Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110009017/sk3373sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110009017/sk3373Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110009017/sk3373IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110009017/sk3373IIIsup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110009017/sk3373IVsup5.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110009017/sk3373Vsup6.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110009017/sk3373VIsup7.hkl |
CCDC references: 774910; 774911; 774912; 774913; 774914; 774915
For the preparation of (I)–(VI), sodium tungstate dihydrate (5–10 mol%), followed by 30% aqueous hydrogen peroxide solution (0.30 mol), were added to a stirred solution of the appropriately substituted 2-allyl-N-alkenylaniline (0.10 mol) in methanol (30 ml). The resulting mixtures were then stirred at ambient temperature for either 8 h [for (I) and (II)] or 72 h [for each of (III)–(VI)]. Each mixture was then filtered and the solvent removed under reduced pressure. Toluene (30 ml) was added to the solid residue and the resulting solution was heated at 355–360 K for 5–7 h. After cooling each solution to ambient temperature, the solvent was removed under reduced pressure and the crude product was purified by chromatography on silica gel using heptane–ethyl acetate (compositions in the range from 90:1 to 10:1 v/v) as eluent. Crystallization from methanol–dichloromethane (1:1 v/v) gave colourless crystals of (I)–(VI) suitable for single-crystal X-ray diffraction.
For (I), yield 58%, m.p. 335–336 K; MS (70 eV) m/z (%) 187 (M+, 31), 170 (18), 157 (10), 130 (22), 105 (38), 104 (100), 78 (36).
For (II), yield 49%, m.p. 350–351 K; MS (70 eV) m/z (%) 249 [M+ (35Cl), 43], 232 (29), 164 (9), 139 (100), 104 (33), 77 (30).
For (III), yield 45%, m.p. 367–368 K; MS (70 eV) m/z (%) 263 [M+ (35Cl), 45], 246 (27), 178 (12), 153 (100), 144 (39), 118 (36), 103 (18), 91 (36).
For (IV), yield 25%, m.p. 380–381 K; MS (70 eV) m/z (%) 263 [M+ (35Cl), 64], 246 (33), 178 (15), 153 (100), 144 (39), 118 (36), 103 (18), 91 (39).
For (V), yield 65%, m.p. 375–376 K; MS (70 eV) m/z (%) 249 [M+ (35Cl), 59], 166 (9), 153 (100), 141 (36), 118 (29), 91 (33), 77 (24).
For (VI), yield 63%, m.p. 370–371 K; MS (70 eV) m/z (%) 269 [M+ (35Cl), 61], 172 (100), 151 (30), 138 (61), 123 (33), 102 (30), 75 (36).
All H atoms were located in difference maps and then treated as riding atoms in geometrically idealized positions, with C—H = 0.95 (aromatic or alkenyl H), 0.98 (CH3), 0.99 (CH2) or 1.00 Å (aliphatic CH), and with Uiso(H) = kUeq(C), where k = 1.5 for the methyl groups, which were permitted to rotate but not to tilt, and 1.2 for all other H atoms. When the initial refinement for (VI) appeared to be complete, the value of the Flack x parameter (Flack, 1983), x = 0.59 (8), indicated that the refinement should be handled as an inversion twin, leading to twin fractions of 0.39 (7) for the (2S,4R) form and 0.61 (7) for the (2R,4S) form.
For all compounds, data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
C12H13NO | F(000) = 400 |
Mr = 187.23 | Dx = 1.294 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2200 reflections |
a = 9.8070 (13) Å | θ = 3.0–27.5° |
b = 7.3982 (7) Å | µ = 0.08 mm−1 |
c = 13.738 (2) Å | T = 120 K |
β = 105.441 (11)° | Block, colourless |
V = 960.8 (2) Å3 | 0.31 × 0.29 × 0.20 mm |
Z = 4 |
Bruker Nonius KappaCCD area-detector diffractometer | 2200 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 1488 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.054 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.0° |
ϕ and ω scans | h = −12→12 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −9→9 |
Tmin = 0.969, Tmax = 0.984 | l = −15→17 |
13902 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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0467P)2 + 0.1879P] where P = (Fo2 + 2Fc2)/3 |
2200 reflections | (Δ/σ)max = 0.001 |
127 parameters | Δρmax = 0.17 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
C12H13NO | V = 960.8 (2) Å3 |
Mr = 187.23 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.8070 (13) Å | µ = 0.08 mm−1 |
b = 7.3982 (7) Å | T = 120 K |
c = 13.738 (2) Å | 0.31 × 0.29 × 0.20 mm |
β = 105.441 (11)° |
Bruker Nonius KappaCCD area-detector diffractometer | 2200 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1488 reflections with I > 2σ(I) |
Tmin = 0.969, Tmax = 0.984 | Rint = 0.054 |
13902 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.17 e Å−3 |
2200 reflections | Δρmin = −0.24 e Å−3 |
127 parameters |
x | y | z | Uiso*/Ueq | ||
O14 | 0.49055 (10) | 0.45113 (14) | 0.10465 (8) | 0.0253 (3) | |
N1 | 0.57935 (12) | 0.40949 (16) | 0.20407 (9) | 0.0207 (3) | |
C2 | 0.67762 (15) | 0.2748 (2) | 0.18020 (12) | 0.0214 (3) | |
H2 | 0.7176 | 0.1959 | 0.2401 | 0.026* | |
C3 | 0.58270 (16) | 0.1630 (2) | 0.09360 (12) | 0.0261 (4) | |
H3A | 0.6278 | 0.1473 | 0.0377 | 0.031* | |
H3B | 0.5624 | 0.0425 | 0.1178 | 0.031* | |
C4 | 0.44854 (16) | 0.2754 (2) | 0.06014 (12) | 0.0262 (4) | |
H4 | 0.4170 | 0.2843 | −0.0152 | 0.031* | |
C5 | 0.32915 (15) | 0.2113 (2) | 0.10149 (12) | 0.0266 (4) | |
H5A | 0.2420 | 0.2797 | 0.0696 | 0.032* | |
H5B | 0.3107 | 0.0815 | 0.0857 | 0.032* | |
C5a | 0.36800 (14) | 0.2388 (2) | 0.21397 (12) | 0.0220 (3) | |
C6 | 0.28380 (15) | 0.1747 (2) | 0.27298 (12) | 0.0254 (4) | |
H6 | 0.1982 | 0.1133 | 0.2417 | 0.031* | |
C7 | 0.32186 (16) | 0.1984 (2) | 0.37583 (13) | 0.0286 (4) | |
H7 | 0.2625 | 0.1542 | 0.4150 | 0.034* | |
C8 | 0.44640 (16) | 0.2864 (2) | 0.42228 (12) | 0.0285 (4) | |
H8 | 0.4738 | 0.3005 | 0.4936 | 0.034* | |
C9 | 0.53088 (15) | 0.3537 (2) | 0.36484 (12) | 0.0242 (4) | |
H9 | 0.6160 | 0.4157 | 0.3963 | 0.029* | |
C9a | 0.49104 (14) | 0.33046 (19) | 0.26153 (11) | 0.0199 (3) | |
C21 | 0.79369 (16) | 0.3709 (2) | 0.15017 (12) | 0.0255 (4) | |
H21 | 0.7684 | 0.4580 | 0.0977 | 0.031* | |
C22 | 0.92861 (16) | 0.3425 (2) | 0.19176 (13) | 0.0312 (4) | |
H22A | 0.9573 | 0.2562 | 0.2445 | 0.037* | |
H22B | 0.9976 | 0.4082 | 0.1692 | 0.037* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O14 | 0.0301 (6) | 0.0237 (6) | 0.0199 (6) | −0.0008 (5) | 0.0029 (4) | 0.0037 (5) |
N1 | 0.0213 (6) | 0.0231 (7) | 0.0170 (7) | 0.0007 (5) | 0.0038 (5) | 0.0021 (5) |
C2 | 0.0237 (7) | 0.0196 (8) | 0.0226 (8) | −0.0003 (6) | 0.0091 (6) | −0.0016 (6) |
C3 | 0.0292 (8) | 0.0251 (8) | 0.0263 (9) | −0.0048 (7) | 0.0113 (7) | −0.0052 (7) |
C4 | 0.0331 (9) | 0.0242 (8) | 0.0192 (8) | −0.0050 (7) | 0.0032 (7) | −0.0023 (7) |
C5 | 0.0247 (8) | 0.0276 (9) | 0.0244 (9) | −0.0035 (6) | 0.0009 (6) | −0.0014 (7) |
C5a | 0.0207 (7) | 0.0190 (8) | 0.0258 (9) | 0.0030 (6) | 0.0054 (6) | 0.0004 (7) |
C6 | 0.0185 (7) | 0.0219 (8) | 0.0363 (10) | 0.0005 (6) | 0.0080 (7) | 0.0008 (7) |
C7 | 0.0293 (8) | 0.0272 (9) | 0.0351 (10) | 0.0032 (7) | 0.0187 (7) | 0.0047 (7) |
C8 | 0.0339 (9) | 0.0309 (9) | 0.0230 (9) | 0.0057 (7) | 0.0117 (7) | 0.0013 (7) |
C9 | 0.0227 (8) | 0.0255 (8) | 0.0245 (9) | 0.0004 (6) | 0.0067 (6) | −0.0017 (7) |
C9a | 0.0200 (7) | 0.0184 (8) | 0.0223 (8) | 0.0031 (6) | 0.0075 (6) | 0.0019 (6) |
C21 | 0.0314 (8) | 0.0220 (8) | 0.0271 (9) | −0.0024 (7) | 0.0145 (7) | −0.0018 (7) |
C22 | 0.0294 (9) | 0.0268 (9) | 0.0415 (11) | −0.0040 (7) | 0.0168 (8) | −0.0050 (8) |
O14—N1 | 1.4441 (15) | C5a—C6 | 1.386 (2) |
O14—C4 | 1.4488 (18) | C5a—C9a | 1.387 (2) |
N1—C9a | 1.4419 (18) | C6—C7 | 1.373 (2) |
N1—C2 | 1.4822 (18) | C6—H6 | 0.9500 |
C2—C21 | 1.490 (2) | C7—C8 | 1.381 (2) |
C2—C3 | 1.542 (2) | C7—H7 | 0.9500 |
C2—H2 | 1.0000 | C8—C9 | 1.380 (2) |
C3—C4 | 1.521 (2) | C8—H8 | 0.9500 |
C3—H3A | 0.9900 | C9—C9a | 1.379 (2) |
C3—H3B | 0.9900 | C9—H9 | 0.9500 |
C4—C5 | 1.508 (2) | C21—C22 | 1.311 (2) |
C4—H4 | 1.0000 | C21—H21 | 0.9500 |
C5—C5a | 1.504 (2) | C22—H22A | 0.9500 |
C5—H5A | 0.9900 | C22—H22B | 0.9500 |
C5—H5B | 0.9900 | ||
N1—O14—C4 | 103.88 (10) | C4—C5—H5B | 109.8 |
C9a—N1—O14 | 107.78 (10) | H5A—C5—H5B | 108.2 |
C9a—N1—C2 | 111.67 (11) | C6—C5a—C9a | 118.10 (14) |
O14—N1—C2 | 101.42 (10) | C6—C5a—C5 | 121.82 (13) |
N1—C2—C21 | 109.30 (12) | C9a—C5a—C5 | 120.08 (13) |
