organic compounds
Ethyl 4-(5-bromo-1H-indol-3-yl)-2,6,6-trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate
aHacettepe University, Faculty of Pharmacy, Department of Pharmaceutical Chemistry, 06100 Sihhiye-Ankara, Turkey, bDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA, and cDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey
*Correspondence e-mail: rbutcher99@yahoo.com
The title compound, C23H25BrN2O3, crystallizes with two independent molecules in the (Z′ = 2) which differ in the twist of the 5-bromo-1H-indole ring with respect to the plane of the 4-methyl-1,4,5,6,7,8-hexahydroquinoline ring [dihedral angles of 78.55 (9) and 89.70 (8)° in molecules A and B, respectively]. The indole ring is planar in both molecules [maximum deviations = 0.021 (3) and −0.020 (3) Å for the N atom] while the cyclohexene ring has adopts a sofa conformation. In the crystal, molecules are linked by pairs of N—H⋯O hydrogen bonds, forming dimers with R12(6) ring motifs. These dimers are connected by N—H⋯O hydrogen bonds, generating chains along [110]. A C—H⋯O contact occurs between the independent molecules.
Related literature
For biological properties of 1,4-dihydropyridines, see: Triggle, (2003); Şafak & Şimşek (2006). For the introduction of nifedipine into clinical use, see: Gordeev et al. (1998). For a description of the Cambridge Structural Database, see: Allen, (2002). For geometric analysis, see: Cremer & Pople (1975). For hydrogen-bond motifs, see: Bernstein et al. (1995); Etter et al. (1990). For similar structures, see: El-Khouly et al. (2012); Öztürk Yildirim et al. (2012).
Experimental
Crystal data
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Refinement
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Data collection: CrysAlis PRO (Agilent, 2011); cell CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536812046909/hg5269sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812046909/hg5269Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812046909/hg5269Isup3.cml
The title compound was prepared by refluxing 4,4-dimethyl-1,3-cyclohexanedione (0.001 mol), ethyl acetoacetate (0.001 mol), 6-bromoindole-2-carbaldehyde (0.001 mol) and ammonium acetate (0.005 mol) in methanol for 8 h. Crystals were grown by slow evaporation of a methanol solution. The structure of the compound was elucidated by IR, 1H-NMR and elemental analysis. M.p. 487 K; IR (cm-1): 3297, 3087, 2983, 1688; 1H-NMR δ (p.p.m.) 0.9–1.0 (6H; s; 2xCH3), 1.1 (3H; t; CH2CH3), 1.6–1.8 (6H; m; quinoline H7,8), 2.2 (3H; s; CH3), 4.0 (2H; m; CH2CH3), 5.2 (1H; s; quinoline H4), 6.9 (1H; s; indole H3), 7.1–7.7 (3H; m; aromatic), 9.2 (1H; s; quinoline NH), 10.8 (1H; s; indole NH). Anal. for C23H25BrN2O3 calculated: C, 60.40; H, 5.51; N, 6.13; found: C, 59.89; H, 5.86; N, 6.36. The compound demonstrated calcium channel blocker activity in isolated rat ileum and lamb carotid artery.
All H atoms were placed in idealized positions (C—H = 0.95–0.99 Å and N—H = 0.88 Å) and refined as riding atoms with Uiso(H) = 1.2Ueq(C or N) or 1.5 Ueq(Cmethyl). A rotating-group model was applied for the methyl groups. The highest residual electron density peak and the deepest hole are located at 0.86 and 0.82 Å from Br1B, respectively. Forty three outliers,(1 0 0), (-3 6 2), (2 4 0(, (-1 2 7), (1 3 6), (-4 6 2), (1 4 1), (3 1 3), (4 5 1), (-1 0 4), (-11 5 5), (-2 0 12), (-8 6 10), (-3 1 8), (-4 2 4), (3 1 2), (0 5 3), (6 2 1), (-2 1 8), (4 8 9), (-3 3 9), (-7 0 12), (-3 2 8), (-9 3 5), (-8 7 6), (-1 1 1), (-1 1 10), (-4 4 1), (-4 2 5), (-9 9 20), (-3 9 1), (-6 2 3), (-2 0 6), (-9 4 5), (-1 7 3), (3 1 5), (2 4 3), (2 4 4), (-11 3 5), (0 0 6), (0 1 10), (-5 3 2) and (1 8 3), were omitted in the final refinement.
Data collection: CrysAlis PRO (Agilent, 2011); cell
CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C23H25BrN2O3 | F(000) = 1888 |
Mr = 457.36 | Dx = 1.417 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54184 Å |
Hall symbol: -P 2ybc | Cell parameters from 6306 reflections |
a = 14.0044 (6) Å | θ = 3.3–75.5° |
b = 16.8802 (5) Å | µ = 2.83 mm−1 |
c = 18.8341 (7) Å | T = 123 K |
