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Both title compounds, C30H33BrN2O3 and C23H27BrN2O2, respectively, are brominated derivatives of the potent opioid cis-[beta]-hydroxy-3-methyl­fentanyl (ohmefentanyl). Ohmefentanyl has three asymmetric C atoms and, therefore, has eight possible stereoisomers. The absolute configurations of the title compounds were determined to assign the proper configuration of two of these stereoisomers and the compounds have the same stereochemistry at two of the three asymmetric C atoms.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102006443/sk1544sup1.cif
Contains datablocks global, II, III

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102006443/sk1544IIsup2.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102006443/sk1544IIIsup3.hkl
Contains datablock III

CCDC references: 188627; 188628

Comment top

(±)-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.

Experimental top

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.

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. View of (II) shown with 20% probability displacement ellipsoids. H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. Least-squares fit of the two molecules in the asymmetric unit of (II). The r.m.s. deviation for the eight atoms used (six atoms in the heterocyclic ring plus N7 and C1') was 0.097 Å.
[Figure 3] Fig. 3. View of (III) shown with 20% probability displacement ellipsoids. H atoms are shown as small spheres of arbitrary radii.
[Figure 4] Fig. 4. Superimposition of (II) and (III) showing that, despite the opposite stereochemistry at C2', the aromatic rings on C2' are still in close proximity. Only the labeled atoms were used to align the structures.
(II) (1R)-2-[(3R,4S)-3-Methyl-4-(N-phenyl-N-propionylamino)pyridyl]-1- phenylethyl p-bromobenzoate top
Crystal data top
C30H33BrN2O3F(000) = 1144
Mr = 549.49Dx = 1.296 Mg m3
Monoclinic, P21Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2ybCell parameters from 6392 reflections
a = 10.8806 (2) Åθ = 3.9–66.8°
b = 22.4670 (5) ŵ = 2.24 mm1
c = 11.5313 (3) ÅT = 153 K
β = 92.208 (1)°Prism, colorless
V = 2816.78 (11) Å30.56 × 0.44 × 0.24 mm
Z = 4
Data collection top
Bruker CCD area-detector
diffractometer
7419 independent reflections
Radiation source: rotating anode6654 reflections with I > 2σ(I)
Gobel mirrors monochromatorRint = 0.024
ω scansθmax = 67.0°, θmin = 3.9°
Absorption correction: integration
(Bruker, 2001)
h = 1212
Tmin = 0.608, Tmax = 0.931k = 2326
13643 measured reflectionsl = 1213
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-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 = 1.07Δρmax = 0.23 e Å3
7419 reflectionsΔρmin = 0.45 e Å3
650 parametersExtinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraintExtinction coefficient: 0.0386 (10)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983)
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.032 (15)
Crystal data top
C30H33BrN2O3V = 2816.78 (11) Å3
Mr = 549.49Z = 4
Monoclinic, P21Cu Kα radiation
a = 10.8806 (2) ŵ = 2.24 mm1
b = 22.4670 (5) ÅT = 153 K
c = 11.5313 (3) Å0.56 × 0.44 × 0.24 mm
β = 92.208 (1)°
Data collection top
Bruker CCD area-detector
diffractometer
7419 independent reflections
Absorption correction: integration
(Bruker, 2001)
6654 reflections with I > 2σ(I)
Tmin = 0.608, Tmax = 0.931Rint = 0.024
13643 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.047H-atom parameters constrained
wR(F2) = 0.122Δρmax = 0.23 e Å3
S = 1.07Δρmin = 0.45 e Å3
7419 reflectionsAbsolute structure: Flack (1983)
650 parametersAbsolute structure parameter: 0.032 (15)
1 restraint
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br11.31391 (4)0.70497 (3)0.08320 (8)0.1492 (3)
N10.6620 (2)0.53291 (11)0.2724 (2)0.0698 (5)
C20.6512 (3)0.46973 (14)0.3022 (3)0.0754 (7)
H2A0.66980.44570.23510.090*
H2B0.56730.46130.32230.090*
C30.7381 (3)0.45283 (14)0.4034 (3)0.0733 (7)
H3A0.72030.41140.42370.088*
C40.7076 (3)0.49106 (13)0.5071 (2)0.0696 (6)
H4A0.62190.48230.52410.083*
C50.7123 (4)0.55663 (14)0.4767 (3)0.0832 (8)
H5A0.79600.56790.46040.100*
H5B0.68620.58020.54180.100*
C60.6281 (4)0.56853 (16)0.3709 (3)0.0856 (9)
H6A0.54390.55960.38960.103*
H6B0.63240.61040.35070.103*
N70.7828 (2)0.47563 (11)0.6141 (2)0.0719 (6)
C80.7520 (3)0.42505 (14)0.6712 (3)0.0760 (7)
O80.6656 (2)0.39404 (11)0.6390 (2)0.0890 (6)
C90.8341 (4)0.40870 (17)0.7771 (3)0.0928 (10)
