5,7-Dihydro­dibenzo[c,e]thiepine

Yoshinari, N.; Konno, T.

doi:10.1107/S1600536809008769

organic compounds

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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page o774

doi:10.1107/S1600536809008769

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5,7-Dihydrodibenzo[c,e]thiepine

Nobuto Yoshinari ^a and Takumi Konno ^a ^*

^aDepartment of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan
^*Correspondence e-mail: konno@chem.sci.osaka-u.ac.jp

(Received 26 February 2009; accepted 10 March 2009; online 14 March 2009)

In the title compound, C₁₄H₁₂S, the central seven-membered C₆S ring has a twist-boat conformation. The dihedral angle between the two benzene rings is 52.4 (1)°.

Related literature

For the preparation of a pair of atrop diastereomeric Rh^III complexes having a 2,2′-bis(2-aminoethylthiomethyl)-1,1′-biphenyl ligand, see: Yoshinari & Konno (2008 ). For the synthesis, see: Foubelo et al. (2005 ).

Experimental

Crystal data

C₁₄H₁₂S
M_r = 212.30
Monoclinic, P 2₁ /n
a = 5.645 (3) Å
b = 17.316 (9) Å
c = 11.398 (5) Å
β = 92.444 (19)°
V = 1113.1 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 200 K
0.15 × 0.15 × 0.10 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.962, T_max = 0.975
7548 measured reflections
2464 independent reflections
1324 reflections with I > 2σ(I)
R_int = 0.114

Refinement

R[F² > 2σ(F²)] = 0.063
wR(F²) = 0.165
S = 1.06
2464 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: PROCESS-AUTO (Rigaku, 1998 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: Mercury (Macrae et al., 2006 ); software used to prepare material for publication: publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809008769/is2397sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809008769/is2397Isup2.hkl

checkCIF report

Comment top

As a part of our ongoing studies on the synthesis and structures of the transition metal complexes with thioether donor groups, we prepared a pair of atrop diastereomeric Rh^III complexes having a 2,2'-bis(2-aminoethylthiomethyl)-1,1'-biphenyl ligand (Yoshinari & Konno, 2008). We report herein the structure of the title compound, 5,7-dihydrodibenzo[c,e]thiepine, (I), which was accidentally obtained in the course of a direct synthesis of 2,2'-bis(2-aminoethylthiomethyl)-1,1'-biphenyl from 2,2'-bis(bromomethyl)-1,1'-biphenyl and 2-aminoethanethiol.

In the crystal structure of (I), two aromatic rings (C2—C7 and C8—C13) are inclined around the C7—C8 bond with a dihedral angle of 52.4 (1)°.

This compound (I) has been synthesized by treatment of 2,2'-bis(bromomethyl)-1,1'-biphenyl with sulfide anion, but has not been structurally characterized (Foubelo et al. 2005).

Related literature top

For the preparation of a pair of atrop diastereomeric Rh^III complexes having a 2,2'-bis(2-aminoethylthiomethyl)-1,1'-biphenyl ligand, see: Yoshinari & Konno (2008). For the synthesis, see: Foubelo et al. (2005).

Experimental top

The reaction of 2,2'-bis(bromomethyl)-1,1'-biphenyl with 2-aminoethanethiol in ethanol gave a colorless solution. To the resulting solution was added diethylether, followed by allowing to stand in a refrigerator, which produced colorless stick crystals of (I) as a byproduct.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top

	Fig. 1. Perspective view of the title compound, (I), with the atom numbering scheme. Displacement ellipsoids are at the 70% probability level. H atoms are drawn as spheres of arbitrary radii.
	Fig. 2. The crystal packing of title compound, (I). Displacement ellipsoids are at the 70% probability level. H atoms are drawn as spheres of arbitrary radii.

5,7-Dihydrodibenzo[c,e]thiepine top

Crystal data top

C₁₄H₁₂S	F(000) = 448
M_r = 212.30	D_x = 1.267 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2yn	Cell parameters from 4537 reflections
a = 5.645 (3) Å	θ = 3.6–27.5°
b = 17.316 (9) Å	µ = 0.25 mm⁻¹
c = 11.398 (5) Å	T = 200 K
β = 92.444 (19)°	Prismatic, colourless
V = 1113.1 (10) Å³	0.15 × 0.15 × 0.10 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	2464 independent reflections
Radiation source: fine-focus sealed tube	1324 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.114
Detector resolution: 10.00 pixels mm^-1	θ_max = 27.5°, θ_min = 3.6°
ω scans	h = −4→7
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −22→22
T_min = 0.962, T_max = 0.975	l = −14→14
7548 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.165	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0655P)²] where P = (F_o² + 2F_c²)/3
2464 reflections	(Δ/σ)_max < 0.001
136 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³
0 constraints