β = 105.582 (4)° | Irregular, colorless |
V = 4288.7 (3) Å3 | 0.83 × 0.69 × 0.48 mm |
Z = 8 |
Agilent Xcalibur (Ruby, Gemini) diffractometer | 8621 independent reflections |
Radiation source: Enhance (Cu) X-ray Source | 7227 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
Detector resolution: 10.5081 pixels mm-1 | θmax = 75.7°, θmin = 3.6° |
ω scans | h = −17→16 |
Absorption correction: analytical [(Clark & Reid, 1995) implemented in CrysAlis RED (Agilent (2011)] | k = −18→21 |
Tmin = 0.270, Tmax = 0.514 | l = −23→22 |
17300 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)] = 0.058 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.159 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.078P)2 + 4.2146P] where P = (Fo2 + 2Fc2)/3 |
8621 reflections | (Δ/σ)max = 0.001 |
531 parameters | Δρmax = 1.31 e Å−3 |
0 restraints | Δρmin = −1.01 e Å−3 |
C23H25BrN2O3 | V = 4288.7 (3) Å3 |
Mr = 457.36 | Z = 8 |
Monoclinic, P21/c | Cu Kα radiation |
a = 14.0044 (6) Å | µ = 2.83 mm−1 |
b = 16.8802 (5) Å | T = 123 K |
c = 18.8341 (7) Å | 0.83 × 0.69 × 0.48 mm |
β = 105.582 (4)° |
Agilent Xcalibur (Ruby, Gemini) diffractometer | 8621 independent reflections |
Absorption correction: analytical [(Clark & Reid, 1995) implemented in CrysAlis RED (Agilent (2011)] | 7227 reflections with I > 2σ(I) |
Tmin = 0.270, Tmax = 0.514 | Rint = 0.038 |
17300 measured reflections |
R[F2 > 2σ(F2)] = 0.058 | 0 restraints |
wR(F2) = 0.159 | H-atom parameters constrained |
S = 1.02 | Δρmax = 1.31 e Å−3 |
8621 reflections | Δρmin = −1.01 e Å−3 |
531 parameters |
Experimental. The crystals were very fragile. On cutting the crystals shattered so the smallest viable crystal was selected and an incident collimator of 1.0 mm was used. Analytical numeric absorption correction using a multifaceted crystal model (Clark & Reid, 1995). |
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 | 0.13692 (3) | 0.37770 (3) | 0.09007 (2) | 0.05924 (14) | |
O1A | −0.15665 (18) | 0.27492 (13) | 0.32627 (17) | 0.0493 (6) | |
O2A | −0.09319 (17) | 0.55281 (13) | 0.41215 (13) | 0.0420 (5) | |
O3A | 0.05958 (19) | 0.60408 (13) | 0.43578 (15) | 0.0469 (5) | |
N1A | 0.15943 (18) | 0.38895 (14) | 0.36909 (15) | 0.0355 (5) | |
H1AA | 0.2210 | 0.3836 | 0.3668 | 0.043* | |
N2A | −0.22154 (19) | 0.49209 (15) | 0.17494 (17) | 0.0400 (6) | |
H2AC | −0.2782 | 0.5135 | 0.1505 | 0.048* | |
C1A | 0.0954 (2) | 0.32637 (17) | 0.34815 (18) | 0.0365 (6) | |
C2A | 0.1409 (2) | 0.24903 (18) | 0.3337 (2) | 0.0473 (8) | |
H2AA | 0.1666 | 0.2200 | 0.3807 | 0.057* | |
H2AB | 0.1970 | 0.2595 | 0.3124 | 0.057* | |
C3A | 0.0613 (3) | 0.1980 (2) | 0.2793 (3) | 0.0539 (9) | |
H3AA | 0.0440 | 0.2235 | 0.2301 | 0.065* | |
H3AB | 0.0896 | 0.1452 | 0.2743 | 0.065* | |
C4A | −0.0320 (2) | 0.18776 (18) | 0.3045 (2) | 0.0411 (7) | |
C5A | −0.0703 (2) | 0.26800 (17) | 0.3243 (2) | 0.0396 (7) | |
C6A | −0.0030 (2) | 0.33535 (16) | 0.34118 (18) | 0.0359 (6) | |
C7A | −0.0463 (2) | 0.41683 (16) | 0.34580 (18) | 0.0331 (6) | |
H7AA | −0.0962 | 0.4119 | 0.3749 | 0.040* | |
C8A | 0.0331 (2) | 0.47467 (16) | 0.38612 (17) | 0.0335 (6) | |
C9A | 0.1307 (2) | 0.46069 (17) | 0.39384 (17) | 0.0348 (6) | |
C10A | −0.1001 (2) | 0.44528 (16) | 0.26938 (17) | 0.0326 (6) | |
C11A | −0.0690 (2) | 0.43850 (16) | 0.20286 (17) | 0.0331 (6) | |
C12A | 0.0175 (2) | 0.41221 (17) | 0.18585 (18) | 0.0366 (6) | |
H12A | 0.0727 | 0.3937 | 0.2234 | 0.044* | |
C13A | 0.0202 (3) | 0.41393 (19) | 0.1136 (2) | 0.0424 (7) | |
C14A | −0.0594 (3) | 0.4412 (2) | 0.0561 (2) | 0.0476 (8) | |
H14A | −0.0549 | 0.4403 | 0.0067 | 0.057* | |
C15A | −0.1440 (3) | 0.4691 (2) | 0.0719 (2) | 0.0461 (7) | |
H15A | −0.1980 | 0.4889 | 0.0340 | 0.055* | |
C16A | −0.1481 (2) | 0.46742 (17) | 0.14475 (19) | 0.0379 (6) | |
C17A | −0.1929 (2) | 0.47820 (16) | 0.24887 (19) | 0.0358 (6) | |
H17A | −0.2320 | 0.4898 | 0.2818 | 0.043* | |
C18A | −0.0062 (2) | 0.54629 (17) | 0.41275 (17) | 0.0360 (6) | |
C19A | 0.0234 (3) | 0.6765 (2) | 0.4605 (2) | 0.0510 (8) | |
H19A | −0.0025 | 0.6659 | 0.5036 | 0.061* | |
H19B | −0.0306 | 0.6994 | 0.4207 | 0.061* | |
C20A | 0.1085 (4) | 0.7317 (2) | 0.4809 (3) | 0.0671 (12) | |
