Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109008336/gz3158sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109008336/gz3158Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109008336/gz3158IIsup3.hkl |
CCDC references: 730101; 730102
For the preparation of (I), a mixture of 1-methyl-4-piperidone (1.13 g, 0.01 mol) and 2-thiophene carboxaldehyde (2.24 g, 0.02 mol) was treated with alcoholic NaOH (50 ml, 10%) and stirred at room temperature for 30 min. The crude product was filtered and recrystallized from ethanol to give yellow plate-like crystals of (I) (yield 2.41 g, 80%; m.p. 385–387 K). Analysis: 1H NMR (CDCl3, 300 MHz, δ, p.p.m.): 7.89 [s, 2H, CH (vinyl)], 7.11–7.52 [m, 6H, CH (thiophene)], 3.76 (s, 4H, CH2), 2.55 (s, 3H, CH3).
For the preparation of (II), a mixture of 1-methyl-4-piperidone (1.13 g, 0.01 mol) and 5-bromo-2-thiophene carboxaldehyde (3.82 g, 0.02 mol) was treated with alcoholic NaOH (50 ml, 10%) and stirred at room temperature for 30 min. The crude product was filtered and recrystallized from methanol to give pink needle-like crystals of (II) (yield 4.32 g, 94%; m.p. 422–423 K). Analysis: 1H NMR (300 MHz, CDCl3, δ, p.p.m.): 7.74 [s, 2H, CH (vinyl)], 7.04–7.09 [m, 4H, CH (thiophene)], 3.67 (s, 4H, CH2), 2.56 (s, 3H, CH3).
H atoms were placed in calculated positions and refined in the riding model, with C—H = 0.95–0.99 Å [Please check added text] and with Uiso(H) = 1.5Ueq(C) for CH3 groups or 1.2Ueq(C) for other groups.
Twenty distance restraints were used to fit the ideal conformations for both orientations of the disordered thiophene ring in compound (I). The S—C distances were fixed at 1.740 (2) (S1—C7 and S1'—C7) and 1.710 (2) Å (S1—C10 and S1'—C10') (four restraints). Single-bond C—C distances were fixed at 1.420 (2) Å (two restraints), and double-bond C═C distances were fixed at 1.400 (2) (C7═C8 and C7═C8') and 1.360 (2) Å (C9═C10 and C9'═C10') (four restraints). 1–3 [Meaning?] S···C distances were fixed at 2.570 (2) (S1···C9 and S1'···C9') and 2.550 (2) Å (S1···C8 and S1'···C8') (four restraints). 1–3 [Meaning?] C···C distances were fixed at 2.490 (2) (C7···C10 and C7···C10'), 2.340 (2) (C7···C9 and C7···C9') and 2.320 (2) Å (C8···C10 and C8···C10') (six restraints). Moreover, it was taken into account that the thiophene ring is flat (two restraints), and the anisotropic displacement parameters for both the S atoms and the corresponding C atoms of the thiophene ring are equal (three restraints). Twenty on [twenty one?] reflections, with experimentally observed F2 deviating significantly from the theoretically calculated F2, were omitted from the refinement.
For both compounds, data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
C16H15NOS2 | F(000) = 632 |
Mr = 301.41 | Dx = 1.400 Mg m−3 |
Monoclinic, P21/c | Melting point = 385–387 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 15.108 (5) Å | Cell parameters from 4122 reflections |
b = 12.609 (4) Å | θ = 2.7–29.9° |
c = 7.523 (2) Å | µ = 0.37 mm−1 |
β = 93.962 (4)° | T = 100 K |
V = 1429.8 (8) Å3 | Plate, yellow |
Z = 4 | 0.55 × 0.24 × 0.12 mm |
Bruker APEXII CCD diffractometer | 3779 independent reflections |
Radiation source: fine-focus sealed tube | 2841 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.057 |
ϕ and ω scans | θmax = 29.0°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −20→20 |
Tmin = 0.824, Tmax = 0.957 | k = −17→17 |
14615 measured reflections | l = −10→10 |
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) = 0.121 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.058P)2 + 0.8P] where P = (Fo2 + 2Fc2)/3 |
3779 reflections | (Δ/σ)max = 0.001 |
188 parameters | Δρmax = 0.51 e Å−3 |
24 restraints | Δρmin = −0.49 e Å−3 |
C16H15NOS2 | V = 1429.8 (8) Å3 |
Mr = 301.41 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 15.108 (5) Å | µ = 0.37 mm−1 |
b = 12.609 (4) Å | T = 100 K |
c = 7.523 (2) Å | 0.55 × 0.24 × 0.12 mm |
β = 93.962 (4)° |
Bruker APEXII CCD diffractometer | 3779 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2841 reflections with I > 2σ(I) |
Tmin = 0.824, Tmax = 0.957 | Rint = 0.057 |
14615 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 24 restraints |
wR(F2) = 0.121 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.51 e Å−3 |
3779 reflections | Δρmin = −0.49 e Å−3 |
188 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 | Occ. (<1) | |
S1 | 0.46374 (4) | 0.30311 (5) | 0.14860 (9) | 0.02256 (15) | 0.90 |
S1' | 0.4277 (3) | 0.0812 (4) | 0.1280 (10) | 0.02256 (15) | 0.10 |
O1 | 0.76774 (10) | 0.07327 (11) | 0.05425 (19) | 0.0222 (3) | |
N1 | 0.74434 (11) | 0.37859 (13) | −0.0014 (2) | 0.0176 (3) | |
C1 | 0.75997 (13) | 0.16789 (17) | 0.0867 (3) | 0.0182 (4) | |
