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Acta Crystallogr Sect E Struct Rep Online. 2009 November 1; 65(Pt 11): o2951.
Published online 2009 October 31. doi:  10.1107/S1600536809044985
PMCID: PMC2971043

1,5-Bis[(E)-1-(2-hydroxy­phen­yl)ethyl­idene]carbonohydrazide dimethyl sulfoxide solvate

Abstract

The title dimethyl sulfoxide (DMSO) solvate, C17H18N4O3·C2H6OS, shows the disubstituted urea derivative to adopt an almost planar geometry (r.m.s. deviation for non-H atoms = 0.132 Å); the mol­ecule has non-crystallographic twofold mol­ecular symmetry. This conformation is stabilized by two intra­molecular O—H(...)N hydrogen bonds. The components of the crystal are connected by N—H(...)O hydrogen bonds, whereby both amine H atoms are connected to a DMSO O atom, and C—H(...)O contacts involving the DMSO H and urea carbonyl atoms, forming a supra­molecular chain along the c axis. The chains associate via C—H(...)π inter­actions.

Related literature

For background and recent studies on the biological activity of tin/organotin compounds, see: Gielen & Tiekink (2005 [triangle]); Affan et al. (2009 [triangle]).

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Object name is e-65-o2951-scheme1.jpg

Experimental

Crystal data

  • C17H18N4O3·C2H6OS
  • M r = 404.48
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2951-efi1.jpg
  • a = 15.3260 (19) Å
  • b = 7.1248 (7) Å
  • c = 18.439 (2) Å
  • β = 102.724 (2)°
  • V = 1964.0 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.20 mm−1
  • T = 153 K
  • 0.32 × 0.30 × 0.15 mm

Data collection

  • Rigaku Saturn724 diffractometer
  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995 [triangle]) T min = 0.661, T max = 1.000
  • 21771 measured reflections
  • 4493 independent reflections
  • 4369 reflections with I > 2σ(I)
  • R int = 0.030

Refinement

  • R[F 2 > 2σ(F 2)] = 0.041
  • wR(F 2) = 0.110
  • S = 1.08
  • 4493 reflections
  • 269 parameters
  • 4 restraints
  • H-atom parameters constrained
  • Δρmax = 0.32 e Å−3
  • Δρmin = −0.32 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SIR97 (Altomare et al., 1999 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: DIAMOND (Brandenburg, 2006 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks general, I. DOI: 10.1107/S1600536809044985/hb5198sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809044985/hb5198Isup2.hkl

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

Acknowledgments

The authors thank CNPq and FAPESP for support. The authors would also like to express their gratitude to the Ministry of Higher Education (MOHE) for a research grant [FRGS/01(05)610/2006(43)] and Universiti Malaysia Sarawak (UNIMAS) for the facilities to carry out the research work.

supplementary crystallographic information

Comment

The title compound, (I), was prepared as a part of on-going studies into the biological activity of organotin compounds (Gielen & Tiekink, 2005; Affan et al., 2009). Crystals of (I) comprise equal quantities of a disubstituted urea molecule and a solvent dimethyl sulfoxide molecule, Fig. 1. The urea derivative, which has molecular twofold symmetry (non-crystallographic), is essentially planar as seen in the r.m.s. value of 0.132 Å for all non-H atoms. The arrangement is stabilized by two internal O–H···N hydrogen bonds, Table 1.

In the crystal structure, the two amine-H atoms form hydrogen bonds to the DMSO-O atom to generate a supramolecular dimer, Table 1. The dimers thus formed are connected into a supramolecular chain along the c axis via C–H···O contacts involving the carbonyl-O4 atoms and DMSO-H atoms, Table 1 and Fig. 2. The chains are connected by C–H···π contacts to consolidate the crystal structure, Table 1 and Fig. 3.

