
Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102008636/gg1113sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S0108270102008636/gg1113IIsup2.hkl |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S0108270102008636/gg1113IIIsup3.hkl |
CCDC references: 192969; 192970
The title compounds, (II) and (III), were synthesized as described by Martirosyan et al. (2000). Recrystallization from ethanol afforded colourless crystals suitable for X-ray analysis.
Both molecules (II) and (III) crystallized in the monoclinic system, space group P21/c as determined from the systematic absences. H atoms were constrained, with C—H = 0.93–9.97 Å and N—H = 0.86 Å. Are these the correct constraints?
For both compounds, data collection: CAD-4 Software (Enraf-Nonius, 1988); cell refinement: SETANG in CAD-4 Software; data reduction: local program; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
C18H17ClN2O2 | F(000) = 688 |
Mr = 328.79 | Dx = 1.280 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 22 reflections |
a = 10.661 (2) Å | θ = 13.9–20.0° |
b = 11.690 (2) Å | µ = 0.23 mm−1 |
c = 20.698 (4) Å | T = 293 K |
β = 138.60 (3)° | Prism, colourless |
V = 1706.1 (11) Å3 | 0.20 × 0.13 × 0.10 mm |
Z = 4 |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.022 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 2.1° |
Graphite monochromator | h = −12→11 |
ω/2θ scans | k = 0→13 |
3296 measured reflections | l = −11→24 |
2948 independent reflections | 3 standard reflections every 60 min |
1928 reflections with I > 2σ(I) | intensity decay: variation +−1.0% |
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.148 | H-atom parameters constrained |
S = 0.95 | w = 1/[σ2(Fo2) + (0.0453P)2 + 0.4186P] where P = (Fo2 + 2Fc2)/3 |
2948 reflections | (Δ/σ)max < 0.001 |
208 parameters | Δρmax = 0.17 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
0 constraints |
C18H17ClN2O2 | V = 1706.1 (11) Å3 |
Mr = 328.79 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.661 (2) Å | µ = 0.23 mm−1 |
b = 11.690 (2) Å | T = 293 K |
c = 20.698 (4) Å | 0.20 × 0.13 × 0.10 mm |
β = 138.60 (3)° |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.022 |
3296 measured reflections | 3 standard reflections every 60 min |
2948 independent reflections | intensity decay: variation +−1.0% |
1928 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.148 | H-atom parameters constrained |
S = 0.95 | Δρmax = 0.17 e Å−3 |
2948 reflections | Δρmin = −0.27 e Å−3 |
208 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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) Mean-plane data from final SHELXL refinement run:- Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) - 7.3815(0.0092)x + 8.0424(0.0105)y + 7.7720(0.0222)z = 3.5064(0.0121) * -0.0006 (0.0017) C17 * 0.0042 (0.0017) C18 * -0.0037 (0.0020) C19 * -0.0004 (0.0022) C20 * 0.0040 (0.0024) C21 * -0.0035 (0.0022) C22 Rms deviation of fitted atoms = 0.0032 1.6738 (0.0116)x - 8.7969(0.0087)y + 6.3182(0.0225)z = 2.8236(0.0163) Angle to previous plane (with approximate e.s.d.) = 40.05 (0.12) * 0.0050 (0.0016) C8 * -0.0069 (0.0018) C9 * 0.0029 (0.0020) C10 * 0.0029 (0.0021) C11 * -0.0046 (0.0020) C12 * 0.0007 (0.0017) C13 Rms deviation of fitted atoms = 0.0043 - 1.2833(0.0131)x + 6.8014(0.0113)y + 12.8802(0.0202)z = 11.4644(0.0085) Angle to previous plane (with approximate e.s.d.) = 86.69 (0.10) * 0.1488 (0.0013) C1 * -0.0121 (0.0014) N2 * -0.1301 (0.0015) C3 * 0.2353 (0.0016) C4 * -0.2418 (0.0014) C5 Rms deviation of fitted atoms = 0.1749 - 7.3815(0.0092)x + 8.0424(0.0105)y + 7.7720(0.0222)z = 3.5064(0.0121) Angle to previous plane (with approximate e.s.d.) = 72.02 (0.10) * -0.0006 (0.0017) C17 * 0.0042 (0.0017) C18 * -0.0037 (0.0020) C19 * -0.0004 (0.0022) C20 * 0.0040 (0.0024) C21 * -0.0035 (0.0022) C22 Rms deviation of fitted atoms = 0.0032 |