H20A | 0.0874 | 0.7816 | 0.4985 | 0.101* | |
H20B | 0.1330 | 0.7420 | 0.4376 | 0.101* | |
H20C | 0.1616 | 0.7080 | 0.5200 | 0.101* | |
C21A | 0.2166 (2) | 0.5128 (2) | 0.4294 (2) | 0.0444 (7) | |
H21A | 0.2141 | 0.5260 | 0.4796 | 0.067* | |
H21B | 0.2133 | 0.5616 | 0.4007 | 0.067* | |
H21C | 0.2787 | 0.4849 | 0.4314 | 0.067* | |
C22A | −0.0118 (3) | 0.1373 (2) | 0.3741 (3) | 0.0598 (10) | |
H22A | 0.0372 | 0.1639 | 0.4140 | 0.090* | |
H22B | 0.0139 | 0.0855 | 0.3645 | 0.090* | |
H22C | −0.0735 | 0.1301 | 0.3885 | 0.090* | |
C23A | −0.1124 (3) | 0.1468 (3) | 0.2437 (3) | 0.0639 (11) | |
H23A | −0.0875 | 0.0956 | 0.2317 | 0.096* | |
H23B | −0.1294 | 0.1803 | 0.1996 | 0.096* | |
H23C | −0.1716 | 0.1383 | 0.2611 | 0.096* | |
Br1B | 0.63774 (4) | 0.23757 (4) | 0.06648 (3) | 0.07158 (17) | |
O1B | 0.34556 (15) | 0.34914 (12) | 0.34170 (13) | 0.0369 (4) | |
O2B | 0.40595 (16) | 0.06588 (13) | 0.38178 (14) | 0.0421 (5) | |
O3B | 0.55806 (17) | 0.01606 (12) | 0.39880 (14) | 0.0423 (5) | |
N1B | 0.65221 (18) | 0.23898 (14) | 0.34324 (16) | 0.0354 (5) | |
H1BA | 0.7118 | 0.2459 | 0.3371 | 0.042* | |
N2B | 0.2680 (2) | 0.14747 (15) | 0.14840 (16) | 0.0416 (6) | |
H2BC | 0.2096 | 0.1298 | 0.1233 | 0.050* | |
C1B | 0.5887 (2) | 0.30229 (16) | 0.33371 (16) | 0.0314 (5) | |
C2B | 0.6358 (2) | 0.38185 (17) | 0.3312 (2) | 0.0415 (7) | |
H2BA | 0.6851 | 0.3781 | 0.3023 | 0.050* | |
H2BB | 0.6708 | 0.3988 | 0.3818 | 0.050* | |
C3B | 0.5566 (3) | 0.44283 (18) | 0.2960 (2) | 0.0419 (7) | |
H3BA | 0.5316 | 0.4313 | 0.2427 | 0.050* | |
H3BB | 0.5871 | 0.4962 | 0.3013 | 0.050* | |
C4B | 0.4689 (2) | 0.44316 (16) | 0.33058 (17) | 0.0351 (6) | |
C5B | 0.4289 (2) | 0.35879 (16) | 0.33301 (15) | 0.0298 (5) | |
C6B | 0.4914 (2) | 0.29147 (15) | 0.32859 (15) | 0.0291 (5) | |
C7B | 0.44794 (19) | 0.20870 (15) | 0.32303 (15) | 0.0280 (5) | |
H7BA | 0.3990 | 0.2077 | 0.3531 | 0.034* | |
C8B | 0.5283 (2) | 0.14830 (16) | 0.35610 (16) | 0.0304 (5) | |
C9B | 0.6255 (2) | 0.16410 (16) | 0.36236 (17) | 0.0327 (6) | |
C10B | 0.3929 (2) | 0.18810 (15) | 0.24485 (16) | 0.0298 (5) | |
C11B | 0.4259 (2) | 0.19214 (15) | 0.17849 (16) | 0.0321 (6) | |
C12B | 0.5150 (2) | 0.21294 (17) | 0.16260 (18) | 0.0377 (6) | |
H12B | 0.5711 | 0.2292 | 0.2005 | 0.045* | |
C13B | 0.5185 (3) | 0.2090 (2) | 0.09021 (19) | 0.0448 (7) | |
C14B | 0.4370 (3) | 0.1861 (2) | 0.03215 (19) | 0.0516 (9) | |
H14B | 0.4424 | 0.1855 | −0.0170 | 0.062* | |
C15B | 0.3497 (3) | 0.16487 (18) | 0.04660 (18) | 0.0475 (8) | |
H15B | 0.2941 | 0.1493 | 0.0079 | 0.057* | |
C16B | 0.3447 (2) | 0.16667 (16) | 0.11969 (18) | 0.0394 (7) | |
C17B | 0.2974 (2) | 0.16038 (16) | 0.22313 (19) | 0.0376 (6) | |
H17B | 0.2570 | 0.1513 | 0.2555 | 0.045* | |
C18B | 0.4912 (2) | 0.07421 (16) | 0.37957 (16) | 0.0321 (6) | |
C19B | 0.5237 (3) | −0.05911 (17) | 0.42088 (19) | 0.0424 (7) | |
H19C | 0.4734 | −0.0832 | 0.3792 | 0.051* | |
H19D | 0.4938 | −0.0512 | 0.4624 | 0.051* | |
C20B | 0.6131 (3) | −0.1108 (2) | 0.4437 (3) | 0.0647 (12) | |
H20D | 0.5960 | −0.1597 | 0.4655 | 0.097* | |
H20E | 0.6655 | −0.0829 | 0.4801 | 0.097* | |
H20F | 0.6364 | −0.1238 | 0.4005 | 0.097* | |
C21B | 0.7139 (2) | 0.11148 (19) | 0.3907 (2) | 0.0474 (8) | |
H21D | 0.6951 | 0.0563 | 0.3777 | 0.071* | |
H21E | 0.7375 | 0.1165 | 0.4444 | 0.071* | |
H21F | 0.7667 | 0.1272 | 0.3684 | 0.071* | |
C22B | 0.5021 (3) | 0.47315 (19) | 0.4104 (2) | 0.0448 (7) | |
H22D | 0.5232 | 0.5285 | 0.4108 | 0.067* | |
H22E | 0.5576 | 0.4409 | 0.4385 | 0.067* | |
H22F | 0.4467 | 0.4692 | 0.4328 | 0.067* | |
C23B | 0.3868 (3) | 0.49594 (19) | 0.2847 (2) | 0.0476 (8) | |
H23G | 0.4127 | 0.5496 | 0.2825 | 0.071* | |
H23D | 0.3317 | 0.4978 | 0.3075 | 0.071* | |
H23E | 0.3635 | 0.4744 | 0.2348 | 0.071* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1A | 0.0535 (2) | 0.0716 (3) | 0.0595 (2) | 0.01058 (19) | 0.02695 (19) | 0.00035 (19) |
O1A | 0.0372 (12) | 0.0293 (10) | 0.0884 (19) | 0.0001 (9) | 0.0288 (12) | 0.0013 (11) |
O2A | 0.0417 (12) | 0.0342 (11) | 0.0516 (13) | 0.0121 (9) | 0.0150 (10) | 0.0003 (9) |
O3A | 0.0480 (13) | 0.0313 (11) | 0.0597 (14) | 0.0078 (9) | 0.0117 (11) | −0.0068 (10) |
