Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807019617/ci2369sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807019617/ci2369Isup2.hkl |
CCDC reference: 647717
The title compound was prepared as described by Odabaşoğlu et al. (2005), using m-bromoaniline and ethyl 4-chloroacetoacetate as starting materials (yield 91%, m.p. 415–417 K). Crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of an absolute acetic acid solution at room temperature.
The H atom bonded to N1 was refined freely. All other H atoms were placed in calculated positions and constrained to ride on their parent atoms, with C—H = 0.93–0.97 Å and Uiso(H) = 1.2 Ueq(C) or 1.5Ueq(methyl C).
As part of our project to study the crystal structures of a series of phenylhydrazones and their stereochemistry, the crystal structure of the title compound, (I), has been determined.
The molecular structure and atom-labelling scheme of (I) are shown in Fig. 1. There is significant elongation of the N1—N2 bond (1.304 (2) Å) and contraction of the C1—N1 bond (1.402 (2) Å) in comparison with azo compounds. For example, the N═N and C—N distances in azobenzene are 1.249 (4) and 1.431 (4) Å, respectively (Harada et al., 1997).
The molecule is approximately planar with the dihedral angle between the aromatic C1—C6 ring and the mean plane of the C9—C14/O2—O4/Cl1 aliphatic chain being 10.5 (1)°.
An intramolecular N—H···O hydrogen bond generates an S(6) ring motif (Bernstein et al., 1995). In the crystal structure of (I), the molecules are linked into centrosymmetric R22(24) dimers by C—H···O intermolecular hydrogen bonds (Fig.2 and Table 1).
For ring motif details, see: Bernstein et al. (1995). For related literature, see: Harada et al. (1997). For preparation details, see: Odabaşoğlu et al. (2005).
Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
C14H15ClN2O4 | F(000) = 648 |
Mr = 310.73 | Dx = 1.391 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 20436 reflections |
a = 8.6018 (5) Å | θ = 2.2–27.1° |
b = 18.9829 (16) Å | µ = 0.27 mm−1 |
c = 9.1035 (6) Å | T = 296 K |
β = 93.591 (5)° | Prism, yellow |
V = 1483.57 (18) Å3 | 0.80 × 0.53 × 0.35 mm |
Z = 4 |
Stoe IPDSII diffractometer | 2916 independent reflections |
Radiation source: fine-focus sealed tube | 2277 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
Detector resolution: 6.67 pixels mm-1 | θmax = 26.0°, θmin = 2.2° |
ω scans | h = −10→10 |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | k = −23→23 |
Tmin = 0.854, Tmax = 0.914 | l = −11→11 |
15055 measured reflections |
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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.130 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0701P)2 + 0.264P] where P = (Fo2 + 2Fc2)/3 |
2916 reflections | (Δ/σ)max = 0.001 |
195 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
C14H15ClN2O4 | V = 1483.57 (18) Å3 |
Mr = 310.73 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.6018 (5) Å | µ = 0.27 mm−1 |
b = 18.9829 (16) Å | T = 296 K |
c = 9.1035 (6) Å | 0.80 × 0.53 × 0.35 mm |
β = 93.591 (5)° |
