Hexa-kis-(thio-urea-κS)nickel(II) nitrate: a redetermination.

A preliminary X-ray study of the title mol-ecular salt, [Ni(CH(4)N(2)S)(6)](NO(3))(2), has been reported twice previously, by Maďar [Acta Cryst. (1961), 14, 894] and Rodriguez, Cubero, Vega, Morente & Vazquez [Acta Cryst. (1961), 14, 1101], using film methods. We confirm the previous studies, but to modern standards of precision and with all H atoms located. The central Ni atom (site symmetry ) of the dication is octa-hedrally coordinated by six S-bound thio-urea mol-ecules. The crystal structure is stabilized by intra- and inter-molecular N-H⋯S and N-H⋯O hydrogen bonds.

Related literature

The structure of the title complex at room temperature has been reported twice previously, see: Maďar (1961 ▶); Rodriguez et al. (1961 ▶). For the biological and non-linear optical properties and applications of metal complexes of thio­urea-type ligands, see: Arslan et al. (2009 ▶); Emre et al. (2009 ▶); Bhaskaran et al. (2007 ▶); Eaton & Law(1975 ▶); Figgis & Reynolds (1986 ▶). For the crystal structures of some similar Ni complexes, see: Suescun et al. (2000 ▶); Zhu et al. (2009 ▶). For reference structural data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

[Ni(CH4N2S)6](NO3)2

M = 639.50

Monoclinic,

a = 22.4433 (6) Å

b = 9.2398 (3) Å

c = 16.3136 (5) Å

β = 129.724 (1)°

V = 2601.96 (14) Å3

Z = 4

Mo Kα radiation

μ = 1.28 mm−1

T = 296 K

0.25 × 0.10 × 0.06 mm

Data collection

Bruker APEXII CCD diffractometer

11568 measured reflections

3129 independent reflections

2542 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.068

S = 1.03

3129 reflections

151 parameters

H-atom parameters constrained

Δρmax = 0.35 e Å−3

Δρmin = −0.29 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810026668/hb5527sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810026668/hb5527Isup2.hkl

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

[Ni(CH4N2S)6](NO3)2	F(000) = 1320
Mr = 639.50	Dx = 1.633 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4823 reflections
a = 22.4433 (6) Å	θ = 2.5–28.2°
b = 9.2398 (3) Å	µ = 1.28 mm−1
c = 16.3136 (5) Å	T = 296 K
β = 129.724 (1)°	Needle, light green
V = 2601.96 (14) Å3	0.25 × 0.10 × 0.06 mm
Z = 4

Bruker APEXII CCD diffractometer	2542 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.033
graphite	θmax = 28.3°, θmin = 2.5°
φ and ω scans	h = −29→21
11568 measured reflections	k = −11→12
3129 independent reflections	l = −21→21

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.068	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0256P)2 + 1.7568P] where P = (Fo2 + 2Fc2)/3
3129 reflections	(Δ/σ)max < 0.001
151 parameters	Δρmax = 0.35 e Å−3
0 restraints	Δρmin = −0.29 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 on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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	0.25000	0.25000	0.00000	0.0246 (1)
S1	0.38321 (3)	0.34540 (6)	0.10478 (4)	0.0362 (2)
S2	0.28084 (3)	−0.01160 (5)	0.01164 (4)	0.0331 (1)
S3	0.28343 (3)	0.27376 (5)	0.17786 (4)	0.0311 (1)
N1	0.49791 (11)	0.3572 (3)	0.10299 (17)	0.0630 (8)
N2	0.42272 (13)	0.1592 (2)	0.02330 (19)	0.0630 (9)
N3	0.40567 (10)	0.00546 (19)	0.21644 (13)	0.0475 (6)
N4	0.36277 (12)	−0.2195 (2)	0.14917 (16)	0.0621 (7)
N5	0.20704 (11)	0.0325 (2)	0.14718 (15)	0.0516 (7)
N6	0.29045 (13)	0.1162 (2)	0.31643 (15)	0.0687 (8)
C1	0.43826 (11)	0.2808 (2)	0.07398 (16)	0.0341 (6)
C2	0.35527 (11)	−0.0788 (2)	0.13536 (15)	0.0324 (6)
C3	0.25769 (12)	0.1293 (2)	0.21517 (16)	0.0363 (7)
O1	0.41450 (9)	0.6847 (2)	−0.02032 (13)	0.0604 (6)
O2	0.50573 (11)	0.6706 (2)	0.14802 (14)	0.0786 (7)
O3	0.48990 (11)	0.86552 (19)	0.06598 (15)	0.0676 (7)
N7	0.46952 (10)	0.7413 (2)	0.06486 (15)	0.0429 (6)
H1A	0.52660	0.32720	0.08860	0.0940*
H1B	0.50850	0.43750	0.13650	0.0940*
H2A	0.45170	0.12990	0.00920	0.0940*
H2B	0.38350	0.10840	0.00400	0.0940*
H3A	0.44270	−0.03180	0.27720	0.0570*
H3B	0.40160	0.09790	0.20880	0.0570*
H4A	0.40020	−0.25490	0.21050	0.0930*
H4B	0.33030	−0.27630	0.09690	0.0930*
H5A	0.19560	−0.03860	0.16890	0.0620*
H5B	0.18520	0.03990	0.08080	0.0620*
H6A	0.27850	0.04460	0.33710	0.0820*
H6B	0.32380	0.17910	0.36190	0.0820*