H9A0.91700.40130.75240.111*
H9B0.83730.44200.83060.111*
C100.7883 (5)0.3544 (2)0.8388 (4)0.1120 (13)
H10A0.84220.34570.90450.168*
H10B0.78650.32110.78660.168*
H10C0.70690.36180.86470.168*
C1A0.8760 (3)0.51521 (15)0.6590 (3)0.0808 (8)
C6A0.8415 (5)0.56342 (17)0.7281 (3)0.0957 (11)
H6AA0.75940.56940.74440.115*
C5A0.9312 (8)0.6020 (2)0.7715 (4)0.131 (2)
H5AA0.90930.63480.81520.157*
C4A1.0528 (8)0.5916 (3)0.7498 (6)0.148 (3)
H4AA1.11300.61750.77930.177*
C3A1.0859 (6)0.5439 (3)0.6855 (6)0.142 (2)
H3AA1.16880.53720.67320.170*
C2A0.9984 (4)0.5050 (2)0.6379 (4)0.1019 (11)
H2AA1.02170.47290.59280.122*
C1'0.5864 (3)0.54758 (16)0.1685 (3)0.0750 (7)
H1'A0.56990.59000.16750.090*
H1'B0.50820.52700.17160.090*
C2'0.6476 (3)0.53051 (14)0.0583 (2)0.0703 (7)
H2'A0.67030.48830.06230.084*
C1B0.5714 (3)0.54131 (14)0.0503 (2)0.0708 (7)
C6B0.5606 (4)0.49751 (19)0.1339 (3)0.0934 (9)
H6BA0.60030.46130.12140.112*
C5B0.4918 (4)0.5063 (2)0.2364 (4)0.1066 (13)
H5BA0.48680.47650.29240.128*
C4B0.4314 (4)0.5591 (3)0.2544 (4)0.1085 (14)
H4BA0.38560.56540.32310.130*
C3B0.4383 (4)0.6027 (2)0.1714 (4)0.1123 (14)
H3BA0.39460.63790.18260.135*
C2B0.5105 (4)0.59443 (19)0.0703 (3)0.0940 (10)
H2BA0.51770.62490.01580.113*
O110.75949 (19)0.56638 (9)0.05400 (19)0.0746 (5)
C12X0.8672 (3)0.53824 (14)0.0593 (3)0.0737 (7)
O120.8776 (2)0.48459 (11)0.0566 (3)0.0994 (7)
C1C0.9738 (3)0.57982 (14)0.0691 (3)0.0714 (7)
C6C0.9585 (3)0.64092 (18)0.0714 (3)0.0909 (9)
H6CA0.87960.65700.07090.109*
C5C1.0593 (4)0.67826 (19)0.0746 (5)0.1072 (13)
H5CA1.04950.71940.07360.129*
C4C1.1755 (3)0.65304 (19)0.0794 (4)0.0977 (11)
C3C1.1926 (3)0.59317 (19)0.0764 (4)0.0977 (10)
H3CA1.27150.57720.07750.117*
C2C1.0909 (3)0.55651 (18)0.0714 (3)0.0902 (9)
H2CA1.10150.51550.06970.108*
C3'0.8706 (4)0.4553 (2)0.3692 (3)0.0980 (11)
H3'A0.92330.44450.43450.147*
H3'B0.89000.49500.34490.147*
H3'C0.88280.42810.30650.147*
N110.3408 (2)0.30120 (12)0.8114 (2)0.0780 (6)
Br110.34520 (5)0.14363 (3)0.57529 (8)0.1575 (3)
C120.3757 (4)0.36120 (19)0.8462 (3)0.0946 (10)
H12A0.37320.38690.77860.114*
H12B0.45930.36090.87850.114*
C130.2903 (4)0.38568 (16)0.9356 (3)0.0877 (9)
H13A0.32380.42420.96130.105*
C140.2958 (3)0.34423 (16)1.0410 (3)0.0763 (7)
H14A0.38130.34431.07090.092*
C150.2663 (3)0.28030 (15)1.0042 (3)0.0835 (8)
H15A0.27700.25401.07050.100*
H15B0.18130.27770.97600.100*
C160.3508 (3)0.26102 (18)0.9093 (3)0.0874 (9)
H16A0.43510.26040.93970.105*
H16B0.32910.22110.88400.105*
N170.2197 (2)0.36480 (12)1.1372 (2)0.0737 (6)
C180.2643 (3)0.41108 (18)1.2029 (3)0.0845 (8)
O180.3590 (2)0.43685 (15)1.1791 (2)0.1107 (9)
C190.1906 (4)0.4295 (2)1.3054 (4)0.0988 (11)
H19A0.10940.44201.27760.119*
H19B0.18060.39531.35560.119*
C200.2490 (6)0.4787 (3)1.3742 (6)0.148 (3)
H20A0.19850.48861.43790.223*
H20B0.25750.51301.32550.223*
H20C0.32870.46631.40350.223*
C11A0.1114 (3)0.33283 (14)1.1701 (2)0.0707 (7)
C12A0.1226 (4)0.28576 (18)1.2477 (3)0.0918 (10)
H12C0.19950.27451.27810.110*
C13A0.0174 (6)0.25561 (19)1.2794 (4)0.1134 (15)
H13B0.02400.22351.33010.136*
C14A0.0949 (5)0.2729 (3)1.2367 (4)0.1196 (16)
H14B0.16470.25281.25950.143*
C15A0.1070 (4)0.3191 (3)1.1611 (4)0.1117 (14)
H15C0.18440.33031.13170.134*
C16A0.0040 (3)0.34938 (18)1.1285 (3)0.0869 (8)
H16C0.01230.38141.07770.104*
C11'0.4041 (3)0.28139 (17)0.7090 (3)0.0802 (8)
H11A0.41100.23830.70980.096*
H11B0.48650.29790.71040.096*
C12'0.3342 (3)0.30112 (16)0.5995 (3)0.0778 (7)
H12D0.32020.34420.60210.093*
C11B0.3966 (3)0.28517 (14)0.4889 (3)0.0743 (7)
C16B0.4690 (4)0.32519 (19)0.4352 (3)0.0980 (11)
H1CA0.48200.36250.46850.118*
C15B0.5236 (5)0.3117 (2)0.3325 (4)0.1121 (13)
H15D0.57200.33990.29690.135*
C14B0.5067 (4)0.2573 (2)0.2833 (3)0.1044 (12)
H14C0.54430.24800.21460.125*
C13B0.4333 (5)0.2159 (2)0.3356 (4)0.1095 (12)
H13C0.42000.17880.30140.131*
C12B0.3797 (4)0.22966 (17)0.4394 (4)0.0973 (10)
H12E0.33220.20140.47590.117*
O210.21741 (19)0.27019 (11)0.5997 (2)0.0810 (5)
C220.1136 (3)0.30167 (15)0.5851 (2)0.0734 (7)
O220.1111 (3)0.35448 (13)0.5727 (3)0.1037 (7)
C11C0.0040 (3)0.26211 (15)0.5863 (2)0.0714 (7)
C16C0.1106 (3)0.28650 (18)0.5620 (3)0.0918 (9)
H16D0.11780.32710.54790.110*
C15C0.2147 (4)0.2513 (2)0.5585 (4)0.0977 (10)
H15E0.29180.26760.54150.117*
C14C0.2014 (3)0.1925 (2)0.5803 (4)0.0990 (11)
C13C0.0908 (4)0.1661 (2)0.6040 (5)0.1201 (15)
H13D0.08510.12530.61730.144*
C12C0.0137 (3)0.20201 (19)0.6078 (4)0.0959 (10)
H12F0.09040.18530.62500.115*
C13'0.1613 (5)0.3970 (2)0.8846 (3)0.1101 (13)
