4-(4-Bromo­phenyl)-2-methyl-2,6-di­phenyl-2H-thio­pyran

Abstract

The six-membered thio­pyran ring in the title compound, C₂₄H₁₉BrS, adopts an approximate envelope conformation, with the S atom displaced by 0.26 (1) Å and the 2-methyl­ene C atom by −0.54 (1) Å from the plane of the other four sp ²-hydridized C atoms. The methyl substituent on the methyl­ene carbon lies in a pseudo-axial position with the phenyl ring in a pseudo-equatorial position.

Related literature

For the background to 4-alkyl-2,4,6-triaryl-4H-thio­pyrans, see: Rahmani et al. (2009 ▶). For the general synthesis from a Grignard reaction, see: Suld & Price (1962 ▶).

Experimental

Crystal data

• C₂₄H₁₉BrS

• M _r = 419.36

• Orthorhombic,

• a = 23.3348 (8) Å

• b = 5.9991 (2) Å

• c = 13.6866 (5) Å

• V = 1916.0 (1) ų

• Z = 4

• Mo Kα radiation

• μ = 2.26 mm⁻¹

• T = 115 K

• 0.40 × 0.15 × 0.05 mm

Data collection

• Bruker SMART APEX diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.465, T _max = 0.895

• 16215 measured reflections

• 4407 independent reflections

• 3017 reflections with I > 2σ(I)

• R _int = 0.093

Refinement

• R[F ² > 2σ(F ²)] = 0.075

• wR(F ²) = 0.190

• S = 1.09

• 4407 reflections

• 236 parameters

• 145 restraints

• H-atom parameters constrained

• Δρ_max = 1.53 e Å⁻³

• Δρ_min = −0.91 e Å⁻³

• Absolute structure: Flack (1983 ▶), 2108 Friedel pairs

• Flack parameter: 0.01 (2)

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2009 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Experimental

The compound was obtained as the rearranged product from the reaction of methyl magnesium bromide and 4-(4-bromophenyl)-2,6-diphenyl thiopyrylium perchlorate in dry ether under an argon atmosphere according to a reported method (Suld & Price, 1962). The product was isolated by TLC on neutral alumina (petroleum ether 40–60 °C) and purified by recrystalization from ethanol.

Refinement

Carbon-bound H-atoms were placed in calculated positions (C–H 0.95 to 0.98 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2 to 1.5U(C).

The final difference Fourier map had a large peak/deep hole in the vicinity of the bromine.

Figures

Fig. 1.

Thermal ellisoid plot (Barbour, 2001) of C24H19BrS; probability levels are set at 70% and H-atoms are drawn as spheres of arbitrary radius.

Crystal data

C24H19BrS	F(000) = 856
Mr = 419.36	Dx = 1.454 Mg m−3
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 2506 reflections
a = 23.3348 (8) Å	θ = 2.3–22.9°
b = 5.9991 (2) Å	µ = 2.26 mm−1
c = 13.6866 (5) Å	T = 115 K
V = 1916.0 (1) Å3	Prism, pale yellow
Z = 4	0.40 × 0.15 × 0.05 mm

Data collection

Bruker SMART APEX diffractometer	4407 independent reflections
Radiation source: fine-focus sealed tube	3017 reflections with I > 2σ(I)
graphite	Rint = 0.093
ω scans	θmax = 27.5°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −30→29
Tmin = 0.465, Tmax = 0.895	k = −7→7
16215 measured reflections	l = −17→17

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.075	H-atom parameters constrained
wR(F2) = 0.190	w = 1/[σ2(Fo2) + (0.0672P)2 + 10.0175P] where P = (Fo2 + 2Fc2)/3
S = 1.09	(Δ/σ)max = 0.001
4407 reflections	Δρmax = 1.53 e Å−3
236 parameters	Δρmin = −0.91 e Å−3
145 restraints	Absolute structure: Flack (1983), 2108 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.01 (2)