	U11	U22	U33	U12	U13	U23
Ni1	0.0289 (2)	0.0234 (2)	0.0217 (2)	−0.0015 (1)	0.0164 (1)	−0.0012 (1)
S1	0.0328 (2)	0.0410 (3)	0.0373 (3)	−0.0076 (2)	0.0235 (2)	−0.0106 (2)
S2	0.0400 (3)	0.0251 (2)	0.0238 (2)	0.0030 (2)	0.0156 (2)	0.0008 (2)
S3	0.0450 (3)	0.0272 (2)	0.0274 (2)	−0.0046 (2)	0.0260 (2)	−0.0013 (2)
N1	0.0430 (11)	0.0898 (17)	0.0669 (14)	−0.0207 (11)	0.0401 (11)	−0.0293 (12)
N2	0.0735 (14)	0.0459 (12)	0.1040 (18)	−0.0078 (11)	0.0727 (15)	−0.0195 (12)
N3	0.0421 (10)	0.0372 (10)	0.0320 (9)	0.0044 (8)	0.0093 (8)	0.0021 (8)
N4	0.0577 (13)	0.0333 (10)	0.0432 (12)	0.0039 (9)	0.0082 (10)	0.0092 (9)
N5	0.0610 (12)	0.0463 (11)	0.0399 (11)	−0.0225 (10)	0.0288 (10)	0.0010 (9)
N6	0.0915 (16)	0.0746 (15)	0.0338 (11)	−0.0326 (13)	0.0372 (12)	0.0040 (10)
C1	0.0305 (9)	0.0398 (12)	0.0301 (10)	0.0053 (8)	0.0185 (9)	0.0076 (9)
C2	0.0315 (9)	0.0325 (11)	0.0298 (10)	0.0033 (8)	0.0180 (8)	0.0039 (8)
C3	0.0413 (11)	0.0390 (12)	0.0309 (11)	−0.0049 (9)	0.0242 (9)	0.0030 (9)
O1	0.0486 (9)	0.0701 (12)	0.0348 (9)	−0.0114 (8)	0.0138 (8)	−0.0145 (8)
O2	0.0811 (13)	0.0679 (12)	0.0360 (10)	−0.0217 (11)	0.0139 (10)	−0.0029 (9)
O3	0.0798 (13)	0.0451 (11)	0.0654 (12)	−0.0100 (9)	0.0406 (11)	−0.0064 (9)
N7	0.0398 (10)	0.0498 (12)	0.0358 (10)	−0.0052 (9)	0.0226 (9)	−0.0074 (9)

