3-Benzyl-7-bromo-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/S1600536809045875

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 12| December 2009| Pages o3001-o3002

doi:10.1107/S1600536809045875

Open

access

3-Benzyl-7-bromo-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 30 October 2009; accepted 1 November 2009; online 7 November 2009)

In the title compound, C₃₁H₂₉BrN₂O₂S, the pyrrolidine ring is in a twist conformation and the tetrahydropyridine ring adopts an envelope conformation with the methine C atom adjacent to the NH group as the flap atom; the two rings are trans-fused. The bromobenzene ring and the nearest phenyl ring form a dihedral angle of 82.72 (10)°. The benzyl phenyl and the tosyl phenyl rings are oriented at a dihedral angle of 75.57 (11)°. An intramolecular N—H⋯π interaction is observed. In the crystal, molecules are linked into chains running along [101] by C—H⋯O hydrogen bonds and the chains are cross-linked via weak C—H⋯π interactions.

Related literature

For the biological activity of pyrroloquinoline derivatives, see: Peng et al. (2002 ); Metobo et al. (2009 ); Ferlin et al. (2005 ); Ryu et al. (2009 ); Tsuji et al. (1995 ); Ferlin et al. (2001 ). For the crystal structures of chlorine and unbrominated analogues, see: Chinnakali et al. (2009a ,b ). For ring puckering parameters, see: Cremer & Pople (1975 ). For asymmetry parameters, see: Duax et al. (1976 ).

Experimental

Crystal data

C₃₁H₂₉BrN₂O₂S
M_r = 573.53
Monoclinic, P 2₁ /c
a = 8.8992 (2) Å
b = 27.5824 (5) Å
c = 13.3668 (2) Å
β = 127.190 (1)°
V = 2613.78 (9) Å³
Z = 4
Mo Kα radiation
μ = 1.69 mm⁻¹
T = 100 K
0.39 × 0.28 × 0.13 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.641, T_max = 0.805
43436 measured reflections
7624 independent reflections
6348 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.096
S = 1.06
7624 reflections
339 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.82 e Å⁻³
Δρ_min = −0.71 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C28—H28⋯O2ⁱ	0.93	2.57	3.207 (3)	126
N2—H1N2⋯Cg3	0.83 (3)	2.53 (3)	3.289 (2)	152 (3)
C3—H3⋯Cg3ⁱⁱ	0.98	2.98	3.924 (2)	162
C18—H18A⋯Cg2ⁱⁱⁱ	0.96	2.94	3.737 (3)	141
C21—H21⋯Cg1^iv	0.93	2.80	3.676 (2)	158
Symmetry codes: (i) $[x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) -x+2, -y, -z+2; (iv) -x+1, -y, -z+1. Cg1, Cg2 and Cg3 are the centroids of the C4–C9, C12–C17 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/S1600536809045875/hb5202sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809045875/hb5202Isup2.hkl

checkCIF report

Comment top

Pyrroloquinoline derivatives act as potent inhibitors for PI3-kinase related kinases (Peng et al., 2002) and as HIV integrase inhibitors (Metobo et al., 2009). These derivatives have been investigated as potential anticancer drugs (Ferlin et al., 2005) and are found to exhibit antifungal (Ryu et al., 2009), antibacterial (Tsuji et al., 1995) and antiproliferative (Ferlin et al., 2001) activities. As part of our studies on pyrroloquinoline derivatives, we report here the crystal structure of the title compound.

Bond lengths and angles are comparable with those in chlorine (Chinnakali et al., 2009a) and unbrominated (Chinnakali et al., 2009b) analouges. The pyrrolidine ring adopts a twist conformation, with puckering parameters (Cremer & Pople, 1975) q₂ = 0.408 (2) Å and ϕ = 82.2 (3)°. The tetrahydropyridine ring adopts an envelope conformation with C10, the envelope flap, lying 0.713 (2) Å out of the plane formed by the rest of the atoms (N2/C2—C4/C9) of the ring (r.m.s. deviation 0.053 Å). The asymmetry parameter (Duax et al., 1976) ΔC_s[C10] = 12.1 (2)° and the puckering parameters (Cremer & Pople, 1975) Q = 0.537 (2) Å, θ = 128.5 (2)° and ϕ = 103.2 (3)°. The dihedral angle between the C4—C9 and C19—C24 rings is 82.72 (10)° and that between the C12—C17 and C26—C31 rings is 75.57 (11)°.

