Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103017554/gg1178sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103017554/gg1178Isup2.hkl |
CCDC reference: 224646
The compound was prepared from aniline (9.8 ml, 0.1 mol) and ethyl chlorooxoacetate (12.0 m, 0.1 mol) according to reported procedures (Martínez-Martínez et al., 1998), yielding, after crystallization from hexane, a white solid (11.8 g; yield 60%; m.p. 347 K). IR (KBr, cm−1): 3345 (NH), 1708 (CO); 1H NMR (300.08 MHz, DMSO-d6, p.p.m.): 7.86 (d, 2H), 7.48 (t, 2H), 7.26 (t, 1H), 4.40 (q, 2H), 1.43 (t, 3H); 13C NMR (75.46 MHz, DMSO-d6, p.p.m.): 161.4 (COO), 156.2 (CON), 138.2 (Ci), 129.5 (Cm), 125.4 (Cp), 121.2 (Co), 63.0 (CH2), 14.5 (CH3). Crystals suitable for X-ray analysis were obtained after slow crystallization from toluene. The melting point was measured on an electrothermal IA 9100 apparatus and is uncorrected. The IR spectrum was recorded using a Perkin–Elmer 16 F PC IR spectrophotometer, and the NMR spectra were recorded using a Varian Mercury 300 MHz instrument.
Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXL97 and WinGX (Farrugia, 1999).
C10H11NO3 | Z = 4 |
Mr = 193.20 | F(000) = 408 |
Triclinic, P1 | Dx = 1.351 Mg m−3 |
Hall symbol: -P 1 | Melting point: 347 K |
a = 7.8033 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.6424 (7) Å | Cell parameters from 600 reflections |
c = 13.2432 (9) Å | θ = 20–25° |
α = 108.491 (1)° | µ = 0.10 mm−1 |
β = 96.081 (1)° | T = 100 K |
γ = 110.165 (1)° | Rhombohedron, colourless |
V = 950.03 (11) Å3 | 0.50 × 0.47 × 0.43 mm |
Bruker Smart area-detector diffractometer | 4107 independent reflections |
Radiation source: fine-focus sealed tube | 3637 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
Detector resolution: 3 pixels mm-1 | θmax = 27.0°, θmin = 1.7° |
ϕ and ω scans | h = −9→9 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −13→13 |
Tmin = 0.952, Tmax = 0.967 | l = −16→16 |
10719 measured reflections |
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)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.114 | w = 1/[σ2(Fo2) + (0.0535P)2 + 0.3757P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
4107 reflections | Δρmax = 0.35 e Å−3 |
256 parameters | Δρmin = −0.28 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0054 (13) |
C10H11NO3 | γ = 110.165 (1)° |
Mr = 193.20 | V = 950.03 (11) Å3 |
Triclinic, P1 | Z = 4 |
a = 7.8033 (5) Å | Mo Kα radiation |
b = 10.6424 (7) Å | µ = 0.10 mm−1 |
c = 13.2432 (9) Å | T = 100 K |
α = 108.491 (1)° | 0.50 × 0.47 × 0.43 mm |
β = 96.081 (1)° |
Bruker Smart area-detector diffractometer | 4107 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3637 reflections with I > 2σ(I) |
