Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100003486/qa0236sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100003486/qa0236Isup2.hkl | |
Portable Document Format (PDF) file https://doi.org/10.1107/S0108270100003486/qa0236sup3.pdf |
N-3,5-Dinitrobenzoyl-L-leucine was synthesized by the reaction of 3,5-dinitrobenzoyl chloride with the parent L-leucine. Recrystallization from ethanol/water afforded colourless plate-like crystals suitable for X-ray analysis [m.p. 451–453 K (uncorrected); literature 187° (Vogel, 1989)]. IR νmax(KBr): 3400, 1725, 1650, 1550, 1350 cm-1. 1H NMR data (400 MHz, δ, DMSO): 0.87–0.94 [6H, d, J = 6.4 Hz, C(CH3)2], 1.59–1.82 (3H, m, CH2CH), 4.47–4.53 (1H, m, NCHCO2), 8.38 (1H, d, J = 7.9 Hz, NH), 8.96 (1H, t, J = 2 Hz, ArH-para), 9.10 (2H, d, J = 2 Hz, ArH-ortho).
Molecule (I) crystallized in the triclinic system, space group P1 or P1. The molecule is chiral and space group P1 was chosen and confirmed by the analysis. The absolute configuration is based on L-leucine. The crystal diffracted quite weakly but sufficient data (hemisphere) were collected to establish the structure and elucidate the hydrogen bonding interactions. The absolute structure is not reliably determined by this X-ray analysis, but is inferred from the known absolute configuration of the L-leucine used in the synthesis.
Data collection: CAD-4-PC Software (Enraf-Nonius, 1992); cell refinement: SET4 and CELDIM (Enraf-Nonius, 1992); data reduction: DATRD2 in NRCVAX96 (Gabe et al., 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: NRCVAX96 and SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: NRCVAX96, SHELXL97 and PREP8 (Ferguson, 1998).
C13H15N3O7 | F(000) = 340 |
Mr = 325.28 | Dx = 1.471 Mg m−3 |
Triclinic, P1 | Melting point: 452 K |
a = 5.8046 (3) Å | Mo Kα radiation, λ = 0.7107 Å |
b = 10.6400 (17) Å | Cell parameters from 25 reflections |
c = 12.9556 (14) Å | θ = 9.3–22.0° |
α = 109.428 (11)° | µ = 0.12 mm−1 |
β = 102.416 (7)° | T = 294 K |
γ = 90.250 (8)° | Plate, colourless |
V = 734.44 (15) Å3 | 0.30 × 0.20 × 0.05 mm |
Z = 2 |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.00 |
Radiation source: X-ray tube | θmax = 25.0°, θmin = 1.7° |
Graphite monochromator | h = 0→6 |
ω–2θ scans | k = −12→12 |
2621 measured reflections | l = −15→14 |
2621 independent reflections | 3 standard reflections every 60 min |
1326 reflections with I > 2σ(I) | intensity decay: <1% |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.045 | Calculated w = 1/[σ2(Fo2) + (0.0242P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.079 | (Δ/σ)max = 0.001 |
S = 0.94 | Δρmax = 0.19 e Å−3 |
2621 reflections | Δρmin = −0.18 e Å−3 |
418 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
3 restraints | Extinction coefficient: 0.0111 (17) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983) |
Secondary atom site location: difference Fourier map | Absolute structure parameter: −0.1 (16) |
C13H15N3O7 | γ = 90.250 (8)° |
Mr = 325.28 | V = 734.44 (15) Å3 |
Triclinic, P1 | Z = 2 |
a = 5.8046 (3) Å | Mo Kα radiation |
b = 10.6400 (17) Å | µ = 0.12 mm−1 |
c = 12.9556 (14) Å | T = 294 K |
α = 109.428 (11)° | 0.30 × 0.20 × 0.05 mm |
β = 102.416 (7)° |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.00 |
2621 measured reflections | 3 standard reflections every 60 min |
2621 independent reflections | intensity decay: <1% |
