1-(4-Chloro­butano­yl)-3-(3-chloro­phen­yl)thio­urea

Abosadiya, H.M.; Hasbullah, S.A.; Yamin, B.M.; Fadzil, A.H.

doi:10.1107/S1600536814009295

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 6| June 2014| Page o675

doi:10.1107/S1600536814009295

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1-(4-Chlorobutanoyl)-3-(3-chlorophenyl)thiourea

Hamza M. Abosadiya,^a Siti Aishah Hasbullah,^a Bohari M. Yamin ^b and Adibatul H. Fadzil ^c ^*

^aSchool of Chemical Sciences and Food Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor D.E., Malaysia, ^bLow Carbon Research Group, School of Chemical Sciences and Food Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor D.E., Malaysia, and ^cFaculty of Applied Sciences, Universiti Teknologi MARA (UiTM), 40450 Shah Alam, Selangor D.E., Malaysia
^*Correspondence e-mail: adibatul@salam.uitm.edu.my

(Received 16 April 2014; accepted 24 April 2014; online 17 May 2014)

The two independent molecules in the asymmetric unit of the title compound, C₁₁H₁₂Cl₂N₂OS, exhibit different conformations, with the benzene ring and the N₂CS thiourea group forming dihedral angles of 87.40 (18) and 69.42 (15)°. An intramolecular N—H⋯O hydrogen bond is present in each molecule. Two further N—H⋯O hydrogen bonds link the independent molecules into a dimer. In the crystal, the dimers are linked by N—H⋯S and C—H⋯S hydrogen bonds, forming chains parallel to the c axis.

CCDC reference: 999317

Related literature

For applications and biological activities of thiourea derivatives, see: Abbas et al. (2013 ). For the crystal structure of a related compound, see: Yusof et al. (2012 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₁H₁₂Cl₂N₂OS
M_r = 291.19
Monoclinic, P 2₁ /c
a = 14.7762 (8) Å
b = 10.9400 (6) Å
c = 17.8153 (10) Å
β = 111.327 (2)°
V = 2682.7 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.62 mm⁻¹
T = 296 K
0.41 × 0.35 × 0.30 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.784, T_max = 0.835
49874 measured reflections
4987 independent reflections
3897 reflections with I > 2σ(I)
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.162
S = 1.05
4987 reflections
323 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.51 e Å⁻³
Δρ_min = −0.83 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1	0.89 (4)	1.97 (4)	2.679 (4)	136 (3)
N2—H2⋯O2	0.89 (4)	2.37 (3)	3.089 (4)	139 (3)
N4—H4⋯O1	0.88 (3)	2.38 (3)	3.106 (4)	140 (3)
N4—H4⋯O2	0.88 (3)	1.97 (3)	2.656 (4)	134 (3)
N1—H1⋯S2ⁱ	0.88 (3)	2.57 (2)	3.425 (3)	167 (3)
N3—H3⋯S1ⁱⁱ	0.87 (2)	2.54 (2)	3.397 (3)	169 (3)
C3—H3B⋯S1ⁱⁱⁱ	0.97	2.87	3.792 (3)	160
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) -x+2, -y+2, -z+1.

Data collection: SMART (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 999317

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536814009295/rz5121sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814009295/rz5121Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814009295/rz5121Isup3.cml

checkCIF report

Comment top

Halogeno-carbonoylthiourea derivatives are useful starting materials for the synthesis of other derivatives through the reactivity of the C-halogen bonds. It is also known that the compounds are an important class of organic compounds due to their potential application as ligands and to their biological activities (Abbas et al., 2013).

The title compound (Fig. 1) is an isomer of the previously reported compound 1-(4-chlorobutanoyl)-3-(2-chlorophenyl)thiourea (Yusof et al., 2012) where the chlorine atom is at position-3 of the phenyl group. The asymmetric unit consists of two crystallographically independent molecules. Both molecules maintain the trans-cis configuration with respect to the position of the 4-chlorobutanoyl and 3-chlorophenyl groups, respectively, relative to the thiono S1 and S2 atoms across their C—N bonds. The thiourea moities, (N1/N2/C5/S1/C6 and N3/N4/C15/S2/C16) and benzene rings, (C6—C11 and C17–C22) in both molecules are planar with a maximum deviation of 0.023 (3) Å for atom N2. In one molecule, the benzene ring is almost perpendicular to the thiourea moiety with a dihedral angle of 87.40 (18), while in the other molecule the dihedral angle is 69.42 (15)°. Bond lengths and angles are in normal ranges (Allen et al., 1987) and comparable to those in found 1-(4-chlorobutanoyl)-3-(2-chlorophenyl)thiourea. There are intramolecular hydrogen bonds between the carbonyl oxygen atom and thioamide hydrogen atom, N2—H2··· O1 and N4—H4···O2 in both molecules (Table 1). In addition, the two molecules are connected by N2—H2···O2 and N4—H4···O1 hydrogen bonds. In the crystal packing the molecules are linked by N—H···O, N—H···S and C—H···S hydrogen bonds to form one-dimensional chains along the c axis (Fig. 2).