H13E0.16580.42330.81920.165*
H13F0.11200.41500.94230.165*
H13G0.12490.36000.86000.165*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0749 (3)0.1135 (4)0.2608 (7)0.0262 (3)0.0293 (3)0.0646 (4)
N10.0604 (13)0.0668 (13)0.0818 (13)0.0044 (10)0.0032 (10)0.0024 (10)
C20.0724 (19)0.0672 (16)0.0857 (17)0.0001 (13)0.0079 (13)0.0013 (12)
C30.0710 (18)0.0626 (15)0.0857 (17)0.0045 (13)0.0054 (13)0.0009 (12)
C40.0559 (14)0.0713 (16)0.0811 (16)0.0021 (12)0.0015 (11)0.0027 (12)
C50.097 (2)0.0644 (16)0.0871 (18)0.0093 (16)0.0042 (15)0.0071 (13)
C60.088 (2)0.0750 (19)0.0931 (19)0.0225 (17)0.0008 (15)0.0028 (14)
N70.0673 (14)0.0659 (13)0.0818 (13)0.0046 (11)0.0047 (10)0.0025 (10)
C80.0732 (19)0.0656 (16)0.0885 (17)0.0001 (14)0.0041 (13)0.0021 (12)
O80.0803 (15)0.0799 (14)0.1052 (14)0.0178 (12)0.0160 (11)0.0117 (11)
C90.095 (3)0.080 (2)0.101 (2)0.0075 (19)0.0230 (17)0.0151 (16)
C100.123 (4)0.094 (3)0.116 (3)0.015 (2)0.023 (2)0.033 (2)
C1A0.081 (2)0.0761 (18)0.0840 (17)0.0162 (16)0.0081 (13)0.0053 (13)
C6A0.119 (3)0.075 (2)0.092 (2)0.019 (2)0.0059 (18)0.0027 (15)
C5A0.200 (7)0.088 (3)0.101 (3)0.044 (4)0.029 (3)0.001 (2)
C4A0.164 (6)0.137 (5)0.137 (4)0.079 (5)0.053 (4)0.016 (3)
C3A0.096 (3)0.159 (5)0.168 (4)0.053 (4)0.034 (3)0.014 (4)
C2A0.074 (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)
C1B0.0603 (15)0.0707 (16)0.0819 (16)0.0092 (13)0.0093 (11)0.0079 (12)
C6B0.090 (2)0.087 (2)0.102 (2)0.0160 (19)0.0004 (17)0.0041 (17)
C5B0.103 (3)0.123 (3)0.094 (2)0.034 (3)0.0028 (19)0.003 (2)
C4B0.084 (3)0.145 (4)0.096 (2)0.030 (3)0.0089 (17)0.039 (3)
C3B0.106 (3)0.123 (4)0.108 (3)0.020 (3)0.003 (2)0.040 (3)
C2B0.100 (3)0.088 (2)0.094 (2)0.009 (2)0.0027 (17)0.0181 (16)
O110.0551 (11)0.0634 (11)0.1057 (13)0.0011 (9)0.0069 (9)0.0063 (9)
C12X0.0610 (17)0.0709 (18)0.0894 (17)0.0042 (13)0.0050 (12)0.0015 (13)
O120.0695 (14)0.0673 (14)0.162 (2)0.0058 (11)0.0090 (13)0.0056 (13)
C1C0.0576 (16)0.0703 (16)0.0866 (17)0.0007 (13)0.0064 (12)0.0025 (12)
C6C0.0621 (17)0.080 (2)0.131 (3)0.0064 (16)0.0093 (16)0.0160 (18)
C5C0.076 (2)0.074 (2)0.172 (4)0.0079 (18)0.017 (2)0.027 (2)
C4C0.0645 (19)0.091 (3)0.139 (3)0.0130 (19)0.0135 (18)0.028 (2)
C3C0.0538 (17)0.095 (3)0.145 (3)0.0040 (17)0.0056 (17)0.015 (2)
C2C0.0646 (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)
N110.0698 (15)0.0767 (15)0.0883 (15)0.0014 (12)0.0144 (11)0.0065 (12)
Br110.0800 (3)0.1343 (5)0.2563 (8)0.0328 (3)0.0163 (4)0.0087 (5)
C120.091 (2)0.097 (2)0.097 (2)0.018 (2)0.0196 (16)0.0066 (17)
C130.101 (3)0.0740 (19)0.0894 (19)0.0136 (18)0.0190 (16)0.0082 (15)
C140.0542 (16)0.088 (2)0.0868 (17)0.0005 (14)0.0050 (12)0.0068 (14)
C150.085 (2)0.0739 (19)0.0921 (19)0.0067 (16)0.0124 (15)0.0005 (14)
C160.075 (2)0.087 (2)0.100 (2)0.0170 (17)0.0107 (15)0.0034 (16)
N170.0587 (14)0.0781 (15)0.0844 (14)0.0034 (11)0.0035 (10)0.0064 (11)
C180.0661 (18)0.096 (2)0.0909 (19)0.0073 (17)0.0008 (13)0.0165 (15)
O180.0795 (16)0.137 (3)0.1162 (17)0.0384 (17)0.0149 (13)0.0342 (16)
C190.081 (2)0.102 (3)0.115 (2)0.016 (2)0.0187 (18)0.026 (2)
C200.128 (4)0.148 (5)0.173 (5)0.051 (4)0.047 (4)0.080 (4)
C11A0.0641 (17)0.0712 (16)0.0773 (15)0.0046 (13)0.0085 (11)0.0068 (12)
C12A0.108 (3)0.086 (2)0.0824 (19)0.0041 (19)0.0099 (16)0.0024 (15)
C13A0.161 (5)0.079 (2)0.103 (3)0.019 (3)0.036 (3)0.0011 (18)
C14A0.113 (4)0.132 (4)0.116 (3)0.045 (3)0.033 (3)0.017 (3)
C15A0.071 (2)0.138 (4)0.127 (3)0.015 (2)0.0160 (19)0.019 (3)
C16A0.0631 (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)
C11B0.0641 (17)0.0761 (18)0.0825 (16)0.0046 (14)0.0027 (12)0.0004 (13)
C16B0.094 (3)0.093 (2)0.108 (2)0.021 (2)0.0153 (18)0.0162 (19)
C15B0.115 (3)0.115 (3)0.109 (3)0.027 (3)0.034 (2)0.006 (2)
C14B0.112 (3)0.109 (3)0.093 (2)0.011 (3)0.0194 (19)0.001 (2)
C13B0.125 (3)0.083 (2)0.121 (3)0.005 (2)0.027 (2)0.014 (2)
C12B0.106 (3)0.0714 (19)0.116 (3)0.0064 (19)0.029 (2)0.0006 (17)
O210.0558 (11)0.0744 (12)0.1130 (14)0.0037 (10)0.0044 (9)0.0033 (10)
C220.0621 (17)0.0809 (19)0.0775 (16)0.0022 (14)0.0056 (11)0.0009 (13)
O220.0746 (16)0.0792 (16)0.157 (2)0.0061 (13)0.0019 (13)0.0134 (14)
C11C0.0583 (15)0.0794 (18)0.0766 (15)0.0036 (13)0.0049 (11)0.0011 (12)
C16C0.0647 (19)0.085 (2)0.125 (3)0.0086 (16)0.0065 (17)0.0013 (18)
C15C0.0611 (19)0.105 (3)0.127 (3)0.0067 (18)0.0015 (17)0.000 (2)
C14C0.0606 (19)0.107 (3)0.129 (3)0.0085 (19)0.0020 (17)0.003 (2)
C13C0.084 (3)0.094 (3)0.181 (4)0.012 (2)0.009 (3)0.029 (3)
C12C0.0625 (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)
