11-[3-(Dimethyl­amino)prop­yl]-6,11-dihydro­dibenzo[b,e]thiepin-11-ol

Jerry P Jasinski; Ray J Butcher; Q N M Hakim Al-arique; H S Yathirajan; AR Ramesha

doi:10.1107/S1600536809053434

. 2009 Dec 16;66(Pt 1):o161–o162. doi: 10.1107/S1600536809053434

11-[3-(Dimethylamino)propyl]-6,11-dihydrodibenzo[b,e]thiepin-11-ol

Jerry P Jasinski ^a,^*, Ray J Butcher ^b, Q N M Hakim Al-arique ^c, H S Yathirajan ^c, AR Ramesha ^d

PMCID: PMC2980032 PMID: 21580050

Abstract

There are two independent molecules (A and B) in the asymmetric unit of the title compound, C₁₉H₂₃NOS. In each molecule, the seven-membered thiepine ring is bent into a slightly twisted V-shape. The dihedral angles between the mean planes of the two benzene rings fused to the thiepine ring are 75.7 (5) in molecule A and 73.8 (4)° in molecule B. In both molecules, an intramolecular O—H⋯N hydrogen bond occurs. In the crystal, weak intermolecular C—H⋯O and C—H⋯π-ring interactions are observed.

Related literature

For related structures, see: Bandoli & Nicolini, (1982 ▶); Blaton et al. (1995 ▶); Ieawsuwan et al. (2006 ▶); Linden et al. (2004 ▶); Portalone et al. (2007 ▶); Roszak et al. (1996 ▶); Rudorf et al. (1999 ▶); Yoshinari & Konno, (2009 ▶); Zhang et al. (2008 ▶,2008a ▶). For related background, see: Rudorf et al. (1999 ▶). For antidepressant and anti-inflammatory properties, see: Rajsner et al. (1969 ▶, 1971 ▶); Rooks et al. (1980 ▶); Tomascovic et al. (2000 ▶); Truce et al. (1956 ▶). For pharmacological synthesis and studies, see: Ikuo et al. (1978 ▶); Uchida et al. (1979 ▶); Wyatt et al. (2006 ▶). For NMR, Ir and X-ray studies, see: Kolehmainen et al. (2007 ▶). For density functional theory (DFT), see: Becke (1988 ▶, 1993 ▶); Frisch et al. (2004 ▶); Hehre et al. (1986 ▶); Lee et al. (1988 ▶); Schmidt & Polik (2007 ▶).

Experimental

Crystal data

C₁₉H₂₃NOS
M _r = 313.44
Monoclinic,
a = 7.7215 (4) Å
b = 15.3729 (10) Å
c = 27.9274 (16) Å
β = 95.401 (6)°
V = 3300.3 (3) Å³
Z = 8
Cu Kα radiation
μ = 1.74 mm⁻¹
T = 110 K
0.51 × 0.42 × 0.14 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Ruby (Gemini Cu) detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 ▶) T _min = 0.432, T _max = 1.000
14666 measured reflections
6565 independent reflections
5490 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.054
wR(F ²) = 0.153
S = 1.05
6565 reflections
403 parameters
H-atom parameters constrained
Δρ_max = 0.58 e Å⁻³
Δρ_min = −0.56 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2007 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809053434/lh2968sup1.cif

e-66-0o161-sup1.cif^{(30.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809053434/lh2968Isup2.hkl

e-66-0o161-Isup2.hkl^{(321.3KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1A—H1A⋯N1A	0.84	1.86	2.693 (2)	170
O1B—H1B⋯N1B	0.84	1.84	2.679 (2)	174
C4A—H4AA⋯O1B	0.95	2.51	3.253 (2)	135
C3A—H3AA⋯Cg7ⁱ	0.95	2.74	3.526 (6)	140
C17A—H17A⋯Cg1ⁱⁱ	0.99	2.67	3.537 (7)	147
C17A—H17B⋯Cg2ⁱⁱ	0.99	2.75	3.720 (3)	167
C17B—H17C⋯Cg8ⁱⁱⁱ	0.99	2.68	3.663 (6)	170
C17B—17D⋯Cg7ⁱⁱⁱ	0.99	2.64	3.538 (1)	149

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) . Cg1, Cg2, Cg7 and Cg8 are the centroids of the C1A—C6A, C8A—C13A, C1B–C6B and C8B—C13B rings, respectively.

