Hexa-kis-(N,N'-dimethyl-thio-urea-κS)nickel(II) nitrate.

The title complex salt, [Ni(C(3)H(8)N(2)S)(6)](NO(3))(2), consists of an [Ni(Dmtu)(6)](2+) (Dmtu is N,N'-dimethyl-thio-urea) dication and two nitrate counter-anions. The Ni(II) atom (site symmetry ) is coordinated by the S atoms of six Dmtu ligands within a slightly distorted octa-hedral environment. The crystal structure is characterized by weak intra-molecular N-H⋯S inter-actions and by inter-molecular N-H⋯O hydrogen bonds involving the nitrate anion (site symmetry 3.). These inter-molecular inter-actions lead to the formation of two-dimensional networks lying parallel to the ab plane. The networks are linked via non-classical inter-molecular C-H⋯O hydrogen bonds, forming a three-dimensional arrangement.

Related literature

For background to nickel(II) complexes of thio­urea and its derivatives, see: Ambujam et al. (2006 ▶); Basso et al. (1969 ▶); Bentley & Waters (1974 ▶); Chiesi et al. (1971 ▶); Crane & Herod (2004 ▶); Eaton & Zaw (1975 ▶); El-Bahy et al. (2003 ▶); Figgis & Reynolds (1986 ▶); Monim-ul-Mehboob et al. (2010 ▶); Sonar et al. (1979 ▶); Weininger et al. (1969 ▶); Weininger & Amma (1976 ▶). For the crystal structures of similar nickel(II) complexes, see: Bentley & Waters (1974 ▶); El-Bahy et al. (2003 ▶); Monim-ul-Mehboob et al. (2010 ▶); Weininger et al. (1969 ▶).

Experimental

Crystal data

[Ni(C3H8N2S)6](NO3)2

M = 807.77

Trigonal,

a = 13.7166 (10) Å

c = 35.332 (3) Å

V = 5756.9 (8) Å3

Z = 6

Mo Kα radiation

μ = 0.88 mm−1

T = 223 K

0.30 × 0.26 × 0.24 mm

Data collection

Stoe IPDS 2 diffractometer

Absorption correction: multi-scan (MULscanABS; Spek, 2009 ▶) T min = 0.963, T max = 1.000

3491 measured reflections

1199 independent reflections

851 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.056

S = 1.00

1199 reflections

79 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.17 e Å−3

Δρmin = −0.18 e Å−3

Data collection: X-AREA (Stoe & Cie, 2009 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2009 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97, PLATON and publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810040031/wm2412sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810040031/wm2412Isup2.hkl

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

[Ni(C3H8N2S)6](NO3)2	Dx = 1.398 Mg m−3
Mr = 807.77	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3c	Cell parameters from 2717 reflections
Hall symbol: -R 3 2"c	θ = 2.9–26.1°
a = 13.7166 (10) Å	µ = 0.88 mm−1
c = 35.332 (3) Å	T = 223 K
V = 5756.9 (8) Å3	Block, pale green
Z = 6	0.30 × 0.26 × 0.24 mm
F(000) = 2556

Stoe IPDS 2 diffractometer	1199 independent reflections
Radiation source: fine-focus sealed tube	851 reflections with I > 2σ(I)
graphite	Rint = 0.028
φ + ω scans	θmax = 25.6°, θmin = 2.9°
Absorption correction: multi-scan (MULscanABS; Spek, 2009)	h = −4→14
Tmin = 0.963, Tmax = 1.000	k = −16→9
3491 measured reflections	l = −42→40

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.056	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ2(Fo2) + (0.0271P)2] where P = (Fo2 + 2Fc2)/3
1199 reflections	(Δ/σ)max = 0.001
79 parameters	Δρmax = 0.17 e Å−3
2 restraints	Δρmin = −0.18 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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.

	x	y	z	Uiso*/Ueq
Ni1	0.66667	0.33333	0.08333	0.0208 (1)
S1	0.50780 (4)	0.25803 (5)	0.03726 (1)	0.0262 (1)
N1	0.35924 (14)	0.17766 (18)	0.09365 (4)	0.0319 (5)
N2	0.29514 (15)	0.09027 (15)	0.03650 (5)	0.0295 (5)
C1	0.37831 (17)	0.16823 (15)	0.05723 (5)	0.0246 (6)
C2	0.25557 (19)	0.10275 (19)	0.11355 (6)	0.0399 (7)
C3	0.3066 (2)	0.0703 (2)	−0.00341 (6)	0.0409 (8)
O1	0.05182 (15)	0.10490 (12)	0.05290 (4)	0.0449 (5)
N3	0.00000	0.00000	0.05255 (7)	0.0300 (6)
H1N	0.4165 (16)	0.2300 (15)	0.1053 (5)	0.029 (6)*
H2A	0.19490	0.11240	0.10370	0.0600*
H2B	0.26520	0.12040	0.14040	0.0600*
H2C	0.23750	0.02540	0.10990	0.0600*
H2N	0.2303 (14)	0.0569 (17)	0.0455 (5)	0.021 (5)*
H3A	0.34410	0.14160	−0.01680	0.0610*
H3B	0.23250	0.02290	−0.01430	0.0610*
H3C	0.35070	0.03320	−0.00570	0.0610*

