(7-Chloro-2-oxo-2H-chromen-4-yl)methyl pyrrolidine-1-carbodi­thio­ate

Kotresh, O.; Devarajegowda, H.C.; Shirahatti, A.; Kumar, K.M.; Mahabhaleshwaraiah, N.M.

doi:10.1107/S1600536813028080

organic compounds

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ISSN: 2056-9890

Volume 69| Part 11| November 2013| Pages o1684-o1685

doi:10.1107/S1600536813028080

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(7-Chloro-2-oxo-2H-chromen-4-yl)methyl pyrrolidine-1-carbodithioate

O. Kotresh,^a H. C. Devarajegowda,^b ^* Arunkumar Shirahatti,^a K. Mahesh Kumar ^a and N. M. Mahabhaleshwaraiah ^a

^aDepartment of Chemistry, Karnatak University's Karnatak Science College, Dharwad, Karnataka 580 001, India, and ^bDepartment of Physics, Yuvaraja's College (Constituent College), University of Mysore, Mysore 570 005, Karnataka, India
^*Correspondence e-mail: devarajegowda@yahoo.com

(Received 7 August 2013; accepted 13 October 2013; online 23 October 2013)

In the title compound, C₁₅H₁₄ClNO₂S₂, the 2H-chromene ring system is essentially planar, with a maximum deviation of 0.0133 (10) Å. Three C atoms and their attached H atoms of the pyrrolidine ring are disordered [occupany ratio 0.874 (7):0.126 (7)] with both disorder components adopting a twisted conformation. The dihedral angle between the 2H-chromene ring system and the major occupancy component of the pyrrolidine ring is 89.45 (7)°. In the crystal, inversion dimers linked by pairs of C—H⋯S and C—H⋯O interactions generate R²₂(24) and R²₂(10) loops, respectively. Further C—H⋯O hydrogen bonds link the dimers into [100] chains. C—H⋯π interactions also occur and there is very weak π–π stacking [interplanar spacing = 3.650 (5) Å; centroid–centroid distance = 4.095 (7) Å] between inversion-related chlorobenzene rings.

CCDC reference: 966208

Related literature

For biological applications of coumarins and dithiocarbamates, see: Brillon (1992 ); Burns et al. (2010 ); Kawaii et al. (2001 ); Khan et al. (2004 ); Yu et al. (2003 ). For details of the synthesis and a related structure with comparison bond lengths, see: Mahabaleshwaraiah et al. (2012 ).

Experimental

Crystal data

C₁₅H₁₄ClNO₂S₂
M_r = 339.84
Triclinic, $[P \overline 1]$
a = 7.9073 (2) Å
b = 9.2891 (2) Å
c = 10.8865 (2) Å
α = 84.474 (1)°
β = 79.798 (1)°
γ = 72.437 (1)°
V = 749.52 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.54 mm⁻¹
T = 296 K
0.22 × 0.18 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ) T_min = 0.770, T_max = 1.000
16446 measured reflections
3417 independent reflections
3136 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.102
S = 1.18
3417 reflections
201 parameters
6 restraints
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg4 is the centroid of the C7–C12 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9⋯S3ⁱ	0.93	2.87	3.7910 (16)	170
C21—H21B⋯O5ⁱⁱ	0.97	2.60	3.3434 (19)	134
C16—H16B⋯Cg4ⁱⁱ	0.97	2.93	3.761 (1)	144
Symmetry codes: (i) -x+1, -y+1, -z; (ii) -x, -y+1, -z+1.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: SHELXL97.

Supporting information

CCDC reference: 966208

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813028080/pk2494sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813028080/pk2494Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813028080/pk2494Isup3.cml

checkCIF report

Comment top

Coumarin derivatives are an interesting class of heterocyclic systems, since the coumarin ring is an essential core moiety for a variety of natural and synthetic biologically active compounds. The biological activities include anticoagulation, antibiotic, antifungal, antipsoriasis, antitumor, anti-HIV, anti-inflammatory properties (Khan et al., 2004; Kawaii et al., 2001; Yu et al., 2003). For a number of years, due to their important biological, biomedical and laser dye properties, coumarins have been the subject of a number of investigations, particularly on their photophysical characteristics, solvent effects on electronic absorption, structural properties and fluorescence spectra. The molecular manipulation of promising lead compounds is still a major line of approach to develop new drugs. It involves an effort to combine the separate pharmacophoric groups of similar activity into one compound, thereby affecting biological activity. The functionalization of the carbamate moiety is an effective technique for preparation of derivatives, which may have important therapeutic and biological properties (Brillon, 1992). In this regard, the introduction of new strategies to prepare dithiocarbamate derivatives with different substitution patterns at the thiol group has become a field of increasing interest in synthetic organic chemistry. There are several publications illustrating intramolecular or intermolecular oxygen sulfur exchange (Burns et al., 2010).

