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Acta Crystallogr Sect E Struct Rep Online. 2008 November 1; 64(Pt 11): o2144.
Published online 2008 October 18. doi:  10.1107/S1600536808033515
PMCID: PMC2959582

The cocrystal 2-hydr­oxy-4-methyl-N-propanoylbenzohydrazide–2-hydr­oxy-N-(2-hydr­oxy-4-methyl­benzo­yl)-6-methyl­benzohydrazide (2/1)

Abstract

The asymmetric unit of the title compound, 2C11H14N2O3·C16H16N2O4, contains one mol­ecule of 2-hydr­oxy-4-methyl-N-propanoylbenzohydrazide and one-half of a mol­ecule of 2-hydr­oxy-N-(2-hydr­oxy-4-methyl­benzo­yl)-6-methyl­benzohydrazide. The latter is located on a centre of inversion. Intra­molecular N—H(...)O inter­actions stabilize the conformations of both mol­ecules. The crystal structure is stabilized by inter­molecular N—H(...)O and O—H(...)O hydrogen bonds.

Related literature

For related literature, see: John et al. (2007 [triangle]); Majumder et al. (2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o2144-scheme1.jpg

Experimental

Crystal data

  • 2C11H14N2O3·C16H16N2O4
  • M r = 744.79
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2144-efi1.jpg
  • a = 6.5778 (10) Å
  • b = 10.7618 (17) Å
  • c = 13.936 (2) Å
  • α = 109.522 (3)°
  • β = 93.608 (1)°
  • γ = 104.448 (4)°
  • V = 888.8 (2) Å3
  • Z = 1
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 296 (2) K
  • 0.54 × 0.30 × 0.25 mm

Data collection

  • Bruker APEXII diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.964, T max = 0.975
  • 5076 measured reflections
  • 4125 independent reflections
  • 1865 reflections with I > 2σ(I)
  • R int = 0.022

Refinement

  • R[F 2 > 2σ(F 2)] = 0.037
  • wR(F 2) = 0.110
  • S = 0.90
  • 4125 reflections
  • 246 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.20 e Å−3
  • Δρmin = −0.22 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: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808033515/bt2793sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808033515/bt2793Isup2.hkl

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

Acknowledgments

This project was supported by the Talent Fund of Ningbo University (grant No. 2006668) and sponsored by the K. C. Wong Magna Fund of Ningbo University.

supplementary crystallographic information

Comment

N-Acylsalicylhydrazides are an interesting class of compounds because of their unique properties. They have been used extensively as ligands in coordination chemistry. N-acylsalicylhydrazide compounds show photoluminescence in the solid state by proton transfer from O atom to the imine N atom (Majumder et al., 2006). The nuclearity and the shape of the metallamacrocycles could be modulated by controlling the steric interactions caused by N-acyl tails of the ligands (John et al., 2007).

A view of the title structure is illustrated in Fig. 1. The asymmetric unit contains one molecule of 2-hydroxy-4-methyl-N-propanoylbenzohydrazide and half a molecule of 2-hydroxy-N-(2-hydroxy-4-methylbenzoyl)-6-methylbenzohydrazide.

The molecular conformation is characterized by N—H···O hydrogen bonds and the crystal packing is stabilized by N—H···O and O—H···O hydrogen bonds (Fig. 2).

Experimental

Propionic anhydride (0.26 g, 2.00 mmol) and 2-hydroxy-4-methylbenzohydrazide (0.31 g, 1.80 mmol) were stirred with an external ice-water bath in DMF (20 ml) for 6 h. The filtrate was evaporated on a rotary evaporator. After recrystallization, the title compound were obtained.

Refinement

All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms (C—H = 0.93 Å; N—H = 0.86 Å; O—H = 0.82 Å) and Uiso(H) values were set to 1.2Ueq(C, N) and 1.5Ueq(O).

Figures

Fig. 1.
The structure of (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme [symmetry code: (A) -x + 2, -y + 1, -z].
Fig. 2.
Packing diagram of the title compound.

