Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102006443/sk1544sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102006443/sk1544IIsup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102006443/sk1544IIIsup3.hkl |
CCDC references: 188627; 188628
The title compounds were synthesized at the Research Triangle Institute in North Carolina (Brine et al., 1992). Crystal of both compounds were grown by slow evaporation from diisopropyl ether solutions.
The H atoms of compound (II) were refined as riding (C—H = 0.93–0.98 Å), as were the H atoms of compound (III), except for the hydroxy H atom, which was refined freely.
Data collection: SMART (Bruker 2001) for (II); SMART (Bruker, 2001) for (III). For both compounds, cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001). Software used to prepare material for publication: SHELXTL (Bruker, 2001) for (III).
C30H33BrN2O3 | F(000) = 1144 |
Mr = 549.49 | Dx = 1.296 Mg m−3 |
Monoclinic, P21 | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: P 2yb | Cell parameters from 6392 reflections |
a = 10.8806 (2) Å | θ = 3.9–66.8° |
b = 22.4670 (5) Å | µ = 2.24 mm−1 |
c = 11.5313 (3) Å | T = 153 K |
β = 92.208 (1)° | Prism, colorless |
V = 2816.78 (11) Å3 | 0.56 × 0.44 × 0.24 mm |
Z = 4 |
Bruker CCD area-detector diffractometer | 7419 independent reflections |
Radiation source: rotating anode | 6654 reflections with I > 2σ(I) |
Gobel mirrors monochromator | Rint = 0.024 |
ω scans | θmax = 67.0°, θmin = 3.9° |
Absorption correction: integration (Bruker, 2001) | h = −12→12 |
Tmin = 0.608, Tmax = 0.931 | k = −23→26 |
13643 measured reflections | l = −12→13 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.047 | w = 1/[σ2(Fo2) + (0.0803P)2 + 0.154P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.122 | (Δ/σ)max = 0.001 |
S = 1.07 | Δρmax = 0.23 e Å−3 |
7419 reflections | Δρmin = −0.45 e Å−3 |
650 parameters | Extinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1 restraint | Extinction coefficient: 0.0386 (10) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983) |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.032 (15) |
C30H33BrN2O3 | V = 2816.78 (11) Å3 |
Mr = 549.49 | Z = 4 |
Monoclinic, P21 | Cu Kα radiation |
a = 10.8806 (2) Å | µ = 2.24 mm−1 |
b = 22.4670 (5) Å | T = 153 K |
c = 11.5313 (3) Å | 0.56 × 0.44 × 0.24 mm |
β = 92.208 (1)° |
Bruker CCD area-detector diffractometer | 7419 independent reflections |
Absorption correction: integration (Bruker, 2001) | 6654 reflections with I > 2σ(I) |
Tmin = 0.608, Tmax = 0.931 | Rint = 0.024 |
13643 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | H-atom parameters constrained |
wR(F2) = 0.122 | Δρmax = 0.23 e Å−3 |
S = 1.07 | Δρmin = −0.45 e Å−3 |
7419 reflections | Absolute structure: Flack (1983) |
650 parameters | Absolute structure parameter: 0.032 (15) |
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 | ||
Br1 | 1.31391 (4) | 0.70497 (3) | 0.08320 (8) | 0.1492 (3) | |
N1 | 0.6620 (2) | 0.53291 (11) | 0.2724 (2) | 0.0698 (5) | |
C2 | 0.6512 (3) | 0.46973 (14) | 0.3022 (3) | 0.0754 (7) | |
H2A | 0.6698 | 0.4457 | 0.2351 | 0.090* | |
H2B | 0.5673 | 0.4613 | 0.3223 | 0.090* | |
C3 | 0.7381 (3) | 0.45283 (14) | 0.4034 (3) | 0.0733 (7) | |
H3A | 0.7203 | 0.4114 | 0.4237 | 0.088* | |
C4 | 0.7076 (3) | 0.49106 (13) | 0.5071 (2) | 0.0696 (6) | |
H4A | 0.6219 | 0.4823 | 0.5241 | 0.083* | |
C5 | 0.7123 (4) | 0.55663 (14) | 0.4767 (3) | 0.0832 (8) | |
H5A | 0.7960 | 0.5679 | 0.4604 | 0.100* | |
H5B | 0.6862 | 0.5802 | 0.5418 | 0.100* | |
C6 | 0.6281 (4) | 0.56853 (16) | 0.3709 (3) | 0.0856 (9) | |
H6A | 0.5439 | 0.5596 | 0.3896 | 0.103* | |
H6B | 0.6324 | 0.6104 | 0.3507 | 0.103* | |
N7 | 0.7828 (2) | 0.47563 (11) | 0.6141 (2) | 0.0719 (6) | |
C8 | 0.7520 (3) | 0.42505 (14) | 0.6712 (3) | 0.0760 (7) | |
O8 | 0.6656 (2) | 0.39404 (11) | 0.6390 (2) | 0.0890 (6) | |
C9 | 0.8341 (4) | 0.40870 (17) | 0.7771 (3) | 0.0928 (10) | |
H9A | 0.9170 | 0.4013 | 0.7524 | 0.111* | |
H9B | 0.8373 | 0.4420 | 0.8306 | 0.111* | |
C10 | 0.7883 (5) | 0.3544 (2) | 0.8388 (4) | 0.1120 (13) | |
H10A | 0.8422 | 0.3457 | 0.9045 | 0.168* | |
H10B | 0.7865 | 0.3211 | 0.7866 | 0.168* | |
H10C | 0.7069 | 0.3618 | 0.8647 | 0.168* | |
C1A | 0.8760 (3) | 0.51521 (15) | 0.6590 (3) | 0.0808 (8) | |
C6A | 0.8415 (5) | 0.56342 (17) | 0.7281 (3) | 0.0957 (11) | |
H6AA | 0.7594 | 0.5694 | 0.7444 | 0.115* | |
C5A | 0.9312 (8) | 0.6020 (2) | 0.7715 (4) | 0.131 (2) | |
H5AA | 0.9093 | 0.6348 | 0.8152 | 0.157* | |
C4A | 1.0528 (8) | 0.5916 (3) | 0.7498 (6) | 0.148 (3) | |
H4AA | 1.1130 | 0.6175 | 0.7793 | 0.177* | |
C3A | 1.0859 (6) | 0.5439 (3) | 0.6855 (6) | 0.142 (2) | |
H3AA | 1.1688 | 0.5372 | 0.6732 | 0.170* | |
C2A | 0.9984 (4) | 0.5050 (2) | 0.6379 (4) | 0.1019 (11) | |
H2AA | 1.0217 | 0.4729 | 0.5928 | 0.122* | |
C1' | 0.5864 (3) | 0.54758 (16) | 0.1685 (3) | 0.0750 (7) | |
H1'A | 0.5699 | 0.5900 | 0.1675 | 0.090* | |
H1'B | 0.5082 | 0.5270 | 0.1716 | 0.090* | |
C2' | 0.6476 (3) | 0.53051 (14) | 0.0583 (2) | 0.0703 (7) | |
H2'A | 0.6703 | 0.4883 | 0.0623 | 0.084* | |
C1B | 0.5714 (3) | 0.54131 (14) | −0.0503 (2) | 0.0708 (7) | |
C6B | 0.5606 (4) | 0.49751 (19) | −0.1339 (3) | 0.0934 (9) | |
H6BA | 0.6003 | 0.4613 | −0.1214 | 0.112* | |
C5B | 0.4918 (4) | 0.5063 (2) | −0.2364 (4) | 0.1066 (13) | |
H5BA | 0.4868 | 0.4765 | −0.2924 | 0.128* | |
C4B | 0.4314 (4) | 0.5591 (3) | −0.2544 (4) | 0.1085 (14) | |
H4BA | 0.3856 | 0.5654 | −0.3231 | 0.130* | |
C3B | 0.4383 (4) | 0.6027 (2) | −0.1714 (4) | 0.1123 (14) | |
H3BA | 0.3946 | 0.6379 | −0.1826 | 0.135* | |
C2B | 0.5105 (4) | 0.59443 (19) | −0.0703 (3) | 0.0940 (10) | |
H2BA | 0.5177 | 0.6249 | −0.0158 | 0.113* | |
O11 | 0.75949 (19) | 0.56638 (9) | 0.05400 (19) | 0.0746 (5) | |
C12X | 0.8672 (3) | 0.53824 (14) | 0.0593 (3) | 0.0737 (7) | |
O12 | 0.8776 (2) | 0.48459 (11) | 0.0566 (3) | 0.0994 (7) | |
C1C | 0.9738 (3) | 0.57982 (14) | 0.0691 (3) | 0.0714 (7) | |
C6C | 0.9585 (3) | 0.64092 (18) | 0.0714 (3) | 0.0909 (9) | |
H6CA | 0.8796 | 0.6570 | 0.0709 | 0.109* | |
C5C | 1.0593 (4) | 0.67826 (19) | 0.0746 (5) | 0.1072 (13) | |