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

	x	y	z	Uiso*/Ueq
Br1	0.55183 (4)	0.84726 (15)	0.50001 (7)	0.0381 (3)
S1	0.76405 (9)	−0.1684 (4)	0.84041 (14)	0.0245 (4)
C1	0.7867 (4)	−0.2735 (13)	0.6484 (6)	0.0260 (18)
H1A	0.8005	−0.2273	0.5838	0.039*
H1B	0.7469	−0.3246	0.6431	0.039*
H1C	0.8107	−0.3952	0.6730	0.039*
C2	0.7898 (3)	−0.0738 (13)	0.7196 (5)	0.0198 (16)
C3	0.7503 (3)	0.1075 (12)	0.6851 (5)	0.0206 (17)
H3	0.7669	0.2372	0.6571	0.025*
C4	0.6924 (3)	0.0971 (13)	0.6915 (5)	0.0191 (16)
C5	0.6643 (3)	−0.0773 (13)	0.7470 (5)	0.0183 (16)
H5	0.6252	−0.1083	0.7332	0.022*
C6	0.6907 (4)	−0.1988 (12)	0.8174 (5)	0.0204 (17)
C7	0.8509 (3)	0.0024 (14)	0.7371 (5)	0.0202 (17)
C8	0.8986 (4)	−0.1115 (16)	0.7095 (6)	0.032 (2)
H8	0.8937	−0.2494	0.6764	0.039*
C9	0.9534 (4)	−0.0388 (16)	0.7267 (6)	0.033 (2)
H9	0.9852	−0.1234	0.7039	0.040*
C10	0.9623 (4)	0.1547 (18)	0.7762 (7)	0.034 (2)
H10	1.0000	0.2016	0.7922	0.041*
C11	0.9148 (4)	0.2837 (15)	0.8034 (6)	0.0263 (19)
H11	0.9206	0.4238	0.8342	0.032*
C12	0.8604 (4)	0.2107 (13)	0.7863 (5)	0.0225 (17)
H12	0.8287	0.2979	0.8069	0.027*
C13	0.6567 (3)	0.2668 (12)	0.6448 (5)	0.0168 (15)
C14	0.6740 (4)	0.3678 (14)	0.5562 (5)	0.0236 (17)
H14	0.7081	0.3187	0.5253	0.028*
C15	0.6422 (3)	0.5366 (13)	0.5137 (6)	0.0274 (18)
H15	0.6552	0.6058	0.4553	0.033*
C16	0.5923 (4)	0.6028 (14)	0.5560 (6)	0.0276 (19)
C17	0.5729 (4)	0.5021 (14)	0.6414 (5)	0.0223 (17)
H17	0.5376	0.5474	0.6698	0.027*
C18	0.6048 (4)	0.3370 (14)	0.6844 (6)	0.0230 (17)
H18	0.5912	0.2691	0.7427	0.028*
C19	0.6600 (4)	−0.3593 (13)	0.8826 (5)	0.0222 (17)
C20	0.6058 (4)	−0.2976 (14)	0.9198 (6)	0.0258 (19)
H20	0.5896	−0.1564	0.9046	0.031*
C21	0.5766 (4)	−0.4471 (14)	0.9787 (5)	0.0284 (19)
H21	0.5393	−0.4106	1.0017	0.034*
C22	0.6007 (4)	−0.6463 (15)	1.0043 (8)	0.0363 (19)
H22	0.5808	−0.7436	1.0473	0.044*
C23	0.6542 (4)	−0.7082 (13)	0.9679 (6)	0.0259 (19)
H23	0.6702	−0.8489	0.9843	0.031*
C24	0.6841 (4)	−0.5623 (13)	0.9073 (5)	0.0214 (17)
H24	0.7209	−0.6021	0.8831	0.026*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Br1	0.0382 (5)	0.0361 (4)	0.0401 (5)	0.0017 (4)	−0.0071 (5)	0.0148 (5)
S1	0.0254 (10)	0.0295 (11)	0.0186 (9)	−0.0016 (9)	−0.0016 (8)	0.0090 (9)
C1	0.041 (5)	0.014 (4)	0.023 (4)	−0.005 (3)	−0.002 (4)	0.000 (3)
C2	0.029 (4)	0.015 (3)	0.016 (3)	0.004 (3)	0.001 (3)	0.001 (3)
C3	0.027 (4)	0.021 (4)	0.014 (3)	0.001 (3)	−0.003 (3)	0.005 (3)
C4	0.031 (4)	0.018 (4)	0.008 (3)	−0.002 (3)	−0.003 (3)	0.006 (3)
C5	0.023 (4)	0.016 (4)	0.016 (3)	−0.002 (3)	0.001 (3)	0.000 (3)
C6	0.031 (4)	0.015 (4)	0.015 (3)	0.000 (3)	−0.001 (3)	0.002 (3)
C7	0.031 (4)	0.020 (4)	0.010 (3)	0.004 (3)	0.000 (3)	0.007 (3)
C8	0.028 (4)	0.041 (5)	0.028 (4)	0.004 (4)	0.003 (3)	0.010 (4)
C9	0.028 (4)	0.042 (5)	0.028 (4)	0.005 (4)	0.005 (4)	0.005 (4)
C10	0.020 (4)	0.047 (5)	0.036 (4)	−0.007 (4)	−0.004 (3)	0.010 (4)
C11	0.032 (5)	0.023 (4)	0.024 (4)	−0.001 (4)	−0.002 (4)	0.010 (3)
C12	0.033 (4)	0.020 (4)	0.015 (3)	0.002 (3)	0.005 (3)	0.004 (3)
C13	0.022 (4)	0.014 (3)	0.015 (3)	−0.002 (3)	−0.004 (3)	0.004 (3)
C14	0.025 (4)	0.030 (4)	0.016 (3)	−0.004 (3)	−0.002 (3)	0.004 (3)
C15	0.036 (4)	0.029 (4)	0.017 (4)	−0.006 (3)	−0.001 (3)	0.010 (3)
C16	0.035 (5)	0.024 (4)	0.024 (4)	−0.004 (3)	0.002 (4)	0.012 (3)
C17	0.029 (4)	0.025 (4)	0.013 (3)	0.001 (3)	−0.001 (3)	0.007 (3)
C18	0.025 (4)	0.026 (4)	0.017 (3)	−0.007 (3)	−0.001 (3)	0.010 (3)
C19	0.032 (4)	0.019 (4)	0.016 (3)	−0.004 (3)	−0.004 (3)	0.002 (3)
C20	0.032 (4)	0.025 (4)	0.020 (3)	−0.002 (3)	−0.001 (3)	0.007 (3)
C21	0.032 (4)	0.032 (4)	0.022 (4)	−0.002 (3)	−0.001 (3)	0.006 (3)
C22	0.043 (4)	0.041 (4)	0.025 (3)	−0.018 (4)	−0.006 (5)	0.009 (4)
C23	0.046 (5)	0.010 (4)	0.022 (4)	−0.003 (3)	−0.006 (3)	0.006 (3)
C24	0.031 (4)	0.020 (4)	0.013 (3)	0.000 (3)	−0.002 (3)	0.002 (3)