Experimental

Carbohydrazide (0.90 g, 10 mmol) and 2-hydroxyacetophenone (2.72 g, 20 mmol) in dry methanol (40 ml) were heated at reflux for 4 h and cooled to ambient temperature. During cooling process, white microcrystals formed and were filtered off. The microcrystals, (I), were washed several times with small amounts of cold methanol and cold hexane. Crude (I) was recrystallized from methanol and dried in vacuo over silica gel. Yield: 1.99 g, 55%; m. pt. 467–468 K. Analysis. Calculated for C17H18N4O3: C, 62.56; H, 5.56; N, 17.17%. Found: C, 62.28; H, 5.61; N, 17.02%. UV-visible (DMSO) λmax: 282, 317, 382 nm. FT—IR (KBr disc) ν: 3453 (m, OH), 3346 (m, NH), 1701 (s, CONH), 1615 (s, C=N), 1000 (w, N—N) cm-1. 1H NMR (DMSO-d6) δ: 10.08 (s, 1H, OH), 8.30 (s, br, 1H, CONH), 7.78–7.76 (d, 1H, phenyl C3—H), 7.56–7.55 (d, 1H, phenyl C6—H), 7.27–7.24 (t, 1H, phenyl C4—H), 6.90–6.86 (t, 1H, phenyl C5—H), 2.31 (s, 3H, N=C—CH3) p.p.m. 13C NMR (CDCl3) δ: 168.19 (1 C, HN—C=O), 158.04 (2 C, C=N), 155.59, 151.98, 130.71, 128.06, 118.77, 117.09 (12 C, benzene ring), 13.16 (2 C, CH3) p.p.m. Crystals for the diffraction study were obtained from a dimethyl sulfoxide solution of (I).

Refinement

Carbon-bound H-atoms were placed in calculated positions (C–H 0.95–0.98 Å) and were included in the refinement in the riding model approximation with Uiso(H) set to 1.2–1.5Ueq(C). The O– and N-bound H-atoms were located in a difference Fourier map and were refined with O–H and N–H restraints of 0.840±0.001 Å and 0.880±0.001 Å, respectively, and with Uiso(H) = 1.2Ueq(N) and 1.5Ueq(O).

Figures

Fig. 1.
Molecular structures of the molecules comprising the asymmetric unit in (I) showing atom-labelling scheme and displacement ellipsoids at the 70% probability level.
Fig. 2.
Supramolecular chain formation along the c axis in (I) mediated by N–H···O (orange dashed lines) hydrogen bonds and C–H···O (green dashed lines) contacts.
Fig. 3.
View in projection down the a axis of the crystal packing in (I), highlighting the C–H···π interactions (purple dashed lines). The N–H···O (orange dashed lines) hydrogen bonds and ...

Crystal data

C17H18N4O3·C2H6OSF(000) = 856
Mr = 404.48Dx = 1.368 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 6256 reflections
a = 15.3260 (19) Åθ = 2.7–30.3°
b = 7.1248 (7) ŵ = 0.20 mm1
c = 18.439 (2) ÅT = 153 K
β = 102.724 (2)°Prism, colourless
V = 1964.0 (4) Å30.32 × 0.30 × 0.15 mm
Z = 4

Data collection

Rigaku Saturn724 diffractometer4493 independent reflections
Radiation source: sealed tube4369 reflections with I > 2σ(I)
graphiteRint = 0.030
Detector resolution: 28.5714 pixels mm-1θmax = 27.5°, θmin = 2.3°
ω scansh = −19→18
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)k = −9→9
Tmin = 0.661, Tmax = 1.000l = −23→23
21771 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.110H-atom parameters constrained
S = 1.08w = 1/[σ2(Fo2) + (0.0572P)2 + 0.8148P] where P = (Fo2 + 2Fc2)/3
4493 reflections(Δ/σ)max = 0.001
269 parametersΔρmax = 0.32 e Å3
4 restraintsΔρmin = −0.32 e Å3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

