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The title compound, C10H11ClN2O2, crystallizes with two independent, but essentially identical mol­ecules in the asymmetric unit. Each planar mol­ecule is in the E configuration about the C=N bond. Inter­molecular N—H...O hydrogen bonds link mol­ecules into a one-dimensional chain aligned along the [101] direction.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807051410/tk2199sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807051410/tk2199Isup2.hkl
Contains datablock I

CCDC reference: 667428

Key indicators

  • Single-crystal X-ray study
  • T = 193 K
  • Mean [sigma](C-C)= 0.003 Å
  • R factor = 0.049
  • wR factor = 0.111
  • Data-to-parameter ratio = 14.6

checkCIF/PLATON results

No syntax errors found


No errors found in this datablock

Comment top

Chlorobenzaldehydehydrazone derivatives are important intermediates in the synthesis of 1,4-dihydrotetrazines, which demonstrate anti-tumour activity (Hu et al., 2005). A representative crystal structure, namely methyl (E)-2-(4-chlorobenzylidene)hydrazinecarboxylate has been reported recently (Meng et al., 2007). Herein, the crystal structure of the title compound, C10H11ClN3O2 (I), is described.

Compound (I) crystallizes with two chemically equivalent but crystallographically independent molecules in the asymmetric unit (Fig. 1). Each essentially planar molecule is in an E-conformation with respect to the N=C double bond. The bond lengths and angles defining the C=N—N(H)—C groups are close to those of the reported literature (Shi, 2005).

Intermolecular N—H···O hydrogen bonds (Table 1) serve to link molecules into a 1-D chain aligned along the (101) direction (Fig. 2).

Related literature top

For general background, see: Hu et al. (2005). For related structures, see: Meng et al. (2007); Shi (2005).

Experimental top

4-Chlorobenzaldehyde (7 g, 0.1 mol) and ethyl hydrazinecarboxylate (5.2 g 0.05 mol) were dissolved in a stirred methanol (50 ml) solution and left to stand for 3 h at room temperature. The resulting solid was filtered off and recrystallized from an ethanol solution to yield (I) in 80% yield. Crystals suitable for X-ray analysis were obtained by the slow evaporation of an ethanol solution of (I) held at room temperature; m.p. 463–465 K.

Refinement top

The H atoms were included in the riding model approximation with N—H = 0.88 Å and C—H = 0.95–0.99 Å, and with Uiso(H) = 1.2–1.5Ueq(N, C).

Structure description top

Chlorobenzaldehydehydrazone derivatives are important intermediates in the synthesis of 1,4-dihydrotetrazines, which demonstrate anti-tumour activity (Hu et al., 2005). A representative crystal structure, namely methyl (E)-2-(4-chlorobenzylidene)hydrazinecarboxylate has been reported recently (Meng et al., 2007). Herein, the crystal structure of the title compound, C10H11ClN3O2 (I), is described.

Compound (I) crystallizes with two chemically equivalent but crystallographically independent molecules in the asymmetric unit (Fig. 1). Each essentially planar molecule is in an E-conformation with respect to the N=C double bond. The bond lengths and angles defining the C=N—N(H)—C groups are close to those of the reported literature (Shi, 2005).

Intermolecular N—H···O hydrogen bonds (Table 1) serve to link molecules into a 1-D chain aligned along the (101) direction (Fig. 2).

For general background, see: Hu et al. (2005). For related structures, see: Meng et al. (2007); Shi (2005).

Computing details top

Data collection: CrystalClear (Rigaku, 2001); cell refinement: CrystalClear (Rigaku, 2001); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL (Bruker, 1998).

