Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107053206/av3112sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107053206/av3112Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107053206/av3112IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107053206/av3112IIIsup4.hkl |
CCDC references: 672554; 672555; 672556
For related literature, see: Allen et al. (1987); Auffinger et al. (2004); Bernstein et al. (1995); Cheng et al. (2004); Cremer & Pople (1975); Curphey (2002); Elliott et al. (2006); Etter et al. (1990); Michael et al. (1999, 2001, 2002); Negri et al. (2004); Ponnuswamy & Sony (2006); Roth et al. (1971); Stanovnik & Svete (2004).
The synthesis of compounds (I)–(III) was adapted from the procedure described by Roth et al. (1971) for the preparation of (I). 4-Bromophenacyl bromide (1.05 equivalents) was added to a solution of the appropriate thiolactam [pyrrolidine-2-thione, piperidine-2-thione or azepane-2-thione; 1.0 equivalent; cf. Curphey (2002)] in CHCl3 (5 ml per mmol). After 30 min at room temperature, the solvent was removed on a rotary evaporator. The resulting mixture was kept at room temperature for 48 h to ensure that the reaction went to completion. The resulting solid was partitioned between CH2Cl2 and aqueous saturated K2CO3 solution. The organic phase was separated off and the aqueous phase was extracted with a further portion of CH2Cl2. The combined organic extracts were dried (MgSO4) and evaporated to yield the crude S-alkylated intermediate. This was dissolved in dry CHCl3 (10 ml per mmol) to which triphenylphosphine (2 equivalents) was added. The solution was heated at reflux for 24 h, after which the solvent was evaporated. The crude enaminone product was purified by chromatography on silica gel with dichloromethane as eluant, followed by ethyl acetate–hexane (2:3), to afford the desired products, (I)–(III); characterization as described below.
For compound (I), yield 66%; m.p. 443–446 K [literature value 446–447 K (Roth et al., 1971)]. Spectroscopic analysis: 1H NMR (300 MHz, CDCl3, Me4Si, δ, p.p.m.): 2.00–2.10 (2H, m, 5-H), 2.74 (2H, m, 4-H), 3.66 (2H, m, 6-H), 5.75 (1H, s, 2-H), 7.52 and 7.74 (4H, 2 × m, 8-H, 9-H, 11-H, 12-H), 10.28 (1H, s, NH); 13C NMR (75 MHz, CDCl3, Me4Si, δ, p.p.m.): 186.4 (C═O), 170.0 (C3), 138.9 (C7), 131.3 and 128.7 (C8, C9, C11, C12), 125.1 (C10), 85.9 (C2), 47.9 (C6), 33.0 (C4), 21.3 (C5).
For compound (II), yield 55%; m.p. 388–390 K. Spectroscopic analysis: IR [Any data to be included here?]; 1H NMR (300 MHz, CDCl3, Me4Si, δ, p.p.m.): 1.76–1.88 (4H, m, 5-H and 6-H), 2.50 (2H, t, 4-H), 3.40 (2H, t, 7-H), 5.51 (1H, s, 2-H), 7.50 and 7.71 (4H, 2 × d, J = 8.2 Hz, 9-H, 10-H, 12-H, 13-H), 11.70 (1H, s, NH); 13C NMR (75 MHz, CDCl3, Me4Si, δ, p.p.m.): 185.9 (C═ O), 166.6 (C3), 139.9 (C8), 131.6 and 128.8 (C9, C10, C12, C13), 125.0 (C11), 90.5 (C2), 41.6 (C7), 29.3 (C4), 22.5 and 19.6 (C5, C6). HRMS (EI), found: 281.0216; C13H1481BrNO requires: 281.0238.
For compound (III), yield 76%; m.p. 418–421 K. Spectroscopic analysis: IR [Any data to be included here?]; 1H NMR (300 MHz, CDCl3, Me4Si, δ, p.p.m.): 1.68–1.77 (6H, m, 5-H, 6-H, and 7-H), 2.44 (2H, m, 4-H), 3.43 (2H, d, 8-H), 5.61 (1H, s, 2-H), 7.51 and 7.73 (4H, 2 × m, 10-H, 11-H, 13-H, and 14-H), 11.54 (1H, s, NH); 13C NMR (75 MHz, CDCl3, Me4Si, δ, p.p.m.): 186.6 (C═O), 171.8 (C3), 139.4 (C9), 128.5 and 131.3 (C10, C11, C13, C14), 124.9 (C12), 90.8 (C2), 44.5 (C8), 35.4, 30.6, 29.2 and 25.7 (C4, C5, C6, C7). HRMS (EI), found: 295.0402; C14H1681BrNO requires: 295.0395.
For all three compounds, with the exception of atoms H1, all H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H bond lengths of 0.95 (aromatic CH), 0.99 (CH2) or 0.98 Å (CH3). Isotropic displacement parameters for these atoms were set equal to 1.2 (CH and CH2) or 1.5 (CH3) times Ueq of the parent atom. Atoms H1 were found in difference Fourier maps and refined freely.
For all compounds, data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT-NT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2003).
