11-[(E)-Benzyl­idene]-14-hy­droxy-8-phenyl-6-thia-3,13-diaza­hepta­cyclo­[13.7.1.19,13.02,9.02,14.03,7.019,23]tetra­cosa-1(22),15(23),16,18,20-pentaen-10-one

Kumar, R.S.; Osman, H.; Almansour, A.I.; Arshad, S.; Razak, I.A.

doi:10.1107/S1600536812024270

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 7| July 2012| Pages o2013-o2014

https://doi.org/10.1107/S1600536812024270

Open

access

11-[(E)-Benzylidene]-14-hydroxy-8-phenyl-6-thia-3,13-diazaheptacyclo[13.7.1.1^9,13.0^2,9.0^2,14.0^3,7.0^19,23]tetracosa-1(22),15(23),16,18,20-pentaen-10-one

Raju Suresh Kumar,^a Hasnah Osman,^a ‡ Abdulrahman I. Almansour,^b Suhana Arshad ^c and Ibrahim Abdul Razak ^c ^*§

^aSchool of Chemical Sciences, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, ^bDepartment of Chemistry, College of Sciences, King Saud University, PO Box 2455, Riyadh 11451, Saudi Arabia, and ^cSchool of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: arazaki@usm.my

(Received 16 May 2012; accepted 28 May 2012; online 13 June 2012)

In the title compound, C₃₄H₂₈N₂O₂S, the piperidine ring adopts a chair conformation. One of the pyrrolidine rings adopts an envelope conformation with the methylene C atom at the flap whereas the other pyrrolidine ring and the thiazolidine ring adopt half-chair conformations. The mean plane of the dihydroacenaphthylene ring system [maximum deviation = 0.067 (1) Å] makes dihedral angles of 28.31 (5) and 31.32 (6)° with the two terminal benzene rings. An intramolecular O—H⋯N hydrogen bond forms an S(5) ring motif. In the crystal, molecules are linked by C—H⋯O and C—H⋯S hydrogen bonds into layers lying parallel to the ac plane.

Related literature

For general background to heterocycles, see: Corey et al. (2007 ); Padwa (1984 ); Lee et al. (2001 ); Lalezari & Schwartz (1988 ); Aicher et al. (1998 ). For related structures, see: Kumar et al. (2010a ,b , 2011 ). For ring conformations, see: Cremer & Pople (1975 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₃₄H₂₈N₂O₂S
M_r = 528.64
Monoclinic, P 2₁ /c
a = 11.2911 (1) Å
b = 15.4317 (2) Å
c = 15.1920 (2) Å
β = 92.790 (1)°
V = 2643.93 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.16 mm⁻¹
T = 100 K
0.45 × 0.41 × 0.31 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.932, T_max = 0.953
37231 measured reflections
9686 independent reflections
8170 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.129
S = 1.04
9686 reflections
344 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.18 e Å⁻³
Δρ_min = −1.12 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H1O2⋯N2	0.86 (2)	1.95 (2)	2.6277 (12)	134.4 (18)
C8—H8A⋯O1ⁱ	0.99	2.55	3.1981 (14)	123
C15—H15A⋯S1ⁱⁱ	0.95	2.72	3.4970 (13)	139
C18—H18A⋯O1ⁱⁱⁱ	0.95	2.60	3.2550 (15)	127
C24—H24A⋯O2^iv	0.95	2.59	3.4077 (18)	145
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) -x+2, -y+1, -z+2; (iv) -x+2, -y, -z+2.

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); 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: https://doi.org/10.1107/S1600536812024270/hb6800sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812024270/hb6800Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812024270/hb6800Isup3.cml

checkCIF report

Comment top

The synthesis and chemistry of heterocyclic compounds has been an interesting field in view of their structural diversity and remarkable ability to serve as biomimetics and active pharmacophores. Many of the most famous natural alkaloids or unnatural drugs consist of at least one heterocyclic ring (Corey et al., 2007). 1,3-Dipolar cycloaddition of azomethine ylides to olefinic dipolarophiles affords five membered heterocyclic rings of biological importance (Padwa, 1984). Heterocycles with piperidine sub-structures are being used as synthons in the construction of alkaloid natural products (Lee et al., 2001). Pyrrolothiazole ring possesses antineoplastic (Lalezari & Schwartz, 1988) and hypoglycemic (Aicher et al., 1998) activity. The importance of aforesaid heterocycles, incited us to investigate the X-ray diffraction study of the title compound and report the results in this paper.

In the molecular structure (Fig. 1), the piperidine ring (N1/C1–C5) adopts a chair conformation with puckering parameters (Cremer & Pople, 1975), Q= 0.6090 (10) Å, Θ= 37.98 (10)° and Φ= 303.45 (16)°.