The asymmetric unit of (7-chloro-2-oxo-2H-chromen-4-yl)methyl pyrrolidine-1-carbodithioate is shown in Fig. 1. The 2H- chromene (O4/C7–C15) ring system is planar, with a maximum deviation of 0.0133 (10) Å for atom C10, and the pyrrolidine ring adopts a twisted conformation. The dihedral angle between the 2H-chromene ring (O4/C7–C15) and the pyrrolidine ring (N6/C18–C21) is 89.45 (7)°. In the crystal, inversion dimers linked by pairs of C13—H13···S2 and C9—H9···O5 interactions generate R²₂(24) and R²₂(10) loops, respectively. Further C9—H9···O5 hydrogen bonds link the dimers into [100] chains. C16—H16B···π Cg4(C7–C12) (Table 1) interactions also occur and there is π-π Cg4 (C7–C12) stacking of inversion-related molecules, with interplanar spacings of 3.650 (5) Å and chlorobenzene ring centroid–centroid distances of 4.095 (7) Å. The packing of the molecules is depicted in Fig. 2. Disorder is observed at the pyrrolidine flap carbon (C20, C20') atom [occupancy ratio 0.876 (5):0.124 (5)].

Related literature top

For biological applications of coumarins and dithiocarbamates, see: Brillon (1992); Burns et al. (2010); Kawaii et al. (2001); Khan et al. (2004); Yu et al. (2003). For details of the synthesis and a related structure with comparison bond lengths, see: Mahabaleshwaraiah et al. (2012).

Experimental top

All the chemicals used were of analytical reagent grade and were used directly without further purification. The title compound was synthesized according to the reported method (Mahabaleshwaraiah et al., 2012). The compound is recrystallized by ethanol-chloroform mixture. Colourless needles of the title compound were grown from a mixed solution of Ethanol/Chloroform (V/V = 2/1) by slow evaporation at room temperature. Yield = 74%, m.p. 445–447 K.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen atoms are shown as spheres of arbitrary radius. Only the major conformation of disorder at atom C20 is shown.
	Fig. 2. A packing diagram of the title compound.

(7-Chloro-2-oxo-2H-chromen-4-yl)methyl pyrrolidine-1-carbodithioate top

Crystal data top

C₁₅H₁₄ClNO₂S₂	Z = 2
M_r = 339.84	F(000) = 352
Triclinic, P1	D_x = 1.506 Mg m⁻³
Hall symbol: -P 1	Melting point: 447 K
a = 7.9073 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.2891 (2) Å	Cell parameters from 3417 reflections
c = 10.8865 (2) Å	θ = 1.9–27.5°
α = 84.474 (1)°	µ = 0.54 mm⁻¹
β = 79.798 (1)°	T = 296 K
γ = 72.437 (1)°	Plate, colourless
V = 749.52 (3) Å³	0.22 × 0.18 × 0.12 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	3417 independent reflections
Radiation source: fine-focus sealed tube	3136 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ω and ϕ scans	θ_max = 27.5°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	h = −10→10
T_min = 0.770, T_max = 1.000	k = −12→12
16446 measured reflections	l = −14→14

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)] = 0.031	H-atom parameters constrained
wR(F²) = 0.102	w = 1/[σ²(F_o²) + (0.0617P)² + 0.0857P] where P = (F_o² + 2F_c²)/3
S = 1.18	(Δ/σ)_max = 0.004
3417 reflections	Δρ_max = 0.28 e Å⁻³
201 parameters	Δρ_min = −0.31 e Å⁻³
6 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.049 (5)

