Three tetra­hydro-1,4-ep­oxy-1-benzazepines carrying pendent heterocyclic substituents: supra­molecular structures in zero, one or two dimensions

(2SR,4RS)-7-Fluoro-2-exo-(2-furyl)-2,3,4,5-tetra­hydro-1H-1,4-ep­oxy-1-benzazepine, C₁₄H₁₂FNO₂, (I), crystallizes with Z′ = 2 in the space group P2₁/c. A combination of three C—H...O hydrogen bonds and one C—H...N hydrogen bond links the mol­ecules into a complex chain of rings, and pairs of such chains are linked into a tube-like structure by two C—H...π(arene) hydrogen bonds. There are no hydrogen bonds in the structure of racemic (2SR,4RS)-2-exo-(5-bromo-2-thienyl)-7-fluoro-2,3,4,5-tetra­hydro-1H-1,4-epoxy-1-benzazepine, C₁₄H₁₁BrFNOS, (II), while the mol­ecules of (2S,4R)-2-exo-(5-bromo-2-thienyl)-7-trifluoro­meth­oxy-2,3,4,5-tetrahydro-1H-1,4-epoxy-1-benzazepine, C₁₅H₁₄BrF₃NO₂S, (III), are linked into sheets by a combination of two C—H...O hydrogen bonds and one C—H...π(arene) hydrogen bond. The significance of this study lies in its observation of the wide variation in the patterns of supra­molecular aggregation, consequent upon modest changes in the peripheral substituents.

S1. Comment

In a continuation of our structural study of 2-substituted 1,4-epoxy-tetrahydro-1-benzazepines (Acosta et al., 2008; Gómez et al., 2008), itself part of a programme to identify structurally novel anti-parasitic compounds with new modes of action to combat both Trypanosoma cruzi and Leishmania chagasi parasites (Gómez et al., 2006; Yépez et al., 2006), we now report the structures of three examples, (I)–(III), carrying heterocylic substituents at position C2 (Figs. 1–3). The synthesis of compounds (I)–(III) involved treating an appropriately substituted 2-allyl-N-(2'-furylmethyl)aniline or 2-allyl-N-(2'-thienylmethyl)aniline with an excess of hydrogen peroxide solution in the presence of catalytic amounts of sodium tungstate.

Under the synthetic and crystallization conditions employed, (I) and (II) both crystallize as racemic mixtures in space group P2₁/c, where (I) crystallizes with Z' = 2. Compound (III) crystallizes as a single enantiomorph in space group P2₁ and the configuration at C4 is R, as shown by the Flack x parameter (Flack, 1983). Hence the reference molecules for the racemic compounds were selected to have the R configuration at C4. On this basis, the reference molecules in (I)–(III) all have the S configuration at C2.

The shapes of the heterobicyclic ring systems in (I)–(III), as defined by the ring-puckering parameters (Cremer & Pople, 1975), are all very similar (Table 1). The five-membered rings in (II) and (III) adopt half-chair conformations, for which the ideal puckering angle ϕ is (36k + 18)°, where k represents an integer, while for both independent molecules in (I) the conformations are intermediate between an envelope form, where the ideal value of ϕ is 36k°, and the half-chair form observed in the other examples. The conformations of the six-membered heterocyclic rings are intermediate between a half-chair form, where the idealized values of the ring-puckering angles are θ = 50.8° and ϕ = (60k + 30)°, and an envelope form, where the idealized values are θ = 54.7° and ϕ = 60k°.

The values of the torsion angle N1—C2—C21—C22 in (I)–(III), which defines the orientation of the pendent heterocyclic substituent, have rather similar values in the two independent molecules in (I) [86.7 (3) and 74.5 (3)°], but very different values in (II) [-60.1 (3)°] and (III) [36.6 (4)°], indicative of almost orthogonal orientations for the thienyl groups in these two compounds. There is no obvious simple interpretation of this observation.

Compound (I) crystallizes with Z' = 2, in space group P2₁/c. There are six independent hydrogen bonds in the crystal structure (Table 2), leading to the formation of a structure of some complexity but which can in fact be readily analysed in terms of simple motifs. Type 1 molecules (containing atom N11), which are related by translation, are linked by a three-centre C—H···(O,N) interaction. The C—H···O and C—H···N components individually generate C(4) and C(5) (Bernstein et al., 1995) chains, while their combination generates a C(4)C(5)[R²₁(3)] chain of rings running parallel to the [100] direction (Fig. 4). By contrast, the type 2 molecules (containing atom N21), related by translation, are linked only by a C—H···O hydrogen bond, forming a simple C(4) chain parallel to [100]. The two independent molecules are linked within the asymmetric unit by a further C—H···O hydrogen bond, so that the combination of all the C—H···O and C—H···N interactions generates a chain of rings based on an R³₄(20) motif (Fig. 4). An antiparallel pair of such chains, related to one another by inversion, are then linked by two independent C—H···π(arene) hydrogen bonds to form a complex tubular structure (Fig. 5).

There are no hydrogen bonds of any type in the structure of (II). Instead, the molecules are weakly linked in pairs by a single aromatic π–π stacking interaction to form dimeric units (Fig. 6). The fluoro-substituted aryl rings of the molecules at (x, y, z) and (1 - x, 1 - y, 1 - z) are parallel, with an interplanar spacing of 3.450 (2) Å; the corresponding ring-centroid separation is 3.853 (2) Å, giving a ring offset of 1.716 (2) Å.

In the structure of the trifluoromethoxy analogue, (III), by contrast, there are three hydrogen bonds, two of C—H···O type and one of C—H···π(arene) type (Table 2), and they give rise to a sheet the formation of which is very simply analysed in terms of two simple substructures. Aryl atom C9 in the molecule at (x, y, z) acts as hydrogen-bond donor to atom O14 in the molecule at (-x, 1/2 + y, 1 - z), so linking molecules related by the 2₁ screw axis along (0, y, 1/2) into a C(5) chain running parallel to the [010] direction. At the same time, thienyl atom C23 at (x, y, z) acts as hydrogen-bond donor to atom O14 in the molecule at (1 + x, y, z), thus generating by translation a C(6) chain running parallel to the [100] direction. The combination of these two chain motifs then generates a sheet parallel to (001) and built from R³₄(20) rings (Fig. 7). In addition, the substructure along [100] is reinforced by the C—H···π(arene) hydrogen bond, but there are no direction-specific interactions between adjacent sheets.

S2. Experimental

For each of compounds (I)–(III), to a stirred solution of the appropriately substituted 2-allylaniline (0.10 mol) in methanol (40 ml) was added sodium tungstate dihydrate, Na₂WO₄.2H₂O (5 mol%), followed by 30% aqueous hydrogen peroxide solution (0.30 mol). The resulting mixtures were then stirred at ambient temperature for periods ranging from 18 to 60 h. Each mixture was then filtered and the solvent was removed under reduced pressure. Toluene (50 ml) was added to the solid residue and the resulting solution was heated under reflux for periods ranging from 6 to 8 h. After cooling the solution to ambient temperature, the solvent was removed under reduced pressure and the crude product was purified by chromatography on silica using heptane–ethyl acetate (compositions ranged from 10:1 to 60:1 v/v) as eluent. Crystallization from heptane gave crystals of compounds (I)–(III) suitable for single-crystal X-ray diffraction.