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 | ||
Cl | 0.38166 (9) | 0.39708 (8) | 0.89412 (5) | 0.1006 (3) | |
C1 | 0.7034 (2) | 0.27365 (16) | 0.82721 (13) | 0.0492 (5) | |
N2 | 0.54952 (18) | 0.24601 (13) | 0.81398 (10) | 0.0468 (4) | |
C3 | 0.5887 (3) | 0.13935 (18) | 0.86505 (15) | 0.0598 (6) | |
H3A | 0.5056 | 0.0781 | 0.8189 | 0.072* | |
H3B | 0.5728 | 0.1506 | 0.9050 | 0.072* | |
C4 | 0.7932 (3) | 0.11314 (19) | 0.92763 (15) | 0.0657 (6) | |
H4A | 0.8793 | 0.1512 | 0.9905 | 0.079* | |
H4B | 0.8173 | 0.0315 | 0.9380 | 0.079* | |
C5 | 0.8132 (3) | 0.15965 (18) | 0.86803 (15) | 0.0617 (6) | |
H5A | 0.7585 | 0.1076 | 0.8155 | 0.074* | |
H5B | 0.9455 | 0.1722 | 0.9084 | 0.074* | |
C6 | 0.3931 (2) | 0.30874 (17) | 0.76166 (12) | 0.0481 (5) | |
O7 | 0.36799 (17) | 0.40254 (13) | 0.72605 (10) | 0.0643 (4) | |
C8 | 0.2414 (2) | 0.26030 (17) | 0.74616 (13) | 0.0504 (5) | |
C9 | 0.2215 (3) | 0.2977 (2) | 0.80155 (15) | 0.0643 (6) | |
C10 | 0.0791 (3) | 0.2580 (3) | 0.78564 (17) | 0.0836 (8) | |
H10A | 0.0692 | 0.2832 | 0.8243 | 0.100* | |
C11 | −0.0484 (3) | 0.1809 (3) | 0.71209 (19) | 0.0868 (8) | |
H11A | −0.1456 | 0.1537 | 0.7007 | 0.104* | |
C12 | −0.0343 (3) | 0.1436 (3) | 0.65522 (19) | 0.0818 (8) | |
H12A | −0.1222 | 0.0918 | 0.6050 | 0.098* | |
C13 | 0.1115 (3) | 0.1833 (2) | 0.67266 (15) | 0.0653 (6) | |
H13A | 0.1215 | 0.1574 | 0.6341 | 0.078* | |
C14 | 0.8327 (3) | 0.36954 (18) | 0.90327 (14) | 0.0554 (5) | |
N15 | 0.7537 (2) | 0.45281 (16) | 0.90496 (13) | 0.0702 (5) | |
H15A | 0.8222 | 0.5078 | 0.9462 | 0.084* | |
H15B | 0.6332 | 0.4527 | 0.8649 | 0.084* | |
O16 | 1.00387 (19) | 0.36549 (15) | 0.95883 (12) | 0.0816 (6) | |
C17 | 0.6261 (2) | 0.30452 (18) | 0.73065 (13) | 0.0536 (5) | |
C18 | 0.7097 (3) | 0.38739 (19) | 0.72489 (15) | 0.0626 (5) | |
H18A | 0.8121 | 0.4288 | 0.7804 | 0.075* | |
C19 | 0.6427 (3) | 0.4094 (2) | 0.63752 (18) | 0.0822 (7) | |
H19A | 0.7012 | 0.4648 | 0.6347 | 0.099* | |
C20 | 0.4912 (3) | 0.3501 (3) | 0.55536 (18) | 0.0923 (9) | |
H20B | 0.4459 | 0.3653 | 0.4966 | 0.111* | |
C21 | 0.4058 (4) | 0.2681 (3) | 0.55967 (18) | 0.1004 (10) | |
H21A | 0.3020 | 0.2279 | 0.5037 | 0.120* | |
C22 | 0.4731 (3) | 0.2453 (3) | 0.64620 (16) | 0.0805 (7) | |
H22A | 0.4150 | 0.1889 | 0.6485 | 0.097* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl | 0.0938 (3) | 0.1270 (6) | 0.0864 (3) | −0.0225 (4) | 0.0692 (2) | −0.0389 (4) |
C1 | 0.0447 (6) | 0.0371 (10) | 0.0613 (8) | −0.0065 (7) | 0.0385 (6) | −0.0074 (7) |
N2 | 0.0467 (5) | 0.0363 (8) | 0.0534 (6) | 0.0006 (6) | 0.0364 (5) | 0.0016 (6) |
C3 | 0.0611 (8) | 0.0419 (11) | 0.0704 (10) | 0.0077 (9) | 0.0476 (7) | 0.0142 (9) |
C4 | 0.0575 (9) | 0.0440 (12) | 0.0708 (11) | 0.0074 (9) | 0.0409 (8) | 0.0088 (9) |
C5 | 0.0513 (7) | 0.0428 (11) | 0.0805 (11) | −0.0018 (8) | 0.0463 (7) | −0.0077 (9) |
C6 | 0.0503 (7) | 0.0414 (11) | 0.0473 (8) | 0.0045 (8) | 0.0350 (6) | 0.0032 (7) |
O7 | 0.0657 (6) | 0.0481 (8) | 0.0733 (7) | 0.0113 (6) | 0.0505 (5) | 0.0162 (6) |
