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Acta Crystallogr Sect E Struct Rep Online. 2010 December 1; 66(Pt 12): o3142.
Published online 2010 November 13. doi:  10.1107/S1600536810045782
PMCID: PMC3011783

4-{[2-(2,4-Dinitro­phen­yl)hydrazinyl­idene]meth­yl}phenol ethanol hemisolvate

Abstract

In the title compound, C13H10N4O5·0.5C2H5OH, the two benzene rings form a dihedral angle of 4.29 (9)°. The ethanol solvent mol­ecule was treated as disordered between two orientations related by symmetry (center of inversion), with occupancies fixed at 0.5. The crystal packing, stabilized by inter­molecular O—H(...)O and N—H(...)O hydrogen bonds and π–π inter­actions [indicated by the short distance of 3.7299 (7) Å between the centroids of benzene rings from neighbouring mol­ecules], exhibits short inter­molecular O(...)O contacts of 2.8226 (3) Å.

Related literature

For related structures, see: Baughman et al. (2004 [triangle]); Shi et al. (2008 [triangle]); Ji & Shi (2008 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o3142-scheme1.jpg

Experimental

Crystal data

  • C13H10N4O5·0.5C2H6O
  • M r = 325.28
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o3142-efi1.jpg
  • a = 7.0935 (16) Å
  • b = 7.2888 (17) Å
  • c = 14.458 (3) Å
  • α = 100.156 (4)°
  • β = 96.378 (4)°
  • γ = 100.604 (4)°
  • V = 715.2 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.12 mm−1
  • T = 295 K
  • 0.15 × 0.12 × 0.10 mm

Data collection

  • Bruker SMART APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.982, T max = 0.988
  • 4065 measured reflections
  • 2776 independent reflections
  • 1543 reflections with I > 2σ(I)
  • R int = 0.020

Refinement

  • R[F 2 > 2σ(F 2)] = 0.064
  • wR(F 2) = 0.230
  • S = 1.04
  • 2776 reflections
  • 227 parameters
  • 3 restraints
  • H-atom parameters constrained
  • Δρmax = 0.46 e Å−3
  • Δρmin = −0.25 e Å−3

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: SAINT (Bruker, 2005 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; 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/S1600536810045782/cv2785sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810045782/cv2785Isup2.hkl

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

supplementary crystallographic information

Comment

As a contribution to structural studies of 2,4-dinitrophenylhydrazones (Baughman et al., 2004; Shi et al., 2008; Ji et al., 2008;) we present here the crystal structure of the title compound (I).

In (I) (Fig. 1), all bond lengths and angles are normal (Allen et al., 1987). The crystal packing, stabilized by intermolecular O—H···O and N—H···O hydrogen bonds (Table 1) and π–π interactions proved by short distance of 3.7299 (7) Å between the centroids of benzene rings from the neighbouring molecules, exhibits short intermolecular O···O contacts of 2.8226 (3) Å.

Experimental

The title compound was synthesized by the reaction of (2,4-dinitro-phenyl)-hydrazine (1 mmol, 198.1 mg) with 4-hydroxy-benzaldehyde (1 mmol, 122.1 mg) in ethanol (20 ml) under reflux conditions (338 K) for 4 h. The solvent was removed and the solid product recrystallized from ethanol. After five days brown crystals were obtained that were suitable for X-ray diffraction study.

Refinement

All H atoms were placed in idealized positions (C—H = 0.93–0.97 Å, N—H = 0.86 Å) and refined as riding atoms. For those bound to C, Uiso(H) = 1.2 or 1.5Ueq(C). while for those bound to N, Uiso(H) = 1.2 Ueq(N). The ethanol solvent molecule has been treated as disordered between two orientations related by symmetry (center of inversion) with occupancies fixed to 0.5 and with C—O, C—C and O···C distances restrained to 1.40 (1), 1.45 (1) and 2.40 (1) Å, respectively.

Figures

Fig. 1.
View of the title compound showing the atomic labeling and 30% probability displacement ellipsoids. Solvent molecule omitted for clarity.