For (I): yellow crystals, yield 35%, m.p. 357–358 K; MS (70 eV) m/z (%): 245 (M⁺, 32), 228 (9), 215 (10), 148 (8), 123 (52), 122 (100), 94 (32). Analysis, found: C 68.8, H 4.8, N 5.6%; C₁₄H₁₂FNO₂ requires: C 68.6, H 4.9, N 5.7%.

For (II): yellow crystals, yield 61%, m.p. 380–381 K; MS (70 eV) m/z (%): 339 (M⁺, ⁷⁹Br, 13), 309 (3), 188 (27), 148 (9), 123 (76), 122 (100). Analysis, found: C 49.2, H 3.5, N 4.2%; C₁₄H₁₁BrFNOS requires: C 49.4, H 3.3, N 4.1%.

For (III): yellow crystals, yield 61%, m.p. 372–373 K; MS (70 eV) m/z (%): 405 (M⁺, ⁷⁹Br, 19), 388 (13), 375 (7), 214 (6), 189 (60), 188 (100). Analysis, found: C 44.3, H 2.6, N 3.5%. C₁₅H₁₁BrF₃NO₂S requires: C 44.4, H 2.7, N 3.5%.

S3. Refinement

Unique assignments of space groups were made from the systematic absences for compounds (I) and (II), both P2₁/c. For compound (III), the systematic absences permitted P2₁ or P2₁/m as possible space groups; P2₁ was selected, and confirmed by the subsequent structure analyses. All H atoms were located in difference maps and then treated as riding atoms in geometrically idealized positions, with C—H = 0.95 (aromatic, heteroaromatic and alkene), 0.99 (CH₂) or 1.00 Å (aliphatic CH), and with U_iso(H) = 1.2U_eq(C). For compound (III), the correct enantiomorph, having the R configuration at C4, was established by means of the Flack x parameter (Flack, 1983). The reference molecules in (I) and (II) were therefore chosen as those having the R configuration at C4.

Computing details

For all compounds, data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. The molecular structure of compound (I), showing the atom-labelling scheme. (a) Molecule 1. (b) Molecule 2. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The molecular structure of compound (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 3. The molecular structure of compound (III), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 4. A stereoview of part of the crystal structure of compound (I), showing the formation of a hydrogen-bonded chain of edge-fused R^34(20) rings along [100]. For the sake of clarity, H atoms bonded to C atoms which are not involved in the motif shown have been omitted.
	Fig. 5. A stereoview of part of the crystal structure of compound (I), showing the formation of a hydrogen-bonded tube along [100], formed by the linking of an antiparallel pair of chains of rings by means of C—H···π(arene) hydrogen bonds. For the sake of clarity, H atoms bonded to C atoms which are not involved in the motif shown have been omitted.
	Fig. 6. A stereoview of part of the crystal structure of compound (II), showing the formation of a π-stacked dimer. For the sake of clarity, all H atoms have been omitted.
	Fig. 7. A stereoview of part of the crystal structure of compound (III), showing the formation of a hydrogen-bonded sheet parallel to (001). For the sake of clarity, H atoms bonded to C atoms which are not involved in the motif shown have been omitted.

(I) (2SR,4RS)-7-Fluoro-2-exo-(2-furyl)-2,3,4,5-tetrahydro-1H-1,4-epoxy- 1-benzazepine

Crystal data

C14H12FNO2	F(000) = 1024
Mr = 245.25	Dx = 1.457 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5130 reflections
a = 5.5314 (10) Å	θ = 3.1–27.5°
b = 15.430 (4) Å	µ = 0.11 mm^−1
c = 26.229 (6) Å	T = 120 K
β = 92.960 (17)°	Lath, yellow
V = 2235.6 (9) Å^3	0.38 × 0.16 × 0.09 mm
Z = 8

