Crystal structures of 2-(2-bromo-5-fluoro-phen-yl)-8-eth-oxy-3-nitro-2H-thio-chromene and 2-(2-bromo-5-fluoro-phen-yl)-7-meth-oxy-3-nitro-2H-thio-chromene.

Two thio-chromene com-pounds containing Br and F atoms, namely 2-(2-bromo-5-fluoro-phen-yl)-8-eth-oxy-3-nitro-2H-thio-chromene (C17H13BrFNO3S, A) and 2-(2-bromo-5-fluoro-phen-yl)-7-meth-oxy-3-nitro-2H-thio-chromene (C16H11BrFNO3S, B), were prepared via the condensation reaction between 2-mer-capto-benzaldehyde and nitro-styrene derivatives. In both com-pounds, the thio-chromene plane is almost perpendicular to the phenyl ring. In the structure of A, mol-ecules are assembled via π-π stacking and C-H⋯O and C-F⋯π inter-actions. In the crystal packing of B, mol-ecules are linked by C-H⋯F, C-H⋯O, C-H⋯π and π-π inter-actions. © Pham et al. 2019.

Chemical context

2H-Chromenes (or 2H-benzo­pyrans) are heterocyclic com­pounds found in many natural plants. This class of mol­ecules shows a wide variety of biological activities, such as anti­cancer, anti-inflammation and anti-HIV (Horton et al., 2003 ▸). Recently, we have shown that 3-nitro-2H-chromene can act as a selective mTOR/Pi3K inhibitor, which can lead to a new com­pound to treat breast cancer (Fouqué et al., 2015 ▸). Inter­estingly, we observed that thio­chromene derivatives, where the O atom is replaced by an S atom, can increase significantly the biological activity of these com­pounds. With the goal in mind to synthesize a chemical library of thio­chromene com­pounds (Nguyen et al., 2016 ▸), we have now successfully prepared 2-(2-bromo-5-fluoro­phen­yl)-8-eth­oxy-3-nitro-2H-thio­chromene (A) and 2-(2-bromo-5-fluoro­phen­yl)-7-meth­oxy-3-nitro-2H-thio­chromene (B). Crystal structure determination can help to understand the role of halogenated substituents in the biological activity of these com­pounds.

Structural commentary

Compound (A) crystallizes in the triclinic space group P , while com­pound (B) crystallizes in the space group P21/c, both with one mol­ecule in the asymmetric unit (Figs. 1 ▸ and 2 ▸). In both com­pounds, the conformation of the thio­chromene ring is similar. In A, the thio­chromene ring makes an angle of 89.3 (2)° with phenyl ring C1–C6, while in B, this angle is 86.94 (8)°, which indicates that the 2-bromo-5-fluoro­phenyl ring is roughly perpendicular to the thio­chromene plane. Both 2H-thio­pyran rings have a screw-boat conformation, with atom C7 having the largest deviation from the best plane through atoms S1/C7–C11 [puckering parameters Q = 0.388 (4) Å, θ = 119.6 (7)° and φ = 202.2 (9)° for A, and Q = 0.5111 (18) Å, θ = 118.2 (2)° and φ = 208.1 (3)° for B]. The C—S bond lengths are almost equal [C7—S1 = 1.828 (4) Å and C11—S1 = 1.8307 (19) Å for A, and 1.758 (5) and 1.7574 (19) Å for B, respectively]. The C11—S1—C7 bond angle is 102.5 (2)° in A and 100.47 (9)° in B. The N—O bond lengths in com­pound B [1.232 (2) and 1.221 (2) Å] are slightly longer than those in com­pound A [both 1.219 (5) Å]. The nitro group is situated in the thio­chromene plane, as illustrated by the torsion angle O2—N8—C8—C9 of 1.3 (7)° in A and 9.5 (3)° in B.

Figure 1

The mol­ecular structure of 2-(2-bromo-5-fluoro­phen­yl)-8-eth­oxy-3-nitro-2H-thio­chromene (A), showing the atom labeling. Displacement ellipsoids are drawn at the 50% probability level.

Figure 2

The mol­ecular structure of 2-(2-bromo-5-fluoro­phen­yl)-7-meth­oxy-3-nitro-2H-thio­chromene (B), showing the atom labeling. Displacement ellipsoids are drawn at the 50% probability level.