H5CA | 1.0495 | 0.7194 | 0.0736 | 0.129* | |
C4C | 1.1755 (3) | 0.65304 (19) | 0.0794 (4) | 0.0977 (11) | |
C3C | 1.1926 (3) | 0.59317 (19) | 0.0764 (4) | 0.0977 (10) | |
H3CA | 1.2715 | 0.5772 | 0.0775 | 0.117* | |
C2C | 1.0909 (3) | 0.55651 (18) | 0.0714 (3) | 0.0902 (9) | |
H2CA | 1.1015 | 0.5155 | 0.0697 | 0.108* | |
C3' | 0.8706 (4) | 0.4553 (2) | 0.3692 (3) | 0.0980 (11) | |
H3'A | 0.9233 | 0.4445 | 0.4345 | 0.147* | |
H3'B | 0.8900 | 0.4950 | 0.3449 | 0.147* | |
H3'C | 0.8828 | 0.4281 | 0.3065 | 0.147* | |
N11 | 0.3408 (2) | 0.30120 (12) | 0.8114 (2) | 0.0780 (6) | |
Br11 | −0.34520 (5) | 0.14363 (3) | 0.57529 (8) | 0.1575 (3) | |
C12 | 0.3757 (4) | 0.36120 (19) | 0.8462 (3) | 0.0946 (10) | |
H12A | 0.3732 | 0.3869 | 0.7786 | 0.114* | |
H12B | 0.4593 | 0.3609 | 0.8785 | 0.114* | |
C13 | 0.2903 (4) | 0.38568 (16) | 0.9356 (3) | 0.0877 (9) | |
H13A | 0.3238 | 0.4242 | 0.9613 | 0.105* | |
C14 | 0.2958 (3) | 0.34423 (16) | 1.0410 (3) | 0.0763 (7) | |
H14A | 0.3813 | 0.3443 | 1.0709 | 0.092* | |
C15 | 0.2663 (3) | 0.28030 (15) | 1.0042 (3) | 0.0835 (8) | |
H15A | 0.2770 | 0.2540 | 1.0705 | 0.100* | |
H15B | 0.1813 | 0.2777 | 0.9760 | 0.100* | |
C16 | 0.3508 (3) | 0.26102 (18) | 0.9093 (3) | 0.0874 (9) | |
H16A | 0.4351 | 0.2604 | 0.9397 | 0.105* | |
H16B | 0.3291 | 0.2211 | 0.8840 | 0.105* | |
N17 | 0.2197 (2) | 0.36480 (12) | 1.1372 (2) | 0.0737 (6) | |
C18 | 0.2643 (3) | 0.41108 (18) | 1.2029 (3) | 0.0845 (8) | |
O18 | 0.3590 (2) | 0.43685 (15) | 1.1791 (2) | 0.1107 (9) | |
C19 | 0.1906 (4) | 0.4295 (2) | 1.3054 (4) | 0.0988 (11) | |
H19A | 0.1094 | 0.4420 | 1.2776 | 0.119* | |
H19B | 0.1806 | 0.3953 | 1.3556 | 0.119* | |
C20 | 0.2490 (6) | 0.4787 (3) | 1.3742 (6) | 0.148 (3) | |
H20A | 0.1985 | 0.4886 | 1.4379 | 0.223* | |
H20B | 0.2575 | 0.5130 | 1.3255 | 0.223* | |
H20C | 0.3287 | 0.4663 | 1.4035 | 0.223* | |
C11A | 0.1114 (3) | 0.33283 (14) | 1.1701 (2) | 0.0707 (7) | |
C12A | 0.1226 (4) | 0.28576 (18) | 1.2477 (3) | 0.0918 (10) | |
H12C | 0.1995 | 0.2745 | 1.2781 | 0.110* | |
C13A | 0.0174 (6) | 0.25561 (19) | 1.2794 (4) | 0.1134 (15) | |
H13B | 0.0240 | 0.2235 | 1.3301 | 0.136* | |
C14A | −0.0949 (5) | 0.2729 (3) | 1.2367 (4) | 0.1196 (16) | |
H14B | −0.1647 | 0.2528 | 1.2595 | 0.143* | |
C15A | −0.1070 (4) | 0.3191 (3) | 1.1611 (4) | 0.1117 (14) | |
H15C | −0.1844 | 0.3303 | 1.1317 | 0.134* | |
C16A | −0.0040 (3) | 0.34938 (18) | 1.1285 (3) | 0.0869 (8) | |
H16C | −0.0123 | 0.3814 | 1.0777 | 0.104* | |
C11' | 0.4041 (3) | 0.28139 (17) | 0.7090 (3) | 0.0802 (8) | |
H11A | 0.4110 | 0.2383 | 0.7098 | 0.096* | |
H11B | 0.4865 | 0.2979 | 0.7104 | 0.096* | |
C12' | 0.3342 (3) | 0.30112 (16) | 0.5995 (3) | 0.0778 (7) | |
H12D | 0.3202 | 0.3442 | 0.6021 | 0.093* | |
C11B | 0.3966 (3) | 0.28517 (14) | 0.4889 (3) | 0.0743 (7) | |
C16B | 0.4690 (4) | 0.32519 (19) | 0.4352 (3) | 0.0980 (11) | |
H1CA | 0.4820 | 0.3625 | 0.4685 | 0.118* | |
C15B | 0.5236 (5) | 0.3117 (2) | 0.3325 (4) | 0.1121 (13) | |
H15D | 0.5720 | 0.3399 | 0.2969 | 0.135* | |
C14B | 0.5067 (4) | 0.2573 (2) | 0.2833 (3) | 0.1044 (12) | |
H14C | 0.5443 | 0.2480 | 0.2146 | 0.125* | |
C13B | 0.4333 (5) | 0.2159 (2) | 0.3356 (4) | 0.1095 (12) | |
H13C | 0.4200 | 0.1788 | 0.3014 | 0.131* | |
C12B | 0.3797 (4) | 0.22966 (17) | 0.4394 (4) | 0.0973 (10) | |
H12E | 0.3322 | 0.2014 | 0.4759 | 0.117* | |
O21 | 0.21741 (19) | 0.27019 (11) | 0.5997 (2) | 0.0810 (5) | |
C22 | 0.1136 (3) | 0.30167 (15) | 0.5851 (2) | 0.0734 (7) | |
O22 | 0.1111 (3) | 0.35448 (13) | 0.5727 (3) | 0.1037 (7) | |
C11C | 0.0040 (3) | 0.26211 (15) | 0.5863 (2) | 0.0714 (7) | |
C16C | −0.1106 (3) | 0.28650 (18) | 0.5620 (3) | 0.0918 (9) | |
H16D | −0.1178 | 0.3271 | 0.5479 | 0.110* | |
C15C | −0.2147 (4) | 0.2513 (2) | 0.5585 (4) | 0.0977 (10) | |
H15E | −0.2918 | 0.2676 | 0.5415 | 0.117* | |
C14C | −0.2014 (3) | 0.1925 (2) | 0.5803 (4) | 0.0990 (11) | |
C13C | −0.0908 (4) | 0.1661 (2) | 0.6040 (5) | 0.1201 (15) | |
H13D | −0.0851 | 0.1253 | 0.6173 | 0.144* | |
C12C | 0.0137 (3) | 0.20201 (19) | 0.6078 (4) | 0.0959 (10) | |
H12F | 0.0904 | 0.1853 | 0.6250 | 0.115* | |
C13' | 0.1613 (5) | 0.3970 (2) | 0.8846 (3) | 0.1101 (13) | |
H13E | 0.1658 | 0.4233 | 0.8192 | 0.165* | |
H13F | 0.1120 | 0.4150 | 0.9423 | 0.165* | |
H13G | 0.1249 | 0.3600 | 0.8600 | 0.165* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0749 (3) | 0.1135 (4) | 0.2608 (7) | −0.0262 (3) | 0.0293 (3) | −0.0646 (4) |
N1 | 0.0604 (13) | 0.0668 (13) | 0.0818 (13) | 0.0044 (10) | −0.0032 (10) | 0.0024 (10) |
C2 | 0.0724 (19) | 0.0672 (16) | 0.0857 (17) | −0.0001 (13) | −0.0079 (13) | −0.0013 (12) |
C3 | 0.0710 (18) | 0.0626 (15) | 0.0857 (17) | 0.0045 (13) | −0.0054 (13) | 0.0009 (12) |
C4 | 0.0559 (14) | 0.0713 (16) | 0.0811 (16) | 0.0021 (12) | −0.0015 (11) | 0.0027 (12) |
C5 | 0.097 (2) | 0.0644 (16) | 0.0871 (18) | 0.0093 (16) | −0.0042 (15) | −0.0071 (13) |
C6 | 0.088 (2) | 0.0750 (19) | 0.0931 (19) | 0.0225 (17) | −0.0008 (15) | 0.0028 (14) |
N7 | 0.0673 (14) | 0.0659 (13) | 0.0818 (13) | −0.0046 (11) | −0.0047 (10) | 0.0025 (10) |
C8 | 0.0732 (19) | 0.0656 (16) | 0.0885 (17) | 0.0001 (14) | −0.0041 (13) | 0.0021 (12) |
O8 | 0.0803 (15) | 0.0799 (14) | 0.1052 (14) | −0.0178 (12) | −0.0160 (11) | 0.0117 (11) |
C9 | 0.095 (3) | 0.080 (2) | 0.101 (2) | −0.0075 (19) | −0.0230 (17) | 0.0151 (16) |
C10 | 0.123 (4) | 0.094 (3) | 0.116 (3) | −0.015 (2) | −0.023 (2) | 0.033 (2) |
C1A | 0.081 (2) | 0.0761 (18) | 0.0840 (17) | −0.0162 (16) | −0.0081 (13) | 0.0053 (13) |
C6A | 0.119 (3) | 0.075 (2) | 0.092 (2) | −0.019 (2) | −0.0059 (18) | 0.0027 (15) |
C5A | 0.200 (7) | 0.088 (3) | 0.101 (3) | −0.044 (4) | −0.029 (3) | 0.001 (2) |
C4A | 0.164 (6) | 0.137 (5) | 0.137 (4) | −0.079 (5) | −0.053 (4) | 0.016 (3) |
C3A | 0.096 (3) | 0.159 (5) | 0.168 (4) | −0.053 (4) | −0.034 (3) | 0.014 (4) |
C2A | 0.074 (2) | 0.107 (3) | 0.123 (3) | −0.018 (2) | −0.0201 (18) | 0.004 (2) |
C1' | 0.0546 (15) | 0.0824 (18) | 0.0877 (17) | 0.0011 (13) | 0.0003 (12) | 0.0108 (14) |
C2' | 0.0570 (16) | 0.0635 (15) | 0.0905 (17) | −0.0030 (12) | 0.0035 (12) | 0.0089 (12) |