N1A | 0.0272 (11) | 0.0303 (12) | 0.0479 (14) | 0.0071 (9) | 0.0080 (10) | 0.0030 (10) |
N2A | 0.0297 (12) | 0.0289 (11) | 0.0574 (16) | 0.0030 (9) | 0.0051 (11) | 0.0022 (11) |
C1A | 0.0356 (15) | 0.0258 (13) | 0.0509 (17) | 0.0055 (11) | 0.0165 (13) | 0.0037 (12) |
C2A | 0.0373 (16) | 0.0276 (14) | 0.081 (3) | 0.0062 (12) | 0.0234 (16) | 0.0005 (15) |
C3A | 0.050 (2) | 0.0388 (17) | 0.078 (3) | 0.0002 (15) | 0.0267 (19) | −0.0095 (17) |
C4A | 0.0418 (16) | 0.0277 (14) | 0.0564 (19) | 0.0020 (12) | 0.0178 (14) | −0.0016 (13) |
C5A | 0.0382 (15) | 0.0262 (13) | 0.0571 (19) | 0.0022 (11) | 0.0176 (14) | 0.0046 (13) |
C6A | 0.0355 (15) | 0.0229 (12) | 0.0516 (17) | 0.0065 (11) | 0.0156 (13) | 0.0039 (12) |
C7A | 0.0301 (13) | 0.0219 (12) | 0.0488 (16) | 0.0040 (10) | 0.0130 (12) | 0.0033 (11) |
C8A | 0.0350 (14) | 0.0259 (12) | 0.0399 (15) | 0.0045 (11) | 0.0103 (12) | 0.0022 (11) |
C9A | 0.0358 (14) | 0.0267 (13) | 0.0396 (15) | 0.0051 (11) | 0.0062 (12) | 0.0027 (11) |
C10A | 0.0276 (13) | 0.0224 (12) | 0.0471 (16) | 0.0001 (10) | 0.0087 (11) | 0.0015 (11) |
C11A | 0.0314 (13) | 0.0221 (12) | 0.0429 (15) | −0.0021 (10) | 0.0052 (11) | −0.0011 (11) |
C12A | 0.0335 (14) | 0.0285 (13) | 0.0470 (16) | −0.0004 (11) | 0.0092 (12) | −0.0008 (12) |
C13A | 0.0420 (16) | 0.0352 (15) | 0.0526 (18) | 0.0009 (13) | 0.0172 (14) | −0.0037 (13) |
C14A | 0.056 (2) | 0.0425 (17) | 0.0423 (17) | 0.0034 (15) | 0.0088 (15) | −0.0020 (14) |
C15A | 0.0499 (19) | 0.0361 (15) | 0.0445 (17) | 0.0011 (14) | −0.0005 (14) | −0.0015 (13) |
C16A | 0.0347 (15) | 0.0252 (13) | 0.0494 (17) | −0.0020 (11) | 0.0040 (12) | −0.0022 (12) |
C17A | 0.0302 (13) | 0.0223 (12) | 0.0560 (18) | 0.0012 (10) | 0.0132 (12) | 0.0021 (12) |
C18A | 0.0402 (16) | 0.0285 (13) | 0.0375 (14) | 0.0084 (11) | 0.0076 (12) | 0.0032 (11) |
C19A | 0.059 (2) | 0.0340 (16) | 0.059 (2) | 0.0102 (15) | 0.0152 (17) | −0.0085 (15) |
C20A | 0.069 (3) | 0.0410 (19) | 0.083 (3) | 0.0050 (18) | 0.007 (2) | −0.018 (2) |
C21A | 0.0352 (15) | 0.0387 (16) | 0.0541 (19) | 0.0032 (13) | 0.0027 (13) | −0.0076 (14) |
C22A | 0.063 (2) | 0.0441 (19) | 0.077 (3) | 0.0123 (17) | 0.027 (2) | 0.0091 (19) |
C23A | 0.058 (2) | 0.057 (2) | 0.076 (3) | −0.0062 (19) | 0.017 (2) | −0.016 (2) |
Br1B | 0.0723 (3) | 0.0922 (4) | 0.0617 (3) | 0.0128 (2) | 0.0379 (2) | 0.0172 (2) |
O1B | 0.0324 (10) | 0.0288 (9) | 0.0510 (12) | −0.0011 (8) | 0.0135 (9) | −0.0036 (9) |
O2B | 0.0337 (11) | 0.0357 (11) | 0.0547 (13) | −0.0089 (9) | 0.0079 (9) | 0.0096 (10) |
O3B | 0.0449 (12) | 0.0246 (10) | 0.0602 (14) | −0.0025 (9) | 0.0186 (10) | 0.0083 (9) |
N1B | 0.0276 (11) | 0.0269 (11) | 0.0525 (15) | −0.0039 (9) | 0.0120 (10) | 0.0034 (10) |
N2B | 0.0397 (14) | 0.0270 (11) | 0.0487 (15) | −0.0048 (10) | −0.0046 (11) | −0.0049 (11) |
C1B | 0.0325 (13) | 0.0238 (12) | 0.0385 (14) | −0.0049 (10) | 0.0105 (11) | −0.0016 (11) |
C2B | 0.0378 (15) | 0.0251 (13) | 0.065 (2) | −0.0073 (12) | 0.0198 (15) | −0.0005 (13) |
C3B | 0.0513 (18) | 0.0253 (13) | 0.0535 (18) | −0.0050 (12) | 0.0219 (15) | 0.0047 (13) |
C4B | 0.0403 (15) | 0.0230 (12) | 0.0430 (16) | −0.0018 (11) | 0.0130 (13) | 0.0011 (11) |
C5B | 0.0327 (13) | 0.0244 (12) | 0.0309 (13) | −0.0025 (10) | 0.0060 (10) | −0.0011 (10) |
C6B | 0.0324 (13) | 0.0227 (12) | 0.0315 (13) | −0.0064 (10) | 0.0074 (10) | −0.0018 (10) |
C7B | 0.0264 (12) | 0.0216 (11) | 0.0357 (13) | −0.0045 (10) | 0.0080 (10) | −0.0014 (10) |
C8B | 0.0314 (13) | 0.0233 (12) | 0.0355 (13) | −0.0044 (10) | 0.0071 (11) | 0.0007 (10) |
C9B | 0.0317 (14) | 0.0232 (12) | 0.0411 (15) | −0.0022 (10) | 0.0061 (11) | 0.0007 (11) |
C10B | 0.0282 (13) | 0.0197 (11) | 0.0388 (14) | −0.0009 (9) | 0.0045 (11) | −0.0022 (10) |
C11B | 0.0388 (15) | 0.0199 (11) | 0.0343 (14) | 0.0031 (10) | 0.0041 (11) | −0.0008 (10) |
C12B | 0.0418 (16) | 0.0310 (14) | 0.0396 (15) | 0.0049 (12) | 0.0099 (12) | 0.0031 (12) |
C13B | 0.057 (2) | 0.0372 (16) | 0.0438 (17) | 0.0116 (14) | 0.0189 (15) | 0.0057 (13) |
C14B | 0.084 (3) | 0.0338 (15) | 0.0340 (16) | 0.0142 (17) | 0.0113 (16) | 0.0003 (13) |
C15B | 0.071 (2) | 0.0264 (14) | 0.0344 (15) | 0.0070 (14) | −0.0033 (15) | −0.0045 (12) |
