Redetermination of nickel bis­(di­thio­carbamate) at 100 K

As part of our studies on Ni^II complexes, the structure of the title compound, [Ni(CH₂NS₂)₂], was redetermined at 100 K. The crystal structure reveals a square-planar coordination geometry, with two di­thio­carbamate ligands. The crystal packing is stabilized by N—H...S intermolecular interactions.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](N-C) = 0.005 Å
• R factor = 0.033
• wR factor = 0.094
• Data-to-parameter ratio = 16.5

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

The structure of (I) was originally determined by Gasparri et al. (1967) using data measured from Weissenberg photographs. In the present redetermination, data were collected at low temperature, using a CCD area-detector diffractometer, in order to obtain more precise structural results.

As shown in Fig. 1, the structure of the title compound, (I), is composed of neutral [Ni(S₂CNH₂)₂] complex molecules. The results show that the cordination around Ni^II is square planar, with four dithiocarbamate S atoms from two separate groups bonded to Ni [Ni—S1 = 2.2118 (9) Å, Ni—S2 = 2.2106 (9) Å, Ni—S3 = 2.2082 (10) Å and Ni—S4 = 2.2082 (10) Å]. The S—C bond lengths in (I) are between the mean values obtained for a single covalent bond (≈ 1.642 Å) and a double covalent bond (≈ 1.760 Å) (Table 1), found in the September 2002 version of the Cambridge Structural Database (Allen, 2002) (see Figs. 2 and 3).

The structure is stabilized by intermolecular N—H···S hydrogen bonds between the NH₂ groups and the S atoms of neighbouring molecules (Table 2). These intermolecular interactions give rise to a three-dimensional network.

S2. Experimental

Ammonium dithiocarbamate was prepared according to the literature (Booth et al., 1939) and mixed with a nickel^II chloride aqueos solution. The green crystals obtained was recrystallized from ethanol furnishing green crystals. The IR spectrum showed the same bands reported in the literature (Nakamoto et al., 1963).

S3. Refinement

H atoms were placed in calculated positions, with N—H = 0.88 Å and angles of 120°, and were included in the final cycles of refinement riding on their parent N atoms.

Computing details

Data collection: COLLECT (Nonius, 1997-2000); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. View of the title molecule, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Distribuition of the single S—C bond lengths.
	Fig. 3. Distribuition of the double S—C bond lengths.

(I)

Crystal data

[Ni(CH2NS2)2]	F(000) = 488
Mr = 243.02	Dx = 2.096 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6006 reflections
a = 7.1310 (4) Å	θ = 1.0–27.5°
b = 12.9170 (8) Å	µ = 3.51 mm^−1
c = 10.9590 (5) Å	T = 100 K
β = 130.293 (3)°	Prism, brown
V = 769.95 (7) Å^3	0.21 × 0.2 × 0.04 mm
Z = 4

Data collection

KappaCCD diffractometer	1201 reflections with I > 2σ(I)
CCD rotation images, thick slices scans	Rint = 0.045
Absorption correction: analytical (Alcock, 1970)	θmax = 25°, θmin = 2.9°
Tmin = 0.478, Tmax = 0.858	h = −8→8
4294 measured reflections	k = −15→13
1355 independent reflections	l = −12→12

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.033	w = 1/[σ^2(Fo^2) + (0.0583P)^2 + 1.443P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.094	(Δ/σ)max < 0.001
S = 0.93	Δρmax = 1.20 e Å^−3
1355 reflections	Δρmin = −0.53 e Å^−3
82 parameters

