Methyl (2E)-2-(4-chloro­benzyl­idene)­hydrazinecarboxyl­ate

The title compound, C₉H₉ClN₂O₂, crystallizes with two independent mol­ecules in the asymmetric unit, the conformations of which are slightly different. Inter­molecular N—H...O hydrogen bonds link the mol­ecules into ladder-type ribbons extending along the c axis.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C)= 0.003 Å
• R factor = 0.037
• wR factor = 0.126
• Data-to-parameter ratio = 16.4

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Computing details

Data collection: SMART (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2005); software used to prepare material for publication: SHELXTL.

Methyl (2E)-2-(4-chlorobenzylidene)hydrazinecarboxylate

Crystal data

C9H9ClN2O2	F(000) = 880
Mr = 212.63	Dx = 1.419 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3859 reflections
a = 13.492 (2) Å	θ = 2.6–26.9°
b = 9.5342 (14) Å	µ = 0.36 mm^−1
c = 15.527 (2) Å	T = 296 K
β = 94.800 (2)°	Prism, colourless
V = 1990.4 (5) Å^3	0.30 × 0.20 × 0.10 mm
Z = 8

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	4322 independent reflections
Radiation source: fine-focus sealed tube	3235 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
φ and ω scans	θmax = 27.0°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −17→16
Tmin = 0.900, Tmax = 0.955	k = −10→12
12107 measured reflections	l = −17→19

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.126	w = 1/[σ^2(Fo^2) + (0.0705P)^2 + 0.0746P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.001
4322 reflections	Δρmax = 0.27 e Å^−3
264 parameters	Δρmin = −0.18 e Å^−3
2 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0162 (17)

Special details

Experimental. IR:(KBr, cm^-1): 3237, 1708, 1557, 736.