C1B | 0.0603 (15) | 0.0707 (16) | 0.0819 (16) | −0.0092 (13) | 0.0093 (11) | 0.0079 (12) |
C6B | 0.090 (2) | 0.087 (2) | 0.102 (2) | −0.0160 (19) | −0.0004 (17) | 0.0041 (17) |
C5B | 0.103 (3) | 0.123 (3) | 0.094 (2) | −0.034 (3) | −0.0028 (19) | 0.003 (2) |
C4B | 0.084 (3) | 0.145 (4) | 0.096 (2) | −0.030 (3) | −0.0089 (17) | 0.039 (3) |
C3B | 0.106 (3) | 0.123 (4) | 0.108 (3) | 0.020 (3) | 0.003 (2) | 0.040 (3) |
C2B | 0.100 (3) | 0.088 (2) | 0.094 (2) | 0.009 (2) | 0.0027 (17) | 0.0181 (16) |
O11 | 0.0551 (11) | 0.0634 (11) | 0.1057 (13) | 0.0011 (9) | 0.0069 (9) | 0.0063 (9) |
C12X | 0.0610 (17) | 0.0709 (18) | 0.0894 (17) | 0.0042 (13) | 0.0050 (12) | 0.0015 (13) |
O12 | 0.0695 (14) | 0.0673 (14) | 0.162 (2) | 0.0058 (11) | 0.0090 (13) | −0.0056 (13) |
C1C | 0.0576 (16) | 0.0703 (16) | 0.0866 (17) | 0.0007 (13) | 0.0064 (12) | −0.0025 (12) |
C6C | 0.0621 (17) | 0.080 (2) | 0.131 (3) | 0.0064 (16) | 0.0093 (16) | −0.0160 (18) |
C5C | 0.076 (2) | 0.074 (2) | 0.172 (4) | −0.0079 (18) | 0.017 (2) | −0.027 (2) |
C4C | 0.0645 (19) | 0.091 (3) | 0.139 (3) | −0.0130 (19) | 0.0135 (18) | −0.028 (2) |
C3C | 0.0538 (17) | 0.095 (3) | 0.145 (3) | 0.0040 (17) | 0.0056 (17) | −0.015 (2) |
C2C | 0.0646 (19) | 0.080 (2) | 0.126 (3) | 0.0069 (16) | 0.0069 (16) | −0.0047 (18) |
C3' | 0.075 (2) | 0.121 (3) | 0.097 (2) | 0.029 (2) | 0.0014 (15) | −0.0101 (19) |
N11 | 0.0698 (15) | 0.0767 (15) | 0.0883 (15) | 0.0014 (12) | 0.0144 (11) | −0.0065 (12) |
Br11 | 0.0800 (3) | 0.1343 (5) | 0.2563 (8) | −0.0328 (3) | −0.0163 (4) | 0.0087 (5) |
C12 | 0.091 (2) | 0.097 (2) | 0.097 (2) | −0.018 (2) | 0.0196 (16) | −0.0066 (17) |
C13 | 0.101 (3) | 0.0740 (19) | 0.0894 (19) | −0.0136 (18) | 0.0190 (16) | −0.0082 (15) |
C14 | 0.0542 (16) | 0.088 (2) | 0.0868 (17) | −0.0005 (14) | 0.0050 (12) | −0.0068 (14) |
C15 | 0.085 (2) | 0.0739 (19) | 0.0921 (19) | 0.0067 (16) | 0.0124 (15) | 0.0005 (14) |
C16 | 0.075 (2) | 0.087 (2) | 0.100 (2) | 0.0170 (17) | 0.0107 (15) | −0.0034 (16) |
N17 | 0.0587 (14) | 0.0781 (15) | 0.0844 (14) | −0.0034 (11) | 0.0035 (10) | −0.0064 (11) |
C18 | 0.0661 (18) | 0.096 (2) | 0.0909 (19) | −0.0073 (17) | 0.0008 (13) | −0.0165 (15) |
O18 | 0.0795 (16) | 0.137 (3) | 0.1162 (17) | −0.0384 (17) | 0.0149 (13) | −0.0342 (16) |
C19 | 0.081 (2) | 0.102 (3) | 0.115 (2) | −0.016 (2) | 0.0187 (18) | −0.026 (2) |
C20 | 0.128 (4) | 0.148 (5) | 0.173 (5) | −0.051 (4) | 0.047 (4) | −0.080 (4) |
C11A | 0.0641 (17) | 0.0712 (16) | 0.0773 (15) | −0.0046 (13) | 0.0085 (11) | −0.0068 (12) |
C12A | 0.108 (3) | 0.086 (2) | 0.0824 (19) | 0.0041 (19) | 0.0099 (16) | 0.0024 (15) |
C13A | 0.161 (5) | 0.079 (2) | 0.103 (3) | −0.019 (3) | 0.036 (3) | 0.0011 (18) |
C14A | 0.113 (4) | 0.132 (4) | 0.116 (3) | −0.045 (3) | 0.033 (3) | −0.017 (3) |
C15A | 0.071 (2) | 0.138 (4) | 0.127 (3) | −0.015 (2) | 0.0160 (19) | −0.019 (3) |
C16A | 0.0631 (18) | 0.094 (2) | 0.104 (2) | 0.0001 (16) | 0.0087 (14) | −0.0016 (17) |
C11' | 0.0574 (16) | 0.097 (2) | 0.0872 (18) | 0.0035 (15) | 0.0081 (12) | −0.0079 (15) |
C12' | 0.0597 (17) | 0.0765 (18) | 0.0975 (19) | 0.0023 (14) | 0.0089 (13) | −0.0039 (14) |
C11B | 0.0641 (17) | 0.0761 (18) | 0.0825 (16) | 0.0046 (14) | 0.0027 (12) | −0.0004 (13) |
C16B | 0.094 (3) | 0.093 (2) | 0.108 (2) | −0.021 (2) | 0.0153 (18) | −0.0162 (19) |
C15B | 0.115 (3) | 0.115 (3) | 0.109 (3) | −0.027 (3) | 0.034 (2) | −0.006 (2) |
C14B | 0.112 (3) | 0.109 (3) | 0.093 (2) | 0.011 (3) | 0.0194 (19) | −0.001 (2) |
C13B | 0.125 (3) | 0.083 (2) | 0.121 (3) | 0.005 (2) | 0.027 (2) | −0.014 (2) |
C12B | 0.106 (3) | 0.0714 (19) | 0.116 (3) | 0.0064 (19) | 0.029 (2) | 0.0006 (17) |
O21 | 0.0558 (11) | 0.0744 (12) | 0.1130 (14) | 0.0037 (10) | 0.0044 (9) | −0.0033 (10) |
C22 | 0.0621 (17) | 0.0809 (19) | 0.0775 (16) | 0.0022 (14) | 0.0056 (11) | 0.0009 (13) |
O22 | 0.0746 (16) | 0.0792 (16) | 0.157 (2) | 0.0061 (13) | 0.0019 (13) | 0.0134 (14) |
C11C | 0.0583 (15) | 0.0794 (18) | 0.0766 (15) | 0.0036 (13) | 0.0049 (11) | 0.0011 (12) |
C16C | 0.0647 (19) | 0.085 (2) | 0.125 (3) | 0.0086 (16) | 0.0065 (17) | 0.0013 (18) |
C15C | 0.0611 (19) | 0.105 (3) | 0.127 (3) | 0.0067 (18) | −0.0015 (17) | 0.000 (2) |
C14C | 0.0606 (19) | 0.107 (3) | 0.129 (3) | −0.0085 (19) | −0.0020 (17) | 0.003 (2) |
C13C | 0.084 (3) | 0.094 (3) | 0.181 (4) | −0.012 (2) | −0.009 (3) | 0.029 (3) |
C12C | 0.0625 (18) | 0.094 (2) | 0.131 (3) | −0.0025 (18) | −0.0054 (16) | 0.023 (2) |
C13' | 0.122 (3) | 0.113 (3) | 0.095 (2) | 0.038 (3) | −0.003 (2) | 0.010 (2) |
Br1—C4C | 1.904 (4) | N11—C16 | 1.446 (5) |
N1—C6 | 1.449 (4) | N11—C12 | 1.453 (5) |
N1—C1' | 1.465 (4) | N11—C11' | 1.459 (4) |
N1—C2 | 1.466 (4) | Br11—C14C | 1.910 (4) |
C2—C3 | 1.522 (4) | C12—C13 | 1.518 (5) |
C2—H2A | 0.9700 | C12—H12A | 0.9700 |
C2—H2B | 0.9700 | C12—H12B | 0.9700 |
C3—C3' | 1.510 (5) | C13—C13' | 1.522 (6) |
C3—C4 | 1.520 (4) | C13—C14 | 1.530 (5) |
C3—H3A | 0.9800 | C13—H13A | 0.9800 |
C4—N7 | 1.494 (3) | C14—N17 | 1.483 (4) |
C4—C5 | 1.515 (4) | C14—C15 | 1.528 (5) |
C4—H4A | 0.9800 | C14—H14A | 0.9800 |
C5—C6 | 1.521 (5) | C15—C16 | 1.520 (5) |
C5—H5A | 0.9700 | C15—H15A | 0.9700 |
C5—H5B | 0.9700 | C15—H15B | 0.9700 |
C6—H6A | 0.9700 | C16—H16A | 0.9700 |
C6—H6B | 0.9700 | C16—H16B | 0.9700 |
N7—C8 | 1.362 (4) | N17—C18 | 1.364 (4) |
N7—C1A | 1.431 (4) | N17—C11A | 1.444 (4) |
C8—O8 | 1.217 (4) | C18—O18 | 1.222 (4) |
C8—C9 | 1.530 (4) | C18—C19 | 1.511 (5) |
C9—C10 | 1.507 (6) | C19—C20 | 1.489 (6) |
C9—H9A | 0.9700 | C19—H19A | 0.9700 |
C9—H9B | 0.9700 | C19—H19B | 0.9700 |
C10—H10A | 0.9600 | C20—H20A | 0.9600 |
C10—H10B | 0.9600 | C20—H20B | 0.9600 |
C10—H10C | 0.9600 | C20—H20C | 0.9600 |
C1A—C2A | 1.382 (6) | C11A—C16A | 1.377 (5) |
C1A—C6A | 1.404 (6) | C11A—C12A | 1.388 (5) |
C6A—C5A | 1.384 (7) | C12A—C13A | 1.392 (7) |
C6A—H6AA | 0.9300 | C12A—H12C | 0.9300 |
C5A—C4A | 1.376 (10) | C13A—C14A | 1.356 (8) |
C5A—H5AA | 0.9300 | C13A—H13B | 0.9300 |
C4A—C3A | 1.359 (11) | C14A—C15A | 1.359 (8) |
C4A—H4AA | 0.9300 | C14A—H14B | 0.9300 |
C3A—C2A | 1.390 (7) | C15A—C16A | 1.376 (6) |
C3A—H3AA | 0.9300 | C15A—H15C | 0.9300 |
C2A—H2AA | 0.9300 | C16A—H16C | 0.9300 |
