Literature DB >> 22091213

A monoclinic polymorph of (1E,5E)-1,5-bis-(2-hy-droxy-benzyl-idene)thio-carbono-hydrazide.

Bonell Schmitt1, Thomas Gerber, Eric Hosten, Richard Betz.   

Abstract

The title compound, C(15)H(14)N(4)O(2)S, is a derivative of thio-ureadihydrazide. In contrast to the previously reported polymorph (ortho-rhom-bic, space group Pbca, Z = 8), the current study revealed monoclinic symmetry (space group P2(1)/n, Z = 4). The mol-ecule shows non-crystallographic C(2) as well as approximate C(s) symmetry. Intra-molecular bifurcated O-H⋯(N,S) hydrogen bonds, are present. In the crystal, inter-molecular N-H⋯S hydrogen bonds and C-H⋯π contacts connect the mol-ecules into undulating chains along the b axis. The shortest centroid-centroid distance between two aromatic systems is 4.5285 (12) Å.

Entities:  

Year:  2011        PMID： 22091213      PMCID： PMC3213636          DOI： 10.1107/S1600536811030340

Source DB:  PubMed          Journal:  Acta Crystallogr Sect E Struct Rep Online        ISSN： 1600-5368


Related literature

For the crystal structure of the ortho­rhom­bic polymorph of the title compound reported without three-dimensional coordinates, see: Yanping et al. (1999 ▶). For the crystal structure of a methyl­ated derivative of the title compound, see: Affan et al. (2010 ▶). For graph-set analysis of hydrogen bonds, see: Etter et al. (1990 ▶); Bernstein et al. (1995 ▶). Structures containing similar C=S distances were retrieved from the Cambridge Structural Database (Allen, 2002 ▶). For chelate ligands in coordination chemistry, see: Gade (1998 ▶).