C12H12BrNO | F(000) = 536 |
Mr = 266.14 | Dx = 1.645 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 4950 reflections |
a = 5.6636 (3) Å | θ = 2.3–28.3° |
b = 18.9255 (9) Å | µ = 3.80 mm−1 |
c = 10.0500 (5) Å | T = 173 K |
β = 94.136 (1)° | Irregular, colourless |
V = 1074.42 (9) Å3 | 0.37 × 0.30 × 0.20 mm |
Z = 4 |
Bruker APEXII CCD area-detector diffractometer | 2595 independent reflections |
Radiation source: fine-focus sealed tube | 2307 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
ϕ and ω scans | θmax = 28.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS in SAINT-NT; Bruker, 2005) Ratio of minimum to maximum apparent transmission: 0.688943. In the Tmin line above, Tmin=Tmax*min_to_max_ratio | h = −7→7 |
Tmin = 0.334, Tmax = 0.517 | k = −25→25 |
9815 measured reflections | l = −12→13 |
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)] = 0.024 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.068 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0387P)2 + 0.4602P] where P = (Fo2 + 2Fc2)/3 |
2595 reflections | (Δ/σ)max = 0.001 |
140 parameters | Δρmax = 0.52 e Å−3 |
0 restraints | Δρmin = −0.60 e Å−3 |
C12H12BrNO | V = 1074.42 (9) Å3 |
Mr = 266.14 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 5.6636 (3) Å | µ = 3.80 mm−1 |
b = 18.9255 (9) Å | T = 173 K |
c = 10.0500 (5) Å | 0.37 × 0.30 × 0.20 mm |
β = 94.136 (1)° |
Bruker APEXII CCD area-detector diffractometer | 2595 independent reflections |
Absorption correction: multi-scan (SADABS in SAINT-NT; Bruker, 2005) Ratio of minimum to maximum apparent transmission: 0.688943. In the Tmin line above, Tmin=Tmax*min_to_max_ratio | 2307 reflections with I > 2σ(I) |
Tmin = 0.334, Tmax = 0.517 | Rint = 0.020 |
9815 measured reflections |
R[F2 > 2σ(F2)] = 0.024 | 0 restraints |
wR(F2) = 0.068 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.52 e Å−3 |
2595 reflections | Δρmin = −0.60 e Å−3 |
140 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.9730 (3) | 0.44906 (9) | 0.25700 (16) | 0.0210 (3) | |
C2 | 1.1484 (3) | 0.49029 (9) | 0.32778 (16) | 0.0226 (3) | |
H2 | 1.1654 | 0.4864 | 0.4222 | 0.027* | |
C3 | 1.2965 (3) | 0.53606 (9) | 0.26607 (16) | 0.0207 (3) | |
C4 | 1.5059 (3) | 0.57216 (9) | 0.33749 (17) | 0.0244 (3) | |
H4A | 1.6340 | 0.5379 | 0.3618 | 0.029* | |
H4B | 1.4601 | 0.5961 | 0.4193 | 0.029* | |
C5 | 1.5838 (4) | 0.62588 (11) | 0.2353 (2) | 0.0344 (4) | |
H5A | 1.5132 | 0.6729 | 0.2499 | 0.041* | |
H5B | 1.7583 | 0.6305 | 0.2404 | 0.041* | |
C6 | 1.4912 (3) | 0.59493 (10) | 0.10163 (18) | 0.0259 (4) | |
H6A | 1.4393 | 0.6326 | 0.0377 | 0.031* | |
H6B | 1.6128 | 0.5655 | 0.0623 | 0.031* | |
C7 | 0.8607 (3) | 0.39012 (9) | 0.33071 (16) | 0.0206 (3) | |
C8 | 0.9786 (3) | 0.35747 (10) | 0.44009 (17) | 0.0243 (3) | |
H8 | 1.1283 | 0.3751 | 0.4737 | 0.029* | |
C9 | 0.8816 (3) | 0.29946 (9) | 0.50130 (19) | 0.0267 (4) | |
H9 | 0.9644 | 0.2771 | 0.5754 | 0.032* | |
C10 | 0.6626 (3) | 0.27499 (9) | 0.45221 (18) | 0.0239 (3) | |
C11 | 0.5389 (3) | 0.30677 (9) | 0.34419 (18) | 0.0250 (4) | |
H11 | 0.3880 | 0.2895 | 0.3120 | 0.030* | |
C12 | 0.6394 (3) | 0.36434 (9) | 0.28375 (17) | 0.0236 (3) | |
H12 | 0.5564 | 0.3864 | 0.2095 | 0.028* | |
N1 | 1.2910 (3) | 0.55212 (8) | 0.13813 (15) | 0.0233 (3) | |
O1 | 0.9111 (2) | 0.45751 (7) | 0.13607 (12) | 0.0269 (3) | |
Br1 | 0.53114 (3) | 0.195674 (10) | 0.535138 (19) | 0.03230 (8) | |
H1 | 1.196 (4) | 0.5339 (12) | 0.088 (2) | 0.029 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0214 (8) | 0.0221 (8) | 0.0194 (7) | 0.0025 (6) | 0.0011 (6) | −0.0006 (6) |
C2 | 0.0256 (8) | 0.0246 (8) | 0.0172 (7) | −0.0012 (6) | −0.0013 (6) | −0.0010 (6) |
C3 | 0.0221 (8) | 0.0193 (7) | 0.0202 (7) | 0.0024 (6) | −0.0015 (6) | −0.0022 (6) |
C4 | 0.0243 (8) | 0.0280 (8) | 0.0200 (8) | −0.0030 (6) | −0.0028 (6) | −0.0026 (7) |
C5 | 0.0393 (11) | 0.0355 (10) | 0.0278 (9) | −0.0141 (8) | −0.0015 (8) | 0.0000 (8) |
C6 | 0.0253 (8) | 0.0288 (9) | 0.0237 (8) | −0.0030 (7) | 0.0016 (7) | 0.0031 (7) |
C7 | 0.0218 (8) | 0.0219 (7) | 0.0183 (7) | 0.0009 (6) | 0.0030 (6) | −0.0035 (6) |
C8 | 0.0211 (8) | 0.0274 (8) | 0.0240 (8) | −0.0023 (6) | −0.0015 (6) | 0.0012 (7) |
C9 | 0.0259 (9) | 0.0277 (9) | 0.0260 (9) | 0.0004 (7) | −0.0013 (7) | 0.0035 (7) |
C10 | 0.0252 (8) | 0.0222 (8) | 0.0250 (8) | −0.0023 (6) | 0.0060 (7) | −0.0019 (7) |
C11 | 0.0219 (8) | 0.0288 (9) | 0.0241 (8) | −0.0033 (6) | 0.0012 (7) | −0.0055 (7) |