Crystal data top

C₁₅H₁₄ClNO₂S₂	γ = 72.437 (1)°
M_r = 339.84	V = 749.52 (3) Å³
Triclinic, P1	Z = 2
a = 7.9073 (2) Å	Mo Kα radiation
b = 9.2891 (2) Å	µ = 0.54 mm⁻¹
c = 10.8865 (2) Å	T = 296 K
α = 84.474 (1)°	0.22 × 0.18 × 0.12 mm
β = 79.798 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3417 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	3136 reflections with I > 2σ(I)
T_min = 0.770, T_max = 1.000	R_int = 0.023
16446 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	6 restraints
wR(F²) = 0.102	H-atom parameters constrained
S = 1.18	Δρ_max = 0.28 e Å⁻³
3417 reflections	Δρ_min = −0.31 e Å⁻³
201 parameters

Special details top

Experimental. IR (KBr, cm^-1): 1731 (C=O), 1374 (C=S), 866(C—N). GCMS: m/e:339. ¹H NMR (400 MHz, CDCl₃, \?, p.p.m): 1.89 (m, 2H, CH₂), 2.00 (m, 2H, CH₂), 3.63(m, 2H, N—CH₂), 3.77 (m, 2H, N—CH₂), 4.81 (s,2H, C4—CH₂),6.60 (s,1H, C3—H, Ar—H), 7.46 (m, H, Ar—H), 7.62 (m, 1H, Ar—H), 7.91 (s, 1H, Ar—H). Mol. Formula: C₁₅H₁₄Cl N O₂S₂. Elemental analysis: C, 53.01; H, 4.15; N, 4.12 (calculated); C, 52.98; H, 4.10; N, 4.09 (found).