Supra­molecular features

In the crystal of A, mol­ecules form inversion dimers via C—H⋯O hydrogen bonds (Table 1 ▸ and Fig. 3 ▸) and π–π inter­actions [Cg3⋯Cg3i = 3.646 (3) Å; symmetry code: (i) −x, −y + 2, −z; Cg3 is the centroid of the C10–C15 ring]. Neighbouring dimers inter­act through C—F⋯π and short Br1⋯H5ii inter­actions [F4⋯Cg3ii = 3.328 (4) Å and Br1⋯H5iii = 2.96 Å; symmetry codes: (ii) −x, −y + 1, −z + 1; (iii) x + 1, y, z].

Table 1

Hydrogen-bond geometry (Å, °) for A

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9⋯O2i	0.93	2.50	3.419 (7)	168

Symmetry code: (i) .

Figure 3

Packing diagram for A, showing C—H⋯O, C—F⋯π, π–π and H⋯Br inter­actions [symmetry codes: (i) −x, −y + 1, −z + 1; (ii) −x, −y + 2, −z; (iii) −x + 1, −y + 1, −z + 1; (iv) −x, −y + 1, −z]. Cg3 is the centroid of the C10–C15 ring.

In the crystal of com­pound B, two mol­ecules form dimers through C—H⋯F hydrogen bonds (Table 2 ▸ and Fig. 4 ▸). These dimers form chains running in the c direction through π–π inter­actions [Cg2⋯Cg2i = 3.8458 (13) Å; symmetry code: (i) −x + 2, −y + 1, −z + 1; Cg2 is the centroid of the C1–C6 ring]. Parallel chains inter­act via C—H⋯O and C—H⋯π inter­actions.

Table 2

Hydrogen-bond geometry (Å, °) for B

Cg3 is the centroid of the C10–C15 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9⋯O1i	0.93	2.60	3.418 (3)	148
C15—H15⋯F4ii	0.93	2.54	3.268 (2)	136
C16—C16B⋯Cg3iii	0.96	2.86	3.668 (3)	143

Symmetry codes: (i) ; (ii) ; (iii) .

Figure 4

Packing diagram for B, showing C—H⋯O, C—H⋯F, C—H⋯π and π–π inter­actions [symmetry codes: (i) x, −y + , z − ; (ii) −x + 2, −y + 1, −z + 2; (iii) −x + 1, y − , −z + ; (iv) −x + 1, −y + 1, −z + 1]. Cg2 and Cg3 are the centroids of the C1–C6 and C10–C15 rings, respectively.

Database survey

The Cambridge Structural Database (CSD, Version 5.40, update of May 2019; Groom et al., 2016 ▸) contains seven phenyl-2H-thio­chromene derivatives, of which three contain halogen atoms [CSD refcodes IFOZIO (Choudhury & Mukherjee, 2013 ▸), QAPSAE (Simlandy & Mukherjee, 2017 ▸) and WAPCUO (Sangeetha & Sekar, 2017 ▸)] and only one structure contains a nitro substituent on the 2H-thio­chromene ring (NOGDIZ; Le et al., 2019 ▸). In all seven structures, the phenyl ring is roughly perpendicular to the thio­chromene plane, with dihedral angles between 87.73 and 98.89°. Four of the seven structures display inter­molecular inter­actions between the S atom and a C—H bond. However, in the two structures presented here, this type of inter­action has not been observed.

Synthesis and crystallization

To a round-bottomed flask was added 2-mercaptobenzaldehyde (1 equiv.), nitro­styrene (1 equiv.) and K2CO3 (1 equiv.) in toluene and the reaction mixture was stirred at room temperature for 2 h. After com­pletion of the reaction, the solvent was evaporated under reduced pressure and the crude product was purified by flash chromatography on silica gel (yield 90%). Crystals suitable for single-crystal X-ray diffraction data collection were obtained by slow evaporation from an ethanol solution.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. All H atoms bonded to C atoms were placed at calculated positions, with C—H = 0.93–0.98 Å, and refined as riding, with U iso(H) = 1.2U eq(C) for Csp 2—H and U iso(H) = 1.5U eq(C) for Csp 3—H. A rotating-group model was applied for methyl-group C17 in A and C16 in B.