For the two pyrrolidine rings, N1/C4/C5/C10/C11 is in envelope conformation with atom C5 deviating by 0.298 (1) Å from the mean plane through the remaining atoms [puckering parameters Q= 0.4579 (10) Å and φ=29.43 (13)°] whereas N2/C4/C6/C7/C10 is twisted about C6–C4 bond, [puckering parameters, Q= 0.3869 (10) Å and φ= 261.97 (15)°] adopting a half-chair conformation. The thiazolidine ring, S1/N2/C7–C9 is twisted about C8–S1 bond [puckering parameters, Q= 0.4519 (10) Å and φ= 333.87 (14)°] thereby, also adopting a half-chair conformations.

The mean plane of the dihydroacenaphthylene ring system [C10/C11/C25–C33, maximum deviation = 0.067 (1) Å at atom C10] makes dihedral angles of 28.31 (5) and 31.32 (6)°, respectively, with the two terminal benzene rings (C13–C18 & C19–C24).

An intramolecular O2—H1O2···N2 hydrogen bond (Table 1) forms an S(5) ring motif (Bernstein et al., 1995). The bond lengths and angles are within normal ranges and comparable to the related structure (Kumar et al., 2010a,b; Kumar et al., 2011).

The crystal packing is shown in Fig. 2. The intermolecular C8—H8A···O1, C15—H15A···S1, C18—H18A···O1 and C24—H24A···O2 (Table 1) hydrogen bonds link the molecules into two-dimensional network parallel to ac-plane.

Related literature top

For general background to heterocycles, see: Corey et al. (2007); Padwa (1984); Lee et al. (2001); Lalezari & Schwartz (1988); Aicher et al. (1998). For related structures, see: Kumar et al. (2010a,b, 2011). For ring conformations, see: Cremer & Pople (1975). For hydrogen-bond motifs, see: Bernstein et al. (1995). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

Experimental top

A mixture of 3,5-bis[(E)-phenylmethylidene] tetrahydro-4(1H)-pyridinone (1 mmol), acenaphthenequinone (1 mmol), and thiazolidine-2-carboxylic acid (1 mmol) were dissolved in methanol (5 ml) and refluxed for 1 h. After completion of the reaction as evident from TLC, the mixture was poured into water (50 ml). The precipitated solid was filtered and washed with water to obtain the product which was further purified by recrystallization from pet.ether-ethyl acetate mixture to obtain colourless blocks.

Structure description top

For general background to heterocycles, see: Corey et al. (2007); Padwa (1984); Lee et al. (2001); Lalezari & Schwartz (1988); Aicher et al. (1998). For related structures, see: Kumar et al. (2010a,b, 2011). For ring conformations, see: Cremer & Pople (1975). For hydrogen-bond motifs, see: Bernstein et al. (1995). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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 the title compound, showing 30% probability displacement ellipsoids.
	Fig. 2. The crystal packing of the title compound. The H atoms not involved in the intermolecular interactions (dashed lines) have been omitted for clarity.

11-[(E)-Benzylidene]-14-hydroxy-8-phenyl-6-thia-3,13- diazaheptacyclo[13.7.1.1^9,13.0^2,9.0^2,14.0^3,7.0^19,23]tetracosa- 1(22),15(23),16,18,20-pentaen-10-one top

Crystal data top

C₃₄H₂₈N₂O₂S	F(000) = 1112
M_r = 528.64	D_x = 1.328 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9915 reflections
a = 11.2911 (1) Å	θ = 2.2–32.7°
b = 15.4317 (2) Å	µ = 0.16 mm⁻¹
c = 15.1920 (2) Å	T = 100 K
β = 92.790 (1)°	Block, colourless
V = 2643.93 (5) Å³	0.45 × 0.41 × 0.31 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD diffractometer	9686 independent reflections
Radiation source: fine-focus sealed tube	8170 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
φ and ω scans	θ_max = 32.7°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −17→17
T_min = 0.932, T_max = 0.953	k = −23→15
37231 measured reflections	l = −23→23

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.129	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0652P)² + 1.2561P] where P = (F_o² + 2F_c²)/3
9686 reflections	(Δ/σ)_max = 0.001
344 parameters	Δρ_max = 1.18 e Å⁻³
0 restraints	Δρ_min = −1.12 e Å⁻³

Crystal data top

C₃₄H₂₈N₂O₂S	V = 2643.93 (5) Å³
M_r = 528.64	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.2911 (1) Å	µ = 0.16 mm⁻¹
b = 15.4317 (2) Å	T = 100 K
c = 15.1920 (2) Å	0.45 × 0.41 × 0.31 mm
β = 92.790 (1)°

