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The title compound, [Ni(C
2H
5N
4S)
2], has a twofold axis. The Ni
II atom is coordinated in a deformed square-planar geometry by four imino N atoms of two atu ligands (Hatu = amidinothiourea). Two six-membered chelate rings including the Ni atom are twisted with a dihedral angle of 17.24 (16)°. The [Ni(atu)
2] units make a two-dimensional layer
via N—H
S hydrogen bonds.
Supporting information
CCDC reference: 198314
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (N-C) = 0.006 Å
- R factor = 0.053
- wR factor = 0.134
- Data-to-parameter ratio = 13.6
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
PLAT_420 Alert C D-H Without Acceptor N(1) - H(1) ?
PLAT_420 Alert C D-H Without Acceptor N(4) - H(5) ?
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check
To a solution of nickel acetate monohydrate (0.019 g, 0.1 mmol) in H2O (5 ml), amidininothiourea (0.0236 g, 0.2 mmol) in methanol (5 ml) was added without mixing the two solutions. Orange crystals of (I) began to form at ambient temperature in two weeks. One of these crystals was used for X-ray crystallography. Calculated for C4H10N8NiS2: C 16.39, H 3.44, N 38.24%; found: C 16.35, H 3.36, N 37.93%.
The H-atom coordinates were refined with a fixed Ueq value of 0.031 Å2.
Data collection: Please provide software and reference; cell refinement: Please provide software and reference; data reduction: Please provide software and reference; 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: SHELXL97.
cis-bis(amidinothioureato-N,
N)
2Nickel(II)
top
Crystal data top
[Ni(C2H5N4S)2] | F(000) = 600 |
Mr = 293.03 | Dx = 1.964 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -C 2yc | Cell parameters from 20 reflections |
a = 14.804 (2) Å | θ = 2.5–10° |
b = 7.8988 (14) Å | µ = 2.36 mm−1 |
c = 9.1216 (13) Å | T = 295 K |
β = 111.732 (12)° | Block, orange |
V = 990.8 (3) Å3 | 0.2 × 0.1 × 0.1 mm |
Z = 4 | |
Data collection top
MXC3 diffractometer | 906 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.013 |
Graphite monochromator | θmax = 27.5°, θmin = 3.0° |
ω scans | h = −19→17 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→10 |
Tmin = 0.753, Tmax = 0.790 | l = 0→11 |
1257 measured reflections | 3 standard reflections every 100 reflections |
1141 independent reflections | intensity decay: none |
Refinement top
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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.134 | Only H-atom coordinates refined |
S = 0.99 | w = 1/[σ2(Fo2) + (0.0696P)2] where P = (Fo2 + 2Fc2)/3 |
1140 reflections | (Δ/σ)max = 0.001 |
84 parameters | Δρmax = 0.80 e Å−3 |
0 restraints | Δρmin = −0.66 e Å−3 |
Crystal data top
[Ni(C2H5N4S)2] | V = 990.8 (3) Å3 |
Mr = 293.03 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 14.804 (2) Å | µ = 2.36 mm−1 |
b = 7.8988 (14) Å | T = 295 K |
c = 9.1216 (13) Å | 0.2 × 0.1 × 0.1 mm |
β = 111.732 (12)° | |
Data collection top
MXC3 diffractometer | 906 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.013 |
Tmin = 0.753, Tmax = 0.790 | 3 standard reflections every 100 reflections |
1257 measured reflections | intensity decay: none |
1141 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.134 | Only H-atom coordinates refined |
S = 0.99 | Δρmax = 0.80 e Å−3 |
1140 reflections | Δρmin = −0.66 e Å−3 |
84 parameters | |
Special details top
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. |