Table 3

Experimental details

	A	B
Crystal data
Chemical formula	C17H13BrFNO3S	C16H11BrFNO3S
M r	410.25	396.23
Crystal system, space group	Triclinic, P	Monoclinic, P21/c
Temperature (K)	273	273
a, b, c (Å)	7.6695 (12), 10.6867 (18), 12.2767 (19)	7.6231 (4), 17.3484 (8), 11.8345 (6)
α, β, γ (°)	64.686 (4), 80.760 (4), 70.395 (4)	90, 106.016 (2), 90
V (Å3)	856.7 (2)	1504.35 (13)
Z	2	4
Radiation type	Mo Kα	Mo Kα
μ (mm−1)	2.55	2.90
Crystal size (mm)	0.25 × 0.2 × 0.15	0.30 × 0.22 × 0.11
Data collection
Diffractometer	Bruker D8 Quest CMOS	Bruker D8 Quest CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2016 ▸)	Multi-scan (SADABS; Bruker, 2016 ▸)
T min, T max	0.621, 0.745	0.599, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	12684, 3255, 2291	31660, 3745, 3018
R int	0.037	0.032
(sin θ/λ)max (Å−1)	0.611	0.669
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.052, 0.128, 1.04	0.029, 0.070, 1.04
No. of reflections	3255	3745
No. of parameters	218	209
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.53, −0.49	0.52, −0.49

Computer programs: APEX2 (Bruker, 2013 ▸), SAINT (Bruker, 2013 ▸), SHELXT (Sheldrick, 2015a ▸), SHELXL2014 (Sheldrick, 2015b ▸) and OLEX2 (Dolomanov et al., 2009 ▸).

Crystal structure: contains datablock(s) A, B, global. DOI: 10.1107/S2056989019014178/vm2223sup1.cif

Structure factors: contains datablock(s) A. DOI: 10.1107/S2056989019014178/vm2223Asup8.hkl

Structure factors: contains datablock(s) B. DOI: 10.1107/S2056989019014178/vm2223Bsup9.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989019014178/vm2223Asup4.cml

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989019014178/vm2223Bsup5.cml

CCDC references: 1950406, 1953121, 1950406, 1953121

Additional supporting information: crystallographic information; 3D view; checkCIF report

C17H13BrFNO3S	Z = 2
Mr = 410.25	F(000) = 412
Triclinic, P1	Dx = 1.590 Mg m−3
a = 7.6695 (12) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.6867 (18) Å	Cell parameters from 5933 reflections
c = 12.2767 (19) Å	θ = 3.0–25.6°
α = 64.686 (4)°	µ = 2.55 mm−1
β = 80.760 (4)°	T = 273 K
γ = 70.395 (4)°	Triangular-prism, clear light yellow
V = 856.7 (2) Å3	0.25 × 0.2 × 0.15 mm

Bruker D8 Quest CMOS diffractometer	2291 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.037
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θmax = 25.7°, θmin = 3.0°
Tmin = 0.621, Tmax = 0.745	h = −9→9
12684 measured reflections	k = −13→13
3255 independent reflections	l = −14→14

Refinement on F2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.052	H-atom parameters constrained
wR(F2) = 0.128	w = 1/[σ2(Fo2) + (0.0419P)2 + 2.0237P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
3255 reflections	Δρmax = 0.53 e Å−3
218 parameters	Δρmin = −0.49 e Å−3
0 restraints