C16B | 0.0461 (17) | 0.0216 (12) | 0.0434 (16) | 0.0048 (11) | −0.0003 (13) | −0.0036 (11) |
C17B | 0.0347 (15) | 0.0248 (12) | 0.0495 (17) | −0.0036 (11) | 0.0045 (12) | −0.0049 (12) |
C18B | 0.0346 (14) | 0.0257 (12) | 0.0337 (13) | −0.0052 (11) | 0.0051 (11) | 0.0019 (10) |
C19B | 0.0531 (19) | 0.0238 (13) | 0.0491 (18) | −0.0075 (12) | 0.0116 (15) | 0.0051 (12) |
C20B | 0.055 (2) | 0.0290 (16) | 0.104 (4) | −0.0019 (15) | 0.011 (2) | 0.0128 (19) |
C21B | 0.0295 (15) | 0.0347 (15) | 0.071 (2) | −0.0013 (12) | 0.0016 (14) | 0.0097 (15) |
C22B | 0.0519 (19) | 0.0329 (15) | 0.0503 (18) | −0.0120 (13) | 0.0150 (15) | −0.0102 (13) |
C23B | 0.0540 (19) | 0.0320 (15) | 0.057 (2) | 0.0067 (14) | 0.0151 (16) | 0.0089 (14) |
Br1A—C13A | 1.906 (3) | Br1B—C13B | 1.903 (4) |
O1A—C5A | 1.225 (4) | O1B—C5B | 1.232 (4) |
O2A—C18A | 1.220 (4) | O2B—C18B | 1.214 (4) |
O3A—C18A | 1.332 (4) | O3B—C18B | 1.338 (4) |
O3A—C19A | 1.447 (4) | O3B—C19B | 1.457 (3) |
N1A—C1A | 1.374 (4) | N1B—C1B | 1.371 (4) |
N1A—C9A | 1.395 (4) | N1B—C9B | 1.393 (4) |
N1A—H1AA | 0.8800 | N1B—H1BA | 0.8800 |
N2A—C17A | 1.362 (5) | N2B—C16B | 1.365 (5) |
N2A—C16A | 1.367 (4) | N2B—C17B | 1.374 (4) |
N2A—H2AC | 0.8800 | N2B—H2BC | 0.8800 |
C1A—C6A | 1.356 (4) | C1B—C6B | 1.353 (4) |
C1A—C2A | 1.509 (4) | C1B—C2B | 1.503 (4) |
C2A—C3A | 1.556 (5) | C2B—C3B | 1.528 (5) |
C2A—H2AA | 0.9900 | C2B—H2BA | 0.9900 |
C2A—H2AB | 0.9900 | C2B—H2BB | 0.9900 |
C3A—C4A | 1.515 (5) | C3B—C4B | 1.536 (4) |
C3A—H3AA | 0.9900 | C3B—H3BA | 0.9900 |
C3A—H3AB | 0.9900 | C3B—H3BB | 0.9900 |
C4A—C22A | 1.524 (5) | C4B—C23B | 1.526 (4) |
C4A—C23A | 1.538 (5) | C4B—C22B | 1.535 (5) |
C4A—C5A | 1.539 (4) | C4B—C5B | 1.536 (4) |
C5A—C6A | 1.457 (4) | C5B—C6B | 1.450 (4) |
C6A—C7A | 1.516 (4) | C6B—C7B | 1.516 (3) |
C7A—C10A | 1.512 (4) | C7B—C10B | 1.508 (4) |
C7A—C8A | 1.521 (4) | C7B—C8B | 1.523 (4) |
C7A—H7AA | 1.0000 | C7B—H7BA | 1.0000 |
C8A—C9A | 1.356 (4) | C8B—C9B | 1.360 (4) |
C8A—C18A | 1.472 (4) | C8B—C18B | 1.468 (4) |
C9A—C21A | 1.495 (4) | C9B—C21B | 1.500 (4) |
C10A—C17A | 1.371 (4) | C10B—C17B | 1.371 (4) |
C10A—C11A | 1.437 (4) | C10B—C11B | 1.446 (4) |
C11A—C12A | 1.405 (4) | C11B—C12B | 1.403 (4) |
C11A—C16A | 1.419 (4) | C11B—C16B | 1.424 (4) |
C12A—C13A | 1.371 (5) | C12B—C13B | 1.379 (5) |
C12A—H12A | 0.9500 | C12B—H12B | 0.9500 |
C13A—C14A | 1.406 (5) | C13B—C14B | 1.406 (6) |
C14A—C15A | 1.380 (5) | C14B—C15B | 1.369 (6) |
C14A—H14A | 0.9500 | C14B—H14B | 0.9500 |
C15A—C16A | 1.389 (5) | C15B—C16B | 1.397 (5) |
C15A—H15A | 0.9500 | C15B—H15B | 0.9500 |
C17A—H17A | 0.9500 | C17B—H17B | 0.9500 |
C19A—C20A | 1.480 (6) | C19B—C20B | 1.491 (5) |
C19A—H19A | 0.9900 | C19B—H19C | 0.9900 |
C19A—H19B | 0.9900 | C19B—H19D | 0.9900 |
C20A—H20A | 0.9800 | C20B—H20D | 0.9800 |
C20A—H20B | 0.9800 | C20B—H20E | 0.9800 |
C20A—H20C | 0.9800 | C20B—H20F | 0.9800 |
C21A—H21A | 0.9800 | C21B—H21D | 0.9800 |
C21A—H21B | 0.9800 | C21B—H21E | 0.9800 |
C21A—H21C | 0.9800 | C21B—H21F | 0.9800 |
C22A—H22A | 0.9800 | C22B—H22D | 0.9800 |
C22A—H22B | 0.9800 | C22B—H22E | 0.9800 |
C22A—H22C | 0.9800 | C22B—H22F | 0.9800 |
C23A—H23A | 0.9800 | C23B—H23G | 0.9800 |
C23A—H23B | 0.9800 | C23B—H23D | 0.9800 |
C23A—H23C | 0.9800 | C23B—H23E | 0.9800 |
C18A—O3A—C19A | 116.9 (3) | C18B—O3B—C19B | 117.1 (2) |
C1A—N1A—C9A | 122.6 (3) | C1B—N1B—C9B | 122.1 (2) |
C1A—N1A—H1AA | 118.7 | C1B—N1B—H1BA | 118.9 |
C9A—N1A—H1AA | 118.7 | C9B—N1B—H1BA | 118.9 |
C17A—N2A—C16A | 109.0 (3) | C16B—N2B—C17B | 108.5 (3) |
C17A—N2A—H2AC | 125.5 | C16B—N2B—H2BC | 125.8 |
C16A—N2A—H2AC | 125.5 | C17B—N2B—H2BC | 125.8 |
C6A—C1A—N1A | 120.6 (3) | C6B—C1B—N1B | 120.6 (2) |
C6A—C1A—C2A | 123.1 (3) | C6B—C1B—C2B | 124.1 (3) |
N1A—C1A—C2A | 116.2 (3) | N1B—C1B—C2B | 115.2 (2) |
C1A—C2A—C3A | 109.6 (3) | C1B—C2B—C3B | 110.0 (3) |
C1A—C2A—H2AA | 109.8 | C1B—C2B—H2BA | 109.7 |
C3A—C2A—H2AA | 109.8 | C3B—C2B—H2BA | 109.7 |
C1A—C2A—H2AB | 109.8 | C1B—C2B—H2BB | 109.7 |
C3A—C2A—H2AB | 109.8 | C3B—C2B—H2BB | 109.7 |
H2AA—C2A—H2AB | 108.2 | H2BA—C2B—H2BB | 108.2 |
C4A—C3A—C2A | 112.4 (3) | C2B—C3B—C4B | 112.8 (3) |