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. The hydrogen atoms H2x and H4x were located in deffirence fourier maps and refined isotropically with the N—H bond restraint of 0.86 (2) Å. Methyl H atoms were placed in calculated positions with C—H = 0.96 Å and torsion angles were refined to fit the electron density, U_iso(H) = 1.5U_eq(C). Other H atoms were placed in calculated positions with C—H = 0.93, and refined in riding mode, with U_iso(H) = 1.2U_eq(C).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.46378 (4)	0.35823 (7)	0.19394 (4)	0.0804 (2)
O1	1.13708 (8)	−0.02034 (12)	0.43763 (7)	0.0520 (3)
O2	1.05815 (9)	−0.07399 (13)	0.30750 (7)	0.0549 (3)
N1	0.91822 (9)	0.12394 (14)	0.34158 (8)	0.0443 (3)
N2	1.00549 (10)	0.10212 (14)	0.39238 (9)	0.0481 (3)
H2X	1.0159 (13)	0.1470 (18)	0.4404 (10)	0.058 (5)*
C1	0.72513 (13)	0.38872 (17)	0.33165 (12)	0.0524 (4)
H1	0.7584	0.4547	0.3674	0.063*
C2	0.63151 (13)	0.41939 (19)	0.29352 (13)	0.0565 (4)
H2	0.6019	0.5053	0.3035	0.068*
C3	0.58255 (12)	0.32156 (19)	0.24061 (12)	0.0520 (4)
C4	0.62617 (13)	0.19513 (19)	0.22407 (12)	0.0559 (4)
H4	0.5931	0.1305	0.1872	0.067*
C5	0.71968 (13)	0.16517 (17)	0.26280 (12)	0.0514 (4)
H5	0.7491	0.0794	0.2521	0.062*
C6	0.77031 (11)	0.26100 (16)	0.31744 (10)	0.0426 (4)
C7	0.86850 (12)	0.23067 (16)	0.36151 (11)	0.0454 (4)
H7	0.8948	0.2906	0.4048	0.054*
C8	1.06589 (11)	−0.00442 (17)	0.37307 (10)	0.0429 (4)
C9	1.20953 (14)	−0.1277 (2)	0.42485 (13)	0.0628 (5)
H9A	1.1769	−0.2171	0.4189	0.094*
H9B	1.2581	−0.1299	0.4737	0.094*
H9C	1.2418	−0.1076	0.3734	0.094*
Cl2	0.45724 (4)	0.79068 (7)	0.52155 (4)	0.0865 (2)
O3	1.12939 (9)	0.31423 (12)	0.65130 (8)	0.0571 (3)
O4	1.01265 (9)	0.27845 (13)	0.54046 (8)	0.0567 (3)
N3	0.90320 (10)	0.48677 (14)	0.60707 (9)	0.0480 (3)
N4	0.99583 (11)	0.44717 (15)	0.64190 (10)	0.0503 (4)
H4X	1.0206 (14)	0.4798 (19)	0.6894 (10)	0.057 (5)*
C11	0.72745 (14)	0.76272 (19)	0.64426 (12)	0.0564 (4)
H11	0.7661	0.8143	0.6854	0.068*
C12	0.63339 (15)	0.8103 (2)	0.61582 (14)	0.0622 (5)
H12	0.6089	0.8930	0.6377	0.075*
C13	0.57685 (13)	0.7345 (2)	0.55520 (13)	0.0583 (5)
C14	0.61224 (14)	0.6125 (2)	0.52148 (13)	0.0630 (5)
H14	0.5735	0.5626	0.4796	0.076*
C15	0.70579 (14)	0.56487 (19)	0.55050 (13)	0.0580 (5)
H15	0.7296	0.4819	0.5284	0.070*
C16	0.76500 (12)	0.63951 (16)	0.61244 (11)	0.0466 (4)
