)	0.50408 (10)	0.56264 (13)	0.0318 (3)
N3	0.12478 (8)	0.56856 (10)	0.50132 (15)	0.0376 (3)
N4	0.07395 (8)	0.71317 (11)	0.49656 (17)	0.0422 (3)
N5	0.21534 (7)	0.51429 (10)	0.92075 (14)	0.0345 (3)
N6	0.33784 (7)	0.58110 (9)	0.87569 (13)	0.0322 (3)
N7	0.40248 (8)	0.61137 (11)	0.83749 (15)	0.0405 (3)
N8	0.47653 (9)	0.63277 (13)	0.66593 (19)	0.0510 (4)
C1	0.17121 (8)	0.41842 (12)	0.51582 (16)	0.0351 (3)
C2	0.22784 (9)	0.35631 (12)	0.59529 (17)	0.0373 (3)
C3	0.11569 (11)	0.38175 (14)	0.39472 (19)	0.0484 (4)
H3A	0.1058	0.4288	0.3199	0.073*
H3B	0.0714	0.3668	0.4324	0.073*
H3C	0.1343	0.3261	0.3542	0.073*
C4	0.23136 (14)	0.25422 (14)	0.5599 (3)	0.0642 (6)
H4A	0.2650	0.2233	0.6340	0.096*
H4B	0.2477	0.2468	0.4667	0.096*
H4C	0.1837	0.2268	0.5563	0.096*
C5	0.32848 (9)	0.58058 (12)	1.01105 (16)	0.0363 (3)
C6	0.25807 (9)	0.53975 (12)	1.03697 (16)	0.0360 (3)
C7	0.38261 (11)	0.61688 (17)	1.13467 (19)	0.0564 (5)
H7A	0.4071	0.6708	1.1026	0.085*
H7B	0.4178	0.5687	1.1662	0.085*
H7C	0.3577	0.6344	1.2146	0.085*
C8	0.24030 (12)	0.52761 (18)	1.18843 (19)	0.0585 (6)
H8A	0.1939	0.4968	1.1841	0.088*
H8B	0.2382	0.5882	1.2337	0.088*
H8C	0.2775	0.4901	1.2448	0.088*
C9	0.12641 (8)	0.65727 (11)	0.55863 (16)	0.0336 (3)
C10	0.06787 (12)	0.81258 (14)	0.5282 (2)	0.0518 (5)
H10A	0.1130	0.8444	0.5164	0.062*
H10B	0.0596	0.8208	0.6286	0.062*
C11	0.00570 (14)	0.85451 (17)	0.4263 (3)	0.0682 (6)
H11A	0.0035	0.9210	0.4438	0.102*
H11B	−0.0393	0.8257	0.4429	0.102*
H11C	0.0130	0.8437	0.3270	0.102*
C12	0.41003 (9)	0.61232 (12)	0.69315 (17)	0.0365 (3)
C13	0.49817 (12)	0.64029 (17)	0.5214 (2)	0.0592 (5)
H13A	0.4789	0.6980	0.4747	0.071*
H13B	0.4783	0.5878	0.4612	0.071*
C14	0.58014 (14)	0.64005 (19)	0.5352 (3)	0.0805 (8)
H14A	0.5944	0.6431	0.4395	0.121*
H14B	0.5990	0.5833	0.5831	0.121*
H14C	0.5994	0.6935	0.5916	0.121*
Cl1	0.03036 (3)	0.42615 (5)	0.70489 (5)	0.06167 (15)
Cl2	0.43204 (3)	0.39179 (4)	1.01970 (8)	0.07468 (19)
H1N4	0.0469 (11)	0.6925 (15)	0.440 (2)	0.043 (6)*
H1O2	0.1237 (14)	0.4674 (16)	0.869 (3)	0.063 (7)*
H1N7	0.4416 (12)	0.6072 (15)	0.903 (2)	0.050 (6)*
H1N3	0.0897 (12)	0.5517 (14)	0.456 (2)	0.046 (6)*
H1O1	0.3480 (13)	0.3666 (16)	0.829 (3)	0.055 (7)*