Figures top
[Figure 1] Fig. 1. Molecular structures of the two independent molecules in (I), showing 20% probability displacement ellipsoids and atom numbering.
[Figure 2] Fig. 2. The crystal packing in (I), viewed approximately down the a axis. Dashed lines indicate intermolecular N—H···O hydrogen bonds.
Ethyl (E)-2-(4-chlorobenzylidene)hydrazinecarboxylate top
Crystal data top
C10H11ClN2O2F(000) = 944
Mr = 226.66Dx = 1.364 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71070 Å
Hall symbol: -P 2ynCell parameters from 7392 reflections
a = 16.317 (4) Åθ = 3.3–25.3°
b = 8.3488 (16) ŵ = 0.33 mm1
c = 18.035 (4) ÅT = 193 K
β = 116.014 (4)°Block, colourless
V = 2207.9 (8) Å30.60 × 0.58 × 0.34 mm
Z = 8
Data collection top
Rigaku Mercury
diffractometer
4011 independent reflections
Radiation source: fine-focus sealed tube3479 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.033
Detector resolution: 7.31 pixels mm-1θmax = 25.4°, θmin = 3.3°
ω scansh = 1919
Absorption correction: multi-scan
(Jacobson, 1998)
k = 1010
Tmin = 0.815, Tmax = 0.895l = 1921
20629 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.111H-atom parameters constrained
S = 1.16 w = 1/[σ2(Fo2) + (0.0427P)2 + 0.8029P]
where P = (Fo2 + 2Fc2)/3
4011 reflections(Δ/σ)max = 0.001
274 parametersΔρmax = 0.18 e Å3
0 restraintsΔρmin = 0.28 e Å3
Crystal data top
C10H11ClN2O2V = 2207.9 (8) Å3
Mr = 226.66Z = 8
Monoclinic, P21/nMo Kα radiation
a = 16.317 (4) ŵ = 0.33 mm1
b = 8.3488 (16) ÅT = 193 K
c = 18.035 (4) Å0.60 × 0.58 × 0.34 mm
β = 116.014 (4)°
Data collection top
Rigaku Mercury
diffractometer
4011 independent reflections
Absorption correction: multi-scan
(Jacobson, 1998)
3479 reflections with I > 2σ(I)
Tmin = 0.815, Tmax = 0.895Rint = 0.033
20629 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0490 restraints
wR(F2) = 0.111H-atom parameters constrained
S = 1.16Δρmax = 0.18 e Å3
4011 reflectionsΔρmin = 0.28 e Å3
274 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
xyzUiso*/Ueq
Cl10.25050 (5)0.58597 (9)0.64513 (4)0.0635 (2)
Cl20.45783 (5)0.27646 (10)0.86369 (4)0.0694 (2)
O10.51197 (9)0.07441 (18)0.36647 (8)0.0386 (4)
O20.66600 (9)0.06493 (19)0.42539 (8)0.0406 (4)
O30.78957 (10)0.28077 (19)0.58583 (9)0.0439 (4)
O40.94280 (9)0.30084 (18)0.65519 (8)0.0399 (4)
N10.52594 (11)0.2415 (2)0.50250 (10)0.0335 (4)
N20.60003 (11)0.1871 (2)0.49262 (10)0.0356 (4)
H2A0.65580.20440.53090.043*
N30.78486 (11)0.2701 (2)0.73588 (10)0.0344 (4)
N40.86403 (11)0.2841 (2)0.72690 (10)0.0355 (4)
H40.91730.29030.77040.043*
C10.47229 (13)0.3898 (2)0.58521 (12)0.0324 (5)