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	Occ. (<1)
Cl1	−0.28700 (7)	1.07931 (5)	−0.14180 (5)	0.06885 (16)
S2	0.38730 (4)	0.30580 (4)	0.21169 (3)	0.04235 (13)
S3	0.54060 (5)	0.56231 (4)	0.24009 (4)	0.04455 (13)
O4	−0.19899 (13)	0.79324 (11)	0.26803 (9)	0.0409 (2)
O5	−0.17968 (15)	0.68451 (13)	0.45600 (9)	0.0526 (3)
N6	0.61026 (14)	0.29726 (11)	0.36235 (10)	0.0338 (2)
C7	−0.1734 (2)	0.92725 (17)	−0.05374 (14)	0.0459 (3)
C8	−0.0243 (2)	0.8208 (2)	−0.11117 (14)	0.0520 (4)
H8	0.0130	0.8294	−0.1968	0.062*
C9	0.06851 (19)	0.70194 (18)	−0.04044 (13)	0.0461 (3)
H9	0.1686	0.6303	−0.0791	0.055*
C10	0.01464 (16)	0.68708 (14)	0.08890 (11)	0.0334 (3)
C11	−0.13752 (16)	0.79680 (14)	0.14228 (12)	0.0345 (3)
C12	−0.23300 (19)	0.91664 (16)	0.07278 (14)	0.0427 (3)
H12	−0.3345	0.9880	0.1103	0.051*
C13	0.10823 (15)	0.56837 (14)	0.17036 (11)	0.0324 (2)
C14	0.04298 (16)	0.56563 (14)	0.29272 (12)	0.0354 (3)
H14	0.1019	0.4881	0.3444	0.043*
C15	−0.11598 (17)	0.67905 (15)	0.34721 (12)	0.0370 (3)
C16	0.27739 (18)	0.45665 (17)	0.11144 (13)	0.0425 (3)
H16A	0.3621	0.5117	0.0751	0.051*
H16B	0.2488	0.4124	0.0435	0.051*
C17	0.52248 (15)	0.38901 (13)	0.27966 (11)	0.0327 (2)
C18	0.73425 (19)	0.33810 (16)	0.42944 (14)	0.0418 (3)
H18A	0.6702	0.4194	0.4850	0.050*
H18B	0.8263	0.3692	0.3714	0.050*
C19	0.8152 (2)	0.1946 (2)	0.50227 (18)	0.0558 (4)	0.874 (7)
H19A	0.8384	0.2173	0.5817	0.067*	0.874 (7)
H19B	0.9270	0.1359	0.4555	0.067*	0.874 (7)
C20	0.6762 (3)	0.1094 (2)	0.5219 (2)	0.0480 (6)	0.874 (7)
H20A	0.7317	0.0016	0.5335	0.058*	0.874 (7)
H20B	0.5860	0.1442	0.5941	0.058*	0.874 (7)
C21	0.59481 (19)	0.14500 (14)	0.40330 (14)	0.0413 (3)	0.874 (7)
H21A	0.6606	0.0722	0.3409	0.050*	0.874 (7)
H21B	0.4702	0.1451	0.4192	0.050*	0.874 (7)
C19'	0.8152 (2)	0.1946 (2)	0.50227 (18)	0.0558 (4)	0.126 (7)
H19C	0.9449	0.1723	0.4892	0.067*	0.126 (7)
H19D	0.7715	0.2069	0.5908	0.067*	0.126 (7)
C20'	0.765 (2)	0.0709 (13)	0.4603 (17)	0.052 (4)	0.126 (7)
H20C	0.7430	0.0024	0.5301	0.062*	0.126 (7)
H20D	0.8604	0.0147	0.3986	0.062*	0.126 (7)
C21'	0.59481 (19)	0.14500 (14)	0.40330 (14)	0.0413 (3)	0.126 (7)
H21C	0.5907	0.0899	0.3331	0.050*	0.126 (7)
H21D	0.4883	0.1506	0.4648	0.050*	0.126 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0754 (3)	0.0589 (3)	0.0702 (3)	−0.0126 (2)	−0.0342 (2)	0.0265 (2)
S2	0.0401 (2)	0.0358 (2)	0.0502 (2)	−0.00229 (14)	−0.01778 (15)	−0.00600 (14)
S3	0.0498 (2)	0.03124 (19)	0.0489 (2)	−0.00884 (14)	−0.00686 (15)	0.00535 (14)
O4	0.0416 (5)	0.0369 (5)	0.0365 (5)	−0.0022 (4)	−0.0011 (4)	−0.0042 (4)
O5	0.0544 (6)	0.0595 (7)	0.0336 (5)	−0.0059 (5)	0.0024 (4)	−0.0043 (5)
N6	0.0334 (5)	0.0290 (5)	0.0396 (5)	−0.0082 (4)	−0.0089 (4)	−0.0002 (4)
C7	0.0503 (8)	0.0430 (7)	0.0463 (8)	−0.0135 (6)	−0.0197 (6)	0.0118 (6)
C8	0.0541 (8)	0.0620 (10)	0.0353 (7)	−0.0124 (7)	−0.0084 (6)	0.0084 (6)
C9	0.0411 (7)	0.0555 (8)	0.0344 (7)	−0.0050 (6)	−0.0044 (5)	0.0005 (6)
C10	0.0314 (6)	0.0366 (6)	0.0319 (6)	−0.0091 (5)	−0.0064 (4)	−0.0009 (5)
C11	0.0342 (6)	0.0342 (6)	0.0348 (6)	−0.0092 (5)	−0.0062 (5)	−0.0012 (5)
C12	0.0413 (7)	0.0355 (6)	0.0483 (8)	−0.0050 (5)	−0.0109 (6)	0.0000 (5)
C13	0.0281 (5)	0.0350 (6)	0.0337 (6)	−0.0069 (4)	−0.0074 (4)	−0.0023 (5)
C14	0.0336 (6)	0.0368 (6)	0.0343 (6)	−0.0070 (5)	−0.0074 (5)	−0.0001 (5)
C15	0.0373 (6)	0.0393 (6)	0.0329 (6)	−0.0100 (5)	−0.0036 (5)	−0.0027 (5)
C16	0.0351 (6)	0.0494 (8)	0.0343 (6)	0.0026 (5)	−0.0071 (5)	−0.0051 (5)
C17	0.0295 (5)	0.0298 (6)	0.0342 (6)	−0.0028 (4)	−0.0015 (4)	−0.0042 (4)
C18	0.0424 (7)	0.0397 (7)	0.0484 (7)	−0.0152 (5)	−0.0158 (6)	0.0004 (6)
C19	0.0535 (9)	0.0533 (9)	0.0678 (10)	−0.0193 (7)	−0.0311 (8)	0.0153 (8)
C20	0.0510 (12)	0.0429 (10)	0.0519 (12)	−0.0158 (9)	−0.0173 (10)	0.0130 (8)
C21	0.0450 (7)	0.0286 (6)	0.0521 (8)	−0.0107 (5)	−0.0153 (6)	0.0037 (5)
C19'	0.0535 (9)	0.0533 (9)	0.0678 (10)	−0.0193 (7)	−0.0311 (8)	0.0153 (8)
C20'	0.045 (8)	0.042 (6)	0.062 (10)	−0.002 (5)	−0.018 (7)	0.011 (6)
C21'	0.0450 (7)	0.0286 (6)	0.0521 (8)	−0.0107 (5)	−0.0153 (6)	0.0037 (5)