Geometric parameters (Å, °)

Br1—C16	1.905 (8)	C11—C12	1.363 (12)
S1—C6	1.750 (8)	C11—H11	0.9500
S1—C2	1.849 (8)	C12—H12	0.9500
C1—C2	1.547 (11)	C13—C18	1.391 (11)
C1—H1A	0.9800	C13—C14	1.414 (10)
C1—H1B	0.9800	C14—C15	1.383 (11)
C1—H1C	0.9800	C14—H14	0.9500
C2—C3	1.501 (10)	C15—C16	1.360 (12)
C2—C7	1.516 (11)	C15—H15	0.9500
C3—C4	1.356 (11)	C16—C17	1.392 (11)
C3—H3	0.9500	C17—C18	1.373 (11)
C4—C5	1.448 (10)	C17—H17	0.9500
C4—C13	1.463 (10)	C18—H18	0.9500
C5—C6	1.357 (11)	C19—C24	1.383 (11)
C5—H5	0.9500	C19—C20	1.414 (12)
C6—C19	1.495 (11)	C20—C21	1.385 (11)
C7—C8	1.361 (12)	C20—H20	0.9500
C7—C12	1.436 (11)	C21—C22	1.366 (13)
C8—C9	1.372 (12)	C21—H21	0.9500
C8—H8	0.9500	C22—C23	1.395 (13)
C9—C10	1.360 (14)	C22—H22	0.9500
C9—H9	0.9500	C23—C24	1.393 (11)
C10—C11	1.402 (13)	C23—H23	0.9500
C10—H10	0.9500	C24—H24	0.9500
C6—S1—C2	100.9 (4)	C11—C12—C7	120.3 (8)
C2—C1—H1A	109.5	C11—C12—H12	119.8
C2—C1—H1B	109.5	C7—C12—H12	119.8
H1A—C1—H1B	109.5	C18—C13—C14	116.9 (7)
C2—C1—H1C	109.5	C18—C13—C4	122.4 (6)
H1A—C1—H1C	109.5	C14—C13—C4	120.7 (7)
H1B—C1—H1C	109.5	C15—C14—C13	121.5 (8)
C3—C2—C7	114.1 (7)	C15—C14—H14	119.3
C3—C2—C1	109.5 (6)	C13—C14—H14	119.3
C7—C2—C1	112.2 (7)	C16—C15—C14	119.5 (7)
C3—C2—S1	107.7 (5)	C16—C15—H15	120.2
C7—C2—S1	104.9 (5)	C14—C15—H15	120.2
C1—C2—S1	108.1 (5)	C15—C16—C17	120.7 (8)
C4—C3—C2	123.9 (7)	C15—C16—Br1	118.6 (6)
C4—C3—H3	118.0	C17—C16—Br1	120.7 (7)
C2—C3—H3	118.0	C18—C17—C16	119.8 (8)
C3—C4—C5	121.2 (7)	C18—C17—H17	120.1
C3—C4—C13	120.5 (7)	C16—C17—H17	120.1
C5—C4—C13	118.3 (7)	C17—C18—C13	121.6 (7)
C6—C5—C4	123.7 (7)	C17—C18—H18	119.2
C6—C5—H5	118.1	C13—C18—H18	119.2
C4—C5—H5	118.1	C24—C19—C20	120.4 (7)
C5—C6—C19	123.6 (8)	C24—C19—C6	121.2 (8)
C5—C6—S1	121.0 (6)	C20—C19—C6	118.4 (7)
C19—C6—S1	115.3 (6)	C21—C20—C19	118.7 (8)
C8—C7—C12	116.1 (8)	C21—C20—H20	120.6