N1—C2—C3 | 103.70 (11) | C7—C6—C5a | 121.15 (14) |
C21—C2—C3 | 113.02 (12) | C7—C6—H6 | 119.4 |
N1—C2—H2 | 110.2 | C5a—C6—H6 | 119.4 |
C21—C2—H2 | 110.2 | C6—C7—C8 | 120.01 (14) |
C3—C2—H2 | 110.2 | C6—C7—H7 | 120.0 |
C4—C3—C2 | 103.64 (12) | C8—C7—H7 | 120.0 |
C4—C3—H3A | 111.0 | C9—C8—C7 | 119.83 (15) |
C2—C3—H3A | 111.0 | C9—C8—H8 | 120.1 |
C4—C3—H3B | 111.0 | C7—C8—H8 | 120.1 |
C2—C3—H3B | 111.0 | C9a—C9—C8 | 119.66 (14) |
H3A—C3—H3B | 109.0 | C9a—C9—H9 | 120.2 |
O14—C4—C5 | 106.59 (12) | C8—C9—H9 | 120.2 |
O14—C4—C3 | 103.72 (11) | C9—C9a—C5a | 121.23 (14) |
C5—C4—C3 | 114.21 (13) | C9—C9a—N1 | 117.78 (13) |
O14—C4—H4 | 110.7 | C5a—C9a—N1 | 120.96 (13) |
C5—C4—H4 | 110.7 | C22—C21—C2 | 124.03 (16) |
C3—C4—H4 | 110.7 | C22—C21—H21 | 118.0 |
C5a—C5—C4 | 109.56 (12) | C2—C21—H21 | 118.0 |
C5a—C5—H5A | 109.8 | C21—C22—H22A | 120.0 |
C4—C5—H5A | 109.8 | C21—C22—H22B | 120.0 |
C5a—C5—H5B | 109.8 | H22A—C22—H22B | 120.0 |
C4—O14—N1—C9a | −67.70 (13) | C5—C5a—C6—C7 | 178.92 (14) |
C4—O14—N1—C2 | 49.71 (12) | C5a—C6—C7—C8 | −0.4 (2) |
C9a—N1—C2—C21 | −162.66 (12) | C6—C7—C8—C9 | 1.3 (2) |
O14—N1—C2—C21 | 82.79 (13) | C7—C8—C9—C9a | −0.8 (2) |
C9a—N1—C2—C3 | 76.55 (14) | C8—C9—C9a—C5a | −0.7 (2) |
O14—N1—C2—C3 | −38.00 (13) | C8—C9—C9a—N1 | 177.46 (13) |
N1—C2—C3—C4 | 13.57 (15) | C6—C5a—C9a—C9 | 1.6 (2) |
C21—C2—C3—C4 | −104.67 (14) | C5—C5a—C9a—C9 | −178.38 (14) |
N1—O14—C4—C5 | 80.17 (13) | C6—C5a—C9a—N1 | −176.48 (13) |
N1—O14—C4—C3 | −40.70 (13) | C5—C5a—C9a—N1 | 3.5 (2) |
C2—C3—C4—O14 | 15.76 (15) | O14—N1—C9a—C9 | −151.29 (12) |
C2—C3—C4—C5 | −99.84 (14) | C2—N1—C9a—C9 | 98.15 (15) |
O14—C4—C5—C5a | −46.92 (16) | O14—N1—C9a—C5a | 26.85 (17) |
C3—C4—C5—C5a | 66.99 (17) | C2—N1—C9a—C5a | −83.71 (16) |
C4—C5—C5a—C6 | −173.27 (14) | N1—C2—C21—C22 | 126.62 (16) |
C4—C5—C5a—C9a | 6.71 (19) | C3—C2—C21—C22 | −118.46 (17) |
C9a—C5a—C6—C7 | −1.1 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···O14i | 1.00 | 2.60 | 3.209 (2) | 119 |
C6—H6···Cg1ii | 0.95 | 2.83 | 3.616 (2) | 141 |
C22—H22B···Cg1iii | 0.95 | 2.78 | 3.529 (2) | 136 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1/2, y−1/2, −z+1/2; (iii) −x+3/2, y+1/2, −z+1/2. |
C14H16ClNO | F(000) = 528 |
Mr = 249.73 | Dx = 1.366 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2783 reflections |
a = 5.6445 (5) Å | θ = 2.9–27.5° |
b = 25.744 (3) Å | µ = 0.30 mm−1 |
c = 8.3894 (11) Å | T = 120 K |
β = 95.124 (9)° | Block, colourless |
V = 1214.2 (2) Å3 | 0.44 × 0.24 × 0.20 mm |
Z = 4 |
Bruker Nonius KappaCCD area-detector diffractometer | 2783 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 1929 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.9° |
ϕ and ω scans | h = −7→7 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −31→33 |
Tmin = 0.895, Tmax = 0.943 | l = −10→10 |
15979 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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0562P)2 + 0.6916P] where P = (Fo2 + 2Fc2)/3 |
2783 reflections | (Δ/σ)max = 0.001 |
156 parameters | Δρmax = 0.29 e Å−3 |
0 restraints | Δρmin = −0.30 e Å−3 |
C14H16ClNO | V = 1214.2 (2) Å3 |
Mr = 249.73 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 5.6445 (5) Å | µ = 0.30 mm−1 |
b = 25.744 (3) Å | T = 120 K |
c = 8.3894 (11) Å | 0.44 × 0.24 × 0.20 mm |
β = 95.124 (9)° |
Bruker Nonius KappaCCD area-detector diffractometer | 2783 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1929 reflections with I > 2σ(I) |
Tmin = 0.895, Tmax = 0.943 | Rint = 0.046 |
15979 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.29 e Å−3 |
2783 reflections | Δρmin = −0.30 e Å−3 |
156 parameters |
x | y | z | Uiso*/Ueq | ||
Cl7 | 0.16222 (10) | 0.32441 (2) | 0.23221 (7) | 0.03279 (19) | |
O14 | 0.6846 (3) | 0.09756 (6) | 0.24447 (18) | 0.0245 (4) | |
N1 | 0.7332 (3) | 0.13466 (7) | 0.3718 (2) | 0.0217 (4) | |
C2 | 0.6430 (4) | 0.10686 (8) | 0.5090 (3) | 0.0222 (5) | |
H2 | 0.5999 | 0.1324 | 0.5915 | 0.027* | |
C3 | 0.4167 (4) | 0.07945 (9) | 0.4333 (3) | 0.0272 (5) | |
H3A | 0.4118 | 0.0428 | 0.4681 | 0.033* | |
H3B | 0.2714 | 0.0973 | 0.4624 | 0.033* | |
C4 | 0.4392 (4) | 0.08314 (9) | 0.2551 (3) | 0.0265 (5) | |
H4 | 0.4036 | 0.0489 | 0.2019 | 0.032* | |
C5 | 0.2867 (4) | 0.12530 (9) | 0.1758 (3) | 0.0264 (5) | |
H5A | 0.2946 | 0.1240 | 0.0585 | 0.032* | |
H5B | 0.1191 | 0.1203 | 0.1984 | 0.032* | |
C5a | 0.3753 (4) | 0.17692 (8) | 0.2393 (3) | 0.0223 (5) | |
C6 | 0.2452 (4) | 0.22204 (9) | 0.2096 (3) | 0.0240 (5) | |
H6 | 0.0970 | 0.2208 | 0.1465 | 0.029* | |
C7 | 0.3294 (4) | 0.26844 (9) | 0.2709 (3) | 0.0245 (5) | |
C8 | 0.5437 (4) | 0.27184 (9) | 0.3622 (3) | 0.0269 (5) | |
H8 | 0.6001 | 0.3043 | 0.4039 | 0.032* | |
C9 | 0.6748 (4) | 0.22718 (9) | 0.3921 (3) | 0.0261 (5) | |
H9 | 0.8241 | 0.2288 | 0.4539 | 0.031* | |
C9a | 0.5901 (4) | 0.18016 (8) | 0.3324 (3) | 0.0214 (5) | |
C21 | 0.8280 (4) | 0.07077 (8) | 0.5795 (3) | 0.0228 (5) | |
H21 | 0.9288 | 0.0554 | 0.5080 | 0.027* | |
C22 | 0.8670 (4) | 0.05784 (8) | 0.7323 (3) | 0.0231 (5) | |
C23 | 1.0662 (4) | 0.02214 (9) | 0.7886 (3) | 0.0293 (5) | |
H23A | 1.1590 | 0.0136 | 0.6988 | 0.044* | |
H23B | 1.0010 | −0.0098 | 0.8308 | 0.044* | |
H23C | 1.1692 | 0.0392 | 0.8731 | 0.044* | |
C24 | 0.7217 (4) | 0.07689 (9) | 0.8602 (3) | 0.0303 (5) | |
H24A | 0.5880 | 0.0975 | 0.8119 | 0.045* | |
H24B | 0.8207 | 0.0985 | 0.9357 | 0.045* | |
H24C | 0.6607 | 0.0472 | 0.9171 | 0.045* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl7 | 0.0318 (3) | 0.0249 (3) | 0.0410 (4) | 0.0046 (2) | −0.0002 (3) | 0.0038 (2) |
O14 | 0.0234 (8) | 0.0267 (8) | 0.0236 (8) | 0.0011 (6) | 0.0031 (6) | −0.0062 (6) |
N1 | 0.0253 (10) | 0.0214 (9) | 0.0184 (9) | −0.0004 (7) | 0.0022 (7) | −0.0007 (7) |
C2 | 0.0225 (11) | 0.0224 (11) | 0.0223 (11) | 0.0000 (9) | 0.0054 (9) | 0.0008 (9) |
C3 | 0.0210 (12) | 0.0250 (12) | 0.0359 (13) | −0.0019 (9) | 0.0038 (10) | 0.0050 (10) |
C4 | 0.0240 (12) | 0.0233 (12) | 0.0317 (13) | −0.0032 (9) | −0.0007 (10) | −0.0055 (10) |
C5 | 0.0249 (12) | 0.0283 (12) | 0.0253 (12) | −0.0010 (10) | −0.0016 (9) | −0.0023 (9) |
C5a | 0.0246 (11) | 0.0245 (11) | 0.0179 (11) | −0.0006 (9) | 0.0028 (9) | 0.0004 (9) |
C6 | 0.0211 (11) | 0.0279 (12) | 0.0227 (12) | −0.0003 (9) | 0.0007 (9) | 0.0009 (9) |
C7 | 0.0249 (12) | 0.0237 (11) | 0.0255 (12) | 0.0034 (9) | 0.0050 (9) | 0.0064 (9) |
C8 | 0.0304 (13) | 0.0223 (11) | 0.0279 (13) | −0.0033 (9) | 0.0028 (10) | 0.0011 (9) |
C9 | 0.0257 (12) | 0.0251 (11) | 0.0269 (12) | −0.0040 (9) | −0.0009 (9) | 0.0023 (9) |
C9a | 0.0235 (11) | 0.0222 (11) | 0.0193 (11) | −0.0003 (9) | 0.0051 (9) | 0.0015 (8) |
C21 | 0.0232 (11) | 0.0205 (11) | 0.0252 (12) | −0.0006 (9) | 0.0048 (9) | −0.0011 (9) |
C22 | 0.0218 (11) | 0.0195 (11) | 0.0280 (12) | −0.0034 (9) | 0.0019 (9) | −0.0003 (9) |
C23 | 0.0305 (13) | 0.0275 (12) | 0.0294 (13) | 0.0021 (10) | 0.0004 (10) | 0.0028 (10) |
C24 | 0.0352 (14) | 0.0317 (13) | 0.0238 (12) | 0.0052 (10) | 0.0015 (10) | 0.0004 (10) |
Cl7—C7 | 1.737 (2) | C6—C7 | 1.369 (3) |
O14—N1 | 1.441 (2) | C6—H6 | 0.9500 |
O14—C4 | 1.445 (3) | C7—C8 | 1.376 (3) |
N1—C9a | 1.444 (3) | C8—C9 | 1.378 (3) |
N1—C2 | 1.483 (3) | C8—H8 | 0.9500 |
C2—C21 | 1.481 (3) | C9—C9a | 1.379 (3) |
C2—C3 | 1.545 (3) | C9—H9 | 0.9500 |
C2—H2 | 1.0000 | C21—C22 | 1.324 (3) |
C3—C4 | 1.514 (3) | C21—H21 | 0.9500 |
C3—H3A | 0.9900 | C22—C24 | 1.490 (3) |
C3—H3B | 0.9900 | C22—C23 | 1.496 (3) |
C4—C5 | 1.503 (3) | C23—H23A | 0.9800 |
C4—H4 | 1.0000 | C23—H23B | 0.9800 |
C5—C5a | 1.501 (3) | C23—H23C | 0.9800 |
C5—H5A | 0.9900 | C24—H24A | 0.9800 |
C5—H5B | 0.9900 | C24—H24B | 0.9800 |
C5a—C6 | 1.385 (3) | C24—H24C | 0.9800 |
C5a—C9a | 1.385 (3) | ||
N1—O14—C4 | 104.15 (15) | C7—C6—H6 | 119.9 |
O14—N1—C9a | 107.59 (15) | C5a—C6—H6 | 119.9 |
O14—N1—C2 | 101.51 (15) | C6—C7—C8 | 121.5 (2) |
C9a—N1—C2 | 110.19 (16) | C6—C7—Cl7 | 119.30 (17) |
C21—C2—N1 | 109.52 (17) | C8—C7—Cl7 | 119.16 (18) |
C21—C2—C3 | 113.90 (18) | C7—C8—C9 | 118.7 (2) |
N1—C2—C3 | 103.30 (17) | C7—C8—H8 | 120.7 |
C21—C2—H2 | 110.0 | C9—C8—H8 | 120.7 |
N1—C2—H2 | 110.0 | C8—C9—C9a | 120.2 (2) |
C3—C2—H2 | 110.0 | C8—C9—H9 | 119.9 |
C4—C3—C2 | 103.77 (17) | C9a—C9—H9 | 119.9 |
C4—C3—H3A | 111.0 | C9—C9a—C5a | 121.0 (2) |