Acknowledgments

QNMHA thanks the University of Mysore for use of their research facilities. RJB acknowledges the NSF MRI program (Grant No. CHE-0619278) for funds to purchase an X-ray diffractometer.

supplementary crystallographic information

Comment

The title compound, (I), C₁₉H₂₃NOS, is a derivative of 6,11-dihydrodibenzo[b,e]thiepin-11-one, which is used as an intermediate for the synthesis of dosulepin, an antidepressant of the tricyclic family. The dibenzo[c,e]thiepine derivatives (Truce et al., 1956) exhibit remarkable chiroptical properties (Tomascovic et al., 2000). The anti-inflammatory and analgesic profile of 6,11-dihydrodibenzo[b,e]thiepin-11-one-3-acetic acid (Tiopinac) is reported (Rooks II et al., 1980). Dibenzo[b,e]thiepin-5,5-dioxide derivatives are known to possess antihistaminic and antiallergenic activities (Rajsner et al., 1971). In addition, by aminoalkylation of 6,11-dihydrodibenzo[b,e]thiepin-5,5-dioxide and the corresponding 11-ketone, compounds with neurotropic and psychotropic activities have been reported (Rajsner et al., 1969). Also, the comparative NMR and IR spectral, X-ray structural and theoretical studies of eight 6-arylidenedibenzo[b,e]thiepin-11-one-5,5-dioxides have been reported (Kolehmainen et al., 2007). A pharmacological study of [2-chloro-11-(2-dimethylaminoethoxy)dibenzo(b,f)thiepine] (zotepine), and a new neuroleptic drug are also reported (Uchida et al., 1979). In addition, the synthesis and chemistry of enantiomerically pure 10,11-dihydrobenzo[b,f]thiepines (Wyatt et al., 2006) and the synthesis and pharmacological properties of 8-chloro-10-(2-dimethylaminoethoxy) dibenzo[b,f]thiepine and related compounds have been reported (Ikuo et al., 1978). In view of the importance of thiepines, this paper reports the crystal structure of the title compound, C₁₉H₂₃NOS, (I).

The title compound, C₁₉H₂₃NOS, (I), crystallizes with two independent molecules (A, Fig. 1 & B, Fig. 2) in the asymmetric unit. The seven-membered thiepine ring is bent into a slightly twisted V-shaped arrangement with sp3 hybridized atoms at C7(A & B), C14(A & B)and S1(A & B). The dihedral angles between the mean planes of the two benzene rings fused to the thiepine ring are 75.7 (5)° (A) and 73.8 (4)° (B), respectively. An intramolecular O—H···N hydrogen bond exists between the hydroxy group and the N atom from the (dimethylamino)propyl group both bonded to the C14 atom of the thiepine ring (O1A—H1A···N1A & O1B—H1B···N1; Table 1). While no classical intermolecular hydrogen bonds are present, weak C–H···O and C–H···π-ring intermolecular interactions are observed which contribute to the stability of crystal packing (Fig.3, Table 1,2).

Following a geometry optimization density functional theory calculation (Schmidt & Polik 2007) at the B3LYP 6–31-G(d) level (Becke, 1988, 1993; Lee et al. 1988; Hehre et al. 1986) with the Gaussian03 program package (Frisch at al. 2004) the angle between the mean planes of the two benzene rings changes to 73.4 (4)°, a difference of -2.32° (A) and + 0.40° (B), respectively. These results support the collective effects of the intra and intermolecular hydrogen bonding described above slightly influencing crystal packing.

Experimental

The title compound was obtained as a gift sample from R. L. Fine Chem, Bangalore, India. The compound was used without further purification. X-ray quality crystals (m.p. 433–435 K) of the title compound, (I), were obtained by slow evaporation from acetone solution.