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In the title compound, [Ni(C2H7N3S)2(C3H4N2)2]I2, the NiII ion assumes a centrosymmetric distorted octahedral geometry. The two molecules of S-methylisothiosemicarbazide are coordinated as bidentate ligands via the terminal N atoms, forming five-membered chelate rings. The I atoms are approximately in the equatorial plane of the chelate rings at a similar distance from both. The five-membered chelate rings are almost planar and exhibit flattened envelope conformations. There is a weak intermolecular interaction between the lone pair of electrons of the S atom and the center of the pyrazole ring.
Supporting information
CCDC reference: 174794
Violet monocrystals of the title complex were obtained by the reaction of EtOH
solutions of stoichiometric amounts of Ni(OAc)2.4H2O,
S-methylisothiosemicarbazide hydrogeniodide and excess (25%) pyrazole.
All H atoms were found in ΔF maps, but those connected to C atoms were placed
at calculated positions using a riding model [isotropic displacement
parameters equal to 1.2 (or 1.5 for methyl H atoms) times the equivalent
isotropic displacement parameter of the parent atom]. A Gaussian-type
absorption correction based on the crystal morphology was applied (Spek, 1990,
1998). All the most remarkable spurious peaks on the final difference Fourier
map are located near the I atom.
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: CAD-4 EXPRESS (Enraf-Nonius, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1995).
bis(
S-methylisothiosemicarbazide-
N1,
N4)-bis(pyrazole-N
2)- nickel(II) iodide
top
Crystal data top
[Ni(C2H7N3S)2(C3H4N2)2]I2 | Z = 1 |
Mr = 659.0 | F(000) = 318 |
Triclinic, P1 | Dx = 1.993 Mg m−3 |
a = 7.911 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.798 (3) Å | Cell parameters from 25 reflections |
c = 8.819 (2) Å | θ = 13.2–17.6° |
α = 102.92 (3)° | µ = 3.90 mm−1 |
β = 92.43 (2)° | T = 293 K |
γ = 112.05 (2)° | Prismatic, violet |
V = 549.1 (3) Å3 | 0.36 × 0.29 × 0.25 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | 2119 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.014 |
Graphite monochromator | θmax = 27.0°, θmin = 2.4° |
ω/2θ scans | h = 0→10 |
Absorption correction: gaussian (Spek, 1990) | k = −11→10 |
Tmin = 0.361, Tmax = 0.469 | l = −11→11 |
2556 measured reflections | 2 standard reflections every 60 min |
2378 independent reflections | intensity decay: none |
Refinement top
Refinement on F2 | Primary atom site location: heavy-atom method |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.095 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.11 | w = 1/[σ2(Fo2) + (0.0564P)2 + 0.527P] where P = (Fo2 + 2Fc2)/3 |
2378 reflections | (Δ/σ)max < 0.001 |
135 parameters | Δρmax = 1.49 e Å−3 |
0 restraints | Δρmin = −1.07 e Å−3 |
Crystal data top
[Ni(C2H7N3S)2(C3H4N2)2]I2 | γ = 112.05 (2)° |
Mr = 659.0 | V = 549.1 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.911 (3) Å | Mo Kα radiation |
b = 8.798 (3) Å | µ = 3.90 mm−1 |
c = 8.819 (2) Å | T = 293 K |
α = 102.92 (3)° | 0.36 × 0.29 × 0.25 mm |
β = 92.43 (2)° | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | 2119 reflections with I > 2σ(I) |
Absorption correction: gaussian (Spek, 1990) | Rint = 0.014 |
Tmin = 0.361, Tmax = 0.469 | 2 standard reflections every 60 min |
2556 measured reflections | intensity decay: none |