1326 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.045 | H-atom parameters constrained |
wR(F2) = 0.079 | Δρmax = 0.19 e Å−3 |
S = 0.94 | Δρmin = −0.18 e Å−3 |
2621 reflections | Absolute structure: Flack (1983) |
418 parameters | Absolute structure parameter: −0.1 (16) |
3 restraints |
Experimental. Molecule (I) crystallized in the triclinic system, space group P1 or P-1, the molecule is chiral, space group P1 chosen and confirmed by the analysis. The absolute configuration is based on L-leucine. The plate diffracted quite weakly but sufficient data were collected to establish the structure and elucidate the hydrogen bonding interactions in the crystal structure. |
Geometry. ############################################################# Hydrogen bonds with H.·A < r(A) + 2.000 Angstroms and <DHA> 110 °. D—H d(D—H) d(H.·A) <DHA d(D.·A) A symmetry code O6A—H1 0.82 1.858 173.4 2.675 O5B [x, y - 1, z] N1A—H1A 0.86 2.151 158.1 2.967 O7A [x - 1, y, z] O6B—H2 0.82 1.973 166.9 2.778 O5A N1B—H1B 0.86 2.171 168.2 3.018 O7B [x + 1, y, z] The e.s.d's are provided in the hydrogen bonding table ############################################################# Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 1.4324(0.0226)x - 8.4976(0.0147)y - 3.7862(0.0316)z = 3.8408(0.0171) * -0.0176 (0.0017) O5A * -0.0326 (0.0032) N1A * 0.0355 (0.0035) C1A * 0.0148 (0.0015) C2A Rms deviation of fitted atoms = 0.0267 3.1338(0.0123)x - 7.8681(0.0181)y - 3.1512(0.0293)z = 4.0784(0.0086) Angle to previous plane (with approximate e.s.d.) = 19.1 (4) * -0.0177 (0.0040) C11A * 0.0125 (0.0040) C12A * 0.0013 (0.0041) C13A * -0.0098 (0.0039) C14A * 0.0048 (0.0040) C15A * 0.0090 (0.0040) C16A Rms deviation of fitted atoms = 0.0106 3.2357(0.0198)x + 7.3943(0.0383)y + 0.7900(0.0408)z = 3.7470(0.0266) Angle to previous plane (with approximate e.s.d.) = 66.7 (3) * 0.0032 (0.0017) C11B * -0.0068 (0.0035) C12B * 0.0069 (0.0036) C13B * -0.0033 (0.0017) C14B -0.0158 (0.0112) C15B -0.0073 (0.0108) C16B Rms deviation of fitted atoms = 0.0054 2.0972(0.0252)x + 8.4695(0.0162)y + 1.2906(0.0425)z = 2.5986(0.0194) Angle to previous plane (with approximate e.s.d.) = 12.8 (6) * 0.0087 (0.0018) O5B * 0.0158 (0.0033) N1B * -0.0172 (0.0036) C1B * -0.0073 (0.0015) C2B Rms deviation of fitted atoms = 0.0130 0.1321(0.0174)x - 6.1943(0.0298)y + 12.1178(0.0157)z = 6.9518(0.0191) Angle to previous plane (with approximate e.s.d.) = 86.4 (2) * 0.0027 (0.0014) C2A * -0.0095 (0.0050) C3A * 0.0030 (0.0016) O6A * 0.0038 (0.0020) O7A Rms deviation of fitted atoms = 0.0055 1.9382(0.0158)x - 8.5511(0.0142)y - 3.3487(0.0252)z = 4.1706(0.0096) Angle to previous plane (with approximate e.s.d.) = 85.9 (2) * 0.0718 (0.0027) C11A * -0.0496 (0.0050) C1A * -0.0050 (0.0019) O5A * -0.1004 (0.0038) N1A * 0.0833 (0.0028) C2A 1.4275 (0.0080) C3A 2.4225 (0.0063) O6A 1.5840 (0.0087) O7A Rms deviation of fitted atoms = 0.0702 3.0932(0.0577)x - 6.9842(0.0750)y - 5.0418(0.0556)z = 3.7619(0.0764) Angle to previous plane (with approximate e.s.d.) = 14.5 (9) * 0.0000 (0.0000) O1A * 0.0000 (0.0000) O2A * 0.0000 (0.0000) N13A Rms deviation of fitted atoms = 0.0000 3.1338(0.0123)x - 7.8681(0.0181)y - 3.1512(0.0293)z = 4.0784(0.0086) Angle to previous plane (with approximate e.s.d.) = 9(1) * -0.0177 (0.0040) C11A * 0.0125 (0.0040) C12A * 0.0013 (0.0041) C13A * -0.0098 (0.0039) C14A * 0.0048 (0.0040) C15A * 0.0090 (0.0040) C16A 0.2337 (0.0115) O1A -0.0979 (0.0103) O2A 0.0742 (0.0102) O3A 0.2646 (0.0111) O4A Rms deviation of fitted atoms = 0.0106 2.5273(0.0345)x - 8.6928(0.0806)y - 2.2350(0.1700)z = 4.3002(0.0146) Angle to previous plane (with approximate e.s.d.) = 8(1) * 0.0000 (0.0000) O3A * 0.0000 (0.0000) O4A * 0.0000 (0.0000) N15A Rms deviation of fitted atoms = 0.0000 -0.1072(0.0170)x - 3.3152(0.0310)y + 12.6956(0.0080)z = 3.4061(0.0129) Angle to previous plane (with approximate e.s.d.) = 83.3 (8) * -0.0046 (0.0015) C2B * 0.0161 (0.0052) C3B * -0.0051 (0.0016) O6B * -0.0064 (0.0021) O7B Rms deviation of fitted atoms = 0.0093 2.2650(0.0167)x + 8.4269(0.0167)y + 1.0323(0.0264)z = 2.7078(0.0151) Angle to previous plane (with approximate e.s.d.) = 79.1 (2) * -0.0241 (0.0029) C11B * 0.0110 (0.0052) C1B * 0.0057 (0.0019) O5B * 0.0376 (0.0040) N1B * -0.0302 (0.0030) C2B -1.4508 (0.0079) C3B -2.2726 (0.0070) O6B -1.8396 (0.0092) O7B Rms deviation of fitted atoms = 0.0247 3.0500(0.0548)x + 7.0653(0.0761)y + 1.9481(0.0401)z = 3.4487(0.1058) Angle to previous plane (with approximate e.s.d.) = 11 (1) * 0.0000 (0.0000) O1B * 0.0000 (0.0000) O2B * 0.0000 (0.0000) N13B Rms deviation of fitted atoms = 0.0000 3.2226(0.0115)x + 7.4322(0.0185)y + 0.7487(0.0306)z = 3.7300(0.0152) Angle to previous plane (with approximate e.s.d.) = 5(1) * 0.0056 (0.0040) C11B * -0.0094 (0.0041) C12B * 0.0057 (0.0039) C13B * 0.0019 (0.0040) C14B * -0.0056 (0.0039) C15B * 0.0017 (0.0037) C16B -0.0464 (0.0102) O1B 0.1540 (0.0101) O2B -0.0499 (0.0103) O3B -0.0760 (0.0111) O4B Rms deviation of fitted atoms = 0.0056 3.1236(0.0237)x + 7.6903(0.0834)y + 0.4769(0.1366)z = 3.6761(0.0353) Angle to previous plane (with approximate e.s.d.) = 2(1) * 0.0000 (0.0001) O3B * 0.0000 (0.0000) O4B * 0.0000 (0.0000) N15B Rms deviation of fitted atoms = 0.0000 0.1321(0.0174)x - 6.1943(0.0298)y + 12.1178(0.0157)z = 6.9518(0.0191) Angle to previous plane (with approximate e.s.d.) = 86.5 (6) * 0.0027 (0.0014) C2A * -0.0095 (0.0050) C3A * 0.0030 (0.0016) O6A * 0.0038 (0.0020) O7A Rms deviation of fitted atoms = 0.0055 1.9382(0.0158)x - 8.5511(0.0142)y - 3.3487(0.0252)z = 4.1706(0.0096) Angle to previous plane (with approximate e.s.d.) = 85.9 (2) * 0.0718 (0.0027) C11A * -0.0496 (0.0050) C1A * -0.0050 (0.0019) O5A * -0.1004 (0.0038) N1A * 0.0833 (0.0028) C2A 1.4275 (0.0080) C3A 2.4225 (0.0063) O6A 1.5840 (0.0087) O7A Rms deviation of fitted atoms = 0.0702 ############################################################# |
x | y | z | Uiso*/Ueq | ||
O1A | −0.4819 (9) | −0.7250 (5) | −0.0375 (5) | 0.0719 (17) | |
O2A | −0.6294 (8) | −0.6808 (5) | −0.1891 (4) | 0.0659 (15) | |
O3A | −0.1298 (10) | −0.4481 (6) | −0.3281 (4) | 0.0735 (16) | |
O4A | 0.2254 (10) | −0.3699 (5) | −0.2305 (4) | 0.0773 (19) | |
O5A | 0.5199 (7) | −0.4204 (4) | 0.1304 (3) | 0.0489 (12) | |
O6A | 0.5216 (8) | −0.7293 (5) | 0.1954 (4) | 0.0577 (15) | |
O7A | 0.8415 (8) | −0.5861 (5) | 0.2652 (4) | 0.0562 (14) | |
N1A | 0.2786 (7) | −0.4975 (4) | 0.2161 (4) | 0.0332 (12) | |
N13A | −0.4699 (10) | −0.6702 (6) | −0.1061 (5) | 0.0480 (16) | |
N15A | 0.0309 (13) | −0.4234 (6) | −0.2424 (5) | 0.0599 (18) | |
C1A | 0.3212 (12) | −0.4608 (6) | 0.1319 (5) | 0.0371 (16) | |
C2A | 0.4677 (10) | −0.5118 (6) | 0.3072 (5) | 0.0382 (16) | |
C3A | 0.6341 (11) | −0.6104 (7) | 0.2540 (5) | 0.0373 (16) | |