H1N8	0.5085 (13)	0.6376 (15)	0.742 (2)	0.055 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.02577 (10)	0.03547 (11)	0.02620 (9)	−0.00196 (8)	−0.00457 (6)	−0.00166 (7)
S1	0.0396 (2)	0.0390 (2)	0.0418 (2)	0.00331 (17)	−0.01353 (16)	−0.00551 (16)
S2	0.0354 (2)	0.0605 (3)	0.03009 (18)	−0.00913 (19)	−0.00085 (14)	0.00010 (17)
O1	0.0535 (8)	0.0468 (8)	0.0519 (7)	0.0120 (6)	−0.0134 (6)	−0.0010 (6)
O2	0.0352 (7)	0.0699 (9)	0.0409 (6)	−0.0168 (6)	−0.0004 (5)	0.0024 (6)
N1	0.0325 (7)	0.0383 (7)	0.0339 (6)	0.0037 (5)	−0.0007 (5)	0.0004 (5)
N2	0.0265 (6)	0.0375 (7)	0.0294 (5)	−0.0032 (5)	−0.0027 (4)	−0.0015 (5)
N3	0.0293 (7)	0.0418 (8)	0.0367 (7)	−0.0015 (6)	−0.0116 (5)	−0.0021 (5)
N4	0.0345 (8)	0.0467 (8)	0.0407 (7)	0.0033 (6)	−0.0094 (6)	0.0010 (6)
N5	0.0284 (6)	0.0406 (7)	0.0329 (6)	−0.0031 (5)	−0.0014 (5)	−0.0009 (5)
N6	0.0267 (6)	0.0373 (7)	0.0301 (6)	−0.0021 (5)	−0.0042 (4)	−0.0001 (5)
N7	0.0287 (7)	0.0552 (9)	0.0345 (6)	−0.0070 (6)	−0.0062 (5)	0.0000 (6)
N8	0.0317 (8)	0.0696 (11)	0.0509 (9)	−0.0086 (7)	0.0035 (6)	0.0000 (8)
C1	0.0299 (8)	0.0434 (9)	0.0310 (7)	−0.0063 (6)	0.0010 (5)	−0.0059 (6)
C2	0.0375 (8)	0.0375 (8)	0.0363 (7)	−0.0027 (7)	0.0037 (6)	−0.0039 (6)
C3	0.0464 (10)	0.0529 (11)	0.0416 (8)	−0.0103 (8)	−0.0073 (7)	−0.0127 (8)
C4	0.0733 (15)	0.0421 (11)	0.0715 (14)	0.0015 (10)	−0.0082 (11)	−0.0138 (10)
C5	0.0341 (8)	0.0420 (9)	0.0293 (6)	−0.0019 (7)	−0.0070 (6)	−0.0018 (6)
C6	0.0366 (8)	0.0408 (8)	0.0287 (6)	−0.0006 (7)	−0.0017 (6)	0.0004 (6)
C7	0.0516 (11)	0.0787 (14)	0.0341 (8)	−0.0182 (10)	−0.0090 (7)	−0.0095 (9)
C8	0.0573 (12)	0.0867 (16)	0.0300 (8)	−0.0173 (11)	0.0020 (7)	0.0016 (9)
C9	0.0272 (7)	0.0411 (8)	0.0306 (6)	−0.0015 (6)	−0.0018 (5)	0.0019 (6)
C10	0.0532 (11)	0.0482 (11)	0.0497 (10)	0.0130 (9)	−0.0064 (8)	0.0007 (8)
C11	0.0692 (15)	0.0600 (13)	0.0677 (13)	0.0232 (11)	−0.0153 (11)	0.0093 (11)
C12	0.0301 (8)	0.0401 (8)	0.0379 (7)	−0.0024 (6)	0.0001 (6)	0.0004 (6)
C13	0.0509 (12)	0.0671 (13)	0.0637 (12)	−0.0074 (10)	0.0218 (10)	0.0040 (10)
C14	0.0590 (15)	0.0699 (16)	0.122 (2)	−0.0031 (12)	0.0435 (15)	−0.0051 (15)
Cl1	0.0405 (3)	0.0975 (4)	0.0438 (2)	−0.0219 (3)	−0.00425 (18)	−0.0083 (2)
Cl2	0.0534 (3)	0.0625 (3)	0.0937 (4)	−0.0016 (3)	−0.0363 (3)	0.0016 (3)