2378 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.095 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.11 | Δρmax = 1.49 e Å−3 |
2378 reflections | Δρmin = −1.07 e Å−3 |
135 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Ni | 0.5000 | 0.0000 | 0.5000 | 0.02522 (15) | |
I | 0.19744 (4) | −0.57364 (3) | 0.31790 (4) | 0.05072 (13) | |
S | 0.11687 (14) | 0.21452 (14) | 0.75518 (13) | 0.0437 (2) | |
N1 | 0.2381 (4) | −0.1630 (4) | 0.5372 (4) | 0.0326 (6) | |
N2 | 0.1582 (5) | −0.0600 (4) | 0.6254 (4) | 0.0410 (8) | |
N3 | 0.3887 (4) | 0.1724 (4) | 0.5883 (4) | 0.0300 (6) | |
N4 | 0.3890 (4) | −0.0296 (4) | 0.2669 (4) | 0.0344 (6) | |
N5 | 0.3362 (5) | 0.0825 (5) | 0.2208 (4) | 0.0399 (7) | |
C1 | 0.2385 (4) | 0.1088 (4) | 0.6454 (4) | 0.0287 (6) | |
C2 | 0.2670 (8) | 0.4321 (6) | 0.7893 (7) | 0.0682 (15) | |
C3 | 0.2598 (7) | 0.0282 (6) | 0.0706 (5) | 0.0484 (10) | |
C4 | 0.2619 (7) | −0.1281 (7) | 0.0136 (5) | 0.0501 (10) | |
C5 | 0.3420 (6) | −0.1589 (5) | 0.1400 (5) | 0.0411 (8) | |
H2A | 0.2122 | 0.5020 | 0.8496 | 0.102* | |
H2B | 0.2872 | 0.4599 | 0.6906 | 0.102* | |
H2C | 0.3825 | 0.4517 | 0.8463 | 0.102* | |
H3 | 0.2138 | 0.0862 | 0.0154 | 0.058* | |
H4 | 0.2192 | −0.1985 | −0.0877 | 0.060* | |
H5 | 0.3604 | −0.2580 | 0.1364 | 0.049* | |
H1N1 | 0.236 (6) | −0.237 (6) | 0.586 (5) | 0.036 (11)* | |
H1N2 | 0.065 (7) | −0.096 (6) | 0.655 (5) | 0.039 (12)* | |
H1N3 | 0.435 (6) | 0.290 (6) | 0.613 (5) | 0.035 (11)* | |
H1N5 | 0.343 (7) | 0.163 (7) | 0.276 (6) | 0.040 (13)* | |
H2N1 | 0.166 (10) | −0.247 (9) | 0.453 (8) | 0.08 (2)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni | 0.0212 (3) | 0.0231 (3) | 0.0317 (3) | 0.0091 (2) | 0.0033 (2) | 0.0071 (2) |
I | 0.04079 (18) | 0.02786 (17) | 0.0788 (2) | 0.00839 (12) | 0.01312 (14) | 0.01298 (13) |
S | 0.0402 (5) | 0.0467 (6) | 0.0504 (6) | 0.0252 (4) | 0.0156 (4) | 0.0089 (4) |
N1 | 0.0285 (14) | 0.0245 (14) | 0.0435 (17) | 0.0089 (12) | 0.0079 (12) | 0.0084 (13) |
N2 | 0.0311 (16) | 0.0307 (16) | 0.060 (2) | 0.0085 (13) | 0.0211 (15) | 0.0122 (14) |
N3 | 0.0262 (13) | 0.0247 (14) | 0.0390 (15) | 0.0102 (11) | 0.0067 (11) | 0.0073 (11) |
N4 | 0.0342 (15) | 0.0356 (16) | 0.0369 (15) | 0.0168 (13) | 0.0029 (12) | 0.0110 (12) |
N5 | 0.0457 (19) | 0.0383 (19) | 0.0419 (18) | 0.0215 (15) | 0.0043 (14) | 0.0144 (15) |
C1 | 0.0261 (15) | 0.0340 (17) | 0.0281 (15) | 0.0150 (13) | 0.0016 (12) | 0.0070 (13) |
C2 | 0.068 (3) | 0.042 (3) | 0.086 (4) | 0.028 (2) | 0.010 (3) | −0.010 (2) |
C3 | 0.050 (2) | 0.061 (3) | 0.044 (2) | 0.026 (2) | 0.0041 (18) | 0.026 (2) |
C4 | 0.052 (2) | 0.064 (3) | 0.033 (2) | 0.024 (2) | 0.0000 (17) | 0.0092 (18) |
C5 | 0.046 (2) | 0.038 (2) | 0.042 (2) | 0.0207 (17) | 0.0027 (16) | 0.0072 (15) |
Geometric parameters (Å, º) top
Ni—N1i | 2.120 (3) | N4—N5 | 1.337 (4) |
Ni—N1 | 2.120 (3) | N5—C3 | 1.334 (6) |
Ni—N3 | 2.053 (3) | C2—H2A | 0.9600 |
Ni—N3i | 2.053 (3) | C2—H2B | 0.9600 |
Ni—N4i | 2.122 (3) | C2—H2C | 0.9600 |
Ni—N4 | 2.122 (3) | N3—H1N3 | 0.92 (5) |
C1—N2 | 1.343 (5) | N5—H1N5 | 0.75 (5) |
C1—S | 1.754 (3) | C3—H3 | 0.9300 |
C2—S | 1.780 (6) | C5—H5 | 0.9300 |
C3—C4 | 1.361 (7) | C4—H4 | 0.9300 |
C4—C5 | 1.387 (6) | N2—H1N2 | 0.77 (5) |
N1—N2 | 1.407 (4) | N1—H1N1 | 0.85 (5) |
N3—C1 | 1.287 (4) | N1—H2N1 | 0.91 (7) |
N4—C5 | 1.328 (5) | | |
| | | |
C1—N3—Ni | 113.8 (2) | C3—C4—C5 | 104.6 (4) |
N3i—Ni—N3 | 180.0 | C1—N2—N1 | 118.7 (3) |
N3i—Ni—N1i | 79.00 (12) | N2—N1—Ni | 107.4 (2) |