Crystal data top

C₁₄H₁₂S	V = 1113.1 (10) Å³
M_r = 212.30	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 5.645 (3) Å	µ = 0.25 mm⁻¹
b = 17.316 (9) Å	T = 200 K
c = 11.398 (5) Å	0.15 × 0.15 × 0.10 mm
β = 92.444 (19)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	2464 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1324 reflections with I > 2σ(I)
T_min = 0.962, T_max = 0.975	R_int = 0.114
7548 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.063	0 restraints
wR(F²) = 0.165	H-atom parameters constrained
S = 1.06	Δρ_max = 0.31 e Å⁻³
2464 reflections	Δρ_min = −0.30 e Å⁻³
136 parameters

Special details top

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
S1	1.27862 (17)	0.41043 (5)	−0.05701 (6)	0.0391 (3)
C1	1.3831 (7)	0.39078 (19)	0.0932 (2)	0.0357 (8)
H1	1.4103	0.3346	0.1023	0.043*
H2	1.5369	0.4172	0.1083	0.043*
C2	1.2131 (6)	0.41676 (17)	0.1826 (2)	0.0281 (7)
C3	1.2565 (7)	0.48526 (17)	0.2447 (2)	0.0330 (8)
H3	1.3926	0.5153	0.2294	0.040*
C4	1.1020 (7)	0.50965 (19)	0.3284 (2)	0.0363 (9)
H4	1.1289	0.5572	0.3684	0.044*
C5	0.9098 (6)	0.4648 (2)	0.3532 (2)	0.0363 (9)
H5	0.8061	0.4810	0.4120	0.044*
C6	0.8660 (6)	0.39652 (19)	0.2937 (2)	0.0332 (8)
H6	0.7331	0.3659	0.3123	0.040*
C7	1.0160 (6)	0.37196 (17)	0.2059 (2)	0.0276 (8)
C8	0.9612 (6)	0.30059 (17)	0.1387 (2)	0.0293 (7)
C9	0.9182 (7)	0.23099 (19)	0.1957 (3)	0.0369 (8)
H7	0.9236	0.2295	0.2790	0.044*
C10	0.8682 (7)	0.1646 (2)	0.1335 (3)	0.0420 (9)
H8	0.8406	0.1176	0.1738	0.050*
C11	0.8582 (8)	0.1662 (2)	0.0120 (3)	0.0483 (10)
H9	0.8242	0.1204	−0.0313	0.058*
C12	0.8979 (7)	0.23477 (19)	−0.0461 (3)	0.0395 (9)
H10	0.8892	0.2357	−0.1295	0.047*
C13	0.9499 (6)	0.30201 (17)	0.0150 (2)	0.0270 (7)
C14	0.9761 (6)	0.37741 (18)	−0.0492 (2)	0.0320 (8)
H11	0.8833	0.4175	−0.0095	0.038*
H12	0.9073	0.3716	−0.1300	0.038*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0500 (6)	0.0390 (5)	0.0295 (4)	−0.0065 (5)	0.0140 (4)	0.0003 (4)
C1	0.038 (2)	0.0342 (19)	0.0360 (16)	−0.0057 (17)	0.0081 (14)	−0.0011 (14)
C2	0.041 (2)	0.0229 (16)	0.0206 (13)	0.0035 (15)	0.0040 (12)	0.0033 (12)
C3	0.046 (2)	0.0246 (17)	0.0286 (15)	−0.0038 (16)	0.0003 (14)	0.0045 (13)
C4	0.057 (3)	0.0234 (17)	0.0289 (16)	0.0046 (17)	0.0016 (15)	−0.0023 (13)
C5	0.044 (2)	0.041 (2)	0.0239 (15)	0.0118 (18)	0.0062 (14)	−0.0004 (14)
C6	0.039 (2)	0.039 (2)	0.0226 (14)	−0.0031 (16)	0.0078 (13)	0.0036 (13)
C7	0.038 (2)	0.0242 (17)	0.0213 (14)	0.0017 (15)	0.0039 (13)	0.0045 (12)
C8	0.033 (2)	0.0237 (17)	0.0312 (15)	−0.0039 (15)	0.0029 (13)	0.0009 (12)
C9	0.045 (2)	0.0331 (19)	0.0326 (16)	−0.0082 (17)	−0.0004 (14)	0.0038 (14)
C10	0.048 (3)	0.0267 (19)	0.051 (2)	−0.0082 (18)	−0.0012 (17)	0.0045 (15)
C11	0.069 (3)	0.027 (2)	0.048 (2)	−0.009 (2)	−0.0008 (18)	−0.0093 (15)
C12	0.056 (3)	0.0317 (19)	0.0310 (16)	−0.0033 (18)	0.0023 (15)	−0.0054 (14)
C13	0.0226 (18)	0.0290 (18)	0.0296 (15)	−0.0006 (15)	0.0033 (12)	0.0012 (12)
C14	0.043 (2)	0.0316 (18)	0.0216 (14)	0.0011 (17)	0.0045 (13)	0.0035 (12)