Geometric parameters (Å, º) top

Ni1—N1	2.1247 (14)	C1—C3	1.496 (2)
Ni1—N2	2.0120 (12)	C2—C4	1.491 (3)
Ni1—N5	2.1258 (13)	C3—H3A	0.9600
Ni1—N6	2.0086 (12)	C3—H3B	0.9600
Ni1—S1	2.4089 (5)	C3—H3C	0.9600
Ni1—S2	2.4126 (5)	C4—H4A	0.9600
S1—C9	1.6927 (15)	C4—H4B	0.9600
S2—C12	1.6912 (16)	C4—H4C	0.9600
O1—N1	1.3769 (18)	C5—C6	1.478 (2)
O1—H1O1	0.79 (2)	C5—C7	1.495 (2)
O2—N5	1.3791 (18)	C6—C8	1.495 (2)
O2—H1O2	0.83 (2)	C7—H7A	0.9600
N1—C2	1.290 (2)	C7—H7B	0.9600
N2—C1	1.290 (2)	C7—H7C	0.9600
N2—N3	1.3538 (19)	C8—H8A	0.9600
N3—C9	1.366 (2)	C8—H8B	0.9600
N3—H1N3	0.76 (2)	C8—H8C	0.9600
N4—C9	1.318 (2)	C10—C11	1.497 (3)
N4—C10	1.450 (3)	C10—H10A	0.9700
N4—H1N4	0.73 (2)	C10—H10B	0.9700
N5—C6	1.2873 (19)	C11—H11A	0.9600
N6—C5	1.288 (2)	C11—H11B	0.9600
N6—N7	1.3656 (19)	C11—H11C	0.9600
N7—C12	1.362 (2)	C13—C14	1.503 (3)
N7—H1N7	0.87 (2)	C13—H13A	0.9700
N8—C12	1.324 (2)	C13—H13B	0.9700
N8—C13	1.454 (3)	C14—H14A	0.9600
N8—H1N8	0.85 (2)	C14—H14B	0.9600
C1—C2	1.479 (2)	C14—H14C	0.9600

N6—Ni1—N2	177.98 (5)	C2—C4—H4A	109.5
N6—Ni1—N1	102.68 (5)	C2—C4—H4B	109.5
N2—Ni1—N1	75.81 (5)	H4A—C4—H4B	109.5
N6—Ni1—N5	76.02 (5)	C2—C4—H4C	109.5
N2—Ni1—N5	105.19 (5)	H4A—C4—H4C	109.5
N1—Ni1—N5	88.68 (5)	H4B—C4—H4C	109.5
N6—Ni1—S1	98.49 (4)	N6—C5—C6	114.12 (13)
N2—Ni1—S1	83.14 (4)	N6—C5—C7	124.67 (16)
N1—Ni1—S1	158.21 (4)	C6—C5—C7	121.21 (14)
N5—Ni1—S1	91.49 (4)	N5—C6—C5	114.95 (13)
N6—Ni1—S2	82.53 (4)	N5—C6—C8	123.77 (16)
N2—Ni1—S2	96.22 (4)	C5—C6—C8	121.26 (14)
N1—Ni1—S2	95.08 (4)	C5—C7—H7A	109.5
N5—Ni1—S2	158.53 (4)	C5—C7—H7B	109.5
S1—Ni1—S2	92.701 (19)	H7A—C7—H7B	109.5
C9—S1—Ni1	95.24 (6)	C5—C7—H7C	109.5
C12—S2—Ni1	95.63 (6)	H7A—C7—H7C	109.5
N1—O1—H1O1	107.0 (17)	H7B—C7—H7C	109.5
N5—O2—H1O2	107.9 (17)	C6—C8—H8A	109.5
C2—N1—O1	112.67 (14)	C6—C8—H8B	109.5
C2—N1—Ni1	115.53 (11)	H8A—C8—H8B	109.5
O1—N1—Ni1	131.80 (10)	C6—C8—H8C	109.5
C1—N2—N3	120.53 (13)	H8A—C8—H8C	109.5
C1—N2—Ni1	119.84 (11)	H8B—C8—H8C	109.5
N3—N2—Ni1	119.56 (10)	N4—C9—N3	114.52 (14)
N2—N3—C9	119.17 (12)	N4—C9—S1	122.91 (13)
N2—N3—H1N3	118.9 (16)	N3—C9—S1	122.57 (12)
C9—N3—H1N3	118.3 (16)	N4—C10—C11	109.65 (17)
C9—N4—C10	125.00 (15)	N4—C10—H10A	109.7
C9—N4—H1N4	116.9 (17)	C11—C10—H10A	109.7
C10—N4—H1N4	118.1 (17)	N4—C10—H10B	109.7
C6—N5—O2	113.58 (13)	C11—C10—H10B	109.7
C6—N5—Ni1	114.95 (11)	H10A—C10—H10B	108.2
O2—N5—Ni1	131.47 (10)	C10—C11—H11A	109.5
C5—N6—N7	120.14 (13)	C10—C11—H11B	109.5
C5—N6—Ni1	119.40 (11)	H11A—C11—H11B	109.5
N7—N6—Ni1	120.38 (9)	C10—C11—H11C	109.5
C12—N7—N6	118.52 (13)	H11A—C11—H11C	109.5
C12—N7—H1N7	118.8 (14)	H11B—C11—H11C	109.5
N6—N7—H1N7	118.0 (14)	N8—C12—N7	114.94 (15)
C12—N8—C13	125.52 (17)	N8—C12—S2	122.81 (13)
C12—N8—H1N8	114.4 (15)	N7—C12—S2	122.22 (12)
C13—N8—H1N8	119.9 (15)	N8—C13—C14	109.5 (2)
N2—C1—C2	114.04 (13)	N8—C13—H13A	109.8
N2—C1—C3	124.57 (15)	C14—C13—H13A	109.8
C2—C1—C3	121.38 (15)	N8—C13—H13B	109.8
N1—C2—C1	114.65 (14)	C14—C13—H13B	109.8
N1—C2—C4	123.84 (17)	H13A—C13—H13B	108.2
C1—C2—C4	121.51 (15)	C13—C14—H14A	109.5
C1—C3—H3A	109.5	C13—C14—H14B	109.5
C1—C3—H3B	109.5	H14A—C14—H14B	109.5
H3A—C3—H3B	109.5	C13—C14—H14C	109.5
C1—C3—H3C	109.5	H14A—C14—H14C	109.5
H3A—C3—H3C	109.5	H14B—C14—H14C	109.5
H3B—C3—H3C	109.5