N3—Ni—N1i | 101.00 (12) | S—C2—H2A | 109.5 |
N3i—Ni—N1 | 101.00 (12) | S—C2—H2B | 109.5 |
N3—Ni—N1 | 79.00 (12) | H2A—C2—H2B | 109.5 |
N1i—Ni—N1 | 180.0 | S—C2—H2C | 109.5 |
N3i—Ni—N4i | 91.49 (12) | H2A—C2—H2C | 109.5 |
N3—Ni—N4i | 88.51 (12) | H2B—C2—H2C | 109.5 |
N1i—Ni—N4i | 89.57 (13) | C1—N3—H1N3 | 112 (3) |
N1—Ni—N4i | 90.43 (13) | Ni—N3—H1N3 | 132 (3) |
N3i—Ni—N4 | 88.51 (12) | C3—N5—H1N5 | 125 (4) |
N3—Ni—N4 | 91.49 (12) | N4—N5—H1N5 | 123 (4) |
N1i—Ni—N4 | 90.43 (13) | N5—C3—H3 | 126.5 |
N1—Ni—N4 | 89.57 (13) | C4—C3—H3 | 126.5 |
N4i—Ni—N4 | 180.0 | N4—C5—H5 | 124.2 |
C3—N5—N4 | 112.5 (4) | C4—C5—H5 | 124.2 |
C5—N4—N5 | 104.2 (3) | C3—C4—H4 | 127.7 |
C5—N4—Ni | 131.0 (3) | C5—C4—H4 | 127.7 |
N5—N4—Ni | 124.5 (3) | C1—N2—H1N2 | 118 (4) |
N3—C1—N2 | 119.4 (3) | N1—N2—H1N2 | 123 (4) |
N3—C1—S | 128.6 (3) | N2—N1—H1N1 | 107 (3) |
N2—C1—S | 111.9 (3) | Ni—N1—H1N1 | 117 (3) |
C1—S—C2 | 102.8 (2) | N2—N1—H2N1 | 118 (4) |
N5—C3—C4 | 107.0 (4) | Ni—N1—H2N1 | 117 (4) |
N4—C5—C4 | 111.6 (4) | H1N1—N1—H2N1 | 90 (5) |
Symmetry code: (i) −x+1, −y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H1N2···Iii | 0.77 (5) | 2.94 (5) | 3.548 (4) | 138 (4) |
N3—H1N3···Ii | 0.92 (5) | 2.96 (5) | 3.695 (3) | 137 (3) |
N5—H1N5···Iiii | 0.75 (5) | 2.91 (5) | 3.536 (4) | 143 (5) |
N1—H2N1···I | 0.91 (7) | 2.96 (7) | 3.585 (3) | 128 (5) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y−1, −z+1; (iii) x, y+1, z. |
Experimental details
Crystal data |
Chemical formula | [Ni(C2H7N3S)2(C3H4N2)2]I2 |
Mr | 659.0 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.911 (3), 8.798 (3), 8.819 (2) |
α, β, γ (°) | 102.92 (3), 92.43 (2), 112.05 (2) |
V (Å3) | 549.1 (3) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 3.90 |
Crystal size (mm) | 0.36 × 0.29 × 0.25 |
|
Data collection |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | Gaussian (Spek, 1990) |
Tmin, Tmax | 0.361, 0.469 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2556, 2378, 2119 |
Rint | 0.014 |
(sin θ/λ)max (Å−1) | 0.638 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.095, 1.11 |
No. of reflections | 2378 |
No. of parameters | 135 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.49, −1.07 |
Selected geometric parameters (Å, º) topNi—N1 | 2.120 (3) | C2—S | 1.780 (6) |
Ni—N3 | 2.053 (3) | N3—C1 | 1.287 (4) |
Ni—N4 | 2.122 (3) | N4—C5 | 1.328 (5) |
C1—N2 | 1.343 (5) | N4—N5 | 1.337 (4) |
C1—S | 1.754 (3) | N5—C3 | 1.334 (6) |
| | | |
C1—N3—Ni | 113.8 (2) | C1—N2—N1 | 118.7 (3) |
N3—Ni—N1 | 79.00 (12) | N2—N1—Ni | 107.4 (2) |
N3—C1—N2 | 119.4 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H1N2···Ii | 0.77 (5) | 2.94 (5) | 3.548 (4) | 138 (4) |
N3—H1N3···Iii | 0.92 (5) | 2.96 (5) | 3.695 (3) | 137 (3) |
N5—H1N5···Iiii | 0.75 (5) | 2.91 (5) | 3.536 (4) | 143 (5) |
N1—H2N1···I | 0.91 (7) | 2.96 (7) | 3.585 (3) | 128 (5) |
Symmetry codes: (i) −x, −y−1, −z+1; (ii) −x+1, −y, −z+1; (iii) x, y+1, z. |
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Up to now, X-ray structural analysis has been used to characterize a number of NiII complexes with thiosemicarbazide (TSC), some of which present an octahedral geometry (Hazell, 1968, 1976; Ballard et al., 1974; Kumar et al., 1991; Burrows et al., 1996), the others having a square-planar geometry (Gronbaek & Rasmussen, 1962; Hazell, 1968, 1972; Burrows et al., 1996). Also, structures have been reported with an uncoordinated TSC moiety (Andretti et al., 1970; Gubin et al., 1984; Waskowska, 1998). In these complexes, TSC is coordinated as a neutral ligand, (I). S-Methylisothiosemicarbazide [ITSC, (II)] is also coordinated as a neutral ligand, forming either square-planar (Divjaković & Leovac, 1979; Divjaković et al., 1983; Divjaković, 1984; Obadović et al., 1997) or octahedral complexes (Bourosh et al., 1987) with NiII. However, in contrast to TSC, which is coordinated via the N1 and S atom, ITSC is coordinated via the terminal N1 and N4 atoms.