C20.49353 (14)0.4774 (3)0.65635 (12)0.0372 (5)
H2B0.55570.49600.69300.045*
C30.42629 (15)0.5386 (3)0.67540 (13)0.0421 (5)
H30.44190.59770.72480.051*
C40.33623 (15)0.5122 (3)0.62145 (13)0.0410 (5)
C50.31250 (15)0.4279 (3)0.54926 (14)0.0439 (5)
H50.25020.41200.51230.053*
C60.38014 (14)0.3673 (3)0.53144 (13)0.0394 (5)
H60.36400.30900.48170.047*
C70.54462 (14)0.3241 (2)0.56740 (12)0.0348 (5)
H70.60650.34310.60470.042*
C80.58569 (13)0.1065 (2)0.42305 (12)0.0334 (5)
C90.66132 (15)0.0179 (3)0.35306 (13)0.0456 (6)
H9A0.63140.05060.30360.055*
H9B0.62560.11800.34400.055*
C100.75707 (17)0.0554 (4)0.36796 (16)0.0643 (8)
H10A0.79220.04420.37850.096*
H10B0.75640.10860.31930.096*
H10C0.78520.12630.41590.096*
C110.71148 (13)0.2927 (2)0.82341 (12)0.0323 (5)
C120.70356 (15)0.3895 (3)0.88275 (13)0.0415 (5)
H120.75200.46000.91470.050*
C130.62641 (16)0.3846 (3)0.89583 (13)0.0452 (6)
H130.62100.45270.93560.054*
C140.55750 (15)0.2798 (3)0.85064 (13)0.0420 (5)
C150.56525 (15)0.1782 (3)0.79387 (13)0.0404 (5)
H150.51820.10330.76460.049*
C160.64155 (14)0.1859 (3)0.77987 (13)0.0360 (5)
H160.64640.11740.74000.043*
C170.79131 (14)0.3070 (2)0.80711 (13)0.0364 (5)
H170.84770.34360.84910.044*
C180.85828 (13)0.2881 (2)0.64994 (12)0.0342 (5)
C190.94907 (16)0.3227 (3)0.57822 (14)0.0495 (6)
H19A0.92800.43130.55590.059*
H19B0.91060.24300.53700.059*
C201.04581 (19)0.3012 (5)0.59608 (18)0.0784 (10)
H20A1.08330.37870.63810.118*
H20B1.05310.31840.54560.118*
H20C1.06520.19220.61640.118*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0598 (4)0.0750 (5)0.0709 (4)0.0098 (3)0.0425 (4)0.0035 (3)
Cl20.0548 (4)0.0933 (6)0.0770 (5)0.0089 (4)0.0444 (4)0.0090 (4)
O10.0262 (8)0.0470 (9)0.0341 (8)0.0033 (6)0.0054 (6)0.0007 (7)
O20.0273 (7)0.0576 (10)0.0337 (8)0.0065 (7)0.0105 (6)0.0048 (7)
O30.0292 (8)0.0578 (10)0.0349 (8)0.0052 (7)0.0049 (7)0.0003 (7)
O40.0271 (8)0.0544 (10)0.0362 (8)0.0003 (7)0.0119 (6)0.0004 (7)
N10.0278 (9)0.0369 (10)0.0332 (9)0.0025 (7)0.0110 (7)0.0022 (8)
N20.0222 (8)0.0480 (11)0.0309 (9)0.0025 (8)0.0065 (7)0.0023 (8)
N30.0256 (9)0.0348 (10)0.0391 (10)0.0003 (7)0.0108 (7)0.0035 (8)
N40.0236 (9)0.0441 (11)0.0337 (10)0.0005 (7)0.0076 (7)0.0030 (8)
C10.0319 (11)0.0303 (11)0.0326 (11)0.0002 (9)0.0120 (9)0.0034 (9)
C20.0355 (11)0.0365 (12)0.0332 (11)0.0007 (9)0.0092 (9)0.0003 (9)
C30.0510 (14)0.0383 (12)0.0353 (12)0.0012 (10)0.0174 (10)0.0024 (10)
C40.0439 (13)0.0397 (12)0.0443 (13)0.0059 (10)0.0239 (11)0.0053 (10)
C50.0328 (12)0.0509 (14)0.0458 (13)0.0012 (10)0.0152 (10)0.0011 (11)
C60.0356 (12)0.0455 (13)0.0336 (11)0.0016 (10)0.0119 (9)0.0050 (10)