C2—C3—H3A | 111.0 | C9—C9a—N1 | 117.40 (19) |
C4—C3—H3B | 111.0 | C5a—C9a—N1 | 121.59 (19) |
C2—C3—H3B | 111.0 | C22—C21—C2 | 126.5 (2) |
H3A—C3—H3B | 109.0 | C22—C21—H21 | 116.7 |
O14—C4—C5 | 107.54 (18) | C2—C21—H21 | 116.7 |
O14—C4—C3 | 104.04 (17) | C21—C22—C24 | 124.0 (2) |
C5—C4—C3 | 112.79 (19) | C21—C22—C23 | 121.0 (2) |
O14—C4—H4 | 110.7 | C24—C22—C23 | 114.9 (2) |
C5—C4—H4 | 110.7 | C22—C23—H23A | 109.5 |
C3—C4—H4 | 110.7 | C22—C23—H23B | 109.5 |
C5a—C5—C4 | 108.83 (18) | H23A—C23—H23B | 109.5 |
C5a—C5—H5A | 109.9 | C22—C23—H23C | 109.5 |
C4—C5—H5A | 109.9 | H23A—C23—H23C | 109.5 |
C5a—C5—H5B | 109.9 | H23B—C23—H23C | 109.5 |
C4—C5—H5B | 109.9 | C22—C24—H24A | 109.5 |
H5A—C5—H5B | 108.3 | C22—C24—H24B | 109.5 |
C6—C5a—C9a | 118.3 (2) | H24A—C24—H24B | 109.5 |
C6—C5a—C5 | 121.62 (19) | C22—C24—H24C | 109.5 |
C9a—C5a—C5 | 120.03 (19) | H24A—C24—H24C | 109.5 |
C7—C6—C5a | 120.2 (2) | H24B—C24—H24C | 109.5 |
C4—O14—N1—C9a | −66.33 (19) | C5a—C6—C7—Cl7 | −179.82 (16) |
C4—O14—N1—C2 | 49.39 (18) | C6—C7—C8—C9 | −0.1 (3) |
O14—N1—C2—C21 | 83.46 (19) | Cl7—C7—C8—C9 | −179.96 (17) |
C9a—N1—C2—C21 | −162.74 (18) | C7—C8—C9—C9a | −0.7 (3) |
O14—N1—C2—C3 | −38.25 (19) | C8—C9—C9a—C5a | 1.3 (3) |
C9a—N1—C2—C3 | 75.6 (2) | C8—C9—C9a—N1 | −178.31 (19) |
C21—C2—C3—C4 | −104.3 (2) | C6—C5a—C9a—C9 | −1.0 (3) |
N1—C2—C3—C4 | 14.4 (2) | C5—C5a—C9a—C9 | 180.0 (2) |
N1—O14—C4—C5 | 80.02 (19) | C6—C5a—C9a—N1 | 178.52 (18) |
N1—O14—C4—C3 | −39.8 (2) | C5—C5a—C9a—N1 | −0.4 (3) |
C2—C3—C4—O14 | 14.7 (2) | O14—N1—C9a—C9 | −152.18 (18) |
C2—C3—C4—C5 | −101.6 (2) | C2—N1—C9a—C9 | 98.0 (2) |
O14—C4—C5—C5a | −48.9 (2) | O14—N1—C9a—C5a | 28.2 (3) |
C3—C4—C5—C5a | 65.2 (2) | C2—N1—C9a—C5a | −81.6 (2) |
C4—C5—C5a—C6 | −168.4 (2) | N1—C2—C21—C22 | 146.9 (2) |
C4—C5—C5a—C9a | 10.5 (3) | C3—C2—C21—C22 | −98.0 (3) |
C9a—C5a—C6—C7 | 0.3 (3) | C2—C21—C22—C24 | 2.0 (4) |
C5—C5a—C6—C7 | 179.2 (2) | C2—C21—C22—C23 | −177.9 (2) |
C5a—C6—C7—C8 | 0.3 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5B···O14i | 0.99 | 2.58 | 3.570 (3) | 174 |
Symmetry code: (i) x−1, y, z. |
C15H18ClNO | F(000) = 560 |
Mr = 263.75 | Dx = 1.338 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 3013 reflections |
a = 11.0631 (7) Å | θ = 3.1–27.5° |
b = 5.7212 (5) Å | µ = 0.28 mm−1 |
c = 21.203 (6) Å | T = 120 K |
β = 102.587 (16)° | Prism, colourless |
V = 1309.8 (4) Å3 | 0.40 × 0.19 × 0.12 mm |
Z = 4 |
Bruker Nonius KappaCCD area-detector diffractometer | 2306 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 1661 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.105 |
Detector resolution: 9.091 pixels mm-1 | θmax = 25.1°, θmin = 3.1° |
ϕ and ω scans | h = −13→13 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −6→6 |
Tmin = 0.869, Tmax = 0.967 | l = −25→25 |
16325 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)] = 0.068 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.155 | H-atom parameters constrained |
S = 1.11 | w = 1/[σ2(Fo2) + (0.0562P)2 + 1.9086P] where P = (Fo2 + 2Fc2)/3 |
2306 reflections | (Δ/σ)max = 0.001 |
166 parameters | Δρmax = 0.43 e Å−3 |
0 restraints | Δρmin = −0.39 e Å−3 |
C15H18ClNO | V = 1309.8 (4) Å3 |
Mr = 263.75 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.0631 (7) Å | µ = 0.28 mm−1 |
b = 5.7212 (5) Å | T = 120 K |
c = 21.203 (6) Å | 0.40 × 0.19 × 0.12 mm |
β = 102.587 (16)° |
Bruker Nonius KappaCCD area-detector diffractometer | 2306 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1661 reflections with I > 2σ(I) |
Tmin = 0.869, Tmax = 0.967 | Rint = 0.105 |
16325 measured reflections |
R[F2 > 2σ(F2)] = 0.068 | 0 restraints |
wR(F2) = 0.155 | H-atom parameters constrained |
S = 1.11 | Δρmax = 0.43 e Å−3 |
2306 reflections | Δρmin = −0.39 e Å−3 |
166 parameters |
x | y | z | Uiso*/Ueq | ||
Cl8 | 1.00257 (9) | 0.68005 (19) | 0.25837 (5) | 0.0350 (3) | |
O14 | 0.7434 (2) | 0.6716 (4) | 0.49115 (11) | 0.0227 (6) | |
N1 | 0.7273 (2) | 0.7165 (5) | 0.42340 (13) | 0.0196 (7) | |
C2 | 0.6038 (3) | 0.6127 (6) | 0.39709 (17) | 0.0193 (8) | |
H2 | 0.5947 | 0.5727 | 0.3504 | 0.023* | |
C3 | 0.6066 (3) | 0.3878 (6) | 0.43802 (18) | 0.0249 (9) | |
H3A | 0.5288 | 0.3698 | 0.4534 | 0.030* | |
H3B | 0.6189 | 0.2476 | 0.4128 | 0.030* | |
C4 | 0.7161 (3) | 0.4250 (6) | 0.49432 (18) | 0.0243 (9) | |
H4 | 0.6940 | 0.3848 | 0.5363 | 0.029* | |
C5 | 0.8310 (3) | 0.2957 (6) | 0.48660 (18) | 0.0262 (9) | |
H5A | 0.8951 | 0.3069 | 0.5271 | 0.031* | |
H5B | 0.8111 | 0.1285 | 0.4780 | 0.031* | |
C5a | 0.8797 (3) | 0.3974 (6) | 0.43209 (17) | 0.0198 (8) | |
C6 | 0.9766 (3) | 0.2972 (6) | 0.40988 (18) | 0.0250 (8) | |
H6 | 1.0169 | 0.1634 | 0.4313 | 0.030* | |
C7 | 1.0152 (3) | 0.3863 (6) | 0.35810 (18) | 0.0269 (9) | |
H7 | 1.0830 | 0.3179 | 0.3441 | 0.032* | |
C8 | 0.9545 (3) | 0.5773 (7) | 0.32623 (18) | 0.0252 (9) | |
C9 | 0.8578 (3) | 0.6884 (6) | 0.34598 (16) | 0.0203 (8) | |
C9a | 0.8237 (3) | 0.5961 (6) | 0.39995 (17) | 0.0186 (8) | |
C21 | 0.5061 (3) | 0.7815 (6) | 0.40570 (17) | 0.0196 (8) | |
H21 | 0.5234 | 0.8745 | 0.4437 | 0.024* | |
C22 | 0.3978 (3) | 0.8148 (6) | 0.36585 (17) | 0.0198 (8) | |
C23 | 0.3536 (4) | 0.6824 (7) | 0.30516 (19) | 0.0341 (10) | |
H23A | 0.4235 | 0.6011 | 0.2934 | 0.051* | |
H23B | 0.3166 | 0.7907 | 0.2705 | 0.051* | |
H23C | 0.2913 | 0.5680 | 0.3114 | 0.051* | |
C24 | 0.3078 (3) | 0.9934 (6) | 0.37990 (19) | 0.0265 (9) | |
H24A | 0.3393 | 1.0603 | 0.4229 | 0.040* | |
H24B | 0.2276 | 0.9187 | 0.3786 | 0.040* | |
H24C | 0.2977 | 1.1178 | 0.3474 | 0.040* | |
C91 | 0.7918 (3) | 0.8926 (6) | 0.31029 (18) | 0.0239 (8) | |
H91A | 0.8521 | 0.9976 | 0.2974 | 0.036* | |
H91B | 0.7470 | 0.9768 | 0.3383 | 0.036* | |
H91C | 0.7330 | 0.8374 | 0.2717 | 0.036* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl8 | 0.0258 (5) | 0.0425 (6) | 0.0397 (6) | −0.0035 (5) | 0.0136 (4) | 0.0059 (5) |
O14 | 0.0279 (13) | 0.0155 (12) | 0.0234 (13) | −0.0016 (10) | 0.0030 (10) | −0.0020 (10) |
N1 | 0.0191 (15) | 0.0155 (14) | 0.0238 (16) | −0.0009 (12) | 0.0038 (12) | −0.0001 (12) |
C2 | 0.0169 (17) | 0.0147 (17) | 0.025 (2) | −0.0026 (14) | 0.0027 (14) | −0.0038 (14) |
C3 | 0.0209 (19) | 0.0137 (18) | 0.041 (2) | −0.0017 (14) | 0.0092 (16) | −0.0022 (16) |
C4 | 0.032 (2) | 0.0124 (17) | 0.030 (2) | −0.0016 (16) | 0.0091 (16) | 0.0060 (15) |
C5 | 0.0257 (19) | 0.0176 (18) | 0.032 (2) | −0.0002 (16) | −0.0017 (16) | 0.0024 (17) |
C5a | 0.0176 (17) | 0.0139 (17) | 0.0248 (19) | −0.0021 (14) | −0.0023 (14) | −0.0020 (15) |
C6 | 0.0212 (19) | 0.0172 (18) | 0.034 (2) | 0.0045 (15) | −0.0005 (16) | 0.0010 (17) |
C7 | 0.0113 (17) | 0.029 (2) | 0.038 (2) | 0.0015 (15) | 0.0006 (16) | −0.0019 (18) |
C8 | 0.0149 (17) | 0.026 (2) | 0.034 (2) | −0.0037 (15) | 0.0035 (15) | −0.0023 (17) |
C9 | 0.0159 (17) | 0.0213 (18) | 0.0224 (19) | −0.0051 (15) | 0.0015 (14) | −0.0024 (16) |
C9a | 0.0134 (17) | 0.0141 (17) | 0.0259 (19) | −0.0007 (13) | −0.0014 (14) | −0.0058 (15) |
C21 | 0.0239 (19) | 0.0103 (16) | 0.026 (2) | −0.0009 (14) | 0.0095 (15) | −0.0018 (14) |
C22 | 0.0206 (18) | 0.0134 (16) | 0.0269 (19) | −0.0038 (15) | 0.0085 (14) | 0.0007 (15) |
C23 | 0.027 (2) | 0.034 (2) | 0.039 (2) | 0.0059 (19) | 0.0013 (17) | −0.005 (2) |
C24 | 0.024 (2) | 0.0175 (18) | 0.039 (2) | 0.0037 (16) | 0.0091 (17) | 0.0022 (17) |
C91 | 0.0235 (19) | 0.0196 (18) | 0.029 (2) | −0.0007 (15) | 0.0066 (16) | 0.0011 (16) |
Cl8—C8 | 1.741 (4) | C6—H6 | 0.9500 |
O14—N1 | 1.432 (4) | C7—C8 | 1.380 (5) |
O14—C4 | 1.448 (4) | C7—H7 | 0.9500 |
N1—C9a | 1.446 (4) | C8—C9 | 1.385 (5) |
N1—C2 | 1.482 (4) | C9—C9a | 1.385 (5) |
C2—C21 | 1.491 (5) | C9—C91 | 1.493 (5) |
C2—C3 | 1.548 (5) | C21—C22 | 1.320 (5) |
C2—H2 | 1.0000 | C21—H21 | 0.9500 |
C3—C4 | 1.519 (5) | C22—C23 | 1.481 (5) |
C3—H3A | 0.9900 | C22—C24 | 1.501 (5) |
C3—H3B | 0.9900 | C23—H23A | 0.9800 |
C4—C5 | 1.510 (5) | C23—H23B | 0.9800 |
C4—H4 | 1.0000 | C23—H23C | 0.9800 |
C5—C5a | 1.495 (5) | C24—H24A | 0.9800 |
C5—H5A | 0.9900 | C24—H24B | 0.9800 |
C5—H5B | 0.9900 | C24—H24C | 0.9800 |
C5a—C6 | 1.386 (5) | C91—H91A | 0.9800 |
C5a—C9a | 1.399 (5) | C91—H91B | 0.9800 |
C6—C7 | 1.361 (5) | C91—H91C | 0.9800 |
N1—O14—C4 | 103.9 (2) | C6—C7—H7 | 120.4 |
O14—N1—C9a | 108.7 (2) | C8—C7—H7 | 120.4 |