Ni1—S1	2.4708 (7)	N4—C2	1.312 (3)
Ni1—S2	2.4879 (5)	N5—C3	1.308 (3)
Ni1—S3	2.4995 (6)	N6—C3	1.316 (3)
Ni1—S1i	2.4708 (7)	N1—H1B	0.8600
Ni1—S2i	2.4879 (5)	N1—H1A	0.8600
Ni1—S3i	2.4995 (6)	N2—H2A	0.8600
S1—C1	1.711 (3)	N2—H2B	0.8600
S2—C2	1.715 (2)	N3—H3A	0.8600
S3—C3	1.713 (2)	N3—H3B	0.8600
O1—N7	1.239 (3)	N4—H4B	0.8600
O2—N7	1.232 (3)	N4—H4A	0.8600
O3—N7	1.231 (3)	N5—H5A	0.8600
N1—C1	1.306 (4)	N5—H5B	0.8600
N2—C1	1.304 (3)	N6—H6A	0.8600
N3—C2	1.313 (3)	N6—H6B	0.8600
S1—Ni1—S2	98.00 (2)	C2—N3—H3B	120.00
S1—Ni1—S3	80.37 (2)	C2—N3—H3A	120.00
S1—Ni1—S1i	180.00	H3A—N3—H3B	120.00
S1—Ni1—S2i	82.00 (2)	C2—N4—H4B	120.00
S1—Ni1—S3i	99.63 (2)	C2—N4—H4A	120.00
S2—Ni1—S3	97.72 (2)	H4A—N4—H4B	120.00
S1i—Ni1—S2	82.00 (2)	H5A—N5—H5B	120.00
S2—Ni1—S2i	180.00	C3—N5—H5A	120.00
S2—Ni1—S3i	82.28 (2)	C3—N5—H5B	120.00
S1i—Ni1—S3	99.63 (2)	C3—N6—H6B	120.00
S2i—Ni1—S3	82.28 (2)	H6A—N6—H6B	120.00
S3—Ni1—S3i	180.00	C3—N6—H6A	120.00
S1i—Ni1—S2i	98.00 (2)	O2—N7—O3	120.0 (2)
S1i—Ni1—S3i	80.37 (2)	O1—N7—O2	119.6 (2)
S2i—Ni1—S3i	97.72 (2)	O1—N7—O3	120.29 (19)
Ni1—S1—C1	116.99 (8)	S1—C1—N2	122.4 (2)
Ni1—S2—C2	117.12 (7)	S1—C1—N1	118.06 (18)
Ni1—S3—C3	115.14 (7)	N1—C1—N2	119.5 (3)
C1—N1—H1B	120.00	S2—C2—N4	118.85 (16)
H1A—N1—H1B	120.00	S2—C2—N3	122.36 (15)
C1—N1—H1A	120.00	N3—C2—N4	118.78 (19)
H2A—N2—H2B	120.00	N5—C3—N6	119.2 (2)
C1—N2—H2A	120.00	S3—C3—N5	122.62 (17)
C1—N2—H2B	120.00	S3—C3—N6	118.22 (17)
S2—Ni1—S1—C1	47.38 (8)	S2—Ni1—S3—C3	−38.66 (11)
S3—Ni1—S1—C1	143.91 (8)	S1i—Ni1—S3—C3	44.48 (11)
S2i—Ni1—S1—C1	−132.62 (8)	S2i—Ni1—S3—C3	141.34 (11)
S3i—Ni1—S1—C1	−36.09 (8)	Ni1—S1—C1—N1	159.63 (16)
S1—Ni1—S2—C2	48.29 (12)	Ni1—S1—C1—N2	−20.5 (2)
S3—Ni1—S2—C2	−33.00 (12)	Ni1—S2—C2—N3	−15.4 (3)
S1i—Ni1—S2—C2	−131.71 (12)	Ni1—S2—C2—N4	165.6 (2)
S3i—Ni1—S2—C2	147.00 (12)	Ni1—S3—C3—N5	−17.6 (3)
S1—Ni1—S3—C3	−135.52 (11)	Ni1—S3—C3—N6	162.5 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ii	0.86	2.21	3.037 (4)	161
N1—H1B···O2	0.86	2.17	2.965 (3)	154
N2—H2A···O3iii	0.86	2.56	2.963 (3)	110
N2—H2A···O3ii	0.86	2.30	3.110 (4)	157
N2—H2B···S2	0.86	2.63	3.449 (3)	159
N3—H3A···O3iv	0.86	2.19	3.022 (2)	163
N3—H3B···S1	0.86	2.72	3.5021 (19)	152
N3—H3B···S3	0.86	2.87	3.444 (2)	126
N4—H4A···O2iv	0.86	2.01	2.865 (3)	175
N4—H4B···S2v	0.86	2.75	3.555 (2)	157
N5—H5A···S3vi	0.86	2.82	3.623 (2)	155
N5—H5A···O1i	0.86	2.48	2.922 (3)	113
N5—H5B···S1i	0.86	2.59	3.410 (2)	160
N6—H6A···S2vii	0.86	2.83	3.464 (3)	132
N6—H6A···S3vi	0.86	2.80	3.601 (2)	156
N6—H6B···O1viii	0.86	2.10	2.958 (3)	174

Table 1

Selected bond lengths (Å)

Ni1—S1	2.4708 (7)
Ni1—S2	2.4879 (5)
Ni1—S3	2.4995 (6)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1i	0.86	2.21	3.037 (4)	161
N1—H1B⋯O2	0.86	2.17	2.965 (3)	154
N2—H2A⋯O3ii	0.86	2.56	2.963 (3)	110
N2—H2A⋯O3i	0.86	2.30	3.110 (4)	157
N2—H2B⋯S2	0.86	2.63	3.449 (3)	159
N3—H3A⋯O3iii	0.86	2.19	3.022 (2)	163
N3—H3B⋯S1	0.86	2.72	3.5021 (19)	152
N3—H3B⋯S3	0.86	2.87	3.444 (2)	126
N4—H4A⋯O2iii	0.86	2.01	2.865 (3)	175
N4—H4B⋯S2iv	0.86	2.75	3.555 (2)	157
N5—H5A⋯S3v	0.86	2.82	3.623 (2)	155
N5—H5A⋯O1vi	0.86	2.48	2.922 (3)	113
N5—H5B⋯S1vi	0.86	2.59	3.410 (2)	160
N6—H6A⋯S2vii	0.86	2.83	3.464 (3)	132
N6—H6A⋯S3v	0.86	2.80	3.601 (2)	156
N6—H6B⋯O1viii	0.86	2.10	2.958 (3)	174

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