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Acta Cryst. (2008). E64, o1081    [ doi:10.1107/S1600536808013950 ]

(E)-Methyl 2-[4-(dimethylamino)benzylidene]hydrazinecarboxylate at 123 K

X.-C. Hu, L.-P. Lv, W.-W. Li and W.-B. Yu

Abstract top

The approximately planar molecule of the title compound, C11H15N3O2, is in an E configuration with respect to the N=C double bond. An intermolecular N-H...O hydrogen bond links the molecules into a one-dimensional chain propagating in the [010] direction.

Comment top

Benzaldehydehydrazone derivatives have received considerable attention for many years due to their pharmacological activity (Parashar et al., 1988) and their photochromic properties (Hadjoudis et al., 1987). As a further investigation of this type of material, the crystal structure of the title compound, C11H15N3O2, (I), is described here.

All the nonhydrogen atoms are coplanar to within ±0.1429 (14)Å (Fig. 1) in (I). The molecule is in an E conformation with respect to the N=C double bond. The bond lengths and angles of the C=N—N(H)—C groups are similar to those in related compounds (Shi et al., 2006).

An intermolecular N—H···O hydrogen bond (Table 1) links the molecules into a one-dimensional chain aligned along the b direction (Fig. 2).

Related literature top

For general background, see: Parashar et al. (1988); Hadjoudis et al. (1987). For a related structure, see: Shi & Yuan (2006).

Experimental top

4-(Dimethylamino)benzaldehyde (14.9 g, 0.1 mol) and methyl hydrazinecarboxylate (9.0 g, 0.1 mol) were dissolved in stirred methanol (50 ml) and left for 3 h at room temperature. The resulting solid was filtered off and recrystallized from ethanol to give the title compound in 80% yield. Colourless blocks of (I) were obtained by slow evaporation of a ethanol solution at room temperature (m.p. 452–454 K).