Refinement. Full-matrix least-squares refinement was carried out with anisotropic thermal parameters for all non-hydrogen atoms. 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Ni1 | 1.0000 | 0.10583 (9) | 0.7500 | 0.0192 (3) | |
S1 | 1.13295 (9) | 0.42264 (15) | 0.47612 (16) | 0.0320 (4) | |
N1 | 1.0695 (3) | −0.0598 (5) | 0.6914 (4) | 0.0229 (8) | |
N2 | 1.1584 (3) | 0.1121 (5) | 0.5882 (5) | 0.0226 (8) | |
N3 | 1.0518 (3) | 0.2721 (5) | 0.6605 (5) | 0.0232 (8) | |
N4 | 1.1902 (3) | −0.1706 (6) | 0.6115 (6) | 0.0314 (10) | |
C1 | 1.1363 (3) | −0.0425 (6) | 0.6339 (5) | 0.0209 (9) | |
C2 | 1.1110 (3) | 0.2603 (5) | 0.5852 (5) | 0.0218 (9) | |
H1 | 1.064 (4) | −0.152 (7) | 0.714 (6) | 0.031* | |
H2 | 1.207 (4) | 0.111 (6) | 0.556 (6) | 0.031* | |
H3 | 1.029 (4) | 0.375 (6) | 0.657 (6) | 0.031* | |
H4 | 1.174 (4) | −0.262 (8) | 0.619 (6) | 0.031* | |
H5 | 1.241 (4) | −0.165 (7) | 0.607 (6) | 0.031* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni1 | 0.0237 (4) | 0.0154 (4) | 0.0226 (4) | 0.000 | 0.0134 (3) | 0.000 |
S1 | 0.0369 (7) | 0.0221 (6) | 0.0484 (8) | 0.0055 (5) | 0.0291 (6) | 0.0113 (5) |
N1 | 0.029 (2) | 0.0164 (18) | 0.026 (2) | 0.0017 (16) | 0.0137 (16) | 0.0038 (15) |
N2 | 0.0240 (19) | 0.0200 (19) | 0.0293 (19) | 0.0018 (15) | 0.0165 (16) | 0.0039 (16) |
N3 | 0.030 (2) | 0.0154 (17) | 0.030 (2) | 0.0024 (15) | 0.0185 (16) | −0.0005 (16) |
N4 | 0.034 (2) | 0.019 (2) | 0.049 (3) | 0.0051 (18) | 0.024 (2) | 0.0000 (19) |
C1 | 0.024 (2) | 0.018 (2) | 0.021 (2) | 0.0021 (17) | 0.0076 (18) | −0.0010 (17) |
C2 | 0.024 (2) | 0.018 (2) | 0.024 (2) | −0.0029 (17) | 0.0098 (18) | −0.0013 (17) |
Geometric parameters (Å, º) top
Ni1—N3 | 1.855 (4) | N2—H2 | 0.87 (6) |
Ni1—N1 | 1.860 (4) | N3—C2 | 1.302 (6) |
S1—C2 | 1.726 (4) | N3—H3 | 0.87 (5) |
N1—C1 | 1.288 (6) | N4—C1 | 1.350 (6) |
N1—H1 | 0.76 (5) | N4—H4 | 0.77 (6) |
N2—C2 | 1.360 (6) | N4—H5 | 0.77 (6) |
N2—C1 | 1.368 (5) | | |
| | | |
N3—Ni1—N1 | 90.52 (17) | Ni1—N3—H3 | 118 (4) |
N1—Ni1—N1i | 90.6 (2) | C1—N4—H4 | 118 (4) |
N3—Ni1—N3i | 89.9 (2) | C1—N4—H5 | 128 (4) |
C1—N1—Ni1 | 129.2 (3) | H4—N4—H5 | 113 (6) |
C1—N1—H1 | 112 (4) | N1—C1—N4 | 124.6 (4) |
Ni1—N1—H1 | 118 (4) | N1—C1—N2 | 121.7 (4) |
C2—N2—C1 | 126.5 (4) | N4—C1—N2 | 113.7 (4) |
C2—N2—H2 | 119 (3) | N3—C2—N2 | 119.6 (4) |
C1—N2—H2 | 114 (3) | N3—C2—S1 | 124.0 (4) |
C2—N3—Ni1 | 130.6 (3) | N2—C2—S1 | 116.4 (3) |
C2—N3—H3 | 112 (4) | | |
| | | |
N3—Ni1—N1—C1 | 8.9 (4) | C2—N2—C1—N1 | −5.2 (7) |
N1i—Ni1—N1—C1 | 179.5 (5) | C2—N2—C1—N4 | 174.4 (4) |
N3i—Ni1—N3—C2 | 172.2 (5) | Ni1—N3—C2—N2 | −12.4 (7) |
N1—Ni1—N3—C2 | 1.7 (4) | Ni1—N3—C2—S1 | 166.6 (2) |
Ni1—N1—C1—N4 | 172.2 (4) | C1—N2—C2—N3 | 15.3 (7) |
Ni1—N1—C1—N2 | −8.3 (7) | C1—N2—C2—S1 | −163.7 (4) |
Symmetry code: (i) −x+2, y, −z+3/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···S1ii | 0.77 (6) | 2.77 (6) | 3.434 (5) | 145 (5) |
N2—H2···S1iii | 0.87 (6) | 2.51 (6) | 3.362 (4) | 167 (5) |
Symmetry codes: (ii) x, y−1, z; (iii) −x+5/2, −y+1/2, −z+1. |
Experimental details
Crystal data |
Chemical formula | [Ni(C2H5N4S)2] |
Mr | 293.03 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 295 |
a, b, c (Å) | 14.804 (2), 7.8988 (14), 9.1216 (13) |
β (°) | 111.732 (12) |
V (Å3) | 990.8 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.36 |
Crystal size (mm) | 0.2 × 0.1 × 0.1 |
|
Data collection |
Diffractometer | MXC3 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.753, 0.790 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1257, 1141, 906 |
Rint | 0.013 |
(sin θ/λ)max (Å−1) | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.134, 0.99 |