O14—N1—C2 | 102.1 (2) | C7—C8—C9 | 122.7 (4) |
C9a—N1—C2 | 111.6 (3) | C7—C8—Cl8 | 117.9 (3) |
N1—C2—C21 | 109.1 (3) | C9—C8—Cl8 | 119.3 (3) |
N1—C2—C3 | 102.6 (3) | C8—C9—C9a | 116.2 (3) |
C21—C2—C3 | 113.3 (3) | C8—C9—C91 | 122.0 (3) |
N1—C2—H2 | 110.5 | C9a—C9—C91 | 121.7 (3) |
C21—C2—H2 | 110.5 | C9—C9a—C5a | 122.8 (3) |
C3—C2—H2 | 110.5 | C9—C9a—N1 | 117.2 (3) |
C4—C3—C2 | 103.8 (3) | C5a—C9a—N1 | 120.1 (3) |
C4—C3—H3A | 111.0 | C22—C21—C2 | 126.6 (3) |
C2—C3—H3A | 111.0 | C22—C21—H21 | 116.7 |
C4—C3—H3B | 111.0 | C2—C21—H21 | 116.7 |
C2—C3—H3B | 111.0 | C21—C22—C23 | 124.3 (3) |
H3A—C3—H3B | 109.0 | C21—C22—C24 | 121.3 (3) |
O14—C4—C5 | 106.5 (3) | C23—C22—C24 | 114.3 (3) |
O14—C4—C3 | 103.8 (3) | C22—C23—H23A | 109.5 |
C5—C4—C3 | 113.1 (3) | C22—C23—H23B | 109.5 |
O14—C4—H4 | 111.1 | H23A—C23—H23B | 109.5 |
C5—C4—H4 | 111.1 | C22—C23—H23C | 109.5 |
C3—C4—H4 | 111.1 | H23A—C23—H23C | 109.5 |
C5a—C5—C4 | 110.3 (3) | H23B—C23—H23C | 109.5 |
C5a—C5—H5A | 109.6 | C22—C24—H24A | 109.5 |
C4—C5—H5A | 109.6 | C22—C24—H24B | 109.5 |
C5a—C5—H5B | 109.6 | H24A—C24—H24B | 109.5 |
C4—C5—H5B | 109.6 | C22—C24—H24C | 109.5 |
H5A—C5—H5B | 108.1 | H24A—C24—H24C | 109.5 |
C6—C5a—C9a | 117.6 (3) | H24B—C24—H24C | 109.5 |
C6—C5a—C5 | 122.5 (3) | C9—C91—H91A | 109.5 |
C9a—C5a—C5 | 119.8 (3) | C9—C91—H91B | 109.5 |
C7—C6—C5a | 121.4 (3) | H91A—C91—H91B | 109.5 |
C7—C6—H6 | 119.3 | C9—C91—H91C | 109.5 |
C5a—C6—H6 | 119.3 | H91A—C91—H91C | 109.5 |
C6—C7—C8 | 119.2 (3) | H91B—C91—H91C | 109.5 |
C4—O14—N1—C9a | −67.8 (3) | C7—C8—C9—C9a | −0.4 (5) |
C4—O14—N1—C2 | 50.2 (3) | Cl8—C8—C9—C9a | 179.4 (2) |
O14—N1—C2—C21 | 81.3 (3) | C7—C8—C9—C91 | −179.0 (3) |
C9a—N1—C2—C21 | −162.9 (3) | Cl8—C8—C9—C91 | 0.9 (5) |
O14—N1—C2—C3 | −39.2 (3) | C8—C9—C9a—C5a | −2.1 (5) |
C9a—N1—C2—C3 | 76.7 (3) | C91—C9—C9a—C5a | 176.4 (3) |
N1—C2—C3—C4 | 14.9 (3) | C8—C9—C9a—N1 | 176.9 (3) |
C21—C2—C3—C4 | −102.6 (3) | C91—C9—C9a—N1 | −4.5 (5) |
N1—O14—C4—C5 | 79.8 (3) | C6—C5a—C9a—C9 | 2.8 (5) |
N1—O14—C4—C3 | −39.8 (3) | C5—C5a—C9a—C9 | −174.8 (3) |
C2—C3—C4—O14 | 14.2 (4) | C6—C5a—C9a—N1 | −176.2 (3) |
C2—C3—C4—C5 | −100.7 (3) | C5—C5a—C9a—N1 | 6.1 (5) |
O14—C4—C5—C5a | −45.8 (4) | O14—N1—C9a—C9 | −153.5 (3) |
C3—C4—C5—C5a | 67.6 (4) | C2—N1—C9a—C9 | 94.7 (3) |
C4—C5—C5a—C6 | −173.0 (3) | O14—N1—C9a—C5a | 25.6 (4) |
C4—C5—C5a—C9a | 4.5 (4) | C2—N1—C9a—C5a | −86.2 (4) |
C9a—C5a—C6—C7 | −0.9 (5) | N1—C2—C21—C22 | 144.9 (3) |
C5—C5a—C6—C7 | 176.7 (3) | C3—C2—C21—C22 | −101.5 (4) |
C5a—C6—C7—C8 | −1.5 (5) | C2—C21—C22—C23 | 1.5 (6) |
C6—C7—C8—C9 | 2.2 (5) | C2—C21—C22—C24 | −179.3 (3) |
C6—C7—C8—Cl8 | −177.6 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5A···Cg1i | 0.99 | 2.79 | 3.730 (4) | 158 |
Symmetry code: (i) −x+2, −y+2, −z+1. |
C15H18ClNO | Z = 2 |
Mr = 263.75 | F(000) = 280 |
Triclinic, P1 | Dx = 1.334 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 5.2890 (9) Å | Cell parameters from 3005 reflections |
b = 9.3076 (16) Å | θ = 2.8–27.5° |
c = 13.551 (3) Å | µ = 0.28 mm−1 |
α = 94.554 (15)° | T = 120 K |
β = 94.684 (15)° | Plate, colourless |
γ = 97.298 (14)° | 0.32 × 0.26 × 0.11 mm |
V = 656.7 (2) Å3 |
Bruker Nonius KappaCCD area-detector diffractometer | 3005 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 2348 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.041 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.8° |
ϕ and ω scans | h = −6→6 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −12→12 |
Tmin = 0.932, Tmax = 0.970 | l = −17→17 |
16228 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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.11 | w = 1/[σ2(Fo2) + (0.038P)2 + 0.5092P] where P = (Fo2 + 2Fc2)/3 |
3005 reflections | (Δ/σ)max = 0.001 |
166 parameters | Δρmax = 0.29 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
C15H18ClNO | γ = 97.298 (14)° |
Mr = 263.75 | V = 656.7 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 5.2890 (9) Å | Mo Kα radiation |
b = 9.3076 (16) Å | µ = 0.28 mm−1 |
c = 13.551 (3) Å | T = 120 K |
α = 94.554 (15)° | 0.32 × 0.26 × 0.11 mm |
β = 94.684 (15)° |
Bruker Nonius KappaCCD area-detector diffractometer | 3005 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2348 reflections with I > 2σ(I) |
Tmin = 0.932, Tmax = 0.970 | Rint = 0.041 |
16228 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.11 | Δρmax = 0.29 e Å−3 |
3005 reflections | Δρmin = −0.36 e Å−3 |
166 parameters |
x | y | z | Uiso*/Ueq | ||
Cl8 | 0.73078 (12) | 0.74226 (5) | 0.21073 (4) | 0.03620 (17) | |
O14 | 0.6146 (2) | 0.07431 (14) | 0.12657 (10) | 0.0230 (3) | |
N1 | 0.6629 (3) | 0.18689 (17) | 0.20756 (12) | 0.0191 (3) | |
C2 | 0.5250 (4) | 0.1133 (2) | 0.28500 (15) | 0.0242 (4) | |
H2 | 0.6309 | 0.0404 | 0.3110 | 0.029* | |
C3 | 0.2807 (4) | 0.0301 (2) | 0.22771 (15) | 0.0254 (4) | |
H3A | 0.2483 | −0.0706 | 0.2470 | 0.031* | |
H3B | 0.1300 | 0.0800 | 0.2395 | 0.031* | |
C4 | 0.3402 (4) | 0.0311 (2) | 0.12007 (15) | 0.0234 (4) | |
H4 | 0.2926 | −0.0678 | 0.0840 | 0.028* | |
C5 | 0.2183 (4) | 0.1429 (2) | 0.06578 (15) | 0.0228 (4) | |
H5A | 0.2398 | 0.1281 | −0.0061 | 0.027* | |
H5B | 0.0327 | 0.1321 | 0.0739 | 0.027* | |
C5a | 0.3407 (4) | 0.2930 (2) | 0.10635 (14) | 0.0191 (4) | |
C6 | 0.2486 (4) | 0.4150 (2) | 0.07421 (16) | 0.0274 (5) | |
H6 | 0.1016 | 0.4040 | 0.0277 | 0.033* | |
C7 | 0.3654 (4) | 0.5516 (2) | 0.10817 (16) | 0.0297 (5) | |
H7 | 0.3005 | 0.6349 | 0.0855 | 0.036* | |
C8 | 0.5780 (4) | 0.5666 (2) | 0.17553 (15) | 0.0246 (4) | |
C9 | 0.6787 (4) | 0.4489 (2) | 0.21219 (14) | 0.0194 (4) | |
C9a | 0.5537 (3) | 0.31158 (19) | 0.17540 (13) | 0.0169 (4) | |
C21 | 0.4772 (4) | 0.2126 (2) | 0.37011 (15) | 0.0260 (4) | |
H21 | 0.3520 | 0.2755 | 0.3584 | 0.031* | |
C22 | 0.5935 (4) | 0.2218 (2) | 0.46155 (16) | 0.0297 (5) | |
C23 | 0.8029 (5) | 0.1396 (3) | 0.4932 (2) | 0.0474 (7) | |
H23A | 0.8582 | 0.0874 | 0.4348 | 0.071* | |
H23B | 0.7418 | 0.0697 | 0.5392 | 0.071* | |
H23C | 0.9474 | 0.2071 | 0.5266 | 0.071* | |
C24 | 0.5118 (5) | 0.3198 (3) | 0.54187 (18) | 0.0465 (7) | |
H24A | 0.3681 | 0.3665 | 0.5152 | 0.070* | |
H24B | 0.6551 | 0.3945 | 0.5670 | 0.070* | |
H24C | 0.4583 | 0.2629 | 0.5962 | 0.070* | |
C91 | 0.9103 (4) | 0.4665 (2) | 0.28569 (15) | 0.0255 (4) | |
H91A | 1.0328 | 0.5479 | 0.2703 | 0.038* | |
H91B | 0.9901 | 0.3770 | 0.2820 | 0.038* | |
H91C | 0.8595 | 0.4860 | 0.3529 | 0.038* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl8 | 0.0492 (4) | 0.0189 (2) | 0.0386 (3) | −0.0047 (2) | 0.0108 (3) | −0.0011 (2) |
O14 | 0.0171 (7) | 0.0209 (7) | 0.0292 (8) | 0.0013 (5) | 0.0032 (6) | −0.0088 (6) |
N1 | 0.0174 (8) | 0.0195 (7) | 0.0192 (8) | 0.0025 (6) | −0.0003 (6) | −0.0038 (6) |
C2 | 0.0249 (10) | 0.0244 (10) | 0.0238 (10) | 0.0030 (8) | 0.0023 (8) | 0.0055 (8) |
C3 | 0.0234 (10) | 0.0245 (10) | 0.0270 (11) | −0.0019 (8) | 0.0031 (8) | 0.0013 (8) |
C4 | 0.0189 (10) | 0.0212 (9) | 0.0272 (11) | −0.0027 (7) | 0.0026 (8) | −0.0074 (8) |
C5 | 0.0161 (9) | 0.0304 (10) | 0.0197 (10) | −0.0016 (8) | 0.0012 (8) | −0.0047 (8) |
C5a | 0.0157 (9) | 0.0250 (9) | 0.0163 (9) | 0.0021 (7) | 0.0035 (7) | −0.0010 (7) |
C6 | 0.0247 (11) | 0.0327 (11) | 0.0247 (11) | 0.0062 (9) | −0.0035 (8) | 0.0043 (9) |
C7 | 0.0346 (12) | 0.0259 (10) | 0.0305 (12) | 0.0091 (9) | 0.0018 (9) | 0.0066 (9) |
C8 | 0.0293 (11) | 0.0195 (9) | 0.0242 (10) | −0.0016 (8) | 0.0085 (9) | −0.0022 (8) |
C9 | 0.0175 (9) | 0.0225 (9) | 0.0175 (9) | 0.0004 (7) | 0.0051 (7) | −0.0025 (7) |
C9a | 0.0143 (9) | 0.0203 (9) | 0.0165 (9) | 0.0030 (7) | 0.0048 (7) | −0.0008 (7) |
C21 | 0.0268 (11) | 0.0254 (10) | 0.0261 (11) | 0.0035 (8) | 0.0034 (9) | 0.0043 (8) |
C22 | 0.0261 (11) | 0.0358 (11) | 0.0238 (11) | −0.0089 (9) | 0.0024 (9) | 0.0039 (9) |
C23 | 0.0361 (14) | 0.0610 (17) | 0.0424 (15) | 0.0000 (12) | −0.0087 (12) | 0.0116 (13) |
C24 | 0.0486 (16) | 0.0589 (17) | 0.0268 (12) | −0.0062 (13) | 0.0027 (11) | −0.0066 (11) |
C91 | 0.0200 (10) | 0.0282 (10) | 0.0250 (11) | −0.0032 (8) | −0.0006 (8) | −0.0044 (8) |
Cl8—C8 | 1.741 (2) | C6—H6 | 0.9500 |
O14—N1 | 1.4392 (19) | C7—C8 | 1.375 (3) |
O14—C4 | 1.450 (2) | C7—H7 | 0.9500 |
N1—C9a | 1.442 (2) | C8—C9 | 1.387 (3) |