Tmin = 0.952, Tmax = 0.967 | Rint = 0.025 |
10719 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.35 e Å−3 |
4107 reflections | Δρmin = −0.28 e Å−3 |
256 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 | ||
C1A | 0.40793 (18) | 0.29510 (14) | 0.66506 (11) | 0.0165 (3) | |
C1B | 0.42640 (18) | 1.03245 (14) | 0.16072 (11) | 0.0165 (3) | |
C2A | 0.54894 (19) | 0.31794 (15) | 0.75122 (11) | 0.0188 (3) | |
H2A | 0.6094 | 0.2528 | 0.7426 | 0.023* | |
C2B | 0.41705 (19) | 1.14896 (15) | 0.24227 (11) | 0.0197 (3) | |
H2B | 0.3206 | 1.1812 | 0.2293 | 0.024* | |
C3A | 0.6012 (2) | 0.43530 (15) | 0.84940 (11) | 0.0208 (3) | |
H3A | 0.6969 | 0.4501 | 0.9079 | 0.025* | |
C3B | 0.5482 (2) | 1.21782 (15) | 0.34224 (11) | 0.0215 (3) | |
H3B | 0.5418 | 1.2977 | 0.3975 | 0.026* | |
C4A | 0.5140 (2) | 0.53132 (15) | 0.86238 (12) | 0.0212 (3) | |
H4A | 0.5489 | 0.6113 | 0.9298 | 0.025* | |
C4B | 0.68898 (19) | 1.17088 (15) | 0.36227 (11) | 0.0204 (3) | |
H4B | 0.7777 | 1.2172 | 0.4313 | 0.025* | |
C5A | 0.3757 (2) | 0.50951 (15) | 0.77606 (12) | 0.0207 (3) | |
H5A | 0.3166 | 0.5755 | 0.7847 | 0.025* | |
C5B | 0.69862 (19) | 1.05583 (15) | 0.28059 (12) | 0.0202 (3) | |
H5B | 0.7956 | 1.0241 | 0.2938 | 0.024* | |
C6A | 0.32219 (19) | 0.39249 (15) | 0.67704 (11) | 0.0195 (3) | |
H6A | 0.2282 | 0.3791 | 0.6182 | 0.023* | |
C6B | 0.56872 (19) | 0.98586 (15) | 0.17942 (11) | 0.0187 (3) | |
H6B | 0.5770 | 0.9073 | 0.1238 | 0.022* | |
C8A | 0.20469 (19) | 0.11137 (15) | 0.48511 (11) | 0.0180 (3) | |
C8B | 0.24118 (19) | 0.83553 (15) | −0.01844 (11) | 0.0187 (3) | |
C9A | 0.19617 (18) | −0.02827 (15) | 0.39766 (11) | 0.0170 (3) | |
C9B | 0.07352 (19) | 0.79890 (15) | −0.11143 (11) | 0.0174 (3) | |
C11A | 0.03962 (19) | −0.20379 (15) | 0.22040 (11) | 0.0185 (3) | |
H11A | 0.0101 | −0.2880 | 0.2425 | 0.022* | |
H11B | 0.1595 | −0.1860 | 0.1972 | 0.022* | |
C11B | −0.10753 (19) | 0.63731 (15) | −0.28904 (11) | 0.0200 (3) | |
H11C | −0.0853 | 0.7170 | −0.3160 | 0.024* | |
H11D | −0.2303 | 0.6143 | −0.2691 | 0.024* | |
C12A | −0.1163 (2) | −0.23230 (16) | 0.12800 (11) | 0.0219 (3) | |
H12A | −0.2353 | −0.2551 | 0.1506 | 0.033* | |
H12B | −0.1265 | −0.3142 | 0.0635 | 0.033* | |
H12C | −0.0886 | −0.1462 | 0.1097 | 0.033* | |
C12B | −0.1064 (2) | 0.50599 (16) | −0.37594 (12) | 0.0254 (3) | |
H12D | 0.0175 | 0.5293 | −0.3927 | 0.038* | |
H12E | −0.2027 | 0.4763 | −0.4425 | 0.038* | |
H12F | −0.1333 | 0.4269 | −0.3492 | 0.038* | |
N7A | 0.35830 (16) | 0.17034 (12) | 0.56864 (9) | 0.0177 (2) | |
H7A | 0.4363 | 0.1267 | 0.5627 | 0.021* | |
N7B | 0.28635 (16) | 0.96634 (12) | 0.06075 (9) | 0.0176 (3) | |
H7B | 0.2220 | 1.0161 | 0.0492 | 0.021* | |
O8A | 0.08365 (15) | 0.15708 (11) | 0.47463 (8) | 0.0270 (3) | |