Crystal data

2C11H14N2O3·C16H16N2O4Z = 1
Mr = 744.79F(000) = 394
Triclinic, P1Dx = 1.391 Mg m3
Hall symbol: -P 1Melting point = 488–496 K
a = 6.5778 (10) ÅMo Kα radiation, λ = 0.71073 Å
b = 10.7618 (17) ÅCell parameters from 6530 reflections
c = 13.936 (2) Åθ = 1.0–27.6°
α = 109.522 (3)°µ = 0.10 mm1
β = 93.608 (1)°T = 296 K
γ = 104.448 (4)°Block, colourless
V = 888.8 (2) Å30.54 × 0.30 × 0.25 mm

Data collection

Bruker APEXII diffractometer4125 independent reflections
Radiation source: fine-focus sealed tube1865 reflections with I > 2σ(I)
graphiteRint = 0.022
Detector resolution: 0 pixels mm-1θmax = 27.6°, θmin = 1.0°
ω scansh = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 2005)k = −14→14
Tmin = 0.964, Tmax = 0.975l = −18→18
5076 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)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.110H atoms treated by a mixture of independent and constrained refinement
S = 0.90w = 1/[σ2(Fo2) + (0.0665P)2 + 0.5716P] where P = (Fo2 + 2Fc2)/3
4125 reflections(Δ/σ)max = 0.001
246 parametersΔρmax = 0.20 e Å3
0 restraintsΔρmin = −0.22 e Å3

