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Acta Cryst. (2008). E64, m755    [ doi:10.1107/S1600536808011975 ]

Bis[1,5-bis(1H-indol-3-ylmethylene)thiocarbazonato-[kappa]2N,S]nickel(II) dimethyl sulfoxide disolvate

M. R. Rizal, H. M. Ali and S. W. Ng

Abstract top

The Ni atom in the crystal structure of the centrosymmetric title compound, [Ni(C19H15N6S)2]·2C2H6OS, is N,S-chelated by the deprotonated Schiff bases in a square-planar geometry. The -CH=N-N=C(S)-NH-N=CH- frament is planar. The two indolyl -NH (donor) sites interact with dimethyl sulfoxide molecules to furnish a layer motif.

Comment top

The preceding study reports the nickel derivative of 1H-indole-3-carboxaldehyde thiosemicarbazone (Rizal et al., 2008). With bis(1H-indole-3-carboxaldehyde thiocarbazone) in place of the thiosemicarbazone, the resulting nickel derivative also has the N,S-chelated metal center in a square planar coordination geometry. The compound crystallizes from DMSO as a disolvate (Fig. 1). The oxygen atom of the solvent molecule is a hydrogen bond acceptor to the indolyl amino group of two mononuclear molecules; such a hydrogen bonding scheme gives rise to a layer motif.

Related literature top

For the structure of the unsolvated nickel derivative of 1H-indole-3-carboxaldehyde thiosemicarbazone, see: Rizal et al. (2008). The ligand is known to be a sensitive complexing agent, see: Ghosh et al. (1999).

Experimental top

The Schiff base was synthesized as according to a literature procedure (Ghosh et al., 1999). The Schiff base (2 g, 5.5 mmol) and nickel acetate (0.7 g, 2.8 mmol) were heated in ethanol (50 ml) for 5 h. The brown product was recrystallized from DMSO to give red crystals..

Refinement top

Carbon-bound H-atoms were placed in calculated positions (C—H 0.98 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2–1.5U(C). The nitrogen-bound H-atoms were similarly treated [N–H 0.88 Å].