C4A | 0.6007 (10) | −0.3821 (6) | 0.3917 (5) | 0.0440 (17) | |
C5A | 0.4494 (13) | −0.2787 (7) | 0.4486 (6) | 0.059 (2) | |
C6A | 0.2926 (13) | −0.3303 (7) | 0.5070 (6) | 0.071 (2) | |
C7A | 0.6157 (15) | −0.1592 (7) | 0.5321 (6) | 0.078 (3) | |
C11A | 0.1181 (11) | −0.4819 (6) | 0.0320 (5) | 0.0295 (15) | |
C12A | −0.0895 (11) | −0.5607 (6) | 0.0128 (6) | 0.0429 (18) | |
C13A | −0.2542 (12) | −0.5850 (6) | −0.0868 (5) | 0.0368 (17) | |
C14A | −0.2275 (11) | −0.5394 (6) | −0.1706 (5) | 0.0422 (17) | |
C15A | −0.0151 (12) | −0.4648 (6) | −0.1501 (5) | 0.0396 (17) | |
C16A | 0.1583 (11) | −0.4360 (6) | −0.0511 (5) | 0.0397 (17) | |
O1B | 1.6660 (8) | −0.2243 (5) | −0.0248 (4) | 0.0556 (14) | |
O2B | 1.6924 (8) | −0.1932 (5) | −0.1787 (4) | 0.0589 (14) | |
O3B | 1.1084 (9) | 0.0490 (5) | −0.3425 (4) | 0.0609 (15) | |
O4B | 0.8509 (9) | 0.1480 (5) | −0.2506 (4) | 0.0626 (15) | |
O5B | 0.7998 (8) | 0.0957 (4) | 0.0924 (3) | 0.0495 (13) | |
O6B | 0.8681 (7) | −0.2087 (4) | 0.2207 (4) | 0.0542 (13) | |
O7B | 0.5687 (8) | −0.0807 (5) | 0.2515 (4) | 0.0569 (14) | |
N1B | 1.0817 (8) | 0.0113 (5) | 0.1938 (4) | 0.0357 (13) | |
N13B | 1.6006 (10) | −0.1758 (5) | −0.0983 (5) | 0.0481 (16) | |
N15B | 1.0197 (11) | 0.0801 (6) | −0.2613 (5) | 0.0482 (16) | |
C1B | 0.9895 (11) | 0.0440 (6) | 0.1033 (5) | 0.0333 (15) | |
C2B | 0.9563 (10) | 0.0261 (6) | 0.2828 (5) | 0.0384 (17) | |
C3B | 0.7752 (11) | −0.0901 (7) | 0.2526 (5) | 0.0397 (17) | |
C4B | 1.1331 (10) | 0.0490 (7) | 0.3946 (5) | 0.0403 (17) | |
C5B | 1.2654 (12) | 0.1887 (7) | 0.4399 (6) | 0.0519 (19) | |
C6B | 1.1159 (14) | 0.2964 (7) | 0.4946 (6) | 0.083 (3) | |
C7B | 1.4961 (13) | 0.1931 (9) | 0.5244 (7) | 0.093 (3) | |
C11B | 1.1189 (11) | 0.0163 (6) | 0.0119 (5) | 0.0319 (15) | |
C12B | 1.3046 (11) | −0.0650 (6) | −0.0003 (5) | 0.0365 (17) | |
C13B | 1.3967 (10) | −0.0937 (6) | −0.0917 (5) | 0.0308 (15) | |
C14B | 1.3120 (11) | −0.0488 (6) | −0.1787 (5) | 0.0380 (17) | |
C15B | 1.1246 (12) | 0.0305 (6) | −0.1683 (5) | 0.0351 (16) | |
C16B | 1.0270 (10) | 0.0645 (5) | −0.0764 (4) | 0.0320 (16) | |
H1 | 0.6149 | −0.7810 | 0.1687 | 0.069* | |
H1A | 0.1339 | −0.5135 | 0.2171 | 0.040* | |
H2A | 0.3914 | −0.5536 | 0.3495 | 0.046* | |
H4A1 | 0.7134 | −0.4036 | 0.4492 | 0.053* | |
H4A2 | 0.6902 | −0.3428 | 0.3533 | 0.053* | |
H5A | 0.3486 | −0.2491 | 0.3915 | 0.070* | |
H6A1 | 0.2011 | −0.2603 | 0.5415 | 0.106* | |
H6A2 | 0.3888 | −0.3594 | 0.5637 | 0.106* | |
H6A3 | 0.1883 | −0.4042 | 0.4531 | 0.106* | |
H7A1 | 0.5242 | −0.0914 | 0.5698 | 0.117* | |
H7A2 | 0.7054 | −0.1237 | 0.4924 | 0.117* | |
H7A3 | 0.7216 | −0.1876 | 0.5864 | 0.117* | |
H12A | −0.1161 | −0.5962 | 0.0663 | 0.051* | |
H14A | −0.3432 | −0.5569 | −0.2367 | 0.051* | |
H16A | 0.2990 | −0.3866 | −0.0410 | 0.048* | |
H2 | 0.7646 | −0.2692 | 0.2047 | 0.065* | |
H1B | 1.2190 | −0.0194 | 0.1998 | 0.043* | |
H2B | 0.8704 | 0.1066 | 0.2907 | 0.046* | |
H4B1 | 1.2465 | −0.0182 | 0.3844 | 0.048* | |
H4B2 | 1.0497 | 0.0393 | 0.4492 | 0.048* | |
H5B | 1.3044 | 0.2082 | 0.3765 | 0.062* | |
H6B1 | 0.9707 | 0.2937 | 0.4415 | 0.125* | |
H6B2 | 1.2011 | 0.3824 | 0.5180 | 0.125* | |
H6B3 | 1.0813 | 0.2811 | 0.5588 | 0.125* | |
H7B1 | 1.5909 | 0.1249 | 0.4899 | 0.140* | |
H7B2 | 1.4614 | 0.1778 | 0.5886 | 0.140* | |
H7B3 | 1.5812 | 0.2791 | 0.5478 | 0.140* | |
H12B | 1.3665 | −0.1003 | 0.0556 | 0.044* | |