Geometric parameters (Å, º) top
Br1—C4C1.904 (4)N11—C161.446 (5)
N1—C61.449 (4)N11—C121.453 (5)
N1—C1'1.465 (4)N11—C11'1.459 (4)
N1—C21.466 (4)Br11—C14C1.910 (4)
C2—C31.522 (4)C12—C131.518 (5)
C2—H2A0.9700C12—H12A0.9700
C2—H2B0.9700C12—H12B0.9700
C3—C3'1.510 (5)C13—C13'1.522 (6)
C3—C41.520 (4)C13—C141.530 (5)
C3—H3A0.9800C13—H13A0.9800
C4—N71.494 (3)C14—N171.483 (4)
C4—C51.515 (4)C14—C151.528 (5)
C4—H4A0.9800C14—H14A0.9800
C5—C61.521 (5)C15—C161.520 (5)
C5—H5A0.9700C15—H15A0.9700
C5—H5B0.9700C15—H15B0.9700
C6—H6A0.9700C16—H16A0.9700
C6—H6B0.9700C16—H16B0.9700
N7—C81.362 (4)N17—C181.364 (4)
N7—C1A1.431 (4)N17—C11A1.444 (4)
C8—O81.217 (4)C18—O181.222 (4)
C8—C91.530 (4)C18—C191.511 (5)
C9—C101.507 (6)C19—C201.489 (6)
C9—H9A0.9700C19—H19A0.9700
C9—H9B0.9700C19—H19B0.9700
C10—H10A0.9600C20—H20A0.9600
C10—H10B0.9600C20—H20B0.9600
C10—H10C0.9600C20—H20C0.9600
C1A—C2A1.382 (6)C11A—C16A1.377 (5)
C1A—C6A1.404 (6)C11A—C12A1.388 (5)
C6A—C5A1.384 (7)C12A—C13A1.392 (7)
C6A—H6AA0.9300C12A—H12C0.9300
C5A—C4A1.376 (10)C13A—C14A1.356 (8)
C5A—H5AA0.9300C13A—H13B0.9300
C4A—C3A1.359 (11)C14A—C15A1.359 (8)
C4A—H4AA0.9300C14A—H14B0.9300
C3A—C2A1.390 (7)C15A—C16A1.376 (6)
C3A—H3AA0.9300C15A—H15C0.9300
C2A—H2AA0.9300C16A—H16C0.9300
C1'—C2'1.506 (4)C11'—C12'1.516 (5)
C1'—H1'A0.9700C11'—H11A0.9700
C1'—H1'B0.9700C11'—H11B0.9700
C2'—O111.463 (4)C12'—O211.448 (4)
C2'—C1B1.495 (4)C12'—C11B1.510 (4)
C2'—H2'A0.9800C12'—H12D0.9800
C1B—C6B1.379 (5)C11B—C16B1.361 (5)
C1B—C2B1.380 (5)C11B—C12B1.381 (5)
C6B—C5B1.389 (6)C16B—C15B1.378 (6)
C6B—H6BA0.9300C16B—H1CA0.9300
C5B—C4B1.368 (7)C15B—C14B1.356 (7)
C5B—H5BA0.9300C15B—H15D0.9300
C4B—C3B1.369 (8)C14B—C13B1.381 (7)
C4B—H4BA0.9300C14B—H14C0.9300
C3B—C2B1.394 (6)C13B—C12B1.386 (6)
C3B—H3BA0.9300C13B—H13C0.9300
C2B—H2BA0.9300C12B—H12E0.9300
O11—C12X1.331 (4)O21—C221.338 (4)
C12X—O121.211 (4)C22—O221.195 (4)
C12X—C1C1.490 (4)C22—C11C1.488 (5)
C1C—C2C1.376 (5)C11C—C12C1.376 (5)
C1C—C6C1.383 (5)C11C—C16C1.381 (5)
C6C—C5C1.381 (6)C16C—C15C1.380 (6)
C6C—H6CA0.9300C16C—H16D0.9300
C5C—C4C1.385 (6)C15C—C14C1.352 (7)
C5C—H5CA0.9300C15C—H15E0.9300
C4C—C3C1.358 (6)C14C—C13C1.359 (6)
C3C—C2C1.379 (6)C13C—C12C1.393 (6)
C3C—H3CA0.9300C13C—H13D0.9300
C2C—H2CA0.9300C12C—H12F0.9300
C3'—H3'A0.9600C13'—H13E0.9600
C3'—H3'B0.9600C13'—H13F0.9600
C3'—H3'C0.9600C13'—H13G0.9600
C6—N1—C1'111.4 (2)C16—N11—C12110.6 (3)
C6—N1—C2109.0 (2)C16—N11—C11'114.7 (3)
C1'—N1—C2111.2 (2)C12—N11—C11'112.3 (3)
N1—C2—C3111.6 (2)N11—C12—C13111.3 (3)
N1—C2—H2A109.3N11—C12—H12A109.4
C3—C2—H2A109.3C13—C12—H12A109.4
N1—C2—H2B109.3N11—C12—H12B109.4
C3—C2—H2B109.3C13—C12—H12B109.4
H2A—C2—H2B108.0H12A—C12—H12B108.0
C3'—C3—C4115.1 (3)C12—C13—C13'112.2 (3)
C3'—C3—C2111.2 (3)C12—C13—C14108.2 (3)
C4—C3—C2108.3 (2)C13'—C13—C14114.6 (3)
C3'—C3—H3A107.3C12—C13—H13A107.2
C4—C3—H3A107.3C13'—C13—H13A107.2
C2—C3—H3A107.3C14—C13—H13A107.2
N7—C4—C5113.2 (2)N17—C14—C15112.5 (3)
N7—C4—C3112.9 (2)N17—C14—C13113.5 (3)
C5—C4—C3110.9 (2)C15—C14—C13110.5 (3)
N7—C4—H4A106.4N17—C14—H14A106.6
C5—C4—H4A106.4C15—C14—H14A106.6
C3—C4—H4A106.4C13—C14—H14A106.6
C4—C5—C6109.4 (3)C16—C15—C14110.0 (3)
C4—C5—H5A109.8C16—C15—H15A109.7
C6—C5—H5A109.8C14—C15—H15A109.7
C4—C5—H5B109.8C16—C15—H15B109.7
C6—C5—H5B109.8C14—C15—H15B109.7
H5A—C5—H5B108.3H15A—C15—H15B108.2
N1—C6—C5111.6 (3)N11—C16—C15110.8 (3)
N1—C6—H6A109.3N11—C16—H16A109.5
C5—C6—H6A109.3C15—C16—H16A109.5
N1—C6—H6B109.3N11—C16—H16B109.5
C5—C6—H6B109.3C15—C16—H16B109.5
H6A—C6—H6B108.0H16A—C16—H16B108.1
C8—N7—C1A121.8 (2)C18—N17—C11A120.7 (2)
C8—N7—C4117.1 (2)C18—N17—C14117.1 (3)
C1A—N7—C4120.8 (2)C11A—N17—C14121.7 (2)
O8—C8—N7122.1 (3)O18—C18—N17121.4 (3)
O8—C8—C9121.8 (3)O18—C18—C19121.5 (3)
N7—C8—C9116.1 (3)N17—C18—C19117.1 (3)
C10—C9—C8112.2 (3)C20—C19—C18113.1 (3)
C10—C9—H9A109.2C20—C19—H19A109.0
C8—C9—H9A109.2C18—C19—H19A109.0
C10—C9—H9B109.2C20—C19—H19B109.0
C8—C9—H9B109.2C18—C19—H19B109.0
H9A—C9—H9B107.9H19A—C19—H19B107.8
C9—C10—H10A109.5C19—C20—H20A109.5
C9—C10—H10B109.5C19—C20—H20B109.5
H10A—C10—H10B109.5H20A—C20—H20B109.5
C9—C10—H10C109.5C19—C20—H20C109.5
H10A—C10—H10C109.5H20A—C20—H20C109.5
H10B—C10—H10C109.5H20B—C20—H20C109.5
C2A—C1A—C6A120.5 (3)C16A—C11A—C12A119.2 (3)
C2A—C1A—N7120.5 (3)C16A—C11A—N17121.1 (3)
C6A—C1A—N7118.9 (3)C12A—C11A—N17119.7 (3)
C5A—C6A—C1A119.2 (5)C11A—C12A—C13A119.2 (4)
C5A—C6A—H6AA120.4C11A—C12A—H12C120.4
C1A—C6A—H6AA120.4C13A—C12A—H12C120.4
C4A—C5A—C6A119.8 (6)C14A—C13A—C12A120.3 (4)