Data collection top

Bruker SMART APEXII CCD diffractometer	9686 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	8170 reflections with I > 2σ(I)
T_min = 0.932, T_max = 0.953	R_int = 0.025
37231 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.129	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 1.18 e Å⁻³
9686 reflections	Δρ_min = −1.12 e Å⁻³
344 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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	0.64487 (2)	0.10704 (2)	0.791294 (19)	0.02225 (7)
O1	0.82800 (7)	0.32741 (5)	1.03565 (5)	0.01646 (15)
O2	1.08336 (7)	0.06609 (5)	0.87449 (5)	0.01708 (15)
N1	1.07824 (8)	0.13611 (6)	1.01109 (6)	0.01411 (15)
N2	0.87576 (8)	0.13375 (6)	0.82898 (5)	0.01311 (15)
C1	1.11599 (9)	0.21225 (7)	1.06386 (7)	0.01543 (18)
H1A	1.1960	0.2297	1.0468	0.019*
H1B	1.1224	0.1952	1.1267	0.019*
C2	1.03363 (9)	0.29053 (7)	1.05418 (6)	0.01414 (17)
C3	0.90690 (9)	0.27470 (7)	1.02482 (6)	0.01284 (16)
C4	0.88395 (8)	0.18990 (6)	0.97700 (6)	0.01150 (16)
C5	0.95369 (9)	0.11761 (7)	1.02825 (6)	0.01410 (17)
H5A	0.9402	0.1207	1.0921	0.017*
H5B	0.9301	0.0595	1.0060	0.017*
C6	0.75412 (8)	0.17277 (7)	0.94872 (6)	0.01358 (17)
H6A	0.7215	0.2275	0.9218	0.016*
C7	0.76710 (9)	0.10734 (7)	0.87353 (7)	0.01441 (17)
H7A	0.7781	0.0478	0.8986	0.017*
C8	0.71970 (10)	0.18640 (9)	0.72578 (7)	0.0227 (2)
H8A	0.6907	0.1839	0.6633	0.027*
H8B	0.7080	0.2458	0.7485	0.027*
C9	0.84945 (10)	0.15954 (7)	0.73615 (7)	0.01675 (18)
H9A	0.8648	0.1104	0.6964	0.020*
H9B	0.9010	0.2085	0.7204	0.020*
C10	0.94831 (8)	0.19109 (6)	0.88798 (6)	0.01158 (16)
C11	1.07541 (8)	0.14789 (7)	0.91425 (6)	0.01288 (16)
C12	1.06869 (9)	0.37379 (7)	1.06055 (7)	0.01643 (18)
H12A	1.0092	0.4165	1.0496	0.020*
C13	1.18915 (10)	0.40547 (7)	1.08261 (7)	0.01790 (19)
C14	1.26365 (11)	0.36572 (8)	1.14689 (8)	0.0229 (2)
H14A	1.2363	0.3170	1.1782	0.027*
C15	1.37756 (12)	0.39733 (10)	1.16505 (9)	0.0295 (3)
H15A	1.4276	0.3701	1.2088	0.035*
C16	1.41856 (12)	0.46848 (10)	1.11962 (10)	0.0319 (3)
H16A	1.4971	0.4890	1.1314	0.038*
C17	1.34442 (12)	0.50974 (9)	1.05683 (10)	0.0300 (3)
H17A	1.3718	0.5590	1.0263	0.036*
C18	1.23007 (11)	0.47867 (8)	1.03889 (9)	0.0236 (2)
H18A	1.1793	0.5074	0.9966	0.028*
C19	0.67082 (9)	0.14484 (8)	1.01828 (7)	0.01766 (19)
C20	0.57348 (10)	0.19687 (9)	1.03556 (9)	0.0239 (2)
H20A	0.5620	0.2500	1.0047	0.029*
C21	0.49293 (15)	0.17194 (11)	1.09739 (13)	0.0437 (3)
H21A	0.4269	0.2079	1.1084	0.052*
C22	0.50910 (15)	0.09519 (11)	1.14248 (13)	0.0437 (3)
H22A	0.4536	0.0778	1.1841	0.052*
C23	0.60654 (14)	0.04303 (10)	1.12728 (11)	0.0371 (2)
H23A	0.6186	−0.0092	1.1596	0.045*
C24	0.68645 (15)	0.06729 (10)	1.06466 (11)	0.0371 (2)
H24A	0.7519	0.0309	1.0535	0.045*
C25	0.98054 (10)	0.27898 (7)	0.85111 (6)	0.01490 (17)
C26	0.91211 (11)	0.34901 (7)	0.82466 (7)	0.0203 (2)
H26A	0.8285	0.3478	0.8292	0.024*
C27	0.96887 (15)	0.42305 (8)	0.79049 (8)	0.0287 (3)
H27A	0.9220	0.4714	0.7717	0.034*
C28	1.08990 (15)	0.42668 (8)	0.78384 (8)	0.0307 (3)
H28A	1.1247	0.4764	0.7588	0.037*
C29	1.16320 (12)	0.35705 (8)	0.81394 (8)	0.0248 (2)
C30	1.28876 (13)	0.35283 (10)	0.81486 (9)	0.0326 (3)
H30A	1.3324	0.4002	0.7930	0.039*