O8B | 0.31572 (16) | 0.75229 (12) | −0.02031 (9) | 0.0305 (3) | |
O9A | 0.30585 (13) | −0.08283 (10) | 0.40773 (8) | 0.0203 (2) | |
O9B | −0.01593 (14) | 0.87252 (11) | −0.10624 (8) | 0.0221 (2) | |
O10A | 0.05531 (13) | −0.07642 (10) | 0.31163 (8) | 0.0194 (2) | |
O10B | 0.04368 (14) | 0.67911 (10) | −0.19398 (7) | 0.0199 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1A | 0.0156 (6) | 0.0167 (6) | 0.0155 (6) | 0.0055 (5) | 0.0038 (5) | 0.0050 (5) |
C1B | 0.0151 (6) | 0.0174 (6) | 0.0157 (6) | 0.0047 (5) | 0.0020 (5) | 0.0072 (5) |
C2A | 0.0173 (7) | 0.0185 (7) | 0.0214 (7) | 0.0090 (5) | 0.0040 (5) | 0.0066 (5) |
C2B | 0.0186 (7) | 0.0197 (7) | 0.0211 (7) | 0.0096 (6) | 0.0021 (5) | 0.0068 (6) |
C3A | 0.0176 (7) | 0.0226 (7) | 0.0186 (7) | 0.0071 (6) | −0.0004 (5) | 0.0058 (6) |
C3B | 0.0230 (7) | 0.0185 (7) | 0.0183 (7) | 0.0078 (6) | 0.0028 (6) | 0.0023 (5) |
C4A | 0.0211 (7) | 0.0177 (7) | 0.0195 (7) | 0.0054 (6) | 0.0050 (6) | 0.0030 (5) |
C4B | 0.0179 (7) | 0.0218 (7) | 0.0174 (7) | 0.0040 (6) | −0.0006 (5) | 0.0081 (6) |
C5A | 0.0216 (7) | 0.0181 (7) | 0.0242 (7) | 0.0105 (6) | 0.0068 (6) | 0.0071 (6) |
C5B | 0.0165 (7) | 0.0225 (7) | 0.0239 (7) | 0.0091 (6) | 0.0033 (5) | 0.0110 (6) |
C6A | 0.0188 (7) | 0.0223 (7) | 0.0187 (7) | 0.0097 (6) | 0.0029 (5) | 0.0085 (6) |
C6B | 0.0187 (7) | 0.0195 (7) | 0.0190 (7) | 0.0093 (5) | 0.0047 (5) | 0.0069 (5) |
C8A | 0.0168 (7) | 0.0198 (7) | 0.0167 (6) | 0.0085 (5) | 0.0028 (5) | 0.0053 (5) |
C8B | 0.0196 (7) | 0.0210 (7) | 0.0162 (6) | 0.0105 (6) | 0.0034 (5) | 0.0056 (5) |
C9A | 0.0149 (6) | 0.0198 (7) | 0.0162 (6) | 0.0071 (5) | 0.0031 (5) | 0.0066 (5) |
C9B | 0.0185 (7) | 0.0187 (6) | 0.0153 (6) | 0.0084 (5) | 0.0045 (5) | 0.0057 (5) |
C11A | 0.0179 (7) | 0.0174 (6) | 0.0167 (6) | 0.0068 (5) | 0.0027 (5) | 0.0028 (5) |
C11B | 0.0185 (7) | 0.0220 (7) | 0.0150 (6) | 0.0070 (6) | −0.0005 (5) | 0.0040 (5) |
C12A | 0.0186 (7) | 0.0240 (7) | 0.0180 (7) | 0.0072 (6) | 0.0008 (5) | 0.0042 (6) |
C12B | 0.0254 (8) | 0.0249 (7) | 0.0189 (7) | 0.0094 (6) | 0.0020 (6) | 0.0010 (6) |
N7A | 0.0170 (6) | 0.0195 (6) | 0.0166 (6) | 0.0106 (5) | 0.0022 (4) | 0.0038 (5) |
N7B | 0.0182 (6) | 0.0188 (6) | 0.0156 (6) | 0.0100 (5) | 0.0003 (5) | 0.0045 (5) |
O8A | 0.0241 (6) | 0.0288 (6) | 0.0244 (5) | 0.0173 (5) | −0.0031 (4) | 0.0007 (4) |
O8B | 0.0363 (6) | 0.0281 (6) | 0.0240 (5) | 0.0221 (5) | −0.0056 (5) | −0.0001 (4) |
O9A | 0.0192 (5) | 0.0226 (5) | 0.0188 (5) | 0.0116 (4) | 0.0019 (4) | 0.0049 (4) |
O9B | 0.0229 (5) | 0.0240 (5) | 0.0188 (5) | 0.0139 (4) | 0.0008 (4) | 0.0036 (4) |
O10A | 0.0185 (5) | 0.0203 (5) | 0.0160 (5) | 0.0093 (4) | −0.0002 (4) | 0.0021 (4) |