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: publCIF (Westrip, 2008).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of Ni(C19H15N6S)2.2DMSO at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. The molecule lies on a center-of-inversion. Unlabeled atoms are related to the labeled ones by this symmetry element.
Bis[1,5-bis(1H-indol-3-ylmethylene)thiocarbazonato- κ2N,S]nickel(II) dimethyl sulfoxide disolvate top
Crystal data top
[Ni(C19H15N6S)2]·2C2H6OSF000 = 1944
Mr = 933.83Dx = 1.416 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2255 reflections
a = 19.0340 (5) Åθ = 2.5–23.1º
b = 9.1982 (3) ŵ = 0.69 mm−1
c = 25.1374 (7) ÅT = 100 (2) K
β = 95.672 (2)ºNeedle, red
V = 4379.5 (2) Å30.30 × 0.03 × 0.03 mm
Z = 4
Data collection top
Bruker SMART APEX
diffractometer		5030 independent reflections
Radiation source: fine-focus sealed tube3201 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.092
T = 100(2) Kθmax = 27.5º
φ and ω scansθmin = 1.6º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −24→24
Tmin = 0.821, Tmax = 0.980k = −11→9
27119 measured reflectionsl = −32→32
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.048H-atom parameters constrained
wR(F2) = 0.139  w = 1/[σ2(Fo2) + (0.0695P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
5030 reflectionsΔρmax = 0.60 e Å−3
277 parametersΔρmin = −0.53 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Ni(C19H15N6S)2]·2C2H6OSV = 4379.5 (2) Å3
Mr = 933.83Z = 4
Monoclinic, C2/cMo Kα
a = 19.0340 (5) ŵ = 0.69 mm−1
b = 9.1982 (3) ÅT = 100 (2) K
c = 25.1374 (7) Å0.30 × 0.03 × 0.03 mm
β = 95.672 (2)º
Data collection top
Bruker SMART APEX
diffractometer		5030 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		3201 reflections with I > 2σ(I)
Tmin = 0.821, Tmax = 0.980Rint = 0.092
27119 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.048277 parameters
wR(F2) = 0.139H-atom parameters constrained
S = 1.04Δρmax = 0.60 e Å−3
5030 reflectionsΔρmin = −0.53 e Å−3
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ni10.75000.75000.50000.02112 (17)
S10.71406 (4)0.69712 (10)0.41745 (3)0.0248 (2)
S20.54373 (5)0.32873 (12)0.03925 (4)0.0426 (3)
N10.67553 (16)0.4672 (4)0.14187 (11)0.0407 (8)
H1N0.67490.43840.10840.049*
N20.73446 (14)0.5251 (3)0.32226 (10)0.0275 (6)
N30.77036 (14)0.4729 (3)0.36844 (10)0.0278 (6)
H3N0.79670.39450.36740.033*
N40.80017 (13)0.4836 (3)0.45745 (9)0.0228 (6)
N50.79004 (13)0.5599 (3)0.50425 (9)0.0219 (6)
N60.87026 (13)0.1142 (3)0.54254 (10)0.0256 (6)
H6N0.87700.03050.52690.031*
O10.61523 (12)0.3930 (3)0.03531 (9)0.0361 (6)
C10.71111 (19)0.3994 (5)0.18458 (13)0.0366 (9)
H10.73800.31280.18300.044*
C20.64128 (19)0.5856 (4)0.15846 (13)0.0347 (9)
C30.59816 (19)0.6863 (5)0.13031 (15)0.0410 (10)