C8 | 0.0445 (7) | 0.0473 (11) | 0.0539 (8) | 0.0083 (8) | 0.0353 (6) | 0.0084 (8) |
C9 | 0.0520 (8) | 0.0764 (16) | 0.0595 (9) | 0.0073 (10) | 0.0404 (7) | 0.0054 (10) |
C10 | 0.0649 (9) | 0.115 (2) | 0.0802 (11) | 0.0079 (13) | 0.0572 (8) | 0.0028 (13) |
C11 | 0.0585 (8) | 0.107 (2) | 0.1024 (13) | 0.0039 (13) | 0.0624 (9) | 0.0099 (14) |
C12 | 0.0514 (9) | 0.0802 (18) | 0.0886 (14) | −0.0082 (12) | 0.0451 (10) | −0.0091 (13) |
C13 | 0.0580 (8) | 0.0607 (14) | 0.0741 (10) | −0.0004 (10) | 0.0487 (8) | −0.0033 (10) |
C14 | 0.0566 (8) | 0.0419 (11) | 0.0625 (9) | −0.0050 (9) | 0.0431 (7) | −0.0032 (8) |
N15 | 0.0596 (7) | 0.0466 (10) | 0.0862 (10) | −0.0114 (8) | 0.0494 (7) | −0.0224 (8) |
O16 | 0.0517 (6) | 0.0610 (10) | 0.0937 (9) | −0.0136 (7) | 0.0433 (6) | −0.0282 (8) |
C17 | 0.0543 (7) | 0.0482 (12) | 0.0642 (9) | −0.0052 (8) | 0.0462 (6) | −0.0075 (8) |
C18 | 0.0722 (8) | 0.0471 (12) | 0.0844 (10) | −0.0006 (9) | 0.0633 (7) | −0.0007 (9) |
C19 | 0.1090 (10) | 0.0654 (16) | 0.1142 (13) | 0.0068 (12) | 0.0959 (9) | 0.0124 (11) |
C20 | 0.1021 (11) | 0.113 (2) | 0.0818 (11) | 0.0165 (16) | 0.0748 (9) | 0.0153 (13) |
C21 | 0.0927 (12) | 0.141 (3) | 0.0726 (12) | −0.0289 (17) | 0.0635 (10) | −0.0227 (15) |
C22 | 0.0844 (9) | 0.0936 (19) | 0.0757 (11) | −0.0385 (12) | 0.0636 (8) | −0.0278 (11) |
Cl—C9 | 1.741 (2) | C10—H10A | 0.9300 |
C1—N2 | 1.482 (3) | C11—C12 | 1.366 (4) |
C1—C17 | 1.528 (3) | C11—H11A | 0.9300 |
C1—C14 | 1.543 (3) | C12—C13 | 1.385 (3) |
C1—C5 | 1.542 (3) | C12—H12A | 0.9300 |
N2—C6 | 1.335 (2) | C13—H13A | 0.9300 |
N2—C3 | 1.478 (3) | C14—O16 | 1.227 (2) |
C3—C4 | 1.513 (3) | C14—N15 | 1.305 (3) |
C3—H3A | 0.9700 | N15—H15A | 0.8600 |
C3—H3B | 0.9700 | N15—H15B | 0.8600 |
C4—C5 | 1.502 (4) | C17—C18 | 1.381 (3) |
C4—H4A | 0.9700 | C17—C22 | 1.385 (3) |
C4—H4B | 0.9700 | C18—C19 | 1.382 (3) |
C5—H5A | 0.9700 | C18—H18A | 0.9300 |
C5—H5B | 0.9700 | C19—C20 | 1.364 (4) |
C6—O7 | 1.234 (2) | C19—H19A | 0.9300 |
C6—C8 | 1.504 (3) | C20—C21 | 1.370 (4) |
C8—C13 | 1.372 (3) | C20—H20B | 0.9300 |
C8—C9 | 1.384 (3) | C21—C22 | 1.366 (4) |
C9—C10 | 1.371 (3) | C21—H21A | 0.9300 |
C10—C11 | 1.369 (4) | C22—H22A | 0.9300 |
N2—C1—C17 | 111.95 (13) | C11—C10—C9 | 119.1 (3) |
N2—C1—C14 | 111.40 (17) | C11—C10—H10A | 120.4 |
C17—C1—C14 | 110.84 (17) | C9—C10—H10A | 120.4 |
N2—C1—C5 | 101.13 (16) | C10—C11—C12 | 120.6 (2) |
C17—C1—C5 | 111.34 (18) | C10—C11—H11A | 119.7 |
C14—C1—C5 | 109.81 (14) | C12—C11—H11A | 119.7 |
C6—N2—C3 | 123.68 (17) | C11—C12—C13 | 119.8 (2) |
C6—N2—C1 | 124.50 (16) | C11—C12—H12A | 120.1 |
C3—N2—C1 | 111.82 (14) | C13—C12—H12A | 120.1 |
N2—C3—C4 | 103.66 (17) | C8—C13—C12 | 120.7 (2) |
N2—C3—H3A | 111.0 | C8—C13—H13A | 119.7 |
C4—C3—H3A | 111.0 | C12—C13—H13A | 119.7 |
N2—C3—H3B | 111.0 | O16—C14—N15 | 122.65 (19) |
C4—C3—H3B | 111.0 | O16—C14—C1 | 119.38 (19) |
H3A—C3—H3B | 109.0 | N15—C14—C1 | 117.96 (16) |
C5—C4—C3 | 102.97 (17) | C14—N15—H15A | 120.0 |
C5—C4—H4A | 111.2 | C14—N15—H15B | 120.0 |
C3—C4—H4A | 111.2 | H15A—N15—H15B | 120.0 |
C5—C4—H4B | 111.2 | C18—C17—C22 | 117.8 (2) |
C3—C4—H4B | 111.2 | C18—C17—C1 | 121.94 (17) |
H4A—C4—H4B | 109.1 | C22—C17—C1 | 120.1 (2) |
C4—C5—C1 | 104.23 (18) | C17—C18—C19 | 120.7 (2) |
C4—C5—H5A | 110.9 | C17—C18—H18A | 119.7 |
C1—C5—H5A | 110.9 | C19—C18—H18A | 119.7 |
C4—C5—H5B | 110.9 | C20—C19—C18 | 120.2 (3) |
C1—C5—H5B | 110.9 | C20—C19—H19A | 119.9 |