C31	1.34778 (12)	0.28063 (11)	0.84717 (9)	0.0328 (3)
H31A	1.4318	0.2791	0.8463	0.039*
C32	1.28735 (10)	0.20819 (9)	0.88192 (8)	0.0243 (2)
H32A	1.3300	0.1594	0.9047	0.029*
C33	1.16550 (9)	0.21092 (7)	0.88160 (7)	0.01648 (18)
C34	1.10499 (10)	0.28405 (7)	0.84706 (7)	0.01705 (19)
H1O2	1.0163 (18)	0.0606 (13)	0.8458 (13)	0.037 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01626 (12)	0.03024 (16)	0.01985 (13)	−0.00226 (10)	−0.00317 (9)	−0.00495 (11)
O1	0.0178 (3)	0.0163 (3)	0.0153 (3)	0.0038 (3)	0.0011 (3)	−0.0018 (3)
O2	0.0178 (3)	0.0134 (3)	0.0199 (3)	0.0030 (3)	−0.0001 (3)	−0.0043 (3)
N1	0.0145 (3)	0.0147 (4)	0.0130 (3)	0.0011 (3)	−0.0001 (3)	0.0010 (3)
N2	0.0152 (3)	0.0138 (4)	0.0102 (3)	−0.0011 (3)	0.0004 (3)	0.0001 (3)
C1	0.0167 (4)	0.0163 (4)	0.0130 (4)	0.0018 (3)	−0.0019 (3)	−0.0004 (3)
C2	0.0160 (4)	0.0155 (4)	0.0109 (4)	0.0012 (3)	0.0005 (3)	−0.0008 (3)
C3	0.0158 (4)	0.0135 (4)	0.0092 (3)	0.0009 (3)	0.0008 (3)	0.0007 (3)
C4	0.0132 (4)	0.0113 (4)	0.0101 (3)	0.0010 (3)	0.0012 (3)	0.0010 (3)
C5	0.0161 (4)	0.0135 (4)	0.0127 (4)	0.0012 (3)	0.0014 (3)	0.0037 (3)
C6	0.0131 (4)	0.0139 (4)	0.0137 (4)	0.0008 (3)	0.0008 (3)	0.0002 (3)
C7	0.0141 (4)	0.0150 (4)	0.0141 (4)	−0.0011 (3)	0.0008 (3)	−0.0008 (3)
C8	0.0236 (5)	0.0274 (6)	0.0166 (4)	0.0053 (4)	−0.0042 (4)	0.0018 (4)
C9	0.0213 (4)	0.0184 (5)	0.0104 (4)	0.0016 (4)	−0.0005 (3)	0.0004 (3)
C10	0.0142 (4)	0.0100 (4)	0.0107 (4)	0.0005 (3)	0.0010 (3)	0.0008 (3)
C11	0.0138 (4)	0.0123 (4)	0.0126 (4)	0.0009 (3)	0.0011 (3)	−0.0005 (3)
C12	0.0169 (4)	0.0162 (4)	0.0161 (4)	0.0010 (4)	0.0006 (3)	−0.0019 (4)
C13	0.0181 (4)	0.0170 (5)	0.0186 (4)	−0.0004 (4)	0.0002 (3)	−0.0034 (4)
C14	0.0250 (5)	0.0230 (5)	0.0201 (5)	−0.0039 (4)	−0.0055 (4)	−0.0011 (4)
C15	0.0257 (6)	0.0306 (7)	0.0309 (6)	−0.0037 (5)	−0.0110 (5)	−0.0013 (5)
C16	0.0223 (5)	0.0316 (7)	0.0411 (7)	−0.0075 (5)	−0.0057 (5)	−0.0033 (6)
C17	0.0252 (6)	0.0250 (6)	0.0397 (7)	−0.0075 (5)	−0.0003 (5)	0.0024 (5)
C18	0.0215 (5)	0.0187 (5)	0.0303 (6)	−0.0014 (4)	−0.0015 (4)	0.0022 (4)
C19	0.0151 (4)	0.0200 (5)	0.0182 (4)	−0.0011 (4)	0.0048 (3)	−0.0026 (4)
C20	0.0164 (4)	0.0243 (5)	0.0313 (6)	0.0003 (4)	0.0055 (4)	−0.0074 (5)
C21	0.0380 (5)	0.0378 (6)	0.0585 (7)	−0.0036 (5)	0.0341 (5)	−0.0087 (5)
C22	0.0380 (5)	0.0378 (6)	0.0585 (7)	−0.0036 (5)	0.0341 (5)	−0.0087 (5)
C23	0.0419 (6)	0.0308 (5)	0.0411 (5)	0.0034 (4)	0.0271 (5)	0.0101 (4)
C24	0.0419 (6)	0.0308 (5)	0.0411 (5)	0.0034 (4)	0.0271 (5)	0.0101 (4)
C25	0.0229 (4)	0.0109 (4)	0.0112 (4)	−0.0011 (3)	0.0034 (3)	0.0004 (3)
C26	0.0339 (6)	0.0132 (4)	0.0143 (4)	0.0035 (4)	0.0043 (4)	0.0025 (4)
C27	0.0562 (8)	0.0124 (5)	0.0183 (5)	0.0024 (5)	0.0106 (5)	0.0031 (4)
C28	0.0574 (9)	0.0147 (5)	0.0212 (5)	−0.0100 (5)	0.0148 (5)	0.0009 (4)
C29	0.0382 (6)	0.0201 (5)	0.0169 (5)	−0.0129 (5)	0.0103 (4)	−0.0033 (4)
C30	0.0378 (7)	0.0359 (7)	0.0252 (6)	−0.0224 (6)	0.0142 (5)	−0.0062 (5)
C31	0.0235 (5)	0.0487 (9)	0.0271 (6)	−0.0174 (6)	0.0101 (5)	−0.0098 (6)
C32	0.0169 (4)	0.0349 (7)	0.0213 (5)	−0.0056 (4)	0.0048 (4)	−0.0065 (5)
C33	0.0169 (4)	0.0192 (5)	0.0137 (4)	−0.0037 (4)	0.0040 (3)	−0.0030 (3)
C34	0.0238 (5)	0.0152 (4)	0.0127 (4)	−0.0053 (4)	0.0061 (3)	−0.0020 (3)