H30.58910.68010.09250.049*
C40.5688 (2)0.7948 (5)0.15795 (16)0.0437 (10)
H40.53900.86420.13900.052*
C50.5817 (2)0.8061 (5)0.21364 (16)0.0445 (10)
H50.56060.88270.23180.053*
C60.62496 (18)0.7069 (4)0.24255 (14)0.0344 (9)
H60.63320.71420.28040.041*
C70.65623 (18)0.5962 (4)0.21512 (12)0.0314 (8)
C80.70192 (18)0.4760 (4)0.23012 (12)0.0321 (8)
C90.73595 (18)0.4385 (4)0.28191 (12)0.0307 (8)
H90.76000.34820.28660.037*
C100.76516 (16)0.5425 (4)0.41603 (12)0.0237 (7)
C110.80984 (15)0.4880 (4)0.54786 (12)0.0239 (7)
H110.80510.53880.58020.029*
C120.83747 (16)0.3449 (4)0.55418 (12)0.0237 (7)
C130.84099 (16)0.2324 (4)0.51784 (12)0.0235 (7)
H130.82500.23800.48090.028*
C140.88816 (16)0.1434 (4)0.59618 (13)0.0274 (8)
C150.92233 (17)0.0566 (4)0.63616 (13)0.0346 (9)
H150.9361−0.04030.62930.042*
C160.93510 (19)0.1182 (5)0.68610 (14)0.0410 (10)
H160.95890.06260.71420.049*
C170.91418 (19)0.2594 (5)0.69662 (14)0.0400 (9)
H170.92340.29750.73170.048*
C180.88050 (17)0.3447 (4)0.65717 (12)0.0330 (9)
H180.86610.44080.66470.040*
C190.86766 (16)0.2867 (4)0.60527 (13)0.0252 (7)
C200.5318 (2)0.1994 (5)−0.01409 (19)0.0615 (13)
H20A0.52470.2508−0.04830.092*
H20B0.49040.1390−0.00960.092*
H20C0.57370.1374−0.01360.092*
C210.5542 (2)0.2019 (5)0.09367 (19)0.0580 (13)
H21A0.56170.25510.12750.087*
H21B0.59500.13930.08970.087*
H21C0.51160.14200.09350.087*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0294 (3)0.0185 (3)0.0161 (3)−0.0020 (3)0.0053 (2)−0.0006 (2)
S10.0359 (4)0.0216 (5)0.0173 (4)−0.0002 (4)0.0042 (3)−0.0015 (3)
S20.0332 (5)0.0450 (7)0.0512 (6)0.0053 (5)0.0129 (4)0.0132 (5)
N10.053 (2)0.048 (2)0.0219 (15)0.0008 (17)0.0073 (14)−0.0063 (14)
N20.0343 (15)0.0295 (18)0.0192 (13)−0.0021 (13)0.0053 (11)−0.0032 (12)
N30.0378 (16)0.0256 (17)0.0202 (13)0.0056 (13)0.0041 (11)−0.0039 (12)
N40.0314 (14)0.0211 (16)0.0166 (12)−0.0005 (12)0.0059 (11)−0.0036 (11)
N50.0259 (14)0.0213 (16)0.0192 (12)−0.0018 (12)0.0069 (10)−0.0026 (11)
N60.0275 (14)0.0239 (17)0.0255 (14)0.0023 (12)0.0028 (11)−0.0027 (12)
O10.0355 (13)0.0473 (18)0.0255 (12)−0.0032 (12)0.0031 (10)0.0014 (11)
C10.049 (2)0.039 (2)0.0228 (17)0.0024 (18)0.0068 (16)−0.0055 (16)
C20.039 (2)0.039 (3)0.0268 (18)−0.0054 (18)0.0087 (15)0.0032 (17)
C30.043 (2)0.049 (3)0.0314 (19)−0.002 (2)0.0063 (17)0.0078 (18)
C40.040 (2)0.043 (3)0.047 (2)−0.0003 (19)−0.0002 (18)0.012 (2)
C50.040 (2)0.042 (3)0.054 (2)0.0023 (19)0.0148 (19)0.004 (2)
C60.0386 (19)0.036 (2)0.0304 (18)−0.0014 (17)0.0104 (15)0.0004 (16)
C70.0352 (19)0.037 (2)0.0235 (16)−0.0067 (17)0.0086 (14)0.0000 (15)
C80.040 (2)0.035 (2)0.0218 (16)0.0003 (17)0.0072 (15)−0.0051 (15)
C90.0378 (19)0.030 (2)0.0249 (17)0.0000 (16)0.0079 (14)−0.0034 (15)
C100.0269 (16)0.024 (2)0.0214 (15)−0.0052 (14)0.0077 (13)−0.0041 (14)