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

	x	y	z	Uiso*/Ueq
Br1	0.78831 (7)	0.45042 (7)	0.29672 (6)	0.0676 (2)
S1	0.34737 (16)	0.76031 (13)	0.17001 (11)	0.0459 (3)
F4	0.1093 (5)	0.3152 (4)	0.5616 (3)	0.0878 (11)
O1	0.4800 (5)	0.3584 (4)	0.1158 (3)	0.0627 (10)
N8	0.3239 (6)	0.4388 (5)	0.0863 (4)	0.0514 (10)
O3	0.1347 (6)	0.9891 (4)	0.2321 (4)	0.0800 (12)
C6	0.4041 (5)	0.4707 (4)	0.3176 (4)	0.0317 (9)
C7	0.3916 (5)	0.5738 (5)	0.1873 (4)	0.0344 (10)
H7	0.5137	0.5464	0.1505	0.041*
O2	0.2238 (6)	0.4176 (5)	0.0326 (4)	0.0877 (14)
C1	0.5698 (6)	0.4073 (5)	0.3787 (4)	0.0398 (10)
C5	0.2496 (6)	0.4375 (5)	0.3831 (4)	0.0430 (11)
H5	0.1353	0.4785	0.3463	0.052*
C8	0.2567 (6)	0.5648 (5)	0.1183 (4)	0.0394 (11)
C9	0.0857 (6)	0.6514 (5)	0.0895 (4)	0.0441 (11)
H9	0.0162	0.6300	0.0480	0.053*
C10	0.0005 (6)	0.7756 (5)	0.1180 (4)	0.0449 (12)
C11	0.1047 (6)	0.8283 (5)	0.1624 (4)	0.0440 (11)
C2	0.5820 (7)	0.3155 (5)	0.4989 (5)	0.0540 (13)
H2	0.6945	0.2760	0.5376	0.065*
C4	0.2649 (7)	0.3447 (6)	0.5014 (4)	0.0538 (13)
C12	0.0194 (8)	0.9462 (6)	0.1916 (5)	0.0588 (14)
C3	0.4268 (8)	0.2827 (6)	0.5611 (5)	0.0593 (14)
H3	0.4323	0.2196	0.6420	0.071*
C15	−0.1906 (7)	0.8446 (6)	0.1038 (5)	0.0612 (15)
H15	−0.2617	0.8100	0.0751	0.073*
C13	−0.1723 (9)	1.0141 (6)	0.1749 (6)	0.0758 (19)
H13	−0.2306	1.0946	0.1932	0.091*
C14	−0.2721 (8)	0.9611 (7)	0.1315 (5)	0.0757 (19)
H14	−0.3987	1.0062	0.1209	0.091*
C16	0.0603 (12)	1.1016 (8)	0.2740 (8)	0.108 (3)
H16A	−0.0355	1.0799	0.3348	0.129*
H16B	0.0066	1.1929	0.2080	0.129*
C17	0.2145 (15)	1.1110 (9)	0.3261 (10)	0.140 (4)
H17A	0.3043	1.1391	0.2639	0.211*
H17B	0.2717	1.0182	0.3877	0.211*
H17C	0.1673	1.1819	0.3604	0.211*

	U11	U22	U33	U12	U13	U23
Br1	0.0326 (3)	0.0840 (5)	0.0826 (4)	−0.0170 (3)	−0.0096 (2)	−0.0277 (3)
S1	0.0434 (6)	0.0424 (7)	0.0506 (7)	−0.0164 (5)	−0.0098 (5)	−0.0116 (6)
F4	0.084 (2)	0.116 (3)	0.0506 (19)	−0.054 (2)	0.0178 (17)	−0.0102 (19)
O1	0.056 (2)	0.070 (3)	0.071 (3)	−0.014 (2)	−0.0018 (19)	−0.040 (2)
N8	0.057 (3)	0.069 (3)	0.045 (2)	−0.029 (2)	0.004 (2)	−0.031 (2)
O3	0.094 (3)	0.049 (2)	0.096 (3)	−0.013 (2)	0.003 (2)	−0.036 (2)
C6	0.031 (2)	0.035 (2)	0.034 (2)	−0.0095 (18)	−0.0047 (17)	−0.0171 (19)
C7	0.029 (2)	0.046 (3)	0.034 (2)	−0.0144 (19)	0.0037 (17)	−0.020 (2)
O2	0.078 (3)	0.129 (4)	0.105 (3)	−0.037 (3)	−0.012 (2)	−0.083 (3)
C1	0.038 (2)	0.034 (2)	0.047 (3)	−0.005 (2)	−0.007 (2)	−0.018 (2)
C5	0.038 (2)	0.052 (3)	0.040 (3)	−0.016 (2)	−0.002 (2)	−0.017 (2)
C8	0.037 (2)	0.058 (3)	0.029 (2)	−0.022 (2)	0.0029 (18)	−0.019 (2)
C9	0.039 (2)	0.064 (3)	0.030 (2)	−0.026 (2)	−0.0020 (19)	−0.011 (2)
C10	0.035 (2)	0.051 (3)	0.034 (3)	−0.013 (2)	−0.0046 (19)	−0.002 (2)
C11	0.043 (3)	0.039 (3)	0.031 (2)	−0.008 (2)	0.0030 (19)	−0.002 (2)
C2	0.058 (3)	0.046 (3)	0.050 (3)	−0.004 (3)	−0.023 (3)	−0.013 (2)
C4	0.064 (3)	0.062 (3)	0.040 (3)	−0.030 (3)	0.007 (2)	−0.018 (3)
C12	0.067 (4)	0.039 (3)	0.054 (3)	−0.013 (3)	0.005 (3)	−0.008 (3)
C3	0.083 (4)	0.051 (3)	0.035 (3)	−0.021 (3)	−0.012 (3)	−0.006 (2)
C15	0.043 (3)	0.061 (4)	0.050 (3)	−0.011 (3)	−0.003 (2)	0.002 (3)
C13	0.069 (4)	0.046 (3)	0.069 (4)	0.005 (3)	0.019 (3)	−0.007 (3)
C14	0.048 (3)	0.067 (4)	0.062 (4)	−0.003 (3)	0.006 (3)	0.006 (3)
C16	0.130 (7)	0.070 (5)	0.128 (7)	−0.011 (5)	−0.009 (5)	−0.057 (5)
C17	0.187 (10)	0.072 (5)	0.179 (10)	−0.016 (6)	−0.027 (8)	−0.075 (6)