C12 | 0.0225 (8) | 0.0282 (8) | 0.0198 (8) | 0.0010 (6) | −0.0009 (6) | −0.0025 (7) |
N1 | 0.0243 (7) | 0.0260 (7) | 0.0189 (7) | −0.0038 (6) | −0.0029 (6) | −0.0003 (6) |
O1 | 0.0299 (7) | 0.0317 (7) | 0.0182 (6) | −0.0038 (5) | −0.0040 (5) | 0.0016 (5) |
Br1 | 0.03206 (12) | 0.02948 (12) | 0.03574 (13) | −0.00845 (7) | 0.00510 (8) | 0.00426 (7) |
C1—O1 | 1.251 (2) | C6—H6A | 0.9900 |
C1—C2 | 1.414 (2) | C6—H6B | 0.9900 |
C1—C7 | 1.505 (2) | C7—C8 | 1.389 (2) |
C2—C3 | 1.383 (2) | C7—C12 | 1.395 (2) |
C2—H2 | 0.9500 | C8—C9 | 1.391 (2) |
C3—N1 | 1.319 (2) | C8—H8 | 0.9500 |
C3—C4 | 1.506 (2) | C9—C10 | 1.382 (3) |
C4—C5 | 1.532 (3) | C9—H9 | 0.9500 |
C4—H4A | 0.9900 | C10—C11 | 1.386 (3) |
C4—H4B | 0.9900 | C10—Br1 | 1.8952 (17) |
C5—C6 | 1.524 (3) | C11—C12 | 1.389 (2) |
C5—H5A | 0.9900 | C11—H11 | 0.9500 |
C5—H5B | 0.9900 | C12—H12 | 0.9500 |
C6—N1 | 1.462 (2) | N1—H1 | 0.79 (2) |
O1—C1—C2 | 123.77 (16) | N1—C6—H6B | 111.3 |
O1—C1—C7 | 118.30 (15) | C5—C6—H6B | 111.3 |
C2—C1—C7 | 117.89 (14) | H6A—C6—H6B | 109.2 |
C3—C2—C1 | 123.14 (15) | C8—C7—C12 | 118.74 (16) |
C3—C2—H2 | 118.4 | C8—C7—C1 | 121.53 (15) |
C1—C2—H2 | 118.4 | C12—C7—C1 | 119.60 (15) |
N1—C3—C2 | 127.51 (15) | C7—C8—C9 | 121.23 (16) |
N1—C3—C4 | 108.80 (15) | C7—C8—H8 | 119.4 |
C2—C3—C4 | 123.56 (15) | C9—C8—H8 | 119.4 |
C3—C4—C5 | 103.69 (14) | C10—C9—C8 | 118.67 (17) |
C3—C4—H4A | 111.0 | C10—C9—H9 | 120.7 |
C5—C4—H4A | 111.0 | C8—C9—H9 | 120.7 |
C3—C4—H4B | 111.0 | C9—C10—C11 | 121.62 (16) |
C5—C4—H4B | 111.0 | C9—C10—Br1 | 118.66 (13) |
H4A—C4—H4B | 109.0 | C11—C10—Br1 | 119.73 (13) |
C6—C5—C4 | 103.80 (14) | C10—C11—C12 | 118.88 (16) |
C6—C5—H5A | 111.0 | C10—C11—H11 | 120.6 |
C4—C5—H5A | 111.0 | C12—C11—H11 | 120.6 |
C6—C5—H5B | 111.0 | C11—C12—C7 | 120.85 (16) |
C4—C5—H5B | 111.0 | C11—C12—H12 | 119.6 |
H5A—C5—H5B | 109.0 | C7—C12—H12 | 119.6 |
N1—C6—C5 | 102.45 (14) | C3—N1—C6 | 114.09 (15) |
N1—C6—H6A | 111.3 | C3—N1—H1 | 119.2 (17) |
C5—C6—H6A | 111.3 | C6—N1—H1 | 126.0 (17) |
O1—C1—C2—C3 | −11.1 (3) | C1—C7—C8—C9 | −174.91 (16) |
C7—C1—C2—C3 | 166.75 (15) | C7—C8—C9—C10 | −0.8 (3) |
C1—C2—C3—N1 | 4.6 (3) | C8—C9—C10—C11 | 0.0 (3) |
C1—C2—C3—C4 | −170.83 (16) | C8—C9—C10—Br1 | 179.71 (13) |
N1—C3—C4—C5 | 13.44 (19) | C9—C10—C11—C12 | 0.4 (3) |
C2—C3—C4—C5 | −170.38 (17) | Br1—C10—C11—C12 | −179.25 (13) |
C3—C4—C5—C6 | −24.22 (19) | C10—C11—C12—C7 | −0.2 (3) |
C4—C5—C6—N1 | 25.86 (19) | C8—C7—C12—C11 | −0.5 (2) |
O1—C1—C7—C8 | 152.04 (16) | C1—C7—C12—C11 | 175.47 (15) |
C2—C1—C7—C8 | −26.0 (2) | C2—C3—N1—C6 | −172.20 (17) |
O1—C1—C7—C12 | −23.8 (2) | C4—C3—N1—C6 | 3.8 (2) |
C2—C1—C7—C12 | 158.19 (16) | C5—C6—N1—C3 | −19.3 (2) |
C12—C7—C8—C9 | 1.0 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1 | 0.79 (2) | 2.25 (2) | 2.798 (2) | 128 (2) |
N1—H1···O1i | 0.79 (2) | 2.30 (2) | 2.9124 (19) | 136 (2) |
C6—H6B···O1ii | 0.99 | 2.72 | 3.524 (3) | 139 |
C4—H4B···Cgiii | 0.99 | 2.71 | 3.679 (2) | 166 |
C6—H6A···Br1iv | 0.99 | 2.97 | 3.701 (2) | 132 |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) x+1, y, z; (iii) −x+2, −y+1, −z+1; (iv) −x+3/2, y+1/2, −z+1/2. |
C13H14BrNO | Z = 2 |
Mr = 280.16 | F(000) = 284 |
Triclinic, P1 | Dx = 1.544 Mg m−3 |
Hall symbol: -P 1 | Melting point = 388–390 K |
a = 6.9303 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 7.6280 (2) Å | Cell parameters from 3654 reflections |
c = 12.1060 (3) Å | θ = 2.8–28.2° |
α = 99.844 (2)° | µ = 3.39 mm−1 |
β = 99.545 (1)° | T = 173 K |
γ = 102.189 (2)° | Block, colourless |
V = 602.64 (3) Å3 | 0.49 × 0.19 × 0.17 mm |
Bruker APEXII CCD area-detector diffractometer | 2903 independent reflections |
Radiation source: fine-focus sealed tube | 2387 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ϕ and ω scans | θmax = 28.0°, θmin = 1.8° |
Absorption correction: integration [face-indexed using XPREP (Bruker, 2005)] | h = −9→8 |
Tmin = 0.380, Tmax = 0.593 | k = −10→10 |
7739 measured reflections | l = −14→15 |
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)] = 0.027 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.107 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | w = 1/[σ2(Fo2) + (0.0621P)2] where P = (Fo2 + 2Fc2)/3 |
2903 reflections | (Δ/σ)max < 0.001 |
149 parameters | Δρmax = 0.52 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
C13H14BrNO | γ = 102.189 (2)° |
Mr = 280.16 | V = 602.64 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.9303 (2) Å | Mo Kα radiation |