Refinement top

The H atoms were geometrically placed (C—H = 0.93-0.96Å, N—H = 0.86Å) and refined as riding with Uiso(H) = 1.2Ueq(C, N) or 1.5Ueq(methyl C).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); 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 molecular structure of (I), showing 30% probability displacement ellipsoids for the non-hydrogen atoms.
[Figure 2] Fig. 2. The crystal packing in (II), viewed approximately down the a axis with hydrogen bonds indicated by dashed lines.
(E)-Methyl 2-[4-(dimethylamino)benzylidene]hydrazinecarboxylate top
Crystal data top
C11H15N3O2F000 = 944
Mr = 221.26Dx = 1.228 Mg m−3
Orthorhombic, PbcaMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 2111 reflections
a = 13.051 (3) Åθ = 2.2–25.0º
b = 9.838 (2) ŵ = 0.09 mm−1
c = 18.637 (4) ÅT = 123 (2) K
V = 2392.9 (9) Å3Block, colourless
Z = 80.29 × 0.26 × 0.22 mm
Data collection top
Bruker SMART CCD
diffractometer		2111 independent reflections
Radiation source: fine-focus sealed tube1592 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.038
T = 123(2) Kθmax = 25.0º
ω scansθmin = 2.2º
Absorption correction: multi-scan
(SADABS; Bruker, 2002)		h = −15→15
Tmin = 0.979, Tmax = 0.981k = −11→11
19378 measured reflectionsl = −21→22
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)] = 0.046H-atom parameters constrained
wR(F2) = 0.134  w = 1/[σ2(Fo2) + (0.0719P)2 + 0.3078P]
where P = (Fo2 + 2Fc2)/3
S = 1.11(Δ/σ)max < 0.001
2111 reflectionsΔρmax = 0.23 e Å−3
145 parametersΔρmin = −0.27 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C11H15N3O2V = 2392.9 (9) Å3
Mr = 221.26Z = 8
Orthorhombic, PbcaMo Kα
a = 13.051 (3) ŵ = 0.09 mm−1
b = 9.838 (2) ÅT = 123 (2) K
c = 18.637 (4) Å0.29 × 0.26 × 0.22 mm
Data collection top
Bruker SMART CCD
diffractometer		2111 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2002)		1592 reflections with I > 2σ(I)
Tmin = 0.979, Tmax = 0.981Rint = 0.038
19378 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.046145 parameters
wR(F2) = 0.134H-atom parameters constrained
S = 1.11Δρmax = 0.23 e Å−3
2111 reflectionsΔρmin = −0.27 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 > 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
N20.27645 (11)0.23338 (15)0.56388 (7)0.0539 (4)
C90.29967 (13)0.13610 (19)0.60663 (9)0.0546 (5)
H90.28970.04690.59160.066*
O20.17803 (10)0.22366 (12)0.38955 (6)0.0610 (4)
N30.23964 (12)0.19224 (14)0.49757 (7)0.0554 (4)
H30.23630.10720.48710.067*
O10.20751 (10)0.40732 (12)0.45884 (7)0.0656 (4)
C30.42170 (14)0.20049 (17)0.81830 (9)0.0536 (4)
C80.34112 (13)0.16094 (17)0.67786 (9)0.0513 (4)
C50.40355 (14)0.31063 (17)0.77132 (10)0.0567 (5)
H50.41820.39860.78650.068*
C100.20925 (12)0.28641 (17)0.44977 (9)0.0492 (4)
N10.45818 (14)0.22037 (16)0.88679 (9)0.0725 (5)
C70.36472 (13)0.29041 (18)0.70360 (10)0.0542 (4)
H70.35380.36520.67410.065*
C60.35985 (14)0.05251 (18)0.72400 (10)0.0593 (5)
H60.3453−0.03520.70850.071*
C40.39921 (15)0.07084 (18)0.79189 (10)0.0621 (5)
H40.4111−0.00460.82080.075*
C110.14121 (16)0.30910 (19)0.33264 (10)0.0667 (5)
H11A0.12160.25380.29250.100*
H11B0.19450.37070.31830.100*
H11C0.08300.35990.34910.100*
C10.48056 (19)0.1055 (2)0.93250 (11)0.0833 (7)
H1A0.50570.13730.97790.125*
H1B0.53160.04940.91010.125*
H1C0.41930.05340.93980.125*