C4A—C5A—H5AA120.1C14A—C13A—H13B119.9
C6A—C5A—H5AA120.1C12A—C13A—H13B119.9
C3A—C4A—C5A120.6 (5)C13A—C14A—C15A121.0 (4)
C3A—C4A—H4AA119.7C13A—C14A—H14B119.5
C5A—C4A—H4AA119.7C15A—C14A—H14B119.5
C4A—C3A—C2A121.3 (6)C14A—C15A—C16A119.5 (5)
C4A—C3A—H3AA119.4C14A—C15A—H15C120.2
C2A—C3A—H3AA119.4C16A—C15A—H15C120.2
C1A—C2A—C3A118.4 (5)C15A—C16A—C11A120.8 (4)
C1A—C2A—H2AA120.8C15A—C16A—H16C119.6
C3A—C2A—H2AA120.8C11A—C16A—H16C119.6
N1—C1'—C2'112.3 (2)N11—C11'—C12'110.3 (3)
N1—C1'—H1'A109.1N11—C11'—H11A109.6
C2'—C1'—H1'A109.1C12'—C11'—H11A109.6
N1—C1'—H1'B109.1N11—C11'—H11B109.6
C2'—C1'—H1'B109.1C12'—C11'—H11B109.6
H1'A—C1'—H1'B107.9H11A—C11'—H11B108.1
O11—C2'—C1B108.5 (2)O21—C12'—C11B108.1 (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'A109.0O21—C12'—H12D109.6
C1B—C2'—H2'A109.0C11B—C12'—H12D109.6
C1'—C2'—H2'A109.0C11'—C12'—H12D109.6
C6B—C1B—C2B118.2 (3)C16B—C11B—C12B118.6 (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—C5B121.4 (4)C11B—C16B—C15B121.5 (4)
C1B—C6B—H6BA119.3C11B—C16B—H1CA119.3
C5B—C6B—H6BA119.3C15B—C16B—H1CA119.3
C4B—C5B—C6B119.5 (4)C14B—C15B—C16B120.1 (4)
C4B—C5B—H5BA120.2C14B—C15B—H15D120.0
C6B—C5B—H5BA120.2C16B—C15B—H15D120.0
C5B—C4B—C3B120.1 (4)C15B—C14B—C13B119.8 (4)
C5B—C4B—H4BA120.0C15B—C14B—H14C120.1
C3B—C4B—H4BA120.0C13B—C14B—H14C120.1
C4B—C3B—C2B120.2 (4)C14B—C13B—C12B119.7 (4)
C4B—C3B—H3BA119.9C14B—C13B—H13C120.2
C2B—C3B—H3BA119.9C12B—C13B—H13C120.2
C1B—C2B—C3B120.4 (4)C11B—C12B—C13B120.4 (4)
C1B—C2B—H2BA119.8C11B—C12B—H12E119.8
C3B—C2B—H2BA119.8C13B—C12B—H12E119.8
C12X—O11—C2'118.0 (2)C22—O21—C12'118.9 (3)
O12—C12X—O11123.6 (3)O22—C22—O21123.7 (3)
O12—C12X—C1C123.6 (3)O22—C22—C11C125.5 (3)
O11—C12X—C1C112.8 (3)O21—C22—C11C110.9 (3)
C2C—C1C—C6C119.3 (3)C12C—C11C—C16C119.2 (3)
C2C—C1C—C12X118.7 (3)C12C—C11C—C22122.2 (3)
C6C—C1C—C12X122.0 (3)C16C—C11C—C22118.6 (3)
C5C—C6C—C1C120.4 (3)C15C—C16C—C11C120.8 (4)
C5C—C6C—H6CA119.8C15C—C16C—H16D119.6
C1C—C6C—H6CA119.8C11C—C16C—H16D119.6
C6C—C5C—C4C118.4 (4)C14C—C15C—C16C118.2 (4)
C6C—C5C—H5CA120.8C14C—C15C—H15E120.9
C4C—C5C—H5CA120.8C16C—C15C—H15E120.9
C3C—C4C—C5C122.0 (3)C15C—C14C—C13C123.4 (4)
C3C—C4C—Br1119.9 (3)C15C—C14C—Br11118.3 (3)
C5C—C4C—Br1118.0 (3)C13C—C14C—Br11118.3 (4)
C4C—C3C—C2C118.8 (3)C14C—C13C—C12C118.0 (4)
C4C—C3C—H3CA120.6C14C—C13C—H13D121.0
C2C—C3C—H3CA120.6C12C—C13C—H13D121.0
C1C—C2C—C3C120.9 (4)C11C—C12C—C13C120.4 (4)
C1C—C2C—H2CA119.5C11C—C12C—H12F119.8
C3C—C2C—H2CA119.5C13C—C12C—H12F119.8
C3—C3'—H3'A109.5C13—C13'—H13E109.5
C3—C3'—H3'B109.5C13—C13'—H13F109.5
H3'A—C3'—H3'B109.5H13E—C13'—H13F109.5
C3—C3'—H3'C109.5C13—C13'—H13G109.5
H3'A—C3'—H3'C109.5H13E—C13'—H13G109.5
H3'B—C3'—H3'C109.5H13F—C13'—H13G109.5
C6—N1—C2—C361.9 (3)C16—N11—C12—C1362.5 (4)
C1'—N1—C2—C3174.9 (3)C11'—N11—C12—C13168.0 (3)
N1—C2—C3—C3'68.6 (4)N11—C12—C13—C13'68.5 (5)
N1—C2—C3—C458.8 (3)N11—C12—C13—C1458.9 (4)
C3'—C3—C4—N758.3 (4)C12—C13—C14—N17177.6 (3)
C2—C3—C4—N7176.6 (3)C13'—C13—C14—N1756.4 (4)
C3'—C3—C4—C570.0 (4)C12—C13—C14—C1554.9 (4)
C2—C3—C4—C555.2 (3)C13'—C13—C14—C1571.1 (4)
N7—C4—C5—C6177.0 (3)N17—C14—C15—C16177.5 (3)
C3—C4—C5—C654.9 (4)C13—C14—C15—C1654.4 (4)
C1'—N1—C6—C5175.9 (3)C12—N11—C16—C1560.6 (4)
C2—N1—C6—C560.9 (4)C11'—N11—C16—C15171.1 (3)
C4—C5—C6—N157.9 (4)C14—C15—C16—N1156.7 (4)
C5—C4—N7—C8157.3 (3)C15—C14—N17—C18157.9 (3)
C3—C4—N7—C875.6 (3)C13—C14—N17—C1875.6 (4)
C5—C4—N7—C1A17.7 (4)C15—C14—N17—C11A14.3 (4)
C3—C4—N7—C1A109.4 (3)C13—C14—N17—C11A112.2 (3)
C1A—N7—C8—O8173.3 (3)C11A—N17—C18—O18176.7 (4)
C4—N7—C8—O81.6 (5)C14—N17—C18—O184.4 (5)
C1A—N7—C8—C98.0 (5)C11A—N17—C18—C194.0 (5)
C4—N7—C8—C9177.2 (3)C14—N17—C18—C19176.3 (3)
O8—C8—C9—C104.8 (6)O18—C18—C19—C202.9 (7)
N7—C8—C9—C10176.4 (4)N17—C18—C19—C20177.8 (5)
C8—N7—C1A—C2A85.0 (4)C18—N17—C11A—C16A91.9 (4)
C4—N7—C1A—C2A100.3 (4)C14—N17—C11A—C16A96.2 (4)
C8—N7—C1A—C6A93.0 (4)C18—N17—C11A—C12A86.1 (4)
C4—N7—C1A—C6A81.7 (4)C14—N17—C11A—C12A85.8 (4)
C2A—C1A—C6A—C5A2.3 (5)C16A—C11A—C12A—C13A1.4 (5)
N7—C1A—C6A—C5A179.8 (3)N17—C11A—C12A—C13A179.5 (3)
C1A—C6A—C5A—C4A2.1 (7)C11A—C12A—C13A—C14A1.3 (6)
C6A—C5A—C4A—C3A0.3 (8)C12A—C13A—C14A—C15A1.0 (7)
C5A—C4A—C3A—C2A1.4 (9)C13A—C14A—C15A—C16A0.8 (7)
C6A—C1A—C2A—C3A0.6 (6)C14A—C15A—C16A—C11A0.9 (6)
N7—C1A—C2A—C3A178.6 (4)C12A—C11A—C16A—C15A1.3 (5)
C4A—C3A—C2A—C1A1.2 (8)N17—C11A—C16A—C15A179.3 (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'—O1163.3 (3)N11—C11'—C12'—O2164.3 (3)
N1—C1'—C2'—C1B176.7 (2)N11—C11'—C12'—C11B177.1 (3)