b = 7.6280 (2) Å | µ = 3.39 mm−1 |
c = 12.1060 (3) Å | T = 173 K |
α = 99.844 (2)° | 0.49 × 0.19 × 0.17 mm |
β = 99.545 (1)° |
Bruker APEXII CCD area-detector diffractometer | 2903 independent reflections |
Absorption correction: integration [face-indexed using XPREP (Bruker, 2005)] | 2387 reflections with I > 2σ(I) |
Tmin = 0.380, Tmax = 0.593 | Rint = 0.033 |
7739 measured reflections |
R[F2 > 2σ(F2)] = 0.027 | 0 restraints |
wR(F2) = 0.107 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | Δρmax = 0.52 e Å−3 |
2903 reflections | Δρmin = −0.36 e Å−3 |
149 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.7406 (3) | 0.1877 (3) | 0.5893 (2) | 0.0228 (5) | |
C2 | 0.6673 (4) | 0.2560 (3) | 0.49363 (19) | 0.0256 (5) | |
H2 | 0.5432 | 0.2910 | 0.4903 | 0.031* | |
C3 | 0.7663 (4) | 0.2746 (3) | 0.4045 (2) | 0.0244 (5) | |
C4 | 0.6748 (4) | 0.3425 (4) | 0.3038 (2) | 0.0316 (6) | |
H4A | 0.6088 | 0.4397 | 0.3315 | 0.038* | |
H4B | 0.5690 | 0.2401 | 0.2518 | 0.038* | |
C5 | 0.8283 (4) | 0.4190 (4) | 0.2362 (2) | 0.0348 (6) | |
H5A | 0.7570 | 0.4402 | 0.1636 | 0.042* | |
H5B | 0.9163 | 0.5379 | 0.2814 | 0.042* | |
C6 | 0.9547 (5) | 0.2851 (4) | 0.2105 (2) | 0.0364 (6) | |
H6A | 1.0517 | 0.3329 | 0.1648 | 0.044* | |
H6B | 0.8667 | 0.1663 | 0.1650 | 0.044* | |
C7 | 1.0681 (4) | 0.2569 (4) | 0.3216 (2) | 0.0333 (6) | |
H7A | 1.1257 | 0.1495 | 0.3049 | 0.040* | |
H7B | 1.1815 | 0.3660 | 0.3560 | 0.040* | |
C8 | 0.6293 (3) | 0.1936 (3) | 0.6869 (2) | 0.0216 (5) | |
C9 | 0.4242 (4) | 0.1782 (3) | 0.6708 (2) | 0.0228 (5) | |
H9 | 0.3478 | 0.1635 | 0.5955 | 0.027* | |
C10 | 0.3268 (4) | 0.1840 (3) | 0.7629 (2) | 0.0261 (5) | |
H10 | 0.1850 | 0.1710 | 0.7509 | 0.031* | |
C11 | 0.4411 (4) | 0.2090 (3) | 0.8718 (2) | 0.0272 (5) | |
C12 | 0.6478 (4) | 0.2225 (4) | 0.8905 (2) | 0.0316 (6) | |
H12 | 0.7245 | 0.2378 | 0.9658 | 0.038* | |
C13 | 0.7387 (4) | 0.2131 (4) | 0.7975 (2) | 0.0288 (5) | |
H13 | 0.8793 | 0.2201 | 0.8090 | 0.035* | |
Br1 | 0.31212 (4) | 0.22456 (4) | 0.99788 (2) | 0.04251 (14) | |
N1 | 0.9397 (3) | 0.2276 (3) | 0.40349 (18) | 0.0275 (4) | |
H1 | 0.998 (5) | 0.171 (5) | 0.444 (3) | 0.048 (10)* | |
O1 | 0.8965 (3) | 0.1304 (3) | 0.60014 (15) | 0.0302 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0205 (11) | 0.0259 (11) | 0.0203 (11) | 0.0061 (9) | 0.0026 (9) | 0.0022 (9) |
C2 | 0.0257 (12) | 0.0288 (12) | 0.0219 (12) | 0.0076 (10) | 0.0021 (10) | 0.0060 (10) |
C3 | 0.0248 (12) | 0.0233 (11) | 0.0229 (11) | 0.0049 (9) | 0.0029 (9) | 0.0026 (9) |
C4 | 0.0331 (14) | 0.0394 (14) | 0.0277 (13) | 0.0137 (11) | 0.0086 (11) | 0.0136 (11) |
C5 | 0.0471 (16) | 0.0316 (13) | 0.0279 (13) | 0.0082 (12) | 0.0110 (12) | 0.0114 (11) |
C6 | 0.0493 (17) | 0.0371 (14) | 0.0292 (14) | 0.0126 (13) | 0.0199 (12) | 0.0100 (11) |
C7 | 0.0319 (14) | 0.0370 (14) | 0.0358 (14) | 0.0109 (11) | 0.0168 (12) | 0.0081 (11) |
C8 | 0.0221 (11) | 0.0235 (11) | 0.0208 (11) | 0.0092 (9) | 0.0052 (9) | 0.0043 (9) |
C9 | 0.0231 (11) | 0.0251 (11) | 0.0204 (11) | 0.0079 (9) | 0.0023 (9) | 0.0050 (9) |
C10 | 0.0233 (12) | 0.0276 (12) | 0.0280 (12) | 0.0081 (10) | 0.0052 (10) | 0.0056 (10) |
C11 | 0.0328 (13) | 0.0296 (12) | 0.0200 (11) | 0.0072 (10) | 0.0086 (10) | 0.0052 (9) |
C12 | 0.0297 (13) | 0.0448 (15) | 0.0193 (11) | 0.0104 (11) | 0.0008 (10) | 0.0068 (10) |
C13 | 0.0217 (12) | 0.0419 (14) | 0.0230 (12) | 0.0104 (10) | 0.0024 (9) | 0.0067 (10) |
Br1 | 0.0422 (2) | 0.0624 (2) | 0.02652 (17) | 0.01429 (14) | 0.01652 (12) | 0.00835 (13) |
N1 | 0.0272 (11) | 0.0336 (11) | 0.0237 (10) | 0.0081 (9) | 0.0068 (8) | 0.0090 (9) |
O1 | 0.0251 (9) | 0.0455 (11) | 0.0248 (9) | 0.0166 (8) | 0.0055 (7) | 0.0104 (8) |
C1—O1 | 1.244 (3) | C7—N1 | 1.452 (3) |
C1—C2 | 1.412 (3) | C7—H7A | 0.9900 |
C1—C8 | 1.513 (3) | C7—H7B | 0.9900 |
C2—C3 | 1.382 (3) | C8—C9 | 1.379 (3) |
C2—H2 | 0.9500 | C8—C13 | 1.392 (3) |
C3—N1 | 1.326 (3) | C9—C10 | 1.395 (3) |
C3—C4 | 1.502 (3) | C9—H9 | 0.9500 |
C4—C5 | 1.527 (4) | C10—C11 | 1.381 (3) |
C4—H4A | 0.9900 | C10—H10 | 0.9500 |
C4—H4B | 0.9900 | C11—C12 | 1.391 (4) |
C5—C6 | 1.506 (4) | C11—Br1 | 1.892 (2) |
C5—H5A | 0.9900 | C12—C13 | 1.378 (3) |
C5—H5B | 0.9900 | C12—H12 | 0.9500 |
C6—C7 | 1.514 (4) | C13—H13 | 0.9500 |
C6—H6A | 0.9900 | N1—H1 | 0.82 (4) |
C6—H6B | 0.9900 | ||
O1—C1—C2 | 123.6 (2) | N1—C7—C6 | 112.3 (2) |
O1—C1—C8 | 118.1 (2) | N1—C7—H7A | 109.1 |
C2—C1—C8 | 118.2 (2) | C6—C7—H7A | 109.1 |
C3—C2—C1 | 123.6 (2) | N1—C7—H7B | 109.1 |
