supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers buy article online

cv2302 scheme

Acta Cryst. (2007). E63, o4092    [ doi:10.1107/S1600536807045175 ]

Dimethyl 2,5-bis[2-(2-hydroxybenzoyl)hydrazino]cyclohexa-1,4-diene-1,4-dicarboxylate dimethylformamide disolvate

H. Xu, J. Dou, D. Li and D. Wang

Abstract top

The asymmetric unit of the title compound, C24H24N4O8·2C3H7NO, contains half of the centrosymmetric molecule of dimethyl 2,5-bis[2-(2-hydroxybenzoyl)hydrazino]cyclohexa-1,4-diene-1,4-dicarboxylate and one dimethylformamide solvent molecule. There is a dihedral angle of 61.7 (1)° between the central and two outer rings. The crystal structure involves N-H...O, O-H...O and C-H...O hydrogen bonds.

Comment top

Aroylhydrazone and their metal complexes have been actively investigated for many years due to their wide spread applications in the fields of coordination chemistry (Milway et al., 2004), bioinorganic chemistry (Patole et al., 2003) and catalytic chemistry (Pouralimardan et al., 2007). As an extension of our work on the structural characterization of aroylhydrazone derivatives (Liu et al., 2005; Kang et al., 2007), the title compound, (I), has been synthesized and structurally characterized.

In (I) (Fig. 1), the C8—C9 bond length of 1.354 (5) Å indicates that centrosymmetric aroylhydrazone moiety exists in the enol form with the formation of N2—H2···O4 hydrogen bond (Table 1). The central ring is essentially planar with the mean deviation of 0.0095 Å. The dihedral angle between the central ring and benzene ring C2—C7 is 61.7 (1)°. The intermolecular N—H···O hydrogen bonds and weak C—H···O interactions (Table 1) contribute to the crystal packing stability.

Related literature top

The crystal structures of cobalt and nickel complexes with the related aroylhydrazone derivative have been reported by Milway et al. (2004) and Liu et al. (2005), respectively. The crystal structure of 3-hydroxy-N-[phenyl(2-pyridyl)methylene]- 2-naphthohydrazide was reported by Kang et al. (2007). For the catalytic and biological activities of aroylhydrazones, see: Pouralimardan et al. (2007) and Patole et al. (2003), respectively.

Experimental top

The mixture of dimethyl-1,4-cyclohexanedione-2,5-dicarboxylate (2.28 g, 10 mmol) and salicylhydrazide (3.04 g, 20 mmol) in ethanol (30 ml) were refluxed for 6 h, and then the yellow precipitate was collected, washed with ethanol and dried in vacuo (yield 92%). The yellow solid was dissolved in DMF, then crystals suitable for X-ray diffraction were obtained after three weeks (m.p. 480–482 K). Elemental analysis: calcd. for C30H38N6O10: C 56.07, H 5.91, N 13.07%; found: C 56.15, H 5.59, N 13.13%.