Related literature top

For applications and biological activities of thiourea derivatives, see: Abbas et al. (2013). For the crystal structure of a related compound, see: Yusof et al. (2012). For bond-length data, see: Allen et al. (1987).

Experimental top

An acetone solution (30 mL) of 3-chloroaniline (0.01 mol, 1.27 g m) was added dropwise into a two-necked round-bottomed flask containing an equimolar amount of 4-chlorobutanoylisothiocyanate (0.01 mol, 1.636 g m). The mixture was refluxed for about 4 h, filtered into a beaker and left to evaporate at room temperature. The filtrate gave colourless crystals after 7 days on slow evaporation of the solvent (yield 78%).

Computing details top

Data collection: SMART (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The asymmetric unit of the title compound with displacement ellipsoids drawn at the 50% probability level. The dashed lines indicate intermolecular hydrogen bonds.
	Fig. 2. The crystal packing of the title compound viewed down the b axis. The dashes lines indicate hydrogen bonds.

1-(4-chlorobutanoyl)-3-(3-chlorophenyl)thiourea top

Crystal data top

C₁₁H₁₂Cl₂N₂OS	F(000) = 1200
M_r = 291.19	D_x = 1.442 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9934 reflections
a = 14.7762 (8) Å	θ = 2.9–25.5°
b = 10.9400 (6) Å	µ = 0.62 mm⁻¹
c = 17.8153 (10) Å	T = 296 K
β = 111.327 (2)°	Block, colourless
V = 2682.7 (3) Å³	0.41 × 0.35 × 0.30 mm
Z = 8

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	4987 independent reflections
Radiation source: fine-focus sealed tube	3897 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
Detector resolution: 83.66 pixels mm^-1	θ_max = 25.5°, θ_min = 2.9°
ω scan	h = −17→17
Absorption correction: multi-scan (SADABS; Bruker, 2009)	k = −13→13
T_min = 0.784, T_max = 0.835	l = −21→21
49874 measured reflections

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.162	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0699P)² + 5.078P] where P = (F_o² + 2F_c²)/3
4987 reflections	(Δ/σ)_max = 0.001
323 parameters	Δρ_max = 1.51 e Å⁻³
4 restraints	Δρ_min = −0.83 e Å⁻³