O10B | 0.0217 (5) | 0.0212 (5) | 0.0141 (5) | 0.0107 (4) | −0.0001 (4) | 0.0022 (4) |
O8A—C8A | 1.2165 (16) | C3B—H3B | 0.9500 |
O9A—C9A | 1.2063 (16) | C4A—C5A | 1.387 (2) |
O10A—C9A | 1.3209 (16) | C4A—H4A | 0.9500 |
O10A—C11A | 1.4586 (16) | C4B—C5B | 1.384 (2) |
N7A—C1A | 1.4173 (17) | C4B—H4B | 0.9500 |
N7A—C8A | 1.3470 (17) | C5A—C6A | 1.391 (2) |
C8A—C9A | 1.5421 (19) | C5A—H5A | 0.9500 |
O8B—C8B | 1.2116 (17) | C5B—C6B | 1.3915 (19) |
O9B—C9B | 1.2078 (16) | C5B—H5B | 0.9500 |
O10B—C9B | 1.3161 (16) | C6A—H6A | 0.9500 |
O10B—C11B | 1.4639 (16) | C6B—H6B | 0.9500 |
N7B—C1B | 1.4193 (17) | C11A—C12A | 1.5048 (19) |
N7B—C8B | 1.3488 (17) | C11A—H11A | 0.9900 |
C8B—C9B | 1.5436 (19) | C11A—H11B | 0.9900 |
C1A—C6A | 1.3941 (19) | C11B—C12B | 1.5060 (19) |
C1A—C2A | 1.3948 (19) | C11B—H11C | 0.9900 |
C1B—C2B | 1.3924 (19) | C11B—H11D | 0.9900 |
C1B—C6B | 1.3928 (19) | C12A—H12A | 0.9800 |
C2A—C3A | 1.3868 (19) | C12A—H12B | 0.9800 |
C2A—H2A | 0.9500 | C12A—H12C | 0.9800 |
C2B—C3B | 1.3848 (19) | C12B—H12D | 0.9800 |
C2B—H2B | 0.9500 | C12B—H12E | 0.9800 |
C3A—C4A | 1.389 (2) | C12B—H12F | 0.9800 |
C3A—H3A | 0.9500 | N7A—H7A | 0.8800 |
C3B—C4B | 1.388 (2) | N7B—H7B | 0.8800 |
C6A—C1A—C2A | 119.76 (12) | O8B—C8B—C9B | 121.71 (12) |
C6A—C1A—N7A | 123.31 (12) | N7B—C8B—C9B | 111.28 (11) |
C2A—C1A—N7A | 116.93 (12) | O9A—C9A—O10A | 125.86 (12) |
C2B—C1B—C6B | 119.95 (12) | O9A—C9A—C8A | 123.70 (12) |
C2B—C1B—N7B | 116.98 (12) | O10A—C9A—C8A | 110.43 (11) |
C6B—C1B—N7B | 123.07 (12) | O9B—C9B—O10B | 126.03 (12) |
C3A—C2A—C1A | 120.27 (13) | O9B—C9B—C8B | 123.01 (12) |
C3A—C2A—H2A | 119.9 | O10B—C9B—C8B | 110.96 (11) |
C1A—C2A—H2A | 119.9 | O10A—C11A—C12A | 107.04 (11) |
C3B—C2B—C1B | 120.07 (13) | O10A—C11A—H11A | 110.3 |
C3B—C2B—H2B | 120.0 | C12A—C11A—H11A | 110.3 |
C1B—C2B—H2B | 120.0 | O10A—C11A—H11B | 110.3 |
C2A—C3A—C4A | 120.18 (13) | C12A—C11A—H11B | 110.3 |
C2A—C3A—H3A | 119.9 | H11A—C11A—H11B | 108.6 |
C4A—C3A—H3A | 119.9 | O10B—C11B—C12B | 106.60 (11) |
C2B—C3B—C4B | 120.42 (13) | O10B—C11B—H11C | 110.4 |
C2B—C3B—H3B | 119.8 | C12B—C11B—H11C | 110.4 |
C4B—C3B—H3B | 119.8 | O10B—C11B—H11D | 110.4 |
C5A—C4A—C3A | 119.45 (13) | C12B—C11B—H11D | 110.4 |
C5A—C4A—H4A | 120.3 | H11C—C11B—H11D | 108.6 |
C3A—C4A—H4A | 120.3 | C11A—C12A—H12A | 109.5 |
C5B—C4B—C3B | 119.27 (13) | C11A—C12A—H12B | 109.5 |
C5B—C4B—H4B | 120.4 | H12A—C12A—H12B | 109.5 |
C3B—C4B—H4B | 120.4 | C11A—C12A—H12C | 109.5 |
C4A—C5A—C6A | 120.99 (13) | H12A—C12A—H12C | 109.5 |
C4A—C5A—H5A | 119.5 | H12B—C12A—H12C | 109.5 |
C6A—C5A—H5A | 119.5 | C11B—C12B—H12D | 109.5 |
C4B—C5B—C6B | 121.11 (13) | C11B—C12B—H12E | 109.5 |
C4B—C5B—H5B | 119.4 | H12D—C12B—H12E | 109.5 |
C6B—C5B—H5B | 119.4 | C11B—C12B—H12F | 109.5 |