The molecules are linked into chains running along the [101] by C—H···O hydrogen bonds (Fig.2). The chains are cross-linked into a three-dimensional network via C—H···π interactions (Table 2) involving the C4—C9, C12—C17 and C26—C31 rings.

A superposition of the non-H atoms of the chlorine (Chinnakali et al., 2009a) and unbrominated (Chinnakali et al., 2009b) analouges with those of the title molecule using XP in SHELXTL (Sheldrick, 2008) is shown in Fig.3. The title molecule fits well (r.m.s. deviation 0.415 Å) with the unbrominated analouge. But the chlorine and bromine analouges differ significantly in the orientations of the benzyl group. In the title molecule as well as in the unbrominated derivative, the benzyl phenyl rings is oriented in such a way to form an N—H···π interaction. But in the chlorine analouge, the benzyl group is twisted away from the N—H group to form an N—H···Cl hydrogen bond.

Related literature top

For the biological activity of pyrroloquinoline derivatives, see: Peng et al. (2002); Metobo et al. (2009); Ferlin et al. (2005); Ryu et al. (2009); Tsuji et al. (1995); Ferlin et al. (2001). For the crystal structures of chlorine and unbrominated analogues, see: Chinnakali et al. (2009a,b). For ring puckering parameters, see: Cremer & Pople (1975). For asymmetry parameters, see: Duax et al. (1976). Cg1, Cg2 and Cg3 are the centroids of the C4–C9, C12-C17 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-bromoaniline (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. Colourless blocks of (I) were 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 dotted line indicates an N—H···π interaction.
	Fig. 2. The crystal structure of (I), viewed along the c axis, shows chains running along the [101]. Hydrogen bonds are shown as dashed lines. For the sake of clarity, H atoms not involved in the interactions have been omitted.
	Fig. 3. Super-position fit of (I) (solid lines), with chlorinated (Cl in green) and unchlorinated analogues (dashed lines). H atoms have been omitted for clarity.

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

Crystal data top

C₃₁H₂₉BrN₂O₂S	F(000) = 1184
M_r = 573.53	D_x = 1.457 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9860 reflections
a = 8.8992 (2) Å	θ = 2.4–37.0°
b = 27.5824 (5) Å	µ = 1.69 mm⁻¹
c = 13.3668 (2) Å	T = 100 K
β = 127.190 (1)°	Block, colourless
V = 2613.78 (9) Å³	0.39 × 0.28 × 0.13 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD diffractometer	7624 independent reflections
Radiation source: fine-focus sealed tube	6348 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ϕ and ω scans	θ_max = 30.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −11→12
T_min = 0.641, T_max = 0.805	k = −35→38
43436 measured reflections	l = −18→16

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0447P)² + 2.281P] where P = (F_o² + 2F_c²)/3
7624 reflections	(Δ/σ)_max = 0.001
339 parameters	Δρ_max = 0.82 e Å⁻³
0 restraints	Δρ_min = −0.71 e Å⁻³

Crystal data top

C₃₁H₂₉BrN₂O₂S	V = 2613.78 (9) Å³
M_r = 573.53	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.8992 (2) Å	µ = 1.69 mm⁻¹
b = 27.5824 (5) Å	T = 100 K
c = 13.3668 (2) Å	0.39 × 0.28 × 0.13 mm
β = 127.190 (1)°

Data collection top

Bruker SMART APEXII CCD diffractometer	7624 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	6348 reflections with I > 2σ(I)
T_min = 0.641, T_max = 0.805	R_int = 0.034
43436 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.82 e Å⁻³
7624 reflections	Δρ_min = −0.71 e Å⁻³
339 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
Br1	−0.02354 (3)	0.121549 (7)	0.223962 (19)	0.01926 (6)
S1	1.38753 (6)	0.137930 (17)	0.96077 (4)	0.01528 (10)
O1	1.4895 (2)	0.12512 (5)	0.91282 (14)	0.0208 (3)
O2	1.46953 (19)	0.17022 (5)	1.06590 (13)	0.0203 (3)
N1	1.1910 (2)	0.16359 (6)	0.84519 (15)	0.0142 (3)
N2	0.7082 (2)	0.15745 (6)	0.74366 (15)	0.0142 (3)
H1N2	0.698 (4)	0.1741 (10)	0.791 (3)	0.029 (7)*
C1	1.0890 (3)	0.14242 (7)	0.71672 (18)	0.0162 (4)
H1A	1.1538	0.1140	0.7175	0.019*
H1B	1.0766	0.1659	0.6582	0.019*
C2	0.8972 (3)	0.12908 (6)	0.68243 (17)	0.0132 (3)
H2	0.9089	0.0988	0.7250	0.016*
C3	0.7325 (3)	0.12458 (6)	0.54317 (17)	0.0131 (3)
H3	0.7436	0.1510	0.4990	0.016*
C4	0.5476 (3)	0.13198 (6)	0.52621 (17)	0.0128 (3)
C5	0.3766 (3)	0.12455 (6)	0.40768 (18)	0.0147 (3)
H5	0.3776	0.1149	0.3414	0.018*
C6	0.2054 (3)	0.13134 (6)	0.38721 (18)	0.0148 (4)
C7	0.2001 (3)	0.14504 (7)	0.48506 (19)	0.0167 (4)
H7	0.0853	0.1487	0.4717	0.020*
C8	0.3676 (3)	0.15308 (7)	0.60239 (19)	0.0160 (4)
H8	0.3647	0.1623	0.6681	0.019*
C9	0.5425 (3)	0.14763 (6)	0.62462 (17)	0.0129 (3)
C10	0.8645 (2)	0.17057 (7)	0.74190 (17)	0.0125 (3)
H10	0.8312	0.1998	0.6908	0.015*
C11	1.0543 (2)	0.17848 (7)	0.87013 (17)	0.0133 (3)
H11	1.0652	0.1564	0.9316	0.016*
C12	1.3304 (3)	0.08391 (7)	1.00181 (18)	0.0159 (4)
C13	1.3157 (3)	0.08395 (8)	1.09972 (19)	0.0217 (4)
H13	1.3314	0.1126	1.1416	0.026*
C14	1.2775 (3)	0.04104 (8)	1.1346 (2)	0.0247 (4)
H14	1.2671	0.0413	1.1998	0.030*
C15	1.2546 (3)	−0.00222 (8)	1.0741 (2)	0.0203 (4)
C16	1.2670 (3)	−0.00143 (8)	0.9752 (2)	0.0255 (4)
H16	1.2495	−0.0300	0.9326	0.031*
C17	1.3049 (3)	0.04111 (8)	0.9388 (2)	0.0245 (4)
H17	1.3132	0.0409	0.8727	0.029*
C18	1.2250 (3)	−0.04916 (8)	1.1177 (2)	0.0256 (4)
H18A	1.1229	−0.0455	1.1232	0.038*
H18B	1.3381	−0.0575	1.1988	0.038*
H18C	1.1952	−0.0744	1.0589	0.038*
C19	0.7354 (2)	0.07718 (7)	0.48649 (17)	0.0132 (3)
C20	0.7079 (3)	0.03291 (7)	0.52376 (19)	0.0192 (4)
H20	0.6864	0.0324	0.5837	0.023*
C21	0.7122 (3)	−0.01038 (7)	0.4725 (2)	0.0227 (4)
H21	0.6936	−0.0396	0.4982	0.027*
C22	0.7443 (3)	−0.00997 (8)	0.3832 (2)	0.0233 (4)
H22	0.7474	−0.0389	0.3489	0.028*
C23	0.7717 (3)	0.03359 (8)	0.3452 (2)	0.0234 (4)
H23	0.7941	0.0339	0.2857	0.028*
C24	0.7656 (3)	0.07699 (7)	0.39584 (18)	0.0170 (4)
H24	0.7820	0.1062	0.3688	0.020*
C25	1.0855 (3)	0.23088 (7)	0.91806 (18)	0.0163 (4)
H25A	1.2055	0.2335	1.0008	0.020*
H25B	1.0872	0.2527	0.8618	0.020*
C26	0.9258 (3)	0.24439 (7)	0.92394 (18)	0.0149 (3)
C27	0.7728 (3)	0.27179 (7)	0.82900 (18)	0.0171 (4)
H27	0.7786	0.2870	0.7693	0.021*
C28	0.6109 (3)	0.27661 (7)	0.82256 (19)	0.0190 (4)
H28	0.5094	0.2948	0.7585	0.023*
C29	0.6011 (3)	0.25435 (7)	0.9116 (2)	0.0209 (4)
H29	0.4921	0.2568	0.9062	0.025*
C30	0.7551 (3)	0.22835 (7)	1.00898 (19)	0.0196 (4)
H30	0.7502	0.2139	1.0698	0.023*
C31	0.9168 (3)	0.22381 (7)	1.01571 (19)	0.0182 (4)
H31	1.0201	0.2069	1.0821	0.022*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.01373 (9)	0.02465 (11)	0.01461 (10)	−0.00055 (7)	0.00604 (8)	0.00078 (7)
S1	0.0108 (2)	0.0186 (2)	0.0157 (2)	−0.00166 (16)	0.00767 (18)	−0.00202 (17)
O1	0.0163 (7)	0.0261 (8)	0.0243 (8)	0.0000 (5)	0.0145 (6)	−0.0017 (6)
O2	0.0145 (6)	0.0236 (7)	0.0181 (7)	−0.0042 (5)	0.0074 (6)	−0.0054 (6)
N1	0.0106 (7)	0.0202 (8)	0.0121 (7)	0.0001 (6)	0.0071 (6)	−0.0012 (6)
N2	0.0133 (7)	0.0189 (8)	0.0134 (7)	−0.0022 (6)	0.0098 (6)	−0.0043 (6)
C1	0.0136 (8)	0.0216 (9)	0.0150 (9)	−0.0010 (7)	0.0095 (7)	−0.0023 (7)
C2	0.0143 (8)	0.0140 (9)	0.0122 (8)	−0.0008 (6)	0.0085 (7)	−0.0008 (6)
C3	0.0147 (8)	0.0136 (8)	0.0133 (8)	0.0001 (6)	0.0097 (7)	0.0004 (7)
C4	0.0145 (8)	0.0118 (8)	0.0159 (9)	0.0000 (6)	0.0113 (7)	0.0002 (6)
C5	0.0180 (9)	0.0128 (8)	0.0132 (8)	−0.0001 (6)	0.0094 (7)	0.0003 (7)
C6	0.0152 (8)	0.0131 (8)	0.0126 (8)	0.0002 (6)	0.0065 (7)	0.0005 (6)
C7	0.0152 (8)	0.0165 (9)	0.0210 (9)	0.0013 (7)	0.0123 (8)	0.0004 (7)
C8	0.0167 (9)	0.0178 (9)	0.0181 (9)	−0.0007 (7)	0.0129 (8)	−0.0022 (7)
C9	0.0142 (8)	0.0121 (8)	0.0138 (8)	−0.0003 (6)	0.0092 (7)	0.0002 (6)
C10	0.0143 (8)	0.0138 (8)	0.0113 (8)	−0.0010 (6)	0.0088 (7)	−0.0008 (6)
C11	0.0129 (8)	0.0164 (9)	0.0123 (8)	−0.0004 (6)	0.0084 (7)	−0.0010 (7)
C12	0.0129 (8)	0.0179 (9)	0.0140 (9)	0.0008 (7)	0.0066 (7)	0.0003 (7)
C13	0.0288 (11)	0.0217 (10)	0.0161 (9)	−0.0002 (8)	0.0144 (9)	−0.0021 (8)
C14	0.0318 (12)	0.0256 (11)	0.0208 (10)	0.0016 (9)	0.0180 (10)	0.0017 (8)
C15	0.0152 (9)	0.0222 (10)	0.0218 (10)	0.0010 (7)	0.0103 (8)	0.0029 (8)
C16	0.0346 (12)	0.0185 (10)	0.0288 (11)	−0.0033 (8)	0.0220 (10)	−0.0048 (8)
C17	0.0315 (11)	0.0240 (11)	0.0242 (11)	−0.0025 (9)	0.0201 (10)	−0.0032 (8)
C18	0.0242 (11)	0.0233 (11)	0.0283 (12)	0.0004 (8)	0.0153 (10)	0.0046 (9)
C19	0.0105 (8)	0.0179 (9)	0.0106 (8)	0.0005 (6)	0.0060 (7)	−0.0007 (7)
C20	0.0238 (10)	0.0192 (10)	0.0204 (10)	0.0022 (7)	0.0164 (9)	0.0014 (8)
C21	0.0259 (10)	0.0152 (9)	0.0295 (11)	0.0014 (8)	0.0182 (10)	0.0009 (8)
C22	0.0249 (10)	0.0191 (10)	0.0266 (11)	0.0016 (8)	0.0159 (9)	−0.0063 (8)
C23	0.0271 (11)	0.0273 (11)	0.0236 (11)	−0.0020 (8)	0.0194 (9)	−0.0063 (8)
C24	0.0166 (9)	0.0203 (9)	0.0162 (9)	−0.0031 (7)	0.0111 (8)	−0.0020 (7)
C25	0.0152 (8)	0.0173 (9)	0.0169 (9)	−0.0033 (7)	0.0100 (8)	−0.0030 (7)
C26	0.0173 (9)	0.0142 (8)	0.0144 (9)	−0.0031 (7)	0.0101 (7)	−0.0045 (7)
C27	0.0233 (10)	0.0145 (9)	0.0168 (9)	−0.0010 (7)	0.0139 (8)	−0.0014 (7)
C28	0.0202 (9)	0.0174 (9)	0.0186 (9)	0.0019 (7)	0.0114 (8)	−0.0012 (7)
C29	0.0226 (10)	0.0196 (10)	0.0261 (11)	−0.0015 (8)	0.0176 (9)	−0.0043 (8)
C30	0.0289 (10)	0.0174 (9)	0.0199 (10)	−0.0032 (8)	0.0186 (9)	−0.0027 (7)
C31	0.0216 (9)	0.0176 (9)	0.0152 (9)	0.0004 (7)	0.0111 (8)	−0.0007 (7)

Geometric parameters (Å, º) top

Br1—C6	1.9002 (19)	C14—C15	1.385 (3)
S1—O2	1.4356 (15)	C14—H14	0.93
S1—O1	1.4364 (15)	C15—C16	1.392 (3)
S1—N1	1.6369 (16)	C15—C18	1.507 (3)
S1—C12	1.765 (2)	C16—C17	1.387 (3)
N1—C1	1.493 (2)	C16—H16	0.93
N1—C11	1.500 (2)	C17—H17	0.93
N2—C9	1.394 (2)	C18—H18A	0.96
N2—C10	1.451 (2)	C18—H18B	0.96
N2—H1N2	0.83 (3)	C18—H18C	0.96
C1—C2	1.520 (3)	C19—C24	1.391 (3)
C1—H1A	0.97	C19—C20	1.395 (3)
C1—H1B	0.97	C20—C21	1.388 (3)
C2—C10	1.519 (2)	C20—H20	0.93
C2—C3	1.527 (3)	C21—C22	1.385 (3)
C2—H2	0.98	C21—H21	0.93
C3—C19	1.519 (2)	C22—C23	1.383 (3)
C3—C4	1.533 (2)	C22—H22	0.93
C3—H3	0.98	C23—C24	1.393 (3)
C4—C5	1.397 (3)	C23—H23	0.93
C4—C9	1.411 (2)	C24—H24	0.93
C5—C6	1.388 (3)	C25—C26	1.516 (3)
C5—H5	0.93	C25—H25A	0.97
C6—C7	1.389 (3)	C25—H25B	0.97
C7—C8	1.380 (3)	C26—C27	1.396 (3)
C7—H7	0.93	C26—C31	1.398 (3)
C8—C9	1.405 (2)	C27—C28	1.397 (3)
C8—H8	0.93	C27—H27	0.93
C10—C11	1.529 (3)	C28—C29	1.388 (3)
C10—H10	0.98	C28—H28	0.93
C11—C25	1.537 (3)	C29—C30	1.389 (3)
C11—H11	0.98	C29—H29	0.93
C12—C17	1.387 (3)	C30—C31	1.391 (3)
C12—C13	1.392 (3)	C30—H30	0.93
C13—C14	1.388 (3)	C31—H31	0.93
C13—H13	0.93

O2—S1—O1	120.33 (9)	C14—C13—C12	119.79 (19)
O2—S1—N1	106.05 (9)	C14—C13—H13	120.1
O1—S1—N1	106.73 (8)	C12—C13—H13	120.1
O2—S1—C12	106.91 (9)	C15—C14—C13	121.2 (2)
O1—S1—C12	108.03 (9)	C15—C14—H14	119.4
N1—S1—C12	108.31 (9)	C13—C14—H14	119.4
C1—N1—C11	110.57 (14)	C14—C15—C16	118.21 (19)
C1—N1—S1	118.47 (13)	C14—C15—C18	120.84 (19)
C11—N1—S1	117.12 (12)	C16—C15—C18	120.90 (19)
C9—N2—C10	113.13 (15)	C17—C16—C15	121.5 (2)
C9—N2—H1N2	116.8 (19)	C17—C16—H16	119.3
C10—N2—H1N2	114.8 (18)	C15—C16—H16	119.3
N1—C1—C2	103.47 (14)	C12—C17—C16	119.5 (2)
N1—C1—H1A	111.1	C12—C17—H17	120.3
C2—C1—H1A	111.1	C16—C17—H17	120.3
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	101.27 (14)	C15—C18—H18C	109.5
C10—C2—C3	110.67 (15)	H18A—C18—H18C	109.5
C1—C2—C3	117.55 (15)	H18B—C18—H18C	109.5
C10—C2—H2	109.0	C24—C19—C20	118.40 (17)
C1—C2—H2	109.0	C24—C19—C3	120.53 (17)
C3—C2—H2	109.0	C20—C19—C3	121.07 (16)
C19—C3—C2	112.66 (15)	C21—C20—C19	120.90 (18)
C19—C3—C4	112.38 (15)	C21—C20—H20	119.6
C2—C3—C4	108.85 (15)	C19—C20—H20	119.6
C19—C3—H3	107.6	C22—C21—C20	119.98 (19)
C2—C3—H3	107.6	C22—C21—H21	120.0
C4—C3—H3	107.6	C20—C21—H21	120.0
C5—C4—C9	118.36 (17)	C23—C22—C21	119.88 (19)
C5—C4—C3	118.95 (16)	C23—C22—H22	120.1
C9—C4—C3	122.66 (16)	C21—C22—H22	120.1
C6—C5—C4	121.12 (17)	C22—C23—C24	120.05 (19)
C6—C5—H5	119.4	C22—C23—H23	120.0
C4—C5—H5	119.4	C24—C23—H23	120.0
C5—C6—C7	120.60 (18)	C19—C24—C23	120.78 (19)
C5—C6—Br1	119.63 (14)	C19—C24—H24	119.6
C7—C6—Br1	119.78 (14)	C23—C24—H24	119.6
C8—C7—C6	119.03 (17)	C26—C25—C11	108.30 (15)
C8—C7—H7	120.5	C26—C25—H25A	110.0
C6—C7—H7	120.5	C11—C25—H25A	110.0
C7—C8—C9	121.38 (17)	C26—C25—H25B	110.0
C7—C8—H8	119.3	C11—C25—H25B	110.0
C9—C8—H8	119.3	H25A—C25—H25B	108.4
N2—C9—C8	119.53 (16)	C27—C26—C31	118.40 (17)
N2—C9—C4	121.04 (16)	C27—C26—C25	121.08 (17)
C8—C9—C4	119.44 (17)	C31—C26—C25	119.92 (17)
N2—C10—C2	108.05 (15)	C26—C27—C28	120.74 (18)
N2—C10—C11	115.96 (15)	C26—C27—H27	119.6
C2—C10—C11	105.22 (14)	C28—C27—H27	119.6
N2—C10—H10	109.1	C29—C28—C27	120.12 (19)
C2—C10—H10	109.1	C29—C28—H28	119.9
C11—C10—H10	109.1	C27—C28—H28	119.9
N1—C11—C10	101.94 (13)	C28—C29—C30	119.60 (18)
N1—C11—C25	112.56 (15)	C28—C29—H29	120.2
C10—C11—C25	113.59 (15)	C30—C29—H29	120.2
N1—C11—H11	109.5	C29—C30—C31	120.21 (18)
C10—C11—H11	109.5	C29—C30—H30	119.9
C25—C11—H11	109.5	C31—C30—H30	119.9
C17—C12—C13	119.84 (19)	C30—C31—C26	120.83 (19)
C17—C12—S1	120.14 (15)	C30—C31—H31	119.6
C13—C12—S1	120.00 (15)	C26—C31—H31	119.6

O2—S1—N1—C1	170.23 (13)	C2—C10—C11—N1	30.32 (17)
O1—S1—N1—C1	40.79 (15)	N2—C10—C11—C25	−89.02 (19)
C12—S1—N1—C1	−75.31 (15)	C2—C10—C11—C25	151.67 (15)
O2—S1—N1—C11	−53.17 (15)	O2—S1—C12—C17	−159.73 (17)
O1—S1—N1—C11	177.39 (13)	O1—S1—C12—C17	−28.88 (19)
C12—S1—N1—C11	61.30 (15)	N1—S1—C12—C17	86.37 (18)
C11—N1—C1—C2	−18.81 (19)	O2—S1—C12—C13	18.59 (18)
S1—N1—C1—C2	120.42 (14)	O1—S1—C12—C13	149.44 (16)
N1—C1—C2—C10	36.53 (17)	N1—S1—C12—C13	−95.31 (17)
N1—C1—C2—C3	157.19 (15)	C17—C12—C13—C14	0.7 (3)
C10—C2—C3—C19	−166.61 (15)	S1—C12—C13—C14	−177.66 (16)
C1—C2—C3—C19	77.8 (2)	C12—C13—C14—C15	0.4 (3)
C10—C2—C3—C4	−41.27 (19)	C13—C14—C15—C16	−1.3 (3)
C1—C2—C3—C4	−156.90 (15)	C13—C14—C15—C18	176.2 (2)
C19—C3—C4—C5	−48.0 (2)	C14—C15—C16—C17	1.2 (3)
C2—C3—C4—C5	−173.54 (16)	C18—C15—C16—C17	−176.3 (2)
C19—C3—C4—C9	134.17 (17)	C13—C12—C17—C16	−0.7 (3)
C2—C3—C4—C9	8.7 (2)	S1—C12—C17—C16	177.61 (17)
C9—C4—C5—C6	−1.4 (3)	C15—C16—C17—C12	−0.2 (3)
C3—C4—C5—C6	−179.24 (16)	C2—C3—C19—C24	−113.59 (19)
C4—C5—C6—C7	−1.0 (3)	C4—C3—C19—C24	123.01 (18)
C4—C5—C6—Br1	179.26 (13)	C2—C3—C19—C20	66.4 (2)
C5—C6—C7—C8	1.7 (3)	C4—C3—C19—C20	−57.0 (2)
Br1—C6—C7—C8	−178.53 (14)	C24—C19—C20—C21	0.6 (3)
C6—C7—C8—C9	−0.1 (3)	C3—C19—C20—C21	−179.42 (18)
C10—N2—C9—C8	−155.20 (17)	C19—C20—C21—C22	0.0 (3)
C10—N2—C9—C4	25.2 (2)	C20—C21—C22—C23	−0.1 (3)
C7—C8—C9—N2	178.18 (18)	C21—C22—C23—C24	−0.5 (3)
C7—C8—C9—C4	−2.2 (3)	C20—C19—C24—C23	−1.1 (3)
C5—C4—C9—N2	−177.51 (17)	C3—C19—C24—C23	178.86 (18)
C3—C4—C9—N2	0.3 (3)	C22—C23—C24—C19	1.1 (3)
C5—C4—C9—C8	2.9 (3)	N1—C11—C25—C26	172.70 (15)
C3—C4—C9—C8	−179.28 (16)	C10—C11—C25—C26	57.5 (2)
C9—N2—C10—C2	−58.2 (2)	C11—C25—C26—C27	−99.7 (2)
C9—N2—C10—C11	−175.99 (15)	C11—C25—C26—C31	71.3 (2)
C1—C2—C10—N2	−166.58 (15)	C31—C26—C27—C28	−3.0 (3)
C3—C2—C10—N2	68.01 (18)	C25—C26—C27—C28	168.13 (18)
C1—C2—C10—C11	−42.12 (17)	C26—C27—C28—C29	0.5 (3)
C3—C2—C10—C11	−167.53 (14)	C27—C28—C29—C30	1.7 (3)
C1—N1—C11—C10	−6.89 (19)	C28—C29—C30—C31	−1.3 (3)
S1—N1—C11—C10	−146.72 (12)	C29—C30—C31—C26	−1.2 (3)
C1—N1—C11—C25	−128.95 (16)	C27—C26—C31—C30	3.3 (3)
S1—N1—C11—C25	91.22 (17)	C25—C26—C31—C30	−167.86 (18)
N2—C10—C11—N1	149.63 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O1	0.97	2.53	2.917 (3)	104
C13—H13···O2	0.93	2.56	2.914 (3)	103
C28—H28···O2ⁱ	0.93	2.57	3.207 (3)	126
N2—H1N2···Cg3	0.83 (3)	2.53 (3)	3.289 (2)	152 (3)
C3—H3···Cg3ⁱⁱ	0.98	2.98	3.924 (2)	162
C18—H18A···Cg2ⁱⁱⁱ	0.96	2.94	3.737 (3)	141
C21—H21···Cg1^iv	0.93	2.80	3.676 (2)	158

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

Experimental details

Crystal data
Chemical formula	C₃₁H₂₉BrN₂O₂S
M_r	573.53
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	8.8992 (2), 27.5824 (5), 13.3668 (2)
β (°)	127.190 (1)
V (Å³)	2613.78 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.69
Crystal size (mm)	0.39 × 0.28 × 0.13

Data collection
Diffractometer	Bruker SMART APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.641, 0.805
No. of measured, independent and observed [I > 2σ(I)] reflections	43436, 7624, 6348
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.096, 1.06
No. of reflections	7624
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)	0.82, −0.71

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
C28—H28···O2ⁱ	0.93	2.57	3.207 (3)	126
N2—H1N2···Cg3	0.83 (3)	2.53 (3)	3.289 (2)	152 (3)
C3—H3···Cg3ⁱⁱ	0.98	2.98	3.924 (2)	162
C18—H18A···Cg2ⁱⁱⁱ	0.96	2.94	3.737 (3)	141
C21—H21···Cg1^iv	0.93	2.80	3.676 (2)	158

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

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

Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chinnakali, K., Sudha, D., Jayagobi, M., Raghunathan, R. & Fun, H.-K. (2009a). Acta Cryst. E65, o2923. Web of Science CSD CrossRef IUCr Journals Google Scholar
Chinnakali, K., Sudha, D., Jayagobi, M., Raghunathan, R. & Fun, H.-K. (2009b). Acta Cryst. E65, o2973–o2974. Web of Science CSD CrossRef IUCr Journals Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
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., Gatto, B., Chiarelotto, G. & Palumbo, M. (2001). Bioorg. Med. Chem. 9, 1843–1848. Web of Science CrossRef PubMed CAS Google Scholar
Ferlin, M. G., Marzano, C., Dalla Via, L., Chilin, A., Zagotto, G., Guiotto, A. & Moro, S. (2005). Bioorg. Med. Chem. 13, 4733–4739. Web of Science CrossRef PubMed CAS Google Scholar
Metobo, S., Mish, M., Jin, H., Jabri, S., Lansdown, R., Chen, X., Tsiang, M., Wright, M. & Kim, C. U. (2009). Bioorg. Med. Chem. Lett. 19, 1187–1190. Web of Science CrossRef PubMed CAS Google Scholar
Peng, H., Kim, D.-I., Sarkaria, J. N., Cho, Y.-S., Abraham, R. T. & Zalkow, L. H. (2002). Bioorg. Med. Chem. 10, 167–174. Web of Science CrossRef PubMed CAS Google Scholar
Ryu, C. K., Lee, J. Y., Jeong, S. H. & Nho, J. H. (2009). Bioorg. Med. Chem. Lett. 19, 146–148. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tsuji, K., Tsubouchi, H. & Ishikawa, H. (1995). Chem. Pharm. Bull. (Tokyo), 43, 1678–1682. CrossRef CAS PubMed Web of Science Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 12| December 2009| Pages o3001-o3002

doi:10.1107/S1600536809045875

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

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

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