C110.0260 (16)0.025 (2)0.0210 (15)−0.0025 (14)0.0059 (13)−0.0033 (14)
C120.0243 (16)0.025 (2)0.0221 (15)−0.0018 (14)0.0040 (12)−0.0026 (14)
C130.0241 (15)0.022 (2)0.0241 (16)0.0008 (14)0.0030 (12)0.0015 (14)
C140.0211 (16)0.033 (2)0.0285 (17)−0.0031 (14)0.0039 (13)0.0019 (15)
C150.0316 (19)0.034 (2)0.0370 (19)−0.0002 (16)−0.0006 (15)0.0077 (17)
C160.035 (2)0.050 (3)0.036 (2)−0.0012 (19)−0.0063 (16)0.0151 (19)
C170.043 (2)0.050 (3)0.0260 (18)−0.006 (2)−0.0013 (15)0.0019 (18)
C180.0357 (19)0.039 (2)0.0247 (17)−0.0036 (17)0.0024 (15)−0.0016 (16)
C190.0243 (16)0.024 (2)0.0280 (17)−0.0036 (13)0.0051 (13)0.0024 (14)
C200.042 (2)0.064 (3)0.077 (3)−0.018 (2)−0.005 (2)−0.012 (3)
C210.049 (2)0.053 (3)0.076 (3)0.010 (2)0.026 (2)0.031 (2)
Geometric parameters (Å, °) top
Ni1—N5i1.906 (3)C5—C61.386 (5)
Ni1—N51.906 (3)C5—H50.9500
Ni1—S1i2.1748 (8)C6—C71.396 (5)
Ni1—S12.1748 (8)C6—H60.9500
S1—C101.726 (3)C7—C81.434 (5)
S2—O11.496 (2)C8—C91.438 (5)
S2—C201.790 (5)C9—H90.9500
S2—C211.794 (4)C11—C121.420 (5)
N1—C21.356 (5)C11—H110.9500
N1—C11.362 (4)C12—C131.386 (4)
N1—H1N0.8800C12—C191.456 (4)
N2—C91.293 (4)C13—H130.9500
N2—N31.374 (4)C14—C151.394 (5)
N3—C101.369 (4)C14—C191.400 (5)
N3—H3N0.8800C15—C161.377 (5)
N4—C101.298 (4)C15—H150.9500
N4—N51.400 (3)C16—C171.392 (6)
N5—C111.304 (4)C16—H160.9500
N6—C131.345 (4)C17—C181.372 (5)
N6—C141.384 (4)C17—H170.9500
N6—H6N0.8800C18—C191.408 (4)
C1—C81.370 (5)C18—H180.9500
C1—H10.9500C20—H20A0.9800
C2—C31.385 (5)C20—H20B0.9800
C2—C71.428 (4)C20—H20C0.9800
C3—C41.367 (6)C21—H21A0.9800
C3—H30.9500C21—H21B0.9800
C4—C51.401 (5)C21—H21C0.9800
C4—H40.9500
N5i—Ni1—N5180.000 (1)C7—C8—C9129.1 (3)
N5i—Ni1—S1i86.25 (7)N2—C9—C8121.3 (3)
N5—Ni1—S1i93.75 (7)N2—C9—H9119.3
N5i—Ni1—S193.75 (7)C8—C9—H9119.3
N5—Ni1—S186.25 (7)N4—C10—N3115.5 (3)
S1i—Ni1—S1180.000 (1)N4—C10—S1125.0 (2)
C10—S1—Ni194.55 (10)N3—C10—S1119.5 (2)
O1—S2—C20105.20 (18)N5—C11—C12129.6 (3)
O1—S2—C21105.92 (18)N5—C11—H11115.2
C20—S2—C2197.8 (3)C12—C11—H11115.2
C2—N1—C1110.0 (3)C13—C12—C11131.2 (3)
C2—N1—H1N125.0C13—C12—C19105.5 (3)
C1—N1—H1N125.0C11—C12—C19123.3 (3)
C9—N2—N3113.5 (3)N6—C13—C12110.1 (3)
C10—N3—N2120.1 (3)N6—C13—H13124.9
C10—N3—H3N119.9C12—C13—H13124.9
N2—N3—H3N119.9N6—C14—C15130.1 (3)
C10—N4—N5111.3 (3)N6—C14—C19107.2 (3)
C11—N5—N4113.6 (3)C15—C14—C19122.7 (3)
C11—N5—Ni1126.4 (2)C16—C15—C14116.7 (4)
N4—N5—Ni1120.03 (19)C16—C15—H15121.6
C13—N6—C14110.1 (3)C14—C15—H15121.6
C13—N6—H6N125.0C15—C16—C17122.0 (3)
C14—N6—H6N125.0C15—C16—H16119.0
N1—C1—C8109.2 (4)C17—C16—H16119.0
N1—C1—H1125.4C18—C17—C16121.2 (3)
C8—C1—H1125.4C18—C17—H17119.4
N1—C2—C3131.2 (3)C16—C17—H17119.4
N1—C2—C7107.9 (3)C17—C18—C19118.6 (4)
C3—C2—C7120.9 (4)C17—C18—H18120.7