H5A—C5—H5B | 108.9 | C18—C19—H19A | 119.9 |
O7—C6—N2 | 123.49 (19) | C19—C20—C21 | 119.8 (3) |
O7—C6—C8 | 119.40 (16) | C19—C20—H20B | 120.1 |
N2—C6—C8 | 117.11 (17) | C21—C20—H20B | 120.1 |
C13—C8—C9 | 118.2 (2) | C20—C21—C22 | 120.0 (3) |
C13—C8—C6 | 120.9 (2) | C20—C21—H21A | 120.0 |
C9—C8—C6 | 120.86 (18) | C22—C21—H21A | 120.0 |
C10—C9—C8 | 121.6 (2) | C21—C22—C17 | 121.4 (3) |
C10—C9—Cl | 119.1 (2) | C21—C22—H22A | 119.3 |
C8—C9—Cl | 119.30 (17) | C17—C22—H22A | 119.3 |
C17—C1—N2—C6 | −46.9 (2) | Cl—C9—C10—C11 | 179.2 (2) |
C14—C1—N2—C6 | 77.8 (2) | C9—C10—C11—C12 | 0.1 (4) |
C5—C1—N2—C6 | −165.53 (17) | C10—C11—C12—C13 | 0.6 (4) |
C17—C1—N2—C3 | 132.51 (17) | C9—C8—C13—C12 | −0.5 (3) |
C14—C1—N2—C3 | −102.75 (18) | C6—C8—C13—C12 | −176.4 (2) |
C5—C1—N2—C3 | 13.9 (2) | C11—C12—C13—C8 | −0.4 (4) |
C6—N2—C3—C4 | −169.88 (18) | N2—C1—C14—O16 | 142.9 (2) |
C1—N2—C3—C4 | 10.7 (2) | C17—C1—C14—O16 | −91.7 (2) |
N2—C3—C4—C5 | −31.5 (2) | C5—C1—C14—O16 | 31.7 (3) |
C3—C4—C5—C1 | 40.9 (2) | N2—C1—C14—N15 | −37.7 (3) |
N2—C1—C5—C4 | −33.44 (18) | C17—C1—C14—N15 | 87.7 (2) |
C17—C1—C5—C4 | −152.51 (16) | C5—C1—C14—N15 | −148.9 (2) |
C14—C1—C5—C4 | 84.3 (2) | N2—C1—C17—C18 | 143.89 (19) |
C3—N2—C6—O7 | 173.63 (19) | C14—C1—C17—C18 | 18.8 (3) |
C1—N2—C6—O7 | −7.0 (3) | C5—C1—C17—C18 | −103.7 (2) |
C3—N2—C6—C8 | −6.6 (3) | N2—C1—C17—C22 | −39.1 (3) |
C1—N2—C6—C8 | 172.76 (16) | C14—C1—C17—C22 | −164.2 (2) |
O7—C6—C8—C13 | 96.3 (2) | C5—C1—C17—C22 | 73.3 (2) |
N2—C6—C8—C13 | −83.5 (2) | C22—C17—C18—C19 | −0.5 (3) |
O7—C6—C8—C9 | −79.5 (2) | C1—C17—C18—C19 | 176.6 (2) |
N2—C6—C8—C9 | 100.7 (2) | C17—C18—C19—C20 | 0.8 (4) |
C13—C8—C9—C10 | 1.2 (3) | C18—C19—C20—C21 | −0.3 (4) |
C6—C8—C9—C10 | 177.2 (2) | C19—C20—C21—C22 | −0.4 (5) |
C13—C8—C9—Cl | −178.99 (17) | C20—C21—C22—C17 | 0.7 (5) |
C6—C8—C9—Cl | −3.0 (3) | C18—C17—C22—C21 | −0.3 (4) |
C8—C9—C10—C11 | −1.1 (4) | C1—C17—C22—C21 | −177.4 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N15—H15B···O7 | 0.86 | 2.10 | 2.851 (2) | 146 |
N15—H15A···O16i | 0.86 | 2.01 | 2.865 (2) | 175 |
Symmetry code: (i) −x+2, −y+1, −z+2. |
C16H16N2O3 | F(000) = 600 |
Mr = 284.31 | Dx = 1.307 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 22 reflections |
a = 12.665 (3) Å | θ = 17.7–23.2° |
b = 12.214 (2) Å | µ = 0.09 mm−1 |
c = 9.3453 (19) Å | T = 293 K |
β = 91.98 (3)° | Prism, colourless |
V = 1444.8 (5) Å3 | 0.26 × 0.16 × 0.14 mm |
Z = 4 |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.012 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 1.6° |
Graphite monochromator | h = 0→15 |
ω/2θ scans | k = −14→0 |
2652 measured reflections | l = −11→11 |
2533 independent reflections | 3 standard reflections every 60 min |
2185 reflections with I > 2σ(I) | intensity decay: variation +−1.0% |
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)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.125 | w = 1/[σ2(Fo2) + (0.0453P)2 + 0.4186P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
2533 reflections | Δρmax = 0.20 e Å−3 |
191 parameters | Δρmin = −0.19 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 constraints | Extinction coefficient: 0.081 (6) |
Primary atom site location: structure-invariant direct methods |
C16H16N2O3 | V = 1444.8 (5) Å3 |
Mr = 284.31 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.665 (3) Å | µ = 0.09 mm−1 |
b = 12.214 (2) Å | T = 293 K |