C17	0.86463 (12)	0.59072 (17)	0.64324 (11)	0.0484 (4)
H17	0.8998	0.6358	0.6893	0.058*
C18	1.04217 (12)	0.34018 (16)	0.60540 (11)	0.0449 (4)
C19	1.18885 (14)	0.2043 (2)	0.61855 (14)	0.0640 (5)
H19A	1.1540	0.1167	0.6206	0.096*
H19B	1.2509	0.1980	0.6533	0.096*
H19C	1.2013	0.2249	0.5599	0.096*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0454 (3)	0.1046 (4)	0.0896 (4)	0.0149 (3)	−0.0046 (3)	0.0102 (3)
O1	0.0438 (6)	0.0616 (7)	0.0488 (7)	0.0083 (5)	−0.0064 (5)	−0.0032 (5)
O2	0.0639 (7)	0.0586 (7)	0.0408 (7)	0.0151 (6)	−0.0036 (5)	−0.0040 (5)
N1	0.0417 (7)	0.0483 (7)	0.0419 (7)	0.0023 (6)	−0.0027 (6)	0.0027 (6)
N2	0.0454 (7)	0.0531 (8)	0.0438 (8)	0.0064 (6)	−0.0077 (6)	−0.0086 (6)
C1	0.0549 (10)	0.0456 (9)	0.0559 (11)	0.0007 (7)	0.0004 (8)	−0.0056 (7)
C2	0.0545 (10)	0.0507 (9)	0.0644 (12)	0.0137 (8)	0.0059 (8)	0.0012 (8)
C3	0.0398 (9)	0.0627 (10)	0.0538 (10)	0.0032 (7)	0.0048 (7)	0.0099 (8)
C4	0.0486 (10)	0.0563 (10)	0.0612 (12)	−0.0048 (8)	−0.0040 (8)	−0.0019 (8)
C5	0.0497 (9)	0.0444 (9)	0.0591 (11)	0.0038 (7)	−0.0005 (8)	−0.0048 (8)
C6	0.0406 (8)	0.0435 (8)	0.0437 (9)	0.0009 (6)	0.0037 (7)	0.0038 (7)
C7	0.0463 (9)	0.0446 (8)	0.0443 (9)	−0.0013 (7)	−0.0015 (7)	−0.0015 (7)
C8	0.0414 (8)	0.0474 (8)	0.0393 (9)	0.0005 (7)	0.0000 (6)	0.0035 (7)
C9	0.0468 (10)	0.0707 (12)	0.0695 (13)	0.0152 (8)	−0.0032 (9)	0.0031 (10)
Cl2	0.0562 (3)	0.1107 (5)	0.0907 (5)	0.0146 (3)	−0.0042 (3)	0.0126 (3)
O3	0.0487 (7)	0.0599 (7)	0.0598 (8)	0.0006 (5)	−0.0131 (6)	−0.0079 (6)
O4	0.0553 (7)	0.0651 (7)	0.0478 (7)	−0.0009 (6)	−0.0072 (6)	−0.0121 (6)
N3	0.0500 (8)	0.0492 (8)	0.0436 (8)	−0.0030 (6)	−0.0034 (6)	0.0024 (6)
N4	0.0513 (8)	0.0546 (8)	0.0424 (8)	0.0002 (6)	−0.0102 (6)	−0.0074 (6)
C11	0.0602 (11)	0.0556 (10)	0.0523 (11)	−0.0037 (8)	−0.0021 (8)	−0.0030 (8)
C12	0.0654 (12)	0.0588 (11)	0.0625 (12)	0.0081 (9)	0.0053 (9)	0.0001 (9)
C13	0.0484 (10)	0.0694 (12)	0.0564 (11)	0.0002 (8)	0.0013 (8)	0.0117 (9)
C14	0.0561 (11)	0.0702 (12)	0.0602 (12)	−0.0071 (9)	−0.0098 (9)	−0.0046 (9)
C15	0.0598 (11)	0.0542 (10)	0.0586 (11)	−0.0002 (8)	−0.0039 (9)	−0.0051 (8)
C16	0.0517 (9)	0.0456 (8)	0.0420 (9)	−0.0058 (7)	0.0019 (7)	0.0053 (7)
C17	0.0535 (9)	0.0489 (9)	0.0418 (9)	−0.0069 (7)	−0.0013 (7)	0.0022 (7)
C18	0.0447 (8)	0.0479 (9)	0.0409 (9)	−0.0083 (7)	−0.0029 (7)	0.0015 (7)
C19	0.0530 (10)	0.0638 (11)	0.0741 (14)	0.0030 (9)	−0.0010 (9)	−0.0003 (10)