Geometric parameters (Å, º) top

S1—C8	1.8126 (13)	C14—C15	1.3906 (17)
S1—C7	1.8159 (10)	C14—H14A	0.9500
O1—C3	1.2234 (12)	C15—C16	1.388 (2)
O2—C11	1.4042 (12)	C15—H15A	0.9500
O2—H1O2	0.86 (2)	C16—C17	1.392 (2)
N1—C5	1.4707 (13)	C16—H16A	0.9500
N1—C1	1.4735 (14)	C17—C18	1.3917 (17)
N1—C11	1.4812 (13)	C17—H17A	0.9500
N2—C10	1.4784 (13)	C18—H18A	0.9500
N2—C9	1.4815 (13)	C19—C24	1.3956 (19)
N2—C7	1.4867 (13)	C19—C20	1.3962 (15)
C1—C2	1.5272 (15)	C20—C21	1.3931 (18)
C1—H1A	0.9900	C20—H20A	0.9500
C1—H1B	0.9900	C21—C22	1.376 (3)
C2—C12	1.3465 (15)	C21—H21A	0.9500
C2—C3	1.4980 (14)	C22—C23	1.392 (2)
C3—C4	1.5130 (14)	C22—H22A	0.9500
C4—C6	1.5304 (14)	C23—C24	1.3938 (18)
C4—C5	1.5527 (14)	C23—H23A	0.9500
C4—C10	1.5663 (13)	C24—H24A	0.9500
C5—H5A	0.9900	C25—C26	1.3770 (15)
C5—H5B	0.9900	C25—C34	1.4117 (15)
C6—C19	1.5114 (14)	C26—C27	1.4206 (17)
C6—C7	1.5369 (14)	C26—H26A	0.9500
C6—H6A	1.0000	C27—C28	1.376 (2)
C7—H7A	1.0000	C27—H27A	0.9500
C8—C9	1.5233 (16)	C28—C29	1.418 (2)
C8—H8A	0.9900	C28—H28A	0.9500
C8—H8B	0.9900	C29—C34	1.4093 (15)
C9—H9A	0.9900	C29—C30	1.419 (2)
C9—H9B	0.9900	C30—C31	1.376 (2)
C10—C25	1.5183 (14)	C30—H30A	0.9500
C10—C11	1.6147 (14)	C31—C32	1.4244 (19)
C11—C33	1.5086 (14)	C31—H31A	0.9500
C12—C13	1.4686 (15)	C32—C33	1.3763 (15)
C12—H12A	0.9500	C32—H32A	0.9500
C13—C14	1.3992 (16)	C33—C34	1.4074 (16)
C13—C18	1.4001 (17)