C1'—C2' | 1.506 (4) | C11'—C12' | 1.516 (5) |
C1'—H1'A | 0.9700 | C11'—H11A | 0.9700 |
C1'—H1'B | 0.9700 | C11'—H11B | 0.9700 |
C2'—O11 | 1.463 (4) | C12'—O21 | 1.448 (4) |
C2'—C1B | 1.495 (4) | C12'—C11B | 1.510 (4) |
C2'—H2'A | 0.9800 | C12'—H12D | 0.9800 |
C1B—C6B | 1.379 (5) | C11B—C16B | 1.361 (5) |
C1B—C2B | 1.380 (5) | C11B—C12B | 1.381 (5) |
C6B—C5B | 1.389 (6) | C16B—C15B | 1.378 (6) |
C6B—H6BA | 0.9300 | C16B—H1CA | 0.9300 |
C5B—C4B | 1.368 (7) | C15B—C14B | 1.356 (7) |
C5B—H5BA | 0.9300 | C15B—H15D | 0.9300 |
C4B—C3B | 1.369 (8) | C14B—C13B | 1.381 (7) |
C4B—H4BA | 0.9300 | C14B—H14C | 0.9300 |
C3B—C2B | 1.394 (6) | C13B—C12B | 1.386 (6) |
C3B—H3BA | 0.9300 | C13B—H13C | 0.9300 |
C2B—H2BA | 0.9300 | C12B—H12E | 0.9300 |
O11—C12X | 1.331 (4) | O21—C22 | 1.338 (4) |
C12X—O12 | 1.211 (4) | C22—O22 | 1.195 (4) |
C12X—C1C | 1.490 (4) | C22—C11C | 1.488 (5) |
C1C—C2C | 1.376 (5) | C11C—C12C | 1.376 (5) |
C1C—C6C | 1.383 (5) | C11C—C16C | 1.381 (5) |
C6C—C5C | 1.381 (6) | C16C—C15C | 1.380 (6) |
C6C—H6CA | 0.9300 | C16C—H16D | 0.9300 |
C5C—C4C | 1.385 (6) | C15C—C14C | 1.352 (7) |
C5C—H5CA | 0.9300 | C15C—H15E | 0.9300 |
C4C—C3C | 1.358 (6) | C14C—C13C | 1.359 (6) |
C3C—C2C | 1.379 (6) | C13C—C12C | 1.393 (6) |
C3C—H3CA | 0.9300 | C13C—H13D | 0.9300 |
C2C—H2CA | 0.9300 | C12C—H12F | 0.9300 |
C3'—H3'A | 0.9600 | C13'—H13E | 0.9600 |
C3'—H3'B | 0.9600 | C13'—H13F | 0.9600 |
C3'—H3'C | 0.9600 | C13'—H13G | 0.9600 |
C6—N1—C1' | 111.4 (2) | C16—N11—C12 | 110.6 (3) |
C6—N1—C2 | 109.0 (2) | C16—N11—C11' | 114.7 (3) |
C1'—N1—C2 | 111.2 (2) | C12—N11—C11' | 112.3 (3) |
N1—C2—C3 | 111.6 (2) | N11—C12—C13 | 111.3 (3) |
N1—C2—H2A | 109.3 | N11—C12—H12A | 109.4 |
C3—C2—H2A | 109.3 | C13—C12—H12A | 109.4 |
N1—C2—H2B | 109.3 | N11—C12—H12B | 109.4 |
C3—C2—H2B | 109.3 | C13—C12—H12B | 109.4 |
H2A—C2—H2B | 108.0 | H12A—C12—H12B | 108.0 |
C3'—C3—C4 | 115.1 (3) | C12—C13—C13' | 112.2 (3) |
C3'—C3—C2 | 111.2 (3) | C12—C13—C14 | 108.2 (3) |
C4—C3—C2 | 108.3 (2) | C13'—C13—C14 | 114.6 (3) |
C3'—C3—H3A | 107.3 | C12—C13—H13A | 107.2 |
C4—C3—H3A | 107.3 | C13'—C13—H13A | 107.2 |
C2—C3—H3A | 107.3 | C14—C13—H13A | 107.2 |
N7—C4—C5 | 113.2 (2) | N17—C14—C15 | 112.5 (3) |
N7—C4—C3 | 112.9 (2) | N17—C14—C13 | 113.5 (3) |
C5—C4—C3 | 110.9 (2) | C15—C14—C13 | 110.5 (3) |
N7—C4—H4A | 106.4 | N17—C14—H14A | 106.6 |
C5—C4—H4A | 106.4 | C15—C14—H14A | 106.6 |
C3—C4—H4A | 106.4 | C13—C14—H14A | 106.6 |
C4—C5—C6 | 109.4 (3) | C16—C15—C14 | 110.0 (3) |
C4—C5—H5A | 109.8 | C16—C15—H15A | 109.7 |
C6—C5—H5A | 109.8 | C14—C15—H15A | 109.7 |
C4—C5—H5B | 109.8 | C16—C15—H15B | 109.7 |
C6—C5—H5B | 109.8 | C14—C15—H15B | 109.7 |
H5A—C5—H5B | 108.3 | H15A—C15—H15B | 108.2 |
N1—C6—C5 | 111.6 (3) | N11—C16—C15 | 110.8 (3) |
N1—C6—H6A | 109.3 | N11—C16—H16A | 109.5 |
C5—C6—H6A | 109.3 | C15—C16—H16A | 109.5 |
N1—C6—H6B | 109.3 | N11—C16—H16B | 109.5 |
C5—C6—H6B | 109.3 | C15—C16—H16B | 109.5 |
H6A—C6—H6B | 108.0 | H16A—C16—H16B | 108.1 |
C8—N7—C1A | 121.8 (2) | C18—N17—C11A | 120.7 (2) |
C8—N7—C4 | 117.1 (2) | C18—N17—C14 | 117.1 (3) |
C1A—N7—C4 | 120.8 (2) | C11A—N17—C14 | 121.7 (2) |
O8—C8—N7 | 122.1 (3) | O18—C18—N17 | 121.4 (3) |
O8—C8—C9 | 121.8 (3) | O18—C18—C19 | 121.5 (3) |
N7—C8—C9 | 116.1 (3) | N17—C18—C19 | 117.1 (3) |
C10—C9—C8 | 112.2 (3) | C20—C19—C18 | 113.1 (3) |
C10—C9—H9A | 109.2 | C20—C19—H19A | 109.0 |
C8—C9—H9A | 109.2 | C18—C19—H19A | 109.0 |
C10—C9—H9B | 109.2 | C20—C19—H19B | 109.0 |
C8—C9—H9B | 109.2 | C18—C19—H19B | 109.0 |
H9A—C9—H9B | 107.9 | H19A—C19—H19B | 107.8 |
C9—C10—H10A | 109.5 | C19—C20—H20A | 109.5 |
C9—C10—H10B | 109.5 | C19—C20—H20B | 109.5 |
H10A—C10—H10B | 109.5 | H20A—C20—H20B | 109.5 |
C9—C10—H10C | 109.5 | C19—C20—H20C | 109.5 |
H10A—C10—H10C | 109.5 | H20A—C20—H20C | 109.5 |
H10B—C10—H10C | 109.5 | H20B—C20—H20C | 109.5 |
C2A—C1A—C6A | 120.5 (3) | C16A—C11A—C12A | 119.2 (3) |
C2A—C1A—N7 | 120.5 (3) | C16A—C11A—N17 | 121.1 (3) |
C6A—C1A—N7 | 118.9 (3) | C12A—C11A—N17 | 119.7 (3) |
C5A—C6A—C1A | 119.2 (5) | C11A—C12A—C13A | 119.2 (4) |
C5A—C6A—H6AA | 120.4 | C11A—C12A—H12C | 120.4 |
C1A—C6A—H6AA | 120.4 | C13A—C12A—H12C | 120.4 |
C4A—C5A—C6A | 119.8 (6) | C14A—C13A—C12A | 120.3 (4) |
C4A—C5A—H5AA | 120.1 | C14A—C13A—H13B | 119.9 |
C6A—C5A—H5AA | 120.1 | C12A—C13A—H13B | 119.9 |
C3A—C4A—C5A | 120.6 (5) | C13A—C14A—C15A | 121.0 (4) |
C3A—C4A—H4AA | 119.7 | C13A—C14A—H14B | 119.5 |
C5A—C4A—H4AA | 119.7 | C15A—C14A—H14B | 119.5 |
C4A—C3A—C2A | 121.3 (6) | C14A—C15A—C16A | 119.5 (5) |
C4A—C3A—H3AA | 119.4 | C14A—C15A—H15C | 120.2 |
C2A—C3A—H3AA | 119.4 | C16A—C15A—H15C | 120.2 |
C1A—C2A—C3A | 118.4 (5) | C15A—C16A—C11A | 120.8 (4) |
C1A—C2A—H2AA | 120.8 | C15A—C16A—H16C | 119.6 |
C3A—C2A—H2AA | 120.8 | C11A—C16A—H16C | 119.6 |
N1—C1'—C2' | 112.3 (2) | N11—C11'—C12' | 110.3 (3) |
N1—C1'—H1'A | 109.1 | N11—C11'—H11A | 109.6 |
C2'—C1'—H1'A | 109.1 | C12'—C11'—H11A | 109.6 |
N1—C1'—H1'B | 109.1 | N11—C11'—H11B | 109.6 |
C2'—C1'—H1'B | 109.1 | C12'—C11'—H11B | 109.6 |
H1'A—C1'—H1'B | 107.9 | H11A—C11'—H11B | 108.1 |
O11—C2'—C1B | 108.5 (2) | O21—C12'—C11B | 108.1 (3) |
O11—C2'—C1' | 106.5 (2) | O21—C12'—C11' | 105.7 (3) |
C1B—C2'—C1' | 114.6 (2) | C11B—C12'—C11' | 114.0 (3) |
O11—C2'—H2'A | 109.0 | O21—C12'—H12D | 109.6 |
C1B—C2'—H2'A | 109.0 | C11B—C12'—H12D | 109.6 |
C1'—C2'—H2'A | 109.0 | C11'—C12'—H12D | 109.6 |
C6B—C1B—C2B | 118.2 (3) | C16B—C11B—C12B | 118.6 (3) |
C6B—C1B—C2' | 120.0 (3) | C16B—C11B—C12' | 121.0 (3) |
C2B—C1B—C2' | 121.8 (3) | C12B—C11B—C12' | 120.4 (3) |
C1B—C6B—C5B | 121.4 (4) | C11B—C16B—C15B | 121.5 (4) |
C1B—C6B—H6BA | 119.3 | C11B—C16B—H1CA | 119.3 |
C5B—C6B—H6BA | 119.3 | C15B—C16B—H1CA | 119.3 |
C4B—C5B—C6B | 119.5 (4) | C14B—C15B—C16B | 120.1 (4) |
C4B—C5B—H5BA | 120.2 | C14B—C15B—H15D | 120.0 |
C6B—C5B—H5BA | 120.2 | C16B—C15B—H15D | 120.0 |
C5B—C4B—C3B | 120.1 (4) | C15B—C14B—C13B | 119.8 (4) |
C5B—C4B—H4BA | 120.0 | C15B—C14B—H14C | 120.1 |
C3B—C4B—H4BA | 120.0 | C13B—C14B—H14C | 120.1 |
C4B—C3B—C2B | 120.2 (4) | C14B—C13B—C12B | 119.7 (4) |
C4B—C3B—H3BA | 119.9 | C14B—C13B—H13C | 120.2 |
C2B—C3B—H3BA | 119.9 | C12B—C13B—H13C | 120.2 |