N1—C2 | 1.488 (3) | C9—C9a | 1.396 (2) |
C2—C21 | 1.479 (3) | C9—C91 | 1.497 (3) |
C2—C3 | 1.536 (3) | C21—C22 | 1.329 (3) |
C2—H2 | 1.0000 | C21—H21 | 0.9500 |
C3—C4 | 1.518 (3) | C22—C23 | 1.479 (3) |
C3—H3A | 0.9900 | C22—C24 | 1.491 (3) |
C3—H3B | 0.9900 | C23—H23A | 0.9800 |
C4—C5 | 1.501 (3) | C23—H23B | 0.9800 |
C4—H4 | 1.0000 | C23—H23C | 0.9800 |
C5—C5a | 1.505 (3) | C24—H24A | 0.9800 |
C5—H5A | 0.9900 | C24—H24B | 0.9800 |
C5—H5B | 0.9900 | C24—H24C | 0.9800 |
C5a—C6 | 1.378 (3) | C91—H91A | 0.9800 |
C5a—C9a | 1.388 (3) | C91—H91B | 0.9800 |
C6—C7 | 1.368 (3) | C91—H91C | 0.9800 |
N1—O14—C4 | 104.10 (13) | C6—C7—H7 | 120.4 |
O14—N1—C9a | 107.54 (14) | C8—C7—H7 | 120.4 |
O14—N1—C2 | 100.29 (14) | C7—C8—C9 | 122.85 (18) |
C9a—N1—C2 | 113.92 (15) | C7—C8—Cl8 | 117.31 (16) |
C21—C2—N1 | 114.18 (16) | C9—C8—Cl8 | 119.78 (16) |
C21—C2—C3 | 114.01 (17) | C8—C9—C9a | 116.06 (18) |
N1—C2—C3 | 104.22 (16) | C8—C9—C91 | 122.44 (17) |
C21—C2—H2 | 108.0 | C9a—C9—C91 | 121.50 (17) |
N1—C2—H2 | 108.0 | C5a—C9a—C9 | 122.34 (17) |
C3—C2—H2 | 108.0 | C5a—C9a—N1 | 120.22 (16) |
C4—C3—C2 | 103.08 (16) | C9—C9a—N1 | 117.35 (16) |
C4—C3—H3A | 111.1 | C22—C21—C2 | 125.9 (2) |
C2—C3—H3A | 111.1 | C22—C21—H21 | 117.1 |
C4—C3—H3B | 111.1 | C2—C21—H21 | 117.0 |
C2—C3—H3B | 111.1 | C21—C22—C23 | 125.2 (2) |
H3A—C3—H3B | 109.1 | C21—C22—C24 | 119.9 (2) |
O14—C4—C5 | 106.92 (15) | C23—C22—C24 | 114.9 (2) |
O14—C4—C3 | 103.98 (15) | C22—C23—H23A | 109.5 |
C5—C4—C3 | 113.35 (16) | C22—C23—H23B | 109.5 |
O14—C4—H4 | 110.8 | H23A—C23—H23B | 109.5 |
C5—C4—H4 | 110.8 | C22—C23—H23C | 109.5 |
C3—C4—H4 | 110.8 | H23A—C23—H23C | 109.5 |
C4—C5—C5a | 109.79 (16) | H23B—C23—H23C | 109.5 |
C4—C5—H5B | 109.7 | C22—C24—H24A | 109.5 |
C5a—C5—H5B | 109.7 | C22—C24—H24B | 109.5 |
C4—C5—H5A | 109.7 | H24A—C24—H24B | 109.5 |
C5a—C5—H5A | 109.7 | C22—C24—H24C | 109.5 |
H5B—C5—H5A | 108.2 | H24A—C24—H24C | 109.5 |
C6—C5a—C9a | 118.50 (18) | H24B—C24—H24C | 109.5 |
C6—C5a—C5 | 121.01 (18) | C9—C91—H91A | 109.5 |
C9a—C5a—C5 | 120.47 (17) | C9—C91—H91B | 109.5 |
C7—C6—C5a | 121.11 (19) | H91A—C91—H91B | 109.5 |
C7—C6—H6 | 119.4 | C9—C91—H91C | 109.5 |
C5a—C6—H6 | 119.4 | H91A—C91—H91C | 109.5 |
C6—C7—C8 | 119.13 (19) | H91B—C91—H91C | 109.5 |
C4—O14—N1—C9a | −69.19 (17) | C7—C8—C9—C9a | 1.0 (3) |
C4—O14—N1—C2 | 50.12 (16) | Cl8—C8—C9—C9a | −176.12 (14) |
O14—N1—C2—C21 | −164.40 (16) | C7—C8—C9—C91 | −179.91 (19) |
C9a—N1—C2—C21 | −49.8 (2) | Cl8—C8—C9—C91 | 2.9 (3) |
O14—N1—C2—C3 | −39.38 (17) | C6—C5a—C9a—C9 | −0.8 (3) |
C9a—N1—C2—C3 | 75.18 (19) | C5—C5a—C9a—C9 | 177.59 (17) |
C21—C2—C3—C4 | 140.31 (17) | C6—C5a—C9a—N1 | −177.20 (17) |
N1—C2—C3—C4 | 15.18 (19) | C5—C5a—C9a—N1 | 1.2 (3) |
N1—O14—C4—C5 | 79.45 (17) | C8—C9—C9a—C5a | −0.1 (3) |
N1—O14—C4—C3 | −40.72 (17) | C91—C9—C9a—C5a | −179.21 (17) |
C2—C3—C4—O14 | 14.57 (19) | C8—C9—C9a—N1 | 176.37 (17) |
C2—C3—C4—C5 | −101.17 (18) | C91—C9—C9a—N1 | −2.7 (3) |
O14—C4—C5—C5a | −45.5 (2) | O14—N1—C9a—C5a | 29.7 (2) |
C3—C4—C5—C5a | 68.5 (2) | C2—N1—C9a—C5a | −80.5 (2) |
C4—C5—C5a—C6 | −174.80 (18) | O14—N1—C9a—C9 | −146.86 (15) |
C4—C5—C5a—C9a | 6.9 (2) | C2—N1—C9a—C9 | 102.95 (19) |
C9a—C5a—C6—C7 | 0.9 (3) | N1—C2—C21—C22 | −108.4 (2) |
C5—C5a—C6—C7 | −177.50 (19) | C3—C2—C21—C22 | 132.0 (2) |
C5a—C6—C7—C8 | 0.0 (3) | C2—C21—C22—C23 | 3.6 (4) |
C6—C7—C8—C9 | −1.0 (3) | C2—C21—C22—C24 | −175.6 (2) |
C6—C7—C8—Cl8 | 176.25 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5B···O14i | 0.99 | 2.39 | 3.358 (3) | 166 |
Symmetry code: (i) x−1, y, z. |
C14H16ClNO | F(000) = 528 |
Mr = 249.73 | Dx = 1.382 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2759 reflections |
a = 8.6828 (11) Å | θ = 3.0–27.5° |
b = 10.1456 (6) Å | µ = 0.30 mm−1 |
c = 14.2976 (16) Å | T = 120 K |
β = 107.587 (9)° | Needle, colourless |
V = 1200.6 (2) Å3 | 0.50 × 0.17 × 0.14 mm |
Z = 4 |
Bruker Nonius KappaCCD area-detector diffractometer | 2759 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 2083 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.045 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.0° |
ϕ and ω scans | h = −11→7 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −13→13 |
Tmin = 0.844, Tmax = 0.959 | l = −18→18 |
14152 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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.093 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.033P)2 + 0.6821P] where P = (Fo2 + 2Fc2)/3 |
2759 reflections | (Δ/σ)max = 0.001 |
156 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
C14H16ClNO | V = 1200.6 (2) Å3 |
Mr = 249.73 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.6828 (11) Å | µ = 0.30 mm−1 |
b = 10.1456 (6) Å | T = 120 K |
c = 14.2976 (16) Å | 0.50 × 0.17 × 0.14 mm |
β = 107.587 (9)° |
Bruker Nonius KappaCCD area-detector diffractometer | 2759 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2083 reflections with I > 2σ(I) |
Tmin = 0.844, Tmax = 0.959 | Rint = 0.045 |
14152 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.093 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.31 e Å−3 |
2759 reflections | Δρmin = −0.28 e Å−3 |
156 parameters |
x | y | z | Uiso*/Ueq | ||
Cl8 | 0.17493 (5) | 0.51162 (5) | −0.04294 (3) | 0.02313 (13) | |
O14 | 0.56116 (15) | 0.44942 (12) | 0.39932 (9) | 0.0181 (3) | |
N1 | 0.56968 (17) | 0.44244 (14) | 0.30049 (10) | 0.0154 (3) | |
C2 | 0.7240 (2) | 0.50923 (18) | 0.30829 (13) | 0.0163 (4) | |
H2 | 0.7174 | 0.5504 | 0.2436 | 0.020* | |
C3 | 0.7334 (2) | 0.61983 (18) | 0.38466 (14) | 0.0196 (4) | |
H3A | 0.8390 | 0.6188 | 0.4365 | 0.024* | |
H3B | 0.7167 | 0.7076 | 0.3530 | 0.024* | |
C4 | 0.5964 (2) | 0.58590 (18) | 0.42662 (14) | 0.0186 (4) | |
H4 | 0.6323 | 0.5960 | 0.4996 | 0.022* | |
C5 | 0.4426 (2) | 0.66211 (18) | 0.38113 (13) | 0.0200 (4) | |
H5A | 0.3640 | 0.6436 | 0.4172 | 0.024* | |
H5B | 0.4659 | 0.7578 | 0.3856 | 0.024* | |
C5a | 0.3718 (2) | 0.62281 (17) | 0.27530 (13) | 0.0167 (4) | |
C6 | 0.2428 (2) | 0.69009 (18) | 0.21303 (14) | 0.0188 (4) | |
H6 | 0.1953 | 0.7611 | 0.2378 | 0.023* | |
C7 | 0.1822 (2) | 0.65572 (18) | 0.11573 (14) | 0.0186 (4) | |
H7 | 0.0938 | 0.7025 | 0.0732 | 0.022* | |
C8 | 0.2519 (2) | 0.55219 (18) | 0.08087 (13) | 0.0175 (4) | |
C9 | 0.3788 (2) | 0.47884 (17) | 0.13986 (13) | 0.0163 (4) | |
C9a | 0.4367 (2) | 0.51727 (17) | 0.23824 (13) | 0.0154 (4) | |
C21 | 0.8665 (2) | 0.41759 (18) | 0.33704 (13) | 0.0181 (4) | |
C22 | 0.8561 (2) | 0.29420 (19) | 0.36188 (14) | 0.0239 (4) | |
H22A | 0.9496 | 0.2399 | 0.3789 | 0.029* | |
H22B | 0.7551 | 0.2592 | 0.3628 | 0.029* | |
C23 | 1.0216 (2) | 0.4792 (2) | 0.33394 (16) | 0.0287 (5) | |
H23A | 1.1069 | 0.4122 | 0.3484 | 0.043* | |
H23B | 1.0519 | 0.5498 | 0.3829 | 0.043* | |
H23C | 1.0076 | 0.5159 | 0.2685 | 0.043* | |
C91 | 0.4504 (2) | 0.36465 (18) | 0.10169 (14) | 0.0207 (4) | |
H91A | 0.3637 | 0.3112 | 0.0586 | 0.031* | |
H91B | 0.5136 | 0.3107 | 0.1568 | 0.031* | |
H91C | 0.5210 | 0.3972 | 0.0646 | 0.031* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl8 | 0.0201 (2) | 0.0286 (3) | 0.0186 (2) | −0.00090 (19) | 0.00268 (17) | −0.0012 (2) |
O14 | 0.0235 (7) | 0.0183 (7) | 0.0148 (6) | −0.0017 (5) | 0.0089 (5) | 0.0008 (5) |
N1 | 0.0172 (8) | 0.0166 (8) | 0.0132 (7) | −0.0004 (6) | 0.0056 (6) | 0.0009 (6) |
C2 | 0.0166 (9) | 0.0157 (9) | 0.0170 (9) | −0.0017 (7) | 0.0058 (7) | 0.0010 (7) |
C3 | 0.0188 (9) | 0.0180 (9) | 0.0220 (10) | −0.0020 (7) | 0.0062 (8) | −0.0022 (8) |
C4 | 0.0221 (10) | 0.0168 (9) | 0.0171 (9) | −0.0024 (7) | 0.0060 (7) | −0.0035 (7) |
C5 | 0.0217 (10) | 0.0182 (10) | 0.0215 (10) | −0.0002 (7) | 0.0087 (8) | −0.0036 (8) |
C5a | 0.0166 (9) | 0.0157 (9) | 0.0194 (9) | −0.0030 (7) | 0.0079 (7) | −0.0006 (7) |
C6 | 0.0179 (9) | 0.0150 (9) | 0.0255 (10) | −0.0006 (7) | 0.0097 (8) | 0.0001 (8) |
C7 | 0.0136 (9) | 0.0169 (9) | 0.0249 (10) | −0.0007 (7) | 0.0052 (7) | 0.0029 (8) |
C8 | 0.0168 (9) | 0.0195 (9) | 0.0159 (9) | −0.0042 (7) | 0.0044 (7) | −0.0013 (7) |
C9 | 0.0161 (8) | 0.0150 (9) | 0.0194 (9) | −0.0032 (7) | 0.0078 (7) | −0.0002 (7) |
C9a | 0.0140 (8) | 0.0142 (9) | 0.0196 (9) | −0.0019 (7) | 0.0073 (7) | 0.0013 (7) |
C21 | 0.0179 (9) | 0.0214 (10) | 0.0144 (9) | 0.0024 (7) | 0.0038 (7) | −0.0016 (7) |
