Crystal structures of 2-(2-bromo-5-fluoro­phen­yl)-8-eth­oxy-3-nitro-2H-thio­chromene and 2-(2-bromo-5-fluoro­phen­yl)-7-meth­oxy-3-nitro-2H-thio­chromene

Pham, C.T.; Mac, D.H.; Bui, T.T.T.

doi:10.1107/S2056989019014178

research communications

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ISSN: 2056-9890

Volume 75| Part 11| November 2019| Pages 1783-1786

https://doi.org/10.1107/S2056989019014178

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Crystal structures of 2-(2-bromo-5-fluorophenyl)-8-ethoxy-3-nitro-2H-thiochromene and 2-(2-bromo-5-fluorophenyl)-7-methoxy-3-nitro-2H-thiochromene

Chien Thang Pham,^a Dinh Hung Mac ^a and Thai Thanh Thu Bui ^a ^*

^aFaculty of Chemistry, VNU University of Science, Vietnam National University, Hanoi, 19 Le Thanh Tong, Ha Noi, Vietnam
^*Correspondence e-mail: thaithanhthubui@gmail.com

Edited by L. Van Meervelt, Katholieke Universiteit Leuven, Belgium (Received 4 October 2019; accepted 16 October 2019; online 31 October 2019)

Two thiochromene compounds containing Br and F atoms, namely 2-(2-bromo-5-fluorophenyl)-8-ethoxy-3-nitro-2H-thiochromene (C₁₇H₁₃BrFNO₃S, A) and 2-(2-bromo-5-fluorophenyl)-7-methoxy-3-nitro-2H-thiochromene (C₁₆H₁₁BrFNO₃S, B), were prepared via the condensation reaction between 2-mercaptobenzaldehyde and nitrostyrene derivatives. In both compounds, the thiochromene plane is almost perpendicular to the phenyl ring. In the structure of A, molecules are assembled via π–π stacking and C—H⋯O and C—F⋯π interactions. In the crystal packing of B, molecules are linked by C—H⋯F, C—H⋯O, C—H⋯π and π–π interactions.

Keywords: crystal structure; thiochromene; hydrogen bonding; π–π stacking.

CCDC references: 1950406; 1953121; 1950406; 1953121

1. 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.

2. Structural commentary

Compound (A) crystallizes in the triclinic space group P $[\overline{1}]$ , 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.

3. 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) -x, -y+1, -z.

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) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x+2, -y+1, -z+2; (iii) -x+1, -y+1, -z+2.

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 + $[{1\over 2}]$ , z − $[{1\over 2}]$ ; (ii) −x + 2, −y + 1, −z + 2; (iii) −x + 1, y − $[{1\over 2}]$ , −z + $[{3\over 2}]$ ; (iv) −x + 1, −y + 1, −z + 1]. Cg2 and Cg3 are the centroids of the C1–C6 and C10–C15 rings, respectively.

4. 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.

5. 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.

6. 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 Csp²—H and U_iso(H) = 1.5U_eq(C) for Csp³—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 $[\overline{1}]$	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[F² > 2σ(F²)], wR(F²), 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
Δρ_max, Δρ_min (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 ).

Supporting information

CCDC references: 1950406; 1953121; 1950406; 1953121

Crystal structure: contains datablocks A, B, global. DOI: https://doi.org/10.1107/S2056989019014178/vm2223sup1.cif

Supporting information file. DOI: https://doi.org/10.1107/S2056989019014178/vm2223Asup4.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989019014178/vm2223Bsup5.cml

Structure factors: contains datablock A. DOI: https://doi.org/10.1107/S2056989019014178/vm2223Asup8.hkl

Structure factors: contains datablock B. DOI: https://doi.org/10.1107/S2056989019014178/vm2223Bsup9.hkl

checkCIF report

Computing details top

For both structures, data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

2-(2-Bromo-5-fluorophenyl)-8-ethoxy-3-nitro-2H-thiochromene (A) top

Crystal data top

C₁₇H₁₃BrFNO₃S	Z = 2
M_r = 410.25	F(000) = 412
Triclinic, P1	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0419P)² + 2.0237P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
3255 reflections	Δρ_max = 0.53 e Å⁻³
218 parameters	Δρ_min = −0.49 e Å⁻³
0 restraints

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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

Hydrogen-bond geometry (Å, º) top

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) −x, −y+1, −z.

2-(2-Bromo-5-fluorophenyl)-7-methoxy-3-nitro-2H-thiochromene (B) top

Crystal data top

C₁₆H₁₁BrFNO₃S	F(000) = 792
M_r = 396.23	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0274P)² + 0.9845P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
3745 reflections	Δρ_max = 0.52 e Å⁻³
209 parameters	Δρ_min = −0.49 e Å⁻³
0 restraints

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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

Hydrogen-bond geometry (Å, º) top

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) x, −y+1/2, z+1/2; (ii) −x+2, −y+1, −z+2; (iii) −x+1, −y+1, −z+2.

References

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Volume 75| Part 11| November 2019| Pages 1783-1786

https://doi.org/10.1107/S2056989019014178

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structures of 2-(2-bromo-5-fluoro­phen­yl)-8-eth­­oxy-3-nitro-2H-thio­chromene and 2-(2-bromo-5-fluoro­phen­yl)-7-meth­­oxy-3-nitro-2H-thio­chromene

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

References

research communications

Crystal structures of 2-(2-bromo-5-fluorophenyl)-8-ethoxy-3-nitro-2H-thiochromene and 2-(2-bromo-5-fluorophenyl)-7-methoxy-3-nitro-2H-thiochromene

3. Supramolecular features