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Acta Cryst. (2008). E64, m1615    [ doi:10.1107/S1600536808038580 ]

Bis[benzyl N'-(1H-indol-3-ylmethylene)hydrazinecarbodithioato-[kappa]2N',S]nickel(II) N,N-dimethylformamide disolvate

H. Khaledi, H. Mohd Ali and S. W. Ng

Abstract top

In the title compound, [Ni(C17H14N3S2)2]·2C3H7NO, the Ni atom (site symmetry \overline{1}) is N,S-chelated by two deprotonated Schiff base anions in a distorted square-planar geometry. The dihedral angle between the aromatic ring planes within the ligand is 86.37 (13)°. In the crystal structure, an N-H...O hydrogen bond links the complex to the dimethylformamide solvent molecule.

Comment top

For related structures, see: Ali et al. (2000); Tian et al. (1996a,b); Xue et al. (2003); Zhang et al. (2004); Zhu et al. (2000).

Related literature top

For other square-planar nickel dithiocarbazates, see: Ali et al. (2000); Tian et al. (1996a,b); Xue et al. (2003); Zhang et al. (2004); Zhu et al. (2000).

Experimental top

Benzyl (1H-indol-2-ylmethylene)hydrazinecarbodithioate ethanol hemisolvate (2 mmol, 0.65 g) was dissolved in ethanol (30 ml) along with several drops of triethylamine. To the resulting clear solution was added an ethanol solution (10 ml) containing 1 mmol (0.25 g) of nickel acetate tetrahydrate. The mixture was heated for an hour. The product that separated was recrystallized from DMF to yield brown blocks of (I).

Refinement top

Hydrogen atoms were placed at calculated positions (C–H = 0.95–0.99Å, N–H = 0.88Å) and refined as riding with U(H) = 1.2–1.5 times Ueq(C,N).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: pubCIF (Westrip, 2008).