O11—C2'—C1B—C6B108.4 (3)O21—C12'—C11B—C16B146.8 (3)
C1'—C2'—C1B—C6B132.7 (3)C11'—C12'—C11B—C16B96.0 (4)
O11—C2'—C1B—C2B71.6 (4)O21—C12'—C11B—C12B32.3 (4)
C1'—C2'—C1B—C2B47.3 (4)C11'—C12'—C11B—C12B84.8 (4)
C2B—C1B—C6B—C5B0.8 (5)C12B—C11B—C16B—C15B1.0 (7)
C2'—C1B—C6B—C5B179.2 (3)C12'—C11B—C16B—C15B178.1 (4)
C1B—C6B—C5B—C4B1.2 (6)C11B—C16B—C15B—C14B0.7 (8)
C6B—C5B—C4B—C3B0.5 (6)C16B—C15B—C14B—C13B0.9 (8)
C5B—C4B—C3B—C2B2.5 (7)C15B—C14B—C13B—C12B1.4 (8)
C6B—C1B—C2B—C3B1.3 (6)C16B—C11B—C12B—C13B1.6 (6)
C2'—C1B—C2B—C3B178.7 (3)C12'—C11B—C12B—C13B177.6 (4)
C4B—C3B—C2B—C1B2.9 (6)C14B—C13B—C12B—C11B1.8 (7)
C1B—C2'—O11—C12X120.5 (3)C11B—C12'—O21—C22109.2 (3)
C1'—C2'—O11—C12X115.6 (3)C11'—C12'—O21—C22128.4 (3)
C2'—O11—C12X—O127.2 (4)C12'—O21—C22—O220.7 (4)
C2'—O11—C12X—C1C172.8 (2)C12'—O21—C22—C11C179.2 (2)
O12—C12X—C1C—C2C2.2 (5)O22—C22—C11C—C12C176.1 (4)
O11—C12X—C1C—C2C177.9 (3)O21—C22—C11C—C12C3.9 (4)
O12—C12X—C1C—C6C179.7 (4)O22—C22—C11C—C16C5.6 (5)
O11—C12X—C1C—C6C0.3 (4)O21—C22—C11C—C16C174.3 (3)
C2C—C1C—C6C—C5C0.8 (6)C12C—C11C—C16C—C15C0.4 (5)
C12X—C1C—C6C—C5C176.7 (4)C22—C11C—C16C—C15C177.9 (3)
C1C—C6C—C5C—C4C2.2 (7)C11C—C16C—C15C—C14C0.6 (6)
C6C—C5C—C4C—C3C2.7 (7)C16C—C15C—C14C—C13C1.0 (7)
C6C—C5C—C4C—Br1179.8 (3)C16C—C15C—C14C—Br11179.9 (3)
C5C—C4C—C3C—C2C1.8 (7)C15C—C14C—C13C—C12C1.2 (8)
Br1—C4C—C3C—C2C178.8 (3)Br11—C14C—C13C—C12C179.9 (4)
C6C—C1C—C2C—C3C0.1 (6)C16C—C11C—C12C—C13C0.6 (6)
C12X—C1C—C2C—C3C177.7 (3)C22—C11C—C12C—C13C177.6 (4)
C4C—C3C—C2C—C1C0.3 (6)C14C—C13C—C12C—C11C1.0 (8)
(III) N-{(3R,4S)1-[(2S)-2-(4-bromophenyl)-2-hydroxyethyl]-3-methyl-4-pyridyl}- N-phenylpropenamide top
Crystal data top
C23H27BrN2O2F(000) = 920
Mr = 443.38Dx = 1.339 Mg m3
Orthorhombic, P212121Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2ac 2abCell parameters from 7464 reflections
a = 6.1932 (1) Åθ = 2.7–67.2°
b = 10.7461 (1) ŵ = 2.70 mm1
c = 33.0458 (3) ÅT = 295 K
V = 2199.29 (5) Å3Rod, colorless
Z = 40.48 × 0.08 × 0.03 mm
Data collection top
BrukerCCD area-detector
diffractometer
3605 independent reflections
Radiation source: 5Kw rotating anode3330 reflections with I > 2σ(I'
Gobel mirrors monochromatorRint = 0.027
ω scansθmax = 67.2°, θmin = 2.7°
Absorption correction: integration
a face-indexed absorption correction was followed by a SADABS (Bruker, 2001) correction
h = 77
Tmin = 0.395, Tmax = 0.876k = 1212
9443 measured reflectionsl = 3936
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH 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 = 1.09Δρmax = 0.30 e Å3
3605 reflectionsΔρmin = 0.39 e Å3
254 parametersExtinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.0194 (8)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983)
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.004 (19)
Crystal data top
C23H27BrN2O2V = 2199.29 (5) Å3
Mr = 443.38Z = 4
Orthorhombic, P212121Cu Kα radiation
a = 6.1932 (1) ŵ = 2.70 mm1
b = 10.7461 (1) ÅT = 295 K
c = 33.0458 (3) Å0.48 × 0.08 × 0.03 mm
Data collection top
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 = 0.876Rint = 0.027
9443 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.041H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.105Δρmax = 0.30 e Å3
S = 1.09Δρmin = 0.39 e Å3
3605 reflectionsAbsolute structure: Flack (1983)
254 parametersAbsolute structure parameter: 0.004 (19)
0 restraints
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br10.37695 (7)0.64565 (3)0.904840 (11)0.09159 (19)
N10.3654 (4)1.16624 (19)1.08489 (6)0.0602 (5)
C20.3255 (5)1.1133 (2)1.12504 (8)0.0638 (6)
H2A0.41601.04061.12880.077*
H2B0.17601.08711.12690.077*
C30.3731 (5)1.2076 (3)1.15828 (7)0.0629 (6)
H3A0.33271.16921.18410.075*
C3'0.6091 (6)1.2382 (4)1.16058 (14)0.1041 (13)
H3'A0.63291.29831.18160.156*
H3'B0.65611.27191.13520.156*
H3'C0.68951.16401.16640.156*
C40.2237 (4)1.3200 (2)1.15186 (7)0.0541 (5)
H4A0.07641.28671.15130.065*
C50.2631 (6)1.3751 (3)1.11030 (9)0.0749 (8)
H5A0.40941.40701.10870.090*
H5B0.16421.44361.10560.090*
C60.2293 (6)1.2747 (3)1.07822 (8)0.0774 (8)
H6A0.07911.24901.07840.093*
H6B0.26061.30931.05180.093*
N70.2294 (3)1.41064 (19)1.18537 (6)0.0557 (5)
C80.1118 (4)1.3829 (2)1.21924 (7)0.0563 (5)
O80.0186 (3)1.28299 (19)1.22270 (6)0.0698 (5)
C90.0951 (5)1.4798 (3)1.25136 (9)0.0704 (7)
H90.15831.55741.24750.084*
C100.0074 (6)1.4561 (4)1.28480 (10)0.0883 (10)
H10A0.07061.37861.28870.106*
H10B0.01761.51671.30480.106*
C1A0.3446 (4)1.5269 (2)1.18228 (8)0.0579 (5)