c = 9.3453 (19) Å | 0.26 × 0.16 × 0.14 mm |
β = 91.98 (3)° |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.012 |
2652 measured reflections | 3 standard reflections every 60 min |
2533 independent reflections | intensity decay: variation +−1.0% |
2185 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.125 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.20 e Å−3 |
2533 reflections | Δρmin = −0.19 e Å−3 |
191 parameters |
Geometry. Mean-plane data from final SHELXL refinement run:- Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) - 9.9829(0.0081)x + 0.3869(0.0091)y + 5.9938(0.0065)z = 0.9670(0.0115) * -0.0044 (0.0011) C16 * 0.0002 (0.0014) C17 * 0.0022 (0.0016) C18 * -0.0004 (0.0015) C19 * -0.0038 (0.0013) C20 * 0.0062 (0.0011) C21 Rms deviation of fitted atoms = 0.0036 6.6224(0.0112)x - 6.0077(0.0115)y + 6.3336(0.0080)z = 0.9889(0.0116) Angle to previous plane (with approximate e.s.d.) = 89.99 (0.07) * -0.0018 (0.0011) C8 * 0.0012 (0.0011) O9 * -0.0003 (0.0013) C10 * -0.0007 (0.0013) C11 * 0.0015 (0.0012) C12 Rms deviation of fitted atoms = 0.0012 5.2477(0.0099)x - 0.6201(0.0102)y + 8.3535(0.0056)z = 6.7555(0.0097) Angle to previous plane (with approximate e.s.d.) = 29.04 (0.10) * 0.1418 (0.0009) C1 * 0.0032 (0.0009) N2 * -0.1499 (0.0011) C3 * 0.2513 (0.0012) C4 * -0.2463 (0.0011) C5 Rms deviation of fitted atoms = 0.1824 - 9.9829(0.0081)x + 0.3869(0.0091)y + 5.9938(0.0065)z = 0.9670(0.0115) Angle to previous plane (with approximate e.s.d.) = 76.69 (0.06) * -0.0044 (0.0011) C16 * 0.0002 (0.0014) C17 * 0.0022 (0.0016) C18 * -0.0004 (0.0015) C19 * -0.0038 (0.0013) C20 * 0.0062 (0.0011) C21 Rms deviation of fitted atoms = 0.0036 |
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 | 0.35795 (10) | 0.92974 (11) | 0.66983 (14) | 0.0370 (3) | |
N2 | 0.28449 (9) | 0.83592 (9) | 0.69242 (12) | 0.0393 (3) | |
C3 | 0.32912 (13) | 0.73216 (12) | 0.63835 (19) | 0.0528 (4) | |
H3A | 0.2941 | 0.7103 | 0.5489 | 0.063* | |
H3B | 0.3227 | 0.6737 | 0.7077 | 0.063* | |
C4 | 0.44323 (13) | 0.76008 (13) | 0.6168 (2) | 0.0579 (5) | |
H4A | 0.4730 | 0.7142 | 0.5437 | 0.070* | |
H4B | 0.4850 | 0.7522 | 0.7051 | 0.070* | |
C5 | 0.43776 (12) | 0.87852 (13) | 0.56942 (16) | 0.0469 (4) | |
H5A | 0.4133 | 0.8843 | 0.4702 | 0.056* | |
H5B | 0.5063 | 0.9136 | 0.5806 | 0.056* | |
C6 | 0.18955 (11) | 0.84671 (11) | 0.75226 (15) | 0.0407 (3) | |
O7 | 0.16134 (8) | 0.93179 (8) | 0.81089 (11) | 0.0483 (3) | |
C8 | 0.11512 (12) | 0.75375 (12) | 0.75045 (16) | 0.0467 (4) | |
O9 | 0.12379 (11) | 0.66701 (11) | 0.65957 (15) | 0.0722 (4) | |
C10 | 0.03949 (17) | 0.60068 (17) | 0.6846 (3) | 0.0778 (6) | |
H10A | 0.0256 | 0.5351 | 0.6369 | 0.093* | |
C11 | −0.01849 (16) | 0.64090 (19) | 0.7833 (3) | 0.0774 (6) | |
H11A | −0.0798 | 0.6103 | 0.8181 | 0.093* | |
C12 | 0.02967 (14) | 0.74068 (17) | 0.8279 (2) | 0.0677 (5) | |
H12A | 0.0061 | 0.7880 | 0.8979 | 0.081* | |
C13 | 0.41766 (11) | 0.96223 (11) | 0.81232 (14) | 0.0400 (3) | |
N14 | 0.35976 (10) | 0.98565 (11) | 0.92272 (12) | 0.0461 (3) | |
H14A | 0.3897 | 1.0049 | 1.0028 | 0.055* | |
H14B | 0.2920 | 0.9817 | 0.9147 | 0.055* | |
O15 | 0.51443 (8) | 0.96638 (12) | 0.81726 (12) | 0.0629 (4) | |
C16 | 0.30340 (11) | 1.02866 (11) | 0.59953 (14) | 0.0392 (3) | |
C17 | 0.23334 (15) | 1.01476 (15) | 0.48449 (17) | 0.0613 (5) | |
H17A | 0.2134 | 0.9445 | 0.4561 | 0.074* | |
C18 | 0.19252 (18) | 1.10448 (19) | 0.4111 (2) | 0.0811 (6) | |
