[Hexane-2,5-dione bis-(thio-semi-carba-zon-ato)]nickel(II).

In the title compound, [Ni(C8H14N6S2)], the Ni(II) ion is coordinated by N2S2 donor atoms of the tetradentate thio-semicarbazone ligand, and has a slightly distorted square-planar geometry. In the crystal, inversion-related mol-ecules are linked via pairs of N-H⋯N and N-H⋯S hydrogen bonds, forming R 2 (2)(8) ring motifs. Mol-ecules are further linked by slightly weaker N-H⋯N, N-H⋯S and C-H⋯S hydrogen bonds, forming two-dimensional networks which lie parallel to the bc plane.

Related literature

For standard values of bond lengths, see: Allen et al. (1987 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For related structures, see: Cowley et al. (2004 ▶); Lobana et al. (2011 ▶). The anti­tumor and anti­bacterial activity of thio­semicarbazones and thio­semicarbazides has been attributed to their ability to chelate trace metals, see: Kirschner et al. (1966 ▶). For the preparation of hexan-2,5-dionebis(thio­semicarbazone), see: Nandi et al. (1984 ▶).

Experimental

Crystal data

[Ni(C8H14N6S2)]

M = 317.08

Triclinic,

a = 7.8928 (3) Å

b = 8.0378 (3) Å

c = 11.0889 (4) Å

α = 69.720 (1)°

β = 75.214 (1)°

γ = 85.693 (1)°

V = 637.96 (4) Å3

Z = 2

Mo Kα radiation

μ = 1.84 mm−1

T = 296 K

0.20 × 0.20 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.711, T max = 0.711

7275 measured reflections

3078 independent reflections

2833 reflections with I > 2σ(I)

R int = 0.011

Refinement

R[F 2 > 2σ(F 2)] = 0.021

wR(F 2) = 0.059

S = 0.99

3078 reflections

156 parameters

H-atom parameters constrained

Δρmax = 0.28 e Å−3

Δρmin = −0.21 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT-Plus (Bruker, 2005 ▶); data reduction: SAINT-Plus; 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 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813012816/su2598sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813012816/su2598Isup2.hkl

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

[Ni(C8H14N6S2)]	Z = 2
Mr = 317.08	F(000) = 328
Triclinic, P1	Dx = 1.651 Mg m−3
Hall symbol: -P 1	Melting point < 468 K
a = 7.8928 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.0378 (3) Å	Cell parameters from 4799 reflections
c = 11.0889 (4) Å	θ = 2.7–28.3°
α = 69.720 (1)°	µ = 1.84 mm−1
β = 75.214 (1)°	T = 296 K
γ = 85.693 (1)°	Prism, dark-red
V = 637.96 (4) Å3	0.20 × 0.20 × 0.20 mm

Bruker APEXII CCD diffractometer	3078 independent reflections
Radiation source: fine-focus sealed tube	2833 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.011
φ and ω scans	θmax = 28.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −10→10
Tmin = 0.711, Tmax = 0.711	k = −10→10
7275 measured reflections	l = −14→14

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)] = 0.021	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.059	H-atom parameters constrained
S = 0.99	w = 1/[σ2(Fo2) + (0.0381P)2 + 0.1248P] where P = (Fo2 + 2Fc2)/3
3078 reflections	(Δ/σ)max = 0.001
156 parameters	Δρmax = 0.28 e Å−3
0 restraints	Δρmin = −0.21 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Ni1	0.74078 (2)	0.65209 (2)	0.792634 (16)	0.02818 (7)
S1	0.67960 (5)	0.84581 (4)	0.61696 (4)	0.03729 (9)
S2	0.69288 (5)	0.85168 (4)	0.88575 (4)	0.03624 (9)
N1	0.77048 (15)	0.49799 (14)	0.69038 (11)	0.0297 (2)
N2	0.65361 (17)	0.51991 (15)	0.60798 (12)	0.0336 (2)
N3	0.5029 (2)	0.73756 (19)	0.48368 (16)	0.0567 (4)
H1N3	0.4658	0.8503	0.4602	0.068*
H2N3	0.4647	0.6561	0.4575	0.068*
N4	0.75863 (15)	0.48253 (15)	0.96705 (12)	0.0314 (2)
N5	0.66994 (18)	0.53312 (16)	1.07736 (12)	0.0381 (3)
N6	0.57514 (19)	0.76724 (18)	1.14636 (13)	0.0432 (3)
H1N6	0.5353	0.6876	1.2274	0.052*
H2N6	0.5298	0.8801	1.1246	0.052*
C1	0.6069 (2)	0.68543 (18)	0.56807 (14)	0.0350 (3)
C2	0.64152 (18)	0.70094 (18)	1.04654 (14)	0.0321 (3)
C3	0.8992 (2)	0.2587 (2)	0.60870 (16)	0.0427 (3)
H3A	0.8689	0.3227	0.5264	0.064*
H3B	0.8197	0.1599	0.6581	0.064*
H3C	1.0167	0.2163	0.5910	0.064*
C4	0.88697 (18)	0.37854 (18)	0.68727 (14)	0.0321 (3)
C5	1.01427 (19)	0.3582 (2)	0.77028 (16)	0.0389 (3)
H5A	1.0445	0.4742	0.7680	0.047*
H5B	1.1207	0.3055	0.7337	0.047*
C6	0.9390 (2)	0.24249 (19)	0.91302 (16)	0.0376 (3)
H6A	0.8753	0.1449	0.9115	0.045*
H6B	1.0366	0.1917	0.9514	0.045*
C7	0.82010 (18)	0.32434 (18)	1.00507 (15)	0.0336 (3)
C8	0.7864 (2)	0.2088 (2)	1.14834 (17)	0.0457 (4)
H8A	0.6655	0.2164	1.1913	0.069*
H8B	0.8593	0.2480	1.1909	0.069*
H8C	0.8131	0.0881	1.1543	0.069*