C1B—C2B—C3B | 120.4 (4) | C11B—C12B—C13B | 120.4 (4) |
C1B—C2B—H2BA | 119.8 | C11B—C12B—H12E | 119.8 |
C3B—C2B—H2BA | 119.8 | C13B—C12B—H12E | 119.8 |
C12X—O11—C2' | 118.0 (2) | C22—O21—C12' | 118.9 (3) |
O12—C12X—O11 | 123.6 (3) | O22—C22—O21 | 123.7 (3) |
O12—C12X—C1C | 123.6 (3) | O22—C22—C11C | 125.5 (3) |
O11—C12X—C1C | 112.8 (3) | O21—C22—C11C | 110.9 (3) |
C2C—C1C—C6C | 119.3 (3) | C12C—C11C—C16C | 119.2 (3) |
C2C—C1C—C12X | 118.7 (3) | C12C—C11C—C22 | 122.2 (3) |
C6C—C1C—C12X | 122.0 (3) | C16C—C11C—C22 | 118.6 (3) |
C5C—C6C—C1C | 120.4 (3) | C15C—C16C—C11C | 120.8 (4) |
C5C—C6C—H6CA | 119.8 | C15C—C16C—H16D | 119.6 |
C1C—C6C—H6CA | 119.8 | C11C—C16C—H16D | 119.6 |
C6C—C5C—C4C | 118.4 (4) | C14C—C15C—C16C | 118.2 (4) |
C6C—C5C—H5CA | 120.8 | C14C—C15C—H15E | 120.9 |
C4C—C5C—H5CA | 120.8 | C16C—C15C—H15E | 120.9 |
C3C—C4C—C5C | 122.0 (3) | C15C—C14C—C13C | 123.4 (4) |
C3C—C4C—Br1 | 119.9 (3) | C15C—C14C—Br11 | 118.3 (3) |
C5C—C4C—Br1 | 118.0 (3) | C13C—C14C—Br11 | 118.3 (4) |
C4C—C3C—C2C | 118.8 (3) | C14C—C13C—C12C | 118.0 (4) |
C4C—C3C—H3CA | 120.6 | C14C—C13C—H13D | 121.0 |
C2C—C3C—H3CA | 120.6 | C12C—C13C—H13D | 121.0 |
C1C—C2C—C3C | 120.9 (4) | C11C—C12C—C13C | 120.4 (4) |
C1C—C2C—H2CA | 119.5 | C11C—C12C—H12F | 119.8 |
C3C—C2C—H2CA | 119.5 | C13C—C12C—H12F | 119.8 |
C3—C3'—H3'A | 109.5 | C13—C13'—H13E | 109.5 |
C3—C3'—H3'B | 109.5 | C13—C13'—H13F | 109.5 |
H3'A—C3'—H3'B | 109.5 | H13E—C13'—H13F | 109.5 |
C3—C3'—H3'C | 109.5 | C13—C13'—H13G | 109.5 |
H3'A—C3'—H3'C | 109.5 | H13E—C13'—H13G | 109.5 |
H3'B—C3'—H3'C | 109.5 | H13F—C13'—H13G | 109.5 |
C6—N1—C2—C3 | −61.9 (3) | C16—N11—C12—C13 | −62.5 (4) |
C1'—N1—C2—C3 | 174.9 (3) | C11'—N11—C12—C13 | 168.0 (3) |
N1—C2—C3—C3' | −68.6 (4) | N11—C12—C13—C13' | −68.5 (5) |
N1—C2—C3—C4 | 58.8 (3) | N11—C12—C13—C14 | 58.9 (4) |
C3'—C3—C4—N7 | −58.3 (4) | C12—C13—C14—N17 | 177.6 (3) |
C2—C3—C4—N7 | 176.6 (3) | C13'—C13—C14—N17 | −56.4 (4) |
C3'—C3—C4—C5 | 70.0 (4) | C12—C13—C14—C15 | −54.9 (4) |
C2—C3—C4—C5 | −55.2 (3) | C13'—C13—C14—C15 | 71.1 (4) |
N7—C4—C5—C6 | −177.0 (3) | N17—C14—C15—C16 | −177.5 (3) |
C3—C4—C5—C6 | 54.9 (4) | C13—C14—C15—C16 | 54.4 (4) |
C1'—N1—C6—C5 | −175.9 (3) | C12—N11—C16—C15 | 60.6 (4) |
C2—N1—C6—C5 | 60.9 (4) | C11'—N11—C16—C15 | −171.1 (3) |
C4—C5—C6—N1 | −57.9 (4) | C14—C15—C16—N11 | −56.7 (4) |
C5—C4—N7—C8 | 157.3 (3) | C15—C14—N17—C18 | 157.9 (3) |
C3—C4—N7—C8 | −75.6 (3) | C13—C14—N17—C18 | −75.6 (4) |
C5—C4—N7—C1A | −17.7 (4) | C15—C14—N17—C11A | −14.3 (4) |
C3—C4—N7—C1A | 109.4 (3) | C13—C14—N17—C11A | 112.2 (3) |
C1A—N7—C8—O8 | 173.3 (3) | C11A—N17—C18—O18 | 176.7 (4) |
C4—N7—C8—O8 | −1.6 (5) | C14—N17—C18—O18 | 4.4 (5) |
C1A—N7—C8—C9 | −8.0 (5) | C11A—N17—C18—C19 | −4.0 (5) |
C4—N7—C8—C9 | 177.2 (3) | C14—N17—C18—C19 | −176.3 (3) |
O8—C8—C9—C10 | −4.8 (6) | O18—C18—C19—C20 | −2.9 (7) |
N7—C8—C9—C10 | 176.4 (4) | N17—C18—C19—C20 | 177.8 (5) |
C8—N7—C1A—C2A | 85.0 (4) | C18—N17—C11A—C16A | 91.9 (4) |
C4—N7—C1A—C2A | −100.3 (4) | C14—N17—C11A—C16A | −96.2 (4) |
C8—N7—C1A—C6A | −93.0 (4) | C18—N17—C11A—C12A | −86.1 (4) |
C4—N7—C1A—C6A | 81.7 (4) | C14—N17—C11A—C12A | 85.8 (4) |
C2A—C1A—C6A—C5A | 2.3 (5) | C16A—C11A—C12A—C13A | 1.4 (5) |
N7—C1A—C6A—C5A | −179.8 (3) | N17—C11A—C12A—C13A | 179.5 (3) |
C1A—C6A—C5A—C4A | −2.1 (7) | C11A—C12A—C13A—C14A | −1.3 (6) |
C6A—C5A—C4A—C3A | 0.3 (8) | C12A—C13A—C14A—C15A | 1.0 (7) |
C5A—C4A—C3A—C2A | 1.4 (9) | C13A—C14A—C15A—C16A | −0.8 (7) |
C6A—C1A—C2A—C3A | −0.6 (6) | C14A—C15A—C16A—C11A | 0.9 (6) |
N7—C1A—C2A—C3A | −178.6 (4) | C12A—C11A—C16A—C15A | −1.3 (5) |
C4A—C3A—C2A—C1A | −1.2 (8) | N17—C11A—C16A—C15A | −179.3 (3) |
C6—N1—C1'—C2' | 157.8 (3) | C16—N11—C11'—C12' | 146.2 (3) |
C2—N1—C1'—C2' | −80.4 (3) | C12—N11—C11'—C12' | −86.4 (4) |
N1—C1'—C2'—O11 | −63.3 (3) | N11—C11'—C12'—O21 | −64.3 (3) |
N1—C1'—C2'—C1B | 176.7 (2) | N11—C11'—C12'—C11B | 177.1 (3) |
O11—C2'—C1B—C6B | 108.4 (3) | O21—C12'—C11B—C16B | 146.8 (3) |
C1'—C2'—C1B—C6B | −132.7 (3) | C11'—C12'—C11B—C16B | −96.0 (4) |
O11—C2'—C1B—C2B | −71.6 (4) | O21—C12'—C11B—C12B | −32.3 (4) |
C1'—C2'—C1B—C2B | 47.3 (4) | C11'—C12'—C11B—C12B | 84.8 (4) |
C2B—C1B—C6B—C5B | 0.8 (5) | C12B—C11B—C16B—C15B | 1.0 (7) |
C2'—C1B—C6B—C5B | −179.2 (3) | C12'—C11B—C16B—C15B | −178.1 (4) |
C1B—C6B—C5B—C4B | −1.2 (6) | C11B—C16B—C15B—C14B | −0.7 (8) |
C6B—C5B—C4B—C3B | −0.5 (6) | C16B—C15B—C14B—C13B | 0.9 (8) |
C5B—C4B—C3B—C2B | 2.5 (7) | C15B—C14B—C13B—C12B | −1.4 (8) |
C6B—C1B—C2B—C3B | 1.3 (6) | C16B—C11B—C12B—C13B | −1.6 (6) |
C2'—C1B—C2B—C3B | −178.7 (3) | C12'—C11B—C12B—C13B | 177.6 (4) |
C4B—C3B—C2B—C1B | −2.9 (6) | C14B—C13B—C12B—C11B | 1.8 (7) |
C1B—C2'—O11—C12X | −120.5 (3) | C11B—C12'—O21—C22 | −109.2 (3) |
C1'—C2'—O11—C12X | 115.6 (3) | C11'—C12'—O21—C22 | 128.4 (3) |
C2'—O11—C12X—O12 | 7.2 (4) | C12'—O21—C22—O22 | −0.7 (4) |
C2'—O11—C12X—C1C | −172.8 (2) | C12'—O21—C22—C11C | 179.2 (2) |
O12—C12X—C1C—C2C | 2.2 (5) | O22—C22—C11C—C12C | −176.1 (4) |
O11—C12X—C1C—C2C | −177.9 (3) | O21—C22—C11C—C12C | 3.9 (4) |
O12—C12X—C1C—C6C | 179.7 (4) | O22—C22—C11C—C16C | 5.6 (5) |
O11—C12X—C1C—C6C | −0.3 (4) | O21—C22—C11C—C16C | −174.3 (3) |
C2C—C1C—C6C—C5C | 0.8 (6) | C12C—C11C—C16C—C15C | −0.4 (5) |
C12X—C1C—C6C—C5C | −176.7 (4) | C22—C11C—C16C—C15C | 177.9 (3) |
C1C—C6C—C5C—C4C | −2.2 (7) | C11C—C16C—C15C—C14C | 0.6 (6) |
C6C—C5C—C4C—C3C | 2.7 (7) | C16C—C15C—C14C—C13C | −1.0 (7) |
C6C—C5C—C4C—Br1 | 179.8 (3) | C16C—C15C—C14C—Br11 | −179.9 (3) |
C5C—C4C—C3C—C2C | −1.8 (7) | C15C—C14C—C13C—C12C | 1.2 (8) |
Br1—C4C—C3C—C2C | −178.8 (3) | Br11—C14C—C13C—C12C | −179.9 (4) |
C6C—C1C—C2C—C3C | 0.1 (6) | C16C—C11C—C12C—C13C | 0.6 (6) |
C12X—C1C—C2C—C3C | 177.7 (3) | C22—C11C—C12C—C13C | −177.6 (4) |
C4C—C3C—C2C—C1C | 0.3 (6) | C14C—C13C—C12C—C11C | −1.0 (8) |
C23H27BrN2O2 | F(000) = 920 |
Mr = 443.38 | Dx = 1.339 Mg m−3 |
Orthorhombic, P212121 | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 7464 reflections |
a = 6.1932 (1) Å | θ = 2.7–67.2° |
b = 10.7461 (1) Å | µ = 2.70 mm−1 |
c = 33.0458 (3) Å | T = 295 K |
V = 2199.29 (5) Å3 | Rod, colorless |
Z = 4 | 0.48 × 0.08 × 0.03 mm |