S2 | 1.01848 (4) | 0.37264 (4) | 0.28291 (7) | 0.02318 (15) | |
C2 | 0.67093 (13) | 0.21910 (16) | 0.0923 (2) | 0.0179 (4) | |
C3 | 0.66677 (13) | 0.33782 (16) | 0.0822 (3) | 0.0191 (4) | |
H3A | 0.6120 | 0.3598 | 0.0118 | 0.023* | |
H3B | 0.6650 | 0.3677 | 0.2035 | 0.023* | |
C4 | 0.82526 (13) | 0.35558 (16) | 0.1100 (3) | 0.0189 (4) | |
H4A | 0.8213 | 0.3881 | 0.2289 | 0.023* | |
H4B | 0.8770 | 0.3869 | 0.0551 | 0.023* | |
C5 | 0.83809 (13) | 0.23790 (16) | 0.1298 (2) | 0.0171 (4) | |
C6 | 0.60143 (13) | 0.15425 (17) | 0.1119 (3) | 0.0184 (4) | |
H6A | 0.6154 | 0.0808 | 0.1128 | 0.022* | |
C7 | 0.50961 (8) | 0.17788 (11) | 0.1317 (2) | 0.0184 (4) | |
C8 | 0.44331 (11) | 0.10069 (11) | 0.1357 (3) | 0.0182 (5) | 0.90 |
H8A | 0.4541 | 0.0267 | 0.1283 | 0.022* | 0.90 |
C9 | 0.35798 (10) | 0.14540 (13) | 0.1522 (3) | 0.0245 (4) | 0.90 |
H9A | 0.3055 | 0.1042 | 0.1568 | 0.029* | 0.90 |
C10 | 0.35904 (9) | 0.25310 (13) | 0.1607 (3) | 0.0245 (4) | 0.90 |
H10A | 0.3078 | 0.2955 | 0.1719 | 0.029* | 0.90 |
C8' | 0.4723 (4) | 0.2775 (3) | 0.1595 (17) | 0.0182 (5) | 0.10 |
H8B | 0.5055 | 0.3416 | 0.1661 | 0.022* | 0.10 |
C9' | 0.3795 (5) | 0.2722 (7) | 0.177 (3) | 0.0245 (4) | 0.10 |
H9B | 0.3439 | 0.3327 | 0.1960 | 0.029* | 0.10 |
C10' | 0.3466 (2) | 0.1720 (8) | 0.163 (2) | 0.0245 (4) | 0.10 |
H10B | 0.2859 | 0.1545 | 0.1709 | 0.029* | 0.10 |
C12 | 0.99763 (13) | 0.23799 (16) | 0.2543 (3) | 0.0187 (4) | |
C11 | 0.91457 (13) | 0.19097 (17) | 0.1888 (3) | 0.0195 (4) | |
H11A | 0.9138 | 0.1156 | 0.1871 | 0.023* | |
C13 | 1.07333 (13) | 0.17977 (18) | 0.3098 (3) | 0.0222 (4) | |
H13A | 1.0764 | 0.1046 | 0.3063 | 0.027* | |
C14 | 1.14501 (14) | 0.24562 (18) | 0.3721 (3) | 0.0231 (5) | |
H14A | 1.2014 | 0.2190 | 0.4144 | 0.028* | |
C15 | 1.12484 (14) | 0.35068 (18) | 0.3650 (3) | 0.0244 (5) | |
H15A | 1.1653 | 0.4054 | 0.4016 | 0.029* | |
C16 | 0.73609 (14) | 0.49166 (17) | −0.0372 (3) | 0.0229 (4) | |
H16A | 0.7888 | 0.5166 | −0.0937 | 0.034* | |
H16B | 0.7307 | 0.5299 | 0.0750 | 0.034* | |
H16C | 0.6832 | 0.5047 | −0.1171 | 0.034* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0163 (3) | 0.0271 (3) | 0.0243 (3) | 0.0008 (2) | 0.0017 (2) | 0.0002 (2) |
S1' | 0.0163 (3) | 0.0271 (3) | 0.0243 (3) | 0.0008 (2) | 0.0017 (2) | 0.0002 (2) |
O1 | 0.0197 (8) | 0.0244 (7) | 0.0226 (7) | −0.0002 (6) | 0.0013 (6) | −0.0031 (6) |
N1 | 0.0157 (8) | 0.0232 (8) | 0.0141 (8) | −0.0016 (7) | 0.0017 (6) | 0.0014 (6) |
C1 | 0.0164 (10) | 0.0266 (10) | 0.0114 (9) | −0.0012 (8) | 0.0007 (7) | 0.0003 (7) |
S2 | 0.0194 (3) | 0.0266 (3) | 0.0233 (3) | −0.0034 (2) | −0.0004 (2) | 0.0016 (2) |
C2 | 0.0164 (10) | 0.0244 (10) | 0.0127 (9) | −0.0006 (8) | −0.0012 (7) | 0.0001 (7) |
C3 | 0.0157 (10) | 0.0245 (10) | 0.0174 (9) | 0.0004 (8) | 0.0020 (8) | 0.0003 (8) |
C4 | 0.0163 (10) | 0.0234 (10) | 0.0169 (9) | −0.0020 (8) | −0.0001 (8) | −0.0002 (7) |
C5 | 0.0162 (10) | 0.0238 (10) | 0.0116 (9) | −0.0016 (8) | 0.0029 (7) | −0.0007 (7) |
C6 | 0.0163 (10) | 0.0246 (10) | 0.0142 (9) | −0.0002 (8) | −0.0006 (7) | −0.0002 (7) |
C7 | 0.0163 (10) | 0.0247 (10) | 0.0138 (9) | −0.0005 (8) | −0.0013 (7) | 0.0004 (7) |
C8 | 0.0125 (12) | 0.0251 (13) | 0.0173 (11) | −0.0044 (9) | 0.0023 (9) | 0.0013 (10) |
C9 | 0.0142 (7) | 0.0373 (10) | 0.0219 (8) | −0.0033 (7) | 0.0015 (6) | 0.0077 (8) |
C10 | 0.0142 (7) | 0.0373 (10) | 0.0219 (8) | −0.0033 (7) | 0.0015 (6) | 0.0077 (8) |
C8' | 0.0125 (12) | 0.0251 (13) | 0.0173 (11) | −0.0044 (9) | 0.0023 (9) | 0.0013 (10) |
C9' | 0.0142 (7) | 0.0373 (10) | 0.0219 (8) | −0.0033 (7) | 0.0015 (6) | 0.0077 (8) |
C10' | 0.0142 (7) | 0.0373 (10) | 0.0219 (8) | −0.0033 (7) | 0.0015 (6) | 0.0077 (8) |
C12 | 0.0169 (10) | 0.0226 (9) | 0.0165 (9) | −0.0021 (8) | 0.0012 (7) | 0.0008 (7) |
C11 | 0.0168 (10) | 0.0264 (10) | 0.0157 (9) | −0.0016 (8) | 0.0033 (8) | −0.0001 (8) |
C13 | 0.0155 (10) | 0.0321 (12) | 0.0190 (10) | −0.0029 (8) | 0.0014 (8) | 0.0011 (8) |
C14 | 0.0147 (10) | 0.0323 (12) | 0.0220 (10) | −0.0009 (9) | −0.0010 (8) | 0.0026 (8) |
C15 | 0.0180 (10) | 0.0347 (12) | 0.0206 (10) | −0.0073 (9) | 0.0012 (8) | 0.0007 (9) |
C16 | 0.0217 (11) | 0.0256 (10) | 0.0213 (10) | −0.0017 (9) | 0.0011 (8) | 0.0012 (8) |
S1—C10 | 1.7112 (15) | C7—C8 | 1.399 (3) |
S1—C7 | 1.7326 (14) | C8—C9 | 1.420 (3) |
S1'—C10' | 1.7097 (18) | C8—H8A | 0.9500 |
S1'—C7 | 1.7353 (18) | C9—C10 | 1.360 (4) |
O1—C1 | 1.225 (2) | C9—H9A | 0.9500 |
N1—C16 | 1.455 (3) | C10—H10A | 0.9500 |
N1—C3 | 1.461 (3) | C8'—C9' | 1.419 (4) |
N1—C4 | 1.463 (3) | C8'—H8B | 0.9500 |
C1—C5 | 1.492 (3) | C9'—C10' | 1.359 (4) |
C1—C2 | 1.495 (3) | C9'—H9B | 0.9500 |
S2—C15 | 1.704 (2) | C10'—H10B | 0.9500 |
S2—C12 | 1.737 (2) | C12—C13 | 1.398 (3) |
C2—C6 | 1.347 (3) | C12—C11 | 1.443 (3) |