Geometric parameters (Å, º) top

Cl1—C7	1.7320 (14)	C13—C14	1.3413 (17)
S2—C17	1.7822 (13)	C13—C16	1.5047 (17)
S2—C16	1.7934 (14)	C14—C15	1.4487 (17)
S3—C17	1.6678 (12)	C14—H14	0.9300
O4—C11	1.3699 (15)	C16—H16A	0.9700
O4—C15	1.3796 (16)	C16—H16B	0.9700
O5—C15	1.2015 (16)	C18—C19	1.509 (2)
N6—C17	1.3172 (16)	C18—H18A	0.9700
N6—C18	1.4731 (16)	C18—H18B	0.9700
N6—C21	1.4757 (16)	C19—C20	1.513 (2)
C7—C12	1.379 (2)	C19—H19A	0.9700
C7—C8	1.383 (2)	C19—H19B	0.9700
C8—C9	1.377 (2)	C20—C21	1.508 (2)
C8—H8	0.9300	C20—H20A	0.9700
C9—C10	1.4031 (18)	C20—H20B	0.9700
C9—H9	0.9300	C21—H21A	0.9700
C10—C11	1.3966 (17)	C21—H21B	0.9700
C10—C13	1.4498 (16)	C20'—H20C	0.9700
C11—C12	1.3837 (18)	C20'—H20D	0.9700
C12—H12	0.9300

C17—S2—C16	102.76 (7)	C13—C16—H16A	108.1
C11—O4—C15	121.50 (10)	S2—C16—H16A	108.1
C17—N6—C18	123.15 (11)	C13—C16—H16B	108.1
C17—N6—C21	125.66 (11)	S2—C16—H16B	108.1
C18—N6—C21	111.16 (10)	H16A—C16—H16B	107.3
C12—C7—C8	121.59 (13)	N6—C17—S3	123.58 (10)
C12—C7—Cl1	118.87 (12)	N6—C17—S2	112.65 (9)
C8—C7—Cl1	119.53 (12)	S3—C17—S2	123.75 (7)
C9—C8—C7	119.44 (13)	N6—C18—C19	103.94 (11)
C9—C8—H8	120.3	N6—C18—H18A	111.0
C7—C8—H8	120.3	C19—C18—H18A	111.0
C8—C9—C10	121.17 (14)	N6—C18—H18B	111.0
C8—C9—H9	119.4	C19—C18—H18B	111.0
C10—C9—H9	119.4	H18A—C18—H18B	109.0
C11—C10—C9	117.20 (12)	C18—C19—C20	105.04 (12)
C11—C10—C13	118.25 (11)	C18—C19—H19A	110.7
C9—C10—C13	124.53 (12)	C20—C19—H19A	110.7
O4—C11—C12	115.98 (11)	C18—C19—H19B	110.7
O4—C11—C10	121.51 (11)	C20—C19—H19B	110.7
C12—C11—C10	122.50 (12)	H19A—C19—H19B	108.8
C7—C12—C11	118.08 (13)	C21—C20—C19	103.84 (14)
C7—C12—H12	121.0	C21—C20—H20A	111.0
C11—C12—H12	121.0	C19—C20—H20A	111.0
C14—C13—C10	119.02 (11)	C21—C20—H20B	111.0
C14—C13—C16	123.85 (11)	C19—C20—H20B	111.0
C10—C13—C16	117.11 (11)	H20A—C20—H20B	109.0
C13—C14—C15	122.38 (12)	N6—C21—C20	103.91 (11)
C13—C14—H14	118.8	N6—C21—H21A	111.0
C15—C14—H14	118.8	C20—C21—H21A	111.0
O5—C15—O4	116.97 (12)	N6—C21—H21B	111.0
O5—C15—C14	125.72 (13)	C20—C21—H21B	111.0
O4—C15—C14	117.28 (11)	H21A—C21—H21B	109.0
C13—C16—S2	116.78 (9)	H20C—C20'—H20D	108.7