C4A—C3A—H3AA | 109.1 | C2B—C3B—H3BA | 109.0 |
C2A—C3A—H3AA | 109.1 | C4B—C3B—H3BA | 109.0 |
C4A—C3A—H3AB | 109.1 | C2B—C3B—H3BB | 109.0 |
C2A—C3A—H3AB | 109.1 | C4B—C3B—H3BB | 109.0 |
H3AA—C3A—H3AB | 107.9 | H3BA—C3B—H3BB | 107.8 |
C3A—C4A—C22A | 110.9 (3) | C23B—C4B—C22B | 110.2 (3) |
C3A—C4A—C23A | 109.8 (3) | C23B—C4B—C5B | 109.4 (3) |
C22A—C4A—C23A | 108.6 (3) | C22B—C4B—C5B | 107.1 (2) |
C3A—C4A—C5A | 111.2 (3) | C23B—C4B—C3B | 109.2 (3) |
C22A—C4A—C5A | 106.2 (3) | C22B—C4B—C3B | 110.5 (3) |
C23A—C4A—C5A | 110.1 (3) | C5B—C4B—C3B | 110.4 (2) |
O1A—C5A—C6A | 120.3 (3) | O1B—C5B—C6B | 120.8 (2) |
O1A—C5A—C4A | 120.2 (3) | O1B—C5B—C4B | 119.6 (2) |
C6A—C5A—C4A | 119.5 (3) | C6B—C5B—C4B | 119.6 (2) |
C1A—C6A—C5A | 121.0 (3) | C1B—C6B—C5B | 120.1 (2) |
C1A—C6A—C7A | 120.5 (3) | C1B—C6B—C7B | 120.5 (2) |
C5A—C6A—C7A | 118.4 (3) | C5B—C6B—C7B | 119.3 (2) |
C10A—C7A—C6A | 109.8 (3) | C10B—C7B—C6B | 111.7 (2) |
C10A—C7A—C8A | 112.4 (2) | C10B—C7B—C8B | 111.9 (2) |
C6A—C7A—C8A | 111.1 (2) | C6B—C7B—C8B | 110.5 (2) |
C10A—C7A—H7AA | 107.8 | C10B—C7B—H7BA | 107.5 |
C6A—C7A—H7AA | 107.8 | C6B—C7B—H7BA | 107.5 |
C8A—C7A—H7AA | 107.8 | C8B—C7B—H7BA | 107.5 |
C9A—C8A—C18A | 124.4 (3) | C9B—C8B—C18B | 124.6 (3) |
C9A—C8A—C7A | 121.5 (3) | C9B—C8B—C7B | 121.1 (2) |
C18A—C8A—C7A | 114.0 (2) | C18B—C8B—C7B | 114.3 (2) |
C8A—C9A—N1A | 119.2 (3) | C8B—C9B—N1B | 119.2 (3) |
C8A—C9A—C21A | 127.7 (3) | C8B—C9B—C21B | 128.7 (3) |
N1A—C9A—C21A | 113.0 (3) | N1B—C9B—C21B | 112.1 (2) |
C17A—C10A—C11A | 105.9 (3) | C17B—C10B—C11B | 105.7 (3) |
C17A—C10A—C7A | 126.1 (3) | C17B—C10B—C7B | 124.9 (3) |
C11A—C10A—C7A | 127.9 (3) | C11B—C10B—C7B | 129.4 (2) |
C12A—C11A—C16A | 118.4 (3) | C12B—C11B—C16B | 118.7 (3) |
C12A—C11A—C10A | 134.9 (3) | C12B—C11B—C10B | 134.8 (3) |
C16A—C11A—C10A | 106.8 (3) | C16B—C11B—C10B | 106.5 (3) |
C13A—C12A—C11A | 118.3 (3) | C13B—C12B—C11B | 118.0 (3) |
C13A—C12A—H12A | 120.8 | C13B—C12B—H12B | 121.0 |
C11A—C12A—H12A | 120.8 | C11B—C12B—H12B | 121.0 |
C12A—C13A—C14A | 123.0 (3) | C12B—C13B—C14B | 123.0 (3) |
C12A—C13A—Br1A | 118.5 (3) | C12B—C13B—Br1B | 119.1 (3) |
C14A—C13A—Br1A | 118.5 (3) | C14B—C13B—Br1B | 117.9 (3) |
C15A—C14A—C13A | 119.6 (3) | C15B—C14B—C13B | 119.9 (3) |
C15A—C14A—H14A | 120.2 | C15B—C14B—H14B | 120.0 |
C13A—C14A—H14A | 120.2 | C13B—C14B—H14B | 120.0 |
C14A—C15A—C16A | 118.1 (3) | C14B—C15B—C16B | 118.3 (3) |
C14A—C15A—H15A | 120.9 | C14B—C15B—H15B | 120.9 |
C16A—C15A—H15A | 120.9 | C16B—C15B—H15B | 120.9 |
N2A—C16A—C15A | 129.8 (3) | N2B—C16B—C15B | 129.7 (3) |
N2A—C16A—C11A | 107.6 (3) | N2B—C16B—C11B | 108.2 (3) |
C15A—C16A—C11A | 122.6 (3) | C15B—C16B—C11B | 122.1 (3) |
N2A—C17A—C10A | 110.7 (3) | C10B—C17B—N2B | 111.1 (3) |
N2A—C17A—H17A | 124.6 | C10B—C17B—H17B | 124.4 |
C10A—C17A—H17A | 124.6 | N2B—C17B—H17B | 124.4 |
O2A—C18A—O3A | 122.6 (3) | O2B—C18B—O3B | 121.9 (3) |
O2A—C18A—C8A | 122.4 (3) | O2B—C18B—C8B | 122.7 (3) |
O3A—C18A—C8A | 115.0 (3) | O3B—C18B—C8B | 115.3 (2) |
O3A—C19A—C20A | 106.7 (3) | O3B—C19B—C20B | 106.0 (3) |
O3A—C19A—H19A | 110.4 | O3B—C19B—H19C | 110.5 |
C20A—C19A—H19A | 110.4 | C20B—C19B—H19C | 110.5 |
O3A—C19A—H19B | 110.4 | O3B—C19B—H19D | 110.5 |
C20A—C19A—H19B | 110.4 | C20B—C19B—H19D | 110.5 |
H19A—C19A—H19B | 108.6 | H19C—C19B—H19D | 108.7 |
C19A—C20A—H20A | 109.5 | C19B—C20B—H20D | 109.5 |
C19A—C20A—H20B | 109.5 | C19B—C20B—H20E | 109.5 |
H20A—C20A—H20B | 109.5 | H20D—C20B—H20E | 109.5 |
C19A—C20A—H20C | 109.5 | C19B—C20B—H20F | 109.5 |
H20A—C20A—H20C | 109.5 | H20D—C20B—H20F | 109.5 |
H20B—C20A—H20C | 109.5 | H20E—C20B—H20F | 109.5 |
C9A—C21A—H21A | 109.5 | C9B—C21B—H21D | 109.5 |
C9A—C21A—H21B | 109.5 | C9B—C21B—H21E | 109.5 |
H21A—C21A—H21B | 109.5 | H21D—C21B—H21E | 109.5 |
C9A—C21A—H21C | 109.5 | C9B—C21B—H21F | 109.5 |
H21A—C21A—H21C | 109.5 | H21D—C21B—H21F | 109.5 |
H21B—C21A—H21C | 109.5 | H21E—C21B—H21F | 109.5 |
C4A—C22A—H22A | 109.5 | C4B—C22B—H22D | 109.5 |
C4A—C22A—H22B | 109.5 | C4B—C22B—H22E | 109.5 |
H22A—C22A—H22B | 109.5 | H22D—C22B—H22E | 109.5 |
C4A—C22A—H22C | 109.5 | C4B—C22B—H22F | 109.5 |
H22A—C22A—H22C | 109.5 | H22D—C22B—H22F | 109.5 |
H22B—C22A—H22C | 109.5 | H22E—C22B—H22F | 109.5 |