Crystal data top

C₁₁H₁₂Cl₂N₂OS	V = 2682.7 (3) Å³
M_r = 291.19	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.7762 (8) Å	µ = 0.62 mm⁻¹
b = 10.9400 (6) Å	T = 296 K
c = 17.8153 (10) Å	0.41 × 0.35 × 0.30 mm
β = 111.327 (2)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	4987 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	3897 reflections with I > 2σ(I)
T_min = 0.784, T_max = 0.835	R_int = 0.046
49874 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	4 restraints
wR(F²) = 0.162	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 1.51 e Å⁻³
4987 reflections	Δρ_min = −0.83 e Å⁻³
323 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
Cl1	1.20900 (11)	0.68433 (14)	0.71321 (7)	0.0842 (4)
Cl2	0.53415 (11)	1.04818 (15)	0.11355 (8)	0.0871 (4)
Cl3	0.47334 (9)	0.68932 (12)	0.00986 (9)	0.0842 (4)
Cl4	1.26802 (10)	0.33013 (12)	0.45687 (9)	0.0839 (4)
S1	0.75626 (6)	1.01805 (8)	0.46585 (5)	0.0406 (2)
S2	1.01747 (6)	0.48468 (9)	0.16368 (5)	0.0397 (2)
O1	0.92224 (18)	0.6927 (2)	0.42275 (15)	0.0509 (7)
O2	0.79236 (17)	0.6402 (3)	0.25577 (15)	0.0571 (8)
N1	0.90164 (18)	0.8658 (3)	0.48549 (16)	0.0327 (6)
N2	0.7673 (2)	0.8405 (3)	0.36889 (17)	0.0400 (7)
N3	0.84653 (19)	0.5491 (3)	0.16566 (16)	0.0355 (6)
N4	0.97653 (19)	0.5835 (3)	0.28377 (17)	0.0405 (7)
C1	1.1947 (3)	0.6227 (4)	0.6168 (2)	0.0580 (11)
H1A	1.2353	0.6683	0.5944	0.070*
H1B	1.2167	0.5385	0.6233	0.070*
C2	1.0906 (3)	0.6275 (3)	0.5587 (2)	0.0433 (8)
H2A	1.0863	0.5891	0.5084	0.052*
H2B	1.0502	0.5812	0.5809	0.052*
C3	1.0526 (2)	0.7563 (3)	0.5420 (2)	0.0429 (8)
H3A	1.0506	0.7913	0.5914	0.051*
H3B	1.0974	0.8046	0.5258	0.051*
C4	0.9534 (2)	0.7651 (3)	0.4779 (2)	0.0362 (7)
C5	0.8088 (2)	0.9018 (3)	0.43661 (18)	0.0325 (7)
C6	0.6695 (3)	0.8650 (4)	0.3146 (2)	0.0428 (9)
C7	0.6542 (3)	0.9400 (4)	0.2506 (2)	0.0484 (9)
H7	0.7055	0.9786	0.2417	0.058*
C8	0.5567 (3)	0.9572 (4)	0.1977 (2)	0.0543 (10)
C9	0.4823 (3)	0.9004 (5)	0.2106 (3)	0.0635 (12)
H9	0.4190	0.9126	0.1749	0.076*
C10	0.4990 (3)	0.8265 (5)	0.2745 (3)	0.0674 (13)
H10	0.4475	0.7882	0.2832	0.081*
C11	0.5940 (3)	0.8079 (4)	0.3275 (2)	0.0567 (11)
H11	0.6062	0.7566	0.3717	0.068*
C12	0.4953 (3)	0.6064 (5)	0.1009 (3)	0.0606 (11)
H12A	0.4501	0.6334	0.1256	0.073*
H12B	0.4838	0.5201	0.0885	0.073*
C13	0.5976 (2)	0.6237 (4)	0.1596 (2)	0.0523 (10)
H13A	0.6107	0.7106	0.1674	0.063*
H13B	0.6027	0.5891	0.2111	0.063*
C14	0.6733 (2)	0.5662 (3)	0.1331 (2)	0.0383 (8)
H14A	0.6624	0.4787	0.1278	0.046*
H14B	0.6668	0.5981	0.0806	0.046*
C15	0.7744 (2)	0.5901 (3)	0.1911 (2)	0.0376 (8)
C16	0.9453 (2)	0.5431 (3)	0.20854 (18)	0.0310 (7)
C17	1.0758 (2)	0.5800 (3)	0.33715 (18)	0.0330 (7)
C18	1.1187 (2)	0.4690 (3)	0.3653 (2)	0.0385 (8)
H18	1.0850	0.3961	0.3481	0.046*
C19	1.2132 (3)	0.4690 (3)	0.4198 (2)	0.0414 (8)
C20	1.2647 (2)	0.5753 (4)	0.4454 (2)	0.0473 (9)
H20	1.3286	0.5732	0.4816	0.057*