Geometric parameters (Å, º)

Cl1—C3	1.7381 (17)	Cl2—C13	1.7386 (19)
O1—C8	1.3377 (18)	O3—C18	1.3467 (19)
O1—C9	1.441 (2)	O3—C19	1.438 (2)
O2—C8	1.2122 (19)	O4—C18	1.2060 (19)
N1—C7	1.271 (2)	N3—C17	1.272 (2)
N1—N2	1.3772 (18)	N3—N4	1.3725 (19)
N2—C8	1.352 (2)	N4—C18	1.346 (2)
N2—H2X	0.862 (14)	N4—H4X	0.843 (14)
C1—C2	1.381 (2)	C11—C12	1.385 (3)
C1—C6	1.388 (2)	C11—C16	1.387 (2)
C1—H1	0.9300	C11—H11	0.9300
C2—C3	1.375 (3)	C12—C13	1.368 (3)
C2—H2	0.9300	C12—H12	0.9300
C3—C4	1.375 (2)	C13—C14	1.378 (3)
C4—C5	1.381 (2)	C14—C15	1.381 (3)
C4—H4	0.9300	C14—H14	0.9300
C5—C6	1.387 (2)	C15—C16	1.393 (2)
C5—H5	0.9300	C15—H15	0.9300
C6—C7	1.468 (2)	C16—C17	1.464 (2)
C7—H7	0.9300	C17—H17	0.9300
C9—H9A	0.9599	C19—H19A	0.9599
C9—H9B	0.9599	C19—H19B	0.9599
C9—H9C	0.9599	C19—H19C	0.9599
C8—O1—C9	115.49 (13)	C18—O3—C19	115.80 (13)
C7—N1—N2	115.14 (13)	C17—N3—N4	115.67 (13)
C8—N2—N1	119.27 (13)	C18—N4—N3	118.84 (14)
C8—N2—H2X	120.5 (13)	C18—N4—H4X	118.9 (13)
N1—N2—H2X	119.4 (13)	N3—N4—H4X	121.6 (13)
C2—C1—C6	121.06 (16)	C12—C11—C16	121.10 (17)
C2—C1—H1	119.5	C12—C11—H11	119.5
C6—C1—H1	119.5	C16—C11—H11	119.5
C3—C2—C1	119.28 (16)	C13—C12—C11	119.33 (18)
C3—C2—H2	120.4	C13—C12—H12	120.3
C1—C2—H2	120.4	C11—C12—H12	120.3
C2—C3—C4	120.97 (16)	C12—C13—C14	121.12 (17)
C2—C3—Cl1	119.52 (14)	C12—C13—Cl2	119.63 (16)
C4—C3—Cl1	119.51 (14)	C14—C13—Cl2	119.24 (15)
C3—C4—C5	119.31 (16)	C13—C14—C15	119.33 (18)
C3—C4—H4	120.3	C13—C14—H14	120.3
C5—C4—H4	120.3	C15—C14—H14	120.3
C4—C5—C6	121.01 (16)	C14—C15—C16	120.87 (17)
C4—C5—H5	119.5	C14—C15—H15	119.6
C6—C5—H5	119.5	C16—C15—H15	119.6
C5—C6—C1	118.35 (15)	C11—C16—C15	118.24 (16)
C5—C6—C7	122.30 (14)	C11—C16—C17	120.37 (15)
C1—C6—C7	119.34 (15)	C15—C16—C17	121.39 (16)
N1—C7—C6	121.21 (14)	N3—C17—C16	120.12 (15)
N1—C7—H7	119.4	N3—C17—H17	119.9
C6—C7—H7	119.4	C16—C17—H17	119.9
O2—C8—O1	124.98 (15)	O4—C18—N4	126.10 (15)
O2—C8—N2	125.91 (15)	O4—C18—O3	124.45 (15)
O1—C8—N2	109.11 (13)	N4—C18—O3	109.42 (13)
O1—C9—H9A	109.5	O3—C19—H19A	109.5
O1—C9—H9B	109.5	O3—C19—H19B	109.5
H9A—C9—H9B	109.5	H19A—C19—H19B	109.5
O1—C9—H9C	109.5	O3—C19—H19C	109.5
H9A—C9—H9C	109.5	H19A—C19—H19C	109.5
H9B—C9—H9C	109.5	H19B—C19—H19C	109.5
C7—N1—N2—C8	−176.44 (14)	C17—N3—N4—C18	−178.30 (15)
C6—C1—C2—C3	−0.1 (3)	C16—C11—C12—C13	−0.2 (3)
C1—C2—C3—C4	−1.1 (3)	C11—C12—C13—C14	−0.6 (3)
C1—C2—C3—Cl1	178.86 (14)	C11—C12—C13—Cl2	178.05 (15)
C2—C3—C4—C5	1.4 (3)	C12—C13—C14—C15	1.1 (3)
Cl1—C3—C4—C5	−178.59 (14)	Cl2—C13—C14—C15	−177.58 (15)
C3—C4—C5—C6	−0.5 (3)	C13—C14—C15—C16	−0.8 (3)
C4—C5—C6—C1	−0.7 (3)	C12—C11—C16—C15	0.4 (3)
C4—C5—C6—C7	178.21 (16)	C12—C11—C16—C17	180.00 (16)
C2—C1—C6—C5	0.9 (3)	C14—C15—C16—C11	0.1 (3)
C2—C1—C6—C7	−177.96 (16)	C14—C15—C16—C17	−179.50 (16)
N2—N1—C7—C6	−175.23 (14)	N4—N3—C17—C16	−178.57 (14)
C5—C6—C7—N1	10.8 (2)	C11—C16—C17—N3	−172.03 (16)
C1—C6—C7—N1	−170.35 (16)	C15—C16—C17—N3	7.6 (2)
C9—O1—C8—O2	1.2 (2)	N3—N4—C18—O4	4.6 (3)
C9—O1—C8—N2	−178.00 (14)	N3—N4—C18—O3	−177.27 (13)
N1—N2—C8—O2	10.6 (3)	C19—O3—C18—O4	−0.2 (2)
N1—N2—C8—O1	−170.20 (13)	C19—O3—C18—N4	−178.41 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2X···O4	0.86 (1)	2.00 (2)	2.8434 (19)	166 (2)
N4—H4X···O2^i	0.84 (1)	2.07 (2)	2.9016 (18)	171 (2)

Symmetry code: (i) x, −y+1/2, z+1/2.