C2—C3 | 1.500 (3) | C11—H11A | 0.9500 |
C3—H3A | 0.9900 | C13—C14 | 1.418 (3) |
C3—H3B | 0.9900 | C13—H13A | 0.9500 |
C4—C5 | 1.503 (3) | C14—C15 | 1.360 (3) |
C4—H4A | 0.9900 | C14—H14A | 0.9500 |
C4—H4B | 0.9900 | C15—H15A | 0.9500 |
C5—C11 | 1.346 (3) | C16—H16A | 0.9800 |
C6—C7 | 1.437 (2) | C16—H16B | 0.9800 |
C6—H6A | 0.9500 | C16—H16C | 0.9800 |
C7—C8' | 1.398 (4) | ||
C10—S1—C7 | 92.52 (7) | C9—C8—H8A | 123.8 |
C10'—S1'—C7 | 92.59 (9) | C10—C9—C8 | 113.13 (11) |
C16—N1—C3 | 111.32 (16) | C10—C9—H9A | 123.4 |
C16—N1—C4 | 110.98 (16) | C8—C9—H9A | 123.4 |
C3—N1—C4 | 110.34 (16) | C9—C10—S1 | 111.94 (9) |
O1—C1—C5 | 122.30 (19) | C9—C10—H10A | 124.0 |
O1—C1—C2 | 121.68 (18) | S1—C10—H10A | 124.0 |
C5—C1—C2 | 115.98 (18) | C7—C8'—C9' | 112.48 (12) |
C15—S2—C12 | 92.56 (11) | C7—C8'—H8B | 123.8 |
C6—C2—C1 | 116.78 (19) | C9'—C8'—H8B | 123.8 |
C6—C2—C3 | 125.53 (19) | C10'—C9'—C8' | 113.27 (12) |
C1—C2—C3 | 117.66 (17) | C10'—C9'—H9B | 123.4 |
N1—C3—C2 | 109.93 (16) | C8'—C9'—H9B | 123.4 |
N1—C3—H3A | 109.7 | C9'—C10'—S1' | 111.83 (11) |
C2—C3—H3A | 109.7 | C9'—C10'—H10B | 124.1 |
N1—C3—H3B | 109.7 | S1'—C10'—H10B | 124.1 |
C2—C3—H3B | 109.7 | C13—C12—C11 | 124.1 (2) |
H3A—C3—H3B | 108.2 | C13—C12—S2 | 109.78 (16) |
N1—C4—C5 | 110.46 (16) | C11—C12—S2 | 126.13 (16) |
N1—C4—H4A | 109.6 | C5—C11—C12 | 129.7 (2) |
C5—C4—H4A | 109.6 | C5—C11—H11A | 115.2 |
N1—C4—H4B | 109.6 | C12—C11—H11A | 115.2 |
C5—C4—H4B | 109.6 | C12—C13—C14 | 112.4 (2) |
H4A—C4—H4B | 108.1 | C12—C13—H13A | 123.8 |
C11—C5—C1 | 117.38 (19) | C14—C13—H13A | 123.8 |
C11—C5—C4 | 124.67 (19) | C15—C14—C13 | 113.2 (2) |
C1—C5—C4 | 117.92 (17) | C15—C14—H14A | 123.4 |
C2—C6—C7 | 130.62 (19) | C13—C14—H14A | 123.4 |
C2—C6—H6A | 114.7 | C14—C15—S2 | 112.06 (17) |
C7—C6—H6A | 114.7 | C14—C15—H15A | 124.0 |
C8'—C7—C6 | 127.1 (3) | S2—C15—H15A | 124.0 |
C8—C7—C6 | 123.78 (14) | N1—C16—H16A | 109.5 |
C6—C7—S1 | 126.20 (12) | N1—C16—H16B | 109.5 |
C6—C7—S1' | 123.0 (3) | H16A—C16—H16B | 109.5 |
C8'—C7—S1' | 109.83 (11) | N1—C16—H16C | 109.5 |
C8—C7—S1 | 110.00 (10) | H16A—C16—H16C | 109.5 |
C7—C8—C9 | 112.42 (11) | H16B—C16—H16C | 109.5 |
C7—C8—H8A | 123.8 | ||
O1—C1—C2—C6 | 18.7 (3) | C2—C6—C7—C8 | 174.33 (17) |
C5—C1—C2—C6 | −159.01 (17) | C2—C6—C7—S1 | −4.0 (3) |
O1—C1—C2—C3 | −163.39 (18) | C2—C6—C7—S1' | 171.8 (3) |
C5—C1—C2—C3 | 18.9 (2) | C10—S1—C7—C6 | 178.56 (18) |
C16—N1—C3—C2 | 171.57 (16) | C10'—S1'—C7—C6 | 178.9 (6) |
C4—N1—C3—C2 | −64.8 (2) | C6—C7—C8—C9 | −178.57 (17) |
C6—C2—C3—N1 | −159.61 (18) | C6—C7—C8'—C9' | −178.9 (6) |
C1—C2—C3—N1 | 22.7 (2) | C15—S2—C12—C13 | 0.31 (16) |
C16—N1—C4—C5 | −173.94 (16) | C15—S2—C12—C11 | 178.43 (18) |
C3—N1—C4—C5 | 62.2 (2) | C1—C5—C11—C12 | −174.16 (19) |
O1—C1—C5—C11 | −21.1 (3) | C4—C5—C11—C12 | 3.8 (3) |
C2—C1—C5—C11 | 156.57 (17) | C13—C12—C11—C5 | −179.0 (2) |
O1—C1—C5—C4 | 160.81 (18) | S2—C12—C11—C5 | 3.1 (3) |
C2—C1—C5—C4 | −21.5 (2) | C11—C12—C13—C14 | −178.51 (18) |
N1—C4—C5—C11 | 164.33 (18) | S2—C12—C13—C14 | −0.3 (2) |
N1—C4—C5—C1 | −17.7 (2) | C12—C13—C14—C15 | 0.2 (3) |
C1—C2—C6—C7 | 176.19 (18) | C13—C14—C15—S2 | 0.0 (2) |
C3—C2—C6—C7 | −1.6 (3) | C12—S2—C15—C14 | −0.20 (17) |
C2—C6—C7—C8' | −9.4 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4A···O1i | 0.99 | 2.67 | 3.624 (3) | 161 |
C15—H15A···O1ii | 0.95 | 2.36 | 3.278 (3) | 163 |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+2, y+1/2, −z+1/2. |
C16H13Br2NOS2 | Dx = 1.861 Mg m−3 |
Mr = 459.21 | Melting point = 422–423 K |
Orthorhombic, Pca21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2ac | Cell parameters from 6205 reflections |
a = 23.222 (3) Å | θ = 2.4–26.8° |
b = 5.8840 (7) Å | µ = 5.20 mm−1 |
c = 23.994 (3) Å | T = 100 K |
V = 3278.6 (7) Å3 | Needle, pink |
Z = 8 | 0.50 × 0.30 × 0.20 mm |
F(000) = 1808 |
Bruker APEXII CCD diffractometer | 10192 independent reflections |
Radiation source: fine-focus sealed tube | 7285 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.099 |
ϕ and ω scans | θmax = 30.8°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −33→33 |
Tmin = 0.111, Tmax = 0.353 | k = −8→8 |
49136 measured reflections | l = −34→34 |
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)] = 0.054 | H-atom parameters constrained |
wR(F2) = 0.122 | w = 1/[σ2(Fo2) + (0.060P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
10192 reflections | Δρmax = 1.48 e Å−3 |
400 parameters | Δρmin = −1.20 e Å−3 |
1 restraint | Absolute structure: Flack (1983), with how many Friedel pairs? |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.347 (7) |
C16H13Br2NOS2 | V = 3278.6 (7) Å3 |
Mr = 459.21 | Z = 8 |
Orthorhombic, Pca21 | Mo Kα radiation |
a = 23.222 (3) Å | µ = 5.20 mm−1 |
b = 5.8840 (7) Å | T = 100 K |
c = 23.994 (3) Å | 0.50 × 0.30 × 0.20 mm |