C4A—C23A—H23A | 109.5 | C4B—C23B—H23G | 109.5 |
C4A—C23A—H23B | 109.5 | C4B—C23B—H23D | 109.5 |
H23A—C23A—H23B | 109.5 | H23G—C23B—H23D | 109.5 |
C4A—C23A—H23C | 109.5 | C4B—C23B—H23E | 109.5 |
H23A—C23A—H23C | 109.5 | H23G—C23B—H23E | 109.5 |
H23B—C23A—H23C | 109.5 | H23D—C23B—H23E | 109.5 |
C9A—N1A—C1A—C6A | 9.0 (5) | C9B—N1B—C1B—C6B | −12.8 (5) |
C9A—N1A—C1A—C2A | −171.1 (3) | C9B—N1B—C1B—C2B | 166.0 (3) |
C6A—C1A—C2A—C3A | 25.3 (5) | C6B—C1B—C2B—C3B | −19.8 (4) |
N1A—C1A—C2A—C3A | −154.6 (3) | N1B—C1B—C2B—C3B | 161.5 (3) |
C1A—C2A—C3A—C4A | −52.8 (4) | C1B—C2B—C3B—C4B | 50.6 (4) |
C2A—C3A—C4A—C22A | −67.6 (4) | C2B—C3B—C4B—C23B | −171.3 (3) |
C2A—C3A—C4A—C23A | 172.4 (3) | C2B—C3B—C4B—C22B | 67.4 (3) |
C2A—C3A—C4A—C5A | 50.3 (4) | C2B—C3B—C4B—C5B | −50.9 (4) |
C3A—C4A—C5A—O1A | 160.1 (4) | C23B—C4B—C5B—O1B | −42.1 (4) |
C22A—C4A—C5A—O1A | −79.2 (4) | C22B—C4B—C5B—O1B | 77.3 (3) |
C23A—C4A—C5A—O1A | 38.2 (5) | C3B—C4B—C5B—O1B | −162.4 (3) |
C3A—C4A—C5A—C6A | −20.3 (5) | C23B—C4B—C5B—C6B | 140.8 (3) |
C22A—C4A—C5A—C6A | 100.4 (4) | C22B—C4B—C5B—C6B | −99.8 (3) |
C23A—C4A—C5A—C6A | −142.3 (3) | C3B—C4B—C5B—C6B | 20.6 (4) |
N1A—C1A—C6A—C5A | −175.4 (3) | N1B—C1B—C6B—C5B | 167.9 (3) |
C2A—C1A—C6A—C5A | 4.7 (5) | C2B—C1B—C6B—C5B | −10.7 (5) |
N1A—C1A—C6A—C7A | 8.6 (5) | N1B—C1B—C6B—C7B | −8.2 (4) |
C2A—C1A—C6A—C7A | −171.3 (3) | C2B—C1B—C6B—C7B | 173.1 (3) |
O1A—C5A—C6A—C1A | 171.8 (3) | O1B—C5B—C6B—C1B | −166.9 (3) |
C4A—C5A—C6A—C1A | −7.8 (5) | C4B—C5B—C6B—C1B | 10.1 (4) |
O1A—C5A—C6A—C7A | −12.2 (5) | O1B—C5B—C6B—C7B | 9.3 (4) |
C4A—C5A—C6A—C7A | 168.2 (3) | C4B—C5B—C6B—C7B | −173.7 (2) |
C1A—C6A—C7A—C10A | 103.4 (3) | C1B—C6B—C7B—C10B | −101.1 (3) |
C5A—C6A—C7A—C10A | −72.6 (4) | C5B—C6B—C7B—C10B | 82.7 (3) |
C1A—C6A—C7A—C8A | −21.5 (4) | C1B—C6B—C7B—C8B | 24.2 (4) |
C5A—C6A—C7A—C8A | 162.4 (3) | C5B—C6B—C7B—C8B | −152.0 (2) |
C10A—C7A—C8A—C9A | −103.7 (3) | C10B—C7B—C8B—C9B | 102.7 (3) |
C6A—C7A—C8A—C9A | 19.7 (4) | C6B—C7B—C8B—C9B | −22.5 (4) |
C10A—C7A—C8A—C18A | 74.4 (3) | C10B—C7B—C8B—C18B | −77.3 (3) |
C6A—C7A—C8A—C18A | −162.2 (3) | C6B—C7B—C8B—C18B | 157.5 (2) |
C18A—C8A—C9A—N1A | 177.3 (3) | C18B—C8B—C9B—N1B | −175.1 (3) |
C7A—C8A—C9A—N1A | −4.9 (4) | C7B—C8B—C9B—N1B | 4.8 (4) |
C18A—C8A—C9A—C21A | −0.2 (5) | C18B—C8B—C9B—C21B | 2.4 (5) |
C7A—C8A—C9A—C21A | 177.7 (3) | C7B—C8B—C9B—C21B | −177.6 (3) |
C1A—N1A—C9A—C8A | −10.9 (5) | C1B—N1B—C9B—C8B | 14.5 (5) |
C1A—N1A—C9A—C21A | 166.9 (3) | C1B—N1B—C9B—C21B | −163.5 (3) |
C6A—C7A—C10A—C17A | 132.8 (3) | C6B—C7B—C10B—C17B | −127.5 (3) |
C8A—C7A—C10A—C17A | −102.9 (3) | C8B—C7B—C10B—C17B | 108.0 (3) |
C6A—C7A—C10A—C11A | −42.2 (4) | C6B—C7B—C10B—C11B | 52.7 (4) |
C8A—C7A—C10A—C11A | 82.1 (3) | C8B—C7B—C10B—C11B | −71.8 (3) |
C17A—C10A—C11A—C12A | 178.0 (3) | C17B—C10B—C11B—C12B | −177.8 (3) |
C7A—C10A—C11A—C12A | −6.2 (5) | C7B—C10B—C11B—C12B | 1.9 (5) |
C17A—C10A—C11A—C16A | −1.0 (3) | C17B—C10B—C11B—C16B | 0.7 (3) |
C7A—C10A—C11A—C16A | 174.8 (3) | C7B—C10B—C11B—C16B | −179.5 (3) |
C16A—C11A—C12A—C13A | −1.6 (4) | C16B—C11B—C12B—C13B | 1.2 (4) |
C10A—C11A—C12A—C13A | 179.5 (3) | C10B—C11B—C12B—C13B | 179.7 (3) |
C11A—C12A—C13A—C14A | 0.3 (5) | C11B—C12B—C13B—C14B | 0.8 (5) |
C11A—C12A—C13A—Br1A | −179.6 (2) | C11B—C12B—C13B—Br1B | 179.5 (2) |
C12A—C13A—C14A—C15A | 1.3 (5) | C12B—C13B—C14B—C15B | −1.5 (5) |
Br1A—C13A—C14A—C15A | −178.8 (3) | Br1B—C13B—C14B—C15B | 179.8 (2) |
C13A—C14A—C15A—C16A | −1.5 (5) | C13B—C14B—C15B—C16B | 0.0 (5) |
C17A—N2A—C16A—C15A | 179.6 (3) | C17B—N2B—C16B—C15B | −178.7 (3) |
C17A—N2A—C16A—C11A | −1.4 (3) | C17B—N2B—C16B—C11B | 0.4 (3) |
C14A—C15A—C16A—N2A | 179.1 (3) | C14B—C15B—C16B—N2B | −179.0 (3) |
C14A—C15A—C16A—C11A | 0.2 (5) | C14B—C15B—C16B—C11B | 2.0 (4) |
C12A—C11A—C16A—N2A | −177.7 (2) | C12B—C11B—C16B—N2B | 178.1 (2) |
C10A—C11A—C16A—N2A | 1.5 (3) | C10B—C11B—C16B—N2B | −0.7 (3) |
C12A—C11A—C16A—C15A | 1.4 (4) | C12B—C11B—C16B—C15B | −2.7 (4) |
C10A—C11A—C16A—C15A | −179.4 (3) | C10B—C11B—C16B—C15B | 178.5 (3) |
C16A—N2A—C17A—C10A | 0.8 (3) | C11B—C10B—C17B—N2B | −0.5 (3) |
C11A—C10A—C17A—N2A | 0.1 (3) | C7B—C10B—C17B—N2B | 179.7 (2) |