C70.0291 (11)0.0370 (12)0.0320 (11)0.0009 (9)0.0077 (9)0.0029 (9)
C80.0275 (11)0.0364 (11)0.0330 (11)0.0041 (9)0.0102 (9)0.0055 (9)
C90.0393 (13)0.0608 (15)0.0342 (12)0.0097 (11)0.0140 (10)0.0017 (11)
C100.0471 (15)0.095 (2)0.0555 (16)0.0135 (14)0.0271 (13)0.0069 (15)
C110.0288 (10)0.0314 (11)0.0312 (10)0.0001 (9)0.0080 (8)0.0035 (9)
C120.0407 (12)0.0396 (13)0.0348 (11)0.0039 (10)0.0078 (10)0.0029 (10)
C130.0535 (14)0.0468 (14)0.0364 (12)0.0077 (11)0.0206 (11)0.0016 (10)
C140.0378 (12)0.0498 (14)0.0420 (12)0.0069 (10)0.0206 (10)0.0090 (11)
C150.0340 (12)0.0414 (13)0.0436 (12)0.0045 (10)0.0149 (10)0.0019 (10)
C160.0343 (11)0.0341 (12)0.0376 (11)0.0012 (9)0.0140 (9)0.0000 (9)
C170.0300 (11)0.0365 (12)0.0350 (12)0.0032 (9)0.0072 (9)0.0020 (9)
C180.0262 (11)0.0328 (11)0.0378 (12)0.0005 (8)0.0087 (9)0.0012 (9)
C190.0460 (14)0.0630 (16)0.0424 (13)0.0040 (12)0.0221 (11)0.0002 (11)
C200.0536 (17)0.128 (3)0.0668 (18)0.0082 (18)0.0388 (15)0.0068 (18)
Geometric parameters (Å, º) top
Cl1—C41.744 (2)C6—H60.9500
Cl2—C141.743 (2)C7—H70.9500
O1—C81.218 (2)C9—C101.498 (3)
O2—C81.338 (2)C9—H9A0.9900
O2—C91.449 (3)C9—H9B0.9900
O3—C181.209 (2)C10—H10A0.9800
O4—C181.344 (2)C10—H10B0.9800
O4—C191.447 (3)C10—H10C0.9800
N1—C71.275 (3)C11—C161.388 (3)
N1—N21.374 (2)C11—C121.392 (3)
N2—C81.350 (3)C11—C171.460 (3)
N2—H2A0.8800C12—C131.379 (3)
N3—C171.280 (3)C12—H120.9500
N3—N41.376 (2)C13—C141.375 (3)
N4—C181.350 (3)C13—H130.9500
N4—H40.8800C14—C151.377 (3)
C1—C21.383 (3)C15—C161.376 (3)
C1—C61.399 (3)C15—H150.9500
C1—C71.459 (3)C16—H160.9500
C2—C31.383 (3)C17—H170.9500
C2—H2B0.9500C19—C201.477 (3)
C3—C41.378 (3)C19—H19A0.9900
C3—H30.9500C19—H19B0.9900
C4—C51.378 (3)C20—H20A0.9800
C5—C61.374 (3)C20—H20B0.9800
C5—H50.9500C20—H20C0.9800
C8—O2—C9115.55 (15)C9—C10—H10B109.5
C18—O4—C19116.37 (16)H10A—C10—H10B109.5
C7—N1—N2115.36 (16)C9—C10—H10C109.5
C8—N2—N1118.78 (16)H10A—C10—H10C109.5
C8—N2—H2A120.6H10B—C10—H10C109.5
N1—N2—H2A120.6C16—C11—C12118.5 (2)
C17—N3—N4115.44 (16)C16—C11—C17121.55 (19)
C18—N4—N3118.54 (16)C12—C11—C17119.93 (18)
C18—N4—H4120.7C13—C12—C11120.9 (2)
N3—N4—H4120.7C13—C12—H12119.5
C2—C1—C6118.04 (19)C11—C12—H12119.5
C2—C1—C7120.36 (18)C14—C13—C12119.2 (2)
C6—C1—C7121.60 (19)C14—C13—H13120.4
C1—C2—C3121.51 (19)C12—C13—H13120.4
C1—C2—H2B119.2C13—C14—C15121.0 (2)
C3—C2—H2B119.2C13—C14—Cl2119.94 (18)
C4—C3—C2118.8 (2)C15—C14—Cl2119.08 (18)
C4—C3—H3120.6C16—C15—C14119.5 (2)
C2—C3—H3120.6C16—C15—H15120.2
C5—C4—C3121.3 (2)C14—C15—H15120.2
C5—C4—Cl1119.24 (17)C15—C16—C11120.8 (2)
C3—C4—Cl1119.46 (17)C15—C16—H16119.6
C6—C5—C4119.2 (2)C11—C16—H16119.6