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.
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 > σ(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
C11.5753 (4)1.1759 (2)0.25135 (19)0.0371 (6)
H1A1.62411.27450.28190.056*
H1B1.54481.14830.17770.056*
H1C1.68361.13820.26890.056*
C21.3767 (3)1.1237 (2)0.29126 (16)0.0272 (5)
C31.2717 (3)1.2119 (2)0.35009 (16)0.0302 (5)
H3A1.32471.30620.36590.036*
C41.0896 (3)1.1610 (2)0.38542 (16)0.0272 (5)
H4A1.02271.22220.42510.033*
C51.2941 (3)0.9840 (2)0.27002 (16)0.0271 (5)
H5A1.36390.92360.23170.032*
C61.1100 (3)0.9315 (2)0.30440 (15)0.0243 (5)
C71.0027 (3)1.0199 (2)0.36312 (15)0.0230 (5)
C80.8034 (3)0.9769 (2)0.40407 (15)0.0230 (5)
C90.4670 (3)0.6593 (2)0.40029 (15)0.0272 (5)
C100.2783 (3)0.6153 (2)0.44886 (17)0.0356 (6)
H10A0.24940.69630.49560.043*
H10B0.31170.56250.48900.043*
C110.0800 (4)0.5283 (3)0.3690 (2)0.0434 (6)
H11A−0.03620.50220.40340.065*
H11B0.10710.44720.32320.065*
H11C0.04420.58090.33030.065*
C122.0539 (4)0.8165 (3)−0.0799 (2)0.0423 (6)
H12A2.02820.8592−0.12810.063*
H12B2.11200.7422−0.11220.063*
H12C2.15280.8831−0.02080.063*
C131.8475 (3)0.7613 (2)−0.04652 (17)0.0312 (5)
C141.8192 (3)0.8096 (2)0.05601 (17)0.0331 (5)
H14A1.92930.87690.10540.040*
C151.6810 (3)0.6616 (2)−0.11824 (16)0.0293 (5)
H15A1.69850.6282−0.18700.035*
C161.4884 (3)0.6101 (2)−0.08999 (16)0.0267 (5)
C171.6287 (3)0.7582 (2)0.08499 (17)0.0320 (5)
H17A1.61360.79100.15410.038*
C181.4587 (3)0.6587 (2)0.01368 (16)0.0257 (5)
C191.2600 (3)0.6131 (2)0.05327 (16)0.0252 (5)
N10.7128 (3)0.84114 (17)0.37670 (13)0.0273 (4)
H1D0.76630.78380.33470.033*
N20.5341 (3)0.79291 (17)0.41560 (13)0.0263 (4)
H2A0.46720.84840.44920.032*
O41.2460 (2)0.65694 (15)0.14648 (11)0.0333 (4)
O11.0312 (2)0.79309 (14)0.28105 (11)0.0322 (4)
H1E1.10840.75330.24670.048*
O20.7227 (2)1.06102 (14)0.45964 (11)0.0314 (4)
O30.5567 (2)0.57635 (14)0.34881 (11)0.0329 (4)
N31.0943 (3)0.52334 (18)−0.01587 (15)0.0291 (5)
O51.3246 (2)0.51267 (15)−0.16289 (12)0.0333 (4)
H3B1.104 (4)0.490 (2)−0.0786 (19)0.036 (7)*
H5B1.368 (4)0.481 (3)−0.223 (2)0.055 (8)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0265 (12)0.0416 (14)0.0485 (14)0.0077 (11)0.0136 (10)0.0233 (11)
C20.0192 (11)0.0345 (13)0.0299 (12)0.0067 (10)0.0031 (9)0.0148 (10)
C30.0249 (12)0.0268 (12)0.0401 (13)0.0045 (10)0.0048 (10)0.0158 (10)
C40.0249 (12)0.0262 (12)0.0316 (12)0.0094 (10)0.0067 (9)0.0100 (9)
C50.0226 (12)0.0307 (12)0.0293 (12)0.0108 (10)0.0085 (9)0.0096 (9)
C60.0235 (12)0.0234 (12)0.0256 (11)0.0058 (9)0.0056 (9)0.0089 (9)
C70.0196 (11)0.0280 (12)0.0221 (11)0.0073 (9)0.0038 (8)0.0095 (9)
C80.0208 (11)0.0267 (12)0.0222 (11)0.0079 (10)0.0042 (9)0.0087 (9)
C90.0287 (12)0.0254 (12)0.0253 (11)0.0071 (10)0.0090 (9)0.0060 (9)
C100.0349 (13)0.0255 (12)0.0442 (14)0.0059 (10)0.0223 (11)0.0088 (10)
C110.0267 (13)0.0530 (15)0.0628 (17)0.0105 (12)0.0157 (12)0.0356 (13)
C120.0302 (13)0.0454 (14)0.0524 (15)0.0062 (11)0.0121 (11)0.0216 (12)
C130.0278 (12)0.0308 (12)0.0407 (14)0.0104 (10)0.0087 (10)0.0182 (11)
C140.0267 (13)0.0323 (13)0.0373 (13)0.0046 (10)0.0022 (10)0.0122 (10)
C150.0303 (13)0.0303 (12)0.0302 (12)0.0104 (10)0.0108 (10)0.0123 (10)
C160.0259 (12)0.0248 (11)0.0302 (12)0.0090 (9)0.0061 (9)0.0093 (9)
C170.0333 (13)0.0346 (13)0.0283 (12)0.0126 (11)0.0076 (10)0.0091 (10)
C180.0276 (12)0.0233 (11)0.0313 (12)0.0117 (9)0.0119 (10)0.0120 (9)
C190.0287 (13)0.0233 (11)0.0303 (13)0.0143 (10)0.0126 (10)0.0117 (10)
N10.0245 (10)0.0254 (10)0.0316 (10)0.0066 (8)0.0167 (8)0.0079 (8)
N20.0222 (10)0.0266 (10)0.0321 (10)0.0089 (8)0.0167 (8)0.0097 (8)
O40.0351 (9)0.0339 (9)0.0309 (9)0.0122 (7)0.0152 (7)0.0083 (7)
O10.0301 (9)0.0232 (8)0.0429 (9)0.0079 (7)0.0195 (7)0.0087 (7)
O20.0284 (8)0.0286 (8)0.0383 (9)0.0105 (7)0.0155 (7)0.0101 (7)
O30.0338 (9)0.0282 (8)0.0356 (9)0.0094 (7)0.0166 (7)0.0076 (7)
N30.0258 (10)0.0340 (11)0.0290 (11)0.0080 (9)0.0153 (9)0.0116 (9)
O50.0280 (9)0.0366 (9)0.0262 (9)0.0017 (7)0.0106 (7)0.0044 (7)

Geometric parameters (Å, °)

