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Acta Crystallogr Sect E Struct Rep Online. 2008 December 1; 64(Pt 12): m1615.
Published online 2008 November 26. doi:  10.1107/S1600536808038580
PMCID: PMC2959798

Bis[benzyl N′-(1H-indol-3-ylmethyl­ene)hydrazinecarbodithio­ato-κ2 N′,S]nickel(II) N,N-dimethyl­formamide disolvate

Abstract

In the title compound, [Ni(C17H14N3S2)2]·2C3H7NO, the Ni atom (site symmetry An external file that holds a picture, illustration, etc.
Object name is e-64-m1615-efi1.jpg) 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.

Related literature

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

An external file that holds a picture, illustration, etc.
Object name is e-64-m1615-scheme1.jpg

Experimental

Crystal data

  • [Ni(C17H14N3S2)2]·2C3H7NO
  • M r = 853.77
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-m1615-efi2.jpg
  • a = 10.3808 (3) Å
  • b = 20.0219 (7) Å
  • c = 10.7831 (3) Å
  • β = 117.921 (2)°
  • V = 1980.3 (1) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.75 mm−1
  • T = 100 (2) K
  • 0.12 × 0.12 × 0.06 mm

Data collection

  • Bruker SMART APEX CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.916, T max = 0.957
  • 13342 measured reflections
  • 3481 independent reflections
  • 2615 reflections with I > 2σ(I)
  • R int = 0.062

Refinement

  • R[F 2 > 2σ(F 2)] = 0.040
  • wR(F 2) = 0.094
  • S = 1.03
  • 3481 reflections
  • 252 parameters
  • H-atom parameters constrained
  • Δρmax = 0.50 e Å−3
  • Δρmin = −0.29 e Å−3

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

Table 1
Selected bond lengths (Å)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808038580/hb2849sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808038580/hb2849Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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).

Experimental

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

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).

Figures

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.

Crystal data

[Ni(C17H14N3S2)2]·2C3H7NOF000 = 892
Mr = 853.77Dx = 1.432 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1450 reflections
a = 10.3808 (3) Åθ = 2.2–22.7º
b = 20.0219 (7) ŵ = 0.75 mm1
c = 10.7831 (3) ÅT = 100 (2) K
β = 117.921 (2)ºBlock, brown
V = 1980.3 (1) Å30.12 × 0.12 × 0.06 mm
Z = 2

Data collection

Bruker SMART APEX CCD diffractometer3481 independent reflections
Radiation source: fine-focus sealed tube2615 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.062
T = 100(2) Kθmax = 25.0º
ω scansθmin = 2.0º
Absorption correction: Multi-scan(SADABS; Sheldrick, 1996)h = −12→12
Tmin = 0.916, Tmax = 0.957k = −23→23
13342 measured reflectionsl = −12→12

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.094  w = 1/[σ2(Fo2) + (0.0396P)2 + 0.2888P] where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.001
3481 reflectionsΔρmax = 0.50 e Å3
252 parametersΔρmin = −0.29 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

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)

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, °)

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, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···O10.881.862.739 (3)175

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB2849).

References

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