BrukerCCD area-detector diffractometer | 3605 independent reflections |
Radiation source: 5Kw rotating anode | 3330 reflections with I > 2σ(I' |
Gobel mirrors monochromator | Rint = 0.027 |
ω scans | θmax = 67.2°, θmin = 2.7° |
Absorption correction: integration a face-indexed absorption correction was followed by a SADABS (Bruker, 2001) correction | h = −7→7 |
Tmin = 0.395, Tmax = 0.876 | k = −12→12 |
9443 measured reflections | l = −39→36 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.041 | w = 1/[σ2(Fo2) + (0.0689P)2 + 0.0827P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.105 | (Δ/σ)max = 0.002 |
S = 1.09 | Δρmax = 0.30 e Å−3 |
3605 reflections | Δρmin = −0.39 e Å−3 |
254 parameters | Extinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0194 (8) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983) |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.004 (19) |
C23H27BrN2O2 | V = 2199.29 (5) Å3 |
Mr = 443.38 | Z = 4 |
Orthorhombic, P212121 | Cu Kα radiation |
a = 6.1932 (1) Å | µ = 2.70 mm−1 |
b = 10.7461 (1) Å | T = 295 K |
c = 33.0458 (3) Å | 0.48 × 0.08 × 0.03 mm |
BrukerCCD area-detector diffractometer | 3605 independent reflections |
Absorption correction: integration a face-indexed absorption correction was followed by a SADABS (Bruker, 2001) correction | 3330 reflections with I > 2σ(I' |
Tmin = 0.395, Tmax = 0.876 | Rint = 0.027 |
9443 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.105 | Δρmax = 0.30 e Å−3 |
S = 1.09 | Δρmin = −0.39 e Å−3 |
3605 reflections | Absolute structure: Flack (1983) |
254 parameters | Absolute structure parameter: 0.004 (19) |
0 restraints |
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 | ||
Br1 | 0.37695 (7) | 0.64565 (3) | 0.904840 (11) | 0.09159 (19) | |
N1 | 0.3654 (4) | 1.16624 (19) | 1.08489 (6) | 0.0602 (5) | |
C2 | 0.3255 (5) | 1.1133 (2) | 1.12504 (8) | 0.0638 (6) | |
H2A | 0.4160 | 1.0406 | 1.1288 | 0.077* | |
H2B | 0.1760 | 1.0871 | 1.1269 | 0.077* | |
C3 | 0.3731 (5) | 1.2076 (3) | 1.15828 (7) | 0.0629 (6) | |
H3A | 0.3327 | 1.1692 | 1.1841 | 0.075* | |
C3' | 0.6091 (6) | 1.2382 (4) | 1.16058 (14) | 0.1041 (13) | |
H3'A | 0.6329 | 1.2983 | 1.1816 | 0.156* | |
H3'B | 0.6561 | 1.2719 | 1.1352 | 0.156* | |
H3'C | 0.6895 | 1.1640 | 1.1664 | 0.156* | |
C4 | 0.2237 (4) | 1.3200 (2) | 1.15186 (7) | 0.0541 (5) | |
H4A | 0.0764 | 1.2867 | 1.1513 | 0.065* | |
C5 | 0.2631 (6) | 1.3751 (3) | 1.11030 (9) | 0.0749 (8) | |
H5A | 0.4094 | 1.4070 | 1.1087 | 0.090* | |
H5B | 0.1642 | 1.4436 | 1.1056 | 0.090* | |
C6 | 0.2293 (6) | 1.2747 (3) | 1.07822 (8) | 0.0774 (8) | |
H6A | 0.0791 | 1.2490 | 1.0784 | 0.093* | |
H6B | 0.2606 | 1.3093 | 1.0518 | 0.093* | |
N7 | 0.2294 (3) | 1.41064 (19) | 1.18537 (6) | 0.0557 (5) | |
C8 | 0.1118 (4) | 1.3829 (2) | 1.21924 (7) | 0.0563 (5) | |
O8 | 0.0186 (3) | 1.28299 (19) | 1.22270 (6) | 0.0698 (5) | |
C9 | 0.0951 (5) | 1.4798 (3) | 1.25136 (9) | 0.0704 (7) | |
H9 | 0.1583 | 1.5574 | 1.2475 | 0.084* | |
C10 | −0.0074 (6) | 1.4561 (4) | 1.28480 (10) | 0.0883 (10) | |
H10A | −0.0706 | 1.3786 | 1.2887 | 0.106* | |
H10B | −0.0176 | 1.5167 | 1.3048 | 0.106* | |
C1A | 0.3446 (4) | 1.5269 (2) | 1.18228 (8) | 0.0579 (5) | |
C2A | 0.5383 (5) | 1.5417 (3) | 1.20331 (10) | 0.0758 (8) | |
H2AA | 0.5987 | 1.4755 | 1.2174 | 0.091* | |
C3A | 0.6386 (6) | 1.6562 (4) | 1.20279 (13) | 0.0941 (10) | |
H3AA | 0.7652 | 1.6677 | 1.2174 | 0.113* | |
C4A | 0.5542 (6) | 1.7533 (3) | 1.18097 (12) | 0.0896 (10) | |
H4AA | 0.6249 | 1.8296 | 1.1805 | 0.108* | |
C5A | 0.3658 (7) | 1.7376 (3) | 1.15988 (10) | 0.0835 (9) | |
H5AA | 0.3096 | 1.8032 | 1.1449 | 0.100* | |
C6A | 0.2588 (5) | 1.6247 (3) | 1.16082 (9) | 0.0673 (7) | |
H6AA | 0.1292 | 1.6150 | 1.1470 | 0.081* | |
C1' | 0.3335 (5) | 1.0728 (3) | 1.05314 (8) | 0.0664 (7) | |
H1'A | 0.1810 | 1.0670 | 1.0467 | 0.080* | |
H1'B | 0.3807 | 0.9922 | 1.0629 | 0.080* | |
C2' | 0.4597 (5) | 1.1063 (3) | 1.01494 (8) | 0.0683 (7) | |
H2'A | 0.3947 | 1.1798 | 1.0023 | 0.082* | |
O2' | 0.6772 (4) | 1.1330 (2) | 1.02556 (7) | 0.0846 (6) | |
H2' | 0.683 (7) | 1.161 (4) | 1.0484 (14) | 0.101* | |
C1B | 0.4506 (5) | 0.9983 (3) | 0.98571 (8) | 0.0637 (6) | |
C6B | 0.6066 (6) | 0.9079 (3) | 0.98542 (9) | 0.0741 (7) | |
H6BA | 0.7273 | 0.9164 | 1.0019 | 0.089* | |
C5B | 0.5869 (6) | 0.8037 (3) | 0.96088 (9) | 0.0786 (8) | |
H5BA | 0.6937 | 0.7428 | 0.9608 | 0.094* | |
C4B | 0.4094 (5) | 0.7918 (3) | 0.93692 (8) | 0.0680 (7) | |
C3B | 0.2531 (6) | 0.8811 (3) | 0.93587 (11) | 0.0831 (9) | |
H3BA | 0.1336 | 0.8724 | 0.9191 | 0.100* | |
C2B | 0.2756 (6) | 0.9852 (3) | 0.96038 (10) | 0.0799 (8) | |
H2BA | 0.1707 | 1.0471 | 0.9597 | 0.096* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.1223 (3) | 0.0756 (2) | 0.0769 (2) | 0.01214 (19) | −0.00236 (19) | −0.01571 (16) |
N1 | 0.0760 (13) | 0.0550 (11) | 0.0498 (10) | −0.0080 (10) | 0.0017 (9) | 0.0027 (8) |
C2 | 0.0817 (17) | 0.0552 (13) | 0.0545 (13) | −0.0047 (11) | 0.0037 (11) | 0.0039 (11) |
C3 | 0.0745 (15) | 0.0626 (14) | 0.0515 (12) | 0.0012 (13) | −0.0071 (12) | 0.0051 (11) |
C3' | 0.068 (2) | 0.120 (3) | 0.124 (3) | 0.021 (2) | −0.034 (2) | −0.043 (2) |
C4 | 0.0502 (12) | 0.0585 (14) | 0.0536 (12) | −0.0074 (9) | −0.0042 (9) | −0.0026 (10) |
C5 | 0.111 (2) | 0.0612 (16) | 0.0526 (12) | 0.0103 (15) | −0.0049 (14) | 0.0001 (12) |
C6 | 0.111 (2) | 0.0703 (17) | 0.0512 (13) | 0.0125 (16) | −0.0116 (14) | −0.0016 (13) |
N7 | 0.0622 (11) | 0.0546 (11) | 0.0504 (10) | −0.0065 (8) | −0.0036 (9) | 0.0005 (9) |
C8 | 0.0565 (12) | 0.0600 (13) | 0.0524 (12) | 0.0016 (11) | −0.0050 (10) | 0.0032 (10) |
O8 | 0.0745 (12) | 0.0695 (12) | 0.0655 (11) | −0.0136 (9) | 0.0042 (9) | 0.0035 (9) |
C9 | 0.0850 (18) | 0.0662 (14) | 0.0601 (14) | 0.0046 (14) | 0.0054 (14) | −0.0034 (12) |
C10 | 0.106 (2) | 0.083 (2) | 0.075 (2) | 0.0128 (18) | 0.0225 (18) | −0.0048 (17) |
C1A | 0.0620 (14) | 0.0556 (12) | 0.0561 (12) | −0.0056 (10) | −0.0015 (10) | −0.0045 (11) |
C2A | 0.0722 (17) | 0.0711 (17) | 0.0841 (19) | −0.0080 (13) | −0.0191 (14) | −0.0088 (15) |
C3A | 0.081 (2) | 0.095 (2) | 0.106 (2) | −0.0223 (19) | −0.0166 (18) | −0.024 (2) |