H14B | 1.3769 | −0.0703 | −0.2415 | 0.046* | |
H16B | 0.9017 | 0.1187 | −0.0723 | 0.038* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1A | 0.057 (4) | 0.078 (4) | 0.079 (4) | −0.025 (3) | 0.005 (3) | 0.031 (3) |
O2A | 0.035 (3) | 0.088 (4) | 0.061 (3) | 0.001 (3) | −0.005 (3) | 0.018 (3) |
O3A | 0.085 (4) | 0.089 (4) | 0.048 (3) | 0.009 (3) | 0.008 (3) | 0.030 (3) |
O4A | 0.093 (5) | 0.083 (4) | 0.058 (4) | −0.033 (4) | 0.013 (3) | 0.030 (3) |
O5A | 0.036 (3) | 0.061 (3) | 0.050 (3) | −0.012 (2) | 0.008 (2) | 0.021 (2) |
O6A | 0.043 (3) | 0.048 (3) | 0.071 (4) | 0.006 (3) | 0.021 (3) | −0.001 (3) |
O7A | 0.032 (3) | 0.067 (4) | 0.069 (4) | 0.000 (3) | 0.016 (3) | 0.019 (3) |
N1A | 0.021 (3) | 0.040 (3) | 0.032 (3) | −0.003 (2) | 0.003 (3) | 0.006 (3) |
N13A | 0.030 (4) | 0.055 (4) | 0.050 (4) | 0.001 (3) | 0.005 (3) | 0.008 (3) |
N15A | 0.077 (5) | 0.056 (5) | 0.039 (4) | 0.005 (4) | 0.012 (4) | 0.008 (3) |
C1A | 0.038 (5) | 0.030 (4) | 0.037 (4) | −0.001 (3) | 0.012 (4) | 0.001 (3) |
C2A | 0.031 (4) | 0.044 (4) | 0.037 (4) | −0.002 (3) | 0.007 (3) | 0.011 (3) |
C3A | 0.036 (4) | 0.057 (5) | 0.020 (3) | −0.001 (4) | 0.003 (3) | 0.017 (3) |
C4A | 0.039 (4) | 0.042 (4) | 0.046 (4) | −0.003 (3) | 0.008 (3) | 0.010 (3) |
C5A | 0.060 (5) | 0.052 (5) | 0.057 (5) | −0.003 (4) | 0.011 (4) | 0.012 (4) |
C6A | 0.054 (5) | 0.071 (6) | 0.088 (6) | 0.005 (4) | 0.043 (5) | 0.012 (5) |
C7A | 0.113 (7) | 0.044 (5) | 0.054 (5) | −0.023 (5) | 0.014 (5) | −0.009 (4) |
C11A | 0.031 (4) | 0.033 (4) | 0.031 (4) | 0.006 (3) | 0.014 (3) | 0.014 (3) |
C12A | 0.043 (5) | 0.043 (4) | 0.046 (5) | 0.003 (4) | 0.019 (4) | 0.016 (4) |
C13A | 0.032 (4) | 0.023 (4) | 0.046 (4) | −0.003 (3) | 0.006 (3) | 0.001 (3) |
C14A | 0.041 (5) | 0.033 (4) | 0.046 (4) | 0.010 (3) | 0.006 (3) | 0.007 (3) |
C15A | 0.055 (5) | 0.040 (4) | 0.027 (4) | 0.013 (4) | 0.014 (3) | 0.013 (3) |
C16A | 0.042 (4) | 0.025 (4) | 0.041 (4) | 0.003 (3) | 0.007 (4) | −0.002 (3) |
O1B | 0.059 (4) | 0.064 (4) | 0.050 (3) | 0.028 (3) | 0.020 (3) | 0.022 (3) |
O2B | 0.047 (3) | 0.076 (4) | 0.056 (3) | 0.006 (3) | 0.032 (3) | 0.013 (3) |
O3B | 0.078 (4) | 0.072 (4) | 0.034 (3) | 0.002 (3) | 0.012 (3) | 0.020 (3) |
O4B | 0.077 (4) | 0.076 (4) | 0.039 (3) | 0.028 (3) | 0.013 (3) | 0.024 (3) |
O5B | 0.045 (3) | 0.072 (3) | 0.043 (3) | 0.031 (3) | 0.015 (2) | 0.029 (3) |
O6B | 0.045 (3) | 0.050 (3) | 0.062 (3) | −0.006 (2) | 0.009 (3) | 0.015 (3) |
O7B | 0.027 (3) | 0.081 (4) | 0.064 (3) | 0.008 (3) | 0.013 (2) | 0.026 (3) |
N1B | 0.026 (3) | 0.057 (4) | 0.029 (3) | 0.016 (3) | 0.011 (2) | 0.018 (3) |
N13B | 0.042 (4) | 0.044 (4) | 0.049 (4) | 0.006 (3) | 0.013 (4) | 0.001 (3) |
N15B | 0.060 (5) | 0.046 (4) | 0.038 (4) | −0.001 (3) | 0.012 (3) | 0.013 (3) |
C1B | 0.035 (4) | 0.032 (4) | 0.029 (4) | 0.002 (3) | 0.002 (3) | 0.009 (3) |
C2B | 0.043 (4) | 0.042 (4) | 0.037 (4) | 0.014 (3) | 0.019 (3) | 0.017 (3) |
C3B | 0.036 (4) | 0.048 (5) | 0.038 (4) | 0.006 (4) | 0.005 (3) | 0.021 (3) |
C4B | 0.037 (4) | 0.058 (4) | 0.030 (4) | −0.002 (4) | 0.005 (3) | 0.021 (3) |
C5B | 0.060 (5) | 0.048 (5) | 0.046 (4) | −0.010 (4) | 0.015 (4) | 0.011 (4) |
C6B | 0.116 (8) | 0.038 (5) | 0.076 (6) | 0.006 (5) | 0.016 (5) | −0.001 (4) |
C7B | 0.059 (6) | 0.121 (8) | 0.070 (6) | −0.016 (5) | 0.003 (5) | 0.003 (5) |
C11B | 0.037 (4) | 0.033 (4) | 0.026 (4) | 0.002 (3) | 0.008 (3) | 0.008 (3) |