A consequence of the different coordination modes of these two ligands is the difference in the electronic delocalization in the N2—C3—N4 fragment. Namely, with the ITSC complexes the N2—C3 bond is about 0.05 Å longer than the C3—N4 bond, whereas these two bonds are approximately equal in the TSC complexes. Thus, the ratio of bond lengths does not depend on the type of the Ni complex (octahedral or planar). However, there is a significant difference in the metal–ligand distance depending on metal coordination polyedron. On the one hand, the Ni—N1 distance of the square-planar complexes is about 0.07 Å shorter then in the octahedral complexes, whereas the Ni—N1 distance is approximately the same in the complexes (TSC and ITSC) of the same coordination number. On the other hand, the Ni—N4 distances in the ITSC complexes are always shorter by 0.05–0.06 Å than the Ni—N1 distances. This can be explained by the different hybridization character of the N1 (sp3) and N4 (sp2) atoms, due to the partial π-character of the Ni—N4 bond.
The novel NiII complex presented in this work, [Ni(ITSC)2(pz)2]I2 (pz = pyrazole), (III), has an octahedral centrosymmetric coordination. The chelate rings are almost planar, showing a flattened envelope conformation. The Ni atom is 0.324 (6) Å out of the mean plane defined by the other ring-forming atoms (N1, N2, C1 and N3). The puckering parameters (Cremer & Pople, 1975) for the five-membered chelate ring are Q = 0.155 Å and ϕ = 186.57°. The ITSC ligand is coordinated via the two terminal N atoms [Ni—N1 = 2.119 (4) and Ni—N3 = 2.053 (4) Å]. Therefore, as observed previously for the other ITSC complexes, the Ni—N3 bond is about 0.07 Å shorter than the Ni—N1 bond. Iodine is not involved in metal coordination, the shortest Ni···I distance being 4.556 (2) Å.
Due to the formation of five-membered rings, the coordination around nickel is characterized by deformed equatorial angles [N1—Ni—N3 = 79.2 (2)°]. The I atoms are in the equatorial plane of the chelate ligand (Fig. 1) and lie on the line which approximately bisects the N1—Ni—N3 angle [100.8 (2)°] and they form weak hydrogen bonds with the N1H2 and N2H groups (Table 2).
The S atom is directed to the center (M) of the pyrazole ring at -x, -y, 1 - z, at a distance of 3.45 Å. The angle between the plane through the C1—S—C2 fragment and the mean plane of the pyrazole ring is 89.5 (2)°. Considering these geometrical parameters and also the fact that the angles C2—S—M (128.3°) and C1—S—M (128.8°) are almost identical, it is obvious that some kind of interaction exists between the S atom and pyrazole ring (Fig. 2). The free electron pair of the S atom is ideally oriented toward the ring center, probably due to a partial positive complex cation charge located on the pyrazole ring. This interaction is weak, but it can not be a coincidence, due to the probability of free rotation of the pyrazole ring around the Ni—N4 bond.