Experimental

Crystal data

C15H14N4O2S M = 314.36 Monoclinic, a = 5.6020 (1) Å b = 7.4260 (2) Å c = 34.5220 (8) Å β = 91.225 (1)° V = 1435.80 (6) Å3 Z = 4 Mo Kα radiation μ = 0.24 mm−1 T = 200 K 0.20 × 0.17 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.879, T max = 1.000 13304 measured reflections 3578 independent reflections 2830 reflections with I > 2σ(I) R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.048 wR(F 2) = 0.116 S = 1.11 3578 reflections 209 parameters H atoms treated by a mixture of independent and constrained refinement Δρmax = 0.31 e Å−3 Δρmin = −0.30 e Å−3 Data collection: APEX2 (Bruker, 2010 ▶); cell refinement: SAINT (Bruker, 2010 ▶); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶). Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811030340/kj2182sup1.cif Supplementary material file. DOI: 10.1107/S1600536811030340/kj2182Isup2.cdx Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811030340/kj2182Isup3.hkl Supplementary material file. DOI: 10.1107/S1600536811030340/kj2182Isup4.cml Additional supplementary materials: crystallographic information; 3D view; checkCIF report
C15H14N4O2SF(000) = 656
Mr = 314.36Dx = 1.454 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybcCell parameters from 3781 reflections
a = 5.6020 (1) Åθ = 3.3–28.2°
b = 7.4260 (2) ŵ = 0.24 mm−1
c = 34.5220 (8) ÅT = 200 K
β = 91.225 (1)°Block, colourless
V = 1435.80 (6) Å30.20 × 0.17 × 0.10 mm
Z = 4
Bruker APEXII CCD diffractometer3578 independent reflections
Radiation source: fine-focus sealed tube2830 reflections with I > 2σ(I)
graphiteRint = 0.027
φ and ω scansθmax = 28.3°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2008)h = −7→7
Tmin = 0.879, Tmax = 1.000k = −9→9
13304 measured reflectionsl = −46→45
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116H atoms treated by a mixture of independent and constrained refinement
S = 1.11w = 1/[σ2(Fo2) + (0.0459P)2 + 0.6828P] where P = (Fo2 + 2Fc2)/3
3578 reflections(Δ/σ)max < 0.001
209 parametersΔρmax = 0.31 e Å−3
0 restraintsΔρmin = −0.30 e Å−3
xyzUiso*/Ueq
S10.12373 (8)0.21558 (7)0.258163 (14)0.02903 (14)
O10.1741 (2)0.2387 (2)0.36537 (4)0.0324 (3)
H810.22030.26370.34300.049*
O2−0.1378 (2)0.2458 (2)0.15547 (4)0.0383 (4)
H82−0.03820.27230.17310.057*
N10.5251 (3)0.3922 (2)0.27723 (4)0.0281 (4)
H710.646 (4)0.457 (3)0.2711 (6)0.037 (6)*
N20.4749 (3)0.3542 (2)0.31484 (4)0.0265 (3)
N30.4199 (3)0.4051 (2)0.21391 (5)0.0294 (4)
H730.546 (5)0.466 (4)0.2103 (7)0.053 (8)*
N40.2684 (3)0.3694 (2)0.18331 (4)0.0274 (3)
C10.3648 (3)0.3442 (2)0.24941 (5)0.0248 (4)
C20.6209 (3)0.4048 (2)0.34167 (5)0.0256 (4)
H20.76740.46130.33550.031*
C30.3279 (3)0.4210 (2)0.14954 (5)0.0255 (4)
H30.47390.48340.14600.031*
C110.5583 (3)0.3740 (2)0.38171 (5)0.0237 (4)
C120.3391 (3)0.2956 (3)0.39193 (5)0.0258 (4)
C130.2860 (3)0.2726 (3)0.43090 (6)0.0303 (4)
H130.13910.21860.43780.036*
C140.4458 (4)0.3279 (3)0.45949 (6)0.0319 (4)
H140.40730.31260.48600.038*
C150.6625 (4)0.4057 (3)0.44992 (6)0.0312 (4)
H150.77180.44390.46970.037*
C160.7166 (3)0.4266 (3)0.41139 (6)0.0270 (4)
H160.86560.47830.40490.032*
C210.1696 (3)0.3832 (2)0.11659 (5)0.0239 (4)
C22−0.0524 (3)0.2973 (3)0.12065 (6)0.0287 (4)
C23−0.1919 (4)0.2586 (3)0.08796 (6)0.0345 (5)
H23−0.34130.20000.09070.041*
C24−0.1148 (4)0.3048 (3)0.05168 (6)0.0368 (5)
H24−0.21140.27720.02950.044*
C250.1036 (4)0.3915 (3)0.04711 (6)0.0336 (5)
H250.15620.42340.02210.040*
C260.2414 (3)0.4301 (3)0.07948 (5)0.0277 (4)
H260.38960.49030.07650.033*
U11U22U33U12U13U23
S10.0237 (2)0.0299 (3)0.0336 (3)−0.0028 (2)0.00372 (17)0.0010 (2)
O10.0251 (7)0.0398 (8)0.0323 (7)−0.0086 (6)0.0007 (5)0.0014 (6)
O20.0254 (7)0.0448 (9)0.0447 (8)−0.0075 (6)0.0017 (6)0.0091 (7)
N10.0250 (8)0.0338 (9)0.0255 (8)−0.0060 (7)0.0014 (6)0.0048 (7)
N20.0276 (8)0.0275 (8)0.0245 (8)0.0005 (7)0.0027 (6)0.0037 (6)
N30.0279 (8)0.0351 (10)0.0250 (8)−0.0074 (7)−0.0010 (6)0.0033 (7)