C12B | 0.046 (4) | 0.037 (4) | 0.031 (4) | 0.002 (3) | 0.019 (3) | 0.010 (3) |
C13B | 0.022 (4) | 0.029 (4) | 0.031 (4) | −0.002 (3) | 0.001 (3) | −0.001 (3) |
C14B | 0.036 (4) | 0.039 (4) | 0.034 (4) | −0.007 (3) | 0.014 (3) | 0.002 (3) |
C15B | 0.045 (4) | 0.040 (4) | 0.022 (3) | −0.005 (3) | 0.001 (3) | 0.018 (3) |
C16B | 0.030 (4) | 0.026 (4) | 0.032 (4) | −0.001 (3) | 0.003 (3) | 0.002 (3) |
O1A—N13A | 1.226 (6) | O1B—N13B | 1.220 (6) |
O2A—N13A | 1.232 (6) | O2B—N13B | 1.230 (6) |
O3A—N15A | 1.237 (7) | O3B—N15B | 1.218 (6) |
O4A—N15A | 1.218 (7) | O4B—N15B | 1.224 (6) |
O5A—C1A | 1.235 (7) | O5B—C1B | 1.235 (7) |
O6A—C3A | 1.321 (7) | O6B—C3B | 1.345 (7) |
O7A—C3A | 1.198 (7) | O7B—C3B | 1.201 (7) |
N1A—C1A | 1.343 (7) | N1B—C1B | 1.337 (7) |
N1A—C2A | 1.478 (6) | N1B—C2B | 1.458 (6) |
N13A—C13A | 1.468 (8) | N13B—C13B | 1.474 (7) |
N15A—C15A | 1.477 (7) | N15B—C15B | 1.487 (7) |
C1A—C11A | 1.505 (8) | C1B—C11B | 1.486 (8) |
C2A—C4A | 1.523 (7) | C2B—C3B | 1.509 (8) |
C2A—C3A | 1.524 (8) | C2B—C4B | 1.528 (7) |
C4A—C5A | 1.507 (8) | C4B—C5B | 1.536 (9) |
C5A—C6A | 1.507 (8) | C5B—C6B | 1.517 (9) |
C5A—C7A | 1.531 (9) | C5B—C7B | 1.526 (9) |
C11A—C16A | 1.382 (7) | C11B—C12B | 1.387 (8) |
C11A—C12A | 1.393 (8) | C11B—C16B | 1.409 (7) |
C12A—C13A | 1.375 (7) | C12B—C13B | 1.347 (7) |
C13A—C14A | 1.365 (8) | C13B—C14B | 1.365 (7) |
C14A—C15A | 1.389 (8) | C14B—C15B | 1.381 (8) |
C15A—C16A | 1.390 (7) | C15B—C16B | 1.369 (7) |
C1A—N1A—C2A | 123.3 (5) | C1B—N1B—C2B | 121.9 (5) |
O1A—N13A—O2A | 123.9 (6) | O1B—N13B—O2B | 123.8 (6) |
O1A—N13A—C13A | 118.0 (6) | O1B—N13B—C13B | 118.2 (6) |
O2A—N13A—C13A | 118.1 (6) | O2B—N13B—C13B | 118.0 (6) |
O3A—N15A—O4A | 124.2 (7) | O3B—N15B—O4B | 125.3 (6) |
O3A—N15A—C15A | 117.6 (7) | O3B—N15B—C15B | 117.1 (6) |
O4A—N15A—C15A | 118.2 (6) | O4B—N15B—C15B | 117.6 (6) |
O5A—C1A—N1A | 122.9 (6) | O5B—C1B—N1B | 122.5 (6) |
O5A—C1A—C11A | 120.0 (6) | O5B—C1B—C11B | 118.7 (6) |
N1A—C1A—C11A | 116.9 (6) | N1B—C1B—C11B | 118.8 (6) |
N1A—C2A—C3A | 108.3 (5) | N1B—C2B—C3B | 111.6 (5) |
N1A—C2A—C4A | 115.9 (5) | N1B—C2B—C4B | 110.1 (5) |
C3A—C2A—C4A | 112.1 (5) | C3B—C2B—C4B | 113.0 (5) |
O6A—C3A—O7A | 123.5 (6) | O6B—C3B—O7B | 122.7 (6) |
O6A—C3A—C2A | 111.2 (5) | O6B—C3B—C2B | 112.3 (5) |
O7A—C3A—C2A | 125.2 (6) | O7B—C3B—C2B | 124.9 (6) |
C2A—C4A—C5A | 115.7 (5) | C2B—C4B—C5B | 111.5 (5) |
C4A—C5A—C6A | 113.3 (6) | C4B—C5B—C6B | 112.0 (6) |
C4A—C5A—C7A | 107.5 (6) | C4B—C5B—C7B | 110.8 (6) |
C6A—C5A—C7A | 110.8 (7) | C6B—C5B—C7B | 109.4 (6) |
C12A—C11A—C1A | 123.1 (6) | C12B—C11B—C1B | 125.6 (5) |
C16A—C11A—C1A | 116.7 (6) | C16B—C11B—C1B | 116.6 (5) |
C12A—C11A—C16A | 119.5 (6) | C12B—C11B—C16B | 117.3 (5) |
C11A—C12A—C13A | 118.6 (6) | C11B—C12B—C13B | 121.1 (6) |
C12A—C13A—C14A | 124.6 (6) | C12B—C13B—C14B | 123.0 (6) |
C12A—C13A—N13A | 117.7 (6) | C12B—C13B—N13B | 119.0 (6) |
C14A—C13A—N13A | 117.7 (6) | C14B—C13B—N13B | 117.9 (6) |
C13A—C14A—C15A | 115.2 (6) | C13B—C14B—C15B | 116.3 (6) |
C14A—C15A—N15A | 117.2 (6) | C14B—C15B—C16B | 123.1 (6) |
C14A—C15A—C16A | 123.2 (6) | C14B—C15B—N15B | 119.1 (6) |
C16A—C15A—N15A | 119.6 (6) | C16B—C15B—N15B | 117.8 (6) |
C11A—C16A—C15A | 118.9 (6) | C11B—C16B—C15B | 119.1 (6) |
C2A—N1A—C1A—O5A | −8.9 (9) | C2B—N1B—C1B—O5B | 4.3 (9) |
C2A—N1A—C1A—C11A | 165.9 (5) | C2B—N1B—C1B—C11B | −175.2 (5) |
C1A—N1A—C2A—C4A | 70.8 (7) | C1B—N1B—C2B—C3B | 81.5 (7) |
