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

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

doi:10.1107/S1600536808013950

organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page o1081

doi:10.1107/S1600536808013950

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

Xian-Chao Hu,^a ^* Lu-Ping Lv,^b Wei-Wei Li ^b and Wen-Bo Yu ^b

^aResearch Center of Analysis and Measurement, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China, and ^bDepartment of Chemical Engineering, Hangzhou Vocational and Technical College, Hangzhou 310018, People's Republic of China
^*Correspondence e-mail: zgdhxc@126.com

(Received 7 May 2008; accepted 9 May 2008; online 14 May 2008)

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.

Related literature

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

Experimental

Crystal data

C₁₁H₁₅N₃O₂
M_r = 221.26
Orthorhombic, P b c a
a = 13.051 (3) Å
b = 9.838 (2) Å
c = 18.637 (4) Å
V = 2392.9 (9) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 123 (2) K
0.29 × 0.26 × 0.22 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.979, T_max = 0.981
19378 measured reflections
2111 independent reflections
1592 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.134
S = 1.11
2111 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯O1ⁱ	0.86	2.16	2.976 (2)	157
Symmetry code: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808013950/hb2730sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808013950/hb2730Isup2.hkl

checkCIF report

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).

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

	Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids for the non-hydrogen atoms.
	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

C₁₁H₁₅N₃O₂	F(000) = 944
M_r = 221.26	D_x = 1.228 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2111 reflections
a = 13.051 (3) Å	θ = 2.2–25.0°
b = 9.838 (2) Å	µ = 0.09 mm⁻¹
c = 18.637 (4) Å	T = 123 K
V = 2392.9 (9) Å³	Block, colourless
Z = 8	0.29 × 0.26 × 0.22 mm

Data collection top

Bruker SMART CCD diffractometer	2111 independent reflections
Radiation source: fine-focus sealed tube	1592 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −15→15
T_min = 0.979, T_max = 0.981	k = −11→11
19378 measured reflections	l = −21→22

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.134	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0719P)² + 0.3078P] where P = (F_o² + 2F_c²)/3
2111 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₁₁H₁₅N₃O₂	V = 2392.9 (9) Å³
M_r = 221.26	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 13.051 (3) Å	µ = 0.09 mm⁻¹
b = 9.838 (2) Å	T = 123 K
c = 18.637 (4) Å	0.29 × 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)
T_min = 0.979, T_max = 0.981	R_int = 0.038
19378 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.134	H-atom parameters constrained
S = 1.11	Δρ_max = 0.23 e Å⁻³
2111 reflections	Δρ_min = −0.27 e Å⁻³
145 parameters

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

	x	y	z	U_iso*/U_eq
N2	0.27645 (11)	0.23338 (15)	0.56388 (7)	0.0539 (4)
C9	0.29967 (13)	0.13610 (19)	0.60663 (9)	0.0546 (5)
H9	0.2897	0.0469	0.5916	0.066*
O2	0.17803 (10)	0.22366 (12)	0.38955 (6)	0.0610 (4)
N3	0.23964 (12)	0.19224 (14)	0.49757 (7)	0.0554 (4)
H3	0.2363	0.1072	0.4871	0.067*
O1	0.20751 (10)	0.40732 (12)	0.45884 (7)	0.0656 (4)
C3	0.42170 (14)	0.20049 (17)	0.81830 (9)	0.0536 (4)
C8	0.34112 (13)	0.16094 (17)	0.67786 (9)	0.0513 (4)
C5	0.40355 (14)	0.31063 (17)	0.77132 (10)	0.0567 (5)
H5	0.4182	0.3986	0.7865	0.068*
C10	0.20925 (12)	0.28641 (17)	0.44977 (9)	0.0492 (4)
N1	0.45818 (14)	0.22037 (16)	0.88679 (9)	0.0725 (5)
C7	0.36472 (13)	0.29041 (18)	0.70360 (10)	0.0542 (4)
H7	0.3538	0.3652	0.6741	0.065*
C6	0.35985 (14)	0.05251 (18)	0.72400 (10)	0.0593 (5)
H6	0.3453	−0.0352	0.7085	0.071*
C4	0.39921 (15)	0.07084 (18)	0.79189 (10)	0.0621 (5)
H4	0.4111	−0.0046	0.8208	0.075*
C11	0.14121 (16)	0.30910 (19)	0.33264 (10)	0.0667 (5)
H11A	0.1216	0.2538	0.2925	0.100*
H11B	0.1945	0.3707	0.3183	0.100*
H11C	0.0830	0.3599	0.3491	0.100*
C1	0.48056 (19)	0.1055 (2)	0.93250 (11)	0.0833 (7)
H1A	0.5057	0.1373	0.9779	0.125*
H1B	0.5316	0.0494	0.9101	0.125*
H1C	0.4193	0.0534	0.9398	0.125*
C2	0.48463 (18)	0.3522 (2)	0.91387 (11)	0.0787 (6)
H2A	0.5090	0.3439	0.9623	0.118*
H2B	0.4252	0.4098	0.9130	0.118*
H2C	0.5374	0.3912	0.8845	0.118*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N2	0.0641 (9)	0.0466 (9)	0.0509 (9)	0.0017 (6)	−0.0001 (7)	−0.0056 (7)
C9	0.0610 (10)	0.0438 (10)	0.0590 (11)	0.0027 (8)	0.0039 (8)	−0.0028 (8)
O2	0.0838 (9)	0.0425 (7)	0.0568 (8)	0.0004 (6)	−0.0117 (6)	−0.0050 (6)
N3	0.0736 (10)	0.0383 (8)	0.0544 (9)	0.0020 (6)	−0.0048 (7)	−0.0056 (6)
O1	0.0912 (9)	0.0344 (7)	0.0713 (9)	0.0016 (6)	−0.0085 (7)	−0.0070 (6)
C3	0.0545 (10)	0.0476 (10)	0.0588 (11)	0.0041 (7)	−0.0009 (8)	0.0036 (8)
C8	0.0537 (9)	0.0449 (9)	0.0555 (11)	0.0020 (7)	0.0052 (8)	0.0011 (8)
C5	0.0671 (11)	0.0407 (10)	0.0622 (11)	0.0004 (8)	−0.0026 (9)	0.0013 (8)
C10	0.0564 (9)	0.0376 (9)	0.0537 (10)	−0.0007 (7)	0.0042 (8)	−0.0053 (7)
N1	0.0990 (13)	0.0545 (10)	0.0639 (10)	0.0029 (9)	−0.0233 (9)	0.0063 (8)
C7	0.0626 (10)	0.0429 (9)	0.0571 (11)	0.0038 (8)	0.0000 (8)	0.0074 (8)
C6	0.0717 (11)	0.0401 (9)	0.0660 (12)	0.0005 (8)	−0.0003 (9)	0.0013 (8)
C4	0.0780 (12)	0.0444 (10)	0.0639 (12)	0.0062 (9)	−0.0030 (9)	0.0113 (8)
C11	0.0797 (13)	0.0577 (12)	0.0628 (12)	0.0020 (9)	−0.0115 (10)	0.0015 (9)
C1	0.0978 (16)	0.0752 (15)	0.0768 (14)	0.0021 (12)	−0.0256 (12)	0.0202 (11)
C2	0.0936 (15)	0.0716 (14)	0.0708 (13)	−0.0055 (11)	−0.0135 (11)	−0.0009 (12)