C1—C21.505 (3)C11—H11C0.9600
C1—H1A0.9600C12—C131.508 (3)
C1—H1B0.9600C12—H12A0.9600
C1—H1C0.9600C12—H12B0.9600
C2—C51.385 (3)C12—H12C0.9600
C2—C31.388 (3)C13—C151.382 (3)
C3—C41.380 (3)C13—C141.390 (3)
C3—H3A0.9300C14—C171.381 (3)
C4—C71.399 (3)C14—H14A0.9300
C4—H4A0.9300C15—C161.387 (3)
C5—C61.388 (3)C15—H15A0.9300
C5—H5A0.9300C16—O51.371 (2)
C6—O11.365 (2)C16—C181.407 (3)
C6—C71.400 (3)C17—C181.391 (3)
C7—C81.492 (3)C17—H17A0.9300
C8—O21.234 (2)C18—C191.485 (3)
C8—N11.342 (3)C19—O41.243 (2)
C9—O31.244 (2)C19—N31.330 (3)
C9—N21.332 (3)N1—N21.382 (2)
C9—C101.500 (3)N1—H1D0.8600
C10—C111.526 (3)N2—H2A0.8600
C10—H10A0.9700O1—H1E0.8200
C10—H10B0.9700N3—N3i1.376 (3)
C11—H11A0.9600N3—H3B0.84 (2)
C11—H11B0.9600O5—H5B0.88 (3)
C2—C1—H1A109.5H11A—C11—H11C109.5
C2—C1—H1B109.5H11B—C11—H11C109.5
H1A—C1—H1B109.5C13—C12—H12A109.5
C2—C1—H1C109.5C13—C12—H12B109.5
H1A—C1—H1C109.5H12A—C12—H12B109.5
H1B—C1—H1C109.5C13—C12—H12C109.5
C5—C2—C3118.03 (19)H12A—C12—H12C109.5
C5—C2—C1120.00 (19)H12B—C12—H12C109.5
C3—C2—C1121.96 (19)C15—C13—C14118.5 (2)
C4—C3—C2120.70 (19)C15—C13—C12120.2 (2)
C4—C3—H3A119.6C14—C13—C12121.3 (2)
C2—C3—H3A119.6C17—C14—C13120.4 (2)
C3—C4—C7121.80 (19)C17—C14—H14A119.8
C3—C4—H4A119.1C13—C14—H14A119.8
C7—C4—H4A119.1C13—C15—C16121.5 (2)
C2—C5—C6121.78 (19)C13—C15—H15A119.3
C2—C5—H5A119.1C16—C15—H15A119.3
C6—C5—H5A119.1O5—C16—C15120.35 (18)
O1—C6—C5120.36 (17)O5—C16—C18119.40 (18)
O1—C6—C7119.25 (17)C15—C16—C18120.25 (19)
C5—C6—C7120.39 (18)C14—C17—C18121.9 (2)
C4—C7—C6117.28 (18)C14—C17—H17A119.1
C4—C7—C8117.01 (18)C18—C17—H17A119.1
C6—C7—C8125.70 (18)C17—C18—C16117.49 (19)
O2—C8—N1120.91 (18)C17—C18—C19117.19 (18)
O2—C8—C7122.27 (18)C16—C18—C19125.33 (19)
N1—C8—C7116.81 (17)O4—C19—N3120.78 (19)
O3—C9—N2121.63 (19)O4—C19—C18122.20 (19)
O3—C9—C10122.19 (18)N3—C19—C18117.01 (18)
N2—C9—C10116.18 (18)C8—N1—N2120.37 (16)
C9—C10—C11112.34 (18)C8—N1—H1D119.8
C9—C10—H10A109.1N2—N1—H1D119.8
C11—C10—H10A109.1C9—N2—N1119.05 (16)
C9—C10—H10B109.1C9—N2—H2A120.5
C11—C10—H10B109.1N1—N2—H2A120.5
H10A—C10—H10B107.9C6—O1—H1E109.5
C10—C11—H11A109.5C19—N3—N3i119.9 (2)
C10—C11—H11B109.5C19—N3—H3B121.4 (16)
H11A—C11—H11B109.5N3i—N3—H3B118.6 (16)
C10—C11—H11C109.5C16—O5—H5B110.8 (17)

Symmetry codes: (i) −x+2, −y+1, −z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1D···O10.861.932.620 (2)136
O1—H1E···O40.821.872.682 (2)169
N2—H2A···O2ii0.862.032.866 (2)165
N3—H3B···O50.84 (2)1.94 (3)2.613 (3)136 (2)
N3—H3B···O4i0.84 (2)2.37 (3)2.655 (3)101 (2)
O5—H5B···O3i0.89 (3)1.80 (3)2.685 (2)175 (2)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT2793).

References

  • Bruker (2005). SADABS Bruker AXS Inc. Madison, Wisconsion, USA.
  • Bruker (2007). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • John, R. P., Moon, D. Y. & Lah, M. S. (2007). Supramol. Chem.19, 295–308.
  • Majumder, A., Goswami, S., Batten, S. R., El Fallah, M. S., Ribas, J. & Mitra, S. (2006). Inorg. Chim. Acta, 359, 2375–2382.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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