Refinement top

All H atoms were placed geometrically (O—H 0.82 Å, N—H 0.86 Å, C—H 0.93–0.97 Å) and treated as riding on their parent atoms, with Uiso(H) = 1.2–1.5Ueq(parent atom).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures top
[Figure 1] Fig. 1. A portion of the crystal structure of the title compound showing the atomic numbering and 30% probability displacement ellipsoids. Dashed lines denote hydrogen bonds. Unlabelled atoms are related to the labelled ones by symmetry operation (−x, −y, 1 − z). C-bound H atoms have been omitted for clarity.
Dimethyl 2,5-bis[2-(2-hydroxybenzoyl)hydrazino]cyclohexa- 1,4-diene-1,4-dicarboxylate dimethylformamide disolvate top
Crystal data top
C24H24N4O8·2C3H7NOF000 = 680
Mr = 642.66Dx = 1.339 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
a = 6.227 (2) ÅCell parameters from 1492 reflections
b = 28.113 (9) Åθ = 2.4–25.3º
c = 9.376 (3) ŵ = 0.10 mm−1
β = 103.850 (14)ºT = 298 (2) K
V = 1593.6 (9) Å3Stick, yellow
Z = 20.52 × 0.15 × 0.07 mm
Data collection top
Siemens SMART CCD area-detector
diffractometer		2800 independent reflections
Radiation source: fine-focus sealed tube1471 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.064
T = 298(2) Kθmax = 25.0º
φ and ω scansθmin = 1.5º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −7→7
Tmin = 0.949, Tmax = 0.993k = −33→32
7468 measured reflectionsl = −11→5
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.059H-atom parameters constrained
wR(F2) = 0.189  w = 1/[σ2(Fo2) + (0.0764P)2 + 1.2201P]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
2800 reflectionsΔρmax = 0.24 e Å−3
208 parametersΔρmin = −0.30 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C24H24N4O8·2C3H7NOV = 1593.6 (9) Å3
Mr = 642.66Z = 2
Monoclinic, P21/nMo Kα
a = 6.227 (2) ŵ = 0.10 mm−1
b = 28.113 (9) ÅT = 298 (2) K
c = 9.376 (3) Å0.52 × 0.15 × 0.07 mm
β = 103.850 (14)º
Data collection top
Siemens SMART CCD area-detector
diffractometer		2800 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1471 reflections with I > 2σ(I)
Tmin = 0.949, Tmax = 0.993Rint = 0.064
7468 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.059208 parameters
wR(F2) = 0.189H-atom parameters constrained
S = 1.00Δρmax = 0.24 e Å−3
2800 reflectionsΔρmin = −0.30 e Å−3
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 > 2sigma(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
N10.0085 (5)0.12965 (10)0.4387 (3)0.0401 (8)
H1−0.01060.14030.35050.048*
N20.1573 (5)0.09293 (10)0.4882 (3)0.0419 (8)
H20.29680.09890.51110.050*
N30.2346 (6)0.12473 (12)0.0477 (4)0.0530 (9)
O1−0.0940 (5)0.13189 (9)0.6539 (3)0.0472 (7)
O2−0.4852 (5)0.17016 (9)0.6376 (3)0.0528 (8)
H2A−0.39420.14860.65900.079*
O30.5415 (5)−0.01121 (9)0.7430 (3)0.0591 (9)
O40.5249 (4)0.06460 (9)0.6729 (3)0.0511 (8)
O5−0.0794 (6)0.13231 (13)0.1286 (3)0.0737 (10)
C1−0.1059 (6)0.14848 (12)0.5312 (4)0.0372 (9)
C2−0.2469 (6)0.18971 (12)0.4759 (4)0.0344 (9)
C3−0.4309 (7)0.19869 (13)0.5337 (4)0.0398 (9)
C4−0.5660 (7)0.23722 (14)0.4857 (5)0.0505 (11)
H4−0.68890.24280.52350.061*
C5−0.5186 (8)0.26754 (14)0.3816 (5)0.0553 (12)
H5−0.60990.29350.34960.066*