C4A | 0.100 (2) | 0.0711 (19) | 0.098 (2) | −0.0279 (17) | 0.0132 (19) | −0.0112 (18) |
C5A | 0.109 (2) | 0.0616 (16) | 0.0797 (18) | −0.0117 (18) | 0.0044 (19) | 0.0041 (14) |
C6A | 0.0739 (16) | 0.0617 (16) | 0.0664 (15) | −0.0038 (13) | −0.0034 (12) | −0.0007 (13) |
C1' | 0.0823 (17) | 0.0607 (14) | 0.0562 (13) | −0.0111 (12) | 0.0082 (12) | −0.0051 (12) |
C2' | 0.0871 (19) | 0.0646 (15) | 0.0532 (13) | −0.0026 (13) | 0.0036 (12) | 0.0049 (12) |
O2' | 0.0914 (15) | 0.0886 (15) | 0.0736 (12) | −0.0244 (12) | 0.0116 (11) | −0.0032 (12) |
C1B | 0.0771 (16) | 0.0642 (15) | 0.0498 (12) | 0.0046 (12) | 0.0050 (11) | 0.0052 (12) |
C6B | 0.0760 (17) | 0.0798 (18) | 0.0665 (16) | 0.0104 (15) | −0.0043 (14) | −0.0036 (14) |
C5B | 0.087 (2) | 0.0775 (18) | 0.0717 (16) | 0.0245 (15) | 0.0007 (15) | −0.0052 (16) |
C4B | 0.0863 (18) | 0.0658 (15) | 0.0520 (12) | 0.0072 (13) | 0.0056 (13) | −0.0014 (12) |
C3B | 0.087 (2) | 0.084 (2) | 0.0780 (18) | 0.0120 (16) | −0.0171 (16) | −0.0096 (17) |
C2B | 0.0855 (19) | 0.0783 (19) | 0.0759 (18) | 0.0250 (16) | −0.0125 (15) | −0.0083 (16) |
Br1—C4B | 1.906 (3) | C1A—C6A | 1.375 (4) |
N1—C6 | 1.455 (4) | C1A—C2A | 1.396 (4) |
N1—C2 | 1.465 (3) | C2A—C3A | 1.378 (5) |
N1—C1' | 1.466 (3) | C2A—H2AA | 0.9300 |
C2—C3 | 1.523 (4) | C3A—C4A | 1.372 (6) |
C2—H2A | 0.9700 | C3A—H3AA | 0.9300 |
C2—H2B | 0.9700 | C4A—C5A | 1.370 (6) |
C3—C3' | 1.500 (5) | C4A—H4AA | 0.9300 |
C3—C4 | 1.536 (4) | C5A—C6A | 1.383 (4) |
C3—H3A | 0.9800 | C5A—H5AA | 0.9300 |
C3'—H3'A | 0.9600 | C6A—H6AA | 0.9300 |
C3'—H3'B | 0.9600 | C1'—C2' | 1.528 (4) |
C3'—H3'C | 0.9600 | C1'—H1'A | 0.9700 |
C4—N7 | 1.475 (3) | C1'—H1'B | 0.9700 |
C4—C5 | 1.515 (4) | C2'—O2' | 1.421 (4) |
C4—H4A | 0.9800 | C2'—C1B | 1.511 (4) |
C5—C6 | 1.527 (4) | C2'—H2'A | 0.9800 |
C5—H5A | 0.9700 | O2'—H2' | 0.81 (4) |
C5—H5B | 0.9700 | C1B—C6B | 1.370 (4) |
C6—H6A | 0.9700 | C1B—C2B | 1.377 (4) |
C6—H6B | 0.9700 | C6B—C5B | 1.388 (5) |
N7—C8 | 1.368 (3) | C6B—H6BA | 0.9300 |
N7—C1A | 1.442 (3) | C5B—C4B | 1.361 (5) |
C8—O8 | 1.224 (3) | C5B—H5BA | 0.9300 |
C8—C9 | 1.491 (4) | C4B—C3B | 1.364 (4) |
C9—C10 | 1.300 (4) | C3B—C2B | 1.388 (5) |
C9—H9 | 0.9300 | C3B—H3BA | 0.9300 |
C10—H10A | 0.9300 | C2B—H2BA | 0.9300 |
C10—H10B | 0.9300 | ||
C6—N1—C2 | 110.5 (2) | H10A—C10—H10B | 120.0 |
C6—N1—C1' | 111.2 (2) | C6A—C1A—C2A | 120.1 (3) |
C2—N1—C1' | 111.1 (2) | C6A—C1A—N7 | 120.5 (2) |
N1—C2—C3 | 111.2 (2) | C2A—C1A—N7 | 119.3 (2) |
N1—C2—H2A | 109.4 | C3A—C2A—C1A | 118.9 (3) |
C3—C2—H2A | 109.4 | C3A—C2A—H2AA | 120.6 |
N1—C2—H2B | 109.4 | C1A—C2A—H2AA | 120.6 |
C3—C2—H2B | 109.4 | C4A—C3A—C2A | 120.9 (3) |
H2A—C2—H2B | 108.0 | C4A—C3A—H3AA | 119.5 |
C3'—C3—C2 | 111.8 (3) | C2A—C3A—H3AA | 119.5 |
C3'—C3—C4 | 114.9 (3) | C5A—C4A—C3A | 119.9 (3) |
C2—C3—C4 | 107.9 (2) | C5A—C4A—H4AA | 120.1 |
C3'—C3—H3A | 107.3 | C3A—C4A—H4AA | 120.1 |
C2—C3—H3A | 107.3 | C4A—C5A—C6A | 120.3 (3) |
C4—C3—H3A | 107.3 | C4A—C5A—H5AA | 119.8 |
C3—C3'—H3'A | 109.5 | C6A—C5A—H5AA | 119.8 |
C3—C3'—H3'B | 109.5 | C1A—C6A—C5A | 119.8 (3) |
H3'A—C3'—H3'B | 109.5 | C1A—C6A—H6AA | 120.1 |
C3—C3'—H3'C | 109.5 | C5A—C6A—H6AA | 120.1 |
H3'A—C3'—H3'C | 109.5 | N1—C1'—C2' | 111.2 (2) |
H3'B—C3'—H3'C | 109.5 | N1—C1'—H1'A | 109.4 |
N7—C4—C5 | 114.7 (2) | C2'—C1'—H1'A | 109.4 |
N7—C4—C3 | 113.63 (19) | N1—C1'—H1'B | 109.4 |
C5—C4—C3 | 109.6 (2) | C2'—C1'—H1'B | 109.4 |
N7—C4—H4A | 106.0 | H1'A—C1'—H1'B | 108.0 |
C5—C4—H4A | 106.0 | O2'—C2'—C1B | 110.4 (3) |
C3—C4—H4A | 106.0 | O2'—C2'—C1' | 109.2 (2) |
C4—C5—C6 | 109.3 (2) | C1B—C2'—C1' | 109.2 (2) |
C4—C5—H5A | 109.8 | O2'—C2'—H2'A | 109.4 |
C6—C5—H5A | 109.8 | C1B—C2'—H2'A | 109.4 |
C4—C5—H5B | 109.8 | C1'—C2'—H2'A | 109.4 |
C6—C5—H5B | 109.8 | C2'—O2'—H2' | 110 (3) |
H5A—C5—H5B | 108.3 | C6B—C1B—C2B | 118.5 (3) |
N1—C6—C5 | 112.4 (2) | C6B—C1B—C2' | 121.5 (3) |
N1—C6—H6A | 109.1 | C2B—C1B—C2' | 119.8 (3) |
C5—C6—H6A | 109.1 | C1B—C6B—C5B | 121.0 (3) |
N1—C6—H6B | 109.1 | C1B—C6B—H6BA | 119.5 |
C5—C6—H6B | 109.1 | C5B—C6B—H6BA | 119.5 |
H6A—C6—H6B | 107.9 | C4B—C5B—C6B | 119.1 (3) |
C8—N7—C1A | 120.7 (2) | C4B—C5B—H5BA | 120.5 |
C8—N7—C4 | 117.20 (19) | C6B—C5B—H5BA | 120.5 |
C1A—N7—C4 | 122.1 (2) | C5B—C4B—C3B | 121.5 (3) |
O8—C8—N7 | 121.2 (2) | C5B—C4B—Br1 | 119.1 (2) |
O8—C8—C9 | 120.9 (2) | C3B—C4B—Br1 | 119.4 (2) |
N7—C8—C9 | 117.8 (2) | C4B—C3B—C2B | 118.7 (3) |
C10—C9—C8 | 120.2 (3) | C4B—C3B—H3BA | 120.6 |
C10—C9—H9 | 119.9 | C2B—C3B—H3BA | 120.6 |
C8—C9—H9 | 119.9 | C1B—C2B—C3B | 121.1 (3) |
C9—C10—H10A | 120.0 | C1B—C2B—H2BA | 119.4 |
C9—C10—H10B | 120.0 | C3B—C2B—H2BA | 119.4 |
C6—N1—C2—C3 | −59.9 (3) | C6A—C1A—C2A—C3A | 1.3 (5) |
C1'—N1—C2—C3 | 176.2 (2) | N7—C1A—C2A—C3A | −174.9 (3) |
N1—C2—C3—C3' | −67.0 (4) | C1A—C2A—C3A—C4A | −2.1 (6) |
N1—C2—C3—C4 | 60.3 (3) | C2A—C3A—C4A—C5A | 1.1 (6) |
C3'—C3—C4—N7 | −63.2 (3) | C3A—C4A—C5A—C6A | 0.7 (5) |
C2—C3—C4—N7 | 171.4 (2) | C2A—C1A—C6A—C5A | 0.5 (4) |
C3'—C3—C4—C5 | 66.7 (3) | N7—C1A—C6A—C5A | 176.7 (3) |
C2—C3—C4—C5 | −58.7 (3) | C4A—C5A—C6A—C1A | −1.5 (5) |
N7—C4—C5—C6 | −174.1 (2) | C6—N1—C1'—C2' | 80.2 (3) |
C3—C4—C5—C6 | 56.7 (3) | C2—N1—C1'—C2' | −156.3 (3) |
C2—N1—C6—C5 | 57.5 (3) | N1—C1'—C2'—O2' | 50.4 (3) |
C1'—N1—C6—C5 | −178.6 (3) | N1—C1'—C2'—C1B | 171.1 (2) |
C4—C5—C6—N1 | −56.4 (4) | O2'—C2'—C1B—C6B | 28.1 (4) |
C5—C4—N7—C8 | 153.2 (2) | C1'—C2'—C1B—C6B | −91.9 (3) |
C3—C4—N7—C8 | −79.6 (3) | O2'—C2'—C1B—C2B | −156.1 (3) |
C5—C4—N7—C1A | −23.8 (3) | C1'—C2'—C1B—C2B | 83.9 (3) |
C3—C4—N7—C1A | 103.4 (3) | C2B—C1B—C6B—C5B | −1.5 (5) |
C1A—N7—C8—O8 | −177.8 (2) | C2'—C1B—C6B—C5B | 174.4 (3) |
C4—N7—C8—O8 | 5.2 (4) | C1B—C6B—C5B—C4B | −0.2 (5) |
C1A—N7—C8—C9 | 4.0 (3) | C6B—C5B—C4B—C3B | 1.4 (5) |
C4—N7—C8—C9 | −173.1 (2) | C6B—C5B—C4B—Br1 | −177.5 (2) |
O8—C8—C9—C10 | 4.6 (4) | C5B—C4B—C3B—C2B | −1.0 (5) |
N7—C8—C9—C10 | −177.2 (3) | Br1—C4B—C3B—C2B | 178.0 (3) |
C8—N7—C1A—C6A | −99.6 (3) | C6B—C1B—C2B—C3B | 1.9 (5) |
C4—N7—C1A—C6A | 77.2 (3) | C2'—C1B—C2B—C3B | −174.0 (3) |
C8—N7—C1A—C2A | 76.6 (3) | C4B—C3B—C2B—C1B | −0.7 (5) |
C4—N7—C1A—C2A | −106.5 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2′—H2′···N1 | 0.81 (4) | 2.31 (4) | 2.775 (3) | 117 (4) |