Bruker APEXII CCD diffractometer | 10192 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 7285 reflections with I > 2σ(I) |
Tmin = 0.111, Tmax = 0.353 | Rint = 0.099 |
49136 measured reflections |
R[F2 > 2σ(F2)] = 0.054 | H-atom parameters constrained |
wR(F2) = 0.122 | Δρmax = 1.48 e Å−3 |
S = 1.02 | Δρmin = −1.20 e Å−3 |
10192 reflections | Absolute structure: Flack (1983), with how many Friedel pairs? |
400 parameters | Absolute structure parameter: 0.347 (7) |
1 restraint |
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 | ||
Br1A | 0.689885 (18) | 1.05022 (7) | 0.783258 (18) | 0.02059 (10) | |
Br2A | 0.102389 (19) | 1.04778 (8) | 0.576412 (19) | 0.02223 (10) | |
S1A | 0.56950 (5) | 0.89985 (18) | 0.73920 (5) | 0.0178 (2) | |
S2A | 0.22088 (5) | 0.89080 (19) | 0.62297 (5) | 0.0182 (2) | |
O1A | 0.40998 (13) | 0.3274 (5) | 0.64442 (13) | 0.0207 (7) | |
N1A | 0.37507 (16) | 0.8598 (6) | 0.74114 (15) | 0.0163 (8) | |
C1A | 0.4018 (2) | 0.5155 (7) | 0.66477 (17) | 0.0167 (10) | |
C2A | 0.4502 (2) | 0.6433 (7) | 0.69223 (18) | 0.0165 (10) | |
C3A | 0.43719 (18) | 0.8576 (7) | 0.72381 (19) | 0.0175 (10) | |
H3A | 0.4621 | 0.8669 | 0.7572 | 0.021* | |
H3B | 0.4453 | 0.9912 | 0.7000 | 0.021* | |
C4A | 0.3376 (2) | 0.8555 (7) | 0.69200 (19) | 0.0200 (10) | |
H4A | 0.3464 | 0.9875 | 0.6679 | 0.024* | |
H4B | 0.2969 | 0.8678 | 0.7039 | 0.024* | |
C5A | 0.34581 (18) | 0.6401 (7) | 0.65961 (17) | 0.0155 (10) | |
C6A | 0.5044 (2) | 0.5607 (8) | 0.68478 (18) | 0.0189 (10) | |
H6A | 0.5063 | 0.4228 | 0.6643 | 0.023* | |
C7A | 0.55891 (18) | 0.6464 (8) | 0.70261 (18) | 0.0159 (10) | |
C8A | 0.61105 (18) | 0.5449 (8) | 0.69159 (18) | 0.0173 (10) | |
H8A | 0.6146 | 0.4094 | 0.6703 | 0.021* | |
C9A | 0.6589 (2) | 0.6595 (7) | 0.71462 (18) | 0.0187 (10) | |
H9A | 0.6975 | 0.6072 | 0.7119 | 0.022* | |
C10A | 0.64290 (19) | 0.8546 (8) | 0.7413 (2) | 0.0204 (11) | |
C11A | 0.30750 (19) | 0.5517 (7) | 0.62361 (18) | 0.0175 (10) | |
H11A | 0.3190 | 0.4109 | 0.6077 | 0.021* | |
C12A | 0.2523 (2) | 0.6317 (7) | 0.60489 (17) | 0.0179 (10) | |
C13A | 0.21806 (19) | 0.5186 (7) | 0.5673 (2) | 0.0193 (10) | |
H13A | 0.2280 | 0.3744 | 0.5523 | 0.023* | |
C14A | 0.16653 (19) | 0.6346 (7) | 0.55278 (19) | 0.0178 (10) | |
H14A | 0.1383 | 0.5785 | 0.5276 | 0.021* | |
C15A | 0.16322 (18) | 0.8376 (7) | 0.58004 (18) | 0.0158 (9) | |
C16A | 0.3627 (2) | 1.0627 (8) | 0.77440 (18) | 0.0238 (11) | |
H16A | 0.3258 | 1.0434 | 0.7936 | 0.036* | |
H16B | 0.3607 | 1.1957 | 0.7499 | 0.036* | |
H16C | 0.3934 | 1.0848 | 0.8019 | 0.036* | |
Br1B | 0.505326 (19) | 0.46082 (8) | 0.533274 (19) | 0.02180 (10) | |
Br2B | −0.077918 (19) | 0.40833 (7) | 0.337559 (19) | 0.02079 (9) | |
S1B | 0.38547 (5) | 0.61760 (19) | 0.48936 (5) | 0.0178 (2) | |
S2B | 0.04182 (5) | 0.59775 (19) | 0.37172 (5) | 0.0193 (3) | |
O1B | 0.19818 (13) | 1.1861 (5) | 0.46577 (13) | 0.0194 (7) | |
N1B | 0.23494 (16) | 0.6637 (6) | 0.36820 (15) | 0.0189 (9) | |
C1B | 0.20602 (18) | 0.9974 (7) | 0.44500 (18) | 0.0160 (10) | |
C2B | 0.26185 (19) | 0.8781 (7) | 0.45146 (18) | 0.0174 (10) | |
C3B | 0.27099 (19) | 0.6598 (7) | 0.41848 (18) | 0.0175 (10) | |
H3C | 0.3120 | 0.6459 | 0.4078 | 0.021* | |
H3D | 0.2607 | 0.5271 | 0.4418 | 0.021* | |
C4B | 0.17432 (18) | 0.6648 (7) | 0.38282 (19) | 0.0173 (10) | |
H4C | 0.1652 | 0.5277 | 0.4051 | 0.021* | |
H4D | 0.1508 | 0.6604 | 0.3484 | 0.021* | |
C5B | 0.15931 (18) | 0.8750 (8) | 0.41601 (18) | 0.0166 (10) | |
C6B | 0.29946 (18) | 0.9646 (7) | 0.48745 (19) | 0.0163 (9) | |
H6B | 0.2882 | 1.1059 | 0.5032 | 0.020* | |
C7B | 0.3552 (2) | 0.8799 (7) | 0.50704 (18) | 0.0184 (10) | |
C8B | 0.3908 (2) | 0.9926 (8) | 0.54402 (18) | 0.0199 (11) | |
H8B | 0.3817 | 1.1368 | 0.5595 | 0.024* | |
C9B | 0.4416 (2) | 0.8737 (8) | 0.55655 (18) | 0.0184 (10) | |
H9B | 0.4709 | 0.9303 | 0.5805 | 0.022* | |
C10B | 0.44414 (19) | 0.6701 (8) | 0.53083 (19) | 0.0190 (10) | |
C11B | 0.10501 (19) | 0.9514 (7) | 0.42421 (18) | 0.0169 (10) | |
H11B | 0.1020 | 1.0886 | 0.4449 | 0.020* | |
C12B | 0.05092 (19) | 0.8550 (8) | 0.40612 (19) | 0.0181 (10) | |
C13B | −0.0025 (2) | 0.9548 (8) | 0.41573 (19) | 0.0199 (10) | |
H13B | −0.0068 | 1.0980 | 0.4335 | 0.024* | |
C14B | −0.05021 (19) | 0.8231 (8) | 0.39649 (18) | 0.0192 (11) | |
H14B | −0.0895 | 0.8654 | 0.4007 | 0.023* | |
C15B | −0.0319 (2) | 0.6305 (8) | 0.37156 (19) | 0.0205 (11) | |
C16B | 0.2466 (2) | 0.4643 (7) | 0.33360 (19) | 0.0217 (10) | |
H16D | 0.2288 | 0.4847 | 0.2969 | 0.032* | |
H16E | 0.2306 | 0.3287 | 0.3515 | 0.032* | |
H16F | 0.2883 | 0.4460 | 0.3292 | 0.032* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1A | 0.01337 (19) | 0.0189 (2) | 0.0295 (2) | −0.00084 (16) | −0.00078 (18) | −0.0020 (2) |