C6—C5—H5120.4N3—C17—C11119.62 (18)
C4—C5—H5120.4N3—C17—H17120.2
C5—C6—C1121.2 (2)C11—C17—H17120.2
C5—C6—H6119.4O3—C18—O4124.32 (19)
C1—C6—H6119.4O3—C18—N4126.83 (19)
N1—C7—C1120.97 (18)O4—C18—N4108.85 (16)
N1—C7—H7119.5O4—C19—C20107.08 (19)
C1—C7—H7119.5O4—C19—H19A110.3
O1—C8—O2124.26 (19)C20—C19—H19A110.3
O1—C8—N2126.37 (18)O4—C19—H19B110.3
O2—C8—N2109.37 (16)C20—C19—H19B110.3
O2—C9—C10107.41 (18)H19A—C19—H19B108.6
O2—C9—H9A110.2C19—C20—H20A109.5
C10—C9—H9A110.2C19—C20—H20B109.5
O2—C9—H9B110.2H20A—C20—H20B109.5
C10—C9—H9B110.2C19—C20—H20C109.5
H9A—C9—H9B108.5H20A—C20—H20C109.5
C9—C10—H10A109.5H20B—C20—H20C109.5
C7—N1—N2—C8176.30 (18)C8—O2—C9—C10179.4 (2)
C17—N3—N4—C18163.06 (19)C16—C11—C12—C132.6 (3)
C6—C1—C2—C31.4 (3)C17—C11—C12—C13176.24 (19)
C7—C1—C2—C3178.84 (19)C11—C12—C13—C141.4 (3)
C1—C2—C3—C40.6 (3)C12—C13—C14—C151.2 (3)
C2—C3—C4—C50.6 (3)C12—C13—C14—Cl2177.80 (17)
C2—C3—C4—Cl1179.09 (17)C13—C14—C15—C162.5 (3)
C3—C4—C5—C60.9 (3)Cl2—C14—C15—C16176.50 (16)
Cl1—C4—C5—C6178.77 (17)C14—C15—C16—C111.2 (3)
C4—C5—C6—C10.0 (3)C12—C11—C16—C151.3 (3)
C2—C1—C6—C51.1 (3)C17—C11—C16—C15177.55 (19)
C7—C1—C6—C5179.2 (2)N4—N3—C17—C11178.62 (17)
N2—N1—C7—C1179.72 (17)C16—C11—C17—N325.9 (3)
C2—C1—C7—N1179.19 (19)C12—C11—C17—N3152.9 (2)
C6—C1—C7—N11.1 (3)C19—O4—C18—O36.3 (3)
C9—O2—C8—O12.5 (3)C19—O4—C18—N4174.11 (18)
C9—O2—C8—N2177.92 (18)N3—N4—C18—O30.1 (3)
N1—N2—C8—O10.7 (3)N3—N4—C18—O4179.55 (16)
N1—N2—C8—O2179.73 (16)C18—O4—C19—C20168.9 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4—H4···O1i0.882.082.869 (2)149
N2—H2A···O30.882.062.905 (2)160
Symmetry code: (i) x+1/2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC10H11ClN2O2
Mr226.66
Crystal system, space groupMonoclinic, P21/n
Temperature (K)193
a, b, c (Å)16.317 (4), 8.3488 (16), 18.035 (4)
β (°) 116.014 (4)
V3)2207.9 (8)
Z8
Radiation typeMo Kα
µ (mm1)0.33
Crystal size (mm)0.60 × 0.58 × 0.34
Data collection
DiffractometerRigaku Mercury
Absorption correctionMulti-scan
(Jacobson, 1998)
Tmin, Tmax0.815, 0.895
No. of measured, independent and
observed [I > 2σ(I)] reflections
20629, 4011, 3479
Rint0.033
(sin θ/λ)max1)0.604
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.049, 0.111, 1.16
No. of reflections4011
No. of parameters274
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.18, 0.28

Computer programs: CrystalClear (Rigaku, 2001), CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4—H4···O1i0.882.082.869 (2)149
N2—H2A···O30.882.062.905 (2)160
Symmetry code: (i) x+1/2, y+1/2, z+1/2.
 

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