H18A | 0.1454 | 1.0940 | 0.3338 | 0.097* | |
C19 | 0.22095 (17) | 1.20915 (17) | 0.4512 (2) | 0.0752 (6) | |
H19A | 0.1934 | 1.2693 | 0.4016 | 0.090* | |
C20 | 0.28994 (15) | 1.22343 (14) | 0.5646 (2) | 0.0632 (5) | |
H20A | 0.3101 | 1.2938 | 0.5921 | 0.076* | |
C21 | 0.33032 (12) | 1.13408 (12) | 0.63933 (17) | 0.0484 (4) | |
H21A | 0.3764 | 1.1453 | 0.7176 | 0.058* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0385 (7) | 0.0333 (7) | 0.0393 (7) | −0.0012 (5) | 0.0003 (5) | −0.0004 (5) |
N2 | 0.0412 (6) | 0.0305 (6) | 0.0461 (6) | −0.0016 (5) | −0.0001 (5) | −0.0024 (5) |
C3 | 0.0564 (9) | 0.0337 (8) | 0.0683 (10) | 0.0034 (7) | 0.0030 (8) | −0.0083 (7) |
C4 | 0.0532 (9) | 0.0448 (9) | 0.0761 (11) | 0.0104 (7) | 0.0060 (8) | −0.0100 (8) |
C5 | 0.0463 (8) | 0.0472 (9) | 0.0476 (8) | 0.0014 (7) | 0.0049 (6) | −0.0055 (6) |
C6 | 0.0409 (7) | 0.0382 (7) | 0.0425 (7) | −0.0006 (6) | −0.0049 (6) | 0.0031 (6) |
O7 | 0.0438 (6) | 0.0414 (6) | 0.0598 (6) | 0.0023 (4) | 0.0042 (5) | −0.0046 (5) |
C8 | 0.0457 (8) | 0.0428 (8) | 0.0510 (8) | −0.0058 (6) | −0.0079 (7) | 0.0024 (6) |
O9 | 0.0738 (8) | 0.0615 (8) | 0.0810 (9) | −0.0211 (7) | −0.0014 (7) | −0.0176 (7) |
C10 | 0.0730 (13) | 0.0552 (11) | 0.1033 (16) | −0.0256 (10) | −0.0251 (12) | −0.0007 (11) |
C11 | 0.0582 (11) | 0.0750 (14) | 0.0984 (16) | −0.0272 (10) | −0.0058 (11) | 0.0167 (12) |
C12 | 0.0527 (10) | 0.0725 (12) | 0.0783 (12) | −0.0119 (9) | 0.0088 (9) | −0.0042 (10) |
C13 | 0.0426 (8) | 0.0343 (7) | 0.0428 (7) | −0.0010 (6) | −0.0041 (6) | 0.0010 (6) |
N14 | 0.0463 (7) | 0.0509 (8) | 0.0407 (6) | −0.0036 (6) | −0.0043 (5) | −0.0051 (5) |
O15 | 0.0413 (6) | 0.0906 (9) | 0.0564 (7) | −0.0028 (6) | −0.0056 (5) | −0.0134 (6) |
C16 | 0.0411 (7) | 0.0372 (8) | 0.0395 (7) | 0.0007 (6) | 0.0028 (6) | 0.0029 (6) |
C17 | 0.0772 (12) | 0.0539 (10) | 0.0514 (9) | 0.0010 (8) | −0.0178 (8) | 0.0005 (7) |
C18 | 0.0972 (16) | 0.0805 (15) | 0.0634 (11) | 0.0144 (12) | −0.0279 (11) | 0.0126 (10) |
C19 | 0.0894 (14) | 0.0636 (13) | 0.0724 (12) | 0.0182 (11) | 0.0002 (11) | 0.0282 (10) |
C20 | 0.0715 (11) | 0.0400 (9) | 0.0785 (12) | 0.0008 (8) | 0.0086 (9) | 0.0151 (8) |
C21 | 0.0513 (8) | 0.0378 (8) | 0.0561 (9) | −0.0030 (6) | −0.0004 (7) | 0.0043 (6) |
C1—N2 | 1.4956 (18) | C10—H10A | 0.9300 |
C1—C16 | 1.5288 (19) | C11—C12 | 1.419 (3) |
C1—C5 | 1.5359 (19) | C11—H11A | 0.9300 |
C1—C13 | 1.5599 (19) | C12—H12A | 0.9300 |
N2—C6 | 1.3498 (19) | C13—O15 | 1.2260 (18) |
N2—C3 | 1.4834 (18) | C13—N14 | 1.3175 (19) |
C3—C4 | 1.505 (2) | N14—H14A | 0.8600 |
C3—H3A | 0.9700 | N14—H14B | 0.8600 |
C3—H3B | 0.9700 | C16—C21 | 1.380 (2) |
C4—C5 | 1.514 (2) | C16—C17 | 1.381 (2) |
C4—H4A | 0.9700 | C17—C18 | 1.384 (3) |
C4—H4B | 0.9700 | C17—H17A | 0.9300 |
C5—H5A | 0.9700 | C18—C19 | 1.377 (3) |
C5—H5B | 0.9700 | C18—H18A | 0.9300 |
C6—O7 | 1.2335 (18) | C19—C20 | 1.361 (3) |
C6—C8 | 1.475 (2) | C19—H19A | 0.9300 |
C8—C12 | 1.332 (2) | C20—C21 | 1.384 (2) |
C8—O9 | 1.365 (2) | C20—H20A | 0.9300 |
O9—C10 | 1.367 (2) | C21—H21A | 0.9300 |
C10—C11 | 1.296 (3) | ||
N2—C1—C16 | 113.09 (11) | C11—C10—O9 | 111.23 (18) |
N2—C1—C5 | 101.53 (11) | C11—C10—H10A | 124.4 |
C16—C1—C5 | 110.89 (11) | O9—C10—H10A | 124.4 |
N2—C1—C13 | 111.10 (10) | C10—C11—C12 | 106.65 (18) |
C16—C1—C13 | 111.36 (11) | C10—C11—H11A | 126.7 |
C5—C1—C13 | 108.38 (11) | C12—C11—H11A | 126.7 |
C6—N2—C3 | 125.44 (12) | C8—C12—C11 | 106.99 (18) |