Br2A | 0.01479 (19) | 0.0238 (2) | 0.0281 (2) | 0.00409 (18) | −0.00157 (18) | −0.0022 (2) |
S1A | 0.0125 (5) | 0.0164 (5) | 0.0244 (5) | 0.0002 (4) | −0.0001 (4) | −0.0024 (4) |
S2A | 0.0136 (5) | 0.0167 (5) | 0.0243 (5) | 0.0014 (4) | −0.0024 (4) | −0.0038 (5) |
O1A | 0.0171 (16) | 0.0175 (15) | 0.0274 (16) | −0.0013 (13) | −0.0005 (13) | −0.0063 (13) |
N1A | 0.0151 (17) | 0.0182 (18) | 0.0155 (17) | 0.0041 (15) | −0.0002 (14) | −0.0033 (15) |
C1A | 0.026 (2) | 0.0097 (18) | 0.015 (2) | −0.0042 (17) | −0.0005 (18) | 0.0040 (15) |
C2A | 0.023 (2) | 0.0106 (19) | 0.016 (2) | 0.0004 (17) | −0.0006 (18) | −0.0004 (16) |
C3A | 0.0113 (19) | 0.020 (2) | 0.022 (2) | 0.0029 (16) | −0.0025 (17) | 0.0011 (18) |
C4A | 0.019 (2) | 0.016 (2) | 0.025 (2) | −0.0026 (18) | 0.0045 (19) | −0.0007 (18) |
C5A | 0.014 (2) | 0.018 (2) | 0.015 (2) | 0.0016 (17) | 0.0007 (16) | 0.0038 (17) |
C6A | 0.018 (2) | 0.023 (2) | 0.0148 (19) | 0.0042 (18) | −0.0015 (17) | −0.0022 (18) |
C7A | 0.0105 (19) | 0.020 (2) | 0.017 (2) | −0.0025 (16) | 0.0019 (16) | −0.0007 (17) |
C8A | 0.0121 (19) | 0.019 (2) | 0.020 (2) | 0.0039 (17) | 0.0011 (17) | −0.0031 (18) |
C9A | 0.017 (2) | 0.018 (2) | 0.021 (2) | 0.0017 (17) | −0.0013 (18) | −0.0010 (17) |
C10A | 0.013 (2) | 0.017 (2) | 0.031 (2) | −0.0012 (17) | 0.0091 (19) | −0.0004 (19) |
C11A | 0.019 (2) | 0.0119 (18) | 0.021 (2) | 0.0012 (17) | −0.0027 (17) | −0.0049 (17) |
C12A | 0.022 (2) | 0.018 (2) | 0.0131 (19) | −0.0004 (18) | 0.0019 (17) | 0.0010 (16) |
C13A | 0.015 (2) | 0.0139 (19) | 0.029 (2) | −0.0012 (17) | 0.0008 (18) | −0.0050 (18) |
C14A | 0.0103 (19) | 0.018 (2) | 0.025 (2) | −0.0006 (17) | −0.0011 (17) | −0.0049 (18) |
C15A | 0.0130 (19) | 0.0171 (19) | 0.017 (2) | −0.0019 (16) | −0.0030 (17) | 0.0000 (17) |
C16A | 0.025 (2) | 0.029 (3) | 0.017 (2) | 0.003 (2) | −0.0045 (18) | −0.008 (2) |
Br1B | 0.0140 (2) | 0.0232 (2) | 0.0282 (2) | 0.00452 (18) | −0.00166 (18) | −0.0019 (2) |
Br2B | 0.01694 (19) | 0.02161 (19) | 0.0238 (2) | −0.00367 (17) | −0.00273 (18) | 0.00052 (18) |
S1B | 0.0141 (5) | 0.0175 (5) | 0.0217 (5) | −0.0001 (4) | −0.0029 (4) | −0.0023 (4) |
S2B | 0.0132 (5) | 0.0188 (5) | 0.0258 (6) | −0.0006 (4) | −0.0008 (4) | −0.0032 (5) |
O1B | 0.0109 (14) | 0.0128 (14) | 0.0343 (17) | 0.0006 (12) | −0.0031 (13) | −0.0018 (13) |
N1B | 0.0145 (18) | 0.0189 (18) | 0.0234 (19) | −0.0011 (15) | −0.0021 (15) | −0.0030 (15) |
C1B | 0.0068 (18) | 0.021 (2) | 0.021 (2) | 0.0036 (16) | −0.0008 (16) | −0.0050 (18) |
C2B | 0.013 (2) | 0.017 (2) | 0.022 (2) | −0.0018 (18) | −0.0033 (17) | 0.0002 (18) |
C3B | 0.015 (2) | 0.018 (2) | 0.020 (2) | 0.0011 (17) | −0.0056 (17) | −0.0047 (18) |
C4B | 0.0109 (19) | 0.015 (2) | 0.026 (2) | −0.0028 (16) | 0.0000 (17) | −0.0018 (17) |
C5B | 0.0085 (18) | 0.020 (2) | 0.021 (2) | 0.0005 (17) | −0.0009 (16) | −0.0017 (18) |
C6B | 0.015 (2) | 0.0098 (17) | 0.025 (2) | 0.0032 (16) | 0.0008 (17) | 0.0035 (17) |
C7B | 0.019 (2) | 0.0129 (19) | 0.023 (2) | −0.0020 (17) | −0.0065 (18) | −0.0021 (18) |
C8B | 0.017 (2) | 0.022 (2) | 0.021 (2) | 0.0014 (18) | −0.0006 (17) | 0.0000 (18) |
C9B | 0.016 (2) | 0.021 (2) | 0.018 (2) | 0.0023 (18) | −0.0008 (17) | 0.0018 (18) |
C10B | 0.016 (2) | 0.022 (2) | 0.019 (2) | −0.0004 (17) | 0.0009 (18) | −0.0018 (19) |
C11B | 0.018 (2) | 0.0138 (19) | 0.019 (2) | 0.0000 (17) | −0.0024 (17) | 0.0036 (17) |
C12B | 0.0102 (19) | 0.020 (2) | 0.024 (2) | 0.0023 (17) | 0.0044 (17) | −0.0018 (18) |
C13B | 0.014 (2) | 0.022 (2) | 0.024 (2) | −0.0014 (19) | −0.0026 (18) | −0.0017 (19) |
C14B | 0.010 (2) | 0.023 (2) | 0.025 (2) | −0.0034 (17) | −0.0004 (18) | 0.0002 (19) |
C15B | 0.014 (2) | 0.028 (2) | 0.019 (2) | −0.0069 (19) | −0.0025 (18) | 0.0025 (19) |
C16B | 0.017 (2) | 0.023 (2) | 0.025 (2) | −0.0099 (18) | 0.0049 (19) | −0.006 (2) |
Br1A—C10A | 1.879 (5) | Br1B—C10B | 1.881 (5) |
Br2A—C15A | 1.880 (4) | Br2B—C15B | 1.875 (5) |
S1A—C10A | 1.726 (5) | S1B—C10B | 1.715 (5) |
S1A—C7A | 1.748 (5) | S1B—C7B | 1.748 (4) |
S2A—C15A | 1.718 (4) | S2B—C15B | 1.724 (5) |
S2A—C12A | 1.745 (4) | S2B—C12B | 1.737 (5) |
O1A—C1A | 1.225 (5) | O1B—C1B | 1.231 (5) |
N1A—C16A | 1.464 (6) | N1B—C4B | 1.451 (6) |
N1A—C4A | 1.466 (6) | N1B—C16B | 1.462 (6) |
N1A—C3A | 1.502 (6) | N1B—C3B | 1.469 (6) |
C1A—C5A | 1.497 (6) | C1B—C5B | 1.476 (6) |
C1A—C2A | 1.506 (6) | C1B—C2B | 1.482 (6) |
C2A—C6A | 1.359 (6) | C2B—C6B | 1.330 (6) |
C2A—C3A | 1.502 (6) | C2B—C3B | 1.523 (6) |
C3A—H3A | 0.9900 | C3B—H3C | 0.9900 |
C3A—H3B | 0.9900 | C3B—H3D | 0.9900 |
C4A—C5A | 1.499 (6) | C4B—C5B | 1.512 (6) |
C4A—H4A | 0.9900 | C4B—H4C | 0.9900 |
C4A—H4B | 0.9900 | C4B—H4D | 0.9900 |
C5A—C11A | 1.345 (6) | C5B—C11B | 1.353 (6) |
C6A—C7A | 1.429 (6) | C6B—C7B | 1.465 (6) |
C6A—H6A | 0.9500 | C6B—H6B | 0.9500 |