C22 | 0.0236 (10) | 0.0235 (11) | 0.0237 (10) | 0.0045 (8) | 0.0057 (8) | 0.0007 (8) |
C23 | 0.0181 (10) | 0.0294 (12) | 0.0382 (12) | 0.0028 (8) | 0.0077 (9) | 0.0023 (9) |
C91 | 0.0218 (10) | 0.0204 (10) | 0.0205 (10) | 0.0013 (8) | 0.0072 (8) | −0.0028 (8) |
Cl8—C8 | 1.7420 (18) | C6—C7 | 1.375 (3) |
O14—N1 | 1.4389 (18) | C6—H6 | 0.9500 |
O14—C4 | 1.446 (2) | C7—C8 | 1.379 (3) |
N1—C9a | 1.443 (2) | C7—H7 | 0.9500 |
N1—C2 | 1.476 (2) | C8—C9 | 1.385 (3) |
C2—C21 | 1.502 (2) | C9—C9a | 1.399 (2) |
C2—C3 | 1.551 (2) | C9—C91 | 1.494 (2) |
C2—H2 | 1.0000 | C21—C22 | 1.312 (3) |
C3—C4 | 1.524 (3) | C21—C23 | 1.498 (3) |
C3—H3A | 0.9900 | C22—H22A | 0.9500 |
C3—H3B | 0.9900 | C22—H22B | 0.9500 |
C4—C5 | 1.510 (3) | C23—H23A | 0.9800 |
C4—H4 | 1.0000 | C23—H23B | 0.9800 |
C5—C5a | 1.505 (3) | C23—H23C | 0.9800 |
C5—H5A | 0.9900 | C91—H91A | 0.9800 |
C5—H5B | 0.9900 | C91—H91B | 0.9800 |
C5a—C6 | 1.382 (3) | C91—H91C | 0.9800 |
C5a—C9a | 1.387 (2) | ||
N1—O14—C4 | 104.04 (12) | C7—C6—H6 | 119.5 |
O14—N1—C9a | 108.11 (13) | C5a—C6—H6 | 119.5 |
O14—N1—C2 | 102.60 (12) | C6—C7—C8 | 118.91 (17) |
C9a—N1—C2 | 110.15 (14) | C6—C7—H7 | 120.5 |
N1—C2—C21 | 112.98 (15) | C8—C7—H7 | 120.5 |
N1—C2—C3 | 103.81 (14) | C7—C8—C9 | 123.00 (17) |
C21—C2—C3 | 113.06 (14) | C7—C8—Cl8 | 118.15 (14) |
N1—C2—H2 | 108.9 | C9—C8—Cl8 | 118.84 (14) |
C21—C2—H2 | 108.9 | C8—C9—C9a | 116.15 (16) |
C3—C2—H2 | 108.9 | C8—C9—C91 | 122.45 (16) |
C4—C3—C2 | 103.45 (14) | C9a—C9—C91 | 121.40 (16) |
C4—C3—H3A | 111.1 | C5a—C9a—C9 | 122.37 (16) |
C2—C3—H3A | 111.1 | C5a—C9a—N1 | 120.81 (16) |
C4—C3—H3B | 111.1 | C9—C9a—N1 | 116.82 (15) |
C2—C3—H3B | 111.1 | C22—C21—C23 | 122.83 (18) |
H3A—C3—H3B | 109.0 | C22—C21—C2 | 123.14 (17) |
O14—C4—C5 | 106.64 (14) | C23—C21—C2 | 114.03 (16) |
O14—C4—C3 | 103.70 (14) | C21—C22—H22A | 120.0 |
C5—C4—C3 | 114.12 (16) | C21—C22—H22B | 120.0 |
O14—C4—H4 | 110.7 | H22A—C22—H22B | 120.0 |
C5—C4—H4 | 110.7 | C21—C23—H23A | 109.5 |
C3—C4—H4 | 110.7 | C21—C23—H23B | 109.5 |
C5a—C5—C4 | 109.68 (15) | H23A—C23—H23B | 109.5 |
C5a—C5—H5A | 109.7 | C21—C23—H23C | 109.5 |
C4—C5—H5A | 109.7 | H23A—C23—H23C | 109.5 |
C5a—C5—H5B | 109.7 | H23B—C23—H23C | 109.5 |
C4—C5—H5B | 109.7 | C9—C91—H91A | 109.5 |
H5A—C5—H5B | 108.2 | C9—C91—H91B | 109.5 |
C6—C5a—C9a | 118.60 (17) | H91A—C91—H91B | 109.5 |
C6—C5a—C5 | 121.47 (16) | C9—C91—H91C | 109.5 |
C9a—C5a—C5 | 119.93 (16) | H91A—C91—H91C | 109.5 |
C7—C6—C5a | 120.94 (17) | H91B—C91—H91C | 109.5 |
C4—O14—N1—C9a | −67.83 (15) | C7—C8—C9—C9a | −1.4 (3) |
C4—O14—N1—C2 | 48.57 (15) | Cl8—C8—C9—C9a | 179.20 (13) |
O14—N1—C2—C21 | 87.38 (16) | C7—C8—C9—C91 | 178.36 (17) |
C9a—N1—C2—C21 | −157.70 (14) | Cl8—C8—C9—C91 | −1.1 (2) |
O14—N1—C2—C3 | −35.46 (16) | C6—C5a—C9a—C9 | 1.6 (3) |
C9a—N1—C2—C3 | 79.46 (16) | C5—C5a—C9a—C9 | −178.10 (16) |
N1—C2—C3—C4 | 10.65 (18) | C6—C5a—C9a—N1 | −179.01 (15) |
C21—C2—C3—C4 | −112.14 (16) | C5—C5a—C9a—N1 | 1.3 (3) |
N1—O14—C4—C5 | 79.72 (16) | C8—C9—C9a—C5a | −0.1 (3) |
N1—O14—C4—C3 | −41.07 (16) | C91—C9—C9a—C5a | −179.88 (17) |
C2—C3—C4—O14 | 17.77 (17) | C8—C9—C9a—N1 | −179.53 (15) |
C2—C3—C4—C5 | −97.83 (17) | C91—C9—C9a—N1 | 0.7 (2) |
O14—C4—C5—C5a | −47.42 (19) | O14—N1—C9a—C5a | 28.2 (2) |
C3—C4—C5—C5a | 66.5 (2) | C2—N1—C9a—C5a | −83.20 (19) |
C4—C5—C5a—C6 | −171.23 (16) | O14—N1—C9a—C9 | −152.41 (14) |
C4—C5—C5a—C9a | 8.5 (2) | C2—N1—C9a—C9 | 96.21 (18) |
C9a—C5a—C6—C7 | −1.7 (3) | N1—C2—C21—C22 | −6.3 (2) |
C5—C5a—C6—C7 | 178.05 (17) | C3—C2—C21—C22 | 111.2 (2) |
C5a—C6—C7—C8 | 0.2 (3) | N1—C2—C21—C23 | 173.15 (15) |
C6—C7—C8—C9 | 1.4 (3) | C3—C2—C21—C23 | −69.3 (2) |
C6—C7—C8—Cl8 | −179.22 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···O14i | 1.00 | 2.57 | 3.202 (2) | 121 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
C13H13Cl2NO | F(000) = 280 |
Mr = 270.14 | Dx = 1.483 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 2751 reflections |
a = 10.4753 (13) Å | θ = 3.2–27.5° |
b = 5.4759 (8) Å | µ = 0.52 mm−1 |
c = 10.9632 (12) Å | T = 120 K |
β = 105.791 (13)° | Block, colourless |
V = 605.13 (13) Å3 | 0.30 × 0.25 × 0.16 mm |
Z = 2 |
Bruker Nonius KappaCCD area-detector diffractometer | 2751 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 2385 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.053 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.2° |
ϕ and ω scans | h = −13→12 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −7→7 |
Tmin = 0.826, Tmax = 0.922 | l = −14→14 |
10313 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)] = 0.045 | H-atom parameters constrained |
wR(F2) = 0.115 | w = 1/[σ2(Fo2) + (0.0738P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
2751 reflections | Δρmax = 0.42 e Å−3 |
156 parameters | Δρmin = −0.56 e Å−3 |
1 restraint | Absolute structure: Flack (1983), with 1223 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.61 (7) |
C13H13Cl2NO | V = 605.13 (13) Å3 |
Mr = 270.14 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 10.4753 (13) Å | µ = 0.52 mm−1 |
b = 5.4759 (8) Å | T = 120 K |
c = 10.9632 (12) Å | 0.30 × 0.25 × 0.16 mm |
β = 105.791 (13)° |
Bruker Nonius KappaCCD area-detector diffractometer | 2751 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2385 reflections with I > 2σ(I) |
Tmin = 0.826, Tmax = 0.922 | Rint = 0.053 |
10313 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | H-atom parameters constrained |
wR(F2) = 0.115 | Δρmax = 0.42 e Å−3 |
S = 1.05 | Δρmin = −0.56 e Å−3 |
2751 reflections | Absolute structure: Flack (1983), with 1223 Friedel pairs |
156 parameters | Absolute structure parameter: 0.61 (7) |
1 restraint |
x | y | z | Uiso*/Ueq | ||
Cl7 | 0.27068 (6) | 0.76451 (14) | 0.35134 (6) | 0.0354 (2) | |
Cl9 | 0.51226 (6) | 0.11718 (13) | 0.12174 (6) | 0.03107 (19) | |
O14 | 0.86993 (18) | 0.3899 (4) | 0.38211 (17) | 0.0286 (5) | |
N1 | 0.7617 (2) | 0.3387 (4) | 0.2721 (2) | 0.0235 (5) | |
C2 | 0.8024 (3) | 0.4726 (5) | 0.1711 (3) | 0.0255 (6) | |
H2 | 0.7214 | 0.5193 | 0.1028 | 0.031* | |
C3 | 0.8690 (3) | 0.7046 (5) | 0.2378 (3) | 0.0281 (6) | |
H3A | 0.9553 | 0.7339 | 0.2198 | 0.034* | |
H3B | 0.8115 | 0.8493 | 0.2112 | 0.034* | |
C4 | 0.8875 (3) | 0.6476 (6) | 0.3783 (3) | 0.0299 (6) | |
H4 | 0.9785 | 0.6953 | 0.4296 | 0.036* | |
C5 | 0.7833 (3) | 0.7637 (6) | 0.4311 (2) | 0.0295 (6) | |
H5A | 0.8064 | 0.7395 | 0.5240 | 0.035* | |
H5B | 0.7794 | 0.9414 | 0.4139 | 0.035* | |
C5a | 0.6502 (3) | 0.6495 (5) | 0.3702 (2) | 0.0243 (6) | |
C6 | 0.5347 (3) | 0.7452 (7) | 0.3892 (2) | 0.0282 (6) | |
H6 | 0.5381 | 0.8804 | 0.4443 | 0.034* | |
C7 | 0.4142 (3) | 0.6412 (6) | 0.3269 (2) | 0.0276 (6) | |
C8 | 0.4050 (3) | 0.4469 (6) | 0.2457 (3) | 0.0265 (6) | |
H8 | 0.3214 | 0.3789 | 0.2027 | 0.032* | |
C9 | 0.5213 (3) | 0.3541 (5) | 0.2288 (2) | 0.0256 (6) | |
C9a | 0.6444 (2) | 0.4477 (5) | 0.2917 (2) | 0.0224 (5) | |
C21 | 0.8904 (3) | 0.3158 (5) | 0.1152 (2) | 0.0264 (6) | |
C22 | 0.8488 (3) | 0.2504 (7) | −0.0042 (3) | 0.0401 (7) | |
H22A | 0.9043 | 0.1553 | −0.0412 | 0.048* | |
H22B | 0.7631 | 0.2981 | −0.0536 | 0.048* | |
C23 | 1.0237 (3) | 0.2459 (7) | 0.1965 (3) | 0.0338 (6) | |
H23A | 1.0690 | 0.1443 | 0.1476 | 0.051* | |
H23B | 1.0137 | 0.1537 | 0.2700 | 0.051* | |
H23C | 1.0760 | 0.3935 | 0.2255 | 0.051* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl7 | 0.0247 (3) | 0.0457 (5) | 0.0394 (4) | 0.0035 (3) | 0.0150 (3) | −0.0051 (3) |
Cl9 | 0.0239 (3) | 0.0359 (4) | 0.0342 (3) | −0.0041 (3) | 0.0093 (2) | −0.0080 (3) |
O14 | 0.0199 (9) | 0.0371 (12) | 0.0268 (10) | −0.0008 (8) | 0.0030 (7) | 0.0008 (8) |
N1 | 0.0163 (10) | 0.0292 (12) | 0.0248 (10) | 0.0019 (9) | 0.0052 (8) | 0.0023 (9) |
C2 | 0.0185 (12) | 0.0323 (16) | 0.0273 (13) | −0.0006 (11) | 0.0089 (10) | 0.0055 (11) |
C3 | 0.0245 (13) | 0.0270 (15) | 0.0365 (15) | −0.0020 (11) | 0.0144 (11) | 0.0019 (12) |
C4 | 0.0210 (13) | 0.0355 (18) | 0.0323 (13) | −0.0022 (12) | 0.0057 (10) | −0.0040 (13) |
C5 | 0.0268 (13) | 0.0341 (15) | 0.0278 (13) | −0.0026 (13) | 0.0077 (10) | −0.0067 (14) |
C5a | 0.0227 (12) | 0.0273 (16) | 0.0232 (12) | 0.0016 (12) | 0.0070 (9) | 0.0035 (11) |
C6 | 0.0286 (13) | 0.0346 (16) | 0.0232 (12) | 0.0025 (13) | 0.0101 (10) | 0.0001 (12) |