Geometric parameters (Å, º) top

S1—C14	1.807 (4)	C7—C8	1.480 (4)
S1—C1	1.819 (3)	C8—C9	1.395 (4)
C1—C2	1.499 (4)	C8—C13	1.409 (4)
C1—H1	0.9900	C9—C10	1.374 (5)
C1—H2	0.9900	C9—H7	0.9500
C2—C7	1.391 (4)	C10—C11	1.384 (4)
C2—C3	1.397 (4)	C10—H8	0.9500
C3—C4	1.386 (5)	C11—C12	1.382 (5)
C3—H3	0.9500	C11—H9	0.9500
C4—C5	1.373 (5)	C12—C13	1.382 (4)
C4—H4	0.9500	C12—H10	0.9500
C5—C6	1.381 (4)	C13—C14	1.507 (4)
C5—H5	0.9500	C14—H11	0.9900
C6—C7	1.404 (4)	C14—H12	0.9900
C6—H6	0.9500

C14—S1—C1	99.41 (15)	C9—C8—C13	118.6 (3)
C2—C1—S1	113.1 (3)	C9—C8—C7	121.2 (2)
C2—C1—H1	109.0	C13—C8—C7	120.2 (2)
S1—C1—H1	109.0	C10—C9—C8	121.3 (3)
C2—C1—H2	109.0	C10—C9—H7	119.3
S1—C1—H2	109.0	C8—C9—H7	119.3
H1—C1—H2	107.8	C9—C10—C11	119.8 (3)
C7—C2—C3	120.1 (3)	C9—C10—H8	120.1
C7—C2—C1	120.2 (3)	C11—C10—H8	120.1
C3—C2—C1	119.7 (3)	C12—C11—C10	119.8 (3)
C4—C3—C2	120.3 (3)	C12—C11—H9	120.1
C4—C3—H3	119.8	C10—C11—H9	120.1
C2—C3—H3	119.8	C13—C12—C11	121.2 (3)
C5—C4—C3	119.7 (3)	C13—C12—H10	119.4
C5—C4—H4	120.1	C11—C12—H10	119.4
C3—C4—H4	120.1	C12—C13—C8	119.3 (3)
C4—C5—C6	120.6 (3)	C12—C13—C14	120.6 (3)
C4—C5—H5	119.7	C8—C13—C14	120.0 (3)
C6—C5—H5	119.7	C13—C14—S1	114.2 (2)
C5—C6—C7	120.6 (3)	C13—C14—H11	108.7
C5—C6—H6	119.7	S1—C14—H11	108.7
C7—C6—H6	119.7	C13—C14—H12	108.7
C2—C7—C6	118.6 (3)	S1—C14—H12	108.7
C2—C7—C8	121.2 (3)	H11—C14—H12	107.6
C6—C7—C8	120.2 (3)

C14—S1—C1—C2	−45.4 (3)	C2—C7—C8—C13	−51.6 (5)
S1—C1—C2—C7	79.6 (3)	C6—C7—C8—C13	127.2 (3)
S1—C1—C2—C3	−102.0 (3)	C13—C8—C9—C10	0.7 (5)
C7—C2—C3—C4	−1.0 (5)	C7—C8—C9—C10	−179.7 (4)
C1—C2—C3—C4	−179.4 (3)	C8—C9—C10—C11	−0.5 (5)
C2—C3—C4—C5	2.2 (5)	C9—C10—C11—C12	−0.2 (6)
C3—C4—C5—C6	−1.5 (5)	C10—C11—C12—C13	0.6 (6)
C4—C5—C6—C7	−0.5 (5)	C11—C12—C13—C8	−0.4 (6)
C3—C2—C7—C6	−1.0 (4)	C11—C12—C13—C14	−175.8 (4)
C1—C2—C7—C6	177.4 (3)	C9—C8—C13—C12	−0.3 (5)
C3—C2—C7—C8	177.8 (3)	C7—C8—C13—C12	−179.8 (3)
C1—C2—C7—C8	−3.7 (4)	C9—C8—C13—C14	175.1 (3)
C5—C6—C7—C2	1.8 (4)	C7—C8—C13—C14	−4.4 (5)
C5—C6—C7—C8	−177.1 (3)	C12—C13—C14—S1	−105.8 (3)
C2—C7—C8—C9	128.8 (3)	C8—C13—C14—S1	78.8 (3)
C6—C7—C8—C9	−52.3 (5)	C1—S1—C14—C13	−43.6 (2)

Experimental details

Crystal data
Chemical formula	C₁₄H₁₂S
M_r	212.30
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	200
a, b, c (Å)	5.645 (3), 17.316 (9), 11.398 (5)
β (°)	92.444 (19)
V (Å³)	1113.1 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.15 × 0.15 × 0.10

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.962, 0.975
No. of measured, independent and observed [I > 2σ(I)] reflections	7548, 2464, 1324
R_int	0.114
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.165, 1.06
No. of reflections	2464
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.30

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2004), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2006), publCIF (Westrip, 2009).

Acknowledgements

This work was supported by a Grant-in-Aid for JSPS Fellows from the Japan Society for the Promotion of Science (JSPS).

References

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