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Acta Cryst. (2008). E64, o2144    [ doi:10.1107/S1600536808033515 ]

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

H.-M. Feng, X. Wang and K.-W. Lei

Abstract top

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.

Comment top

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).

Related literature top

For related literature, see: John et al. (2007); Majumder et al. (2006). [Please provide details of recrystallisation solvent to complete the sentence "The filtrate was evaporated using a rotary evaporator and recrystallized from" in the Experimental section]

Experimental top

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 top

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).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SMART (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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The structure of (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme [symmetry code: (A) -x + 2, -y + 1, -z].
[Figure 2] Fig. 2. Packing diagram of the title compound.
2-hydroxy-4-methyl-N-propanoylbenzohydrazide– 2-hydroxy-N-(2-hydroxy-4-methylbenzoyl)-6-methylbenzohydrazide (2/1) top
Crystal data top
2C11H14N2O3·C16H16N2O4Z = 1
Mr = 744.79F(000) = 394
Triclinic, P1Dx = 1.391 Mg m−3
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 mm−1
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 top
Bruker APEXII
diffractometer		4125 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 top
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 = 0.90 w = 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 Å−3
0 restraintsΔρmin = −0.22 e Å−3
Crystal data top
2C11H14N2O3·C16H16N2O4γ = 104.448 (4)°
Mr = 744.79V = 888.8 (2) Å3
Triclinic, P1Z = 1
a = 6.5778 (10) ÅMo Kα radiation
b = 10.7618 (17) ŵ = 0.10 mm−1
c = 13.936 (2) ÅT = 296 K
α = 109.522 (3)°0.54 × 0.30 × 0.25 mm
β = 93.608 (1)°
Data collection top
Bruker APEXII
diffractometer		4125 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2005)		1865 reflections with I > 2σ(I)
Tmin = 0.964, Tmax = 0.975Rint = 0.022
5076 measured reflectionsθmax = 27.6°
Refinement top
R[F2 > 2σ(F2)] = 0.037H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.110Δρmax = 0.20 e Å−3
S = 0.90Δρmin = −0.22 e Å−3
4125 reflectionsAbsolute structure: ?
246 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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.

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) top
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) top
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, °) top
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, °) top
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.
Table 1
Hydrogen-bond geometry (Å, °) top
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···O2i0.862.032.866 (2)165
N3—H3B···O50.84 (2)1.94 (3)2.613 (3)136 (2)
N3—H3B···O4ii0.84 (2)2.37 (3)2.655 (3)101 (2)
O5—H5B···O3ii0.89 (3)1.80 (3)2.685 (2)175 (2)
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+2, −y+1, −z.
Acknowledgements top

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.

references
References top

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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.