C4—C3—C2118.7 (4)C19—C18—H18120.7
C4—C3—H3120.7C14—C19—C18118.8 (3)
C2—C3—H3120.7C14—C19—C12107.1 (3)
C3—C4—C5121.5 (4)C18—C19—C12134.1 (3)
C3—C4—H4119.3S2—C20—H20A109.5
C5—C4—H4119.3S2—C20—H20B109.5
C6—C5—C4120.8 (4)H20A—C20—H20B109.5
C6—C5—H5119.6S2—C20—H20C109.5
C4—C5—H5119.6H20A—C20—H20C109.5
C5—C6—C7118.8 (3)H20B—C20—H20C109.5
C5—C6—H6120.6S2—C21—H21A109.5
C7—C6—H6120.6S2—C21—H21B109.5
C6—C7—C2119.3 (3)H21A—C21—H21B109.5
C6—C7—C8135.2 (3)S2—C21—H21C109.5
C2—C7—C8105.4 (3)H21A—C21—H21C109.5
C1—C8—C7107.5 (3)H21B—C21—H21C109.5
C1—C8—C9123.4 (4)
N5i—Ni1—S1—C10167.97 (12)C7—C8—C9—N2−8.1 (6)
N5—Ni1—S1—C10−12.03 (12)N5—N4—C10—N3−178.4 (2)
C9—N2—N3—C10−170.8 (3)N5—N4—C10—S11.3 (4)
C10—N4—N5—C11164.8 (3)N2—N3—C10—N4179.0 (3)
C10—N4—N5—Ni1−14.8 (3)N2—N3—C10—S1−0.7 (4)
S1i—Ni1—N5—C1117.7 (3)Ni1—S1—C10—N49.5 (3)
S1—Ni1—N5—C11−162.3 (3)Ni1—S1—C10—N3−170.8 (2)
S1i—Ni1—N5—N4−162.8 (2)N4—N5—C11—C12−2.2 (5)
S1—Ni1—N5—N417.2 (2)Ni1—N5—C11—C12177.4 (2)
C2—N1—C1—C8−1.6 (4)N5—C11—C12—C13−12.0 (6)
C1—N1—C2—C3−179.1 (4)N5—C11—C12—C19170.0 (3)
C1—N1—C2—C70.7 (4)C14—N6—C13—C12−0.7 (4)
N1—C2—C3—C4178.5 (4)C11—C12—C13—N6−178.3 (3)
C7—C2—C3—C4−1.3 (6)C19—C12—C13—N60.0 (4)
C2—C3—C4—C50.3 (6)C13—N6—C14—C15−176.7 (3)
C3—C4—C5—C60.0 (6)C13—N6—C14—C191.1 (3)
C4—C5—C6—C70.7 (6)N6—C14—C15—C16177.8 (3)
C5—C6—C7—C2−1.8 (5)C19—C14—C15—C160.4 (5)
C5—C6—C7—C8−179.1 (4)C14—C15—C16—C170.9 (5)
N1—C2—C7—C6−177.7 (3)C15—C16—C17—C18−0.9 (6)
C3—C2—C7—C62.1 (5)C16—C17—C18—C19−0.4 (5)
N1—C2—C7—C80.3 (4)N6—C14—C19—C18−179.5 (3)
C3—C2—C7—C8−179.8 (3)C15—C14—C19—C18−1.6 (5)
N1—C1—C8—C71.8 (4)N6—C14—C19—C12−1.1 (3)
N1—C1—C8—C9−176.2 (3)C15—C14—C19—C12176.9 (3)
C6—C7—C8—C1176.3 (4)C17—C18—C19—C141.5 (5)
C2—C7—C8—C1−1.3 (4)C17—C18—C19—C12−176.4 (3)
C6—C7—C8—C9−5.9 (7)C13—C12—C19—C140.7 (3)
C2—C7—C8—C9176.5 (3)C11—C12—C19—C14179.1 (3)
N3—N2—C9—C8−179.2 (3)C13—C12—C19—C18178.8 (3)
C1—C8—C9—N2169.4 (3)C11—C12—C19—C18−2.7 (6)
Symmetry codes: (i) −x+3/2, −y+3/2, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1n···O10.882.102.890 (4)148
N6—H6n···O1ii0.882.032.855 (4)156
Symmetry codes: (ii) −x+3/2, y−1/2, −z+1/2.
Table 1
Selected geometric parameters (Å) top
Ni1—N51.906 (3)Ni1—S12.1748 (8)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1n···O10.882.102.890 (4)148
N6—H6n···O1i0.882.032.855 (4)156
Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2.
Acknowledgements top

We thank the Science Fund (12–02-03–2031) for supporting this study, and the University of Malaya for the purchase of the diffractometer.

references
References top

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Ghosh, S., Chaudhury, S. P. & Ds, H. R. (1999). J. Ind. Chem. Soc. 76, 463–464.

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