Br1—C1	1.901 (4)	C10—C11	1.400 (7)
S1—C7	1.828 (4)	C10—C15	1.403 (7)
S1—C11	1.758 (5)	C11—C12	1.379 (7)
F4—C4	1.356 (6)	C2—H2	0.9300
O1—N8	1.219 (5)	C2—C3	1.372 (7)
N8—O2	1.219 (5)	C4—C3	1.357 (7)
N8—C8	1.468 (6)	C12—C13	1.408 (8)
O3—C12	1.360 (7)	C3—H3	0.9300
O3—C16	1.418 (8)	C15—H15	0.9300
C6—C7	1.501 (6)	C15—C14	1.353 (9)
C6—C1	1.389 (6)	C13—H13	0.9300
C6—C5	1.381 (6)	C13—C14	1.367 (9)
C7—H7	0.9800	C14—H14	0.9300
C7—C8	1.488 (6)	C16—H16A	0.9700
C1—C2	1.376 (7)	C16—H16B	0.9700
C5—H5	0.9300	C16—C17	1.481 (11)
C5—C4	1.361 (6)	C17—H17A	0.9600
C8—C9	1.325 (6)	C17—H17B	0.9600
C9—H9	0.9300	C17—H17C	0.9600
C9—C10	1.433 (7)
C11—S1—C7	102.5 (2)	C3—C2—C1	119.4 (5)
O1—N8—C8	117.8 (4)	C3—C2—H2	120.3
O2—N8—O1	122.5 (5)	F4—C4—C5	117.7 (5)
O2—N8—C8	119.8 (4)	F4—C4—C3	119.2 (5)
C12—O3—C16	119.7 (5)	C3—C4—C5	123.1 (5)
C1—C6—C7	121.8 (4)	O3—C12—C11	114.8 (5)
C5—C6—C7	121.3 (4)	O3—C12—C13	125.5 (6)
C5—C6—C1	117.0 (4)	C11—C12—C13	119.6 (6)
S1—C7—H7	106.6	C2—C3—H3	120.9
C6—C7—S1	111.5 (3)	C4—C3—C2	118.2 (5)
C6—C7—H7	106.6	C4—C3—H3	120.9
C8—C7—S1	111.0 (3)	C10—C15—H15	119.8
C8—C7—C6	114.2 (3)	C14—C15—C10	120.4 (6)
C8—C7—H7	106.6	C14—C15—H15	119.8
C6—C1—Br1	119.9 (3)	C12—C13—H13	120.2
C2—C1—Br1	117.9 (3)	C14—C13—C12	119.6 (6)
C2—C1—C6	122.3 (4)	C14—C13—H13	120.2
C6—C5—H5	120.0	C15—C14—C13	121.4 (6)
C4—C5—C6	119.9 (4)	C15—C14—H14	119.3
C4—C5—H5	120.0	C13—C14—H14	119.3
N8—C8—C7	113.7 (4)	O3—C16—H16A	110.3
C9—C8—N8	118.5 (4)	O3—C16—H16B	110.3
C9—C8—C7	127.7 (4)	O3—C16—C17	107.3 (7)
C8—C9—H9	117.8	H16A—C16—H16B	108.5
C8—C9—C10	124.5 (4)	C17—C16—H16A	110.3
C10—C9—H9	117.8	C17—C16—H16B	110.3
C11—C10—C9	120.9 (4)	C16—C17—H17A	109.5
C11—C10—C15	119.0 (5)	C16—C17—H17B	109.5
C15—C10—C9	120.1 (5)	C16—C17—H17C	109.5
C10—C11—S1	122.3 (4)	H17A—C17—H17B	109.5
C12—C11—S1	117.5 (4)	H17A—C17—H17C	109.5
C12—C11—C10	120.0 (5)	H17B—C17—H17C	109.5
C1—C2—H2	120.3