xyzUiso*/Ueq
O10.31503 (7)−0.00388 (17)0.72741 (5)0.0315 (2)
H1O0.27760.03520.69010.047*
O20.08573 (6)0.17694 (15)0.63438 (5)0.0258 (2)
O3−0.14836 (6)0.29124 (14)0.62863 (5)0.0248 (2)
H3O−0.10460.275660.60870.037*
N10.24627 (7)0.12659 (16)0.59756 (6)0.0207 (2)
N20.17027 (7)0.17151 (17)0.54592 (6)0.0221 (2)
H2N0.16830.18670.49820.026*
N30.02270 (7)0.24035 (16)0.51181 (6)0.0221 (2)
H3N0.03390.24750.46710.027*
N4−0.05924 (7)0.26766 (15)0.52770 (6)0.0204 (2)
C10.39368 (9)0.00078 (19)0.70500 (8)0.0233 (3)
C20.47033 (10)−0.0498 (2)0.75744 (8)0.0289 (3)
H20.4655−0.08550.80600.035*
C30.55316 (10)−0.0486 (2)0.73960 (9)0.0306 (3)
H30.6050−0.08260.77590.037*
C40.56065 (9)0.0023 (2)0.66867 (9)0.0304 (3)
H40.61760.00360.65620.037*
C50.48487 (9)0.0513 (2)0.61617 (8)0.0259 (3)
H50.49070.08480.56760.031*
C60.39962 (8)0.05313 (17)0.63249 (7)0.0200 (2)
C70.31992 (8)0.10518 (17)0.57510 (7)0.0195 (2)
C80.32461 (9)0.1268 (2)0.49519 (7)0.0256 (3)
H8A0.28590.03320.46510.038*
H8B0.38640.10820.49030.038*
H8C0.30460.25300.47800.038*
C90.09245 (8)0.19450 (18)0.56997 (7)0.0202 (3)
C10−0.12715 (8)0.30637 (18)0.47447 (7)0.0199 (3)
C11−0.12059 (9)0.3222 (2)0.39461 (7)0.0278 (3)
H11A−0.06590.39030.39170.042*
H11B−0.17270.39040.36650.042*
H11C−0.11890.19640.37350.042*
C12−0.21323 (8)0.33360 (17)0.49676 (7)0.0193 (2)
C13−0.21935 (9)0.32848 (18)0.57248 (7)0.0213 (3)
C14−0.30117 (9)0.36037 (19)0.59185 (8)0.0253 (3)
H14−0.30420.36180.64280.030*
C15−0.37788 (9)0.3899 (2)0.53742 (9)0.0282 (3)
H15−0.43330.41090.55120.034*
C16−0.37441 (9)0.3891 (2)0.46264 (8)0.0277 (3)
H16−0.42740.40610.42530.033*
C17−0.29285 (9)0.36309 (19)0.44331 (8)0.0240 (3)
H17−0.29070.36530.39220.029*
S10.88984 (2)0.73077 (5)0.686182 (17)0.02070 (11)
O40.88705 (7)0.75110 (16)0.60411 (5)0.0286 (2)
C180.79058 (9)0.8403 (2)0.70127 (8)0.0286 (3)
H18A0.78590.96730.68040.043*
H18B0.79300.84700.75480.043*
H18C0.73830.76660.67690.043*
C190.96707 (9)0.9044 (2)0.73080 (7)0.0258 (3)