C7A—C10A—C17A—N2A | −175.8 (3) | C16B—N2B—C17B—C10B | 0.1 (3) |
C19A—O3A—C18A—O2A | −0.1 (5) | C19B—O3B—C18B—O2B | 1.6 (4) |
C19A—O3A—C18A—C8A | 178.3 (3) | C19B—O3B—C18B—C8B | −178.7 (3) |
C9A—C8A—C18A—O2A | −171.6 (3) | C9B—C8B—C18B—O2B | 170.5 (3) |
C7A—C8A—C18A—O2A | 10.4 (4) | C7B—C8B—C18B—O2B | −9.5 (4) |
C9A—C8A—C18A—O3A | 10.0 (4) | C9B—C8B—C18B—O3B | −9.3 (4) |
C7A—C8A—C18A—O3A | −168.1 (3) | C7B—C8B—C18B—O3B | 170.7 (2) |
C18A—O3A—C19A—C20A | −178.3 (3) | C18B—O3B—C19B—C20B | −176.5 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2A—H2AB···O1B | 0.99 | 2.51 | 3.296 (4) | 136 |
C21B—H21D···O3B | 0.98 | 2.17 | 2.749 (4) | 116 |
N1A—H1AA···O1B | 0.88 | 2.01 | 2.870 (3) | 165 |
N2A—H2AC···O2Bi | 0.88 | 1.94 | 2.807 (3) | 167 |
N1B—H1BA···O1Aii | 0.88 | 1.97 | 2.845 (3) | 173 |
N2B—H2BC···O2Aiii | 0.88 | 2.05 | 2.889 (3) | 159 |
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) x+1, y, z; (iii) −x, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C23H25BrN2O3 |
Mr | 457.36 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 123 |
a, b, c (Å) | 14.0044 (6), 16.8802 (5), 18.8341 (7) |
β (°) | 105.582 (4) |
V (Å3) | 4288.7 (3) |
Z | 8 |
Radiation type | Cu Kα |
µ (mm−1) | 2.83 |
Crystal size (mm) | 0.83 × 0.69 × 0.48 |
Data collection | |
Diffractometer | Agilent Xcalibur (Ruby, Gemini) diffractometer |
Absorption correction | Analytical [(Clark & Reid, 1995) implemented in CrysAlis RED (Agilent (2011)] |
Tmin, Tmax | 0.270, 0.514 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17300, 8621, 7227 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.629 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.058, 0.159, 1.02 |
No. of reflections | 8621 |
No. of parameters | 531 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.31, −1.01 |
Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
C2A—H2AB···O1B | 0.99 | 2.51 | 3.296 (4) | 136.1 |
N1A—H1AA···O1B | 0.88 | 2.01 | 2.870 (3) | 164.7 |
N2A—H2AC···O2Bi | 0.88 | 1.94 | 2.807 (3) | 167.4 |
N1B—H1BA···O1Aii | 0.88 | 1.97 | 2.845 (3) | 173.0 |
N2B—H2BC···O2Aiii | 0.88 | 2.05 | 2.889 (3) | 158.8 |
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) x+1, y, z; (iii) −x, y−1/2, −z+1/2. |
Acknowledgements
RJB acknowledges the NSF–MRI program (grant No. CHE-0619278) for funds to purchase the diffractometer.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
1,4-Dihydropyridines (DHP), of which nifedipine is the prototype for this group, are one of the known classes of calcium antagonists, which reversibly block Ca2+ influx through L-type calcium channels and are frequently used for the treatment of cardiovascular diseases like angina, hypertension and supraventricular tachycardia (Triggle, 2003; Şafak & Şimşek, 2006).
Since the introduction of nifedipine into clinical use, many modifications have been made such as fusing one of the carbonyl groups into the ring system or substitution of the phenyl ring with heteroaromatic rings in order to elucidate the SARs (severe acute respiratory syndrome) and to enhance calcium-modulating effects (Gordeev et al., 1998). Following on from these results, we synthesized the title compound and determined its structure.
In the title compound (I), (Fig. 1, Fig. 2), the 5-bromo-1H-indole ring is almost planar in both of the molecules with a maximum deviation from the mean plane of 0.021 (3) Å for atom N2A and -0.020 (3) Å for atom N2B. The cyclohexene rings adopt a sofa conformation and are puckered with puckering parameters in molecule A and B (Cremer & Pople, 1975) of QT = 0.472 (4) Å, θ = 120.7 (5) °, ϕ = 295.1 (5) ° and QT = 0.475 (4) Å, θ = 62.7 (4) °, ϕ = 120.5 (4) °, respectively. The values of the bond lengths (Allen, 2002) and angles in (I) are in normal ranges and are comparable with those of related structures (El-Khouly et al., 2012; Öztürk Yildirim et al., 2012).
In the crystal, molecules are linked by pairs of intermolecular N—H···O hydrogen bonds, forming dimers with R12(6) ring motifs (Bernstein et al., 1995; Etter et al., 1990), and these dimers are connected by N—H···O hydrogen bonds, generating one-dimensional chains along [110] (Table 1, Fig. 3).