C6—N2—C1 | 123.44 (11) | C8—C12—H12A | 126.5 |
C3—N2—C1 | 111.12 (11) | C11—C12—H12A | 126.5 |
N2—C3—C4 | 103.35 (12) | O15—C13—N14 | 122.97 (13) |
N2—C3—H3A | 111.1 | O15—C13—C1 | 119.82 (13) |
C4—C3—H3A | 111.1 | N14—C13—C1 | 117.21 (12) |
N2—C3—H3B | 111.1 | C13—N14—H14A | 120.0 |
C4—C3—H3B | 111.1 | C13—N14—H14B | 120.0 |
H3A—C3—H3B | 109.1 | H14A—N14—H14B | 120.0 |
C3—C4—C5 | 102.78 (13) | C21—C16—C17 | 118.09 (14) |
C3—C4—H4A | 111.2 | C21—C16—C1 | 121.19 (13) |
C5—C4—H4A | 111.2 | C17—C16—C1 | 120.41 (13) |
C3—C4—H4B | 111.2 | C16—C17—C18 | 120.52 (17) |
C5—C4—H4B | 111.2 | C16—C17—H17A | 119.7 |
H4A—C4—H4B | 109.1 | C18—C17—H17A | 119.7 |
C4—C5—C1 | 103.60 (12) | C19—C18—C17 | 120.70 (18) |
C4—C5—H5A | 111.0 | C19—C18—H18A | 119.7 |
C1—C5—H5A | 111.0 | C17—C18—H18A | 119.7 |
C4—C5—H5B | 111.0 | C20—C19—C18 | 119.07 (17) |
C1—C5—H5B | 111.0 | C20—C19—H19A | 120.5 |
H5A—C5—H5B | 109.0 | C18—C19—H19A | 120.5 |
O7—C6—N2 | 122.82 (13) | C19—C20—C21 | 120.52 (17) |
O7—C6—C8 | 117.30 (13) | C19—C20—H20A | 119.7 |
N2—C6—C8 | 119.87 (13) | C21—C20—H20A | 119.7 |
C12—C8—O9 | 109.24 (15) | C16—C21—C20 | 121.08 (16) |
C12—C8—C6 | 128.08 (15) | C16—C21—H21A | 119.5 |
O9—C8—C6 | 122.64 (14) | C20—C21—H21A | 119.5 |
C8—O9—C10 | 105.89 (16) | ||
C16—C1—N2—C6 | −48.28 (16) | O9—C10—C11—C12 | 0.0 (3) |
C5—C1—N2—C6 | −167.13 (12) | O9—C8—C12—C11 | −0.3 (2) |
C13—C1—N2—C6 | 77.81 (15) | C6—C8—C12—C11 | 177.31 (16) |
C16—C1—N2—C3 | 130.68 (13) | C10—C11—C12—C8 | 0.2 (2) |
C5—C1—N2—C3 | 11.83 (14) | N2—C1—C13—O15 | 125.78 (14) |
C13—C1—N2—C3 | −103.23 (13) | C16—C1—C13—O15 | −107.19 (15) |
C6—N2—C3—C4 | −167.03 (14) | C5—C1—C13—O15 | 15.05 (18) |
C1—N2—C3—C4 | 14.03 (17) | N2—C1—C13—N14 | −55.12 (16) |
N2—C3—C4—C5 | −34.48 (17) | C16—C1—C13—N14 | 71.92 (16) |
C3—C4—C5—C1 | 42.69 (16) | C5—C1—C13—N14 | −165.85 (12) |
N2—C1—C5—C4 | −33.07 (14) | N2—C1—C16—C21 | 142.35 (13) |
C16—C1—C5—C4 | −153.48 (12) | C5—C1—C16—C21 | −104.37 (15) |
C13—C1—C5—C4 | 84.00 (14) | C13—C1—C16—C21 | 16.40 (18) |
C3—N2—C6—O7 | 171.10 (14) | N2—C1—C16—C17 | −44.18 (18) |
C1—N2—C6—O7 | −10.1 (2) | C5—C1—C16—C17 | 69.10 (18) |
C3—N2—C6—C8 | −8.2 (2) | C13—C1—C16—C17 | −170.12 (13) |
C1—N2—C6—C8 | 170.57 (12) | C21—C16—C17—C18 | 0.6 (3) |
O7—C6—C8—C12 | −14.8 (2) | C1—C16—C17—C18 | −173.06 (17) |
N2—C6—C8—C12 | 164.61 (16) | C16—C17—C18—C19 | 0.0 (3) |
O7—C6—C8—O9 | 162.59 (14) | C17—C18—C19—C20 | −0.1 (3) |
N2—C6—C8—O9 | −18.0 (2) | C18—C19—C20—C21 | −0.5 (3) |
C12—C8—O9—C10 | 0.30 (19) | C17—C16—C21—C20 | −1.2 (2) |
C6—C8—O9—C10 | −177.49 (15) | C1—C16—C21—C20 | 172.43 (14) |
C8—O9—C10—C11 | −0.2 (2) | C19—C20—C21—C16 | 1.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N14—H14A···O15i | 0.86 | 2.07 | 2.919 (2) | 169 |
N14—H14B···O7 | 0.86 | 1.99 | 2.768 (2) | 151 |
Symmetry code: (i) −x+1, −y+2, −z+2. |
Experimental details
(II) | (III) | |
Crystal data | ||
Chemical formula | C18H17ClN2O2 | C16H16N2O3 |
Mr | 328.79 | 284.31 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 10.661 (2), 11.690 (2), 20.698 (4) | 12.665 (3), 12.214 (2), 9.3453 (19) |
β (°) | 138.60 (3) | 91.98 (3) |
V (Å3) | 1706.1 (11) | 1444.8 (5) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.23 | 0.09 |
Crystal size (mm) | 0.20 × 0.13 × 0.10 | 0.26 × 0.16 × 0.14 |
Data collection | ||
Diffractometer | Enraf-Nonius CAD-4 diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3296, 2948, 1928 | 2652, 2533, 2185 |