H19A1.02730.87220.72500.039*
H19B0.96640.90930.78380.039*
H19C0.94991.02710.70810.039*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0242 (5)0.0477 (6)0.0232 (5)0.0023 (5)0.0068 (4)0.0100 (4)
O20.0235 (5)0.0351 (5)0.0197 (4)0.0028 (4)0.0067 (4)0.0018 (4)
O30.0235 (5)0.0322 (5)0.0190 (5)0.0008 (4)0.0053 (4)0.0004 (4)
N10.0187 (5)0.0233 (5)0.0197 (5)0.0011 (4)0.0030 (4)0.0000 (4)
N20.0183 (5)0.0312 (6)0.0165 (5)0.0013 (4)0.0033 (4)0.0017 (4)
N30.0179 (5)0.0305 (6)0.0190 (5)0.0015 (4)0.0062 (4)0.0013 (4)
N40.0177 (5)0.0226 (5)0.0219 (5)0.0000 (4)0.0065 (4)−0.0004 (4)
C10.0229 (6)0.0222 (6)0.0247 (6)−0.0002 (5)0.0051 (5)0.0021 (5)
C20.0289 (7)0.0282 (7)0.0276 (7)−0.0007 (6)0.0017 (5)0.0078 (6)
C30.0241 (7)0.0268 (7)0.0367 (8)0.0028 (6)−0.0026 (6)0.0054 (6)
C40.0204 (6)0.0315 (7)0.0392 (8)0.0020 (6)0.0062 (6)0.0000 (6)
C50.0224 (6)0.0287 (7)0.0272 (7)−0.0001 (5)0.0065 (5)−0.0016 (5)
C60.0193 (6)0.0188 (6)0.0216 (6)−0.0002 (5)0.0039 (5)−0.0014 (5)
C70.0210 (6)0.0190 (6)0.0191 (6)−0.0007 (5)0.0058 (5)−0.0016 (4)
C80.0241 (6)0.0342 (7)0.0194 (6)0.0016 (5)0.0064 (5)0.0000 (5)
C90.0205 (6)0.0200 (6)0.0204 (6)−0.0010 (5)0.0049 (5)−0.0004 (5)
C100.0212 (6)0.0183 (6)0.0204 (6)−0.0014 (5)0.0054 (5)−0.0007 (5)
C110.0242 (6)0.0390 (8)0.0210 (6)0.0024 (6)0.0067 (5)0.0027 (6)
C120.0190 (6)0.0174 (5)0.0217 (6)−0.0012 (5)0.0051 (5)−0.0010 (5)
C130.0225 (6)0.0182 (6)0.0238 (6)−0.0022 (5)0.0062 (5)−0.0011 (5)
C140.0277 (7)0.0238 (6)0.0276 (6)−0.0011 (5)0.0129 (5)−0.0018 (5)
C150.0213 (6)0.0269 (7)0.0395 (8)0.0004 (5)0.0130 (6)−0.0019 (6)
C160.0198 (6)0.0289 (7)0.0328 (7)0.0016 (5)0.0024 (5)0.0000 (6)
C170.0232 (6)0.0242 (6)0.0242 (6)−0.0003 (5)0.0042 (5)−0.0012 (5)
S10.01945 (17)0.02472 (18)0.01720 (17)0.00048 (11)0.00244 (12)−0.00063 (11)
O40.0223 (5)0.0470 (6)0.0162 (5)0.0010 (4)0.0034 (4)−0.0024 (4)
C180.0214 (6)0.0409 (8)0.0241 (6)0.0025 (6)0.0060 (5)−0.0001 (6)
C190.0239 (6)0.0318 (7)0.0206 (6)−0.0056 (5)0.0027 (5)−0.0006 (5)