Stoe IPDSII diffractometer | 2916 independent reflections |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | 2277 reflections with I > 2σ(I) |
Tmin = 0.854, Tmax = 0.914 | Rint = 0.032 |
15055 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.130 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.21 e Å−3 |
2916 reflections | Δρmin = −0.31 e Å−3 |
195 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.3964 (2) | 0.53258 (10) | 0.63530 (19) | 0.0532 (4) | |
C2 | 0.2686 (2) | 0.49933 (11) | 0.5648 (2) | 0.0599 (5) | |
H2 | 0.2413 | 0.4538 | 0.5905 | 0.072* | |
C3 | 0.1830 (2) | 0.53539 (11) | 0.4558 (2) | 0.0607 (5) | |
H3 | 0.0978 | 0.5134 | 0.4074 | 0.073* | |
C4 | 0.2205 (2) | 0.60356 (10) | 0.4163 (2) | 0.0558 (4) | |
C5 | 0.3510 (2) | 0.63541 (10) | 0.4873 (2) | 0.0593 (5) | |
H5 | 0.3796 | 0.6807 | 0.4608 | 0.071* | |
C6 | 0.4373 (2) | 0.60000 (10) | 0.5962 (2) | 0.0599 (5) | |
H6 | 0.5235 | 0.6216 | 0.6436 | 0.072* | |
C7 | 0.1191 (2) | 0.64027 (12) | 0.3018 (2) | 0.0663 (5) | |
C8 | 0.1670 (3) | 0.71088 (12) | 0.2475 (3) | 0.0872 (7) | |
H8A | 0.0867 | 0.7291 | 0.1800 | 0.131* | |
H8B | 0.2620 | 0.7063 | 0.1983 | 0.131* | |
H8C | 0.1830 | 0.7425 | 0.3293 | 0.131* | |
C9 | 0.5394 (2) | 0.40843 (10) | 0.9062 (2) | 0.0533 (4) | |
C10 | 0.4718 (2) | 0.34275 (11) | 0.9629 (2) | 0.0579 (4) | |
C11 | 0.3336 (3) | 0.31351 (13) | 0.8727 (3) | 0.0784 (6) | |
H11A | 0.3654 | 0.3009 | 0.7758 | 0.094* | |
H11B | 0.2540 | 0.3496 | 0.8605 | 0.094* | |
C12 | 0.6893 (2) | 0.43994 (11) | 0.9652 (2) | 0.0568 (4) | |
C13 | 0.9253 (2) | 0.42970 (12) | 1.1078 (3) | 0.0720 (6) | |
H13A | 0.9878 | 0.4393 | 1.0250 | 0.086* | |
H13B | 0.9092 | 0.4736 | 1.1591 | 0.086* | |
C14 | 1.0054 (3) | 0.37880 (13) | 1.2077 (3) | 0.0890 (8) | |
H14A | 1.1045 | 0.3976 | 1.2428 | 0.134* | |
H14B | 1.0210 | 0.3356 | 1.1560 | 0.134* | |
H14C | 0.9432 | 0.3700 | 1.2897 | 0.134* | |
Cl1 | 0.25437 (7) | 0.23854 (3) | 0.95607 (8) | 0.0870 (2) | |
N1 | 0.48968 (19) | 0.49975 (9) | 0.74712 (18) | 0.0576 (4) | |
N2 | 0.45181 (16) | 0.43895 (8) | 0.80112 (16) | 0.0544 (4) | |
O1 | −0.0001 (2) | 0.61212 (11) | 0.2525 (2) | 0.0970 (6) | |
O2 | 0.5234 (2) | 0.31394 (10) | 1.07369 (18) | 0.0892 (5) | |
O3 | 0.73029 (17) | 0.49863 (8) | 0.92995 (17) | 0.0716 (4) | |
O4 | 0.77406 (15) | 0.39936 (8) | 1.05545 (15) | 0.0648 (4) | |
H1 | 0.565 (3) | 0.5192 (13) | 0.787 (3) | 0.079 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0474 (9) | 0.0614 (10) | 0.0506 (10) | 0.0050 (8) | 0.0004 (7) | −0.0017 (8) |
C2 | 0.0522 (10) | 0.0628 (11) | 0.0641 (12) | −0.0038 (8) | −0.0004 (8) | 0.0047 (8) |
C3 | 0.0462 (9) | 0.0723 (13) | 0.0626 (12) | −0.0054 (8) | −0.0042 (8) | −0.0001 (9) |
C4 | 0.0498 (9) | 0.0622 (11) | 0.0551 (10) | 0.0078 (8) | 0.0008 (8) | −0.0027 (8) |
C5 | 0.0597 (10) | 0.0533 (10) | 0.0643 (11) | 0.0018 (8) | −0.0024 (9) | −0.0036 (8) |
C6 | 0.0554 (10) | 0.0613 (11) | 0.0615 (11) | −0.0035 (8) | −0.0072 (8) | −0.0048 (8) |
C7 | 0.0592 (11) | 0.0736 (12) | 0.0651 (12) | 0.0135 (9) | −0.0043 (9) | −0.0014 (10) |
C8 | 0.0988 (17) | 0.0635 (13) | 0.0960 (18) | 0.0180 (12) | −0.0197 (14) | 0.0059 (12) |