Rint | 0.022 | 0.012 |
(sin θ/λ)max (Å−1) | 0.595 | 0.595 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.148, 0.95 | 0.037, 0.125, 1.01 |
No. of reflections | 2948 | 2533 |
No. of parameters | 208 | 191 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.17, −0.27 | 0.20, −0.19 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1988), SETANG in CAD-4 Software, local program, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
N15—H15B···O7 | 0.86 | 2.099 | 2.851 (2) | 146 |
N15—H15A···O16i | 0.86 | 2.007 | 2.865 (2) | 175 |
Symmetry code: (i) −x+2, −y+1, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N14—H14A···O15i | 0.86 | 2.070 | 2.919 (2) | 169 |
N14—H14B···O7 | 0.86 | 1.985 | 2.768 (2) | 151 |
Symmetry code: (i) −x+1, −y+2, −z+2. |
The compounds under current investigation belong to the family of non-nucleoside reverse transcriptase inhibitors (NNRTIs). Formally, the structures of such compounds may be considered as derivatives from Loviride (Pauvels et al., 1993), with a common structural feature being the butterfly-like conformation (De Clercq, 1996). A new method for the synthesis of 1,2-substituted derivatives of 1-(alkyl/arylcarbonyl)-2-phenylpyrrolidine-2-carboxamide, (I), has been developed by Martirosyan et al. (2000), and thus 1-(2-chlorobenzoyl)-2-phenylpyrrolidine-2-carboxamide, (II), and 1-(2-furoyl)-2-phenylpyrrolidine-2-carboxamide, (III), have been synthesized as racemic mixtures. The crystal structures of these two compounds are presented here. \sch
Views of molecules (II) and (III) with the atomic numbering schemes are shown in Figs. 1 and 2, respectively. In the crystal structures of both molecules, two neighbouring asymmetric molecules, related by inversion centres, are connected into a dimeric unit with double hydrogen bonding through the amide groups (Figs. 3 and 4). However, only one of the amide H atoms of each molecule [H15A in (II) and H14A in (III)] takes part in the dimer formed through intermolecular interactions. The other H atoms (H15B and H14B, respectively) of the amide form intramolecular hydrogen bonds with the carbonyl O atoms at O7.
The interatomic distances and angles for the hydrogen bonds in (II) and (III) are listed in Tables 1 and 2, respectively. The formation of intramolecular hydrogen bonds in (II) and (III) could bring additional rigidity to the molecular conformation relative to 1-benzyl-2-phenyl-5-oxopyrrolidine-2-carboxamide (Karapetyan et al., 2002), in which the corresponding H atoms take part in intermolecular bonding.
The dihedral angles between the aryl groups (`wing' planes W1 and W2 in the Scheme) and the pyrrolidine ring (part of the `body' - plane B in the Scheme), describing the orientation relations between the `wings' and `bodies' of these butterfly-like structures, for planes W1/W2, B/W1 and B/W2, are 40.05 (12), 72.02 (10) and 86.69 (10)°, respectively, for (II), and 89.99 (7), 76.69 (6) and 29.04 (10)°, respectively, for (III). The differences in these dihedral angles are caused by the reorientation of plane W2. Probably, in this reorientation, the essential role played by the Cl atom in the o-position of phenyl ring is prominent. In both structures, the pyrrolidine ring has the same half-chair conformation.
Table 1. Short N—H···O contacts (Å, °) for compound (II)
Table 2. Short N—H···O contacts (Å, °) for compound (III)