C6−0.3375 (8)0.25971 (14)0.3248 (5)0.0559 (12)
H6−0.30610.28050.25530.067*
C7−0.2032 (7)0.22132 (13)0.3708 (4)0.0458 (10)
H7−0.08130.21620.33170.055*
C80.0855 (6)0.04753 (12)0.5011 (4)0.0359 (9)
C90.2168 (6)0.01363 (12)0.5801 (4)0.0357 (9)
C100.1455 (6)−0.03709 (12)0.5836 (4)0.0413 (10)
H10A0.2463−0.05690.54540.050*
H10B0.1590−0.04620.68520.050*
C110.4371 (6)0.02576 (13)0.6663 (4)0.0384 (9)
C120.7623 (8)−0.00190 (17)0.8290 (6)0.0767 (16)
H12A0.83510.01970.77670.115*
H12B0.8437−0.03120.84630.115*
H12C0.75500.01200.92130.115*
C130.0200 (8)0.12140 (15)0.0339 (5)0.0543 (11)
H13−0.06440.1098−0.05490.065*
C140.3778 (9)0.1427 (2)0.1822 (6)0.0914 (19)
H14A0.34580.17570.19370.137*
H14B0.52940.13930.17770.137*
H14C0.35280.12500.26430.137*
C150.3392 (9)0.1104 (2)−0.0693 (5)0.0854 (17)
H15A0.22760.1008−0.15390.128*
H15B0.43770.0842−0.03610.128*
H15C0.42120.1367−0.09470.128*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.047 (2)0.0276 (16)0.0475 (19)0.0090 (15)0.0152 (16)0.0056 (14)
N20.0338 (18)0.0298 (17)0.064 (2)0.0019 (14)0.0156 (16)0.0041 (15)
N30.052 (2)0.067 (2)0.043 (2)0.0019 (19)0.0161 (18)−0.0044 (18)
O10.0589 (19)0.0445 (15)0.0371 (15)0.0050 (14)0.0093 (13)0.0086 (13)
O20.0590 (19)0.0457 (16)0.0611 (19)0.0037 (14)0.0289 (15)0.0114 (14)
O30.0461 (18)0.0431 (16)0.076 (2)0.0007 (14)−0.0090 (16)0.0112 (15)
O40.0438 (18)0.0359 (15)0.072 (2)−0.0034 (13)0.0097 (15)0.0013 (14)
O50.060 (2)0.112 (3)0.054 (2)0.0068 (19)0.0235 (17)0.0052 (19)
C10.038 (2)0.0284 (19)0.045 (2)−0.0047 (16)0.0089 (19)−0.0027 (17)
C20.040 (2)0.0275 (18)0.037 (2)−0.0008 (17)0.0125 (17)0.0002 (16)
C30.049 (3)0.032 (2)0.038 (2)−0.0014 (18)0.0108 (19)−0.0011 (17)
C40.054 (3)0.044 (2)0.056 (3)0.008 (2)0.019 (2)−0.002 (2)
C50.071 (3)0.037 (2)0.055 (3)0.019 (2)0.010 (2)0.004 (2)
C60.074 (3)0.043 (2)0.056 (3)0.010 (2)0.026 (2)0.013 (2)
C70.056 (3)0.036 (2)0.049 (2)0.0047 (19)0.021 (2)0.0047 (18)
C80.035 (2)0.0287 (19)0.047 (2)0.0014 (17)0.0158 (18)−0.0045 (17)
C90.036 (2)0.0266 (18)0.044 (2)0.0014 (16)0.0085 (18)0.0001 (16)
C100.040 (2)0.033 (2)0.050 (2)0.0007 (17)0.0081 (19)0.0012 (17)
C110.041 (2)0.030 (2)0.045 (2)0.0061 (18)0.0137 (19)0.0011 (17)
C120.053 (3)0.060 (3)0.097 (4)−0.001 (2)−0.022 (3)0.009 (3)
C130.058 (3)0.058 (3)0.046 (3)0.005 (2)0.011 (2)0.004 (2)
C140.065 (4)0.134 (5)0.075 (4)−0.025 (3)0.016 (3)−0.037 (4)
C150.079 (4)0.133 (5)0.052 (3)0.024 (3)0.031 (3)−0.001 (3)
Geometric parameters (Å, °) top
N1—C11.355 (5)C5—H50.9300
N1—N21.390 (4)C6—C71.370 (5)
N1—H10.8600C6—H60.9300
N2—C81.367 (4)C7—H70.9300
N2—H20.8600C8—C91.355 (5)
N3—C131.315 (6)C8—C10i1.496 (5)
N3—C141.450 (6)C9—C111.456 (5)
N3—C151.460 (5)C9—C101.496 (5)
O1—C11.227 (4)C10—C8i1.496 (5)
O2—C31.366 (4)C10—H10A0.9700
O2—H2A0.8200C10—H10B0.9700
O3—C111.341 (4)C12—H12A0.9600
O3—C121.441 (5)C12—H12B0.9600
O4—C111.216 (4)C12—H12C0.9600
O5—C131.237 (5)C13—H130.9300
C1—C21.472 (5)C14—H14A0.9600
C2—C71.401 (5)C14—H14B0.9600
C2—C31.403 (5)C14—H14C0.9600
C3—C41.379 (5)C15—H15A0.9600
C4—C51.380 (6)C15—H15B0.9600
C4—H40.9300C15—H15C0.9600
C5—C61.375 (6)
C1—N1—N2119.1 (3)N2—C8—C10i115.4 (3)
C1—N1—H1120.4C8—C9—C11120.2 (3)
N2—N1—H1120.4C8—C9—C10122.6 (3)