Crystal data

C13H10N4O5·0.5C2H6OZ = 2
Mr = 325.28F(000) = 338
Triclinic, P1Dx = 1.510 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.0935 (16) ÅCell parameters from 748 reflections
b = 7.2888 (17) Åθ = 2.9–24.3°
c = 14.458 (3) ŵ = 0.12 mm1
α = 100.156 (4)°T = 295 K
β = 96.378 (4)°Block, brown
γ = 100.604 (4)°0.15 × 0.12 × 0.10 mm
V = 715.2 (3) Å3

Data collection

Bruker SMART CCD area-detector diffractometer2776 independent reflections
Radiation source: fine-focus sealed tube1543 reflections with I > 2σ(I)
graphiteRint = 0.020
phi and ω scansθmax = 26.1°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2005)h = −7→8
Tmin = 0.982, Tmax = 0.988k = −8→7
4065 measured reflectionsl = −14→17

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.064H-atom parameters constrained
wR(F2) = 0.230w = 1/[σ2(Fo2) + (0.1117P)2 + 0.1836P] where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
2776 reflectionsΔρmax = 0.46 e Å3
227 parametersΔρmin = −0.25 e Å3
3 restraintsExtinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.017 (7)

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*/UeqOcc. (<1)
O10.6437 (4)0.7313 (3)0.73110 (16)0.0700 (8)
O20.4959 (4)0.5632 (3)0.59767 (16)0.0683 (8)
O30.7183 (5)0.4849 (4)1.00571 (18)0.0973 (11)
O40.5709 (5)0.2032 (4)1.00864 (18)0.1019 (12)
O5−0.1603 (4)−0.6843 (4)0.20416 (18)0.0890 (10)
H5−0.1738−0.66480.14780.134*
N10.3674 (3)0.1977 (3)0.57776 (16)0.0470 (7)
H10.38630.29070.54520.070*
N20.2771 (3)0.0174 (4)0.53066 (17)0.0479 (7)
N30.5558 (4)0.5794 (4)0.68230 (18)0.0499 (7)
N40.6183 (5)0.3288 (5)0.9659 (2)0.0698 (9)
C10.4286 (4)0.2316 (4)0.6718 (2)0.0412 (7)
C20.5213 (4)0.4143 (4)0.7248 (2)0.0420 (7)
C30.5848 (4)0.4436 (4)0.8208 (2)0.0474 (8)
H30.64790.56420.85440.057*
C40.5548 (5)0.2961 (4)0.8656 (2)0.0493 (8)
C50.4642 (5)0.1133 (4)0.8163 (2)0.0511 (8)
H5A0.44530.01310.84850.061*
C60.4040 (4)0.0821 (4)0.7223 (2)0.0467 (8)
H60.3450−0.04050.68990.056*
C70.2242 (4)0.0014 (4)0.4422 (2)0.0473 (8)
H70.24870.10920.41570.057*
C80.1273 (4)−0.1784 (5)0.3812 (2)0.0464 (8)
C90.0970 (5)−0.3493 (5)0.4128 (2)0.0551 (9)
H90.1418−0.35120.47550.066*
C100.0018 (5)−0.5148 (5)0.3525 (2)0.0612 (9)
H10−0.0189−0.62800.37480.073*
C11−0.0638 (5)−0.5156 (5)0.2591 (2)0.0585 (9)
C12−0.0313 (5)−0.3488 (5)0.2267 (2)0.0617 (10)
H12−0.0734−0.34870.16350.074*
C130.0629 (4)−0.1817 (5)0.2868 (2)0.0530 (8)
H130.0838−0.06930.26380.064*
O61.0107 (12)0.7495 (11)0.9734 (7)0.148 (3)0.50
H6A0.92380.65970.98220.222*0.50
C140.9498 (18)0.9229 (13)0.9968 (12)0.115 (5)0.50
H14A1.01020.98451.06020.138*0.50
H14B0.81280.89240.99830.138*0.50
C150.965 (5)1.042 (3)0.9313 (12)0.259 (14)0.50
H15A0.92301.15730.95550.388*0.50
H15B1.09791.07290.92230.388*0.50
H15C0.88610.98020.87170.388*0.50