Geometric parameters (Å, °)

O1—C11.3580 (16)C8—H8B0.9800
O1—H1O0.8401C8—H8C0.9800
O2—C91.2210 (16)C10—C121.4785 (17)
O3—C131.3528 (16)C10—C111.5021 (17)
O3—H3O0.8400C11—H11A0.9800
N1—C71.2942 (16)C11—H11B0.9800
N1—N21.3700 (15)C11—H11C0.9800
N2—C91.3707 (16)C12—C171.4053 (18)
N2—H2N0.8799C12—C131.4202 (17)
N3—N41.3648 (15)C13—C141.3961 (18)
N3—C91.3764 (17)C14—C151.383 (2)
N3—H3N0.8799C14—H140.9500
N4—C101.2933 (17)C15—C161.392 (2)
C1—C21.3944 (19)C15—H150.9500
C1—C61.4103 (18)C16—C171.3856 (19)
C2—C31.380 (2)C16—H160.9500
C2—H20.9500C17—H170.9500
C3—C41.386 (2)S1—O41.5115 (10)
C3—H30.9500S1—C191.7830 (14)
C4—C51.383 (2)S1—C181.7852 (14)
C4—H40.9500C18—H18A0.9800
C5—C61.4039 (18)C18—H18B0.9800
C5—H50.9500C18—H18C0.9800
C6—C71.4765 (17)C19—H19A0.9800
C7—C81.4987 (17)C19—H19B0.9800
C8—H8A0.9800C19—H19C0.9800
C1—O1—H1O103.5N4—C10—C11122.93 (11)
C13—O3—H3O106.0C12—C10—C11121.27 (11)
C7—N1—N2118.23 (11)C10—C11—H11A109.5
N1—N2—C9118.05 (10)C10—C11—H11B109.5
N1—N2—H2N124.1H11A—C11—H11B109.5
C9—N2—H2N117.9C10—C11—H11C109.5
N4—N3—C9117.39 (11)H11A—C11—H11C109.5
N4—N3—H3N124.8H11B—C11—H11C109.5
C9—N3—H3N117.7C17—C12—C13117.26 (11)
C10—N4—N3119.49 (11)C17—C12—C10120.98 (11)
O1—C1—C2116.83 (12)C13—C12—C10121.75 (11)
O1—C1—C6122.81 (11)O3—C13—C14116.90 (12)
C2—C1—C6120.35 (12)O3—C13—C12122.77 (11)
C3—C2—C1120.79 (13)C14—C13—C12120.33 (12)
C3—C2—H2119.6C15—C14—C13120.45 (13)
C1—C2—H2119.6C15—C14—H14119.8
C2—C3—C4119.89 (13)C13—C14—H14119.8
C2—C3—H3120.1C14—C15—C16120.42 (12)
C4—C3—H3120.1C14—C15—H15119.8
C5—C4—C3119.68 (13)C16—C15—H15119.8
C5—C4—H4120.2C17—C16—C15119.28 (13)
C3—C4—H4120.2C17—C16—H16120.4
C4—C5—C6122.01 (13)C15—C16—H16120.4
C4—C5—H5119.0C16—C17—C12122.19 (12)
C6—C5—H5119.0C16—C17—H17118.9
C5—C6—C1117.27 (12)C12—C17—H17118.9
C5—C6—C7120.72 (12)O4—S1—C19105.37 (6)
C1—C6—C7122.01 (11)O4—S1—C18106.08 (6)
N1—C7—C6116.26 (11)C19—S1—C1897.28 (7)
N1—C7—C8122.45 (11)S1—C18—H18A109.5
C6—C7—C8121.28 (11)S1—C18—H18B109.5
C7—C8—H8A109.5H18A—C18—H18B109.5
C7—C8—H8B109.5S1—C18—H18C109.5
H8A—C8—H8B109.5H18A—C18—H18C109.5
C7—C8—H8C109.5H18B—C18—H18C109.5
H8A—C8—H8C109.5S1—C19—H19A109.5
H8B—C8—H8C109.5S1—C19—H19B109.5
O2—C9—N2124.62 (12)H19A—C19—H19B109.5
O2—C9—N3124.39 (12)S1—C19—H19C109.5
N2—C9—N3110.99 (11)H19A—C19—H19C109.5
N4—C10—C12115.80 (11)H19B—C19—H19C109.5
C7—N1—N2—C9−179.85 (12)N1—N2—C9—N3179.57 (11)
C9—N3—N4—C10−178.29 (11)N4—N3—C9—O20.0 (2)
O1—C1—C2—C3−179.82 (13)N4—N3—C9—N2−179.96 (11)
C6—C1—C2—C30.3 (2)N3—N4—C10—C12179.97 (11)
C1—C2—C3—C4−0.4 (2)N3—N4—C10—C110.31 (19)
C2—C3—C4—C5−0.1 (2)N4—C10—C12—C17−175.46 (12)
C3—C4—C5—C60.6 (2)C11—C10—C12—C174.20 (19)
C4—C5—C6—C1−0.6 (2)N4—C10—C12—C133.63 (18)
C4—C5—C6—C7−179.69 (13)C11—C10—C12—C13−176.71 (12)
O1—C1—C6—C5−179.69 (13)C17—C12—C13—O3176.40 (12)
C2—C1—C6—C50.1 (2)C10—C12—C13—O3−2.72 (19)
O1—C1—C6—C7−0.6 (2)C17—C12—C13—C14−2.83 (18)
C2—C1—C6—C7179.18 (12)C10—C12—C13—C14178.05 (12)
N2—N1—C7—C6−178.82 (11)O3—C13—C14—C15−176.70 (12)
N2—N1—C7—C8−0.32 (19)C12—C13—C14—C152.6 (2)
C5—C6—C7—N1−171.33 (12)C13—C14—C15—C16−0.3 (2)
C1—C6—C7—N19.66 (18)C14—C15—C16—C17−1.7 (2)
C5—C6—C7—C810.15 (19)C15—C16—C17—C121.3 (2)
C1—C6—C7—C8−168.86 (12)C13—C12—C17—C160.9 (2)
N1—N2—C9—O2−0.4 (2)C10—C12—C17—C16−179.98 (12)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1o···N10.841.792.5682 (15)153
O3—H3o···N40.841.782.5450 (15)150
N2—H2n···O4i0.881.942.7674 (15)156
N3—H3n···O4i0.881.972.7907 (15)154
C19—H19b···O2ii0.982.493.2167 (17)131
C8—H8A···Cg2iii0.982.833.5018 (16)127

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y+1/2, −z+3/2; (iii) −x, −y, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5198).

References

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