C3—C2—H2 | 118.2 | C6—C7—H7B | 109.1 |
C1—C2—H2 | 118.2 | H7A—C7—H7B | 107.9 |
N1—C3—C2 | 121.3 (2) | C9—C8—C13 | 118.7 (2) |
N1—C3—C4 | 118.3 (2) | C9—C8—C1 | 122.9 (2) |
C2—C3—C4 | 120.3 (2) | C13—C8—C1 | 118.4 (2) |
C3—C4—C5 | 113.4 (2) | C8—C9—C10 | 121.3 (2) |
C3—C4—H4A | 108.9 | C8—C9—H9 | 119.4 |
C5—C4—H4A | 108.9 | C10—C9—H9 | 119.4 |
C3—C4—H4B | 108.9 | C11—C10—C9 | 118.5 (2) |
C5—C4—H4B | 108.9 | C11—C10—H10 | 120.8 |
H4A—C4—H4B | 107.7 | C9—C10—H10 | 120.8 |
C6—C5—C4 | 109.7 (2) | C10—C11—C12 | 121.6 (2) |
C6—C5—H5A | 109.7 | C10—C11—Br1 | 118.87 (19) |
C4—C5—H5A | 109.7 | C12—C11—Br1 | 119.58 (18) |
C6—C5—H5B | 109.7 | C13—C12—C11 | 118.5 (2) |
C4—C5—H5B | 109.7 | C13—C12—H12 | 120.8 |
H5A—C5—H5B | 108.2 | C11—C12—H12 | 120.8 |
C5—C6—C7 | 109.7 (2) | C12—C13—C8 | 121.5 (2) |
C5—C6—H6A | 109.7 | C12—C13—H13 | 119.2 |
C7—C6—H6A | 109.7 | C8—C13—H13 | 119.2 |
C5—C6—H6B | 109.7 | C3—N1—C7 | 126.7 (2) |
C7—C6—H6B | 109.7 | C3—N1—H1 | 131 (3) |
H6A—C6—H6B | 108.2 | C7—N1—H1 | 102 (3) |
O1—C1—C2—C3 | −3.3 (4) | C13—C8—C9—C10 | 0.7 (4) |
C8—C1—C2—C3 | 173.5 (2) | C1—C8—C9—C10 | 179.9 (2) |
C1—C2—C3—N1 | 0.3 (4) | C8—C9—C10—C11 | 1.2 (4) |
C1—C2—C3—C4 | 178.0 (2) | C9—C10—C11—C12 | −2.1 (4) |
N1—C3—C4—C5 | −22.7 (3) | C9—C10—C11—Br1 | 178.10 (18) |
C2—C3—C4—C5 | 159.5 (2) | C10—C11—C12—C13 | 1.0 (4) |
C3—C4—C5—C6 | 49.1 (3) | Br1—C11—C12—C13 | −179.2 (2) |
C4—C5—C6—C7 | −61.0 (3) | C11—C12—C13—C8 | 1.0 (4) |
C5—C6—C7—N1 | 46.2 (3) | C9—C8—C13—C12 | −1.8 (4) |
O1—C1—C8—C9 | −152.0 (2) | C1—C8—C13—C12 | 178.9 (2) |
C2—C1—C8—C9 | 31.1 (3) | C2—C3—N1—C7 | −173.5 (2) |
O1—C1—C8—C13 | 27.2 (3) | C4—C3—N1—C7 | 8.8 (4) |
C2—C1—C8—C13 | −149.7 (2) | C6—C7—N1—C3 | −20.9 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1 | 0.82 (4) | 2.17 (4) | 2.656 (3) | 118 (3) |
N1—H1···O1i | 0.82 (4) | 2.55 (4) | 3.168 (3) | 133 (3) |
C5—H5B···O1ii | 0.99 | 2.63 | 3.609 (3) | 172 |
C7—H7A···O1i | 0.99 | 2.58 | 3.297 (4) | 129 |
C10—H10···O1iii | 0.95 | 2.40 | 3.194 (3) | 141 |
C6—H6A···Br1iv | 0.99 | 3.05 | 3.894 (3) | 144 |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+2, −y+1, −z+1; (iii) x−1, y, z; (iv) x+1, y, z−1. |
C14H16BrNO | F(000) = 600 |
Mr = 294.19 | Dx = 1.518 Mg m−3 |
Monoclinic, P21/c | Melting point = 418–421 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 12.2867 (3) Å | Cell parameters from 4189 reflections |
b = 8.2416 (2) Å | θ = 3.0–28.3° |
c = 12.9404 (4) Å | µ = 3.18 mm−1 |
β = 100.702 (2)° | T = 173 K |
V = 1287.58 (6) Å3 | Plate, colourless |
Z = 4 | 0.49 × 0.44 × 0.15 mm |
Bruker APEXII CCD area-detector diffractometer | 3103 independent reflections |
Radiation source: fine-focus sealed tube | 2401 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.043 |
ϕ and ω scans | θmax = 28.0°, θmin = 1.7° |
Absorption correction: integration [face-indexed using XPREP (Bruker, 2005)] | h = −15→16 |
Tmin = 0.305, Tmax = 0.647 | k = −10→10 |
9654 measured reflections | l = −14→17 |
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)] = 0.025 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.065 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0326P)2] where P = (Fo2 + 2Fc2)/3 |
3103 reflections | (Δ/σ)max = 0.001 |
158 parameters | Δρmax = 0.45 e Å−3 |
0 restraints | Δρmin = −0.41 e Å−3 |
C14H16BrNO | V = 1287.58 (6) Å3 |
Mr = 294.19 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.2867 (3) Å | µ = 3.18 mm−1 |
b = 8.2416 (2) Å | T = 173 K |
c = 12.9404 (4) Å | 0.49 × 0.44 × 0.15 mm |
β = 100.702 (2)° |
Bruker APEXII CCD area-detector diffractometer | 3103 independent reflections |
Absorption correction: integration [face-indexed using XPREP (Bruker, 2005)] | 2401 reflections with I > 2σ(I) |
Tmin = 0.305, Tmax = 0.647 | Rint = 0.043 |
9654 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | 0 restraints |
wR(F2) = 0.065 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.45 e Å−3 |
3103 reflections | Δρmin = −0.41 e Å−3 |
158 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.44846 (13) | 0.25827 (19) | 0.62676 (11) | 0.0219 (3) | |
C2 | 0.53634 (14) | 0.14673 (17) | 0.63321 (12) | 0.0232 (3) | |
H2 | 0.5436 | 0.0654 | 0.6861 | 0.028* | |
C3 | 0.61272 (13) | 0.14880 (18) | 0.56695 (12) | 0.0220 (3) | |
C4 | 0.69894 (13) | 0.01775 (19) | 0.57524 (13) | 0.0282 (4) | |
H4A | 0.6855 | −0.0463 | 0.5094 | 0.034* | |
H4B | 0.6899 | −0.0561 | 0.6334 | 0.034* | |
C5 | 0.81847 (15) | 0.0794 (2) | 0.59455 (14) | 0.0334 (4) | |