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.1033 (19)0.0395 (14)0.0569 (14)−0.0028 (12)0.0025 (13)0.0063 (11)
O20.0965 (19)0.0546 (15)0.0477 (14)0.0023 (13)−0.0027 (13)0.0160 (11)
O30.137 (3)0.078 (2)0.0503 (15)−0.0157 (18)−0.0210 (16)0.0019 (14)
O40.172 (3)0.075 (2)0.0533 (17)0.008 (2)−0.0009 (18)0.0265 (15)
O50.111 (2)0.0689 (18)0.0581 (15)−0.0248 (16)−0.0010 (15)−0.0114 (13)
N10.0544 (15)0.0402 (14)0.0404 (14)0.0029 (11)−0.0003 (11)0.0045 (11)
N20.0490 (15)0.0455 (15)0.0426 (15)0.0056 (11)0.0013 (12)−0.0009 (11)
N30.0627 (17)0.0373 (15)0.0473 (16)0.0055 (12)0.0062 (13)0.0090 (11)
N40.102 (2)0.057 (2)0.0451 (17)0.0100 (17)−0.0015 (16)0.0098 (15)
C10.0406 (15)0.0407 (17)0.0406 (16)0.0074 (12)0.0052 (12)0.0049 (12)
C20.0451 (16)0.0360 (16)0.0441 (16)0.0083 (12)0.0062 (13)0.0060 (12)
C30.0569 (19)0.0370 (17)0.0432 (17)0.0064 (13)0.0034 (14)0.0003 (12)
C40.062 (2)0.0447 (18)0.0381 (16)0.0085 (15)0.0016 (14)0.0058 (13)
C50.066 (2)0.0380 (17)0.0498 (18)0.0065 (14)0.0117 (15)0.0129 (13)
C60.0561 (18)0.0354 (16)0.0456 (17)0.0047 (13)0.0054 (14)0.0066 (13)
C70.0487 (17)0.0467 (18)0.0433 (17)0.0051 (14)0.0039 (14)0.0080 (13)
C80.0381 (16)0.056 (2)0.0401 (16)0.0039 (13)0.0047 (13)0.0020 (14)
C90.065 (2)0.054 (2)0.0402 (17)0.0030 (16)0.0031 (15)0.0072 (14)
C100.071 (2)0.054 (2)0.054 (2)0.0004 (17)0.0107 (17)0.0075 (16)
C110.055 (2)0.058 (2)0.0478 (19)−0.0092 (16)0.0056 (15)−0.0063 (16)
C120.056 (2)0.075 (3)0.0406 (17)−0.0040 (17)−0.0054 (15)0.0027 (16)
C130.0516 (18)0.058 (2)0.0431 (17)0.0020 (15)−0.0005 (14)0.0091 (14)
O60.139 (7)0.123 (7)0.176 (8)−0.003 (5)0.043 (6)0.034 (6)
C140.113 (9)0.044 (5)0.197 (16)0.026 (5)0.058 (10)0.015 (7)
C150.35 (4)0.24 (3)0.20 (3)0.10 (2)0.06 (3)0.01 (2)

Geometric parameters (Å, °)