C7 | 0.0225 (12) | 0.0359 (17) | 0.0269 (13) | −0.0012 (13) | 0.0110 (10) | 0.0032 (13) |
C8 | 0.0184 (12) | 0.0344 (15) | 0.0283 (13) | 0.0000 (11) | 0.0093 (11) | −0.0004 (11) |
C9 | 0.0235 (13) | 0.0310 (16) | 0.0246 (13) | 0.0016 (12) | 0.0106 (10) | 0.0010 (12) |
C9a | 0.0175 (12) | 0.0265 (14) | 0.0245 (13) | 0.0012 (10) | 0.0082 (9) | 0.0032 (11) |
C21 | 0.0182 (12) | 0.0297 (17) | 0.0338 (14) | −0.0027 (11) | 0.0113 (11) | 0.0028 (12) |
C22 | 0.0323 (15) | 0.055 (2) | 0.0368 (15) | 0.0029 (16) | 0.0157 (12) | −0.0042 (17) |
C23 | 0.0216 (13) | 0.0347 (16) | 0.0462 (16) | 0.0006 (13) | 0.0113 (12) | −0.0021 (15) |
Cl7—C7 | 1.734 (3) | C5—H5B | 0.9900 |
Cl9—C9 | 1.735 (3) | C5a—C6 | 1.386 (4) |
O14—C4 | 1.425 (4) | C5a—C9a | 1.391 (4) |
O14—N1 | 1.441 (3) | C6—C7 | 1.383 (4) |
N1—C9a | 1.433 (3) | C6—H6 | 0.9500 |
N1—C2 | 1.483 (3) | C7—C8 | 1.374 (4) |
C2—C21 | 1.508 (4) | C8—C9 | 1.378 (4) |
C2—C3 | 1.536 (4) | C8—H8 | 0.9500 |
C2—H2 | 1.0000 | C9—C9a | 1.385 (4) |
C3—C4 | 1.531 (4) | C21—C22 | 1.312 (4) |
C3—H3A | 0.9900 | C21—C23 | 1.488 (4) |
C3—H3B | 0.9900 | C22—H22A | 0.9500 |
C4—C5 | 1.508 (4) | C22—H22B | 0.9500 |
C4—H4 | 1.0000 | C23—H23A | 0.9800 |
C5—C5a | 1.508 (4) | C23—H23B | 0.9800 |
C5—H5A | 0.9900 | C23—H23C | 0.9800 |
C4—O14—N1 | 104.29 (19) | C6—C5a—C5 | 121.1 (3) |
C9a—N1—O14 | 107.7 (2) | C9a—C5a—C5 | 118.9 (2) |
C9a—N1—C2 | 109.8 (2) | C7—C6—C5a | 119.1 (3) |
O14—N1—C2 | 102.02 (19) | C7—C6—H6 | 120.4 |
N1—C2—C21 | 110.7 (2) | C5a—C6—H6 | 120.4 |
N1—C2—C3 | 103.8 (2) | C8—C7—C6 | 122.2 (3) |
C21—C2—C3 | 114.6 (2) | C8—C7—Cl7 | 119.4 (2) |
N1—C2—H2 | 109.2 | C6—C7—Cl7 | 118.4 (2) |
C21—C2—H2 | 109.2 | C7—C8—C9 | 117.6 (3) |
C3—C2—H2 | 109.2 | C7—C8—H8 | 121.2 |
C4—C3—C2 | 103.1 (2) | C9—C8—H8 | 121.2 |
C4—C3—H3A | 111.1 | C8—C9—C9a | 122.3 (3) |
C2—C3—H3A | 111.1 | C8—C9—Cl9 | 118.6 (2) |
C4—C3—H3B | 111.1 | C9a—C9—Cl9 | 119.1 (2) |
C2—C3—H3B | 111.1 | C9—C9a—C5a | 118.7 (2) |
H3A—C3—H3B | 109.1 | C9—C9a—N1 | 119.4 (2) |
O14—C4—C5 | 107.1 (3) | C5a—C9a—N1 | 121.9 (2) |
O14—C4—C3 | 104.4 (2) | C22—C21—C23 | 122.1 (3) |
C5—C4—C3 | 113.1 (2) | C22—C21—C2 | 119.2 (3) |
O14—C4—H4 | 110.7 | C23—C21—C2 | 118.7 (2) |
C5—C4—H4 | 110.7 | C21—C22—H22A | 120.0 |
C3—C4—H4 | 110.7 | C21—C22—H22B | 120.0 |
C5a—C5—C4 | 109.5 (2) | H22A—C22—H22B | 120.0 |
C5a—C5—H5A | 109.8 | C21—C23—H23A | 109.5 |
C4—C5—H5A | 109.8 | C21—C23—H23B | 109.5 |
C5a—C5—H5B | 109.8 | H23A—C23—H23B | 109.5 |
C4—C5—H5B | 109.8 | C21—C23—H23C | 109.5 |
H5A—C5—H5B | 108.2 | H23A—C23—H23C | 109.5 |
C6—C5a—C9a | 120.0 (3) | H23B—C23—H23C | 109.5 |
C4—O14—N1—C9a | −67.0 (2) | C6—C7—C8—C9 | 0.9 (4) |
C4—O14—N1—C2 | 48.5 (2) | Cl7—C7—C8—C9 | −180.0 (2) |
C9a—N1—C2—C21 | −159.2 (2) | C7—C8—C9—C9a | 0.9 (4) |
O14—N1—C2—C21 | 86.8 (2) | C7—C8—C9—Cl9 | −177.3 (2) |
C9a—N1—C2—C3 | 77.3 (3) | C8—C9—C9a—C5a | −3.0 (4) |
O14—N1—C2—C3 | −36.7 (2) | Cl9—C9—C9a—C5a | 175.2 (2) |
N1—C2—C3—C4 | 12.8 (3) | C8—C9—C9a—N1 | 178.5 (2) |
C21—C2—C3—C4 | −108.1 (3) | Cl9—C9—C9a—N1 | −3.3 (4) |
N1—O14—C4—C5 | 80.3 (2) | C6—C5a—C9a—C9 | 3.3 (4) |
N1—O14—C4—C3 | −39.9 (2) | C5—C5a—C9a—C9 | −175.5 (2) |
C2—C3—C4—O14 | 15.8 (3) | C6—C5a—C9a—N1 | −178.3 (2) |
C2—C3—C4—C5 | −100.2 (3) | C5—C5a—C9a—N1 | 3.0 (4) |
O14—C4—C5—C5a | −47.6 (3) | O14—N1—C9a—C9 | −155.3 (2) |
C3—C4—C5—C5a | 66.8 (3) | C2—N1—C9a—C9 | 94.4 (3) |
C4—C5—C5a—C6 | −171.3 (3) | O14—N1—C9a—C5a | 26.3 (3) |
C4—C5—C5a—C9a | 7.4 (4) | C2—N1—C9a—C5a | −84.0 (3) |
C9a—C5a—C6—C7 | −1.6 (4) | N1—C2—C21—C22 | 115.5 (3) |
C5—C5a—C6—C7 | 177.1 (3) | C3—C2—C21—C22 | −127.5 (3) |
C5a—C6—C7—C8 | −0.5 (4) | N1—C2—C21—C23 | −66.1 (3) |
C5a—C6—C7—Cl7 | −179.7 (2) | C3—C2—C21—C23 | 50.9 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···O14i | 1.00 | 2.48 | 3.389 (4) | 151 |
Symmetry code: (i) −x+2, y+1/2, −z+1. |
Experimental details
(I) | (II) | (III) | (IV) | |
Crystal data | ||||
Chemical formula | C12H13NO | C14H16ClNO | C15H18ClNO | C15H18ClNO |
Mr | 187.23 | 249.73 | 263.75 | 263.75 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21/c | Monoclinic, P21/n | Triclinic, P1 |
Temperature (K) | 120 | 120 | 120 | 120 |
a, b, c (Å) | 9.8070 (13), 7.3982 (7), 13.738 (2) | 5.6445 (5), 25.744 (3), 8.3894 (11) | 11.0631 (7), 5.7212 (5), 21.203 (6) | 5.2890 (9), 9.3076 (16), 13.551 (3) |
α, β, γ (°) | 90, 105.441 (11), 90 | 90, 95.124 (9), 90 | 90, 102.587 (16), 90 | 94.554 (15), 94.684 (15), 97.298 (14) |
V (Å3) | 960.8 (2) | 1214.2 (2) | 1309.8 (4) | 656.7 (2) |
Z | 4 | 4 | 4 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.08 | 0.30 | 0.28 | 0.28 |
Crystal size (mm) | 0.31 × 0.29 × 0.20 | 0.44 × 0.24 × 0.20 | 0.40 × 0.19 × 0.12 | 0.32 × 0.26 × 0.11 |
Data collection | ||||
Diffractometer | Bruker Nonius KappaCCD area-detector diffractometer | Bruker Nonius KappaCCD area-detector diffractometer | Bruker Nonius KappaCCD area-detector diffractometer | Bruker Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.969, 0.984 | 0.895, 0.943 | 0.869, 0.967 | 0.932, 0.970 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13902, 2200, 1488 | 15979, 2783, 1929 | 16325, 2306, 1661 | 16228, 3005, 2348 |
Rint | 0.054 | 0.046 | 0.105 | 0.041 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 | 0.596 | 0.650 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.107, 1.06 | 0.048, 0.129, 1.08 | 0.068, 0.155, 1.11 | 0.049, 0.113, 1.11 |
No. of reflections | 2200 | 2783 | 2306 | 3005 |
No. of parameters | 127 | 156 | 166 | 166 |
No. of restraints | 0 | 0 | 0 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.17, −0.24 | 0.29, −0.30 | 0.43, −0.39 | 0.29, −0.36 |
Absolute structure | ? | ? | ? | ? |
Absolute structure parameter | ? | ? | ? | ? |
(V) | (VI) | |
Crystal data | ||
Chemical formula | C14H16ClNO | C13H13Cl2NO |
Mr | 249.73 | 270.14 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21 |
Temperature (K) | 120 | 120 |
a, b, c (Å) | 8.6828 (11), 10.1456 (6), 14.2976 (16) | 10.4753 (13), 5.4759 (8), 10.9632 (12) |
α, β, γ (°) | 90, 107.587 (9), 90 | 90, 105.791 (13), 90 |
V (Å3) | 1200.6 (2) | 605.13 (13) |
Z | 4 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.30 | 0.52 |
Crystal size (mm) | 0.50 × 0.17 × 0.14 | 0.30 × 0.25 × 0.16 |
Data collection | ||
Diffractometer | Bruker Nonius KappaCCD area-detector diffractometer | Bruker Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.844, 0.959 | 0.826, 0.922 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14152, 2759, 2083 | 10313, 2751, 2385 |
Rint | 0.045 | 0.053 |
(sin θ/λ)max (Å−1) | 0.650 | 0.649 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.093, 1.07 | 0.045, 0.115, 1.05 |
No. of reflections | 2759 | 2751 |
No. of parameters | 156 | 156 |
No. of restraints | 0 | 1 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.31, −0.28 | 0.42, −0.56 |
Absolute structure | ? | Flack (1983), with 1223 Friedel pairs |
Absolute structure parameter | ? | 0.61 (7) |
Computer programs: COLLECT (Nonius, 1999), DIRAX/LSQ (Duisenberg et al., 2000), EVALCCD (Duisenberg et al., 2003), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
Ring-puckering parametersa | |||||
Five-membered ring | Six-membered ring | ||||
Compound | Q2 | ϕ2 | Q | θ | ϕ |
(I) | 0.449 (2) | 196.9 (2) | 0.629 (2) | 53.8 (2) | 345.3 (2) |
(II) | 0.445 (2) | 198.4 (3) | 0.613 (2) | 51.1 (2) | 344.1 (3) |
(III) | 0.449 (3) | 199.1 (5) | 0.631 (3) | 55.6 (3) | 345.3 (4) |
(IV) | 0.445 (2) | 198.8 (3) | 0.623 (2) | 52.7 (2) | 347.9 (2) |
(V) | 0.435 (2) | 193.5 (3) | 0.621 (2) | 52.4 (2) | 345.2 (2) |
(VI) | 0.434 (3) | 196.6 (4) | 0.618 (3) | 53.5 (3) | 344.5 (3) |
Torsion angles N1—C2—C21—C22 | |||||
(I) | 126.62 (16) | ||||
(II) | 146.9 (2) | ||||
(III) | 144.9 (3) | ||||
(IV) | -108.4 (2) | ||||
(V) | -6.3 (2) | ||||
(VI) | 115.5 (3) |
Note: (a) Ring-puckering parameters refer to the atom sequences O14/N1/C2/C3/C4 and O14/N1/C9a/C5a/C5/C4, respectively. |
Compound | D—H···A | D—H | H···A | D···A | D—H···A |
(I) | C4—H4···O14i | 1.00 | 2.60 | 3.209 (2) | 119 |
C6—H6···Cg1ii | 0.95 | 2.58 | 3.469 (5) | 156 | |
C22—H22B···Cg1iii | 0.95 | 2.71 | 3.610 (5) | 158 | |
(II) | C5—H5B···O14iv | 0.99 | 2.58 | 3.570 (3) | 174 |