C5A—C6A—C1A | 119.34 (13) | H12D—C12B—H12F | 109.5 |
C5A—C6A—H6A | 120.3 | H12E—C12B—H12F | 109.5 |
C1A—C6A—H6A | 120.3 | C8A—N7A—C1A | 127.05 (11) |
C5B—C6B—C1B | 119.16 (13) | C8A—N7A—H7A | 116.5 |
C5B—C6B—H6B | 120.4 | C1A—N7A—H7A | 116.5 |
C1B—C6B—H6B | 120.4 | C8B—N7B—C1B | 127.06 (11) |
O8A—C8A—N7A | 127.25 (13) | C8B—N7B—H7B | 116.5 |
O8A—C8A—C9A | 121.34 (12) | C1B—N7B—H7B | 116.5 |
N7A—C8A—C9A | 111.41 (11) | C9A—O10A—C11A | 115.48 (10) |
O8B—C8B—N7B | 127.01 (13) | C9B—O10B—C11B | 115.62 (10) |
O8A—C8A—C9A—O9A | −174.99 (13) | C2B—C1B—C6B—C5B | 0.9 (2) |
N7A—C1A—C2A—C3A | −178.05 (12) | N7A—C8A—C9A—O9A | 5.38 (19) |
C6A—C1A—N7A—C8A | −13.6 (2) | O8A—C8A—C9A—O10A | 5.86 (18) |
N7A—C1A—C6A—C5A | 177.86 (12) | N7A—C8A—C9A—O10A | −173.78 (11) |
O8B—C8B—C9B—O9B | 171.89 (13) | N7B—C8B—C9B—O9B | −7.37 (19) |
N7B—C1B—C2B—C3B | 179.44 (12) | O8B—C8B—C9B—O10B | −7.84 (19) |
C6B—C1B—N7B—C8B | 16.2 (2) | N7B—C8B—C9B—O10B | 172.90 (11) |
N7B—C1B—C6B—C5B | −179.07 (12) | O8A—C8A—N7A—C1A | 3.1 (2) |
C6A—C1A—C2A—C3A | 1.4 (2) | C9A—C8A—N7A—C1A | −177.27 (12) |
C6B—C1B—C2B—C3B | −0.5 (2) | C2A—C1A—N7A—C8A | 165.85 (13) |
C1A—C2A—C3A—C4A | −0.3 (2) | O8B—C8B—N7B—C1B | −2.4 (2) |
C1B—C2B—C3B—C4B | −0.4 (2) | C9B—C8B—N7B—C1B | 176.79 (11) |
C2A—C3A—C4A—C5A | −0.6 (2) | C2B—C1B—N7B—C8B | −163.77 (13) |
C2B—C3B—C4B—C5B | 1.0 (2) | O9A—C9A—O10A—C11A | −2.57 (19) |
C3A—C4A—C5A—C6A | 0.4 (2) | C8A—C9A—O10A—C11A | 176.56 (10) |
C3B—C4B—C5B—C6B | −0.6 (2) | C12A—C11A—O10A—C9A | −174.86 (11) |
C4A—C5A—C6A—C1A | 0.6 (2) | O9B—C9B—O10B—C11B | 2.8 (2) |
C2A—C1A—C6A—C5A | −1.5 (2) | C8B—C9B—O10B—C11B | −177.49 (10) |
C4B—C5B—C6B—C1B | −0.3 (2) | C12B—C11B—O10B—C9B | 175.49 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
N7A—H7A···O9Ai | 0.88 | 2.24 | 3.0867 (17) | 161 |
N7B—H7B···O9Bii | 0.88 | 2.36 | 3.1410 (18) | 148 |
N7A—H7A···O9A | 0.88 | 2.30 | 2.7168 (16) | 109 |
N7B—H7B···O9B | 0.88 | 2.29 | 2.7059 (16) | 109 |
C6A—H6A···O8A | 0.95 | 2.31 | 2.8974 (18) | 120 |
C6B—H6B···O8B | 0.95 | 2.32 | 2.9004 (18) | 119 |
C5A—H5A···O8Biii | 0.95 | 2.67 | 3.294 (2) | 124 |
C5B—H5B···O8Aiv | 0.95 | 2.70 | 3.3418 (18) | 125 |
C5A—H5A···O10Biii | 0.95 | 2.72 | 3.622 (2) | 160 |
C5B—H5B···O10Aiv | 0.95 | 2.62 | 3.5669 (19) | 175 |
C2A—H2A···O9Ai | 0.95 | 2.55 | 3.3309 (19) | 140 |
C2B—H2B···O9Bii | 0.95 | 2.51 | 3.3385 (19) | 146 |
C11B—H11D···Cg1v | 0.99 | 2.79 | 3.6719 (17) | 149 |
C12A—H12A···Cg1vi | 0.98 | 2.62 | 3.4703 (18) | 146 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y+2, −z; (iii) x, y, z+1; (iv) x+1, y+1, z; (v) x−1, y, z−1; (vi) −x, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C10H11NO3 |
Mr | 193.20 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 7.8033 (5), 10.6424 (7), 13.2432 (9) |