C1A—N1A—C2A—C3A | −56.1 (7) | C1B—N1B—C2B—C4B | −152.2 (5) |
N1A—C2A—C3A—O7A | 120.7 (6) | N1B—C2B—C3B—O7B | −124.8 (7) |
C4A—C2A—C3A—O7A | −8.4 (9) | C4B—C2B—C3B—O7B | 110.5 (7) |
N1A—C2A—C3A—O6A | −61.2 (6) | N1B—C2B—C3B—O6B | 52.0 (7) |
C4A—C2A—C3A—O6A | 169.7 (5) | C4B—C2B—C3B—O6B | −72.7 (7) |
N1A—C2A—C4A—C5A | 55.1 (7) | N1B—C2B—C4B—C5B | 71.3 (7) |
C3A—C2A—C4A—C5A | −179.9 (5) | C3B—C2B—C4B—C5B | −163.2 (6) |
C2A—C4A—C5A—C6A | 55.5 (8) | C2B—C4B—C5B—C6B | 78.4 (7) |
C2A—C4A—C5A—C7A | 178.2 (6) | C2B—C4B—C5B—C7B | −159.2 (6) |
O5A—C1A—C11A—C16A | −9.1 (8) | O5B—C1B—C11B—C12B | −165.8 (6) |
N1A—C1A—C11A—C16A | 175.9 (5) | N1B—C1B—C11B—C12B | 13.8 (9) |
O5A—C1A—C11A—C12A | 161.3 (6) | O5B—C1B—C11B—C16B | 6.6 (8) |
N1A—C1A—C11A—C12A | −13.7 (8) | N1B—C1B—C11B—C16B | −173.9 (5) |
C16A—C11A—C12A—C13A | −3.2 (8) | C16B—C11B—C12B—C13B | 1.6 (8) |
C1A—C11A—C12A—C13A | −173.3 (6) | C1B—C11B—C12B—C13B | 173.9 (6) |
C11A—C12A—C13A—C14A | 1.4 (9) | C11B—C12B—C13B—C14B | −1.7 (9) |
C11A—C12A—C13A—N13A | 179.0 (6) | C11B—C12B—C13B—N13B | 177.4 (6) |
O1A—N13A—C13A—C14A | 171.1 (6) | O1B—N13B—C13B—C12B | 6.1 (8) |
O2A—N13A—C13A—C14A | −9.9 (8) | O2B—N13B—C13B—C12B | −175.1 (6) |
O1A—N13A—C13A—C12A | −6.6 (9) | O1B—N13B—C13B—C14B | −174.8 (5) |
O2A—N13A—C13A—C12A | 172.3 (5) | O2B—N13B—C13B—C14B | 4.0 (8) |
C12A—C13A—C14A—C15A | 0.6 (9) | C12B—C13B—C14B—C15B | 0.6 (8) |
N13A—C13A—C14A—C15A | −176.9 (5) | N13B—C13B—C14B—C15B | −178.5 (5) |
C13A—C14A—C15A—C16A | −1.0 (8) | C13B—C14B—C15B—C16B | 0.5 (8) |
C13A—C14A—C15A—N15A | 174.8 (5) | C13B—C14B—C15B—N15B | −178.5 (5) |
O4A—N15A—C15A—C14A | −172.7 (6) | O3B—N15B—C15B—C16B | 180.0 (5) |
O3A—N15A—C15A—C14A | 5.8 (8) | O4B—N15B—C15B—C16B | −0.4 (8) |
O4A—N15A—C15A—C16A | 3.2 (9) | O3B—N15B—C15B—C14B | −1.0 (8) |
O3A—N15A—C15A—C16A | −178.3 (6) | O4B—N15B—C15B—C14B | 178.7 (6) |
C12A—C11A—C16A—C15A | 2.9 (8) | C14B—C15B—C16B—C11B | −0.6 (8) |
C1A—C11A—C16A—C15A | 173.6 (5) | N15B—C15B—C16B—C11B | 178.5 (5) |
C14A—C15A—C16A—C11A | −0.8 (9) | C12B—C11B—C16B—C15B | −0.5 (8) |
N15A—C15A—C16A—C11A | −176.4 (5) | C1B—C11B—C16B—C15B | −173.5 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
O6A—H1···O5Bi | 0.82 | 1.86 | 2.675 (6) | 173 |
N1A—H1A···O7Aii | 0.86 | 2.15 | 2.967 (6) | 158 |
O6B—H2···O5A | 0.82 | 1.97 | 2.778 (6) | 167 |
N1B—H1B···O7Biii | 0.86 | 2.17 | 3.018 (6) | 168 |
Symmetry codes: (i) x, y+1, z; (ii) x+1, y, z; (iii) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C13H15N3O7 |
Mr | 325.28 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 294 |
a, b, c (Å) | 5.8046 (3), 10.6400 (17), 12.9556 (14) |
α, β, γ (°) | 109.428 (11), 102.416 (7), 90.250 (8) |
V (Å3) | 734.44 (15) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.30 × 0.20 × 0.05 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2621, 2621, 1326 |
Rint | 0.00 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.079, 0.94 |
No. of reflections | 2621 |
No. of parameters | 418 |
No. of restraints | 3 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.18 |
Absolute structure | Flack (1983) |
Absolute structure parameter | −0.1 (16) |
Computer programs: CAD-4-PC Software (Enraf-Nonius, 1992), SET4 and CELDIM (Enraf-Nonius, 1992), DATRD2 in NRCVAX96 (Gabe et al., 1989), SHELXS97 (Sheldrick, 1997), NRCVAX96 and SHELXL97 (Sheldrick, 1997), NRCVAX96, SHELXL97 and PREP8 (Ferguson, 1998).