C8—S1—C7	90.98 (5)	C2—C12—H12A	116.6
C11—O2—H1O2	103.5 (14)	C13—C12—H12A	116.6
C5—N1—C1	108.19 (8)	C14—C13—C18	118.93 (11)
C5—N1—C11	103.02 (8)	C14—C13—C12	122.13 (11)
C1—N1—C11	115.73 (8)	C18—C13—C12	118.93 (10)
C10—N2—C9	119.72 (8)	C15—C14—C13	120.23 (12)
C10—N2—C7	109.47 (7)	C15—C14—H14A	119.9
C9—N2—C7	112.04 (8)	C13—C14—H14A	119.9
N1—C1—C2	114.81 (8)	C16—C15—C14	120.42 (12)
N1—C1—H1A	108.6	C16—C15—H15A	119.8
C2—C1—H1A	108.6	C14—C15—H15A	119.8
N1—C1—H1B	108.6	C15—C16—C17	119.90 (12)
C2—C1—H1B	108.6	C15—C16—H16A	120.1
H1A—C1—H1B	107.5	C17—C16—H16A	120.1
C12—C2—C3	116.76 (9)	C18—C17—C16	119.85 (13)
C12—C2—C1	124.91 (9)	C18—C17—H17A	120.1
C3—C2—C1	117.91 (9)	C16—C17—H17A	120.1
O1—C3—C2	122.88 (9)	C17—C18—C13	120.63 (12)
O1—C3—C4	122.07 (9)	C17—C18—H18A	119.7
C2—C3—C4	115.01 (8)	C13—C18—H18A	119.7
C3—C4—C6	115.06 (8)	C24—C19—C20	118.66 (11)
C3—C4—C5	108.05 (8)	C24—C19—C6	121.99 (10)
C6—C4—C5	118.17 (8)	C20—C19—C6	119.33 (11)
C3—C4—C10	109.18 (8)	C21—C20—C19	120.91 (14)
C6—C4—C10	103.77 (7)	C21—C20—H20A	119.5
C5—C4—C10	101.31 (7)	C19—C20—H20A	119.5
N1—C5—C4	103.75 (8)	C22—C21—C20	119.88 (14)
N1—C5—H5A	111.0	C22—C21—H21A	120.1
C4—C5—H5A	111.0	C20—C21—H21A	120.1
N1—C5—H5B	111.0	C21—C22—C23	120.14 (13)
C4—C5—H5B	111.0	C21—C22—H22A	119.9
H5A—C5—H5B	109.0	C23—C22—H22A	119.9
C19—C6—C4	118.24 (8)	C22—C23—C24	120.08 (15)
C19—C6—C7	114.68 (9)	C22—C23—H23A	120.0
C4—C6—C7	101.39 (8)	C24—C23—H23A	120.0
C19—C6—H6A	107.3	C23—C24—C19	120.31 (13)
C4—C6—H6A	107.3	C23—C24—H24A	119.8
C7—C6—H6A	107.3	C19—C24—H24A	119.8
N2—C7—C6	105.60 (8)	C26—C25—C34	119.30 (10)
N2—C7—S1	107.70 (7)	C26—C25—C10	131.87 (10)
C6—C7—S1	114.60 (7)	C34—C25—C10	108.82 (9)
N2—C7—H7A	109.6	C25—C26—C27	118.75 (12)
C6—C7—H7A	109.6	C25—C26—H26A	120.6
S1—C7—H7A	109.6	C27—C26—H26A	120.6
C9—C8—S1	103.36 (8)	C28—C27—C26	121.79 (12)
C9—C8—H8A	111.1	C28—C27—H27A	119.1
S1—C8—H8A	111.1	C26—C27—H27A	119.1
C9—C8—H8B	111.1	C27—C28—C29	120.75 (11)
S1—C8—H8B	111.1	C27—C28—H28A	119.6
H8A—C8—H8B	109.1	C29—C28—H28A	119.6
N2—C9—C8	108.59 (8)	C34—C29—C28	116.47 (12)
N2—C9—H9A	110.0	C34—C29—C30	116.29 (13)
C8—C9—H9A	110.0	C28—C29—C30	127.24 (12)
N2—C9—H9B	110.0	C31—C30—C29	120.46 (12)
C8—C9—H9B	110.0	C31—C30—H30A	119.8
H9A—C9—H9B	108.4	C29—C30—H30A	119.8
N2—C10—C25	116.53 (8)	C30—C31—C32	122.35 (12)
N2—C10—C4	104.46 (7)	C30—C31—H31A	118.8
C25—C10—C4	117.30 (8)	C32—C31—H31A	118.8
N2—C10—C11	111.24 (8)	C33—C32—C31	118.13 (13)
C25—C10—C11	103.53 (8)	C33—C32—H32A	120.9
C4—C10—C11	103.05 (7)	C31—C32—H32A	120.9
O2—C11—N1	108.55 (8)	C32—C33—C34	119.53 (11)
O2—C11—C33	112.33 (8)	C32—C33—C11	131.99 (11)
N1—C11—C33	115.05 (8)	C34—C33—C11	108.47 (9)
O2—C11—C10	109.85 (8)	C33—C34—C29	123.21 (11)
N1—C11—C10	105.79 (7)	C33—C34—C25	113.91 (9)
C33—C11—C10	104.94 (8)	C29—C34—C25	122.84 (11)
C2—C12—C13	126.86 (10)

C5—N1—C1—C2	−50.94 (11)	C4—C10—C11—N1	−6.12 (10)
C11—N1—C1—C2	64.00 (11)	N2—C10—C11—C33	120.40 (8)
N1—C1—C2—C12	−148.69 (10)	C25—C10—C11—C33	−5.50 (9)
N1—C1—C2—C3	23.57 (13)	C4—C10—C11—C33	−128.18 (8)
C12—C2—C3—O1	−25.83 (14)	C3—C2—C12—C13	−176.07 (10)
C1—C2—C3—O1	161.28 (9)	C1—C2—C12—C13	−3.73 (17)
C12—C2—C3—C4	151.68 (9)	C2—C12—C13—C14	−39.53 (17)
C1—C2—C3—C4	−21.21 (12)	C2—C12—C13—C18	141.52 (12)
O1—C3—C4—C6	−3.72 (13)	C18—C13—C14—C15	−1.72 (18)
C2—C3—C4—C6	178.74 (8)	C12—C13—C14—C15	179.33 (12)
O1—C3—C4—C5	−138.19 (9)	C13—C14—C15—C16	−0.1 (2)
C2—C3—C4—C5	44.28 (10)	C14—C15—C16—C17	1.4 (2)
O1—C3—C4—C10	112.43 (10)	C15—C16—C17—C18	−1.0 (2)
C2—C3—C4—C10	−65.10 (10)	C16—C17—C18—C13	−0.8 (2)
C1—N1—C5—C4	74.41 (9)	C14—C13—C18—C17	2.17 (19)
C11—N1—C5—C4	−48.61 (9)	C12—C13—C18—C17	−178.84 (12)
C3—C4—C5—N1	−71.09 (9)	C4—C6—C19—C24	−62.92 (16)
C6—C4—C5—N1	156.08 (8)	C7—C6—C19—C24	56.65 (15)
C10—C4—C5—N1	43.59 (9)	C4—C6—C19—C20	118.64 (11)
C3—C4—C6—C19	−76.10 (11)	C7—C6—C19—C20	−121.79 (11)
C5—C4—C6—C19	53.56 (12)	C24—C19—C20—C21	−0.4 (2)
C10—C4—C6—C19	164.69 (9)	C6—C19—C20—C21	178.11 (13)
C3—C4—C6—C7	157.62 (8)	C19—C20—C21—C22	0.2 (3)
C5—C4—C6—C7	−72.71 (10)	C20—C21—C22—C23	0.8 (3)
C10—C4—C6—C7	38.41 (9)	C21—C22—C23—C24	−1.7 (3)
C10—N2—C7—C6	18.07 (10)	C22—C23—C24—C19	1.4 (3)
C9—N2—C7—C6	−117.21 (9)	C20—C19—C24—C23	−0.4 (2)
C10—N2—C7—S1	140.93 (7)	C6—C19—C24—C23	−178.88 (14)
C9—N2—C7—S1	5.65 (10)	N2—C10—C25—C26	64.02 (14)
C19—C6—C7—N2	−163.63 (8)	C4—C10—C25—C26	−60.86 (15)
C4—C6—C7—N2	−35.04 (9)	C11—C10—C25—C26	−173.53 (11)
C19—C6—C7—S1	78.03 (10)	N2—C10—C25—C34	−117.11 (9)
C4—C6—C7—S1	−153.39 (7)	C4—C10—C25—C34	118.01 (9)
C8—S1—C7—N2	−25.83 (8)	C11—C10—C25—C34	5.34 (10)
C8—S1—C7—C6	91.32 (8)	C34—C25—C26—C27	2.64 (16)
C7—S1—C8—C9	37.74 (8)	C10—C25—C26—C27	−178.58 (10)
C10—N2—C9—C8	−107.21 (10)	C25—C26—C27—C28	−0.48 (18)
C7—N2—C9—C8	22.98 (12)	C26—C27—C28—C29	−2.16 (19)
S1—C8—C9—N2	−40.56 (10)	C27—C28—C29—C34	2.45 (18)
C9—N2—C10—C25	6.48 (13)	C27—C28—C29—C30	−177.20 (12)
C7—N2—C10—C25	−124.83 (9)	C34—C29—C30—C31	−0.30 (18)
C9—N2—C10—C4	137.64 (9)	C28—C29—C30—C31	179.35 (13)
C7—N2—C10—C4	6.32 (10)	C29—C30—C31—C32	−0.9 (2)
C9—N2—C10—C11	−111.85 (9)	C30—C31—C32—C33	0.93 (19)
C7—N2—C10—C11	116.84 (8)	C31—C32—C33—C34	0.29 (16)
C3—C4—C10—N2	−151.48 (8)	C31—C32—C33—C11	−178.52 (11)
C6—C4—C10—N2	−28.32 (9)	O2—C11—C33—C32	−57.92 (15)
C5—C4—C10—N2	94.68 (8)	N1—C11—C33—C32	66.94 (15)
C3—C4—C10—C25	−20.77 (11)	C10—C11—C33—C32	−177.23 (11)
C6—C4—C10—C25	102.38 (10)	O2—C11—C33—C34	123.18 (9)
C5—C4—C10—C25	−134.61 (9)	N1—C11—C33—C34	−111.96 (10)
C3—C4—C10—C11	92.17 (9)	C10—C11—C33—C34	3.87 (10)
C6—C4—C10—C11	−144.67 (8)	C32—C33—C34—C29	−1.56 (16)
C5—C4—C10—C11	−21.66 (9)	C11—C33—C34—C29	177.50 (10)
C5—N1—C11—O2	−84.52 (9)	C32—C33—C34—C25	−179.63 (10)
C1—N1—C11—O2	157.64 (8)	C11—C33—C34—C25	−0.57 (12)
C5—N1—C11—C33	148.67 (9)	C28—C29—C34—C33	−178.14 (10)
C1—N1—C11—C33	30.82 (12)	C30—C29—C34—C33	1.55 (16)
C5—N1—C11—C10	33.32 (10)	C28—C29—C34—C25	−0.24 (16)
C1—N1—C11—C10	−84.52 (9)	C30—C29—C34—C25	179.45 (10)
N2—C10—C11—O2	−0.56 (10)	C26—C25—C34—C33	175.75 (9)
C25—C10—C11—O2	−126.46 (8)	C10—C25—C34—C33	−3.29 (12)
C4—C10—C11—O2	110.86 (8)	C26—C25—C34—C29	−2.33 (16)
N2—C10—C11—N1	−117.53 (8)	C10—C25—C34—C29	178.64 (9)
C25—C10—C11—N1	116.56 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1O2···N2	0.86 (2)	1.95 (2)	2.6277 (12)	134.4 (18)
C8—H8A···O1ⁱ	0.99	2.55	3.1981 (14)	123
C15—H15A···S1ⁱⁱ	0.95	2.72	3.4970 (13)	139
C18—H18A···O1ⁱⁱⁱ	0.95	2.60	3.2550 (15)	127
C24—H24A···O2^iv	0.95	2.59	3.4077 (18)	145