C7A—C8A | 1.376 (6) | C7B—C8B | 1.381 (6) |
C8A—C9A | 1.412 (6) | C8B—C9B | 1.404 (6) |
C8A—H8A | 0.9500 | C8B—H8B | 0.9500 |
C9A—C10A | 1.366 (6) | C9B—C10B | 1.349 (6) |
C9A—H9A | 0.9500 | C9B—H9B | 0.9500 |
C11A—C12A | 1.437 (6) | C11B—C12B | 1.445 (6) |
C11A—H11A | 0.9500 | C11B—H11B | 0.9500 |
C12A—C13A | 1.375 (6) | C12B—C13B | 1.391 (6) |
C13A—C14A | 1.421 (6) | C13B—C14B | 1.429 (6) |
C13A—H13A | 0.9500 | C13B—H13B | 0.9500 |
C14A—C15A | 1.364 (6) | C14B—C15B | 1.350 (7) |
C14A—H14A | 0.9500 | C14B—H14B | 0.9500 |
C16A—H16A | 0.9800 | C16B—H16D | 0.9800 |
C16A—H16B | 0.9800 | C16B—H16E | 0.9800 |
C16A—H16C | 0.9800 | C16B—H16F | 0.9800 |
C10A—S1A—C7A | 91.2 (2) | C10B—S1B—C7B | 91.1 (2) |
C15A—S2A—C12A | 91.0 (2) | C15B—S2B—C12B | 91.4 (2) |
C16A—N1A—C4A | 109.6 (3) | C4B—N1B—C16B | 108.7 (3) |
C16A—N1A—C3A | 110.2 (3) | C4B—N1B—C3B | 110.8 (3) |
C4A—N1A—C3A | 110.4 (3) | C16B—N1B—C3B | 110.4 (3) |
O1A—C1A—C5A | 123.0 (4) | O1B—C1B—C5B | 121.5 (4) |
O1A—C1A—C2A | 120.6 (4) | O1B—C1B—C2B | 120.9 (4) |
C5A—C1A—C2A | 116.2 (4) | C5B—C1B—C2B | 117.4 (4) |
C6A—C2A—C3A | 123.6 (4) | C6B—C2B—C1B | 117.5 (4) |
C6A—C2A—C1A | 117.1 (4) | C6B—C2B—C3B | 124.7 (4) |
C3A—C2A—C1A | 119.3 (4) | C1B—C2B—C3B | 117.8 (4) |
N1A—C3A—C2A | 109.9 (4) | N1B—C3B—C2B | 109.5 (3) |
N1A—C3A—H3A | 109.7 | N1B—C3B—H3C | 109.8 |
C2A—C3A—H3A | 109.7 | C2B—C3B—H3C | 109.8 |
N1A—C3A—H3B | 109.7 | N1B—C3B—H3D | 109.8 |
C2A—C3A—H3B | 109.7 | C2B—C3B—H3D | 109.8 |
H3A—C3A—H3B | 108.2 | H3C—C3B—H3D | 108.2 |
N1A—C4A—C5A | 110.8 (4) | N1B—C4B—C5B | 110.8 (3) |
N1A—C4A—H4A | 109.5 | N1B—C4B—H4C | 109.5 |
C5A—C4A—H4A | 109.5 | C5B—C4B—H4C | 109.5 |
N1A—C4A—H4B | 109.5 | N1B—C4B—H4D | 109.5 |
C5A—C4A—H4B | 109.5 | C5B—C4B—H4D | 109.5 |
H4A—C4A—H4B | 108.1 | H4C—C4B—H4D | 108.1 |
C11A—C5A—C1A | 116.0 (4) | C11B—C5B—C1B | 117.0 (4) |
C11A—C5A—C4A | 125.2 (4) | C11B—C5B—C4B | 124.3 (4) |
C1A—C5A—C4A | 118.8 (4) | C1B—C5B—C4B | 118.6 (4) |
C2A—C6A—C7A | 130.9 (4) | C2B—C6B—C7B | 131.2 (4) |
C2A—C6A—H6A | 114.6 | C2B—C6B—H6B | 114.4 |
C7A—C6A—H6A | 114.6 | C7B—C6B—H6B | 114.4 |
C8A—C7A—C6A | 124.7 (4) | C8B—C7B—C6B | 124.8 (4) |
C8A—C7A—S1A | 110.1 (3) | C8B—C7B—S1B | 109.9 (3) |
C6A—C7A—S1A | 125.2 (3) | C6B—C7B—S1B | 125.3 (3) |
C7A—C8A—C9A | 114.2 (4) | C7B—C8B—C9B | 113.6 (4) |
C7A—C8A—H8A | 122.9 | C7B—C8B—H8B | 123.2 |
C9A—C8A—H8A | 122.9 | C9B—C8B—H8B | 123.2 |
C10A—C9A—C8A | 111.8 (4) | C10B—C9B—C8B | 112.4 (4) |
C10A—C9A—H9A | 124.1 | C10B—C9B—H9B | 123.8 |
C8A—C9A—H9A | 124.1 | C8B—C9B—H9B | 123.8 |
C9A—C10A—S1A | 112.6 (3) | C9B—C10B—S1B | 113.0 (3) |
C9A—C10A—Br1A | 127.5 (3) | C9B—C10B—Br1B | 126.9 (4) |
S1A—C10A—Br1A | 119.6 (2) | S1B—C10B—Br1B | 120.0 (3) |
C5A—C11A—C12A | 131.6 (4) | C5B—C11B—C12B | 129.5 (4) |
C5A—C11A—H11A | 114.2 | C5B—C11B—H11B | 115.3 |
C12A—C11A—H11A | 114.2 | C12B—C11B—H11B | 115.3 |
C13A—C12A—C11A | 124.2 (4) | C13B—C12B—C11B | 124.0 (4) |
C13A—C12A—S2A | 110.1 (3) | C13B—C12B—S2B | 109.8 (3) |
C11A—C12A—S2A | 125.6 (3) | C11B—C12B—S2B | 126.2 (3) |
C12A—C13A—C14A | 114.6 (4) | C12B—C13B—C14B | 114.2 (4) |
C12A—C13A—H13A | 122.7 | C12B—C13B—H13B | 122.9 |
C14A—C13A—H13A | 122.7 | C14B—C13B—H13B | 122.9 |
C15A—C14A—C13A | 110.5 (4) | C15B—C14B—C13B | 110.8 (4) |
C15A—C14A—H14A | 124.7 | C15B—C14B—H14B | 124.6 |
C13A—C14A—H14A | 124.7 | C13B—C14B—H14B | 124.6 |
C14A—C15A—S2A | 113.8 (3) | C14B—C15B—S2B | 113.9 (3) |
C14A—C15A—Br2A | 126.6 (3) | C14B—C15B—Br2B | 126.8 (4) |
S2A—C15A—Br2A | 119.6 (2) | S2B—C15B—Br2B | 119.3 (3) |
N1A—C16A—H16A | 109.5 | N1B—C16B—H16D | 109.5 |
N1A—C16A—H16B | 109.5 | N1B—C16B—H16E | 109.5 |
H16A—C16A—H16B | 109.5 | H16D—C16B—H16E | 109.5 |
N1A—C16A—H16C | 109.5 | N1B—C16B—H16F | 109.5 |
H16A—C16A—H16C | 109.5 | H16D—C16B—H16F | 109.5 |
H16B—C16A—H16C | 109.5 | H16E—C16B—H16F | 109.5 |
O1A—C1A—C2A—C6A | 11.3 (6) | O1B—C1B—C2B—C6B | 10.4 (7) |
C5A—C1A—C2A—C6A | −163.4 (4) | C5B—C1B—C2B—C6B | −165.7 (4) |
O1A—C1A—C2A—C3A | −171.4 (4) | O1B—C1B—C2B—C3B | −172.3 (4) |
C5A—C1A—C2A—C3A | 13.9 (6) | C5B—C1B—C2B—C3B | 11.6 (6) |
C16A—N1A—C3A—C2A | 177.1 (4) | C4B—N1B—C3B—C2B | −64.2 (4) |
C4A—N1A—C3A—C2A | −61.6 (4) | C16B—N1B—C3B—C2B | 175.3 (4) |
C6A—C2A—C3A—N1A | −160.7 (4) | C6B—C2B—C3B—N1B | −156.7 (4) |
C1A—C2A—C3A—N1A | 22.1 (5) | C1B—C2B—C3B—N1B | 26.2 (5) |
C16A—N1A—C4A—C5A | −175.4 (4) | C16B—N1B—C4B—C5B | −176.9 (4) |
C3A—N1A—C4A—C5A | 63.1 (4) | C3B—N1B—C4B—C5B | 61.7 (5) |
O1A—C1A—C5A—C11A | −10.5 (6) | O1B—C1B—C5B—C11B | −15.0 (6) |
C2A—C1A—C5A—C11A | 164.1 (4) | C2B—C1B—C5B—C11B | 161.0 (4) |
O1A—C1A—C5A—C4A | 172.3 (4) | O1B—C1B—C5B—C4B | 169.3 (4) |
C2A—C1A—C5A—C4A | −13.1 (6) | C2B—C1B—C5B—C4B | −14.6 (6) |
N1A—C4A—C5A—C11A | 158.6 (4) | N1B—C4B—C5B—C11B | 163.6 (4) |