C9 | 0.0469 (9) | 0.0629 (11) | 0.0497 (9) | 0.0053 (7) | −0.0010 (7) | −0.0039 (8) |
C10 | 0.0512 (9) | 0.0664 (11) | 0.0549 (10) | 0.0048 (8) | −0.0064 (8) | −0.0001 (8) |
C11 | 0.0664 (12) | 0.0841 (15) | 0.0815 (15) | −0.0147 (11) | −0.0198 (11) | 0.0172 (12) |
C12 | 0.0532 (10) | 0.0659 (12) | 0.0505 (10) | 0.0054 (8) | −0.0028 (8) | −0.0054 (8) |
C13 | 0.0593 (11) | 0.0729 (13) | 0.0809 (14) | −0.0110 (9) | −0.0186 (10) | 0.0019 (11) |
C14 | 0.0744 (14) | 0.0777 (15) | 0.1103 (19) | −0.0128 (11) | −0.0308 (13) | 0.0152 (13) |
Cl1 | 0.0707 (4) | 0.0790 (4) | 0.1079 (5) | −0.0144 (3) | −0.0203 (3) | 0.0178 (3) |
N1 | 0.0505 (9) | 0.0621 (10) | 0.0591 (10) | 0.0010 (7) | −0.0054 (7) | 0.0022 (7) |
N2 | 0.0470 (8) | 0.0632 (9) | 0.0528 (8) | 0.0058 (6) | 0.0009 (6) | −0.0007 (7) |
O1 | 0.0690 (10) | 0.1116 (13) | 0.1057 (13) | −0.0014 (9) | −0.0305 (9) | 0.0230 (10) |
O2 | 0.0887 (11) | 0.0929 (11) | 0.0812 (10) | −0.0223 (9) | −0.0319 (9) | 0.0260 (9) |
O3 | 0.0642 (8) | 0.0690 (9) | 0.0792 (10) | −0.0077 (7) | −0.0154 (7) | 0.0044 (7) |
O4 | 0.0525 (7) | 0.0696 (8) | 0.0702 (9) | −0.0038 (6) | −0.0134 (6) | 0.0051 (6) |
C1—C6 | 1.380 (3) | C9—C10 | 1.482 (3) |
C1—C2 | 1.390 (3) | C9—C12 | 1.490 (3) |
C1—N1 | 1.402 (2) | C10—O2 | 1.207 (2) |
C2—C3 | 1.379 (3) | C10—C11 | 1.508 (3) |
C2—H2 | 0.93 | C11—Cl1 | 1.769 (2) |
C3—C4 | 1.387 (3) | C11—H11A | 0.97 |
C3—H3 | 0.93 | C11—H11B | 0.97 |
C4—C5 | 1.397 (3) | C12—O3 | 1.218 (2) |
C4—C7 | 1.490 (3) | C12—O4 | 1.313 (2) |
C5—C6 | 1.376 (3) | C13—C14 | 1.469 (3) |
C5—H5 | 0.93 | C13—O4 | 1.474 (2) |
C6—H6 | 0.93 | C13—H13A | 0.97 |
C7—O1 | 1.217 (3) | C13—H13B | 0.97 |
C7—C8 | 1.495 (3) | C14—H14A | 0.96 |
C8—H8A | 0.96 | C14—H14B | 0.96 |
C8—H8B | 0.96 | C14—H14C | 0.96 |
C8—H8C | 0.96 | N1—N2 | 1.304 (2) |
C9—N2 | 1.315 (2) | N1—H1 | 0.82 (2) |
C6—C1—C2 | 120.60 (17) | O2—C10—C9 | 122.72 (17) |
C6—C1—N1 | 117.13 (16) | O2—C10—C11 | 121.60 (19) |
C2—C1—N1 | 122.27 (17) | C9—C10—C11 | 115.68 (16) |
C3—C2—C1 | 118.56 (18) | C10—C11—Cl1 | 111.99 (15) |
C3—C2—H2 | 120.7 | C10—C11—H11A | 109.2 |
C1—C2—H2 | 120.7 | Cl1—C11—H11A | 109.2 |
C2—C3—C4 | 121.82 (17) | C10—C11—H11B | 109.2 |
C2—C3—H3 | 119.1 | Cl1—C11—H11B | 109.2 |
C4—C3—H3 | 119.1 | H11A—C11—H11B | 107.9 |
C3—C4—C5 | 118.49 (17) | O3—C12—O4 | 122.89 (17) |
C3—C4—C7 | 118.85 (17) | O3—C12—C9 | 122.02 (17) |
C5—C4—C7 | 122.65 (18) | O4—C12—C9 | 115.08 (18) |
C6—C5—C4 | 120.22 (19) | C14—C13—O4 | 108.28 (17) |
C6—C5—H5 | 119.9 | C14—C13—H13A | 110.0 |
C4—C5—H5 | 119.9 | O4—C13—H13A | 110.0 |
C5—C6—C1 | 120.29 (17) | C14—C13—H13B | 110.0 |
C5—C6—H6 | 119.9 | O4—C13—H13B | 110.0 |
C1—C6—H6 | 119.9 | H13A—C13—H13B | 108.4 |
O1—C7—C4 | 119.7 (2) | C13—C14—H14A | 109.5 |
O1—C7—C8 | 121.0 (2) | C13—C14—H14B | 109.5 |
C4—C7—C8 | 119.31 (19) | H14A—C14—H14B | 109.5 |
C7—C8—H8A | 109.5 | C13—C14—H14C | 109.5 |
C7—C8—H8B | 109.5 | H14A—C14—H14C | 109.5 |
H8A—C8—H8B | 109.5 | H14B—C14—H14C | 109.5 |
C7—C8—H8C | 109.5 | N2—N1—C1 | 121.46 (16) |
H8A—C8—H8C | 109.5 | N2—N1—H1 | 116.2 (17) |
H8B—C8—H8C | 109.5 | C1—N1—H1 | 122.1 (17) |