C8—N2—N1121.1 (3)C11—C9—C10117.1 (3)
C8—N2—H2119.4C8i—C10—C9115.3 (3)
N1—N2—H2119.4C8i—C10—H10A108.4
C13—N3—C14120.6 (4)C9—C10—H10A108.4
C13—N3—C15122.1 (4)C8i—C10—H10B108.4
C14—N3—C15117.2 (4)C9—C10—H10B108.4
C3—O2—H2A109.5H10A—C10—H10B107.5
C11—O3—C12115.7 (3)O4—C11—O3121.0 (4)
O1—C1—N1121.9 (3)O4—C11—C9126.2 (3)
O1—C1—C2121.8 (4)O3—C11—C9112.8 (3)
N1—C1—C2116.3 (3)O3—C12—H12A109.5
C7—C2—C3118.1 (3)O3—C12—H12B109.5
C7—C2—C1123.2 (4)H12A—C12—H12B109.5
C3—C2—C1118.6 (3)O3—C12—H12C109.5
O2—C3—C4117.3 (4)H12A—C12—H12C109.5
O2—C3—C2122.3 (3)H12B—C12—H12C109.5
C4—C3—C2120.4 (4)O5—C13—N3125.7 (4)
C3—C4—C5119.9 (4)O5—C13—H13117.2
C3—C4—H4120.0N3—C13—H13117.2
C5—C4—H4120.0N3—C14—H14A109.5
C6—C5—C4120.6 (4)N3—C14—H14B109.5
C6—C5—H5119.7H14A—C14—H14B109.5
C4—C5—H5119.7N3—C14—H14C109.5
C7—C6—C5120.0 (4)H14A—C14—H14C109.5
C7—C6—H6120.0H14B—C14—H14C109.5
C5—C6—H6120.0N3—C15—H15A109.5
C6—C7—C2121.0 (4)N3—C15—H15B109.5
C6—C7—H7119.5H15A—C15—H15B109.5
C2—C7—H7119.5N3—C15—H15C109.5
C9—C8—N2122.5 (3)H15A—C15—H15C109.5
C9—C8—C10i122.0 (3)H15B—C15—H15C109.5
C1—N1—N2—C876.3 (4)C1—C2—C7—C6−178.8 (4)
N2—N1—C1—O1−5.3 (5)N1—N2—C8—C9−163.9 (3)
N2—N1—C1—C2175.2 (3)N1—N2—C8—C10i18.7 (5)
O1—C1—C2—C7153.0 (4)N2—C8—C9—C115.5 (6)
N1—C1—C2—C7−27.5 (5)C10i—C8—C9—C11−177.3 (3)
O1—C1—C2—C3−25.3 (5)N2—C8—C9—C10−174.5 (3)
N1—C1—C2—C3154.2 (3)C10i—C8—C9—C102.7 (6)
C7—C2—C3—O2−179.3 (3)C8—C9—C10—C8i−2.6 (6)
C1—C2—C3—O2−1.0 (5)C11—C9—C10—C8i177.4 (3)
C7—C2—C3—C41.1 (5)C12—O3—C11—O4−1.4 (6)
C1—C2—C3—C4179.4 (4)C12—O3—C11—C9179.0 (4)
O2—C3—C4—C5179.5 (4)C8—C9—C11—O4−2.4 (6)
C2—C3—C4—C5−0.9 (6)C10—C9—C11—O4177.6 (4)
C3—C4—C5—C60.1 (7)C8—C9—C11—O3177.2 (3)
C4—C5—C6—C70.5 (7)C10—C9—C11—O3−2.8 (5)
C5—C6—C7—C2−0.2 (7)C14—N3—C13—O5−0.4 (7)
C3—C2—C7—C6−0.5 (6)C15—N3—C13—O5179.1 (4)
Symmetry codes: (i) −x, −y, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O50.862.032.827 (5)153
N2—H2···O40.862.052.641 (4)125
O2—H2A···O10.821.942.634 (4)142
C15—H15A···O1ii0.962.513.320 (6)142
Symmetry codes: (ii) x, y, z−1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O50.862.032.827 (5)153
N2—H2···O40.862.052.641 (4)125
O2—H2A···O10.821.942.634 (4)142
C15—H15A···O1i0.962.513.320 (6)142
Symmetry codes: (i) x, y, z−1.
Acknowledgements top

The authors acknowledge the support of the National Natural Science Foundation of China (grant No. 20671048).

references
References top

Kang, W.-J., Dou, J.-M., Li, D.-C. & Wang, D.-Q. (2007). Acta Cryst. E63, o3328–?.

Liu, M.-L., Dou, J.-M., Wang, D.-Q. & Li, D.-C. (2005). Acta Cryst. E61, m1366–m1367.

Milway, V. A., Thompson, L. K. & Miller, D. O. (2004). Chem. Commun. pp. 1790–1791.

Patole, J., Sandbhor, U., Padhye, S., Deobagkar, D. N., Anson, C. E. & Powell, A. (2003). Bioorg. Med. Chem. Lett. pp. 51–55.

Pouralimardan, O., Chamayou, A. C., Janiak, C. & Hassan, H. M. (2007). Inorg. Chim. Acta, pp. 1599–1608.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997a). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Sheldrick, G. M. (1997b). SHELXTL. Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA.

Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.