C8—C7—C2	125.1 (8)	C19—C20—H20	120.6
C12—C7—C2	118.8 (7)	C22—C21—C20	120.9 (8)
C7—C8—C9	123.8 (9)	C22—C21—H21	119.6
C7—C8—H8	118.1	C20—C21—H21	119.6
C9—C8—H8	118.1	C21—C22—C23	120.6 (9)
C10—C9—C8	119.9 (9)	C21—C22—H22	119.7
C10—C9—H9	120.1	C23—C22—H22	119.7
C8—C9—H9	120.1	C24—C23—C22	119.6 (8)
C9—C10—C11	118.9 (8)	C24—C23—H23	120.2
C9—C10—H10	120.5	C22—C23—H23	120.2
C11—C10—H10	120.5	C19—C24—C23	119.7 (8)
C12—C11—C10	120.8 (9)	C19—C24—H24	120.2
C12—C11—H11	119.6	C23—C24—H24	120.2
C10—C11—H11	119.6
C6—S1—C2—C3	46.9 (6)	C2—C7—C12—C11	179.8 (7)
C6—S1—C2—C7	168.8 (5)	C3—C4—C13—C18	−146.5 (8)
C6—S1—C2—C1	−71.3 (6)	C5—C4—C13—C18	31.7 (11)
C7—C2—C3—C4	−160.3 (7)	C3—C4—C13—C14	33.4 (11)
C1—C2—C3—C4	73.0 (9)	C5—C4—C13—C14	−148.5 (7)
S1—C2—C3—C4	−44.3 (9)	C18—C13—C14—C15	3.2 (12)
C2—C3—C4—C5	10.0 (11)	C4—C13—C14—C15	−176.6 (7)
C2—C3—C4—C13	−171.9 (7)	C13—C14—C15—C16	−2.1 (13)
C3—C4—C5—C6	19.9 (12)	C14—C15—C16—C17	−0.2 (13)
C13—C4—C5—C6	−158.2 (7)	C14—C15—C16—Br1	176.4 (6)
C4—C5—C6—C19	172.4 (7)	C15—C16—C17—C18	1.2 (13)
C4—C5—C6—S1	−5.3 (11)	Br1—C16—C17—C18	−175.3 (7)
C2—S1—C6—C5	−26.8 (7)	C16—C17—C18—C13	0.0 (13)
C2—S1—C6—C19	155.3 (6)	C14—C13—C18—C17	−2.2 (12)
C3—C2—C7—C8	−136.8 (8)	C4—C13—C18—C17	177.7 (8)
C1—C2—C7—C8	−11.5 (11)	C5—C6—C19—C24	139.8 (8)
S1—C2—C7—C8	105.6 (8)	S1—C6—C19—C24	−42.3 (9)
C3—C2—C7—C12	43.0 (9)	C5—C6—C19—C20	−40.9 (11)
C1—C2—C7—C12	168.3 (6)	S1—C6—C19—C20	136.9 (7)
S1—C2—C7—C12	−74.6 (7)	C24—C19—C20—C21	−1.9 (12)
C12—C7—C8—C9	0.4 (12)	C6—C19—C20—C21	178.8 (7)
C2—C7—C8—C9	−179.8 (8)	C19—C20—C21—C22	2.9 (13)
C7—C8—C9—C10	1.9 (13)	C20—C21—C22—C23	−3.0 (14)
C8—C9—C10—C11	−4.1 (13)	C21—C22—C23—C24	2.0 (13)
C9—C10—C11—C12	4.2 (13)	C20—C19—C24—C23	1.0 (11)
C10—C11—C12—C7	−1.9 (12)	C6—C19—C24—C23	−179.7 (7)
C8—C7—C12—C11	−0.4 (11)	C22—C23—C24—C19	−1.0 (12)