C2A0.5383 (5)1.5417 (3)1.20331 (10)0.0758 (8)
H2AA0.59871.47551.21740.091*
C3A0.6386 (6)1.6562 (4)1.20279 (13)0.0941 (10)
H3AA0.76521.66771.21740.113*
C4A0.5542 (6)1.7533 (3)1.18097 (12)0.0896 (10)
H4AA0.62491.82961.18050.108*
C5A0.3658 (7)1.7376 (3)1.15988 (10)0.0835 (9)
H5AA0.30961.80321.14490.100*
C6A0.2588 (5)1.6247 (3)1.16082 (9)0.0673 (7)
H6AA0.12921.61501.14700.081*
C1'0.3335 (5)1.0728 (3)1.05314 (8)0.0664 (7)
H1'A0.18101.06701.04670.080*
H1'B0.38070.99221.06290.080*
C2'0.4597 (5)1.1063 (3)1.01494 (8)0.0683 (7)
H2'A0.39471.17981.00230.082*
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*
C1B0.4506 (5)0.9983 (3)0.98571 (8)0.0637 (6)
C6B0.6066 (6)0.9079 (3)0.98542 (9)0.0741 (7)
H6BA0.72730.91641.00190.089*
C5B0.5869 (6)0.8037 (3)0.96088 (9)0.0786 (8)
H5BA0.69370.74280.96080.094*
C4B0.4094 (5)0.7918 (3)0.93692 (8)0.0680 (7)
C3B0.2531 (6)0.8811 (3)0.93587 (11)0.0831 (9)
H3BA0.13360.87240.91910.100*
C2B0.2756 (6)0.9852 (3)0.96038 (10)0.0799 (8)
H2BA0.17071.04710.95970.096*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.1223 (3)0.0756 (2)0.0769 (2)0.01214 (19)0.00236 (19)0.01571 (16)
N10.0760 (13)0.0550 (11)0.0498 (10)0.0080 (10)0.0017 (9)0.0027 (8)
C20.0817 (17)0.0552 (13)0.0545 (13)0.0047 (11)0.0037 (11)0.0039 (11)
C30.0745 (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)
C40.0502 (12)0.0585 (14)0.0536 (12)0.0074 (9)0.0042 (9)0.0026 (10)
C50.111 (2)0.0612 (16)0.0526 (12)0.0103 (15)0.0049 (14)0.0001 (12)
C60.111 (2)0.0703 (17)0.0512 (13)0.0125 (16)0.0116 (14)0.0016 (13)
N70.0622 (11)0.0546 (11)0.0504 (10)0.0065 (8)0.0036 (9)0.0005 (9)
C80.0565 (12)0.0600 (13)0.0524 (12)0.0016 (11)0.0050 (10)0.0032 (10)
O80.0745 (12)0.0695 (12)0.0655 (11)0.0136 (9)0.0042 (9)0.0035 (9)
C90.0850 (18)0.0662 (14)0.0601 (14)0.0046 (14)0.0054 (14)0.0034 (12)
C100.106 (2)0.083 (2)0.075 (2)0.0128 (18)0.0225 (18)0.0048 (17)
C1A0.0620 (14)0.0556 (12)0.0561 (12)0.0056 (10)0.0015 (10)0.0045 (11)
C2A0.0722 (17)0.0711 (17)0.0841 (19)0.0080 (13)0.0191 (14)0.0088 (15)
C3A0.081 (2)0.095 (2)0.106 (2)0.0223 (19)0.0166 (18)0.024 (2)
C4A0.100 (2)0.0711 (19)0.098 (2)0.0279 (17)0.0132 (19)0.0112 (18)
C5A0.109 (2)0.0616 (16)0.0797 (18)0.0117 (18)0.0044 (19)0.0041 (14)
C6A0.0739 (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)
C1B0.0771 (16)0.0642 (15)0.0498 (12)0.0046 (12)0.0050 (11)0.0052 (12)
C6B0.0760 (17)0.0798 (18)0.0665 (16)0.0104 (15)0.0043 (14)0.0036 (14)
C5B0.087 (2)0.0775 (18)0.0717 (16)0.0245 (15)0.0007 (15)0.0052 (16)
C4B0.0863 (18)0.0658 (15)0.0520 (12)0.0072 (13)0.0056 (13)0.0014 (12)
C3B0.087 (2)0.084 (2)0.0780 (18)0.0120 (16)0.0171 (16)0.0096 (17)
C2B0.0855 (19)0.0783 (19)0.0759 (18)0.0250 (16)0.0125 (15)0.0083 (16)
Geometric parameters (Å, º) top
Br1—C4B1.906 (3)C1A—C6A1.375 (4)
N1—C61.455 (4)C1A—C2A1.396 (4)
N1—C21.465 (3)C2A—C3A1.378 (5)
N1—C1'1.466 (3)C2A—H2AA0.9300
C2—C31.523 (4)C3A—C4A1.372 (6)
C2—H2A0.9700C3A—H3AA0.9300
C2—H2B0.9700C4A—C5A1.370 (6)
C3—C3'1.500 (5)C4A—H4AA0.9300
C3—C41.536 (4)C5A—C6A1.383 (4)
C3—H3A0.9800C5A—H5AA0.9300
C3'—H3'A0.9600C6A—H6AA0.9300
C3'—H3'B0.9600C1'—C2'1.528 (4)
C3'—H3'C0.9600C1'—H1'A0.9700
C4—N71.475 (3)C1'—H1'B0.9700
C4—C51.515 (4)C2'—O2'1.421 (4)
C4—H4A0.9800C2'—C1B1.511 (4)
C5—C61.527 (4)C2'—H2'A0.9800
C5—H5A0.9700O2'—H2'0.81 (4)
C5—H5B0.9700C1B—C6B1.370 (4)
C6—H6A0.9700C1B—C2B1.377 (4)
C6—H6B0.9700C6B—C5B1.388 (5)
N7—C81.368 (3)C6B—H6BA0.9300
N7—C1A1.442 (3)C5B—C4B1.361 (5)
C8—O81.224 (3)C5B—H5BA0.9300
C8—C91.491 (4)C4B—C3B1.364 (4)
C9—C101.300 (4)C3B—C2B1.388 (5)
C9—H90.9300C3B—H3BA0.9300
C10—H10A0.9300C2B—H2BA0.9300
C10—H10B0.9300
C6—N1—C2110.5 (2)H10A—C10—H10B120.0
C6—N1—C1'111.2 (2)C6A—C1A—C2A120.1 (3)
C2—N1—C1'111.1 (2)C6A—C1A—N7120.5 (2)
N1—C2—C3111.2 (2)C2A—C1A—N7119.3 (2)
N1—C2—H2A109.4C3A—C2A—C1A118.9 (3)
C3—C2—H2A109.4C3A—C2A—H2AA120.6
N1—C2—H2B109.4C1A—C2A—H2AA120.6
C3—C2—H2B109.4C4A—C3A—C2A120.9 (3)
H2A—C2—H2B108.0C4A—C3A—H3AA119.5
C3'—C3—C2111.8 (3)C2A—C3A—H3AA119.5
C3'—C3—C4114.9 (3)C5A—C4A—C3A119.9 (3)
C2—C3—C4107.9 (2)C5A—C4A—H4AA120.1
C3'—C3—H3A107.3C3A—C4A—H4AA120.1
C2—C3—H3A107.3C4A—C5A—C6A120.3 (3)
C4—C3—H3A107.3C4A—C5A—H5AA119.8
C3—C3'—H3'A109.5C6A—C5A—H5AA119.8
C3—C3'—H3'B109.5C1A—C6A—C5A119.8 (3)
H3'A—C3'—H3'B109.5C1A—C6A—H6AA120.1
C3—C3'—H3'C109.5C5A—C6A—H6AA120.1
H3'A—C3'—H3'C109.5N1—C1'—C2'111.2 (2)
H3'B—C3'—H3'C109.5N1—C1'—H1'A109.4
N7—C4—C5114.7 (2)C2'—C1'—H1'A109.4
N7—C4—C3113.63 (19)N1—C1'—H1'B109.4
C5—C4—C3109.6 (2)C2'—C1'—H1'B109.4
N7—C4—H4A106.0H1'A—C1'—H1'B108.0