Figures top
[Figure 1] Fig. 1. View of (I) at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius. The unlabelled atoms are generated by the symmetry operation (1–x, 1–y, 1–z) and the hydrogen bonds are shown as dashed lines.
Bis[benzyl N'-(1H-indol-3-ylmethylene)hydrazinecarbodithioato- κ2N',S]nickel(II) N,N-dimethylformamide disolvate top
Crystal data top
[Ni(C17H14N3S2)2]·2C3H7NOF(000) = 892
Mr = 853.77Dx = 1.432 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1450 reflections
a = 10.3808 (3) Åθ = 2.2–22.7°
b = 20.0219 (7) ŵ = 0.75 mm−1
c = 10.7831 (3) ÅT = 100 K
β = 117.921 (2)°Block, brown
V = 1980.3 (1) Å30.12 × 0.12 × 0.06 mm
Z = 2
Data collection top
Bruker SMART APEX CCD
diffractometer		3481 independent reflections
Radiation source: fine-focus sealed tube2615 reflections with I > 2σ(I)
graphiteRint = 0.062
ω scansθmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −12→12
Tmin = 0.916, Tmax = 0.957k = −23→23
13342 measured reflectionsl = −12→12
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.094H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0396P)2 + 0.2888P]
where P = (Fo2 + 2Fc2)/3
3481 reflections(Δ/σ)max = 0.001
252 parametersΔρmax = 0.50 e Å−3
0 restraintsΔρmin = −0.29 e Å−3
Crystal data top
[Ni(C17H14N3S2)2]·2C3H7NOV = 1980.3 (1) Å3
Mr = 853.77Z = 2
Monoclinic, P21/cMo Kα radiation
a = 10.3808 (3) ŵ = 0.75 mm−1
b = 20.0219 (7) ÅT = 100 K
c = 10.7831 (3) Å0.12 × 0.12 × 0.06 mm
β = 117.921 (2)°
Data collection top
Bruker SMART APEX CCD
diffractometer		3481 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2615 reflections with I > 2σ(I)
Tmin = 0.916, Tmax = 0.957Rint = 0.062
13342 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.094Δρmax = 0.50 e Å−3
S = 1.03Δρmin = −0.29 e Å−3
3481 reflectionsAbsolute structure: ?
252 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ni10.50000.50000.50000.01710 (15)
S10.48640 (8)0.60841 (4)0.48343 (8)0.0236 (2)
S20.38426 (8)0.70431 (4)0.62163 (8)0.0234 (2)
O10.1755 (3)0.56685 (12)1.1091 (2)0.0472 (7)
N10.2818 (3)0.49406 (11)0.9618 (2)0.0220 (6)
H10.25200.51911.01050.026*
N20.4331 (2)0.51020 (11)0.6371 (2)0.0182 (5)
N30.3953 (2)0.57357 (11)0.6685 (2)0.0192 (5)
N40.0849 (3)0.57529 (12)1.2634 (2)0.0252 (6)
C10.2942 (3)0.42563 (14)0.9707 (3)0.0192 (6)
C20.2658 (3)0.38131 (15)1.0548 (3)0.0232 (7)
H20.23510.39671.12000.028*
C30.2842 (3)0.31463 (15)1.0393 (3)0.0260 (7)
H30.26470.28321.09450.031*
C40.3308 (3)0.29162 (15)0.9445 (3)0.0250 (7)
H40.34120.24500.93540.030*
C50.3621 (3)0.33626 (15)0.8636 (3)0.0219 (7)
H50.39550.32050.80050.026*
C60.3437 (3)0.40438 (14)0.8763 (3)0.0187 (6)
C70.3625 (3)0.46401 (14)0.8099 (3)0.0188 (6)
C80.3220 (3)0.51697 (15)0.8678 (3)0.0223 (7)
H80.32270.56270.84430.027*
C90.4138 (3)0.46239 (15)0.7091 (3)0.0198 (7)
H90.43820.41910.69070.024*
C100.4193 (3)0.62076 (14)0.6009 (3)0.0191 (6)
C110.3353 (3)0.70343 (15)0.7620 (3)0.0245 (7)
H11A0.40280.67260.83540.029*
H11B0.35350.74870.80390.029*
C120.1817 (3)0.68378 (14)0.7277 (3)0.0206 (7)
C130.0673 (3)0.68232 (15)0.5927 (3)0.0259 (7)
H130.08380.69390.51590.031*
C14−0.0716 (3)0.66398 (16)0.5687 (3)0.0309 (8)
H14−0.14900.66220.47540.037*