N1A—C4A—C5A—C1A | −24.5 (5) | N1B—C4B—C5B—C1B | −21.1 (6) |
C3A—C2A—C6A—C7A | −0.6 (8) | C1B—C2B—C6B—C7B | 174.0 (4) |
C1A—C2A—C6A—C7A | 176.6 (4) | C3B—C2B—C6B—C7B | −3.1 (8) |
C2A—C6A—C7A—C8A | −179.4 (5) | C2B—C6B—C7B—C8B | 178.2 (5) |
C2A—C6A—C7A—S1A | −1.9 (7) | C2B—C6B—C7B—S1B | −4.3 (7) |
C10A—S1A—C7A—C8A | −2.6 (4) | C10B—S1B—C7B—C8B | −0.8 (4) |
C10A—S1A—C7A—C6A | 179.6 (4) | C10B—S1B—C7B—C6B | −178.5 (4) |
C6A—C7A—C8A—C9A | −178.8 (4) | C6B—C7B—C8B—C9B | 179.3 (4) |
S1A—C7A—C8A—C9A | 3.4 (5) | S1B—C7B—C8B—C9B | 1.6 (5) |
C7A—C8A—C9A—C10A | −2.6 (6) | C7B—C8B—C9B—C10B | −1.8 (6) |
C8A—C9A—C10A—S1A | 0.5 (5) | C8B—C9B—C10B—S1B | 1.1 (5) |
C8A—C9A—C10A—Br1A | 174.4 (3) | C8B—C9B—C10B—Br1B | 177.2 (3) |
C7A—S1A—C10A—C9A | 1.2 (4) | C7B—S1B—C10B—C9B | −0.2 (4) |
C7A—S1A—C10A—Br1A | −173.2 (3) | C7B—S1B—C10B—Br1B | −176.6 (3) |
C1A—C5A—C11A—C12A | −174.7 (4) | C1B—C5B—C11B—C12B | −173.4 (4) |
C4A—C5A—C11A—C12A | 2.3 (8) | C4B—C5B—C11B—C12B | 2.0 (8) |
C5A—C11A—C12A—C13A | −179.9 (5) | C5B—C11B—C12B—C13B | −177.8 (5) |
C5A—C11A—C12A—S2A | 3.9 (7) | C5B—C11B—C12B—S2B | 4.5 (7) |
C15A—S2A—C12A—C13A | 0.2 (4) | C15B—S2B—C12B—C13B | −0.3 (4) |
C15A—S2A—C12A—C11A | 176.9 (4) | C15B—S2B—C12B—C11B | 177.8 (4) |
C11A—C12A—C13A—C14A | −177.1 (4) | C11B—C12B—C13B—C14B | −177.0 (4) |
S2A—C12A—C13A—C14A | −0.4 (5) | S2B—C12B—C13B—C14B | 1.1 (5) |
C12A—C13A—C14A—C15A | 0.4 (6) | C12B—C13B—C14B—C15B | −1.6 (6) |
C13A—C14A—C15A—S2A | −0.2 (5) | C13B—C14B—C15B—S2B | 1.4 (5) |
C13A—C14A—C15A—Br2A | −177.9 (3) | C13B—C14B—C15B—Br2B | −177.8 (3) |
C12A—S2A—C15A—C14A | 0.0 (4) | C12B—S2B—C15B—C14B | −0.7 (4) |
C12A—S2A—C15A—Br2A | 177.9 (3) | C12B—S2B—C15B—Br2B | 178.5 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C4A—H4A···O1Ai | 0.99 | 2.55 | 3.441 (6) | 150 |
C4B—H4C···O1Bii | 0.99 | 2.60 | 3.493 (6) | 150 |
C13A—H13A···O1Bii | 0.95 | 2.45 | 3.159 (6) | 131 |
C8B—H8B···O1Ai | 0.95 | 2.42 | 3.144 (6) | 133 |
Symmetry codes: (i) x, y+1, z; (ii) x, y−1, z. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C16H15NOS2 | C16H13Br2NOS2 |
Mr | 301.41 | 459.21 |
Crystal system, space group | Monoclinic, P21/c | Orthorhombic, Pca21 |
Temperature (K) | 100 | 100 |
a, b, c (Å) | 15.108 (5), 12.609 (4), 7.523 (2) | 23.222 (3), 5.8840 (7), 23.994 (3) |
α, β, γ (°) | 90, 93.962 (4), 90 | 90, 90, 90 |
V (Å3) | 1429.8 (8) | 3278.6 (7) |
Z | 4 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.37 | 5.20 |
Crystal size (mm) | 0.55 × 0.24 × 0.12 | 0.50 × 0.30 × 0.20 |
Data collection | ||
Diffractometer | Bruker APEXII CCD diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.824, 0.957 | 0.111, 0.353 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14615, 3779, 2841 | 49136, 10192, 7285 |
Rint | 0.057 | 0.099 |
(sin θ/λ)max (Å−1) | 0.682 | 0.720 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.121, 1.01 | 0.054, 0.122, 1.02 |
No. of reflections | 3779 | 10192 |
No. of parameters | 188 | 400 |
No. of restraints | 24 | 1 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.51, −0.49 | 1.48, −1.20 |
Absolute structure | ? | Flack (1983), with how many Friedel pairs? |
Absolute structure parameter | ? | 0.347 (7) |
Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2001), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
(I) within stacks | ||||
C4—H4A···O1iv | 0.99 | 2.67 | 3.624 (3) | 161 |
(I) between stacks | ||||
C15—H15A···O1v | 0.95 | 2.36 | 3.278 (3) | 163 |
(II) within stacks | ||||
C4A—H4A···O1Aiii | 0.99 | 2.55 | 3.441 (6) | 150 |
C4B—H4C···O1Bvi | 0.99 | 2.60 | 3.493 (6) | 150 |
(II) between stacks | ||||
C13A—H13A···O1Bvi | 0.95 | 2.45 | 3.159 (6) | 131 |
C8B—H8B···O1Aiii | 0.95 | 2.42 | 3.144 (6) | 133 |
(III) within stacks | ||||
C3—H1···O1i | 0.97 | 2.62 | 3.421 (7) | 140 |
(III) between stacks | ||||
C16—H14···O1ii | 0.93 | 2.46 | 3.333 (7) | 157 |
(IV) within stacks | ||||
C3—H1···O1iii | 0.97 | 2.57 | 3.441 (3) | 149 |
Symmetry codes: (i) x, -y + 1/2, z - 1/2; (ii) -x + 1, y - 1/2, -z + 1/2; (iii) x, y + 1, z; (iv) x, -y + 1/2, z + 1/2; (v) -x + 2, y + 1/2, -z + 1/2; (vi) x, y - 1, z. |
Cross-conjugated dienones of the bis-arylidenecycloalkanone series and related piperidones have recently attracted considerable attention. These compounds are used in the construction of different polymers (Yakimansky et al., 2002; Aly et al., 2003), and in the design of crystals with nonlinear optical (Kishore & Kishore, 1993; Kawamata et al., 1995, 1996; Sarkisov et al., 2005) and fluorescent (Nesterov et al., 2003, 2008) properties. Furthermore, it is well known that they possess a variety of biological activities, such as antiviral (El-Subbagh et al., 2000), antibacterial (Lyrand et al., 1999; Amal Raj et al., 2003) and antiphlogistic (Rovnyak et al., 1982).