N2—C9—C10 | 113.87 (15) | N1—N2—C9 | 121.27 (16) |
N2—C9—C12 | 121.93 (17) | C12—O4—C13 | 114.65 (16) |
C10—C9—C12 | 124.15 (16) | ||
C6—C1—C2—C3 | −0.5 (3) | N2—C9—C10—C11 | 12.1 (2) |
N1—C1—C2—C3 | −179.95 (17) | C12—C9—C10—C11 | −170.44 (19) |
C1—C2—C3—C4 | −0.5 (3) | O2—C10—C11—Cl1 | 4.1 (3) |
C2—C3—C4—C5 | 1.5 (3) | C9—C10—C11—Cl1 | −176.18 (15) |
C2—C3—C4—C7 | −177.58 (18) | N2—C9—C12—O3 | 7.6 (3) |
C3—C4—C5—C6 | −1.5 (3) | C10—C9—C12—O3 | −169.67 (18) |
C7—C4—C5—C6 | 177.56 (18) | N2—C9—C12—O4 | −171.31 (16) |
C4—C5—C6—C1 | 0.5 (3) | C10—C9—C12—O4 | 11.4 (3) |
C2—C1—C6—C5 | 0.5 (3) | C6—C1—N1—N2 | 173.36 (17) |
N1—C1—C6—C5 | 179.98 (17) | C2—C1—N1—N2 | −7.2 (3) |
C3—C4—C7—O1 | 5.2 (3) | C1—N1—N2—C9 | −179.82 (16) |
C5—C4—C7—O1 | −173.9 (2) | C10—C9—N2—N1 | 175.03 (16) |
C3—C4—C7—C8 | −173.91 (19) | C12—C9—N2—N1 | −2.5 (3) |
C5—C4—C7—C8 | 7.0 (3) | O3—C12—O4—C13 | −1.6 (3) |
N2—C9—C10—O2 | −168.1 (2) | C9—C12—O4—C13 | 177.30 (16) |
C12—C9—C10—O2 | 9.3 (3) | C14—C13—O4—C12 | 179.58 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O3 | 0.82 (2) | 1.90 (2) | 2.573 (2) | 139 (2) |
C11—H11B···O1i | 0.97 | 2.47 | 3.334 (3) | 149 |
Symmetry code: (i) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C14H15ClN2O4 |
Mr | 310.73 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 8.6018 (5), 18.9829 (16), 9.1035 (6) |
β (°) | 93.591 (5) |
V (Å3) | 1483.57 (18) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.27 |
Crystal size (mm) | 0.80 × 0.53 × 0.35 |
Data collection | |
Diffractometer | Stoe IPDSII |
Absorption correction | Integration (X-RED32; Stoe & Cie, 2002) |
Tmin, Tmax | 0.854, 0.914 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15055, 2916, 2277 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.130, 1.05 |
No. of reflections | 2916 |
No. of parameters | 195 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.21, −0.31 |
Computer programs: X-AREA (Stoe & Cie, 2002), X-AREA, X-RED32 (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O3 | 0.82 (2) | 1.90 (2) | 2.573 (2) | 139 (2) |
C11—H11B···O1i | 0.97 | 2.47 | 3.334 (3) | 149 |
Symmetry code: (i) −x, −y+1, −z+1. |
As part of our project to study the crystal structures of a series of phenylhydrazones and their stereochemistry, the crystal structure of the title compound, (I), has been determined.
The molecular structure and atom-labelling scheme of (I) are shown in Fig. 1. There is significant elongation of the N1—N2 bond (1.304 (2) Å) and contraction of the C1—N1 bond (1.402 (2) Å) in comparison with azo compounds. For example, the N═N and C—N distances in azobenzene are 1.249 (4) and 1.431 (4) Å, respectively (Harada et al., 1997).
The molecule is approximately planar with the dihedral angle between the aromatic C1—C6 ring and the mean plane of the C9—C14/O2—O4/Cl1 aliphatic chain being 10.5 (1)°.
An intramolecular N—H···O hydrogen bond generates an S(6) ring motif (Bernstein et al., 1995). In the crystal structure of (I), the molecules are linked into centrosymmetric R22(24) dimers by C—H···O intermolecular hydrogen bonds (Fig.2 and Table 1).