C15−0.0977 (3)0.64846 (16)0.6793 (3)0.0320 (8)
H15−0.19300.63640.66270.038*
C160.0152 (3)0.65049 (15)0.8139 (3)0.0291 (8)
H16−0.00200.63980.89080.035*
C170.1540 (3)0.66816 (15)0.8379 (3)0.0243 (7)
H170.23120.66960.93130.029*
C180.1381 (4)0.54196 (18)1.1919 (3)0.0376 (9)
H180.14850.49501.20540.045*
C190.0701 (3)0.64730 (15)1.2501 (3)0.0289 (8)
H19A0.07550.66161.16580.043*
H19B0.14890.66841.33290.043*
H19C−0.02410.66061.24270.043*
C200.0490 (3)0.54232 (15)1.3634 (3)0.0293 (7)
H20A0.05900.49391.35790.044*
H20B−0.05160.55311.34120.044*
H20C0.11540.55781.45840.044*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0178 (3)0.0178 (3)0.0192 (3)−0.0001 (2)0.0116 (2)−0.0001 (2)
S10.0326 (5)0.0197 (4)0.0292 (4)0.0005 (3)0.0234 (4)0.0002 (3)
S20.0297 (5)0.0183 (4)0.0296 (4)−0.0010 (3)0.0201 (4)−0.0016 (3)
O10.0752 (19)0.0443 (17)0.0405 (14)0.0204 (13)0.0424 (14)0.0058 (12)
N10.0274 (14)0.0212 (15)0.0242 (13)−0.0007 (11)0.0178 (11)−0.0028 (11)
N20.0186 (13)0.0152 (14)0.0220 (12)0.0001 (10)0.0106 (10)−0.0005 (10)
N30.0197 (13)0.0175 (14)0.0223 (13)0.0009 (10)0.0114 (11)−0.0031 (10)
N40.0265 (15)0.0263 (16)0.0239 (13)0.0015 (11)0.0129 (12)−0.0056 (11)
C10.0192 (16)0.0213 (17)0.0180 (14)−0.0012 (13)0.0094 (12)0.0003 (12)
C20.0225 (17)0.0289 (19)0.0212 (15)−0.0016 (14)0.0128 (13)0.0023 (13)
C30.0232 (17)0.030 (2)0.0264 (16)0.0009 (14)0.0128 (14)0.0100 (14)
C40.0229 (17)0.0197 (17)0.0319 (17)0.0021 (13)0.0123 (14)0.0079 (13)
C50.0188 (16)0.0253 (18)0.0229 (15)0.0023 (13)0.0110 (13)0.0003 (13)
C60.0129 (15)0.0237 (18)0.0205 (15)0.0019 (12)0.0088 (12)0.0023 (12)
C70.0172 (16)0.0200 (17)0.0203 (15)−0.0010 (12)0.0098 (13)−0.0001 (12)
C80.0243 (17)0.0242 (18)0.0217 (15)−0.0019 (13)0.0134 (13)0.0033 (12)
C90.0172 (16)0.0201 (18)0.0237 (16)0.0008 (12)0.0107 (13)−0.0002 (12)
C100.0162 (16)0.0222 (17)0.0183 (14)−0.0012 (12)0.0076 (12)−0.0008 (12)
C110.0304 (18)0.0232 (18)0.0263 (16)−0.0054 (14)0.0186 (14)−0.0074 (13)
C120.0251 (17)0.0148 (16)0.0282 (16)0.0002 (13)0.0177 (14)−0.0055 (12)
C130.0301 (19)0.0247 (18)0.0265 (17)0.0025 (14)0.0164 (15)−0.0007 (13)
C140.0224 (18)0.032 (2)0.0314 (18)0.0053 (14)0.0071 (15)−0.0008 (15)
C150.0232 (18)0.031 (2)0.044 (2)0.0045 (14)0.0177 (16)0.0048 (15)
C160.0322 (19)0.0273 (19)0.0366 (19)0.0018 (14)0.0234 (16)0.0042 (14)
C170.0246 (18)0.0256 (18)0.0264 (16)−0.0007 (14)0.0150 (14)−0.0043 (13)
C180.048 (2)0.034 (2)0.0333 (19)0.0081 (17)0.0206 (18)−0.0021 (16)
C190.034 (2)0.028 (2)0.0260 (17)0.0037 (15)0.0150 (15)−0.0037 (14)
C200.0300 (18)0.029 (2)0.0324 (18)−0.0026 (14)0.0177 (15)−0.0049 (14)
Geometric parameters (Å, °) top
Ni1—N2i1.916 (2)C6—C71.451 (4)
Ni1—N21.916 (2)C7—C81.391 (4)
Ni1—S12.1770 (7)C7—C91.418 (4)
Ni1—S1i2.1770 (7)C8—H80.9500
S1—C101.725 (3)C9—H90.9500
S2—C101.748 (3)C11—C121.511 (4)
S2—C111.808 (3)C11—H11A0.9900
O1—C181.233 (4)C11—H11B0.9900
N1—C81.346 (3)C12—C171.383 (4)
N1—C11.375 (3)C12—C131.382 (4)
N1—H10.8800C13—C141.390 (4)
N2—C91.306 (3)C13—H130.9500
N2—N31.416 (3)C14—C151.377 (4)
N3—C101.287 (3)C14—H140.9500
N4—C181.321 (4)C15—C161.375 (4)
N4—C201.454 (4)C15—H150.9500
N4—C191.450 (4)C16—C171.385 (4)
C1—C21.395 (4)C16—H160.9500
C1—C61.404 (4)C17—H170.9500
