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

Abstract

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,

• a = 13.051 (3) Å

• b = 9.838 (2) Å

• c = 18.637 (4) Å

• V = 2392.9 (9) ų

• 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[F ² > 2σ(F ²)] = 0.046

• wR(F ²) = 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

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.

Supplementary Material

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

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) .

supplementary crystallographic information

Comment

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).

Experimental

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

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

Figures

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.

Crystal data

C11H15N3O2	F000 = 944
Mr = 221.26	Dx = 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 = 2.2–25.0º
b = 9.838 (2) Å	µ = 0.09 mm−1
c = 18.637 (4) Å	T = 123 (2) K
V = 2392.9 (9) Å3	Block, colourless
Z = 8	0.29 × 0.26 × 0.22 mm

Data collection

Bruker SMART CCD diffractometer	2111 independent reflections
Radiation source: fine-focus sealed tube	1592 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.038
T = 123(2) K	θmax = 25.0º
ω scans	θmin = 2.2º
Absorption correction: multi-scan(SADABS; Bruker, 2002)	h = −15→15
Tmin = 0.979, Tmax = 0.981	k = −11→11
19378 measured reflections	l = −21→22

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.046	H-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 reflections	Δρmax = 0.23 e Å−3
145 parameters	Δρmin = −0.27 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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

Symmetry codes: (i) −x+1/2, y−1/2, z.