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	5130 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	2690 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.081
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.1°
ϕ and ω scans	h = −7→7
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −20→19
Tmin = 0.969, Tmax = 0.990	l = −34→33
35661 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.167	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0621P)^2 + 1.7109P] where P = (Fo^2 + 2Fc^2)/3
5130 reflections	(Δ/σ)max < 0.001
325 parameters	Δρmax = 0.38 e Å^−3
0 restraints	Δρmin = −0.34 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
F17	0.1130 (4)	0.27532 (14)	0.80841 (8)	0.0649 (6)
O114	0.5413 (3)	0.20270 (12)	0.60167 (7)	0.0301 (5)
O121	0.7679 (5)	−0.04606 (18)	0.63394 (9)	0.0656 (8)
N11	0.5857 (4)	0.14877 (14)	0.64589 (8)	0.0253 (5)
C12	0.4624 (5)	0.06686 (18)	0.62986 (10)	0.0280 (6)
C13	0.2469 (5)	0.0963 (2)	0.59544 (12)	0.0384 (8)
C14	0.2872 (5)	0.1922 (2)	0.58882 (11)	0.0339 (7)
C15	0.1503 (5)	0.2466 (2)	0.62510 (11)	0.0343 (7)
C15a	0.2464 (5)	0.23186 (18)	0.67851 (11)	0.0292 (7)
C16	0.1329 (5)	0.2624 (2)	0.72028 (12)	0.0386 (8)
C17	0.2305 (6)	0.2467 (2)	0.76785 (12)	0.0420 (8)
C18	0.4447 (6)	0.2044 (2)	0.77686 (12)	0.0420 (8)
C19	0.5605 (5)	0.17425 (19)	0.73547 (11)	0.0329 (7)
C19a	0.4617 (5)	0.18658 (18)	0.68708 (10)	0.0264 (6)
C122	0.6298 (5)	0.00788 (19)	0.60513 (11)	0.0315 (7)
C123	0.6867 (5)	0.0015 (2)	0.55730 (10)	0.0326 (7)
C124	0.8592 (6)	−0.0640 (2)	0.55476 (13)	0.0464 (9)
C125	0.9068 (6)	−0.0921 (2)	0.60072 (14)	0.0524 (10)
F27	1.3742 (4)	0.58437 (12)	0.22306 (7)	0.0542 (6)
O214	0.9908 (3)	0.52076 (12)	0.43570 (7)	0.0275 (5)
O221	0.7575 (3)	0.28128 (13)	0.40684 (7)	0.0343 (5)
N21	0.9452 (4)	0.46388 (14)	0.39285 (8)	0.0255 (5)
C22	1.0801 (5)	0.38467 (18)	0.40951 (11)	0.0285 (7)
C23	1.2985 (5)	0.41829 (19)	0.44195 (12)	0.0358 (7)
C24	1.2481 (5)	0.51444 (19)	0.44657 (11)	0.0303 (7)
C25	1.3721 (5)	0.56837 (19)	0.40792 (11)	0.0317 (7)
C25a	1.2683 (5)	0.54893 (18)	0.35527 (10)	0.0278 (6)
C26	1.3721 (5)	0.57739 (18)	0.31170 (12)	0.0337 (7)
C27	1.2678 (6)	0.5565 (2)	0.26531 (12)	0.0377 (8)
C28	1.0588 (6)	0.5101 (2)	0.25904 (11)	0.0376 (8)
C29	0.9526 (5)	0.48240 (19)	0.30232 (11)	0.0315 (7)
C29a	1.0577 (5)	0.50058 (18)	0.34970 (10)	0.0258 (6)
C222	0.9238 (5)	0.32513 (18)	0.43708 (11)	0.0291 (7)
C223	0.9063 (6)	0.3013 (2)	0.48554 (12)	0.0380 (8)
C224	0.7192 (6)	0.2393 (2)	0.48664 (14)	0.0462 (9)
C225	0.6357 (6)	0.2293 (2)	0.43859 (14)	0.0437 (8)
H12	0.4011	0.0376	0.6607	0.034*
H13A	0.2442	0.0660	0.5621	0.046*
H13B	0.0925	0.0850	0.6117	0.046*
H14	0.2478	0.2101	0.5527	0.041*
H15A	0.1666	0.3086	0.6162	0.041*
H15B	−0.0237	0.2313	0.6221	0.041*
H16	−0.0134	0.2945	0.7158	0.046*
H18	0.5113	0.1961	0.8106	0.050*
H19	0.7104	0.1446	0.7404	0.039*
H123	0.6221	0.0353	0.5295	0.039*
H124	0.9294	−0.0843	0.5247	0.056*
H125	1.0184	−0.1368	0.6101	0.063*
H22	1.1388	0.3544	0.3788	0.034*
H23A	1.3090	0.3902	0.4759	0.043*
H23B	1.4512	0.4079	0.4248	0.043*
H24	1.2919	0.5352	0.4820	0.036*
H25A	1.3503	0.6306	0.4156	0.038*
H25B	1.5477	0.5557	0.4099	0.038*
H26	1.5154	0.6114	0.3141	0.040*
H28	0.9892	0.4975	0.2260	0.045*
H29	0.8056	0.4505	0.2995	0.038*
H223	1.0019	0.3222	0.5141	0.046*
H224	0.6640	0.2104	0.5159	0.055*
H225	0.5083	0.1911	0.4279	0.052*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F17	0.0828 (15)	0.0612 (14)	0.0538 (13)	0.0040 (11)	0.0334 (11)	−0.0185 (10)
O114	0.0234 (10)	0.0376 (12)	0.0293 (11)	−0.0010 (9)	0.0011 (8)	0.0110 (9)
O121	0.0696 (18)	0.081 (2)	0.0474 (15)	0.0316 (15)	0.0179 (13)	0.0115 (14)
N11	0.0251 (12)	0.0249 (13)	0.0259 (12)	−0.0016 (10)	0.0012 (9)	0.0053 (10)
C12	0.0284 (15)	0.0271 (16)	0.0290 (15)	−0.0027 (12)	0.0064 (12)	−0.0001 (12)
C13	0.0262 (16)	0.042 (2)	0.0466 (19)	−0.0022 (14)	−0.0008 (14)	−0.0092 (15)
C14	0.0189 (14)	0.047 (2)	0.0353 (17)	−0.0005 (13)	−0.0022 (12)	0.0062 (14)
C15	0.0225 (15)	0.0329 (17)	0.0475 (19)	0.0002 (13)	0.0012 (13)	0.0056 (14)
C15a	0.0234 (15)	0.0247 (16)	0.0402 (17)	−0.0043 (12)	0.0075 (12)	0.0012 (13)
C16	0.0330 (17)	0.0299 (18)	0.054 (2)	−0.0016 (14)	0.0114 (15)	−0.0064 (15)
C17	0.049 (2)	0.0369 (19)	0.042 (2)	−0.0053 (16)	0.0222 (16)	−0.0128 (15)
C18	0.054 (2)	0.039 (2)	0.0323 (18)	−0.0045 (16)	0.0030 (15)	−0.0031 (14)
C19	0.0377 (17)	0.0289 (17)	0.0321 (17)	−0.0008 (14)	0.0018 (13)	−0.0012 (13)
C19a	0.0268 (15)	0.0235 (15)	0.0295 (16)	−0.0055 (12)	0.0064 (12)	0.0005 (12)
C122	0.0274 (16)	0.0261 (17)	0.0406 (18)	−0.0007 (13)	−0.0031 (13)	0.0010 (13)
C123	0.0267 (15)	0.0490 (19)	0.0219 (15)	0.0073 (14)	0.0003 (11)	0.0104 (13)
C124	0.046 (2)	0.059 (2)	0.0345 (19)	−0.0108 (18)	0.0132 (15)	−0.0180 (17)
C125	0.054 (2)	0.039 (2)	0.067 (3)	0.0207 (17)	0.0319 (19)	0.0124 (18)
F27	0.0728 (14)	0.0462 (12)	0.0466 (11)	−0.0127 (10)	0.0316 (10)	−0.0025 (9)
O214	0.0231 (10)	0.0320 (11)	0.0272 (10)	0.0038 (8)	0.0011 (8)	−0.0072 (8)
O221	0.0326 (11)	0.0333 (12)	0.0378 (12)	−0.0056 (9)	0.0087 (9)	0.0001 (9)
N21	0.0261 (12)	0.0254 (13)	0.0250 (12)	0.0024 (10)	0.0019 (10)	−0.0036 (10)
C22	0.0249 (15)	0.0266 (16)	0.0344 (16)	0.0037 (12)	0.0042 (12)	−0.0012 (13)
C23	0.0271 (16)	0.0325 (18)	0.0471 (19)	0.0038 (13)	−0.0061 (14)	−0.0025 (14)
C24	0.0227 (15)	0.0346 (17)	0.0330 (16)	0.0017 (13)	−0.0056 (12)	−0.0074 (13)
C25	0.0218 (15)	0.0312 (17)	0.0418 (18)	0.0029 (12)	−0.0010 (12)	−0.0080 (13)
C25a	0.0239 (15)	0.0241 (15)	0.0353 (17)	0.0032 (12)	0.0022 (12)	−0.0051 (12)
C26	0.0295 (16)	0.0250 (17)	0.0477 (19)	−0.0042 (13)	0.0124 (14)	−0.0044 (14)
C27	0.0443 (19)	0.0347 (18)	0.0358 (18)	0.0001 (15)	0.0188 (15)	0.0014 (14)
C28	0.050 (2)	0.0336 (18)	0.0296 (17)	−0.0027 (15)	0.0038 (14)	−0.0044 (14)
C29	0.0311 (16)	0.0302 (17)	0.0333 (17)	−0.0029 (13)	0.0032 (13)	−0.0021 (13)
C29a	0.0232 (14)	0.0263 (15)	0.0284 (15)	0.0023 (12)	0.0060 (11)	−0.0022 (12)
C222	0.0279 (15)	0.0271 (16)	0.0325 (16)	0.0074 (13)	0.0026 (12)	−0.0033 (13)
C223	0.0437 (19)	0.0352 (19)	0.0357 (18)	0.0134 (15)	0.0072 (14)	0.0055 (14)
C224	0.050 (2)	0.038 (2)	0.054 (2)	0.0156 (16)	0.0270 (17)	0.0167 (17)
C225	0.0360 (18)	0.0314 (19)	0.066 (2)	−0.0040 (14)	0.0223 (17)	0.0045 (16)

Geometric parameters (Å, º)

