PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2008 June 1; 64(Pt 6): m755.
Published online 2008 May 3. doi:  10.1107/S1600536808011975
PMCID: PMC2961539

Bis[1,5-bis­(1H-indol-3-ylmethyl­ene)thio­carbazonato-κ2 N,S]nickel(II) dimethyl sulfoxide disolvate

Abstract

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.

Related literature

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

An external file that holds a picture, illustration, etc.
Object name is e-64-0m755-scheme1.jpg

Experimental

Crystal data

  • [Ni(C19H15N6S)2]·2C2H6OS
  • M r = 933.83
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0m755-efi1.jpg
  • a = 19.0340 (5) Å
  • b = 9.1982 (3) Å
  • c = 25.1374 (7) Å
  • β = 95.672 (2)°
  • V = 4379.5 (2) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.69 mm−1
  • T = 100 (2) K
  • 0.30 × 0.03 × 0.03 mm

Data collection

  • Bruker SMART APEX diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.821, T max = 0.980
  • 27119 measured reflections
  • 5030 independent reflections
  • 3201 reflections with I > 2σ(I)
  • R int = 0.092

Refinement

  • R[F 2 > 2σ(F 2)] = 0.048
  • wR(F 2) = 0.139
  • S = 1.03
  • 5030 reflections
  • 277 parameters
  • H-atom parameters constrained
  • Δρmax = 0.60 e Å−3
  • Δρmin = −0.53 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: publCIF (Westrip, 2008 [triangle]).

Table 1
Selected bond lengths (Å)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808011975/bt2702sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808011975/bt2702Isup2.hkl

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

Acknowledgments

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

supplementary crystallographic information

Comment

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.

Experimental

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

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].

Figures

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 ...

Crystal data

[Ni(C19H15N6S)2]·2C2H6OSF000 = 1944
Mr = 933.83Dx = 1.416 Mg m3
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 mm1
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

Bruker SMART APEX diffractometer5030 independent reflections
Radiation source: fine-focus sealed tube3201 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.092
T = 100(2) Kθmax = 27.5º
[var phi] 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

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 Å3
277 parametersΔρmin = −0.53 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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)

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)

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, °)

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, °)

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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT2702).

References

  • 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.
  • Rizal, M. R., Ali, H. M. & Ng, S. W. (2008). Acta Cryst. E64 submitted (sg2241).
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2008). publCIF In preparation.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography