3-Benzyl-7-chloro-9-phenyl-2-tosyl-2,3,3a,4,9,9a-hexa­hydro-1H-pyrrolo[3,4-b]quinoline

Chinnakali, K.; Sudha, D.; Jayagobi, M.; Raghunathan, R.; Fun, H.-K.

doi:10.1107/S1600536809045267

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Pages o2973-o2974

doi:10.1107/S1600536809045267

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3-Benzyl-7-chloro-9-phenyl-2-tosyl-2,3,3a,4,9,9a-hexahydro-1H-pyrrolo[3,4-b]quinoline

K. Chinnakali,^a ^* D. Sudha,^a ‡ M. Jayagobi,^b R. Raghunathan ^b and Hoong-Kun Fun ^c §

^aDepartment of Physics, Anna University Chennai, Chennai 600 025, India, ^bDepartment of Organic Chemistry, University of Madras, Guindy Campus, Chennai 600 025, India, and ^cX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: kali@annauniv.edu

(Received 27 October 2009; accepted 29 October 2009; online 4 November 2009)

In the title compound, C₃₁H₂₉ClN₂O₂S, the pyrrolidine ring adopts an envelope conformation with the methine C atom adjacent to the NH group as the flap atom. The tetrahydropyridine ring has a half-chair conformation. The two rings are trans-fused. The chlorobenzene ring and the adjacent phenyl ring form a dihedral angle of 77.9 (1)°. The benzyl phenyl and the tosyl phenyl rings are oriented at a dihedral angle of 88.0 (1)°. In the crystal, molecules are linked into chains along the a axis by N—H⋯Cl and C—H⋯Cl hydrogen bonds and the adjacent chains are cross-linked via C—H⋯π interactions.

Related literature

For the caspase-3 inhibitory, vasorelaxing and antileukemic activities of pyrroloquinoline compounds, see: Kravchenko et al. (2005 ); Ferlin et al. (2002 ); Anderson et al. (1988 ). For related structures, see: Sudha et al. (2007 , 2008a ,b ). For the crystal structure of the unchlorinated analogue, see: Chinnakali et al. (2009 ). For ring puckering parameters, see: Cremer & Pople (1975 ). For asymmetry parameters, see: Duax et al. (1976 ).

Experimental

Crystal data

C₃₁H₂₉ClN₂O₂S
M_r = 529.07
Orthorhombic, P 2₁ 2₁ 2₁
a = 10.0106 (1) Å
b = 11.8612 (1) Å
c = 21.8256 (2) Å
V = 2591.52 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 100 K
0.28 × 0.25 × 0.15 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.930, T_max = 0.962
35839 measured reflections
8047 independent reflections
7259 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.090
S = 1.02
8047 reflections
339 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.31 e Å⁻³
Absolute structure: Flack (1983 ), 3555 Friedel pairs
Flack parameter: 0.02 (4)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N2⋯Cl1ⁱ	0.84 (2)	2.83 (2)	3.5947 (13)	153 (2)
C27—H27⋯Cl1ⁱ	0.93	2.77	3.5980 (16)	149
C17—H17⋯Cg2ⁱⁱ	0.93	2.70	3.5403 (16)	151
C29—H29⋯Cg1ⁱⁱⁱ	0.93	2.68	3.6014 (19)	170
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ . Cg1 and Cg2 are the centroids of the C19–C24 and C26–C31 rings, respectively.

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809045267/hb5197sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809045267/hb5197Isup2.hkl

checkCIF report

Comment top

Pyrroloquinoline derivatives have been found to exhibit caspase-3 inhibitory (Kravchenko et al., 2005), vasorelaxing (Ferlin et al., 2002) and antileukemic (Anderson et al., 1988) activities. Previously, we have reported crystal structures of some pyrroloquinoline derivatives (Sudha et al., 2007,2008a,b). Now, herein the crystal structure of the title compound is reported.

The pyrrolidine ring adopts an envelope conformation with C10, the envelope flap, lying 0.695 (2) Å out of the plane formed by the rest of the atoms of the ring (r.m.s. deviation 0.019 Å). The asymmetry parameter (Duax et al., 1976) ΔC_s[C10] = 5.3 (1)° and the puckering parameters (Cremer & Pople, 1975) q₂ = 0.464 (2) Å and ϕ = 102.7 (2)°. The tosyl group is attached to the pyrrolidine ring in a equtorial position. The tetrahydropyridine ring adopts a half-chair conformation, with the local twofold rotation axis running through the midpoint of bonds C2—C10 and C4—C9 [asymmetry parameter ΔC₂[C2—C10] = 3.6 (2)°]. The phenyl ring attached to the tetrahydropyridine ring is in a biaxial position. The dihedral angle between the C4—C9 and C19—C24 rings is 77.9 (1)° and that between the C12—C17 and C26—C31 rings is 88.0 (1)°. Bond lengths and angles are comparable with those in the unchlorinated derivative, 3-benzyl-9-phenyl-2-tosyl-2,3,3a,4,9,9a-hexahydro-1H-pyrrolo[3,4-b]quinoline (Chinnakali et al., 2009).

The N2—H1N2···Cl1 and C27—H27···Cl1 hydrogen bonds (Table 1) form a pair of bifurcated acceptor bonds, generating a ring of graph-set motif R¹₂(9). These hydrogen bonds link the molecules into a chain along the a axis (Fig. 2). The adjacent chains are crosslinked via C—H···π interactions involving the benzyl phenyl and the phenyl ring bound to the fused ring system.

A superposition of the non-H atoms (except the N-bound H atom) of the unchlorinated derivative (Chinnakali et al., 2009) with those of the title molecule using XP in SHELXTL (Sheldrick, 2008), gave an r.m.s. deviation of 1.27 Å (Fig. 3). In the unchlorinated derivative, the benzyl phenyl ring is oriented in such a way to form an N—H···π interaction. But in the title molecule, the benzyl group is twisted away from the N—H group to make it available for participation in an N—H···Cl hydrogen bond.

Related literature top

For the caspase-3 inhibitory, vasorelaxing and antileukemic activities of pyrroloquinoline compounds, see: Kravchenko et al. (2005); Ferlin et al. (2002); Anderson et al. (1988). For related structures, see: Sudha et al. (2007, 2008a,b). For the crystal structure of the unchlorinated analogue, see: Chinnakali et al. (2009). For ring puckering parameters, see: Cremer & Pople (1975). For asymmetry parameters, see: Duax et al. (1976). Cg1 and Cg2 are the centroids of the C19–C24 and C26–C31 rings, respectively.

Experimental top

InCl₃ (20 mol%) was added to a mixture of S-2-(N-cinnamyl-N-tosylamino)-3-phenyl propanal (1 mmol) and p-chloroaniline (1 mmol) in acetonitrile (20 ml). The reaction mixture was stirred at room temperature for 1 min. On completion of the reaction, as indicated by TLC, the mixture was quenched with water and extracted with ethyl acetate. The organic layer was washed with brine and dried over Na₂SO₄. The solvent was evaporated in vacuo and the crude product was chromatographed on silica gel using a hexane-ethyl acetate (8.5:1.5 v/v) mixture to obtain the title compound. The compound was recrystallized from ethyl acetate solution by slow evaporation.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of (I), showing 50% probability displacement ellipsoids. The dashed line indicates a hydrogen bond.
	Fig. 2. The crystal structure of (I), viewed along the c axis. Hydrogen bonds are shown as dashed lines. For the sake of clarity, H atoms not involved in the interactions have been omitted.
	Fig. 3. Fit of the title molecule (solid lines) with its unchlorinated analogue (dashed lines). C-bound H atoms have been omitted for clarity.

3-Benzyl-7-chloro-9-phenyl-2-tosyl-2,3,3a,4,9,9a-hexahydro-1H- pyrrolo[3,4-b]quinoline top

Crystal data top

C₃₁H₂₉ClN₂O₂S	F(000) = 1112
M_r = 529.07	D_x = 1.356 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 9900 reflections
a = 10.0106 (1) Å	θ = 2.5–29.9°
b = 11.8612 (1) Å	µ = 0.26 mm⁻¹
c = 21.8256 (2) Å	T = 100 K
V = 2591.52 (4) Å³	Block, colourless
Z = 4	0.28 × 0.25 × 0.15 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	8047 independent reflections
Radiation source: fine-focus sealed tube	7259 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
ϕ and ω scans	θ_max = 30.7°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −13→14
T_min = 0.930, T_max = 0.962	k = −17→17
35839 measured reflections	l = −31→30

Refinement top

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)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.090	w = 1/[σ²(F_o²) + (0.0502P)² + 0.3209P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
8047 reflections	Δρ_max = 0.42 e Å⁻³
339 parameters	Δρ_min = −0.31 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 3555 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.02 (4)

Crystal data top

C₃₁H₂₉ClN₂O₂S	V = 2591.52 (4) Å³
M_r = 529.07	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 10.0106 (1) Å	µ = 0.26 mm⁻¹
b = 11.8612 (1) Å	T = 100 K
c = 21.8256 (2) Å	0.28 × 0.25 × 0.15 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	8047 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	7259 reflections with I > 2σ(I)
T_min = 0.930, T_max = 0.962	R_int = 0.045
35839 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.090	Δρ_max = 0.42 e Å⁻³
S = 1.02	Δρ_min = −0.31 e Å⁻³
8047 reflections	Absolute structure: Flack (1983), 3555 Friedel pairs
339 parameters	Absolute structure parameter: 0.02 (4)
0 restraints

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
Cl1	0.99020 (3)	0.23630 (3)	0.611010 (16)	0.01750 (8)
S1	0.87572 (4)	0.74890 (3)	0.237629 (16)	0.01701 (8)
O1	1.00459 (12)	0.75400 (9)	0.20897 (5)	0.0229 (2)
O2	0.75758 (13)	0.75019 (10)	0.20046 (5)	0.0256 (2)
N1	0.87251 (14)	0.63195 (10)	0.27756 (6)	0.0150 (2)
N2	0.72707 (13)	0.48831 (11)	0.40955 (6)	0.0159 (2)
H1N2	0.654 (2)	0.4565 (17)	0.4026 (10)	0.027 (5)*
C1	0.99589 (16)	0.60584 (12)	0.31441 (7)	0.0160 (3)
H1A	1.0509	0.6725	0.3196	0.019*
H1B	1.0486	0.5472	0.2950	0.019*
C2	0.94008 (14)	0.56589 (12)	0.37568 (7)	0.0137 (3)
H2	0.9205	0.6320	0.4011	0.016*
C3	1.02378 (14)	0.48294 (12)	0.41319 (7)	0.0132 (3)
H3	1.0572	0.4246	0.3853	0.016*
C4	0.93338 (14)	0.42593 (12)	0.46062 (7)	0.0131 (3)
C5	0.99179 (15)	0.36541 (11)	0.50869 (7)	0.0142 (3)
H5	1.0843	0.3619	0.5118	0.017*
C6	0.91344 (15)	0.31068 (12)	0.55164 (7)	0.0141 (3)
C7	0.77481 (15)	0.31665 (12)	0.54938 (7)	0.0149 (3)
H7	0.7228	0.2811	0.5789	0.018*
C8	0.71615 (15)	0.37664 (13)	0.50226 (7)	0.0155 (3)
H8	0.6235	0.3817	0.5004	0.019*
C9	0.79311 (14)	0.43009 (12)	0.45709 (7)	0.0134 (3)
C10	0.80912 (14)	0.51222 (12)	0.35619 (7)	0.0133 (3)
H10	0.8266	0.4425	0.3335	0.016*
C11	0.75027 (16)	0.60125 (12)	0.31332 (7)	0.0147 (3)
H11	0.7237	0.6666	0.3379	0.018*
C12	0.86417 (16)	0.86286 (11)	0.28916 (7)	0.0159 (3)
C13	0.73961 (16)	0.90828 (13)	0.30416 (8)	0.0201 (3)
H13	0.6617	0.8776	0.2880	0.024*
C14	0.73412 (16)	0.99983 (13)	0.34358 (8)	0.0212 (3)
H14	0.6516	1.0306	0.3537	0.025*
C15	0.85024 (15)	1.04677 (12)	0.36832 (7)	0.0170 (3)
C16	0.97308 (15)	0.99944 (12)	0.35296 (7)	0.0175 (3)
H16	1.0509	1.0297	0.3694	0.021*
C17	0.98130 (15)	0.90773 (12)	0.31342 (7)	0.0157 (3)
H17	1.0638	0.8768	0.3033	0.019*
C18	0.84443 (18)	1.14674 (14)	0.41044 (8)	0.0236 (3)
H18A	0.9244	1.1907	0.4059	0.035*
H18B	0.8369	1.1212	0.4520	0.035*
H18C	0.7683	1.1922	0.4003	0.035*
C19	1.14346 (15)	0.53881 (12)	0.44351 (7)	0.0158 (3)
C20	1.12450 (17)	0.61970 (14)	0.48937 (7)	0.0217 (3)
H20	1.0382	0.6402	0.5006	0.026*
C21	1.2328 (2)	0.66992 (16)	0.51843 (9)	0.0292 (4)
H21	1.2188	0.7245	0.5483	0.035*
C22	1.36117 (19)	0.63871 (17)	0.50286 (9)	0.0324 (4)
H22	1.4338	0.6714	0.5227	0.039*
C23	1.38142 (17)	0.55904 (16)	0.45789 (10)	0.0318 (4)
H23	1.4680	0.5380	0.4474	0.038*
C24	1.27344 (16)	0.50968 (14)	0.42795 (8)	0.0221 (3)
H24	1.2885	0.4568	0.3973	0.027*
C25	0.62882 (16)	0.56231 (13)	0.27564 (7)	0.0171 (3)
H25A	0.5588	0.5405	0.3040	0.020*
H25B	0.5961	0.6264	0.2525	0.020*
C26	0.65082 (14)	0.46589 (12)	0.23147 (7)	0.0150 (3)
C27	0.65518 (16)	0.35343 (13)	0.25089 (7)	0.0192 (3)
H27	0.6466	0.3369	0.2924	0.023*
C28	0.67212 (16)	0.26635 (13)	0.20928 (8)	0.0237 (3)
H28	0.6760	0.1922	0.2230	0.028*
C29	0.68336 (18)	0.28986 (14)	0.14704 (8)	0.0253 (4)
H29	0.6945	0.2315	0.1190	0.030*
C30	0.67796 (17)	0.40097 (14)	0.12689 (8)	0.0239 (3)
H30	0.6850	0.4171	0.0853	0.029*
C31	0.66208 (16)	0.48796 (13)	0.16892 (7)	0.0189 (3)
H31	0.6589	0.5621	0.1551	0.023*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.01853 (15)	0.02012 (16)	0.01386 (15)	0.00295 (13)	0.00000 (12)	0.00457 (12)
S1	0.02840 (18)	0.01221 (14)	0.01041 (15)	−0.00087 (15)	−0.00294 (13)	0.00055 (13)
O1	0.0372 (6)	0.0165 (5)	0.0151 (5)	−0.0010 (6)	0.0072 (5)	0.0006 (4)
O2	0.0404 (6)	0.0180 (5)	0.0185 (5)	−0.0022 (5)	−0.0136 (5)	0.0016 (5)
N1	0.0210 (6)	0.0123 (5)	0.0117 (6)	0.0001 (5)	−0.0011 (5)	0.0020 (4)
N2	0.0138 (6)	0.0219 (6)	0.0120 (6)	−0.0002 (5)	−0.0011 (5)	0.0026 (5)
C1	0.0179 (7)	0.0172 (6)	0.0130 (7)	0.0009 (6)	0.0002 (6)	0.0031 (5)
C2	0.0168 (6)	0.0134 (6)	0.0108 (7)	0.0004 (5)	−0.0010 (5)	0.0000 (5)
C3	0.0155 (6)	0.0127 (6)	0.0114 (6)	0.0007 (5)	0.0016 (5)	−0.0006 (5)
C4	0.0146 (6)	0.0124 (6)	0.0121 (7)	−0.0003 (5)	0.0012 (5)	−0.0013 (5)
C5	0.0144 (6)	0.0142 (6)	0.0139 (7)	0.0004 (5)	−0.0002 (5)	−0.0003 (5)
C6	0.0188 (7)	0.0140 (6)	0.0096 (7)	0.0020 (5)	−0.0031 (5)	−0.0001 (5)
C7	0.0164 (7)	0.0161 (6)	0.0121 (7)	−0.0012 (5)	0.0015 (5)	−0.0011 (5)
C8	0.0148 (6)	0.0174 (7)	0.0145 (7)	−0.0009 (5)	0.0002 (5)	−0.0015 (5)
C9	0.0155 (6)	0.0138 (6)	0.0109 (7)	0.0006 (5)	0.0003 (5)	−0.0021 (5)
C10	0.0162 (6)	0.0129 (6)	0.0109 (7)	0.0004 (5)	−0.0014 (5)	0.0002 (5)
C11	0.0187 (7)	0.0141 (6)	0.0112 (7)	0.0016 (5)	−0.0005 (6)	−0.0008 (5)
C12	0.0227 (7)	0.0122 (6)	0.0129 (7)	−0.0002 (5)	−0.0008 (6)	0.0000 (5)
C13	0.0178 (7)	0.0176 (7)	0.0250 (9)	−0.0002 (6)	−0.0048 (6)	−0.0004 (6)
C14	0.0179 (7)	0.0186 (7)	0.0272 (8)	0.0028 (6)	0.0003 (6)	−0.0009 (6)
C15	0.0203 (7)	0.0145 (6)	0.0163 (7)	0.0007 (5)	0.0030 (6)	0.0005 (5)
C16	0.0177 (7)	0.0174 (7)	0.0175 (7)	−0.0021 (5)	−0.0002 (5)	−0.0018 (6)
C17	0.0156 (7)	0.0145 (6)	0.0171 (7)	0.0020 (5)	−0.0002 (6)	−0.0001 (5)
C18	0.0277 (8)	0.0205 (7)	0.0225 (8)	0.0014 (6)	0.0042 (7)	−0.0066 (6)
C19	0.0164 (7)	0.0158 (6)	0.0152 (7)	−0.0012 (5)	−0.0012 (5)	0.0054 (5)
C20	0.0224 (8)	0.0236 (7)	0.0190 (8)	−0.0030 (7)	−0.0015 (6)	−0.0008 (6)
C21	0.0353 (10)	0.0311 (9)	0.0211 (9)	−0.0126 (8)	−0.0070 (7)	−0.0008 (7)
C22	0.0266 (9)	0.0339 (9)	0.0366 (11)	−0.0130 (8)	−0.0166 (8)	0.0158 (8)
C23	0.0153 (7)	0.0314 (9)	0.0486 (12)	0.0014 (7)	−0.0031 (8)	0.0182 (8)
C24	0.0174 (7)	0.0178 (7)	0.0311 (9)	0.0020 (6)	0.0026 (6)	0.0071 (6)
C25	0.0182 (7)	0.0201 (6)	0.0129 (7)	0.0040 (6)	−0.0020 (6)	0.0005 (5)
C26	0.0135 (6)	0.0176 (6)	0.0139 (7)	−0.0005 (5)	−0.0010 (5)	−0.0008 (5)
C27	0.0188 (7)	0.0206 (7)	0.0181 (8)	−0.0038 (6)	0.0006 (6)	0.0030 (6)
C28	0.0229 (7)	0.0157 (7)	0.0325 (9)	−0.0040 (6)	−0.0003 (7)	0.0000 (6)
C29	0.0283 (8)	0.0223 (7)	0.0253 (9)	−0.0029 (6)	−0.0037 (7)	−0.0103 (6)
C30	0.0297 (8)	0.0273 (8)	0.0148 (8)	−0.0015 (7)	−0.0033 (6)	−0.0037 (6)
C31	0.0234 (7)	0.0194 (7)	0.0141 (7)	−0.0009 (6)	−0.0039 (6)	0.0011 (6)

Geometric parameters (Å, º) top

Cl1—C6	1.7459 (15)	C14—C15	1.397 (2)
S1—O2	1.4341 (12)	C14—H14	0.93
S1—O1	1.4349 (12)	C15—C16	1.393 (2)
S1—N1	1.6386 (12)	C15—C18	1.502 (2)
S1—C12	1.7623 (15)	C16—C17	1.391 (2)
N1—C11	1.496 (2)	C16—H16	0.93
N1—C1	1.506 (2)	C17—H17	0.93
N2—C9	1.4107 (19)	C18—H18A	0.96
N2—C10	1.4531 (19)	C18—H18B	0.96
N2—H1N2	0.84 (2)	C18—H18C	0.96
C1—C2	1.525 (2)	C19—C24	1.388 (2)
C1—H1A	0.97	C19—C20	1.399 (2)
C1—H1B	0.97	C20—C21	1.390 (2)
C2—C10	1.518 (2)	C20—H20	0.93
C2—C3	1.530 (2)	C21—C22	1.380 (3)
C2—H2	0.98	C21—H21	0.93
C3—C19	1.521 (2)	C22—C23	1.377 (3)
C3—C4	1.532 (2)	C22—H22	0.93
C3—H3	0.98	C23—C24	1.392 (3)
C4—C5	1.399 (2)	C23—H23	0.93
C4—C9	1.4072 (19)	C24—H24	0.93
C5—C6	1.384 (2)	C25—C26	1.512 (2)
C5—H5	0.93	C25—H25A	0.97
C6—C7	1.390 (2)	C25—H25B	0.97
C7—C8	1.382 (2)	C26—C31	1.394 (2)
C7—H7	0.93	C26—C27	1.400 (2)
C8—C9	1.403 (2)	C27—C28	1.386 (2)
C8—H8	0.93	C27—H27	0.93
C10—C11	1.529 (2)	C28—C29	1.391 (3)
C10—H10	0.98	C28—H28	0.93
C11—C25	1.539 (2)	C29—C30	1.390 (2)
C11—H11	0.98	C29—H29	0.93
C12—C17	1.392 (2)	C30—C31	1.390 (2)
C12—C13	1.397 (2)	C30—H30	0.93
C13—C14	1.386 (2)	C31—H31	0.93
C13—H13	0.93

O2—S1—O1	119.63 (7)	C14—C13—C12	118.86 (15)
O2—S1—N1	107.08 (7)	C14—C13—H13	120.6
O1—S1—N1	106.57 (7)	C12—C13—H13	120.6
O2—S1—C12	107.38 (7)	C13—C14—C15	121.25 (15)
O1—S1—C12	107.75 (7)	C13—C14—H14	119.4
N1—S1—C12	107.97 (7)	C15—C14—H14	119.4
C11—N1—C1	110.00 (11)	C16—C15—C14	118.75 (14)
C11—N1—S1	119.97 (10)	C16—C15—C18	119.99 (14)
C1—N1—S1	116.23 (10)	C14—C15—C18	121.27 (14)
C9—N2—C10	114.84 (12)	C17—C16—C15	121.11 (14)
C9—N2—H1N2	108.8 (14)	C17—C16—H16	119.4
C10—N2—H1N2	115.8 (14)	C15—C16—H16	119.4
N1—C1—C2	103.40 (12)	C16—C17—C12	119.01 (14)
N1—C1—H1A	111.1	C16—C17—H17	120.5
C2—C1—H1A	111.1	C12—C17—H17	120.5
N1—C1—H1B	111.1	C15—C18—H18A	109.5
C2—C1—H1B	111.1	C15—C18—H18B	109.5
H1A—C1—H1B	109.0	H18A—C18—H18B	109.5
C10—C2—C1	101.60 (12)	C15—C18—H18C	109.5
C10—C2—C3	110.69 (11)	H18A—C18—H18C	109.5
C1—C2—C3	117.94 (12)	H18B—C18—H18C	109.5
C10—C2—H2	108.7	C24—C19—C20	118.21 (15)
C1—C2—H2	108.7	C24—C19—C3	121.56 (14)
C3—C2—H2	108.7	C20—C19—C3	120.21 (13)
C19—C3—C2	112.59 (11)	C21—C20—C19	120.94 (17)
C19—C3—C4	111.32 (12)	C21—C20—H20	119.5
C2—C3—C4	108.78 (12)	C19—C20—H20	119.5
C19—C3—H3	108.0	C22—C21—C20	119.93 (18)
C2—C3—H3	108.0	C22—C21—H21	120.0
C4—C3—H3	108.0	C20—C21—H21	120.0
C5—C4—C9	118.43 (13)	C23—C22—C21	119.78 (17)
C5—C4—C3	119.09 (13)	C23—C22—H22	120.1
C9—C4—C3	122.47 (13)	C21—C22—H22	120.1
C6—C5—C4	120.78 (14)	C22—C23—C24	120.57 (17)
C6—C5—H5	119.6	C22—C23—H23	119.7
C4—C5—H5	119.6	C24—C23—H23	119.7
C5—C6—C7	121.18 (14)	C19—C24—C23	120.54 (16)
C5—C6—Cl1	119.37 (11)	C19—C24—H24	119.7
C7—C6—Cl1	119.42 (12)	C23—C24—H24	119.7
C8—C7—C6	118.47 (14)	C26—C25—C11	116.91 (13)
C8—C7—H7	120.8	C26—C25—H25A	108.1
C6—C7—H7	120.8	C11—C25—H25A	108.1
C7—C8—C9	121.50 (14)	C26—C25—H25B	108.1
C7—C8—H8	119.2	C11—C25—H25B	108.1
C9—C8—H8	119.2	H25A—C25—H25B	107.3
C8—C9—C4	119.59 (14)	C31—C26—C27	118.21 (14)
C8—C9—N2	118.73 (13)	C31—C26—C25	119.60 (13)
C4—C9—N2	121.67 (13)	C27—C26—C25	122.14 (14)
N2—C10—C2	110.21 (12)	C28—C27—C26	121.02 (15)
N2—C10—C11	114.05 (12)	C28—C27—H27	119.5
C2—C10—C11	102.39 (11)	C26—C27—H27	119.5
N2—C10—H10	110.0	C27—C28—C29	120.02 (15)
C2—C10—H10	110.0	C27—C28—H28	120.0
C11—C10—H10	110.0	C29—C28—H28	120.0
N1—C11—C10	99.92 (12)	C30—C29—C28	119.71 (16)
N1—C11—C25	116.13 (12)	C30—C29—H29	120.1
C10—C11—C25	115.10 (12)	C28—C29—H29	120.1
N1—C11—H11	108.4	C31—C30—C29	119.96 (16)
C10—C11—H11	108.4	C31—C30—H30	120.0
C25—C11—H11	108.4	C29—C30—H30	120.0
C17—C12—C13	121.01 (13)	C30—C31—C26	121.07 (14)
C17—C12—S1	118.72 (12)	C30—C31—H31	119.5
C13—C12—S1	120.25 (12)	C26—C31—H31	119.5

O2—S1—N1—C11	−50.80 (12)	C2—C10—C11—N1	43.40 (13)
O1—S1—N1—C11	−179.92 (10)	N2—C10—C11—C25	−72.42 (16)
C12—S1—N1—C11	64.55 (12)	C2—C10—C11—C25	168.55 (12)
O2—S1—N1—C1	172.80 (10)	O2—S1—C12—C17	−155.56 (12)
O1—S1—N1—C1	43.67 (12)	O1—S1—C12—C17	−25.46 (14)
C12—S1—N1—C1	−71.85 (12)	N1—S1—C12—C17	89.29 (13)
C11—N1—C1—C2	−3.90 (14)	O2—S1—C12—C13	23.14 (15)
S1—N1—C1—C2	136.63 (10)	O1—S1—C12—C13	153.24 (12)
N1—C1—C2—C10	30.84 (14)	N1—S1—C12—C13	−92.01 (13)
N1—C1—C2—C3	151.97 (12)	C17—C12—C13—C14	0.4 (2)
C10—C2—C3—C19	−169.50 (12)	S1—C12—C13—C14	−178.31 (12)
C1—C2—C3—C19	74.18 (16)	C12—C13—C14—C15	−0.1 (2)
C10—C2—C3—C4	−45.62 (15)	C13—C14—C15—C16	−0.4 (2)
C1—C2—C3—C4	−161.95 (12)	C13—C14—C15—C18	179.29 (15)
C19—C3—C4—C5	−41.60 (17)	C14—C15—C16—C17	0.5 (2)
C2—C3—C4—C5	−166.23 (12)	C18—C15—C16—C17	−179.16 (14)
C19—C3—C4—C9	139.71 (14)	C15—C16—C17—C12	−0.2 (2)
C2—C3—C4—C9	15.08 (19)	C13—C12—C17—C16	−0.2 (2)
C9—C4—C5—C6	0.2 (2)	S1—C12—C17—C16	178.46 (11)
C3—C4—C5—C6	−178.56 (13)	C2—C3—C19—C24	−115.72 (15)
C4—C5—C6—C7	−1.8 (2)	C4—C3—C19—C24	121.83 (15)
C4—C5—C6—Cl1	−179.87 (11)	C2—C3—C19—C20	65.90 (17)
C5—C6—C7—C8	1.5 (2)	C4—C3—C19—C20	−56.56 (17)
Cl1—C6—C7—C8	179.53 (11)	C24—C19—C20—C21	0.2 (2)
C6—C7—C8—C9	0.5 (2)	C3—C19—C20—C21	178.68 (15)
C7—C8—C9—C4	−2.1 (2)	C19—C20—C21—C22	−1.1 (3)
C7—C8—C9—N2	178.85 (14)	C20—C21—C22—C23	1.0 (3)
C5—C4—C9—C8	1.7 (2)	C21—C22—C23—C24	0.0 (3)
C3—C4—C9—C8	−179.61 (12)	C20—C19—C24—C23	0.7 (2)
C5—C4—C9—N2	−179.25 (12)	C3—C19—C24—C23	−177.67 (14)
C3—C4—C9—N2	−0.5 (2)	C22—C23—C24—C19	−0.9 (2)
C10—N2—C9—C8	−162.78 (13)	N1—C11—C25—C26	54.31 (17)
C10—N2—C9—C4	18.1 (2)	C10—C11—C25—C26	−61.90 (18)
C9—N2—C10—C2	−49.72 (16)	C11—C25—C26—C31	−103.37 (17)
C9—N2—C10—C11	−164.22 (12)	C11—C25—C26—C27	79.21 (19)
C1—C2—C10—N2	−168.63 (12)	C31—C26—C27—C28	0.9 (2)
C3—C2—C10—N2	65.30 (15)	C25—C26—C27—C28	178.35 (14)
C1—C2—C10—C11	−46.93 (14)	C26—C27—C28—C29	−0.8 (2)
C3—C2—C10—C11	−172.99 (11)	C27—C28—C29—C30	0.2 (3)
C1—N1—C11—C10	−24.29 (13)	C28—C29—C30—C31	0.3 (3)
S1—N1—C11—C10	−163.12 (9)	C29—C30—C31—C26	−0.3 (3)
C1—N1—C11—C25	−148.72 (12)	C27—C26—C31—C30	−0.4 (2)
S1—N1—C11—C25	72.44 (15)	C25—C26—C31—C30	−177.87 (15)
N2—C10—C11—N1	162.44 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···Cl1ⁱ	0.84 (2)	2.83 (2)	3.5947 (13)	153 (2)
C25—H25B···O2	0.97	2.46	3.0529 (19)	119
C27—H27···Cl1ⁱ	0.93	2.77	3.5980 (16)	149
C17—H17···Cg2ⁱⁱ	0.93	2.70	3.5403 (16)	151
C29—H29···Cg1ⁱⁱⁱ	0.93	2.68	3.6014 (19)	170

Symmetry codes: (i) x−1/2, −y+1/2, −z+1; (ii) −x+2, y+1/2, −z+1/2; (iii) −x+2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₃₁H₂₉ClN₂O₂S
M_r	529.07
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	100
a, b, c (Å)	10.0106 (1), 11.8612 (1), 21.8256 (2)
V (Å³)	2591.52 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.28 × 0.25 × 0.15

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.930, 0.962
No. of measured, independent and observed [I > 2σ(I)] reflections	35839, 8047, 7259
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.719

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.090, 1.02
No. of reflections	8047
No. of parameters	339
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.31
Absolute structure	Flack (1983), 3555 Friedel pairs
Absolute structure parameter	0.02 (4)

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···Cl1ⁱ	0.84 (2)	2.83 (2)	3.5947 (13)	153 (2)
C27—H27···Cl1ⁱ	0.93	2.77	3.5980 (16)	149
C17—H17···Cg2ⁱⁱ	0.93	2.70	3.5403 (16)	151
C29—H29···Cg1ⁱⁱⁱ	0.93	2.68	3.6014 (19)	170

Symmetry codes: (i) x−1/2, −y+1/2, −z+1; (ii) −x+2, y+1/2, −z+1/2; (iii) −x+2, y−1/2, −z+1/2.

Footnotes

‡Working at: Department of Physics, R. M. K. Engineering Collge, R. S. M. Nagar, Kavaraipettai 601 206, Tamil Nadu, India.

§Additional correspondence author, e-mail: hkfun@usm.my.

Acknowledgements

HKF thanks Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012.

References

Anderson, W. K., Heider, A. R., Raju, N. & Yucht, J. A. (1988). J. Med. Chem. 31, 2097–2102. CrossRef CAS PubMed Web of Science Google Scholar
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Chinnakali, K., Sudha, D., Jayagobi, M., Raghunathan, R. & Fun, H.-K. (2009). Acta Cryst. E65, o2923. Web of Science CSD CrossRef IUCr Journals Google Scholar
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Duax, W. L., Weeks, C. M. & Rohrer, D. C. (1976). Topics in Stereochemistry, Vol. 9, edited by E. L. Eliel & N. L. Allinger, pp. 271–383. New York: John Wiley. Google Scholar
Ferlin, M. G., Chiarelotto, G., Antonucci, F., Caparrotta, L. & Froldi, G. (2002). Eur. J. Med. Chem. 37, 427–434. Web of Science CrossRef PubMed CAS Google Scholar
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Volume 65| Part 12| December 2009| Pages o2973-o2974

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

3-Benzyl-7-chloro-9-phenyl-2-tosyl-2,3,3a,4,9,9a-hexa­hydro-1H-pyrrolo[3,4-b]quinoline

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Footnotes

Acknowledgements

References

organic compounds

3-Benzyl-7-chloro-9-phenyl-2-tosyl-2,3,3a,4,9,9a-hexahydro-1H-pyrrolo[3,4-b]quinoline