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ni1	0.88596 (7)	0.12825 (3)	0.02346 (5)	0.02028 (19)
S1	0.53494 (16)	0.13003 (7)	−0.22613 (10)	0.0259 (3)
S2	1.22705 (16)	0.13200 (7)	0.27658 (10)	0.0259 (3)
S3	0.83187 (16)	−0.01067 (7)	0.11501 (10)	0.0286 (3)
S4	0.92893 (15)	0.27244 (7)	−0.06459 (10)	0.0245 (2)
N1	1.2054 (6)	−0.0218 (3)	0.4327 (4)	0.0335 (7)
H1A	1.1329	−0.0758	0.4353	0.04*
H1B	1.3459	0.0009	0.5215	0.04*
N2	0.5427 (5)	0.2907 (2)	−0.3787 (4)	0.0279 (7)
H2A	0.3993	0.2703	−0.4673	0.033*
H2B	0.6138	0.3462	−0.3793	0.033*
C1	1.1049 (6)	0.0248 (3)	0.2973 (4)	0.0275 (8)
C2	0.6502 (6)	0.2387 (3)	−0.2458 (4)	0.0240 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0183 (3)	0.0204 (3)	0.0139 (3)	0.00065 (15)	0.0066 (2)	0.00106 (16)
S1	0.0228 (5)	0.0252 (5)	0.0153 (5)	−0.0032 (3)	0.0059 (4)	0.0017 (3)
S2	0.0203 (4)	0.0293 (5)	0.0167 (5)	−0.0019 (3)	0.0068 (4)	0.0000 (3)
S3	0.0272 (5)	0.0225 (5)	0.0218 (5)	−0.0048 (4)	0.0095 (4)	−0.0004 (3)
S4	0.0206 (4)	0.0251 (5)	0.0201 (4)	−0.0014 (3)	0.0097 (4)	0.0007 (4)
N1	0.0274 (16)	0.0327 (18)	0.0250 (17)	−0.0010 (14)	0.0100 (14)	0.0039 (14)
N2	0.0256 (15)	0.0269 (17)	0.0218 (16)	−0.0046 (12)	0.0111 (13)	0.0011 (13)
C1	0.0312 (18)	0.0261 (19)	0.0235 (19)	0.0051 (15)	0.0169 (16)	0.0007 (15)
C2	0.0228 (16)	0.0275 (19)	0.0208 (17)	0.0027 (14)	0.0137 (15)	0.0001 (15)

Geometric parameters (Å, º)

Ni1—S4	2.2082 (10)	S4—C2	1.726 (3)
Ni1—S3	2.2082 (10)	N1—C1	1.304 (5)
Ni1—S2	2.2106 (9)	N2—C2	1.310 (5)
Ni1—S1	2.2118 (9)	N1—H1A	0.88
S1—C2	1.709 (4)	N1—H1B	0.88
S2—C1	1.728 (4)	N2—H2A	0.88
S3—C1	1.721 (4)	N2—H2B	0.88
S4—Ni1—S3	176.68 (4)	N1—C1—S2	124.5 (3)
S4—Ni1—S2	100.30 (3)	S3—C1—S2	110.4 (2)
S3—Ni1—S2	79.71 (3)	N2—C2—S1	125.3 (3)
S4—Ni1—S1	79.44 (3)	N2—C2—S4	124.1 (3)
S3—Ni1—S1	100.36 (3)	S1—C2—S4	110.6 (2)
S2—Ni1—S1	176.81 (4)	C1—N1—H1A	120.0
C2—S1—Ni1	84.98 (12)	C1—N1—H1B	120.0
C1—S2—Ni1	84.73 (12)	C2—N2—H2A	120.0
C1—S3—Ni1	84.97 (13)	C2—N2—H2B	120.0
C2—S4—Ni1	84.71 (13)	H1A—N1—H1B	120.0
N1—C1—S3	125.1 (3)	H2A—N2—H2B	120.0
S4—Ni1—S1—C2	3.24 (12)	Ni1—S3—C1—N1	175.8 (3)
S3—Ni1—S1—C2	179.87 (12)	Ni1—S3—C1—S2	−3.59 (16)
S4—Ni1—S2—C1	173.97 (12)	Ni1—S2—C1—N1	−175.8 (3)
S3—Ni1—S2—C1	−2.66 (12)	Ni1—S2—C1—S3	3.59 (16)
S2—Ni1—S3—C1	2.67 (12)	Ni1—S1—C2—N2	176.4 (3)
S1—Ni1—S3—C1	−174.08 (12)	Ni1—S1—C2—S4	−4.36 (16)
S2—Ni1—S4—C2	−179.98 (11)	Ni1—S4—C2—N2	−176.4 (3)
S1—Ni1—S4—C2	−3.21 (11)	Ni1—S4—C2—S1	4.37 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S4^i	0.88	2.62	3.445 (4)	157
N1—H1B···S1^ii	0.88	2.73	3.461 (4)	142
N2—H2A···S2^iii	0.88	2.85	3.541 (3)	137
N2—H2A···S4^iv	0.88	2.84	3.527 (4)	136
N2—H2B···S3^v	0.88	2.66	3.538 (3)	178

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