F17—C17	1.349 (3)	F27—C27	1.352 (3)
O114—C14	1.438 (3)	O214—N21	1.438 (3)
O114—N11	1.438 (3)	O214—C24	1.440 (3)
O121—C122	1.337 (4)	O221—C225	1.359 (3)
O121—C125	1.386 (4)	O221—C222	1.363 (3)
N11—C19a	1.433 (3)	N21—C29a	1.436 (3)
N11—C12	1.486 (3)	N21—C22	1.486 (3)
C12—C122	1.472 (4)	C22—C222	1.476 (4)
C12—C13	1.527 (4)	C22—C23	1.532 (4)
C12—H12	1.00	C22—H22	1.00
C13—C14	1.509 (4)	C23—C24	1.516 (4)
C13—H13A	0.99	C23—H23A	0.99
C13—H13B	0.99	C23—H23B	0.99
C14—C15	1.502 (4)	C24—C25	1.504 (4)
C14—H14	1.00	C24—H24	1.00
C15—C15a	1.490 (4)	C25—C25a	1.498 (4)
C15—H15A	0.99	C25—H25A	0.99
C15—H15B	0.99	C25—H25B	0.99
C15a—C16	1.374 (4)	C25a—C26	1.377 (4)
C15a—C19a	1.389 (4)	C25a—C29a	1.385 (4)
C16—C17	1.356 (5)	C26—C27	1.358 (4)
C16—H16	0.95	C26—H26	0.95
C17—C18	1.363 (5)	C27—C28	1.363 (4)
C18—C19	1.370 (4)	C28—C29	1.373 (4)
C18—H18	0.95	C28—H28	0.95
C19—C19a	1.369 (4)	C29—C29a	1.374 (4)
C19—H19	0.95	C29—H29	0.95
C122—C123	1.313 (4)	C222—C223	1.332 (4)
C123—C124	1.394 (4)	C223—C224	1.411 (5)
C123—H123	0.95	C223—H223	0.95
C124—C125	1.295 (5)	C224—C225	1.329 (5)
C124—H124	0.95	C224—H224	0.95
C125—H125	0.95	C225—H225	0.95
C14—O114—N11	104.36 (19)	N21—O214—C24	104.19 (18)
C122—O121—C125	106.4 (3)	C225—O221—C222	106.1 (2)
C19a—N11—O114	107.7 (2)	C29a—N21—O214	108.0 (2)
C19a—N11—C12	109.2 (2)	C29a—N21—C22	108.9 (2)
O114—N11—C12	101.95 (19)	O214—N21—C22	101.94 (19)
C122—C12—N11	111.1 (2)	C222—C22—N21	111.0 (2)
C122—C12—C13	114.4 (2)	C222—C22—C23	113.8 (2)
N11—C12—C13	104.3 (2)	N21—C22—C23	104.7 (2)
C122—C12—H12	108.9	C222—C22—H22	109.1
N11—C12—H12	108.9	N21—C22—H22	109.1
C13—C12—H12	108.9	C23—C22—H22	109.1
C14—C13—C12	104.1 (2)	C24—C23—C22	103.5 (2)
C14—C13—H13A	110.9	C24—C23—H23A	111.1
C12—C13—H13A	110.9	C22—C23—H23A	111.1
C14—C13—H13B	110.9	C24—C23—H23B	111.1
C12—C13—H13B	110.9	C22—C23—H23B	111.1
H13A—C13—H13B	108.9	H23A—C23—H23B	109.0
O114—C14—C15	107.9 (2)	O214—C24—C25	108.0 (2)
O114—C14—C13	103.4 (2)	O214—C24—C23	103.6 (2)
C15—C14—C13	113.1 (3)	C25—C24—C23	113.3 (2)
O114—C14—H14	110.7	O214—C24—H24	110.6
C15—C14—H14	110.7	C25—C24—H24	110.6
C13—C14—H14	110.7	C23—C24—H24	110.6
C15a—C15—C14	110.1 (2)	C25a—C25—C24	110.1 (2)
C15a—C15—H15A	109.6	C25a—C25—H25A	109.6
C14—C15—H15A	109.6	C24—C25—H25A	109.6
C15a—C15—H15B	109.6	C25a—C25—H25B	109.6
C14—C15—H15B	109.6	C24—C25—H25B	109.6
H15A—C15—H15B	108.2	H25A—C25—H25B	108.1
C16—C15a—C19a	117.9 (3)	C26—C25a—C29a	118.0 (3)
C16—C15a—C15	122.8 (3)	C26—C25a—C25	123.0 (3)
C19a—C15a—C15	119.4 (2)	C29a—C25a—C25	119.0 (2)
C17—C16—C15a	119.7 (3)	C27—C26—C25a	119.5 (3)
C17—C16—H16	120.1	C27—C26—H26	120.3
C15a—C16—H16	120.1	C25a—C26—H26	120.3
F17—C17—C16	118.8 (3)	F27—C27—C26	118.5 (3)
F17—C17—C18	118.0 (3)	F27—C27—C28	118.1 (3)
C16—C17—C18	123.1 (3)	C26—C27—C28	123.4 (3)
C17—C18—C19	117.6 (3)	C27—C28—C29	117.4 (3)
C17—C18—H18	121.2	C27—C28—H28	121.3
C19—C18—H18	121.2	C29—C28—H28	121.3
C19a—C19—C18	120.5 (3)	C28—C29—C29a	120.3 (3)
C19a—C19—H19	119.8	C28—C29—H29	119.8
C18—C19—H19	119.8	C29a—C29—H29	119.8
C19—C19a—C15a	121.2 (3)	C29—C29a—C25a	121.3 (3)
C19—C19a—N11	117.3 (3)	C29—C29a—N21	116.9 (2)
C15a—C19a—N11	121.5 (2)	C25a—C29a—N21	121.7 (2)
C123—C122—O121	109.6 (3)	C223—C222—O221	109.8 (3)
C123—C122—C12	130.9 (3)	C223—C222—C22	135.5 (3)
O121—C122—C12	119.3 (3)	O221—C222—C22	114.8 (2)
C122—C123—C124	107.4 (3)	C222—C223—C224	107.2 (3)
C122—C123—H123	126.3	C222—C223—H223	126.4
C124—C123—H123	126.3	C224—C223—H223	126.4
C125—C124—C123	107.7 (3)	C225—C224—C223	106.2 (3)
C125—C124—H124	126.1	C225—C224—H224	126.9
C123—C124—H124	126.1	C223—C224—H224	126.9
C124—C125—O121	108.7 (3)	C224—C225—O221	110.7 (3)
C124—C125—H125	125.6	C224—C225—H225	124.6
O121—C125—H125	125.6	O221—C225—H225	124.6
C14—O114—N11—C19a	−67.5 (2)	C24—O214—N21—C29a	−67.2 (2)
C14—O114—N11—C12	47.4 (2)	C24—O214—N21—C22	47.5 (2)
C19a—N11—C12—C122	−155.5 (2)	C29a—N21—C22—C222	−155.6 (2)
O114—N11—C12—C122	90.8 (2)	O214—N21—C22—C222	90.4 (2)
C19a—N11—C12—C13	80.8 (3)	C29a—N21—C22—C23	81.2 (3)
O114—N11—C12—C13	−32.9 (2)	O214—N21—C22—C23	−32.8 (2)
C122—C12—C13—C14	−113.7 (3)	C222—C22—C23—C24	−114.0 (3)
N11—C12—C13—C14	7.9 (3)	N21—C22—C23—C24	7.4 (3)
N11—O114—C14—C15	77.9 (3)	N21—O214—C24—C25	77.7 (2)
N11—O114—C14—C13	−42.2 (3)	N21—O214—C24—C23	−42.8 (3)
C12—C13—C14—O114	20.1 (3)	C22—C23—C24—O214	20.7 (3)
C12—C13—C14—C15	−96.4 (3)	C22—C23—C24—C25	−96.1 (3)
O114—C14—C15—C15a	−47.3 (3)	O214—C24—C25—C25a	−47.5 (3)
C13—C14—C15—C15a	66.4 (3)	C23—C24—C25—C25a	66.6 (3)
C14—C15—C15a—C16	−169.7 (3)	C24—C25—C25a—C26	−168.8 (3)
C14—C15—C15a—C19a	11.3 (4)	C24—C25—C25a—C29a	11.5 (3)
C19a—C15a—C16—C17	−1.0 (4)	C29a—C25a—C26—C27	−0.8 (4)
C15—C15a—C16—C17	−179.9 (3)	C25—C25a—C26—C27	179.5 (3)
C15a—C16—C17—F17	−178.3 (3)	C25a—C26—C27—F27	−179.3 (3)
C15a—C16—C17—C18	2.8 (5)	C25a—C26—C27—C28	1.9 (5)
F17—C17—C18—C19	178.8 (3)	F27—C27—C28—C29	−179.9 (3)
C16—C17—C18—C19	−2.2 (5)	C26—C27—C28—C29	−1.1 (5)
C17—C18—C19—C19a	−0.2 (5)	C27—C28—C29—C29a	−0.7 (4)
C18—C19—C19a—C15a	1.9 (4)	C28—C29—C29a—C25a	1.7 (4)
C18—C19—C19a—N11	−176.4 (3)	C28—C29—C29a—N21	−175.5 (3)
C16—C15a—C19a—C19	−1.3 (4)	C26—C25a—C29a—C29	−0.9 (4)
C15—C15a—C19a—C19	177.7 (3)	C25—C25a—C29a—C29	178.7 (3)
C16—C15a—C19a—N11	176.9 (2)	C26—C25a—C29a—N21	176.2 (2)
C15—C15a—C19a—N11	−4.1 (4)	C25—C25a—C29a—N21	−4.2 (4)
O114—N11—C19a—C19	−149.8 (2)	O214—N21—C29a—C29	−150.9 (2)
C12—N11—C19a—C19	100.2 (3)	C22—N21—C29a—C29	99.1 (3)
O114—N11—C19a—C15a	31.9 (3)	O214—N21—C29a—C25a	31.9 (3)
C12—N11—C19a—C15a	−78.0 (3)	C22—N21—C29a—C25a	−78.1 (3)
C125—O121—C122—C123	−4.0 (4)	C225—O221—C222—C223	0.1 (3)
C125—O121—C122—C12	−179.3 (3)	C225—O221—C222—C22	178.9 (2)
N11—C12—C122—C123	−87.5 (4)	N21—C22—C222—C223	−107.1 (4)
C13—C12—C122—C123	30.3 (4)	C23—C22—C222—C223	10.8 (5)
N11—C12—C122—O121	86.7 (3)	N21—C22—C222—O221	74.5 (3)
C13—C12—C122—O121	−155.5 (3)	C23—C22—C222—O221	−167.6 (2)
O121—C122—C123—C124	4.0 (4)	O221—C222—C223—C224	−0.2 (3)
C12—C122—C123—C124	178.6 (3)	C22—C222—C223—C224	−178.6 (3)
C122—C123—C124—C125	−2.4 (4)	C222—C223—C224—C225	0.2 (3)
C123—C124—C125—O121	0.0 (4)	C223—C224—C225—O221	−0.1 (3)
C122—O121—C125—C124	2.4 (4)	C222—O221—C225—C224	0.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15B···O114^i	0.99	2.48	3.460 (3)	171
C15—H15B···N11^i	0.99	2.61	3.536 (4)	156
C25—H25B···O214^ii	0.99	2.57	3.539 (3)	168
C224—H224···O114	0.95	2.39	3.271 (4)	154
C16—H16···Cg1^iii	0.95	2.90	3.661 (3)	138
C26—H26···Cg2^iv	0.95	2.97	3.696 (3)	134

Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z; (iii) −x+1, −y+1, −z+1; (iv) −x+2, −y+1, −z+1.

(II) (2SR,4RS)-2-exo-(5-bromo-2-thienyl)-7-fluoro- 2,3,4,5-tetrahydro-1H-1,4-epoxy-1-benzazepine

Crystal data

C14H11BrFNOS	F(000) = 680
Mr = 340.21	Dx = 1.777 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2903 reflections
a = 8.1835 (6) Å	θ = 5.2–27.5°
b = 10.9447 (8) Å	µ = 3.40 mm^−1
c = 14.6940 (12) Å	T = 120 K
β = 104.969 (6)°	Plate, yellow
V = 1271.42 (17) Å^3	0.45 × 0.21 × 0.08 mm
Z = 4

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	2903 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	2026 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.072
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 5.2°
ϕ and ω scans	h = −10→9
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −14→14
Tmin = 0.307, Tmax = 0.762	l = −19→19
19445 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.089	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0323P)^2 + 1.6689P] where P = (Fo^2 + 2Fc^2)/3
2903 reflections	(Δ/σ)max < 0.001
172 parameters	Δρmax = 0.55 e Å^−3
0 restraints	Δρmin = −0.64 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Br25	0.01210 (5)	0.27137 (3)	−0.14994 (2)	0.03408 (13)
S21	0.26676 (11)	0.35924 (8)	0.03230 (6)	0.0245 (2)
F7	0.8291 (3)	0.4530 (2)	0.61798 (13)	0.0347 (5)
O14	0.5776 (3)	0.3860 (2)	0.19190 (15)	0.0240 (5)
N1	0.4699 (3)	0.3605 (2)	0.25306 (18)	0.0191 (6)
C2	0.3310 (4)	0.4476 (3)	0.2172 (2)	0.0206 (7)
C3	0.4208 (4)	0.5642 (3)	0.1971 (3)	0.0270 (8)
C4	0.5963 (4)	0.5183 (3)	0.1968 (2)	0.0263 (8)
C5	0.7286 (4)	0.5475 (3)	0.2851 (2)	0.0266 (8)
C5a	0.6899 (4)	0.4796 (3)	0.3658 (2)	0.0198 (7)
C6	0.7777 (4)	0.5001 (3)	0.4576 (2)	0.0227 (7)
C7	0.7366 (4)	0.4354 (3)	0.5283 (2)	0.0239 (8)
C8	0.6071 (4)	0.3537 (3)	0.5126 (2)	0.0249 (8)
C9	0.5184 (4)	0.3317 (3)	0.4204 (2)	0.0221 (7)
C9a	0.5617 (4)	0.3921 (3)	0.3477 (2)	0.0193 (7)
C22	0.2075 (4)	0.3974 (3)	0.1330 (2)	0.0198 (7)
C23	0.0401 (4)	0.3812 (3)	0.1197 (2)	0.0230 (7)
C24	−0.0448 (4)	0.3392 (3)	0.0291 (2)	0.0262 (8)
H2	0.2721	0.4648	0.2676	0.025*
H3A	0.3623	0.5999	0.1354	0.032*
H3B	0.4269	0.6262	0.2469	0.032*
H4	0.6302	0.5499	0.1405	0.032*
H5A	0.7301	0.6365	0.2973	0.032*
H5B	0.8414	0.5233	0.2783	0.032*
H6	0.8663	0.5587	0.4720	0.027*
H8	0.5785	0.3130	0.5635	0.030*
H9	0.4275	0.2750	0.4072	0.027*
H23	−0.0163	0.3968	0.1674	0.028*
H24	−0.1629	0.3237	0.0090	0.031*
C25	0.0629 (4)	0.3241 (3)	−0.0252 (2)	0.0241 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br25	0.0388 (2)	0.0337 (2)	0.0253 (2)	−0.00331 (18)	0.00033 (15)	−0.00637 (16)
S21	0.0240 (5)	0.0281 (5)	0.0215 (4)	−0.0007 (4)	0.0061 (3)	−0.0048 (3)
F7	0.0301 (12)	0.0500 (13)	0.0200 (10)	0.0033 (10)	−0.0005 (9)	−0.0108 (9)
O14	0.0273 (13)	0.0230 (12)	0.0233 (12)	0.0008 (10)	0.0095 (10)	−0.0011 (9)
N1	0.0219 (15)	0.0182 (14)	0.0185 (13)	0.0003 (11)	0.0075 (11)	0.0001 (10)
C2	0.0222 (18)	0.0190 (17)	0.0195 (16)	0.0031 (14)	0.0033 (13)	−0.0004 (13)
C3	0.030 (2)	0.0168 (17)	0.0303 (19)	0.0013 (14)	0.0008 (15)	0.0036 (14)
C4	0.033 (2)	0.0194 (17)	0.0277 (18)	−0.0037 (15)	0.0103 (16)	0.0054 (14)
C5	0.0253 (19)	0.0253 (19)	0.0300 (19)	−0.0051 (15)	0.0084 (15)	−0.0018 (14)
C5a	0.0187 (17)	0.0175 (16)	0.0229 (17)	0.0033 (13)	0.0048 (14)	−0.0028 (13)
C6	0.0147 (17)	0.0195 (17)	0.0321 (19)	0.0010 (13)	0.0029 (14)	−0.0070 (14)
C7	0.0212 (18)	0.0287 (19)	0.0184 (17)	0.0083 (15)	−0.0011 (14)	−0.0069 (14)
C8	0.0252 (19)	0.0283 (19)	0.0230 (18)	0.0097 (15)	0.0095 (14)	0.0024 (14)
C9	0.0241 (18)	0.0181 (17)	0.0243 (17)	0.0033 (14)	0.0065 (14)	0.0002 (13)
C9a	0.0177 (16)	0.0180 (16)	0.0211 (16)	0.0039 (13)	0.0028 (13)	−0.0030 (12)
C22	0.0260 (18)	0.0131 (15)	0.0204 (16)	0.0012 (14)	0.0061 (14)	0.0030 (12)
C23	0.0234 (18)	0.0223 (18)	0.0245 (17)	0.0009 (14)	0.0082 (14)	0.0049 (13)
C24	0.0232 (18)	0.0216 (18)	0.0296 (19)	−0.0030 (14)	−0.0006 (15)	0.0076 (14)
C25	0.029 (2)	0.0181 (16)	0.0221 (17)	−0.0018 (15)	0.0007 (15)	0.0006 (13)

