Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803001600/lh6028sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803001600/lh6028Isup2.hkl |
CCDC reference: 204662
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (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
Ammonium dithiocarbamate was prepared according to the literature (Booth et al., 1939) and mixed with a nickelII 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).
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.
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).
[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) Å3 | 0.21 × 0.2 × 0.04 mm |
Z = 4 |
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 on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.033 | w = 1/[σ2(Fo2) + (0.0583P)2 + 1.443P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 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 |
[Ni(CH2NS2)2] | V = 769.95 (7) Å3 |
Mr = 243.02 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.1310 (4) Å | µ = 3.51 mm−1 |
b = 12.9170 (8) Å | T = 100 K |
c = 10.9590 (5) Å | 0.21 × 0.2 × 0.04 mm |
β = 130.293 (3)° |
KappaCCD diffractometer | 1355 independent reflections |
Absorption correction: analytical (Alcock, 1970) | 1201 reflections with I > 2σ(I) |
Tmin = 0.478, Tmax = 0.858 | Rint = 0.045 |
4294 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.094 | H-atom parameters constrained |
S = 0.93 | Δρmax = 1.20 e Å−3 |
1355 reflections | Δρmin = −0.53 e Å−3 |
82 parameters |
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. |
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) |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···S4i | 0.88 | 2.62 | 3.445 (4) | 157 |
N1—H1B···S1ii | 0.88 | 2.73 | 3.461 (4) | 142 |
N2—H2A···S2iii | 0.88 | 2.85 | 3.541 (3) | 137 |
N2—H2A···S4iv | 0.88 | 2.84 | 3.527 (4) | 136 |
N2—H2B···S3v | 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. |
Experimental details
Crystal data | |
Chemical formula | [Ni(CH2NS2)2] |
Mr | 243.02 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 7.1310 (4), 12.9170 (8), 10.9590 (5) |
β (°) | 130.293 (3) |
V (Å3) | 769.95 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.51 |
Crystal size (mm) | 0.21 × 0.2 × 0.04 |
Data collection | |
Diffractometer | KappaCCD diffractometer |
Absorption correction | Analytical (Alcock, 1970) |
Tmin, Tmax | 0.478, 0.858 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4294, 1355, 1201 |
Rint | 0.045 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.094, 0.93 |
No. of reflections | 1355 |
No. of parameters | 82 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.20, −0.53 |
Computer programs: COLLECT (Nonius, 1997-2000), HKL SCALEPACK (Otwinowski & Minor, 1997), HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
Ni1—S4 | 2.2082 (10) | S2—C1 | 1.728 (4) |
Ni1—S3 | 2.2082 (10) | S3—C1 | 1.721 (4) |
Ni1—S2 | 2.2106 (9) | S4—C2 | 1.726 (3) |
Ni1—S1 | 2.2118 (9) | N1—C1 | 1.304 (5) |
S1—C2 | 1.709 (4) | N2—C2 | 1.310 (5) |
S4—Ni1—S3 | 176.68 (4) | C1—S3—Ni1 | 84.97 (13) |
S4—Ni1—S2 | 100.30 (3) | C2—S4—Ni1 | 84.71 (13) |
S3—Ni1—S2 | 79.71 (3) | N1—C1—S3 | 125.1 (3) |
S4—Ni1—S1 | 79.44 (3) | N1—C1—S2 | 124.5 (3) |
S3—Ni1—S1 | 100.36 (3) | S3—C1—S2 | 110.4 (2) |
S2—Ni1—S1 | 176.81 (4) | N2—C2—S1 | 125.3 (3) |
C2—S1—Ni1 | 84.98 (12) | N2—C2—S4 | 124.1 (3) |
C1—S2—Ni1 | 84.73 (12) | S1—C2—S4 | 110.6 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···S4i | 0.88 | 2.62 | 3.445 (4) | 157 |
N1—H1B···S1ii | 0.88 | 2.73 | 3.461 (4) | 142 |
N2—H2A···S2iii | 0.88 | 2.85 | 3.541 (3) | 137 |
N2—H2A···S4iv | 0.88 | 2.84 | 3.527 (4) | 136 |
N2—H2B···S3v | 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. |
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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 NiII 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.