O1—N31.219 (3)C7—H70.9300
O2—N31.227 (3)C8—C131.385 (4)
O3—N41.229 (4)C8—C91.390 (5)
O4—N41.210 (4)C9—C101.368 (4)
O5—C111.356 (4)C9—H90.9300
O5—H50.8500C10—C111.376 (5)
N1—C11.346 (3)C10—H100.9300
N1—N21.370 (3)C11—C121.369 (5)
N1—H10.8900C12—C131.372 (4)
N2—C71.270 (4)C12—H120.9300
N3—O21.227 (3)C13—H130.9300
N3—C21.439 (4)O6—C141.407 (8)
N4—O31.229 (4)O6—C15i1.827 (19)
N4—C41.435 (4)O6—H6A0.8500
C1—C61.410 (4)C14—C15i1.11 (2)
C1—C21.413 (4)C14—C14i1.20 (2)
C2—C31.377 (4)C14—C151.394 (9)
C3—C41.346 (4)C14—H14A0.9600
C3—H30.9300C14—H14B0.9600
C4—C51.394 (4)C15—C14i1.11 (2)
C5—C61.344 (4)C15—O6i1.828 (19)
C5—H5A0.9300C15—H15A0.9601
C6—H60.9300C15—H15B0.9600
C7—C81.447 (4)C15—H15C0.9600
C11—O5—H5105.5C9—C10—C11120.6 (3)
C1—N1—N2119.9 (3)C9—C10—H10119.7
C1—N1—H1120.9C11—C10—H10119.7
N2—N1—H1119.2O5—C11—C12123.4 (3)
C7—N2—N1114.8 (3)O5—C11—C10117.2 (3)
O1—N3—O2121.8 (3)C12—C11—C10119.3 (3)
O1—N3—O2121.8 (3)C11—C12—C13120.5 (3)
O1—N3—C2119.3 (3)C11—C12—H12119.8
O2—N3—C2119.0 (2)C13—C12—H12119.8
O2—N3—C2119.0 (2)C12—C13—C8120.8 (3)
O4—N4—O3122.2 (3)C12—C13—H13119.6
O4—N4—O3122.2 (3)C8—C13—H13119.6
O4—N4—C4119.2 (3)C14—O6—H6A108.9
O3—N4—C4118.5 (3)C15i—O6—H6A109.4
O3—N4—C4118.5 (3)C15i—C14—C14i74.4 (13)
N1—C1—C6120.5 (3)C15i—C14—C15124.3 (13)
N1—C1—C2122.8 (3)C14i—C14—C1549.9 (12)
C6—C1—C2116.7 (3)C15i—C14—O692.5 (13)
C3—C2—C1121.3 (3)C14i—C14—O6124.7 (14)
C3—C2—N3116.1 (3)C15—C14—O6117.0 (10)
C1—C2—N3122.5 (3)C14i—C14—H14A65.2
C4—C3—C2119.4 (3)C15—C14—H14A113.8
C4—C3—H3120.3O6—C14—H14A108.3
C2—C3—H3120.3C15i—C14—H14B112.3
C3—C4—C5121.3 (3)C14i—C14—H14B127.7
C3—C4—N4119.0 (3)C15—C14—H14B102.9
C5—C4—N4119.7 (3)O6—C14—H14B107.2
C6—C5—C4119.9 (3)H14A—C14—H14B106.8
C6—C5—H5A120.0C14i—C15—C1455.7 (13)
C4—C5—H5A120.0C14i—C15—O6i50.3 (8)
C5—C6—C1121.3 (3)C14—C15—O6i90.5 (11)
C5—C6—H6119.3C14i—C15—H15A81.5
C1—C6—H6119.3C14—C15—H15A109.7
N2—C7—C8122.5 (3)C14i—C15—H15B74.1
N2—C7—H7118.8C14—C15—H15B108.2
C8—C7—H7118.8O6i—C15—H15B93.5
C13—C8—C9118.2 (3)H15A—C15—H15B109.5
C13—C8—C7118.9 (3)C14i—C15—H15C165.6
C9—C8—C7122.9 (3)C14—C15—H15C110.5
C10—C9—C8120.5 (3)O6i—C15—H15C140.8
C10—C9—H9119.7H15A—C15—H15C109.5
C8—C9—H9119.7H15B—C15—H15C109.5

Symmetry codes: (i) −x+2, −y+2, −z+2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···O20.891.972.605 (3)127
O6—H6A···O30.851.862.702 (9)174
O5—H5···O6ii0.852.262.882 (9)130
O5—H5···O4iii0.852.473.116 (4)133
O5—H5···O3iii0.852.603.404 (4)159
N1—H1···O2iv0.892.633.449 (4)153

Symmetry codes: (ii) −x+1, −y, −z+1; (iii) x−1, y−1, z−1; (iv) −x+1, −y+1, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CV2785).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Baughman, R. G., Martin, K. L., Singh, R. K. & Stoffer, J. O. (2004). Acta Cryst. C60, o103–o106. [PubMed]
  • Bruker (2005). APEX2, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Ji, N.-N. & Shi, Z.-Q. (2008). Acta Cryst. E64, o2141. [PMC free article] [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Shi, Z.-Q., Ji, N.-N. & Li, X.-Y. (2008). Acta Cryst. E64, o2135. [PMC free article] [PubMed]

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