Geometric parameters (Å, º)

Br25—C25	1.864 (3)	C5—H5A	0.99
S21—C25	1.708 (3)	C5—H5B	0.99
S21—C22	1.723 (3)	C5a—C6	1.374 (4)
F7—C7	1.354 (4)	C5a—C9a	1.394 (4)
O14—N1	1.440 (3)	C6—C7	1.368 (5)
O14—C4	1.455 (4)	C6—H6	0.95
N1—C9a	1.442 (4)	C7—C8	1.360 (5)
N1—C2	1.473 (4)	C8—C9	1.383 (5)
C2—C22	1.487 (4)	C8—H8	0.95
C2—C3	1.539 (5)	C9—C9a	1.378 (4)
C2—H2	1.00	C9—H9	0.95
C3—C4	1.523 (5)	C22—C23	1.344 (5)
C3—H3A	0.99	C23—C24	1.410 (5)
C3—H3B	0.99	C23—H23	0.95
C4—C5	1.494 (5)	C24—C25	1.342 (5)
C4—H4	1.00	C24—H24	0.95
C5—C5a	1.500 (5)
C25—S21—C22	91.34 (16)	C6—C5a—C5	122.1 (3)
N1—O14—C4	103.6 (2)	C9a—C5a—C5	119.5 (3)
O14—N1—C9a	107.7 (2)	C7—C6—C5a	119.5 (3)
O14—N1—C2	101.1 (2)	C7—C6—H6	120.3
C9a—N1—C2	110.5 (2)	C5a—C6—H6	120.3
N1—C2—C22	110.7 (2)	F7—C7—C8	118.2 (3)
N1—C2—C3	104.1 (3)	F7—C7—C6	118.7 (3)
C22—C2—C3	113.7 (3)	C8—C7—C6	123.1 (3)
N1—C2—H2	109.4	C7—C8—C9	118.0 (3)
C22—C2—H2	109.4	C7—C8—H8	121.0
C3—C2—H2	109.4	C9—C8—H8	121.0
C4—C3—C2	103.0 (3)	C9a—C9—C8	120.1 (3)
C4—C3—H3A	111.2	C9a—C9—H9	120.0
C2—C3—H3A	111.2	C8—C9—H9	120.0
C4—C3—H3B	111.2	C9—C9a—C5a	120.9 (3)
C2—C3—H3B	111.2	C9—C9a—N1	117.3 (3)
H3A—C3—H3B	109.1	C5a—C9a—N1	121.8 (3)
O14—C4—C5	107.4 (3)	C23—C22—C2	128.1 (3)
O14—C4—C3	104.0 (3)	C23—C22—S21	110.2 (2)
C5—C4—C3	113.5 (3)	C2—C22—S21	121.6 (2)
O14—C4—H4	110.6	C22—C23—C24	114.5 (3)
C5—C4—H4	110.6	C22—C23—H23	122.7
C3—C4—H4	110.6	C24—C23—H23	122.7
C4—C5—C5a	109.0 (3)	C25—C24—C23	111.2 (3)
C4—C5—H5A	109.9	C25—C24—H24	124.4
C5a—C5—H5A	109.9	C23—C24—H24	124.4
C4—C5—H5B	109.9	C24—C25—S21	112.7 (3)
C5a—C5—H5B	109.9	C24—C25—Br25	127.5 (3)
H5A—C5—H5B	108.3	S21—C25—Br25	119.8 (2)
C6—C5a—C9a	118.4 (3)
C4—O14—N1—C9a	−65.7 (3)	C8—C9—C9a—C5a	−2.8 (5)
C4—O14—N1—C2	50.2 (3)	C8—C9—C9a—N1	176.9 (3)
O14—N1—C2—C22	82.4 (3)	C6—C5a—C9a—C9	3.1 (5)
C9a—N1—C2—C22	−163.8 (3)	C5—C5a—C9a—C9	−177.3 (3)
O14—N1—C2—C3	−40.2 (3)	C6—C5a—C9a—N1	−176.6 (3)
C9a—N1—C2—C3	73.7 (3)	C5—C5a—C9a—N1	3.0 (5)
N1—C2—C3—C4	16.0 (3)	O14—N1—C9a—C9	−153.7 (3)
C22—C2—C3—C4	−104.5 (3)	C2—N1—C9a—C9	96.7 (3)
N1—O14—C4—C5	80.8 (3)	O14—N1—C9a—C5a	26.0 (4)
N1—O14—C4—C3	−39.8 (3)	C2—N1—C9a—C5a	−83.6 (4)
C2—C3—C4—O14	13.8 (3)	N1—C2—C22—C23	124.0 (3)
C2—C3—C4—C5	−102.7 (3)	C3—C2—C22—C23	−119.3 (4)
O14—C4—C5—C5a	−48.9 (3)	N1—C2—C22—S21	−60.1 (3)
C3—C4—C5—C5a	65.4 (4)	C3—C2—C22—S21	56.6 (4)
C4—C5—C5a—C6	−171.8 (3)	C25—S21—C22—C23	0.6 (3)
C4—C5—C5a—C9a	8.6 (4)	C25—S21—C22—C2	−176.0 (3)
C9a—C5a—C6—C7	−0.5 (5)	C2—C22—C23—C24	175.8 (3)
C5—C5a—C6—C7	180.0 (3)	S21—C22—C23—C24	−0.5 (4)
C5a—C6—C7—F7	177.2 (3)	C22—C23—C24—C25	0.1 (4)
C5a—C6—C7—C8	−2.6 (5)	C23—C24—C25—S21	0.4 (4)
F7—C7—C8—C9	−176.9 (3)	C23—C24—C25—Br25	−179.6 (2)
C6—C7—C8—C9	2.9 (5)	C22—S21—C25—C24	−0.6 (3)
C7—C8—C9—C9a	−0.2 (5)	C22—S21—C25—Br25	179.4 (2)