C5—C4—H4A106.0O2'—C2'—C1B110.4 (3)
C3—C4—H4A106.0O2'—C2'—C1'109.2 (2)
C4—C5—C6109.3 (2)C1B—C2'—C1'109.2 (2)
C4—C5—H5A109.8O2'—C2'—H2'A109.4
C6—C5—H5A109.8C1B—C2'—H2'A109.4
C4—C5—H5B109.8C1'—C2'—H2'A109.4
C6—C5—H5B109.8C2'—O2'—H2'110 (3)
H5A—C5—H5B108.3C6B—C1B—C2B118.5 (3)
N1—C6—C5112.4 (2)C6B—C1B—C2'121.5 (3)
N1—C6—H6A109.1C2B—C1B—C2'119.8 (3)
C5—C6—H6A109.1C1B—C6B—C5B121.0 (3)
N1—C6—H6B109.1C1B—C6B—H6BA119.5
C5—C6—H6B109.1C5B—C6B—H6BA119.5
H6A—C6—H6B107.9C4B—C5B—C6B119.1 (3)
C8—N7—C1A120.7 (2)C4B—C5B—H5BA120.5
C8—N7—C4117.20 (19)C6B—C5B—H5BA120.5
C1A—N7—C4122.1 (2)C5B—C4B—C3B121.5 (3)
O8—C8—N7121.2 (2)C5B—C4B—Br1119.1 (2)
O8—C8—C9120.9 (2)C3B—C4B—Br1119.4 (2)
N7—C8—C9117.8 (2)C4B—C3B—C2B118.7 (3)
C10—C9—C8120.2 (3)C4B—C3B—H3BA120.6
C10—C9—H9119.9C2B—C3B—H3BA120.6
C8—C9—H9119.9C1B—C2B—C3B121.1 (3)
C9—C10—H10A120.0C1B—C2B—H2BA119.4
C9—C10—H10B120.0C3B—C2B—H2BA119.4
C6—N1—C2—C359.9 (3)C6A—C1A—C2A—C3A1.3 (5)
C1'—N1—C2—C3176.2 (2)N7—C1A—C2A—C3A174.9 (3)
N1—C2—C3—C3'67.0 (4)C1A—C2A—C3A—C4A2.1 (6)
N1—C2—C3—C460.3 (3)C2A—C3A—C4A—C5A1.1 (6)
C3'—C3—C4—N763.2 (3)C3A—C4A—C5A—C6A0.7 (5)
C2—C3—C4—N7171.4 (2)C2A—C1A—C6A—C5A0.5 (4)
C3'—C3—C4—C566.7 (3)N7—C1A—C6A—C5A176.7 (3)
C2—C3—C4—C558.7 (3)C4A—C5A—C6A—C1A1.5 (5)
N7—C4—C5—C6174.1 (2)C6—N1—C1'—C2'80.2 (3)
C3—C4—C5—C656.7 (3)C2—N1—C1'—C2'156.3 (3)
C2—N1—C6—C557.5 (3)N1—C1'—C2'—O2'50.4 (3)
C1'—N1—C6—C5178.6 (3)N1—C1'—C2'—C1B171.1 (2)
C4—C5—C6—N156.4 (4)O2'—C2'—C1B—C6B28.1 (4)
C5—C4—N7—C8153.2 (2)C1'—C2'—C1B—C6B91.9 (3)
C3—C4—N7—C879.6 (3)O2'—C2'—C1B—C2B156.1 (3)
C5—C4—N7—C1A23.8 (3)C1'—C2'—C1B—C2B83.9 (3)
C3—C4—N7—C1A103.4 (3)C2B—C1B—C6B—C5B1.5 (5)
C1A—N7—C8—O8177.8 (2)C2'—C1B—C6B—C5B174.4 (3)
C4—N7—C8—O85.2 (4)C1B—C6B—C5B—C4B0.2 (5)
C1A—N7—C8—C94.0 (3)C6B—C5B—C4B—C3B1.4 (5)
C4—N7—C8—C9173.1 (2)C6B—C5B—C4B—Br1177.5 (2)
O8—C8—C9—C104.6 (4)C5B—C4B—C3B—C2B1.0 (5)
N7—C8—C9—C10177.2 (3)Br1—C4B—C3B—C2B178.0 (3)
C8—N7—C1A—C6A99.6 (3)C6B—C1B—C2B—C3B1.9 (5)
C4—N7—C1A—C6A77.2 (3)C2'—C1B—C2B—C3B174.0 (3)
C8—N7—C1A—C2A76.6 (3)C4B—C3B—C2B—C1B0.7 (5)
C4—N7—C1A—C2A106.5 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···N10.81 (4)2.31 (4)2.775 (3)117 (4)

Experimental details

(II)(III)
Crystal data
Chemical formulaC30H33BrN2O3C23H27BrN2O2
Mr549.49443.38
Crystal system, space groupMonoclinic, P21Orthorhombic, P212121
Temperature (K)153295
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), 9090, 90, 90
V3)2816.78 (11)2199.29 (5)
Z44
Radiation typeCu KαCu Kα
µ (mm1)2.242.70
Crystal size (mm)0.56 × 0.44 × 0.240.48 × 0.08 × 0.03
Data collection
DiffractometerBruker CCD area-detector
diffractometer
BrukerCCD area-detector
diffractometer
Absorption correctionIntegration
(Bruker, 2001)
Integration
a face-indexed absorption correction was followed by a SADABS (Bruker, 2001) correction
Tmin, Tmax0.608, 0.9310.395, 0.876
No. of measured, independent and
observed reflections
13643, 7419, 6654 [I > 2σ(I)]9443, 3605, 3330 [I > 2σ(I']
Rint0.0240.027
(sin θ/λ)max1)0.5970.598
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.122, 1.07 0.041, 0.105, 1.09
No. of reflections74193605
No. of parameters650254
No. of restraints10
H-atom treatmentH-atom parameters constrainedH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.23, 0.450.30, 0.39
Absolute structureFlack (1983)Flack (1983)
Absolute structure parameter0.032 (15)0.004 (19)

Computer programs: SMART (Bruker 2001), SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL (Bruker, 2001).

Selected geometric parameters (Å, º) for (II) top
Br1—C4C1.904 (4)N11—C161.446 (5)
N1—C61.449 (4)N11—C121.453 (5)
N1—C1'1.465 (4)N11—C11'1.459 (4)
N1—C21.466 (4)Br11—C14C1.910 (4)
C4—N71.494 (3)C14—N171.483 (4)
N7—C81.362 (4)N17—C181.364 (4)
N7—C1A1.431 (4)N17—C11A1.444 (4)
C6—N1—C1'111.4 (2)C16—N11—C12110.6 (3)
C6—N1—C2109.0 (2)C16—N11—C11'114.7 (3)
C1'—N1—C2111.2 (2)C12—N11—C11'112.3 (3)
C8—N7—C1A121.8 (2)C18—N17—C11A120.7 (2)
C8—N7—C4117.1 (2)C18—N17—C14117.1 (3)
C1A—N7—C4120.8 (2)C11A—N17—C14121.7 (2)
Selected geometric parameters (Å, º) for (III) top
Br1—C4B1.906 (3)N7—C81.368 (3)
N1—C61.455 (4)N7—C1A1.442 (3)
N1—C21.465 (3)C9—C101.300 (4)
N1—C1'1.466 (3)C2'—O2'1.421 (4)
C4—N71.475 (3)
C6—N1—C2110.5 (2)C8—N7—C1A120.7 (2)
C6—N1—C1'111.2 (2)C8—N7—C4117.20 (19)
C2—N1—C1'111.1 (2)C1A—N7—C4122.1 (2)
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
O2'—H2'···N10.81 (4)2.31 (4)2.775 (3)117 (4)
 

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