	U11	U22	U33	U12	U13	U23
Ni1	0.03387 (10)	0.02086 (9)	0.03506 (10)	0.00579 (6)	−0.01551 (7)	−0.01199 (7)
S1	0.0556 (2)	0.02174 (16)	0.04102 (19)	0.00748 (14)	−0.02323 (16)	−0.01184 (14)
S2	0.0531 (2)	0.02249 (16)	0.03655 (18)	0.00501 (14)	−0.01499 (15)	−0.01232 (13)
N1	0.0350 (6)	0.0238 (5)	0.0344 (6)	0.0044 (4)	−0.0139 (4)	−0.0118 (4)
N2	0.0452 (6)	0.0261 (5)	0.0369 (6)	0.0078 (5)	−0.0209 (5)	−0.0136 (5)
N3	0.0945 (12)	0.0322 (7)	0.0674 (9)	0.0223 (7)	−0.0587 (9)	−0.0231 (7)
N4	0.0343 (6)	0.0259 (5)	0.0382 (6)	0.0036 (4)	−0.0154 (5)	−0.0119 (5)
N5	0.0465 (7)	0.0305 (6)	0.0376 (6)	0.0068 (5)	−0.0131 (5)	−0.0111 (5)
N6	0.0557 (8)	0.0364 (7)	0.0375 (7)	0.0089 (6)	−0.0092 (6)	−0.0156 (5)
C1	0.0487 (8)	0.0267 (6)	0.0352 (7)	0.0080 (6)	−0.0181 (6)	−0.0132 (5)
C2	0.0335 (6)	0.0296 (6)	0.0371 (7)	0.0023 (5)	−0.0138 (5)	−0.0129 (5)
C3	0.0498 (9)	0.0348 (7)	0.0471 (8)	0.0102 (6)	−0.0098 (7)	−0.0219 (7)
C4	0.0337 (6)	0.0249 (6)	0.0372 (7)	0.0026 (5)	−0.0084 (5)	−0.0106 (5)
C5	0.0307 (6)	0.0355 (7)	0.0549 (9)	0.0079 (5)	−0.0151 (6)	−0.0190 (7)
C6	0.0402 (7)	0.0279 (7)	0.0519 (8)	0.0116 (6)	−0.0239 (6)	−0.0158 (6)
C7	0.0341 (6)	0.0259 (6)	0.0448 (7)	0.0034 (5)	−0.0200 (6)	−0.0105 (6)
C8	0.0503 (9)	0.0325 (7)	0.0487 (9)	0.0077 (6)	−0.0185 (7)	−0.0038 (6)