(III) (2S,4R)-2-exo-(5-bromo-2-thienyl)-7-trifluoromethoxy- 2,3,4,5-tetrahydro-1H-1,4-epoxy-1-benzazepine

Crystal data

C15H11BrF3NO2S	F(000) = 404
Mr = 406.22	Dx = 1.791 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 3393 reflections
a = 5.6913 (6) Å	θ = 3.6–27.5°
b = 10.1187 (6) Å	µ = 2.91 mm^−1
c = 13.2996 (13) Å	T = 120 K
β = 100.497 (8)°	Block, yellow
V = 753.09 (12) Å^3	0.27 × 0.22 × 0.21 mm
Z = 2

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	3393 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	2756 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.047
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.6°
ϕ and ω scans	h = −7→7
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −13→12
Tmin = 0.477, Tmax = 0.543	l = −17→17
12890 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.034	w = 1/[σ^2(Fo^2) + (0.0311P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.071	(Δ/σ)max = 0.001
S = 1.09	Δρmax = 0.37 e Å^−3
3393 reflections	Δρmin = −0.36 e Å^−3
209 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.0043 (11)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), with 1567 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.094 (9)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Br25	0.21328 (6)	0.76274 (5)	0.12720 (2)	0.02705 (12)
S21	0.19394 (13)	0.75061 (11)	0.35577 (6)	0.01558 (18)
F71	−0.3327 (4)	0.9133 (3)	1.01923 (18)	0.0396 (7)
F72	−0.3664 (4)	0.7288 (2)	0.9412 (2)	0.0363 (7)
F73	−0.4707 (4)	0.9041 (3)	0.85953 (18)	0.0340 (6)
O7	−0.0879 (4)	0.8719 (3)	0.92012 (19)	0.0207 (6)
O14	0.1230 (4)	0.5383 (2)	0.56126 (17)	0.0146 (5)
N1	0.1434 (5)	0.6798 (3)	0.5608 (2)	0.0135 (6)
C2	0.3995 (5)	0.6954 (4)	0.5543 (3)	0.0145 (7)
C3	0.5259 (6)	0.5857 (4)	0.6216 (3)	0.0169 (8)
C4	0.3213 (6)	0.4967 (4)	0.6385 (3)	0.0168 (8)
C5	0.2497 (6)	0.5177 (4)	0.7412 (2)	0.0163 (7)
C5a	0.1367 (6)	0.6499 (3)	0.7439 (2)	0.0131 (7)
C6	0.0688 (6)	0.6982 (4)	0.8307 (3)	0.0174 (8)
C7	−0.0307 (6)	0.8195 (4)	0.8289 (3)	0.0164 (8)
C8	−0.0696 (6)	0.8993 (4)	0.7441 (3)	0.0183 (8)
C9	−0.0079 (6)	0.8501 (4)	0.6564 (3)	0.0169 (8)
C9a	0.0932 (6)	0.7278 (3)	0.6562 (3)	0.0144 (8)
C22	0.4203 (6)	0.6842 (4)	0.4449 (3)	0.0146 (7)
C23	0.5981 (6)	0.6386 (4)	0.4006 (3)	0.0160 (7)
C24	0.5571 (6)	0.6570 (4)	0.2934 (3)	0.0195 (8)
C25	0.3483 (6)	0.7184 (3)	0.2609 (3)	0.0174 (8)
C71	−0.3115 (7)	0.8543 (4)	0.9339 (3)	0.0251 (9)
H2	0.4589	0.7836	0.5818	0.017*
H3A	0.6393	0.5376	0.5866	0.020*
H3B	0.6134	0.6212	0.6872	0.020*
H4	0.3607	0.4018	0.6289	0.020*
H5A	0.1357	0.4480	0.7532	0.020*
H5B	0.3925	0.5117	0.7961	0.020*
H6	0.0916	0.6468	0.8914	0.021*
H8	−0.1366	0.9851	0.7460	0.022*
H9	−0.0356	0.9013	0.5955	0.020*
H23	0.7379	0.5979	0.4376	0.019*
H24	0.6635	0.6295	0.2501	0.023*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br25	0.02826 (19)	0.0382 (2)	0.01405 (16)	−0.0019 (2)	0.00213 (12)	0.0023 (2)
S21	0.0139 (3)	0.0181 (5)	0.0145 (4)	0.0004 (5)	0.0018 (3)	0.0013 (5)
F71	0.0374 (13)	0.0567 (18)	0.0285 (14)	0.0022 (13)	0.0165 (11)	−0.0127 (12)
F72	0.0366 (13)	0.0345 (19)	0.0417 (14)	−0.0051 (12)	0.0171 (10)	0.0066 (12)
F73	0.0179 (11)	0.0492 (16)	0.0347 (14)	0.0073 (11)	0.0041 (10)	0.0078 (12)
O7	0.0199 (13)	0.0254 (15)	0.0177 (13)	−0.0004 (11)	0.0056 (10)	−0.0066 (11)
O14	0.0161 (11)	0.0123 (13)	0.0145 (12)	−0.0016 (10)	0.0004 (9)	−0.0001 (10)
N1	0.0142 (14)	0.0108 (15)	0.0156 (15)	0.0001 (12)	0.0027 (11)	0.0009 (12)
C2	0.0116 (15)	0.0166 (18)	0.0146 (17)	−0.0018 (14)	0.0002 (12)	−0.0011 (15)
C3	0.0176 (17)	0.019 (2)	0.0137 (18)	0.0009 (15)	0.0021 (13)	0.0036 (15)
C4	0.0170 (17)	0.0145 (18)	0.0184 (19)	0.0020 (15)	0.0015 (13)	0.0023 (15)
C5	0.0182 (18)	0.0167 (18)	0.0140 (18)	−0.0006 (14)	0.0031 (13)	0.0044 (15)
C5a	0.0127 (16)	0.0135 (18)	0.0130 (17)	−0.0023 (13)	0.0018 (12)	0.0012 (14)
C6	0.0158 (18)	0.022 (2)	0.0133 (18)	−0.0015 (16)	0.0005 (14)	0.0030 (15)
C7	0.0158 (18)	0.020 (2)	0.0148 (19)	−0.0015 (16)	0.0066 (15)	−0.0052 (14)
C8	0.0173 (17)	0.0143 (19)	0.023 (2)	0.0011 (15)	0.0032 (14)	−0.0016 (15)
C9	0.0188 (18)	0.021 (2)	0.0116 (18)	−0.0031 (16)	0.0046 (14)	0.0049 (15)
C9a	0.0129 (15)	0.017 (2)	0.0126 (16)	−0.0013 (13)	0.0005 (12)	−0.0018 (13)
C22	0.0126 (15)	0.0118 (18)	0.0176 (18)	−0.0005 (14)	−0.0019 (13)	0.0024 (15)
C23	0.0105 (16)	0.0183 (19)	0.0178 (19)	−0.0008 (14)	−0.0011 (13)	0.0018 (15)
C24	0.0175 (17)	0.023 (2)	0.0192 (19)	−0.0016 (16)	0.0068 (14)	−0.0022 (16)
C25	0.0193 (17)	0.020 (2)	0.0127 (17)	−0.0060 (13)	0.0016 (13)	0.0010 (13)
C71	0.022 (2)	0.031 (2)	0.025 (2)	0.0012 (19)	0.0107 (16)	−0.0017 (19)