α, β, γ (°) | 108.491 (1), 96.081 (1), 110.165 (1) |
V (Å3) | 950.03 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.50 × 0.47 × 0.43 |
Data collection | |
Diffractometer | Bruker Smart area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.952, 0.967 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10719, 4107, 3637 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.114, 1.05 |
No. of reflections | 4107 |
No. of parameters | 256 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.35, −0.28 |
Computer programs: SMART (Bruker, 2000), SMART, SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000), SHELXL97 and WinGX (Farrugia, 1999).
O8A—C8A | 1.2165 (16) | O8B—C8B | 1.2116 (17) |
O9A—C9A | 1.2063 (16) | O9B—C9B | 1.2078 (16) |
O10A—C9A | 1.3209 (16) | O10B—C9B | 1.3161 (16) |
O10A—C11A | 1.4586 (16) | O10B—C11B | 1.4639 (16) |
N7A—C1A | 1.4173 (17) | N7B—C1B | 1.4193 (17) |
N7A—C8A | 1.3470 (17) | N7B—C8B | 1.3488 (17) |
C8A—C9A | 1.5421 (19) | C8B—C9B | 1.5436 (19) |
O8A—C8A—C9A—O9A | −174.99 (13) | O8B—C8B—C9B—O9B | 171.89 (13) |
N7A—C1A—C2A—C3A | −178.05 (12) | N7B—C1B—C2B—C3B | 179.44 (12) |
C6A—C1A—N7A—C8A | −13.6 (2) | C6B—C1B—N7B—C8B | 16.2 (2) |
N7A—C1A—C6A—C5A | 177.86 (12) | N7B—C1B—C6B—C5B | −179.07 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
N7A—H7A···O9Ai | 0.88 | 2.24 | 3.0867 (17) | 161 |
N7B—H7B···O9Bii | 0.88 | 2.36 | 3.1410 (18) | 148 |
N7A—H7A···O9A | 0.88 | 2.30 | 2.7168 (16) | 109 |
N7B—H7B···O9B | 0.88 | 2.29 | 2.7059 (16) | 109 |
C6A—H6A···O8A | 0.95 | 2.31 | 2.8974 (18) | 120 |
C6B—H6B···O8B | 0.95 | 2.32 | 2.9004 (18) | 119 |
C5A—H5A···O8Biii | 0.95 | 2.67 | 3.294 (2) | 124 |
C5B—H5B···O8Aiv | 0.95 | 2.70 | 3.3418 (18) | 125 |
C5A—H5A···O10Biii | 0.95 | 2.72 | 3.622 (2) | 160 |
C5B—H5B···O10Aiv | 0.95 | 2.62 | 3.5669 (19) | 175 |
C2A—H2A···O9Ai | 0.95 | 2.55 | 3.3309 (19) | 140 |
C2B—H2B···O9Bii | 0.95 | 2.51 | 3.3385 (19) | 146 |
C11B—H11D···Cg1v | 0.99 | 2.79 | 3.6719 (17) | 149 |
C12A—H12A···Cg1vi | 0.98 | 2.62 | 3.4703 (18) | 146 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y+2, −z; (iii) x, y, z+1; (iv) x+1, y+1, z; (v) x−1, y, z−1; (vi) −x, −y, −z+1. |
Ethyl oxamates have been used as intermediates in the synthesis of oxamide compounds (Martínez-Martínez et al., 1988) and more recently they have been used to design molecular clefts (Padilla-Martínez et al., 2003). In spite of the growing importance of such compounds, there are few known? examples of crystalline structures bearing aromatic oxamates and those that are known are at least disubstituted. We analyse here the crystalline structure of the title compound, (I), which bears an ethyl oxamate group as the only substituent.