C20.48463 (18)0.3522 (2)0.91387 (11)0.0787 (6)
H2A0.50900.34390.96230.118*
H2B0.42520.40980.91300.118*
H2C0.53740.39120.88450.118*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N20.0641 (9)0.0466 (9)0.0509 (9)0.0017 (6)−0.0001 (7)−0.0056 (7)
C90.0610 (10)0.0438 (10)0.0590 (11)0.0027 (8)0.0039 (8)−0.0028 (8)
O20.0838 (9)0.0425 (7)0.0568 (8)0.0004 (6)−0.0117 (6)−0.0050 (6)
N30.0736 (10)0.0383 (8)0.0544 (9)0.0020 (6)−0.0048 (7)−0.0056 (6)
O10.0912 (9)0.0344 (7)0.0713 (9)0.0016 (6)−0.0085 (7)−0.0070 (6)
C30.0545 (10)0.0476 (10)0.0588 (11)0.0041 (7)−0.0009 (8)0.0036 (8)
C80.0537 (9)0.0449 (9)0.0555 (11)0.0020 (7)0.0052 (8)0.0011 (8)
C50.0671 (11)0.0407 (10)0.0622 (11)0.0004 (8)−0.0026 (9)0.0013 (8)
C100.0564 (9)0.0376 (9)0.0537 (10)−0.0007 (7)0.0042 (8)−0.0053 (7)
N10.0990 (13)0.0545 (10)0.0639 (10)0.0029 (9)−0.0233 (9)0.0063 (8)
C70.0626 (10)0.0429 (9)0.0571 (11)0.0038 (8)0.0000 (8)0.0074 (8)
C60.0717 (11)0.0401 (9)0.0660 (12)0.0005 (8)−0.0003 (9)0.0013 (8)
C40.0780 (12)0.0444 (10)0.0639 (12)0.0062 (9)−0.0030 (9)0.0113 (8)
C110.0797 (13)0.0577 (12)0.0628 (12)0.0020 (9)−0.0115 (10)0.0015 (9)
C10.0978 (16)0.0752 (15)0.0768 (14)0.0021 (12)−0.0256 (12)0.0202 (11)
C20.0936 (15)0.0716 (14)0.0708 (13)−0.0055 (11)−0.0135 (11)−0.0009 (12)
Geometric parameters (Å, °) top
N2—C91.282 (2)N1—C21.434 (3)
N2—N31.386 (2)N1—C11.445 (2)
C9—C81.454 (2)C7—H70.9300
C9—H90.9300C6—C41.377 (3)
O2—C101.344 (2)C6—H60.9300
O2—C111.436 (2)C4—H40.9300
N3—C101.345 (2)C11—H11A0.9600
N3—H30.8600C11—H11B0.9600
O1—C101.202 (2)C11—H11C0.9600
C3—N11.376 (2)C1—H1A0.9600
C3—C41.398 (2)C1—H1B0.9600
C3—C51.413 (2)C1—H1C0.9600
C8—C61.392 (2)C2—H2A0.9600
C8—C71.395 (2)C2—H2B0.9600
C5—C71.374 (3)C2—H2C0.9600
C5—H50.9300
C9—N2—N3114.71 (15)C8—C7—H7119.0
N2—C9—C8122.00 (16)C4—C6—C8122.19 (17)
N2—C9—H9119.0C4—C6—H6118.9
C8—C9—H9119.0C8—C6—H6118.9
C10—O2—C11116.70 (13)C6—C4—C3121.41 (16)
C10—N3—N2119.44 (14)C6—C4—H4119.3
C10—N3—H3120.3C3—C4—H4119.3
N2—N3—H3120.3O2—C11—H11A109.5
N1—C3—C4121.92 (16)O2—C11—H11B109.5
N1—C3—C5121.59 (16)H11A—C11—H11B109.5
C4—C3—C5116.49 (16)O2—C11—H11C109.5
C6—C8—C7116.64 (16)H11A—C11—H11C109.5
C6—C8—C9120.04 (16)H11B—C11—H11C109.5
C7—C8—C9123.32 (16)N1—C1—H1A109.5
C7—C5—C3121.32 (16)N1—C1—H1B109.5
C7—C5—H5119.3H1A—C1—H1B109.5
C3—C5—H5119.3N1—C1—H1C109.5
O1—C10—O2124.50 (16)H1A—C1—H1C109.5
O1—C10—N3126.45 (16)H1B—C1—H1C109.5
O2—C10—N3109.03 (14)N1—C2—H2A109.5
C3—N1—C2122.56 (16)N1—C2—H2B109.5
C3—N1—C1120.36 (17)H2A—C2—H2B109.5
C2—N1—C1116.83 (17)N1—C2—H2C109.5
C5—C7—C8121.95 (16)H2A—C2—H2C109.5
C5—C7—H7119.0H2B—C2—H2C109.5
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3···O1i0.862.162.976 (2)157
Symmetry codes: (i) −x+1/2, y−1/2, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3···O1i0.862.162.976 (2)157
Symmetry codes: (i) −x+1/2, y−1/2, z.
Acknowledgements top

The author acknowledges the financial support of Zhejiang University of Technology, China.

references
References top

Bruker (2002). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Hadjoudis, E., Vittorakis, M. & Moustakali-Mavridis, J. (1987). Tetrahedron, 43, 1345–1360.

Parashar, R. K., Sharma, R. C., Kumar, A. & Mohanm, G. (1988). Inorg. Chim. Acta, 151, 201–208.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Shi, X.-F. & Yuan, C.-C. (2006). Acta Cryst. E62, o3290–o3291.