Geometric parameters (Å, º)

Br25—C25	1.859 (3)	C4—H4	1.00
S21—C25	1.696 (4)	C5—C5a	1.488 (5)
S21—C22	1.721 (3)	C5—H5A	0.99
F71—C71	1.307 (5)	C5—H5B	0.99
F72—C71	1.316 (5)	C5a—C6	1.372 (5)
F73—C71	1.314 (5)	C5a—C9a	1.391 (5)
O7—C71	1.330 (5)	C6—C7	1.350 (5)
O7—C7	1.416 (4)	C6—H6	0.95
O14—N1	1.437 (4)	C7—C8	1.373 (5)
O14—C4	1.443 (4)	C8—C9	1.372 (5)
N1—C9a	1.436 (4)	C8—H8	0.95
N1—C2	1.484 (4)	C9—C9a	1.365 (5)
C2—C22	1.486 (5)	C9—H9	0.95
C2—C3	1.522 (5)	C22—C23	1.342 (5)
C2—H2	1.00	C23—C24	1.415 (5)
C3—C4	1.521 (5)	C23—H23	0.95
C3—H3A	0.99	C24—C25	1.341 (5)
C3—H3B	0.99	C24—H24	0.95
C4—C5	1.510 (5)
C25—S21—C22	90.76 (16)	C7—C6—C5a	119.4 (4)
C71—O7—C7	116.3 (3)	C7—C6—H6	120.3
N1—O14—C4	103.9 (2)	C5a—C6—H6	120.3
C9a—N1—O14	107.7 (2)	C6—C7—C8	123.6 (4)
C9a—N1—C2	111.8 (3)	C6—C7—O7	119.2 (4)
O14—N1—C2	100.8 (2)	C8—C7—O7	117.1 (3)
N1—C2—C22	107.6 (3)	C9—C8—C7	117.2 (3)
N1—C2—C3	104.6 (3)	C9—C8—H8	121.4
C22—C2—C3	114.0 (3)	C7—C8—H8	121.4
N1—C2—H2	110.1	C9a—C9—C8	120.2 (3)
C22—C2—H2	110.1	C9a—C9—H9	119.9
C3—C2—H2	110.1	C8—C9—H9	119.9
C4—C3—C2	103.0 (3)	C9—C9a—C5a	121.5 (3)
C4—C3—H3A	111.2	C9—C9a—N1	117.4 (3)
C2—C3—H3A	111.2	C5a—C9a—N1	121.0 (3)
C4—C3—H3B	111.2	C23—C22—C2	131.1 (3)
C2—C3—H3B	111.2	C23—C22—S21	111.2 (3)
H3A—C3—H3B	109.1	C2—C22—S21	117.5 (2)
O14—C4—C5	107.4 (3)	C22—C23—C24	113.5 (3)
O14—C4—C3	104.1 (3)	C22—C23—H23	123.3
C5—C4—C3	113.0 (3)	C24—C23—H23	123.3
O14—C4—H4	110.7	C25—C24—C23	111.1 (3)
C5—C4—H4	110.7	C25—C24—H24	124.5
C3—C4—H4	110.7	C23—C24—H24	124.5
C5a—C5—C4	109.7 (3)	C24—C25—S21	113.4 (3)
C5a—C5—H5A	109.7	C24—C25—Br25	127.5 (3)
C4—C5—H5A	109.7	S21—C25—Br25	119.04 (19)
C5a—C5—H5B	109.7	F71—C71—F73	108.5 (3)
C4—C5—H5B	109.7	F71—C71—F72	108.4 (4)
H5A—C5—H5B	108.2	F73—C71—F72	106.6 (4)
C6—C5a—C9a	118.0 (3)	F71—C71—O7	107.5 (3)
C6—C5a—C5	121.9 (3)	F73—C71—O7	113.0 (4)
C9a—C5a—C5	120.1 (3)	F72—C71—O7	112.7 (4)
C4—O14—N1—C9a	−67.9 (3)	C8—C9—C9a—N1	177.2 (3)
C4—O14—N1—C2	49.3 (3)	C6—C5a—C9a—C9	1.7 (5)
C9a—N1—C2—C22	−162.4 (3)	C5—C5a—C9a—C9	−179.3 (3)
O14—N1—C2—C22	83.4 (3)	C6—C5a—C9a—N1	−175.4 (3)
C9a—N1—C2—C3	76.0 (3)	C5—C5a—C9a—N1	3.5 (5)
O14—N1—C2—C3	−38.2 (3)	O14—N1—C9a—C9	−149.6 (3)
N1—C2—C3—C4	13.8 (4)	C2—N1—C9a—C9	100.6 (3)
C22—C2—C3—C4	−103.5 (3)	O14—N1—C9a—C5a	27.7 (4)
N1—O14—C4—C5	79.3 (3)	C2—N1—C9a—C5a	−82.1 (4)
N1—O14—C4—C3	−40.7 (3)	N1—C2—C22—C23	−149.1 (4)
C2—C3—C4—O14	15.6 (3)	C3—C2—C22—C23	−33.6 (5)
C2—C3—C4—C5	−100.6 (3)	N1—C2—C22—S21	36.6 (4)
O14—C4—C5—C5a	−45.4 (4)	C3—C2—C22—S21	152.2 (2)
C3—C4—C5—C5a	68.8 (3)	C25—S21—C22—C23	−1.3 (3)
C4—C5—C5a—C6	−175.6 (3)	C25—S21—C22—C2	174.1 (3)
C4—C5—C5a—C9a	5.4 (4)	C2—C22—C23—C24	−174.0 (4)
C9a—C5a—C6—C7	−1.7 (5)	S21—C22—C23—C24	0.5 (4)
C5—C5a—C6—C7	179.3 (3)	C22—C23—C24—C25	0.9 (5)
C5a—C6—C7—C8	0.1 (5)	C23—C24—C25—S21	−1.9 (4)
C5a—C6—C7—O7	−176.4 (3)	C23—C24—C25—Br25	−179.1 (3)
C71—O7—C7—C6	−95.0 (4)	C22—S21—C25—C24	1.8 (3)
C71—O7—C7—C8	88.2 (4)	C22—S21—C25—Br25	179.4 (2)
C6—C7—C8—C9	1.6 (5)	C7—O7—C71—F71	−177.6 (3)
O7—C7—C8—C9	178.2 (3)	C7—O7—C71—F73	−57.8 (5)
C7—C8—C9—C9a	−1.6 (5)	C7—O7—C71—F72	63.1 (5)
C8—C9—C9a—C5a	0.0 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O14^i	0.95	2.48	3.427 (5)	178
C23—H23···O14^ii	0.95	2.56	3.492 (4)	167
C3—H3B···Cg3^ii	0.99	2.82	3.585 (4)	134

Symmetry codes: (i) −x, y+1/2, −z+1; (ii) x+1, y, z.