Compound (I) crystallizes in the triclinic system (P-1, Z = 4), and two independent molecules, which are labelled A and B (Fig. 1), are found in the asymmetric unit. These differ slightly, as evidenced by the O8—C8—C9—O9 torsion angles, which are −174.99 (13) and 171.89 (13)° for molecules A and B, respectively. The geometric features caused by the presence of? the ethyl oxamate group are listed in Table 1. The two carbonyl groups are almost antiperiplanar, with a mean O8—C8—C9—O9 torsion angle of 173.3 (15)°, in agreement with the conformation most frequently adopted by open systems. The C6—C1—N7—C8 mean torsion angle is of 15.0 (1.6)°, showing that the ethyl oxamate group is almost in the mean phenyl-ring plane, in contrast to the out-of-plane conformation adopted by 1,2- (Martin et al., 2002) and 1,3-phenyl dioxamates (Padilla-Martínez et al., 2003). In spite of the planarity exhibited by the oxamate group [mean O8—C8—C9—O9 = 175.5 (15)°], the mean CO—CO distance of 1.543 (3) Å is close to the value for a Csp3—Csp3 single bond (Dewar & Schmeizing, 1968), indicating the absence of conjugation.
The mean N7—CO and N7—Ph distances of 1.348 (3) and 1.418 (3) Å are very similar to those values measured for acetanilide [1.354 (3) and 1.413 (3) Å, respectively; Brown & Corbridge, 1954; Brown, 1966]. Thus, (I) can be described as being composed of an anilide group single bonded to an ethyl carboxylate group, in accordance with the observed chemical reactivity of these systems (Padilla-Martínez et al., 2001). As a result of the lack of conjugation along the ethyl oxamate group, intramolecular hydrogen bonding should contribute to the planarity of the system, allowing the formation of two adjacent S(5) (N7—H7···O9) and S(6) (C6—H6···O8) ring motifs (Bernstein et al., 1995).
The hydrogen-bonding geometry is listed in Table 2. The two types of molecules can form A···B pairs through intermoleular three-centered O8···H5···O10 hydrogen bonds, thus forming R21(6)[DaDb] and R21(6)[DcDd] rings. Alternatively, two molecules of the same kind can form A···A' and B···B' pairs through intermolecular hydrogen bonding in the form of soft C2—H2···O9 and hard N7—H7···O9 (Desiraju, 1996) interactions, thus forming R12(6)[DeDf] and R12(6)[DgDh] ring motifs. By symmetry, the self-complementary R22(10)[De] and R22(10)[Dg] ring motifs appear (Fig. 2). The R12(6) ring motif seems to be the characteristic motif for these systems, since it has been found for other non-substituted aromatic oxamates (García-Báez et al., 2003), whereas the R21(6) motif is typical for aliphatic oxamides (Nguyen, et al., 2001). The resulting paralell layers [1 2 − 3] are interlinked through CH···π(arene) interactions (Umezawa et al., 1998). The CH3 (molecule A) and CH2 (molecule B) moieties are hydrogen bonded to the phenyl ring of molecule A [C12A—H12B···Cg(1) and C11B—H11D···Cg(1), respectively], thus forming a staircase motif that completes the three-dimensional structure along the (0 1 2) direction (Fig. 3).