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O2i	0.93	2.50	3.419 (7)	168

C16H11BrFNO3S	F(000) = 792
Mr = 396.23	Dx = 1.749 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.6231 (4) Å	Cell parameters from 9945 reflections
b = 17.3484 (8) Å	θ = 3.0–28.3°
c = 11.8345 (6) Å	µ = 2.90 mm−1
β = 106.016 (2)°	T = 273 K
V = 1504.35 (13) Å3	Block, yellow
Z = 4	0.30 × 0.22 × 0.11 mm

Bruker D8 Quest CMOS diffractometer	3018 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.032
Absorption correction: multi-scan (SADABS; Bruker, 2016)	θmax = 28.4°, θmin = 3.0°
Tmin = 0.599, Tmax = 0.746	h = −10→10
31660 measured reflections	k = −23→23
3745 independent reflections	l = −15→15

Refinement on F2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.029	H-atom parameters constrained
wR(F2) = 0.070	w = 1/[σ2(Fo2) + (0.0274P)2 + 0.9845P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.001
3745 reflections	Δρmax = 0.52 e Å−3
209 parameters	Δρmin = −0.49 e Å−3
0 restraints

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

	x	y	z	Uiso*/Ueq
Br1	0.57090 (3)	0.36398 (2)	0.38157 (2)	0.04708 (9)
S1	0.52686 (6)	0.31114 (3)	0.66185 (4)	0.03212 (11)
F4	1.0275 (2)	0.57875 (8)	0.73645 (12)	0.0538 (4)
O3	0.2529 (2)	0.42250 (10)	0.96347 (13)	0.0458 (4)
O2	1.1678 (2)	0.23148 (10)	0.82659 (17)	0.0550 (4)
O1	1.0798 (2)	0.26267 (11)	0.64265 (15)	0.0545 (4)
N8	1.0577 (2)	0.26017 (10)	0.74190 (18)	0.0383 (4)
C6	0.7901 (2)	0.40495 (10)	0.61148 (16)	0.0265 (4)
C1	0.7106 (3)	0.43164 (11)	0.49777 (16)	0.0306 (4)
C8	0.8921 (3)	0.29553 (11)	0.75735 (17)	0.0307 (4)
C7	0.7581 (3)	0.32337 (11)	0.64724 (16)	0.0289 (4)
H7	0.7692	0.2893	0.5835	0.035*
C11	0.5550 (3)	0.34811 (11)	0.80401 (16)	0.0288 (4)
C12	0.4044 (3)	0.37801 (11)	0.83133 (17)	0.0325 (4)
H12	0.2966	0.3854	0.7721	0.039*
C10	0.7218 (3)	0.33978 (11)	0.89180 (17)	0.0311 (4)
C5	0.8972 (3)	0.45668 (11)	0.69165 (16)	0.0300 (4)
H5	0.9539	0.4411	0.7682	0.036*
C2	0.7313 (3)	0.50680 (13)	0.46588 (18)	0.0375 (5)
H2	0.6742	0.5232	0.3898	0.045*
C9	0.8784 (3)	0.30534 (11)	0.86622 (17)	0.0338 (4)
H9	0.9746	0.2892	0.9287	0.041*
C4	0.9184 (3)	0.53081 (12)	0.65674 (18)	0.0349 (4)
C14	0.5759 (3)	0.39037 (13)	1.03475 (18)	0.0385 (5)
H14	0.5829	0.4043	1.1118	0.046*
C15	0.7271 (3)	0.36263 (12)	1.00596 (17)	0.0361 (4)
H15	0.8368	0.3589	1.0646	0.043*
C13	0.4121 (3)	0.39734 (12)	0.94672 (18)	0.0347 (4)
C3	0.8361 (3)	0.55789 (12)	0.54603 (19)	0.0386 (5)
H3	0.8503	0.6088	0.5256	0.046*
C16	0.2464 (4)	0.43592 (16)	1.0811 (2)	0.0534 (6)
H16A	0.1254	0.4515	1.0807	0.080*
H16B	0.3313	0.4759	1.1157	0.080*
H16C	0.2781	0.3894	1.1261	0.080*