O1A—N13A | 1.226 (6) | O1B—N13B | 1.220 (6) |
O2A—N13A | 1.232 (6) | O2B—N13B | 1.230 (6) |
O3A—N15A | 1.237 (7) | O3B—N15B | 1.218 (6) |
O4A—N15A | 1.218 (7) | O4B—N15B | 1.224 (6) |
O5A—C1A | 1.235 (7) | O5B—C1B | 1.235 (7) |
O6A—C3A | 1.321 (7) | O6B—C3B | 1.345 (7) |
O7A—C3A | 1.198 (7) | O7B—C3B | 1.201 (7) |
N1A—C1A | 1.343 (7) | N1B—C1B | 1.337 (7) |
N1A—C2A | 1.478 (6) | N1B—C2B | 1.458 (6) |
N13A—C13A | 1.468 (8) | N13B—C13B | 1.474 (7) |
N15A—C15A | 1.477 (7) | N15B—C15B | 1.487 (7) |
C1A—C11A | 1.505 (8) | C1B—C11B | 1.486 (8) |
C2A—C4A | 1.523 (7) | C2B—C3B | 1.509 (8) |
C2A—C3A | 1.524 (8) | C2B—C4B | 1.528 (7) |
C1A—N1A—C2A | 123.3 (5) | C1B—N1B—C2B | 121.9 (5) |
O1A—N13A—O2A | 123.9 (6) | O1B—N13B—O2B | 123.8 (6) |
O3A—N15A—O4A | 124.2 (7) | O3B—N15B—O4B | 125.3 (6) |
O5A—C1A—N1A | 122.9 (6) | O5B—C1B—N1B | 122.5 (6) |
O5A—C1A—C11A | 120.0 (6) | O5B—C1B—C11B | 118.7 (6) |
N1A—C1A—C11A | 116.9 (6) | N1B—C1B—C11B | 118.8 (6) |
N1A—C2A—C3A | 108.3 (5) | N1B—C2B—C3B | 111.6 (5) |
N1A—C2A—C4A | 115.9 (5) | N1B—C2B—C4B | 110.1 (5) |
C3A—C2A—C4A | 112.1 (5) | C3B—C2B—C4B | 113.0 (5) |
O6A—C3A—O7A | 123.5 (6) | O6B—C3B—O7B | 122.7 (6) |
O6A—C3A—C2A | 111.2 (5) | O6B—C3B—C2B | 112.3 (5) |
O7A—C3A—C2A | 125.2 (6) | O7B—C3B—C2B | 124.9 (6) |
C2A—C4A—C5A | 115.7 (5) | C2B—C4B—C5B | 111.5 (5) |
C4A—C5A—C6A | 113.3 (6) | C4B—C5B—C6B | 112.0 (6) |
C12A—C11A—C1A | 123.1 (6) | C12B—C11B—C1B | 125.6 (5) |
C16A—C11A—C1A | 116.7 (6) | C16B—C11B—C1B | 116.6 (5) |
C2A—N1A—C1A—O5A | −8.9 (9) | C2B—N1B—C1B—O5B | 4.3 (9) |
C1A—N1A—C2A—C4A | 70.8 (7) | C1B—N1B—C2B—C3B | 81.5 (7) |
N1A—C2A—C3A—O7A | 120.7 (6) | N1B—C2B—C3B—O7B | −124.8 (7) |
N1A—C2A—C4A—C5A | 55.1 (7) | N1B—C2B—C4B—C5B | 71.3 (7) |
The study of biologically important molecules continues to be of primary importance in medicinal chemistry. Processes such as blood coagulation, hormone processing, viral replication and cancer-cell invasion are critically ependent on protease enzymes which are attractive target molecules in the design of specific and selective drugs. Important protease inhibitors are usually based on modified amino acids incorporating structural features which determine normal enzyme-substrate recognition processes. Structure-based drug design strategies to identify interactions between a potential inhibitor and target receptor require accurate inhibitor structures. We are currently studying structure–activity relationships and molecular-recognition processes in biologically important molecules such as the title compound N-3,5-dinitrobenzoyl-L-leucine, (I), for applications in drug design (Gallagher & Murphy, 1999; Gallagher et al., 1999, 2000).
In (I), two independent molecules are present which differ in conformation in space group P1 (No. 1). The bond lengths are largely in accord with anticipated values (Orpen et al., 1994). The molecules differ in conformation about the N1—C2 bond, with N1—C2—C4 angles of 115.9 (5) and 110.1 (5)°, and C1—N1—C2—C3 torsion angles of -56.1 (7) and 81.5 (7)° in A and B, respectively. The aromatic C1—C11—C12 and C1—C11—C16 angles are 123.1 (6)/116.7 (6)° in molecule A and 125.6 (5)/116.6 (5)° in molecule B. This results from the intramolecular contacts H16A···O5A 2.45 Å and H1A···H12A 2.08 Å in A, and H16B···O5B, 2.42 Å and H1B···H12B, 2.14 Å in B (O5B···H2B 2.48 Å). The aromatic ring planes are oriented at angles of 19.1 (4) (A) and 12.8 (6)° (B) to their respective amide groups (O5/C1/N1/C2) and the nitro groups are almost coplanar (<10° from the aromatic ring planes), with O4A deviating by 0.265 (11) Å from the C6 ring plane. The carboxylate (C2/C3/O6/O7) groups are almost normal to the (C11/C1/O5/N1/C2) planes, with angles of 85.9 (2) and 79.1 (2)° in molecules A and B, respectively.
The molecules are aligned in one-dimensional chains as [A···]n and [B···]n with (amide)[A/B]N—H···O═C[A/B](acid) hydrogen bonds and partial overlap due to π–π stacking of the 3,5-dinitrobenzoyl groups. The N···O distances are 2.967 (6) Å along [A···]n and 3.019 (6) Å along [B···]n. Interactions between the neighbouring A and B chains arise as carboxylate (for A → B) and 2.778 (6) Å (for B → A) (where → indicates the direction of the hydrogen bonding). This association results in the formation of two 20-membered hydrogen-bonded ring systems each consisting of two A and two B molecules and differing by the direction of the hydrogen bonding, [B···]n → [A..]n and [A···]n → [B···]n (where → indicates the carboxylic acid to amide O═C hydrogen bonds). Both rings have graph-set R44(20) which repeats as a two-dimensional network in the lattice (rings J and K in the deposited figure). Examination of the structure with PLATON (Spek, 1998) showed that there were no solvent-accessible voids.
The structure of L-Leucine has been reported previously (Harding & Howieson, 1976; Coll et al., 1986; Görbitz & Dalhus, 1996) and contains two crystallographically independent zwitterions having similar conformations in the asymmetric unit, unlike (I) above, where the two molecules differ significantly in conformation.