Experimental details
(II) | (III) | |
Crystal data | ||
Chemical formula | C30H33BrN2O3 | C23H27BrN2O2 |
Mr | 549.49 | 443.38 |
Crystal system, space group | Monoclinic, P21 | Orthorhombic, P212121 |
Temperature (K) | 153 | 295 |
a, b, c (Å) | 10.8806 (2), 22.4670 (5), 11.5313 (3) | 6.1932 (1), 10.7461 (1), 33.0458 (3) |
α, β, γ (°) | 90, 92.208 (1), 90 | 90, 90, 90 |
V (Å3) | 2816.78 (11) | 2199.29 (5) |
Z | 4 | 4 |
Radiation type | Cu Kα | Cu Kα |
µ (mm−1) | 2.24 | 2.70 |
Crystal size (mm) | 0.56 × 0.44 × 0.24 | 0.48 × 0.08 × 0.03 |
Data collection | ||
Diffractometer | Bruker CCD area-detector diffractometer | BrukerCCD area-detector diffractometer |
Absorption correction | Integration (Bruker, 2001) | Integration a face-indexed absorption correction was followed by a SADABS (Bruker, 2001) correction |
Tmin, Tmax | 0.608, 0.931 | 0.395, 0.876 |
No. of measured, independent and observed reflections | 13643, 7419, 6654 [I > 2σ(I)] | 9443, 3605, 3330 [I > 2σ(I'] |
Rint | 0.024 | 0.027 |
(sin θ/λ)max (Å−1) | 0.597 | 0.598 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.122, 1.07 | 0.041, 0.105, 1.09 |
No. of reflections | 7419 | 3605 |
No. of parameters | 650 | 254 |
No. of restraints | 1 | 0 |
H-atom treatment | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.23, −0.45 | 0.30, −0.39 |
Absolute structure | Flack (1983) | Flack (1983) |
Absolute structure parameter | 0.032 (15) | 0.004 (19) |
Computer programs: SMART (Bruker 2001), SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL (Bruker, 2001).
Br1—C4C | 1.904 (4) | N11—C16 | 1.446 (5) |
N1—C6 | 1.449 (4) | N11—C12 | 1.453 (5) |
N1—C1' | 1.465 (4) | N11—C11' | 1.459 (4) |
N1—C2 | 1.466 (4) | Br11—C14C | 1.910 (4) |
C4—N7 | 1.494 (3) | C14—N17 | 1.483 (4) |
N7—C8 | 1.362 (4) | N17—C18 | 1.364 (4) |
N7—C1A | 1.431 (4) | N17—C11A | 1.444 (4) |
C6—N1—C1' | 111.4 (2) | C16—N11—C12 | 110.6 (3) |
C6—N1—C2 | 109.0 (2) | C16—N11—C11' | 114.7 (3) |
C1'—N1—C2 | 111.2 (2) | C12—N11—C11' | 112.3 (3) |
C8—N7—C1A | 121.8 (2) | C18—N17—C11A | 120.7 (2) |
C8—N7—C4 | 117.1 (2) | C18—N17—C14 | 117.1 (3) |
C1A—N7—C4 | 120.8 (2) | C11A—N17—C14 | 121.7 (2) |
Br1—C4B | 1.906 (3) | N7—C8 | 1.368 (3) |
N1—C6 | 1.455 (4) | N7—C1A | 1.442 (3) |
N1—C2 | 1.465 (3) | C9—C10 | 1.300 (4) |
N1—C1' | 1.466 (3) | C2'—O2' | 1.421 (4) |
C4—N7 | 1.475 (3) | ||
C6—N1—C2 | 110.5 (2) | C8—N7—C1A | 120.7 (2) |
C6—N1—C1' | 111.2 (2) | C8—N7—C4 | 117.20 (19) |
C2—N1—C1' | 111.1 (2) | C1A—N7—C4 | 122.1 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2'—H2'···N1 | 0.81 (4) | 2.31 (4) | 2.775 (3) | 117 (4) |
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(±)-cis-N-[1-(2-Hydroxy-2-phenylethyl)-3-methyl-4-piperidyl]-N– phenylpropanamide, (I), also known as ohmefentanyl or cis-β-hydroxy-3-methylfentanyl, is an extremely potent analgesic exhibiting high selectivity for the µ-opioid receptor (Xu et al., 1987). It is one of the `super potent' analogs of fentanyl that are more potent in producing antinocieption than was predicted on the basis of their µ-receptor affinity (Rothman et al., 1991). With three asymmetric C atoms (C3, C4 and C2'), the compound has eight possible stereoisomers. Four, two pairs of optical isomers, of the eight possible stereoisomers would have a cis arrangements of the substituents on C3 and C4. When the two pairs were separated, one pair was found to be 5.3 times more potent than the other and 6300 times more potent than morphine (Zhu et al., 1983). The more active pair was referred to as ohmefentanyl. A second sample of (I), designated as RTI-4614–4, was determined to be a mixture of all four cis isomers (Brine et al., 1992) and was shown to be 25 000 times more potent than morphine (Aceto et al., 1988). In view of the differing activities and isomeric compositions of ohmefentanyl and RTI-4614–4 it was clearly necessary to resolve (I) into its four stereoisomers (Brine et al., 1995). The title compounds, (II) and (III), are both brominated derivatives of (I) that were sysnthesized to resolve its stereochemistry. The absolute configurations of (II) and (III) are reported here.
The X-ray structure analysis of (II) indicated the absolute configuration to be 2S,3R,4S (Fig. 1). As expected, the substituents on C3 and C4 are cis to one another, with C3'—C3—C4—N7 torsion angles of -58.3 (4) and -56.4 (4)° for the two independent molecules. Ring C (see Fig. 2 for labeling) is approximately parallel to ring A [the angles between the least-squares planes are 33.5 (1) and 29.5 (2)° for the two molecules], while ring B is approximately perpendicular to the other two aromatic rings [the angles between the planes of rings B and A are 58.3 (1) and 85.1 (1)°, and between the planes of rings B and C are 61.7 (1) and 70.9 (1)°]. The differences are due to rotation about the C2'—C1a bond for ring B (Fig. 2).
In compound (III), which crystallized with a single molecule in the asymmetric unit, the absolute configuration is 2R,3R,4S (Fig. 3), with a C3'—C3—C4—N7 torsion angle of -63.2 (3)°. The molecule of (III) has only two aromatic rings, which are approximately parallel to one another [the angle between the planes is 45.2 (1)°], and one intramolecular hydrogen bond [H···N 2.31 (4) Å, O···N 2.775 (3) Å and O—H···N 117 (4)°].
Compounds (II) and (III) differ in the stereochemistry only at C2'. Superimposition of the two compounds using atoms N1, C3 and C4 shows that there is good agreement in the conformation of the central six-membered ring and the substituents on C4 (Fig. 4). Despite a change in the C2—N1—C1'—C2' torsion angle [-80.4 and -156.3° for compounds (II) and (III), respectively], the C rings are still in close proximity and could still bind in a similar manner to a receptor. The change in this torsion angle may be caused by the substitution at O2' in compound (II). Thus, the large difference in potency reported by Brine et al. (1995) can only be attributed to the opposite stereochemistry at C2', which places the hydroxyl group in ohmefentanyl on the opposite side of the molecule.