H5A | 0.8248 | 0.1725 | 0.6437 | 0.040* | |
H5B | 0.8677 | −0.0076 | 0.6291 | 0.040* | |
C6 | 0.85902 (15) | 0.1325 (2) | 0.49493 (15) | 0.0348 (4) | |
H6A | 0.9390 | 0.1578 | 0.5133 | 0.042* | |
H6B | 0.8499 | 0.0409 | 0.4445 | 0.042* | |
C7 | 0.79852 (14) | 0.2789 (2) | 0.44183 (13) | 0.0321 (4) | |
H7A | 0.8297 | 0.3053 | 0.3786 | 0.039* | |
H7B | 0.8130 | 0.3725 | 0.4904 | 0.039* | |
C8 | 0.67445 (14) | 0.2583 (2) | 0.40920 (12) | 0.0296 (4) | |
H8A | 0.6460 | 0.3450 | 0.3584 | 0.035* | |
H8B | 0.6597 | 0.1531 | 0.3723 | 0.035* | |
C9 | 0.35676 (13) | 0.22392 (17) | 0.68635 (11) | 0.0216 (3) | |
C10 | 0.37037 (14) | 0.12603 (18) | 0.77591 (12) | 0.0243 (3) | |
H10 | 0.4409 | 0.0804 | 0.8029 | 0.029* | |
C11 | 0.28215 (14) | 0.09483 (19) | 0.82573 (13) | 0.0274 (4) | |
H11 | 0.2920 | 0.0295 | 0.8873 | 0.033* | |
C12 | 0.17962 (14) | 0.15991 (19) | 0.78479 (13) | 0.0258 (4) | |
C13 | 0.16334 (14) | 0.25755 (19) | 0.69635 (12) | 0.0284 (4) | |
H13 | 0.0924 | 0.3017 | 0.6691 | 0.034* | |
C14 | 0.25294 (14) | 0.28938 (19) | 0.64840 (12) | 0.0266 (4) | |
H14 | 0.2431 | 0.3575 | 0.5882 | 0.032* | |
Br1 | 0.058155 (15) | 0.11948 (2) | 0.852615 (15) | 0.04177 (8) | |
N1 | 0.61284 (12) | 0.26316 (17) | 0.49508 (10) | 0.0246 (3) | |
H1 | 0.5659 (16) | 0.333 (2) | 0.4903 (14) | 0.033 (5)* | |
O1 | 0.43884 (10) | 0.38178 (13) | 0.56911 (9) | 0.0282 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0238 (8) | 0.0200 (8) | 0.0212 (8) | −0.0019 (6) | 0.0021 (6) | −0.0015 (6) |
C2 | 0.0261 (8) | 0.0206 (8) | 0.0225 (8) | 0.0014 (6) | 0.0035 (6) | 0.0025 (6) |
C3 | 0.0212 (8) | 0.0202 (8) | 0.0231 (8) | 0.0003 (6) | 0.0003 (6) | −0.0017 (6) |
C4 | 0.0285 (9) | 0.0220 (8) | 0.0353 (9) | 0.0051 (7) | 0.0086 (7) | 0.0048 (7) |
C5 | 0.0257 (9) | 0.0335 (9) | 0.0399 (10) | 0.0079 (7) | 0.0035 (8) | 0.0073 (8) |
C6 | 0.0249 (9) | 0.0337 (9) | 0.0477 (11) | 0.0037 (8) | 0.0119 (8) | 0.0044 (8) |
C7 | 0.0295 (9) | 0.0334 (9) | 0.0364 (10) | 0.0023 (8) | 0.0139 (8) | 0.0049 (8) |
C8 | 0.0308 (9) | 0.0345 (9) | 0.0249 (8) | 0.0043 (8) | 0.0092 (7) | 0.0035 (7) |
C9 | 0.0241 (8) | 0.0184 (7) | 0.0224 (8) | 0.0007 (6) | 0.0045 (6) | −0.0037 (6) |
C10 | 0.0215 (8) | 0.0251 (8) | 0.0262 (8) | 0.0019 (7) | 0.0039 (6) | 0.0008 (7) |
C11 | 0.0291 (9) | 0.0275 (9) | 0.0263 (8) | −0.0009 (7) | 0.0068 (7) | 0.0032 (7) |
C12 | 0.0229 (8) | 0.0246 (8) | 0.0315 (9) | −0.0047 (6) | 0.0093 (7) | −0.0046 (7) |
C13 | 0.0220 (8) | 0.0289 (8) | 0.0338 (9) | 0.0047 (7) | 0.0037 (7) | −0.0034 (7) |
C14 | 0.0304 (9) | 0.0222 (8) | 0.0266 (8) | 0.0043 (7) | 0.0036 (7) | 0.0021 (6) |
Br1 | 0.02703 (11) | 0.05149 (14) | 0.05033 (14) | −0.00378 (9) | 0.01638 (8) | 0.00420 (9) |
N1 | 0.0243 (7) | 0.0243 (7) | 0.0264 (7) | 0.0074 (6) | 0.0073 (6) | 0.0027 (6) |
O1 | 0.0308 (6) | 0.0232 (6) | 0.0325 (6) | 0.0044 (5) | 0.0106 (5) | 0.0067 (5) |
C1—O1 | 1.2546 (18) | C7—H7A | 0.9900 |
C1—C2 | 1.409 (2) | C7—H7B | 0.9900 |
C1—C9 | 1.506 (2) | C8—N1 | 1.4568 (19) |
C2—C3 | 1.384 (2) | C8—H8A | 0.9900 |
C2—H2 | 0.9500 | C8—H8B | 0.9900 |
C3—N1 | 1.324 (2) | C9—C14 | 1.388 (2) |
C3—C4 | 1.503 (2) | C9—C10 | 1.396 (2) |
C4—C5 | 1.530 (2) | C10—C11 | 1.384 (2) |
C4—H4A | 0.9900 | C10—H10 | 0.9500 |
C4—H4B | 0.9900 | C11—C12 | 1.381 (2) |
C5—C6 | 1.530 (2) | C11—H11 | 0.9500 |
C5—H5A | 0.9900 | C12—C13 | 1.383 (2) |
C5—H5B | 0.9900 | C12—Br1 | 1.8961 (16) |
C6—C7 | 1.514 (2) | C13—C14 | 1.385 (2) |
C6—H6A | 0.9900 | C13—H13 | 0.9500 |
C6—H6B | 0.9900 | C14—H14 | 0.9500 |
C7—C8 | 1.514 (2) | N1—H1 | 0.811 (19) |
O1—C1—C2 | 123.45 (14) | C6—C7—H7B | 108.5 |
O1—C1—C9 | 117.41 (14) | C8—C7—H7B | 108.5 |
C2—C1—C9 | 119.03 (13) | H7A—C7—H7B | 107.5 |
C3—C2—C1 | 123.77 (14) | N1—C8—C7 | 115.03 (13) |
C3—C2—H2 | 118.1 | N1—C8—H8A | 108.5 |
C1—C2—H2 | 118.1 | C7—C8—H8A | 108.5 |
N1—C3—C2 | 122.22 (14) | N1—C8—H8B | 108.5 |
N1—C3—C4 | 117.97 (14) | C7—C8—H8B | 108.5 |
C2—C3—C4 | 119.81 (14) | H8A—C8—H8B | 107.5 |
C3—C4—C5 | 114.55 (14) | C14—C9—C10 | 118.60 (14) |
C3—C4—H4A | 108.6 | C14—C9—C1 | 118.14 (14) |
C5—C4—H4A | 108.6 | C10—C9—C1 | 123.24 (14) |
C3—C4—H4B | 108.6 | C11—C10—C9 | 120.69 (15) |
C5—C4—H4B | 108.6 | C11—C10—H10 | 119.7 |
H4A—C4—H4B | 107.6 | C9—C10—H10 | 119.7 |
C6—C5—C4 | 114.22 (15) | C12—C11—C10 | 119.12 (15) |
C6—C5—H5A | 108.7 | C12—C11—H11 | 120.4 |
C4—C5—H5A | 108.7 | C10—C11—H11 | 120.4 |
C6—C5—H5B | 108.7 | C11—C12—C13 | 121.66 (15) |