Recently, instead of aryl substituents, the use of heterocyclic ligands was suggested, as these are able to bind important metal cations to form diverse coordination associates (Vatsadze et al., 2006). However, to our knowledge, there are a very few structurally characterized compounds of this type in the literature (Vatsadze et al., 2006). In this paper, we describe two new cross-conjugated piperidones with thienylidene substituents in the side chains, 1-methyl-3,5-bis[(E)-2-thienylidene]-4-piperidone, (I), and 3,5-bis[(E)-5-bromo-2-thienylidene]-1-methyl-4-piperidone, (II), which represent modified analogs of the very recently reported compounds 2,6-bis[(2-thienyl)methylidene]cyclohexanone, (III) (Vatsadze et al., 2006), and 2,6-bis[(5-methylthiophene-2-yl)methylene]cyclohexanone, (IV) (Liang et al., 2007) (see first scheme). One purpose of our investigation was to analyze the influence of small structural modifications of the molecules on their structurally dependent properties. It should be noted that these compounds are potential antitumor (anticancer) agents (Dimmock et al., 1992, 1994, 2001), and even small differences in the structures may cause significant changes in their biological activity.
Compound (I) crystallizes in the monoclinic space group P21/c. One thiophene ring is disordered over two positions related by a 180° rotation about the C6—C7 bond. The minor component contribution refined to 0.100 (3) (Fig. 1).
In general, the extended planar structure of conjugated bonds is the more favorable, and deviations from this rule are usually caused by specific reasons such as steric factors, hydrogen bonds and different attractive interactions. Quantum-chemical calculations using the density functional theory method of the GAUSSIAN03 program, B3LYP functional, 6-31G* basis set (Frisch et al., 2003), also show that the minimum of the potential energy surface corresponds to the major conformer (conformer A) found experimentally in the crystal structure of (I) (see second scheme; 1 kcal mol-1 = 4.184 kJ mol-1). Although the energy differences between the three conformers, A, B and C, are not large, there is a clear trend for compounds with larger disruptions of the conjugated system to be less stable. In the crystal structure of (I), the presence of the minor conformer B may be explained by the weak intermolecular C6—H6A···S1'(1-x, -y, -z) hydrogen bond [C6···S1' = 3.487 (2), H6A···S1' = 2.78 Å and C6—H6A···S1' = 132°].
Compound (II) crystallizes in the noncentrosymmetric orthorhombic space group Pca21, with two independent molecules, A and B, in the unit cell (Fig. 2). However, in the crystal structure, molecules A and B are related by a noncrystallographic pseudo-inversion center with coordinates [0.3045 (2), 0.7536 (6), 0.5553 (2)]. Consequently, molecules A and B possess very similar geometries (Fig. 3), and only the average values of the geometric parameters of (II) are discussed below.
In the molecules of both compounds, the central piperidone ring adopts a flattened boat conformation; atoms N1 and C1 lie 0.702 (1) and 0.242 (1) Å in (I), and 0.699 (3) and 0.158 (3) Å in (II), respectively, out of the C2/C3/C4/C5 plane. Atom N1 of the heterocycle has a pyramidal coordination, as revealed by the sums of the bond angles about this atom of 332.6 (2)° in (I) and 330.2 (3)° in (II). The methyl group occupies the more sterically favored equatorial position.
Both (I) and (II) contain three planar fragments. The first of these includes the plane of the piperidone cycle ([Please list atoms] PA), while the planar fragments PB [Please list atoms] and PC [Please list atoms] include a thiophene ring and adjacent atoms. The dihedral angles PA/PB, PA/PC and PB/PC between these fragments are 13.2 (1), 17.0 (1) and 27.4 (1)°, respectively, in (I), and 10.9 (3), 13.9 (3) and 23.4 (3)°, respectively, in (II).
The molecules of (I) and (II) can exist as E,E-, Z,E- and Z,Z-isomers (see third scheme). Evidently, the E,E-isomers observed for (I) and (II), both in the solid state and in solution (see 1H NMR data in Experimental), are preferred due to steric reasons. Nevertheless, they may undergo isomerization into the Z,E- and Z,Z-isomers in solution upon irradiation with visible light (Vatsadze et al., 2006).
Interestingly, the introduction of the Br atoms in the thiophene rings of (II) does not give rise to significant changes to its molecular geometry compared with that of (I). Moreover, their structural features are similar to those of compounds (III) and (IV). It is surprising that, despite the presence of a bulkier N—CH3 fragment on the central piperidone ring compared with a CH2 fragment, compounds (I) and (III) are isostructural. These findings allow us to propose that the molecular structures of compounds (I)–(IV), as well as the crystal structures of compounds (I) and (III), are defined by similar effects.
The molecular geometries of compounds (I)–(IV) are determined by an extensive conjugated system that is quite stable to the influence of substituents of different types. For this reason, neither the introduction of simple substituents (Me, Hal) to peripheral parts, nor the replacement of one fragment on the saturated part of the central piperidone cycle by another of comparable dimensions, can alter its structure substantially. Thus, any small modifications of compounds containing analogous systems will mainly affect their molecular arrangement (or their crystal packing in the case of the solid state), and, consequently, their chemical properties as a whole.
In the case of dibenzylidenecycloalkanones, it has previously been established that intermolecular C—H···O hydrogen bonds between the carbonyl O atom and an H atom of the methylene groups of the central ring are an important factor in the design of crystals with nonlinear optical properties (Kawamata et al., 1998). Hydrogen bonds of this type binding the molecules within stacks along the b axis are also revealed in the crystal structures of (I)–(IV) (Table 1). Apparently, these hydrogen bonds alone are responsible for the isostructurality of (I) and (III). The topologically common structural motif (stacks along the b axis, in which the molecules are bound by C—H···O hydrogen bonds) is also maintained in the crystal structures of (II) and (IV). However, in the crystal structure of (IV), the stacks are shifted relative to each other compared with the crystal structures of (I) and (III), due to the presence of additional peripheral methyl groups, resulting in the space group P21/n.
It is very important to note that the crystal packing of the molecules of (I), (III) and (IV) is centrosymmetric. However, in order for any compound to display nonlinear optical properties, its crystal packing should be noncentrosymmetric. To this end, we decided to use the well known attractive intermolecular interactions of halogen–halogen (Desiraju & Parthasarathy, 1989; Price et al., 1994; Saha et al., 2006) and halogen–nitrogen (Desiraju & Harlow, 1989; Lucassen et al., 2007) types. It was suggested that, owing to these interactions, the introduction of Br atoms at the peripheral positions of the thiophene rings of (III) does not destroy its common structural motif, but results in a shift of the stacks in such a manner that the crystal packing of the compound loses the crystallographic inversion center. Indeed, compound (II) has a noncentrosymmetric crystal structure (see above), while the common structural motif is preserved.
The Br···Br [Br1A···Br2B(1/2 - x, 1 + y, 1/2 + z) = 3.591 (2) Å] and Br···N [Br1A···N1B(1 - x, 2 - y, 1/2 + z) = 3.168 (4) Å] intermolecular interactions result in a very high density for (II) (1.861 Mg m-3), even among bromine-containing compounds. The average crystal density of bromine-containing organic compounds with short Br···Br contacts is 1.75 (2) Mg m-3, but without such contacts the density is lower, at 1.619 (6) Mg m-3 [Cambridge Structural Database (Allen, 2002), 2009 release, [How many hits in each case?]). The crystal packing of (II), which resembles that of dendro-epithelium [Reference?], is presented in Fig. 4.
Comparison of the structures of (I) and (II) with analogous compounds has shown that their molecules are similar to piperidones used as anticancer agents (Das et al., 2007). Their combination of remarkable features suggests potential application of these compounds as agents for cancer treatment.