	U11	U22	U33	U12	U13	U23
Ni1	0.0195 (2)	0.0195 (2)	0.0232 (2)	0.0098 (1)	0.0000	0.0000
S1	0.0203 (2)	0.0277 (3)	0.0272 (2)	0.0095 (3)	−0.0019 (2)	−0.0009 (3)
N1	0.0223 (8)	0.0328 (11)	0.0325 (7)	0.0078 (10)	−0.0009 (6)	−0.0031 (9)
N2	0.0180 (9)	0.0281 (10)	0.0382 (8)	0.0084 (8)	−0.0036 (8)	−0.0040 (8)
C1	0.0218 (10)	0.0222 (11)	0.0336 (9)	0.0138 (8)	−0.0037 (7)	0.0011 (7)
C2	0.0299 (12)	0.0453 (15)	0.0373 (10)	0.0133 (11)	0.0033 (9)	0.0028 (9)
C3	0.0376 (14)	0.0439 (15)	0.0398 (11)	0.0193 (12)	−0.0136 (10)	−0.0131 (10)
O1	0.0306 (10)	0.0206 (7)	0.0794 (10)	0.0097 (9)	0.0077 (10)	0.0079 (7)
N3	0.0261 (9)	0.0261 (9)	0.0379 (13)	0.0131 (5)	0.0000	0.0000

Ni1—S1	2.4929 (6)	N2—C3	1.460 (3)
Ni1—S1i	2.4929 (7)	N2—C1	1.327 (3)
Ni1—S1ii	2.4929 (5)	N1—H1N	0.86 (2)
Ni1—S1iii	2.4929 (5)	N2—H2N	0.83 (2)
Ni1—S1iv	2.4929 (6)	C2—H2B	0.9700
Ni1—S1v	2.4929 (7)	C2—H2C	0.9700
S1—C1	1.727 (2)	C2—H2A	0.9700
O1—N3	1.2462 (14)	C3—H3B	0.9700
N1—C1	1.332 (2)	C3—H3C	0.9700
N1—C2	1.453 (3)	C3—H3A	0.9700
S1—Ni1—S1i	81.98 (2)	C1—N2—H2N	118.9 (13)
S1—Ni1—S1ii	81.98 (2)	C3—N2—H2N	116.8 (13)
S1—Ni1—S1iii	99.78 (2)	O1—N3—O1vi	119.99 (14)
S1—Ni1—S1iv	177.39 (2)	O1vii—N3—O1vi	119.99 (14)
S1—Ni1—S1v	96.33 (2)	O1—N3—O1vii	119.99 (14)
S1i—Ni1—S1ii	81.98 (2)	N1—C1—N2	118.7 (2)
S1i—Ni1—S1iii	96.34 (2)	S1—C1—N2	120.83 (15)
S1i—Ni1—S1iv	99.78 (2)	S1—C1—N1	120.48 (16)
S1i—Ni1—S1v	177.40 (2)	N1—C2—H2B	109.00
S1ii—Ni1—S1iii	177.40 (3)	H2A—C2—H2C	110.00
S1ii—Ni1—S1iv	96.33 (2)	N1—C2—H2C	109.00
S1ii—Ni1—S1v	99.78 (2)	H2A—C2—H2B	110.00
S1iii—Ni1—S1iv	81.98 (2)	N1—C2—H2A	109.00
S1iii—Ni1—S1v	81.98 (2)	H2B—C2—H2C	109.00
S1iv—Ni1—S1v	81.97 (2)	N2—C3—H3C	109.00
Ni1—S1—C1	113.77 (7)	H3A—C3—H3C	109.00
C1—N1—C2	124.68 (19)	H3B—C3—H3C	110.00
C1—N2—C3	123.7 (2)	H3A—C3—H3B	109.00
C1—N1—H1N	113.7 (13)	N2—C3—H3A	110.00
C2—N1—H1N	121.5 (13)	N2—C3—H3B	109.00
S1i—Ni1—S1—C1	124.24 (8)	Ni1—S1—C1—N2	−154.41 (17)
S1ii—Ni1—S1—C1	−152.79 (8)	C2—N1—C1—S1	−176.58 (19)
S1iii—Ni1—S1—C1	29.15 (8)	C2—N1—C1—N2	4.9 (4)
S1v—Ni1—S1—C1	−53.76 (8)	C3—N2—C1—S1	2.9 (3)
Ni1—S1—C1—N1	27.1 (2)	C3—N2—C1—N1	−178.6 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···S1v	0.86 (2)	2.520 (19)	3.367 (2)	168.6 (17)
N2—H2N···O1vi	0.83 (2)	2.14 (2)	2.947 (3)	163.4 (18)
C3—H3B···O1viii	0.97	2.41	3.180 (3)	136

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯S1i	0.86 (2)	2.520 (19)	3.367 (2)	168.6 (17)
N2—H2N⋯O1ii	0.83 (2)	2.14 (2)	2.947 (3)	163.4 (18)
C3—H3B⋯O1iii	0.97	2.41	3.180 (3)	136

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