N40.0258 (8)0.0285 (9)0.0277 (8)−0.0019 (7)−0.0019 (6)−0.0007 (7)
C10.0240 (9)0.0211 (9)0.0292 (9)0.0036 (7)0.0019 (7)0.0003 (7)
C20.0230 (9)0.0236 (9)0.0303 (9)−0.0002 (7)0.0023 (7)0.0041 (7)
C30.0235 (9)0.0235 (9)0.0296 (9)−0.0008 (7)−0.0003 (7)−0.0003 (7)
C110.0233 (8)0.0193 (9)0.0286 (9)0.0021 (7)0.0031 (7)0.0026 (7)
C120.0226 (8)0.0226 (9)0.0322 (9)0.0013 (7)0.0016 (7)0.0008 (8)
C130.0265 (9)0.0299 (10)0.0347 (10)0.0021 (8)0.0073 (8)0.0050 (8)
C140.0372 (11)0.0314 (11)0.0273 (9)0.0063 (9)0.0054 (8)0.0023 (8)
C150.0358 (10)0.0312 (11)0.0264 (9)0.0010 (9)−0.0037 (8)−0.0011 (8)
C160.0234 (9)0.0235 (9)0.0340 (10)−0.0007 (7)−0.0018 (7)0.0009 (7)
C210.0224 (8)0.0197 (9)0.0296 (9)0.0029 (7)−0.0016 (7)−0.0014 (7)
C220.0230 (8)0.0233 (9)0.0397 (10)0.0028 (8)−0.0002 (7)0.0021 (8)
C230.0250 (9)0.0249 (10)0.0534 (13)0.0002 (8)−0.0081 (9)−0.0013 (9)
C240.0354 (11)0.0314 (11)0.0428 (11)0.0076 (9)−0.0158 (9)−0.0074 (9)
C250.0367 (11)0.0353 (12)0.0288 (10)0.0099 (9)−0.0027 (8)−0.0024 (8)
C260.0254 (9)0.0255 (10)0.0319 (10)0.0032 (8)−0.0002 (8)0.0008 (8)
S1—C11.6867 (19)C12—C131.394 (3)
O1—C121.356 (2)C13—C141.381 (3)
O1—H810.8400C13—H130.9500
O2—C221.359 (2)C14—C151.390 (3)
O2—H820.8400C14—H140.9500
N1—C11.349 (2)C15—C161.379 (3)
N1—N21.364 (2)C15—H150.9500
N1—H710.86 (2)C16—H160.9500
N2—C21.279 (2)C21—C261.395 (3)
N3—C11.348 (2)C21—C221.407 (3)
N3—N41.367 (2)C22—C231.389 (3)
N3—H730.85 (3)C23—C241.377 (3)
N4—C31.278 (2)C23—H230.9500
C2—C111.451 (2)C24—C251.394 (3)
C2—H20.9500C24—H240.9500
C3—C211.455 (2)C25—C261.375 (3)
C3—H30.9500C25—H250.9500
C11—C161.396 (3)C26—H260.9500
C11—C121.411 (2)
C12—O1—H81109.5C13—C14—C15120.65 (17)
C22—O2—H82109.5C13—C14—H14119.7
C1—N1—N2118.38 (15)C15—C14—H14119.7
C1—N1—H71119.2 (15)C16—C15—C14119.13 (18)
N2—N1—H71121.9 (15)C16—C15—H15120.4
C2—N2—N1119.14 (16)C14—C15—H15120.4
C1—N3—N4119.14 (16)C15—C16—C11121.80 (18)
C1—N3—H73121.2 (17)C15—C16—H16119.1
N4—N3—H73119.7 (17)C11—C16—H16119.1
C3—N4—N3118.46 (16)C26—C21—C22118.51 (17)
N3—C1—N1113.38 (16)C26—C21—C3119.15 (16)
N3—C1—S1123.54 (14)C22—C21—C3122.33 (17)
N1—C1—S1123.06 (14)O2—C22—C23117.24 (17)
N2—C2—C11118.67 (16)O2—C22—C21123.01 (17)
N2—C2—H2120.7C23—C22—C21119.73 (18)
C11—C2—H2120.7C24—C23—C22120.37 (19)
N4—C3—C21119.25 (17)C24—C23—H23119.8
N4—C3—H3120.4C22—C23—H23119.8
C21—C3—H3120.4C23—C24—C25120.72 (19)
C16—C11—C12118.32 (17)C23—C24—H24119.6
C16—C11—C2119.49 (16)C25—C24—H24119.6
C12—C11—C2122.18 (17)C26—C25—C24118.90 (19)
O1—C12—C13117.24 (16)C26—C25—H25120.6
O1—C12—C11122.97 (16)C24—C25—H25120.6
C13—C12—C11119.79 (17)C25—C26—C21121.76 (18)
C14—C13—C12120.30 (18)C25—C26—H26119.1
C14—C13—H13119.9C21—C26—H26119.1
C12—C13—H13119.9
C1—N1—N2—C2−177.46 (17)C13—C14—C15—C16−0.2 (3)
C1—N3—N4—C3−176.94 (18)C14—C15—C16—C110.8 (3)
N4—N3—C1—N1−178.39 (16)C12—C11—C16—C15−0.7 (3)
N4—N3—C1—S13.2 (3)C2—C11—C16—C15177.92 (17)
N2—N1—C1—N3173.21 (16)N4—C3—C21—C26−176.19 (17)
N2—N1—C1—S1−8.4 (2)N4—C3—C21—C222.4 (3)
N1—N2—C2—C11176.08 (16)C26—C21—C22—O2179.74 (17)
N3—N4—C3—C21179.64 (16)C3—C21—C22—O21.1 (3)
N2—C2—C11—C16179.37 (17)C26—C21—C22—C231.1 (3)
N2—C2—C11—C12−2.0 (3)C3—C21—C22—C23−177.55 (17)
C16—C11—C12—O1−179.45 (17)O2—C22—C23—C24−179.10 (18)
C2—C11—C12—O11.9 (3)C21—C22—C23—C24−0.4 (3)
C16—C11—C12—C130.0 (3)C22—C23—C24—C25−0.2 (3)
C2—C11—C12—C13−178.65 (17)C23—C24—C25—C260.1 (3)
O1—C12—C13—C14−179.87 (17)C24—C25—C26—C210.6 (3)
C11—C12—C13—C140.7 (3)C22—C21—C26—C25−1.2 (3)
C12—C13—C14—C15−0.6 (3)C3—C21—C26—C25177.45 (17)
Cg1 and Cg2 are the centroids of the C11–C16 and C21–C26 rings, respectively.
D—H···AD—HH···AD···AD—H···A
O1—H81···N20.841.872.597 (2)144.
O1—H81···S10.842.993.7096 (14)145.
O2—H82···N40.841.892.617 (2)144.
O2—H82···S10.843.083.8135 (16)147.
N1—H71···S1i0.86 (2)2.53 (2)3.3514 (17)159 (2)
N3—H73···S1i0.85 (3)2.82 (3)3.5605 (18)147 (2)
C16—H16···Cg2i0.952.813.423 (2)123
C26—H26···Cg1i0.952.743.438 (2)130
Table 1