N6—Ni1—S1—C9	176.16 (7)	N1—Ni1—N6—N7	91.00 (12)
N2—Ni1—S1—C9	−2.63 (6)	N5—Ni1—N6—N7	176.39 (13)
N1—Ni1—S1—C9	−17.59 (12)	S1—Ni1—N6—N7	−94.19 (12)
N5—Ni1—S1—C9	−107.75 (6)	S2—Ni1—N6—N7	−2.56 (11)
S2—Ni1—S1—C9	93.31 (6)	C5—N6—N7—C12	−179.00 (16)
N6—Ni1—S2—C12	5.33 (7)	Ni1—N6—N7—C12	−2.5 (2)
N2—Ni1—S2—C12	−173.07 (7)	N3—N2—C1—C2	−179.18 (14)
N1—Ni1—S2—C12	−96.83 (7)	Ni1—N2—C1—C2	4.00 (18)
N5—Ni1—S2—C12	2.54 (13)	N3—N2—C1—C3	−0.5 (2)
S1—Ni1—S2—C12	103.55 (6)	Ni1—N2—C1—C3	−177.35 (13)
N6—Ni1—N1—C2	−176.40 (12)	O1—N1—C2—C1	178.83 (13)
N2—Ni1—N1—C2	2.22 (11)	Ni1—N1—C2—C1	−0.92 (18)
N5—Ni1—N1—C2	108.25 (12)	O1—N1—C2—C4	−0.7 (3)
S1—Ni1—N1—C2	17.54 (19)	Ni1—N1—C2—C4	179.55 (16)
S2—Ni1—N1—C2	−92.93 (12)	N2—C1—C2—N1	−1.9 (2)
N6—Ni1—N1—O1	3.91 (15)	C3—C1—C2—N1	179.44 (15)
N2—Ni1—N1—O1	−177.48 (15)	N2—C1—C2—C4	177.68 (18)
N5—Ni1—N1—O1	−71.44 (15)	C3—C1—C2—C4	−1.0 (3)
S1—Ni1—N1—O1	−162.15 (10)	N7—N6—C5—C6	−175.83 (14)
S2—Ni1—N1—O1	87.38 (14)	Ni1—N6—C5—C6	7.6 (2)
N1—Ni1—N2—C1	−3.45 (12)	N7—N6—C5—C7	3.9 (3)
N5—Ni1—N2—C1	−88.10 (12)	Ni1—N6—C5—C7	−172.64 (15)
S1—Ni1—N2—C1	−177.77 (12)	O2—N5—C6—C5	177.75 (14)
S2—Ni1—N2—C1	90.24 (12)	Ni1—N5—C6—C5	−3.03 (19)
N1—Ni1—N2—N3	179.70 (12)	O2—N5—C6—C8	−0.7 (2)
N5—Ni1—N2—N3	95.05 (12)	Ni1—N5—C6—C8	178.50 (15)
S1—Ni1—N2—N3	5.37 (11)	N6—C5—C6—N5	−2.7 (2)
S2—Ni1—N2—N3	−86.61 (11)	C7—C5—C6—N5	177.58 (17)
C1—N2—N3—C9	176.31 (14)	N6—C5—C6—C8	175.84 (17)
Ni1—N2—N3—C9	−6.9 (2)	C7—C5—C6—C8	−3.9 (3)
N6—Ni1—N5—C6	5.21 (12)	C10—N4—C9—N3	−173.91 (17)
N2—Ni1—N5—C6	−176.46 (12)	C10—N4—C9—S1	5.8 (3)
N1—Ni1—N5—C6	108.63 (12)	N2—N3—C9—N4	−176.40 (14)
S1—Ni1—N5—C6	−93.17 (12)	N2—N3—C9—S1	3.9 (2)
S2—Ni1—N5—C6	8.1 (2)	Ni1—S1—C9—N4	−179.39 (14)
N6—Ni1—N5—O2	−175.74 (15)	Ni1—S1—C9—N3	0.27 (14)
N2—Ni1—N5—O2	2.59 (15)	C9—N4—C10—C11	174.47 (19)
N1—Ni1—N5—O2	−72.32 (14)	C13—N8—C12—N7	−178.54 (19)
S1—Ni1—N5—O2	85.88 (14)	C13—N8—C12—S2	−0.6 (3)
S2—Ni1—N5—O2	−172.89 (10)	N6—N7—C12—N8	−173.06 (16)
N1—Ni1—N6—C5	−92.46 (13)	N6—N7—C12—S2	8.9 (2)
N5—Ni1—N6—C5	−7.07 (12)	Ni1—S2—C12—N8	173.07 (15)
S1—Ni1—N6—C5	82.35 (13)	Ni1—S2—C12—N7	−9.10 (15)
S2—Ni1—N6—C5	173.99 (13)	C12—N8—C13—C14	−165.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H1N4···Cl1ⁱ	0.730 (19)	2.47 (2)	3.1689 (17)	161 (2)
O2—H1O2···Cl1	0.84 (3)	2.20 (3)	3.0062 (14)	161 (2)
N7—H1N7···Cl2ⁱⁱ	0.87 (2)	2.34 (2)	3.1488 (16)	153.9 (17)
N3—H1N3···Cl1ⁱ	0.76 (2)	2.50 (2)	3.2015 (16)	154 (2)
O1—H1O1···Cl2	0.79 (3)	2.20 (3)	2.9396 (16)	157 (2)
N8—H1N8···Cl2ⁱⁱ	0.85 (2)	2.349 (19)	3.1567 (19)	159 (2)