Ni1—N1	1.9155 (11)	N6—H2N6	0.9237
Ni1—N4	1.9751 (12)	C3—C4	1.490 (2)
Ni1—S2	2.1542 (4)	C3—H3A	0.9600
Ni1—S1	2.1718 (4)	C3—H3B	0.9600
S1—C1	1.7434 (14)	C3—H3C	0.9600
S2—C2	1.7374 (15)	C4—C5	1.4922 (19)
N1—C4	1.2816 (18)	C5—C6	1.518 (2)
N1—N2	1.4181 (15)	C5—H5A	0.9700
N2—C1	1.3051 (17)	C5—H5B	0.9700
N3—C1	1.3392 (19)	C6—C7	1.496 (2)
N3—H1N3	0.9003	C6—H6A	0.9700
N3—H2N3	0.9003	C6—H6B	0.9700
N4—C7	1.2923 (17)	C7—C8	1.502 (2)
N4—N5	1.4202 (17)	C8—H8A	0.9600
N5—C2	1.2887 (18)	C8—H8B	0.9600
N6—C2	1.3619 (18)	C8—H8C	0.9600
N6—H1N6	0.8959
N1—Ni1—N4	101.11 (5)	C4—C3—H3B	109.5
N1—Ni1—S2	171.94 (3)	H3A—C3—H3B	109.5
N4—Ni1—S2	86.61 (3)	C4—C3—H3C	109.5
N1—Ni1—S1	83.28 (3)	H3A—C3—H3C	109.5
N4—Ni1—S1	170.95 (4)	H3B—C3—H3C	109.5
S2—Ni1—S1	88.755 (14)	N1—C4—C5	117.00 (12)
C1—S1—Ni1	93.57 (5)	N1—C4—C3	123.93 (13)
C2—S2—Ni1	94.83 (5)	C5—C4—C3	119.06 (13)
C4—N1—N2	116.52 (11)	C4—C5—C6	111.47 (12)
C4—N1—Ni1	126.65 (10)	C4—C5—H5A	109.3
N2—N1—Ni1	116.82 (8)	C6—C5—H5A	109.3
C1—N2—N1	109.69 (11)	C4—C5—H5B	109.3
C1—N3—H1N3	119.4	C6—C5—H5B	109.3
C1—N3—H2N3	118.7	H5A—C5—H5B	108.0
H1N3—N3—H2N3	121.7	C7—C6—C5	118.83 (12)
C7—N4—N5	111.17 (12)	C7—C6—H6A	107.6
C7—N4—Ni1	133.49 (10)	C5—C6—H6A	107.6
N5—N4—Ni1	114.93 (8)	C7—C6—H6B	107.6
C2—N5—N4	113.32 (12)	C5—C6—H6B	107.6
C2—N6—H1N6	116.4	H6A—C6—H6B	107.0
C2—N6—H2N6	117.9	N4—C7—C8	122.59 (14)
H1N6—N6—H2N6	120.2	N4—C7—C6	123.82 (13)
N2—C1—N3	119.68 (13)	C8—C7—C6	113.50 (12)
N2—C1—S1	122.47 (11)	C7—C8—H8A	109.5
N3—C1—S1	117.82 (11)	C7—C8—H8B	109.5
N5—C2—N6	118.33 (13)	H8A—C8—H8B	109.5
N5—C2—S2	124.34 (11)	C7—C8—H8C	109.5
N6—C2—S2	117.25 (11)	H8A—C8—H8C	109.5
C4—C3—H3A	109.5	H8B—C8—H8C	109.5
N1—Ni1—S1—C1	26.73 (7)	Ni1—S1—C1—N3	159.93 (14)
S2—Ni1—S1—C1	−152.05 (6)	N4—N5—C2—N6	−172.75 (12)
N4—Ni1—S2—C2	−17.03 (6)	N4—N5—C2—S2	3.74 (18)
S1—Ni1—S2—C2	155.19 (5)	Ni1—S2—C2—N5	12.62 (13)
N4—Ni1—N1—C4	−46.03 (13)	Ni1—S2—C2—N6	−170.86 (11)
S1—Ni1—N1—C4	141.98 (12)	N2—N1—C4—C5	178.11 (12)
N4—Ni1—N1—N2	135.05 (9)	Ni1—N1—C4—C5	−0.80 (19)
S1—Ni1—N1—N2	−36.94 (9)	N2—N1—C4—C3	−3.2 (2)
C4—N1—N2—C1	−148.40 (13)	Ni1—N1—C4—C3	177.87 (11)
Ni1—N1—N2—C1	30.63 (15)	N1—C4—C5—C6	83.18 (16)
N1—Ni1—N4—C7	18.12 (14)	C3—C4—C5—C6	−95.57 (16)
S2—Ni1—N4—C7	−164.20 (13)	C4—C5—C6—C7	−82.08 (16)
N1—Ni1—N4—N5	−153.75 (9)	N5—N4—C7—C8	4.41 (19)
S2—Ni1—N4—N5	23.93 (9)	Ni1—N4—C7—C8	−167.68 (11)
C7—N4—N5—C2	165.09 (13)	N5—N4—C7—C6	−171.94 (13)
Ni1—N4—N5—C2	−21.23 (15)	Ni1—N4—C7—C6	16.0 (2)
N1—N2—C1—N3	176.82 (15)	C5—C6—C7—N4	9.3 (2)
N1—N2—C1—S1	−1.41 (18)	C5—C6—C7—C8	−167.36 (13)
Ni1—S1—C1—N2	−21.81 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H2N3···N2i	0.90	2.16	3.054 (2)	173
N3—H1N3···S1ii	0.90	2.58	3.4699 (17)	171
N6—H1N6···N2iii	0.90	2.28	3.1248 (19)	156
N6—H2N6···S2iv	0.92	2.67	3.5552 (16)	162
C3—H3B···S2v	0.96	2.87	3.7513 (17)	152

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H2N3⋯N2i	0.90	2.16	3.054 (2)	173
N3—H1N3⋯S1ii	0.90	2.58	3.4699 (17)	171
N6—H1N6⋯N2iii	0.90	2.28	3.1248 (19)	156
N6—H2N6⋯S2iv	0.92	2.67	3.5552 (16)	162
C3—H3B⋯S2v	0.96	2.87	3.7513 (17)	152

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