	U11	U22	U33	U12	U13	U23
Br1	0.05237 (15)	0.05020 (14)	0.03012 (11)	−0.00306 (11)	−0.00293 (9)	−0.00516 (9)
S1	0.0285 (2)	0.0376 (3)	0.0274 (2)	−0.0057 (2)	0.00289 (18)	−0.00232 (19)
F4	0.0685 (9)	0.0376 (7)	0.0489 (8)	−0.0167 (7)	0.0057 (7)	−0.0092 (6)
O3	0.0422 (9)	0.0591 (10)	0.0385 (8)	0.0009 (7)	0.0153 (7)	−0.0034 (7)
O2	0.0376 (9)	0.0477 (10)	0.0733 (12)	0.0126 (7)	0.0044 (8)	0.0180 (9)
O1	0.0390 (9)	0.0724 (12)	0.0530 (10)	0.0034 (8)	0.0143 (8)	−0.0143 (9)
N8	0.0301 (9)	0.0276 (8)	0.0544 (11)	−0.0014 (7)	0.0066 (8)	−0.0011 (8)
C6	0.0260 (9)	0.0271 (9)	0.0274 (9)	0.0028 (7)	0.0091 (7)	0.0009 (7)
C1	0.0301 (9)	0.0346 (10)	0.0264 (9)	0.0027 (8)	0.0068 (7)	−0.0023 (8)
C8	0.0278 (9)	0.0244 (9)	0.0371 (10)	−0.0008 (7)	0.0044 (8)	0.0026 (8)
C7	0.0290 (9)	0.0277 (9)	0.0287 (9)	0.0002 (8)	0.0059 (7)	−0.0012 (7)
C11	0.0319 (10)	0.0275 (9)	0.0250 (9)	−0.0046 (7)	0.0046 (7)	0.0031 (7)
C12	0.0302 (9)	0.0353 (10)	0.0291 (9)	−0.0052 (8)	0.0032 (8)	0.0031 (8)
C10	0.0339 (10)	0.0275 (9)	0.0281 (9)	−0.0027 (8)	0.0019 (8)	0.0059 (7)
C5	0.0326 (10)	0.0312 (10)	0.0257 (9)	0.0012 (8)	0.0070 (7)	−0.0004 (8)
C2	0.0422 (11)	0.0393 (11)	0.0309 (10)	0.0086 (9)	0.0099 (9)	0.0083 (9)
C9	0.0318 (10)	0.0301 (10)	0.0341 (10)	−0.0011 (8)	0.0000 (8)	0.0073 (8)
C4	0.0378 (11)	0.0312 (10)	0.0362 (10)	−0.0032 (8)	0.0114 (8)	−0.0058 (8)
C14	0.0479 (12)	0.0390 (11)	0.0272 (10)	−0.0054 (10)	0.0081 (9)	−0.0003 (8)
C15	0.0381 (11)	0.0369 (11)	0.0273 (9)	−0.0032 (9)	−0.0010 (8)	0.0042 (8)
C13	0.0370 (11)	0.0341 (10)	0.0341 (10)	−0.0042 (9)	0.0115 (8)	0.0020 (8)
C3	0.0469 (12)	0.0295 (10)	0.0421 (11)	0.0029 (9)	0.0169 (10)	0.0051 (9)
C16	0.0579 (15)	0.0655 (16)	0.0437 (13)	−0.0029 (13)	0.0256 (12)	−0.0042 (12)