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

Experimental details

Crystal data
Chemical formula	[Ni(C₇H₁₄N₄OS)₂]Cl₂
M_r	534.17
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	18.4990 (11), 14.2097 (9), 9.2422 (6)
β (°)	98.542 (1)
V (Å³)	2402.5 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.23
Crystal size (mm)	0.42 × 0.20 × 0.12

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.625, 0.869
No. of measured, independent and observed [I > 2σ(I)] reflections	30693, 8190, 6071
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.742

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.089, 1.03
No. of reflections	8190
No. of parameters	292
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.66, −0.36

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Selected bond lengths (Å) top

Ni1—N1	2.1247 (14)	Ni1—N6	2.0086 (12)
Ni1—N2	2.0120 (12)	Ni1—S1	2.4089 (5)
Ni1—N5	2.1258 (13)	Ni1—S2	2.4126 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H1N4···Cl1ⁱ	0.730 (19)	2.47 (2)	3.1689 (17)	161 (2)
O2—H1O2···Cl1	0.84 (3)	2.20 (3)	3.0062 (14)	161 (2)
N7—H1N7···Cl2ⁱⁱ	0.87 (2)	2.34 (2)	3.1488 (16)	153.9 (17)
N3—H1N3···Cl1ⁱ	0.76 (2)	2.50 (2)	3.2015 (16)	154 (2)
O1—H1O1···Cl2	0.79 (3)	2.20 (3)	2.9396 (16)	157 (2)
N8—H1N8···Cl2ⁱⁱ	0.85 (2)	2.349 (19)	3.1567 (19)	159 (2)

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

Footnotes

‡Thomson Reuters ResearcherID: E-9395-2011

§Thomson Reuters ResearcherID: A-3561-2009

Acknowledgements

The authors thank the Malaysian Government and Universiti Sains Malaysia for the RU research grant (1001/PKIMIA/815067). NEE thanks Universiti Sains Malaysia for a post-doctoral fellowship and the International University of Africa (Sudan) for providing research leave. HAF and AQA each thank the Ministry of Higher Education and the University of Sabha (Libya) for a scholarship.

References

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