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

Experimental details

Crystal data
Chemical formula	C₃₄H₂₈N₂O₂S
M_r	528.64
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	11.2911 (1), 15.4317 (2), 15.1920 (2)
β (°)	92.790 (1)
V (Å³)	2643.93 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.16
Crystal size (mm)	0.45 × 0.41 × 0.31

Data collection
Diffractometer	Bruker SMART APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.932, 0.953
No. of measured, independent and observed [I > 2σ(I)] reflections	37231, 9686, 8170
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.761

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.129, 1.04
No. of reflections	9686
No. of parameters	344
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.18, −1.12

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), 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
O2—H1O2···N2	0.86 (2)	1.95 (2)	2.6277 (12)	134.4 (18)
C8—H8A···O1ⁱ	0.99	2.55	3.1981 (14)	123.2
C15—H15A···S1ⁱⁱ	0.95	2.72	3.4970 (13)	139.2
C18—H18A···O1ⁱⁱⁱ	0.95	2.60	3.2550 (15)	127
C24—H24A···O2^iv	0.95	2.59	3.4077 (18)	145

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

Footnotes

‡Additional correspondence email: ohasnah@usm.my.

§Thomson Reuters ResearcherID: A-5599-2009.

Acknowledgements

The authors thank the Malaysian Government and Universiti Sains Malaysia (USM) for the Research University grants Nos. 203/PKIMIA/6711179 and 1001/PFIZIK/811151. RSK and AIM thank the Research Center, Deanship of Scientific Research, College of Science, King Saud University. SA thanks the Malaysian Government and USM for an Academic Staff Training Scheme (ASTS) Fellowship.

References

Aicher, T. D., Balkan, B., Bell, P. A., Brand, L. J., Cheon, S. H., Deems, R. O., Fell, J. B., Fillers, W. S., Fraser, J. D., Gao, J. P., Knorr, D. C., Kahle, G. G., Leone, C. L., Nadelson, J., Simpson, R. & Smith, H. C. J. (1998). Med. Chem. 41, 4556–4566. Web of Science CSD CrossRef CAS Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2009). SADABS, APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Corey, E. J., Czako, B. & Kurti, L. (2007). In Molecules and Medicine. Hoboken: Wiley. Google Scholar
Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105–107. CrossRef CAS Web of Science IUCr Journals Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Kumar, R. S., Osman, H., Ali, M. A., Quah, C. K. & Fun, H.-K. (2010a). Acta Cryst. E66, o1540–o1541. Web of Science CSD CrossRef IUCr Journals Google Scholar
Kumar, R. S., Osman, H., Ali, M. A., Rosli, M. M. & Fun, H.-K. (2010b). Acta Cryst. E66, o2376–o2377. Web of Science CSD CrossRef IUCr Journals Google Scholar
Kumar, R. S., Osman, H., Yeap, C. S. & Fun, H.-K. (2011). Acta Cryst. E67, o211–o212. Web of Science CSD CrossRef IUCr Journals Google Scholar
Lalezari, I. & Schwartz, E. L. J. (1988). Med. Chem. 31, 1427–1429. CrossRef CAS Web of Science Google Scholar
Lee, H. K., Chun, J. S. & Pak, C. S. (2001). Tetrahedron Lett. 42, 3483–3486. Web of Science CrossRef CAS Google Scholar
Padwa, A. (1984). In 1,3-Dipolar Cycloaddition Chemistry. New York: Wiley. 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

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.