C4—C5—H5B | 108.7 | C11—C12—Br1 | 119.64 (12) |
H5A—C5—H5B | 107.6 | C13—C12—Br1 | 118.69 (12) |
C7—C6—C5 | 113.65 (14) | C12—C13—C14 | 118.43 (15) |
C7—C6—H6A | 108.8 | C12—C13—H13 | 120.8 |
C5—C6—H6A | 108.8 | C14—C13—H13 | 120.8 |
C7—C6—H6B | 108.8 | C13—C14—C9 | 121.49 (15) |
C5—C6—H6B | 108.8 | C13—C14—H14 | 119.3 |
H6A—C6—H6B | 107.7 | C9—C14—H14 | 119.3 |
C6—C7—C8 | 114.91 (15) | C3—N1—C8 | 125.78 (14) |
C6—C7—H7A | 108.5 | C3—N1—H1 | 117.9 (13) |
C8—C7—H7A | 108.5 | C8—N1—H1 | 115.1 (13) |
O1—C1—C2—C3 | −9.1 (2) | C14—C9—C10—C11 | 0.1 (2) |
C9—C1—C2—C3 | 166.93 (14) | C1—C9—C10—C11 | −178.08 (14) |
C1—C2—C3—N1 | 4.0 (2) | C9—C10—C11—C12 | 1.0 (2) |
C1—C2—C3—C4 | −175.82 (15) | C10—C11—C12—C13 | −1.1 (2) |
N1—C3—C4—C5 | 56.6 (2) | C10—C11—C12—Br1 | −179.59 (12) |
C2—C3—C4—C5 | −123.64 (16) | C11—C12—C13—C14 | 0.2 (2) |
C3—C4—C5—C6 | −83.04 (18) | Br1—C12—C13—C14 | 178.69 (12) |
C4—C5—C6—C7 | 65.3 (2) | C12—C13—C14—C9 | 0.9 (2) |
C5—C6—C7—C8 | −58.5 (2) | C10—C9—C14—C13 | −1.0 (2) |
C6—C7—C8—N1 | 74.4 (2) | C1—C9—C14—C13 | 177.23 (14) |
O1—C1—C9—C14 | 22.8 (2) | C2—C3—N1—C8 | −167.04 (15) |
C2—C1—C9—C14 | −153.44 (14) | C4—C3—N1—C8 | 12.8 (2) |
O1—C1—C9—C10 | −159.06 (14) | C7—C8—N1—C3 | −71.7 (2) |
C2—C1—C9—C10 | 24.7 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1 | 0.811 (19) | 2.057 (19) | 2.6841 (18) | 134.0 (17) |
N1—H1···O1i | 0.811 (19) | 2.467 (19) | 3.0757 (17) | 132.7 (17) |
C10—H10···O1ii | 0.95 | 2.59 | 3.439 (2) | 149 |
C4—H4B···Cgii | 0.99 | 2.67 | 3.5996 (17) | 157 |
C7—H7A···Br1iii | 0.99 | 2.95 | 3.6838 (18) | 131 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y−1/2, −z+3/2; (iii) x+1, −y+1/2, z−1/2. |
Experimental details
(I) | (II) | (III) | |
Crystal data | |||
Chemical formula | C12H12BrNO | C13H14BrNO | C14H16BrNO |
Mr | 266.14 | 280.16 | 294.19 |
Crystal system, space group | Monoclinic, P21/n | Triclinic, P1 | Monoclinic, P21/c |
Temperature (K) | 173 | 173 | 173 |
a, b, c (Å) | 5.6636 (3), 18.9255 (9), 10.0500 (5) | 6.9303 (2), 7.6280 (2), 12.1060 (3) | 12.2867 (3), 8.2416 (2), 12.9404 (4) |
α, β, γ (°) | 90, 94.136 (1), 90 | 99.844 (2), 99.545 (1), 102.189 (2) | 90, 100.702 (2), 90 |
V (Å3) | 1074.42 (9) | 602.64 (3) | 1287.58 (6) |
Z | 4 | 2 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 3.80 | 3.39 | 3.18 |
Crystal size (mm) | 0.37 × 0.30 × 0.20 | 0.49 × 0.19 × 0.17 | 0.49 × 0.44 × 0.15 |
Data collection | |||
Diffractometer | Bruker APEXII CCD area-detector diffractometer | Bruker APEXII CCD area-detector diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS in SAINT-NT; Bruker, 2005) Ratio of minimum to maximum apparent transmission: 0.688943. In the Tmin line above, Tmin=Tmax*min_to_max_ratio | Integration [face-indexed using XPREP (Bruker, 2005)] | Integration [face-indexed using XPREP (Bruker, 2005)] |
Tmin, Tmax | 0.334, 0.517 | 0.380, 0.593 | 0.305, 0.647 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9815, 2595, 2307 | 7739, 2903, 2387 | 9654, 3103, 2401 |
Rint | 0.020 | 0.033 | 0.043 |
(sin θ/λ)max (Å−1) | 0.660 | 0.661 | 0.661 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.068, 1.06 | 0.027, 0.107, 1.14 | 0.025, 0.065, 1.02 |
No. of reflections | 2595 | 2903 | 3103 |
No. of parameters | 140 | 149 | 158 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.52, −0.60 | 0.52, −0.36 | 0.45, −0.41 |
Computer programs: APEX2 (Bruker, 2005), SAINT-NT (Bruker, 2005), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 1999), WinGX (Farrugia, 1999) and PLATON (Spek, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1 | 0.79 (2) | 2.25 (2) | 2.798 (2) | 128 (2) |
N1—H1···O1i | 0.79 (2) | 2.30 (2) | 2.9124 (19) | 136 (2) |
C6—H6B···O1ii | 0.99 | 2.72 | 3.524 (3) | 139 |
C4—H4B···Cgiii | 0.99 | 2.71 | 3.679 (2) | 166 |
C6—H6A···Br1iv | 0.99 | 2.97 | 3.701 (2) | 132 |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) x+1, y, z; (iii) −x+2, −y+1, −z+1; (iv) −x+3/2, y+1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1 | 0.82 (4) | 2.17 (4) | 2.656 (3) | 118 (3) |
N1—H1···O1i | 0.82 (4) | 2.55 (4) | 3.168 (3) | 133 (3) |
C5—H5B···O1ii | 0.99 | 2.63 | 3.609 (3) | 172 |
C7—H7A···O1i | 0.99 | 2.58 | 3.297 (4) | 129 |
C10—H10···O1iii | 0.95 | 2.40 | 3.194 (3) | 141 |
C6—H6A···Br1iv | 0.99 | 3.05 | 3.894 (3) | 144 |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+2, −y+1, −z+1; (iii) x−1, y, z; (iv) x+1, y, z−1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1 | 0.811 (19) | 2.057 (19) | 2.6841 (18) | 134.0 (17) |