C12—C7—C8—C9	−0.7 (2)	C11—O4—C15—O5	−179.57 (12)
Cl1—C7—C8—C9	178.41 (13)	C11—O4—C15—C14	2.14 (17)
C7—C8—C9—C10	−0.1 (3)	C13—C14—C15—O5	−178.77 (14)
C8—C9—C10—C11	0.6 (2)	C13—C14—C15—O4	−0.64 (19)
C8—C9—C10—C13	−177.89 (13)	C14—C13—C16—S2	3.91 (18)
C15—O4—C11—C12	179.60 (12)	C10—C13—C16—S2	−177.56 (9)
C15—O4—C11—C10	−1.62 (18)	C17—S2—C16—C13	−84.97 (11)
C9—C10—C11—O4	−179.01 (12)	C18—N6—C17—S3	0.16 (17)
C13—C10—C11—O4	−0.43 (18)	C21—N6—C17—S3	178.05 (10)
C9—C10—C11—C12	−0.31 (19)	C18—N6—C17—S2	178.53 (10)
C13—C10—C11—C12	178.27 (12)	C21—N6—C17—S2	−3.57 (16)
C8—C7—C12—C11	1.0 (2)	C16—S2—C17—N6	177.14 (9)
Cl1—C7—C12—C11	−178.15 (10)	C16—S2—C17—S3	−4.49 (9)
O4—C11—C12—C7	178.31 (12)	C17—N6—C18—C19	−174.43 (12)
C10—C11—C12—C7	−0.5 (2)	C21—N6—C18—C19	7.40 (16)
C11—C10—C13—C14	1.87 (18)	N6—C18—C19—C20	−26.24 (19)
C9—C10—C13—C14	−179.66 (13)	C18—C19—C20—C21	35.3 (2)
C11—C10—C13—C16	−176.73 (11)	C17—N6—C21—C20	−163.79 (15)
C9—C10—C13—C16	1.74 (19)	C18—N6—C21—C20	14.32 (17)
C10—C13—C14—C15	−1.34 (18)	C19—C20—C21—N6	−30.1 (2)
C16—C13—C14—C15	177.16 (12)

Hydrogen-bond geometry (Å, º) top

Cg4 is the centroid of the C7–C12 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···S3ⁱ	0.93	2.87	3.7910 (16)	170
C21—H21B···O5ⁱⁱ	0.97	2.60	3.3434 (19)	134
C16—H16B···Cg4ⁱⁱ	0.97	2.93	3.761 (1)	144

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

Hydrogen-bond geometry (Å, º) top

Cg4 is the centroid of the C7–C12 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···S3ⁱ	0.93	2.87	3.7910 (16)	170
C21—H21B···O5ⁱⁱ	0.97	2.60	3.3434 (19)	134
C16—H16B···Cg4ⁱⁱ	0.97	2.93	3.761 (1)	144

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

Acknowledgements

The authors acknowledge the Universities Sophisticated Instrumental Centre, Karnatak University, Dharwad, for CCD X-ray facilities, single-crystal X-ray diffractometer, GCMS, IR, CHNS and NMR data. NMM is grateful to Karnatak Science College, Dharwad, for providing laboratory facilities. He is also thankful to P. C. Jabin Science College, Hubli and UGC for permission to do research under FIP.

References

Brillon, D. (1992). Sulfur Rep. 12, 297–332. CrossRef CAS Google Scholar
Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Burns, M., Lloyd-Jones, G. C., Moseley, J. D. & Renny, J. S. (2010). J. Org. Chem. 75, 6347–6353. Web of Science CrossRef CAS PubMed Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Kawaii, S., Tomono, Y., Ogawa, K., Sugiura, M., Yano, M. & Yoshizawa, Y. (2001). Anticancer Res. 21, 917–923. Web of Science PubMed CAS Google Scholar
Khan, K. M., Saify, Z. S., Khan, M. Z., Zia-Ullah, Choudhary, M. I., Atta-Ur-Rahman, Perveen, S., Chohan, Z. H. & Supuran, C. T. (2004). J. Enzyme Inhib. Med. Chem. 19, 373–379. Web of Science CrossRef PubMed CAS Google Scholar
Mahabaleshwaraiah, N. M., Kumar, K. M., Kotresh, O., Al-eryani, W. F. A. & Devarajegowda, H. C. (2012). Acta Cryst. E68, o1566. CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2007). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yu, D., Suzuki, M., Xie, L., Morris-Natschke, S. L. & Lee, K. H. (2003). Med. Res. Rev. 23, 322–345. Web of Science CrossRef PubMed CAS Google Scholar

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Volume 69| Part 11| November 2013| Pages o1684-o1685

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