C21	1.2201 (3)	0.6843 (4)	0.4166 (3)	0.0521 (10)
H21	1.2539	0.7571	0.4336	0.062*
C22	1.1247 (3)	0.6873 (3)	0.3621 (2)	0.0426 (8)
H22	1.0945	0.7615	0.3429	0.051*
H1	0.923 (2)	0.912 (3)	0.5285 (13)	0.033 (9)*
H3	0.826 (2)	0.521 (3)	0.1164 (9)	0.030 (9)*
H4	0.933 (2)	0.609 (3)	0.303 (2)	0.043 (10)*
H2	0.801 (3)	0.779 (3)	0.360 (2)	0.053 (12)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0966 (10)	0.0931 (9)	0.0404 (6)	0.0185 (8)	−0.0019 (6)	−0.0008 (6)
Cl2	0.0826 (9)	0.1067 (11)	0.0642 (7)	0.0309 (8)	0.0174 (7)	0.0311 (7)
Cl3	0.0508 (6)	0.0749 (8)	0.0930 (9)	0.0089 (6)	−0.0142 (6)	0.0095 (7)
Cl4	0.0744 (8)	0.0630 (7)	0.0882 (9)	0.0298 (6)	−0.0016 (7)	0.0157 (6)
S1	0.0343 (4)	0.0466 (5)	0.0349 (4)	0.0111 (4)	0.0057 (3)	−0.0043 (4)
S2	0.0316 (4)	0.0535 (5)	0.0337 (4)	0.0046 (4)	0.0116 (3)	−0.0006 (4)
O1	0.0388 (14)	0.0542 (16)	0.0470 (15)	0.0099 (12)	0.0005 (12)	−0.0182 (13)
O2	0.0313 (13)	0.087 (2)	0.0415 (14)	0.0122 (13)	−0.0002 (11)	−0.0240 (14)
N1	0.0259 (13)	0.0376 (15)	0.0301 (14)	0.0035 (11)	0.0048 (11)	−0.0062 (12)
N2	0.0285 (14)	0.0493 (18)	0.0343 (15)	0.0103 (13)	0.0018 (12)	−0.0088 (13)
N3	0.0247 (13)	0.0504 (17)	0.0265 (14)	0.0015 (12)	0.0036 (11)	−0.0055 (12)
N4	0.0257 (14)	0.0582 (19)	0.0324 (15)	0.0087 (13)	0.0042 (12)	−0.0090 (13)
C1	0.048 (2)	0.070 (3)	0.046 (2)	0.022 (2)	0.0051 (18)	0.001 (2)
C2	0.0375 (19)	0.047 (2)	0.0403 (19)	0.0074 (16)	0.0084 (15)	−0.0009 (16)
C3	0.0273 (16)	0.045 (2)	0.047 (2)	0.0056 (15)	0.0021 (15)	−0.0064 (16)
C4	0.0287 (16)	0.0417 (19)	0.0355 (17)	0.0030 (14)	0.0086 (14)	−0.0005 (15)
C5	0.0275 (15)	0.0380 (17)	0.0305 (16)	0.0012 (13)	0.0087 (13)	0.0049 (14)
C6	0.0376 (19)	0.051 (2)	0.0306 (17)	0.0129 (16)	0.0015 (14)	−0.0097 (16)
C7	0.046 (2)	0.055 (2)	0.039 (2)	0.0085 (18)	0.0091 (16)	−0.0054 (17)
C8	0.056 (2)	0.059 (2)	0.040 (2)	0.016 (2)	0.0090 (18)	0.0009 (18)
C9	0.037 (2)	0.084 (3)	0.059 (3)	0.010 (2)	0.0051 (19)	−0.007 (2)
C10	0.034 (2)	0.097 (4)	0.062 (3)	−0.001 (2)	0.007 (2)	−0.005 (3)
C11	0.038 (2)	0.077 (3)	0.047 (2)	0.001 (2)	0.0051 (17)	−0.003 (2)
C12	0.0295 (19)	0.080 (3)	0.068 (3)	−0.0057 (19)	0.0134 (19)	−0.016 (2)
C13	0.0291 (18)	0.075 (3)	0.051 (2)	−0.0026 (18)	0.0115 (16)	−0.015 (2)
C14	0.0277 (16)	0.046 (2)	0.0366 (18)	0.0010 (14)	0.0056 (14)	−0.0046 (15)
C15	0.0281 (16)	0.0451 (19)	0.0349 (18)	0.0054 (14)	0.0058 (14)	−0.0021 (15)
C16	0.0264 (15)	0.0327 (16)	0.0300 (16)	0.0016 (12)	0.0055 (13)	0.0039 (13)
C17	0.0257 (15)	0.0437 (19)	0.0269 (15)	0.0046 (14)	0.0065 (13)	−0.0032 (14)
C18	0.0343 (17)	0.0391 (18)	0.0373 (18)	−0.0011 (14)	0.0073 (14)	−0.0051 (15)
C19	0.0353 (18)	0.048 (2)	0.0374 (18)	0.0128 (16)	0.0088 (15)	0.0022 (16)
C20	0.0242 (16)	0.069 (3)	0.042 (2)	0.0025 (17)	0.0035 (14)	−0.0063 (18)
C21	0.037 (2)	0.050 (2)	0.061 (2)	−0.0093 (17)	0.0092 (18)	−0.0112 (19)
C22	0.0369 (18)	0.0385 (19)	0.047 (2)	0.0044 (15)	0.0084 (16)	0.0034 (16)