N1—H1···O1i | 0.811 (19) | 2.467 (19) | 3.0757 (17) | 132.7 (17) |
C10—H10···O1ii | 0.95 | 2.59 | 3.439 (2) | 149 |
C4—H4B···Cgii | 0.99 | 2.67 | 3.5996 (17) | 157 |
C7—H7A···Br1iii | 0.99 | 2.95 | 3.6838 (18) | 131 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y−1/2, −z+3/2; (iii) x+1, −y+1/2, z−1/2. |
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Enaminones (β-acylated enamines) are valuable intermediates for the synthesis of alkaloids and other nitrogen-containing heterocycles (Stanovnik & Svete, 2004; Cheng et al., 2004; Negri et al., 2004; Elliott et al., 2006). These versatile systems play a pivotal role in our own research programme (Michael et al., 1999). We have recently observed discrepancies in the reactivity of N-heterocyclic enaminones of different ring sizes (Michael et al., 2001, 2002). The present investigation was undertaken in order to ascertain whether there might be underlying structural differences in the conjugated enaminone system as the size of the ring containing the N atom is varied. The three title compounds, (I)–(III), were selected as models to probe possible structural differences, in view of their ready preparation by the Eschenmoser sulfide contraction method (Roth et al., 1971).
In the event, the bond lengths and angles for the conjugated and essentially planar enaminone core (N—C═C—C═O) of the three compounds (Figs. 1–3) proved to be effectively the same, and within the expected ranges (Allen et al., 1987). More interesting, however, are their packing arrangements. Compounds (I)–(III) are characterized by bifurcated hydrogen bonds (one intramolecular and one intermolecular) between the secondary amine and carbonyl groups. The intramolecular N—H···O hydrogen bond between the donor atom N1 and the acceptor atom O1 can be described by the graph-set motif S(6) (Etter et al., 1990; Bernstein et al., 1995). In compound (I), atom N1 also acts as an intermolecular hydrogen-bond donor via atom H1 to atom O1 at (2 - x, 1 - y, -z). For compounds (II) and (III), the comparable intermolecular hydrogen bond is from atom N1 to atom O1 at (2 - x, -y, 1 - z) and (1 - x, 1 - y, 1 - z), respectively. This intermolecular hydrogen bonding leads to the formation of dimers described by the R22(12) graph-set motif.
In the crystal structures of each compound there is also a weak C—H···Br interaction (Figs. 4–6) that links the molecules together into chains along the [011], [101] and [101] directions in compounds (I), (II) and (III), respectively. The C—H···Br hydrogen-bond geometries (Tables 1–3) are comparable with values reported in the literature (Ponnuswamy & Sony, 2006).
In addition to C—H···Br interactions in compound (I), the chains of molecules extending along the [011] direction are further stabilized by Br···O interactions [Br1···O1i = 3.161 (2) Å, C10—Br1···O1i = 165.39 (7)° and C1i—O1i···Br1 = 98.2 (1)°; symmetry code: (i) -1/2 + x, 1/2 - y, 1/2 + z] (Fig. 4). These values compare favourably with those obtained from a study of short O···halogen interactions in biological molecules (Auffinger et al., 2004). The crystal structure of (I) also contains a weak C—H···Cg intermolecular interaction that extends along the [001] direction, where Cg is the centroid of the C7–C12 phenyl ring. The pyrrolidine ring has an envelope conformation with atom C5 at the flap. The Cremer & Pople puckering parameters (Cremer & Pople, 1975) for this molecule are q2 = 0.264 (2) Å and ϕ2 = 113.8 (4)°.
The hydrogen-bonded dimers in compound (II) are further reinforced by a weak C—H···O interaction between atom H7A and atom O1 at (2 - x, -y, 1 - z), producing a motif described by the graph set R22(12). A second set of C—H···O interactions, occurring between atom H5 and atom O1 at (2 - x, 1 - y, 1 - z), gives rise to another set of intermolecular bonded dimers described by the R22(14) graph set (Fig. 5). In this structure, the piperidine ring adopts a half-chair conformation [puckering amplitude QT = 0.483 (3) Å, θ = 136.7 (4)° and ϕ = 26.9 (5)°].
In addition to the N—H···O and C—H···Br interactions discussed earlier, the structure of (III) also contains C—H···Oi and C—H···Cgi interactions [symmetry code: (i) 1 - x, -1/2 + y, 3/2 - z] that link molecules together into chains along the [011] direction (Fig. 6). In this structure, the seven-membered ring has a total puckering amplitude Q of 0.7524 (17) Å.