Geometric parameters (Å, º) top

N2—C9	1.282 (2)	N1—C2	1.434 (3)
N2—N3	1.386 (2)	N1—C1	1.445 (2)
C9—C8	1.454 (2)	C7—H7	0.9300
C9—H9	0.9300	C6—C4	1.377 (3)
O2—C10	1.344 (2)	C6—H6	0.9300
O2—C11	1.436 (2)	C4—H4	0.9300
N3—C10	1.345 (2)	C11—H11A	0.9600
N3—H3	0.8600	C11—H11B	0.9600
O1—C10	1.202 (2)	C11—H11C	0.9600
C3—N1	1.376 (2)	C1—H1A	0.9600
C3—C4	1.398 (2)	C1—H1B	0.9600
C3—C5	1.413 (2)	C1—H1C	0.9600
C8—C6	1.392 (2)	C2—H2A	0.9600
C8—C7	1.395 (2)	C2—H2B	0.9600
C5—C7	1.374 (3)	C2—H2C	0.9600
C5—H5	0.9300

C9—N2—N3	114.71 (15)	C8—C7—H7	119.0
N2—C9—C8	122.00 (16)	C4—C6—C8	122.19 (17)
N2—C9—H9	119.0	C4—C6—H6	118.9
C8—C9—H9	119.0	C8—C6—H6	118.9
C10—O2—C11	116.70 (13)	C6—C4—C3	121.41 (16)
C10—N3—N2	119.44 (14)	C6—C4—H4	119.3
C10—N3—H3	120.3	C3—C4—H4	119.3
N2—N3—H3	120.3	O2—C11—H11A	109.5
N1—C3—C4	121.92 (16)	O2—C11—H11B	109.5
N1—C3—C5	121.59 (16)	H11A—C11—H11B	109.5
C4—C3—C5	116.49 (16)	O2—C11—H11C	109.5
C6—C8—C7	116.64 (16)	H11A—C11—H11C	109.5
C6—C8—C9	120.04 (16)	H11B—C11—H11C	109.5
C7—C8—C9	123.32 (16)	N1—C1—H1A	109.5
C7—C5—C3	121.32 (16)	N1—C1—H1B	109.5
C7—C5—H5	119.3	H1A—C1—H1B	109.5
C3—C5—H5	119.3	N1—C1—H1C	109.5
O1—C10—O2	124.50 (16)	H1A—C1—H1C	109.5
O1—C10—N3	126.45 (16)	H1B—C1—H1C	109.5
O2—C10—N3	109.03 (14)	N1—C2—H2A	109.5
C3—N1—C2	122.56 (16)	N1—C2—H2B	109.5
C3—N1—C1	120.36 (17)	H2A—C2—H2B	109.5
C2—N1—C1	116.83 (17)	N1—C2—H2C	109.5
C5—C7—C8	121.95 (16)	H2A—C2—H2C	109.5
C5—C7—H7	119.0	H2B—C2—H2C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O1ⁱ	0.86	2.16	2.976 (2)	157

Symmetry code: (i) −x+1/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₅N₃O₂
M_r	221.26
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	123
a, b, c (Å)	13.051 (3), 9.838 (2), 18.637 (4)
V (Å³)	2392.9 (9)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.29 × 0.26 × 0.22

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.979, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	19378, 2111, 1592
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.134, 1.11
No. of reflections	2111
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.27

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O1ⁱ	0.86	2.16	2.976 (2)	157

Symmetry code: (i) −x+1/2, y−1/2, z.

Acknowledgements

The authors acknowledge the financial support of Zhejiang University of Technology, China.

References

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Parashar, R. K., Sharma, R. C., Kumar, A. & Mohanm, G. (1988). Inorg. Chim. Acta, 151, 201–208. CrossRef CAS Web of Science Google Scholar
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