Br1—C1	1.8961 (19)	C12—H12	0.9300
S1—C7	1.8307 (19)	C12—C13	1.392 (3)
S1—C11	1.7574 (19)	C10—C9	1.440 (3)
F4—C4	1.357 (2)	C10—C15	1.398 (3)
O3—C13	1.355 (3)	C5—H5	0.9300
O3—C16	1.426 (3)	C5—C4	1.374 (3)
O2—N8	1.221 (2)	C2—H2	0.9300
O1—N8	1.232 (2)	C2—C3	1.380 (3)
N8—C8	1.460 (3)	C9—H9	0.9300
C6—C1	1.394 (3)	C4—C3	1.370 (3)
C6—C7	1.516 (3)	C14—H14	0.9300
C6—C5	1.395 (3)	C14—C15	1.376 (3)
C1—C2	1.379 (3)	C14—C13	1.393 (3)
C8—C7	1.497 (3)	C15—H15	0.9300
C8—C9	1.332 (3)	C3—H3	0.9300
C7—H7	0.9800	C16—H16A	0.9600
C11—C12	1.377 (3)	C16—H16B	0.9600
C11—C10	1.410 (3)	C16—H16C	0.9600
C11—S1—C7	100.47 (9)	C4—C5—C6	119.55 (18)
C13—O3—C16	117.99 (18)	C4—C5—H5	120.2
O2—N8—O1	123.58 (19)	C1—C2—H2	119.8
O2—N8—C8	119.36 (19)	C1—C2—C3	120.50 (19)
O1—N8—C8	117.04 (17)	C3—C2—H2	119.8
C1—C6—C7	121.27 (17)	C8—C9—C10	123.18 (18)
C1—C6—C5	117.40 (17)	C8—C9—H9	118.4
C5—C6—C7	121.32 (16)	C10—C9—H9	118.4
C6—C1—Br1	120.14 (15)	F4—C4—C5	117.72 (18)
C2—C1—Br1	118.09 (15)	F4—C4—C3	119.08 (19)
C2—C1—C6	121.77 (18)	C3—C4—C5	123.20 (19)
N8—C8—C7	115.63 (17)	C15—C14—H14	120.5
C9—C8—N8	118.44 (18)	C15—C14—C13	118.98 (19)
C9—C8—C7	125.74 (18)	C13—C14—H14	120.5
S1—C7—H7	107.0	C10—C15—H15	118.8
C6—C7—S1	111.58 (13)	C14—C15—C10	122.39 (19)
C6—C7—H7	107.0	C14—C15—H15	118.8
C8—C7—S1	108.90 (13)	O3—C13—C12	115.12 (18)
C8—C7—C6	114.88 (15)	O3—C13—C14	124.95 (19)
C8—C7—H7	107.0	C12—C13—C14	119.93 (19)
C12—C11—S1	118.22 (14)	C2—C3—H3	121.2
C12—C11—C10	120.41 (18)	C4—C3—C2	117.55 (19)
C10—C11—S1	121.01 (15)	C4—C3—H3	121.2
C11—C12—H12	119.7	O3—C16—H16A	109.5
C11—C12—C13	120.61 (18)	O3—C16—H16B	109.5
C13—C12—H12	119.7	O3—C16—H16C	109.5
C11—C10—C9	121.27 (18)	H16A—C16—H16B	109.5
C15—C10—C11	117.59 (19)	H16A—C16—H16C	109.5
C15—C10—C9	121.07 (18)	H16B—C16—H16C	109.5
C6—C5—H5	120.2

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O1i	0.93	2.60	3.418 (3)	148
C15—H15···F4ii	0.93	2.54	3.268 (2)	136
C16—C16B···Cg3iii	0.96	2.86	3.668 (3)	143