(III) | C5—H5A···Cg1v | 0.99 | 2.79 | 3.730 (4) | 158 |
(IV) | C5—H5B···O14iv | 0.99 | 2.39 | 3.358 (3) | 166 |
(V) | C4—H4···O14vi | 1.00 | 2.57 | 3.202 (2) | 121 |
(VI) | C4—H4···O14vii | 1.00 | 2.48 | 3.389 (4) | 151 |
Note: Cg1 represents the centroid of the C5a/C6–C9/C9a ring. Symmetry codes: (i) 1 - x, 1 - y, -z; (ii) 1/2 - x, -1/2 + y, 1/2 - z; (iii) 3/2 - x, 1/2 + y, 1/2 - z; (iv) -1 + x, y, z; (v) 2 - x, 2 - y, 1 - z; (vi) 1 - x, 1 - y, 1 - z; (vii) 2 - x, 1/2 + y, 1 - z. |
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We report here the structures of six differently-substituted 2-vinyl-2,3,4,5-tetrahydro-1H-1,4-epoxy-1-benzazepines, (I)–(VI) (Fig. 1), which exhibit interesting variations in their intermolecular hydrogen-bonding arrangements. The work reported here is a continuation of a wider structural study of substituted tetrahydroepoxybenzazepines (Acosta et al., 2008, 2010; Blanco et al., 2008; Gómez et al., 2008, 2009, 2010), and the underlying synthetic rationale and the potential applications of these compounds have already been discussed (Acosta et al., 2008).
Compounds (I)–(V) (see scheme and Fig. 1) all crystallize as racemic mixtures in centrosymmetric space groups. In each of (I)–(V), the reference molecule was selected as having the R configuration at atom C4, and on this basis the reference molecules have the S configuration at atom C2 in (I)–(III) and (V), but in (IV) the reference molecule has the R configuration at C2, so that (III) and (IV) are, in fact, diastereoisomers. In addition, (II) and (V) are positional isomers. By contrast, (VI) crystallizes as an inversion twin in the Sohnke space group P21. For the crystal selected for data collection, the twin fractions were found to be unequal, 0.39 (7) for the (2S,4R) form and 0.61 (7) for the (2R,4S) form, although the deviations from 0.5 are not large compared with the experimental uncertainty. As the synthesis of these compounds involves no reagent or solvent capable of imparting any enantiomeric bias, it is to be expected that (V) [(VI)?], as well as (I)–(V), was synthesized as a true racemic mixture, and it is therefore possible that this compound crystallizes with somewhat different twin fractions in the various individual crystals.
The ring-puckering parameters (Cremer & Pople, 1975) for (I)–(VI) (Table 1) show that the overall shape of the fused heterocyclic system varies very little, regardless of the number and location of the methyl groups in the vinyl substituent or the configuration at atom C2. On the other hand, the orientation of the vinyl group relative to the fused bicyclic system, as defined by the values of the N1—C2—C21—C22 torsion angle (Table 1), shows considerable variation, in particular between the two diasteroisomers (III) and (IV), as expected from the different configurations at C2, but less expectedly for the two prop-1-en-2-yl derivatives, (V) and (VI).
The supramolecular aggregation in (I)–(VI) depends upon C—H···O and C—H···π(arene) hydrogen bonds (Table 2), but (I) is the only example in this group where the crystal structure contains two independent C—H···π(arene) hydrogen bonds.
In (I), the hydrogen bond having atom C6 as the donor links molecules related by the 21 screw axis along (1/4, y, 1/4), while the hydrogen bond in which atom C22 acts as the donor links molecules related by the 21 screw axis along (3/4, y, 1/2), so forming two chain motifs, both running parallel to the [010] direction but in opposite senses. The combination of these chains generates a sheet lying parallel to (001) in the domain 0 < z < 1/2 (Fig. 2) in which all of the molecules have the (2S,4R) configuration. A second sheet, lying in the domain 1/2 < z < 1.0, is related to the first sheet by inversion and contains only molecules with the (2R,4S) configuration. Within the sheet, each aryl ring accepts one hydrogen bond on each face and the angle subtended at the ring centroid Cg1 (ring C5a/C6–C9/C9a) of the reference molecule by the two H···Cg contacts, H6i···Cg1···H22ii, is 167° [symmetry codes: (i) 1/2 - x, 1/2 + y, 1/2 - z; (ii) 3/2 - x, -1/2 + y, 1/2 - z]. Between adjacent sheets, the only direction-specific interaction is a C—H···O contact (Table 2) with an H···O distance which is long and a C—H···O angle which is small, so that this contact cannot realistically be regarded as a structurally significant hydrogen bond. Aromatic π–π stacking interactions are absent from the structure of (I), because of the presence of C—H···π(arene) hydrogen bonds on each face of the aryl ring, so that the supramolecular aggregation in (I) is two-dimensional.
In contrast with the crystal structure of (I), those of (II)–(VI) each contain only a single hydrogen bond, all of the C—H···O type apart from (III), where the hydrogen bond is of the C—H···π(arene) type (Table 2). As found for (I), aromatic π–π stacking interactions are absent from the structures of all of (II)–(VI).
In each of (II) and (IV), molecules related by translation are linked by the C—H···O hydrogen bond to form simple C(4) chains (Bernstein et al., 1995) running parallel to the [100] direction (Fig. 3), but it is clear that, although the same donor and acceptor atoms are involved in these two structures, the mutual orientations of the molecules within the chains are different, as are the dimensions of the C—H···O hydrogen bonds. These differences may be associated with either or both of the differences in the molecular configurations, (2SR,4RS) for (II) and (2RS,4RS) for (IV), and in the space groups, P21/c for (II) and P1 for (IV). In the structure of (II) there are four chains passing through each unit cell, but in the structure of (IV) there are only two. In any specific chain, all of the molecules have the same configuration. As there are no direction-specific interactions between the chains in (II) and (IV), these hydrogen-bonded structures are both one-dimensional.
The hydrogen-bonded structures of (III) and (V), by contrast, both consist of centrosymmetric dimers, built from pairs of symmetry-related C—H···π(arene) hydrogen bonds in (III) (Fig. 4) and from pairs of symmetry-related C—H···O hydrogen bonds in (V), so forming an R22(6) ring having a chair-type conformation (Fig. 5). Within each of these dimers, the two molecules involved are of the opposite configuration and the hydrogen-bonded aggregation in (III) and (V) is thus finite, or zero-dimensional.
The single hydrogen bond in the structure of (VI) utilizes the same donor and acceptor atoms as that in (V), but rather than forming a cyclic dimer as in (V), in (VI) this hydrogen bond now generates a C(3) chain running parallel to the [010] direction and linking molecules related by the 21 screw axis along (1, y, 1/2) (Fig. 6). Again, therefore, the hydrogen-bonded structure is one-dimensional and all the molecules in a specific chain are of the same configuration.
In each of (I), (II), (IV) and (VI), the molecules within a given hydrogen-bonded aggregate, whether the sheet in (I) or the chains in (II), (IV) and (VI), all have the same configuration, whereas in (III) and (V) the hydrogen-bonded dimers both contain pairs of molecules having opposite configurations. Hence, the hydrogen bonding appears to mediate molecular-scale enantiomeric sorting in (I), (II) (IV) and (VI), but enantiomeric pairing in (III) and (V). Within the structure of each of (II)–(IV), atom C5 acts as the hydrogen-bond donor. However, in (II) and (IV), where C—H···O hydrogen bonds are present, these involve the bisectional H atom at C5, denoted H5B, and chain motifs result, but in (III), where a C—H···π(arene) hydrogen bond is present, this involves the axial H atom at C5, denoted H5A, and a ring motif results. Similarly, although the same combination of hydrogen-bond donor and acceptor are present in the structures of (V) and (VI), in (V) this interaction gives rise to a ring motif, whereas in (VI) a chain results, so that the hydrogen-bonded structures of (V) and (VI) are of different dimensionalities. These subtle differences in the hydrogen-bonding patterns do not appear to have any simple or readily-accessible explanations.