C2—C31.370 (4)C18—H180.9500
C2—H20.9500C19—H19A0.9800
C3—C41.398 (4)C19—H19B0.9800
C3—H30.9500C19—H19C0.9800
C4—C51.390 (4)C20—H20A0.9800
C4—H40.9500C20—H20B0.9800
C5—C61.393 (4)C20—H20C0.9800
C5—H50.9500
N2i—Ni1—N2180.0C7—C9—H9114.5
N2i—Ni1—S194.36 (7)N3—C10—S1124.2 (2)
N2—Ni1—S185.64 (7)N3—C10—S2121.5 (2)
N2i—Ni1—S1i85.64 (7)S1—C10—S2114.26 (16)
N2—Ni1—S1i94.36 (7)C12—C11—S2118.4 (2)
S1—Ni1—S1i180.0C12—C11—H11A107.7
C10—S1—Ni196.64 (10)S2—C11—H11A107.7
C10—S2—C11104.76 (13)C12—C11—H11B107.7
C8—N1—C1109.9 (2)S2—C11—H11B107.7
C8—N1—H1125.1H11A—C11—H11B107.1
C1—N1—H1125.1C17—C12—C13118.5 (3)
C9—N2—N3112.2 (2)C17—C12—C11118.0 (2)
C9—N2—Ni1126.4 (2)C13—C12—C11123.5 (3)
N3—N2—Ni1121.46 (17)C12—C13—C14120.4 (3)
C10—N3—N2111.9 (2)C12—C13—H13119.8
C18—N4—C20121.8 (3)C14—C13—H13119.8
C18—N4—C19119.9 (3)C15—C14—C13120.4 (3)
C20—N4—C19118.2 (2)C15—C14—H14119.8
N1—C1—C2129.6 (3)C13—C14—H14119.8
N1—C1—C6107.8 (2)C14—C15—C16119.4 (3)
C2—C1—C6122.6 (3)C14—C15—H15120.3
C3—C2—C1117.2 (3)C16—C15—H15120.3
C3—C2—H2121.4C15—C16—C17120.2 (3)
C1—C2—H2121.4C15—C16—H16119.9
C2—C3—C4121.7 (3)C17—C16—H16119.9
C2—C3—H3119.2C12—C17—C16121.0 (3)
C4—C3—H3119.2C12—C17—H17119.5
C5—C4—C3120.7 (3)C16—C17—H17119.5
C5—C4—H4119.7O1—C18—N4125.3 (3)
C3—C4—H4119.7O1—C18—H18117.3
C4—C5—C6119.0 (3)N4—C18—H18117.3
C4—C5—H5120.5N4—C19—H19A109.5
C6—C5—H5120.5N4—C19—H19B109.5
C5—C6—C1118.8 (3)H19A—C19—H19B109.5
C5—C6—C7134.5 (3)N4—C19—H19C109.5
C1—C6—C7106.7 (2)H19A—C19—H19C109.5
C8—C7—C9131.5 (3)H19B—C19—H19C109.5
C8—C7—C6105.5 (2)N4—C20—H20A109.5
C9—C7—C6123.0 (3)N4—C20—H20B109.5
N1—C8—C7110.1 (3)H20A—C20—H20B109.5
N1—C8—H8125.0N4—C20—H20C109.5
C7—C8—H8125.0H20A—C20—H20C109.5
N2—C9—C7131.1 (3)H20B—C20—H20C109.5
N2—C9—H9114.5
N2i—Ni1—S1—C10177.84 (11)C9—C7—C8—N1−179.2 (3)
N2—Ni1—S1—C10−2.16 (11)C6—C7—C8—N10.2 (3)
S1—Ni1—N2—C9−177.9 (2)N3—N2—C9—C70.1 (4)
S1i—Ni1—N2—C92.1 (2)Ni1—N2—C9—C7−178.5 (2)
S1—Ni1—N2—N33.52 (18)C8—C7—C9—N2−2.8 (5)
S1i—Ni1—N2—N3−176.48 (18)C6—C7—C9—N2177.9 (3)
C9—N2—N3—C10177.8 (2)N2—N3—C10—S11.1 (3)
Ni1—N2—N3—C10−3.5 (3)N2—N3—C10—S2−179.25 (17)
C8—N1—C1—C2179.3 (3)Ni1—S1—C10—N31.2 (2)
C8—N1—C1—C6−0.5 (3)Ni1—S1—C10—S2−178.47 (13)
N1—C1—C2—C3178.4 (3)C11—S2—C10—N36.4 (3)
C6—C1—C2—C3−1.9 (4)C11—S2—C10—S1−173.95 (15)
C1—C2—C3—C40.7 (4)C10—S2—C11—C12−80.3 (2)
C2—C3—C4—C50.8 (4)S2—C11—C12—C17165.3 (2)
C3—C4—C5—C6−1.2 (4)S2—C11—C12—C13−16.5 (4)
C4—C5—C6—C10.0 (4)C17—C12—C13—C14−1.5 (4)
C4—C5—C6—C7−178.9 (3)C11—C12—C13—C14−179.7 (3)
N1—C1—C6—C5−178.6 (2)C12—C13—C14—C151.4 (5)
C2—C1—C6—C51.5 (4)C13—C14—C15—C16−0.7 (5)
N1—C1—C6—C70.6 (3)C14—C15—C16—C170.1 (5)
C2—C1—C6—C7−179.3 (3)C13—C12—C17—C160.9 (4)
C5—C6—C7—C8178.6 (3)C11—C12—C17—C16179.2 (3)
C1—C6—C7—C8−0.5 (3)C15—C16—C17—C12−0.2 (5)
C5—C6—C7—C9−2.0 (5)C20—N4—C18—O1−177.4 (3)
C1—C6—C7—C9179.0 (2)C19—N4—C18—O1−1.6 (5)
C1—N1—C8—C70.2 (3)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.881.862.739 (3)175
Table 1
Selected geometric parameters (Å) top
Ni1—N21.916 (2)Ni1—S12.1770 (7)
Acknowledgements top

We thank the University of Malaya for funding this study (Science Fund grants 12–02-03–2031, 12–02-03–2051).

references
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