Hydrogen-bond geometry (Å, °)

C g1 and C g2 are the centroids of the C11–C16 and C21–C26 rings, respectively.

D—H⋯AD—HH⋯AD⋯AD—H⋯A
O1—H81⋯N20.841.872.597 (2)144
O1—H81⋯S10.842.993.7096 (14)145
O2—H82⋯N40.841.892.617 (2)144
O2—H82⋯S10.843.083.8135 (16)147
N1—H71⋯S1i0.86 (2)2.53 (2)3.3514 (17)159 (2)
N3—H73⋯S1i0.85 (3)2.82 (3)3.5605 (18)147 (2)
C16—H16⋯Cg2i0.952.813.423 (2)123
C26—H26⋯Cg1i0.952.743.438 (2)130

Symmetry code: (i) .

  5 in total

1.  The Cambridge Structural Database: a quarter of a million crystal structures and rising.

Authors:  Frank H Allen
Journal:  Acta Crystallogr B       Date:  2002-05-29

2.  A short history of SHELX.

Authors:  George M Sheldrick
Journal:  Acta Crystallogr A       Date:  2007-12-21       Impact factor: 2.290

3.  Graph-set analysis of hydrogen-bond patterns in organic crystals.

Authors:  M C Etter; J C MacDonald; J Bernstein
Journal:  Acta Crystallogr B       Date:  1990-04-01

4.  1,5-Bis[(E)-1-(2-hydroxyphenyl)ethyl-idene]thiocarbonohydrazide mono-hydrate.

Authors:  Md Abu Affan; Dayang N A Chee; Fasihuddin B Ahmad; Edward R T Tiekink
Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2010-02-06

5.  Structure validation in chemical crystallography.

Authors:  Anthony L Spek
Journal:  Acta Crystallogr D Biol Crystallogr       Date:  2009-01-20
  5 in total
  1 in total

1.  1,5-Bis[1-(4-bromo-phen-yl)ethyl-idene]thio-carbonohydrazide.

Authors:  Zhiqing Gao
Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2013-04-13
  1 in total

北京卡尤迪生物科技股份有限公司 © 2022-2023.