No. of reflections | 1140 |
No. of parameters | 84 |
H-atom treatment | Only H-atom coordinates refined |
Δρmax, Δρmin (e Å−3) | 0.80, −0.66 |
Selected geometric parameters (Å, º) topNi1—N3 | 1.855 (4) | N2—C2 | 1.360 (6) |
Ni1—N1 | 1.860 (4) | N2—C1 | 1.368 (5) |
S1—C2 | 1.726 (4) | N3—C2 | 1.302 (6) |
N1—C1 | 1.288 (6) | N4—C1 | 1.350 (6) |
| | | |
N3—Ni1—N1 | 90.52 (17) | N1—C1—N4 | 124.6 (4) |
N1—Ni1—N1i | 90.6 (2) | N1—C1—N2 | 121.7 (4) |
N3—Ni1—N3i | 89.9 (2) | N4—C1—N2 | 113.7 (4) |
C1—N1—Ni1 | 129.2 (3) | N3—C2—N2 | 119.6 (4) |
C2—N2—C1 | 126.5 (4) | N3—C2—S1 | 124.0 (4) |
C2—N3—Ni1 | 130.6 (3) | N2—C2—S1 | 116.4 (3) |
Symmetry code: (i) −x+2, y, −z+3/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···S1ii | 0.77 (6) | 2.77 (6) | 3.434 (5) | 145 (5) |
N2—H2···S1iii | 0.87 (6) | 2.51 (6) | 3.362 (4) | 167 (5) |
Symmetry codes: (ii) x, y−1, z; (iii) −x+5/2, −y+1/2, −z+1. |
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Amidinothiourea (Hatu) can be used to construct a metal complex based module for supra-structures as it has available coordination sites (Vilar et al., 1998). Moreover, SN donors stabilize the lower oxidation states of metal atoms and lower the electron density at NO in metal nitrosyls (Chakrabarty et al., 1990). Hatu has two tautomeric forms (see Scheme). It can coordinate to metal ions using either two N atoms (N,N'-chelating) or one N and one S atom (N,S-chelating). However, very few reports have been appeared on the Hatu ligand (Vilar et al., 1998, 1999; Cheng et al., 2001). Among them one report shows that Hatu is coordinated to NiII ion by N,N'-chelating mode in the trans form (Vilar et al., 1999). During our studies on coordination compounds with Hatu, orange single crystals of the title compound, (I), were obtained. The crystal structure of (I) is presented here.
The crystal structure of (I) consists of a mononuclear complex Ni(atu)2. An ORTEP-3 (Farrugia, 1997) drawing with the atom-numbering scheme is shown in Fig. 1. The NiII atom is coordinated with a deformed square-planar geometry, by four imino N atoms of two atu ligands. The two six-membered rings incorporating the Ni atom are twisted with a dihedral angle of 17.24 (16)°. The Ni—N distances are 1.860 (4) and 1.855 (4) Å (Table 1). The shortness of the C—N bonds (1.29–1.37 Å) indicates the presence of multiple bonding with delocalization of π electrons. This may be due to the interactions of H atoms on the coordinated N atoms. The coordination geometry of (I) is similar to that of [Pd(atu)2]Cl2·1.5H2O (Chakrabarty et al., 1990), but the coordinating atoms (N,S-chelating) are different. On the other hand, trans-Ni(atu)2 has the same coordinating atoms (N,N'-chelating) with similar Ni—N distances (Vilar et al., 1999), but the crystal packing modes of the two compounds are different. The cis coordination mode in (I) has multi-site hydrogen-bonding ability that allows the mononuclear building module to form a hydrogen-bond-supported two-dimensional layer structure. Ni(atu)2 molecules are connected to each other via hydrogen-bonding interactions, which are formed between terminal amino groups and S atoms, forming a straight tape along the b direction. The tapes are hydrogen bonded to form a two-dimensional layer perpendicular to the [101] direction (Fig. 2 and Table 2). The layers make a three-dimensional packing structure through stacking interactions (Fig. 3). The minimum distance between the layers (C—N) is 3.319 (6) Å.