Geometric parameters (Å, º) top

Cl1—C1	1.784 (4)	C6—C7	1.357 (5)
Cl2—C8	1.728 (4)	C6—C11	1.369 (6)
Cl3—C12	1.782 (5)	C7—C8	1.418 (5)
Cl4—C19	1.736 (4)	C7—H7	0.9300
S1—C5	1.669 (3)	C8—C9	1.354 (6)
S2—C16	1.674 (3)	C9—C10	1.343 (7)
O1—C4	1.215 (4)	C9—H9	0.9300
O2—C15	1.215 (4)	C10—C11	1.393 (6)
N1—C4	1.376 (4)	C10—H10	0.9300
N1—C5	1.388 (4)	C11—H11	0.9300
N1—H1	0.876 (10)	C12—C13	1.504 (5)
N2—C5	1.321 (4)	C12—H12A	0.9700
N2—C6	1.441 (4)	C12—H12B	0.9700
N2—H2	0.876 (10)	C13—C14	1.502 (5)
N3—C15	1.376 (4)	C13—H13A	0.9700
N3—C16	1.381 (4)	C13—H13B	0.9700
N3—H3	0.872 (10)	C14—C15	1.497 (4)
N4—C16	1.325 (4)	C14—H14A	0.9700
N4—C17	1.429 (4)	C14—H14B	0.9700
N4—H4	0.874 (10)	C17—C22	1.365 (5)
C1—C2	1.511 (5)	C17—C18	1.378 (5)
C1—H1A	0.9700	C18—C19	1.381 (5)
C1—H1B	0.9700	C18—H18	0.9300
C2—C3	1.506 (5)	C19—C20	1.373 (5)
C2—H2A	0.9700	C20—C21	1.369 (6)
C2—H2B	0.9700	C20—H20	0.9300
C3—C4	1.499 (4)	C21—C22	1.391 (5)
C3—H3A	0.9700	C21—H21	0.9300
C3—H3B	0.9700	C22—H22	0.9300

C4—N1—C5	128.6 (3)	C9—C10—C11	119.5 (4)
C4—N1—H1	121 (2)	C9—C10—H10	120.3
C5—N1—H1	110 (2)	C11—C10—H10	120.3
C5—N2—C6	122.5 (3)	C6—C11—C10	120.1 (4)
C5—N2—H2	116 (3)	C6—C11—H11	120.0
C6—N2—H2	121 (3)	C10—C11—H11	120.0
C15—N3—C16	128.5 (3)	C13—C12—Cl3	111.9 (3)
C15—N3—H3	115 (2)	C13—C12—H12A	109.2
C16—N3—H3	117 (2)	Cl3—C12—H12A	109.2
C16—N4—C17	124.0 (3)	C13—C12—H12B	109.2
C16—N4—H4	118 (2)	Cl3—C12—H12B	109.2
C17—N4—H4	118 (2)	H12A—C12—H12B	107.9
C2—C1—Cl1	112.4 (3)	C14—C13—C12	113.8 (3)
C2—C1—H1A	109.1	C14—C13—H13A	108.8
Cl1—C1—H1A	109.1	C12—C13—H13A	108.8
C2—C1—H1B	109.1	C14—C13—H13B	108.8
Cl1—C1—H1B	109.1	C12—C13—H13B	108.8
H1A—C1—H1B	107.9	H13A—C13—H13B	107.7
C3—C2—C1	112.4 (3)	C15—C14—C13	112.4 (3)
C3—C2—H2A	109.1	C15—C14—H14A	109.1
C1—C2—H2A	109.1	C13—C14—H14A	109.1
C3—C2—H2B	109.1	C15—C14—H14B	109.1
C1—C2—H2B	109.1	C13—C14—H14B	109.1
H2A—C2—H2B	107.9	H14A—C14—H14B	107.9
C4—C3—C2	113.7 (3)	O2—C15—N3	122.0 (3)
C4—C3—H3A	108.8	O2—C15—C14	123.5 (3)
C2—C3—H3A	108.8	N3—C15—C14	114.4 (3)
C4—C3—H3B	108.8	N4—C16—N3	116.9 (3)
C2—C3—H3B	108.8	N4—C16—S2	124.2 (2)
H3A—C3—H3B	107.7	N3—C16—S2	118.8 (2)
O1—C4—N1	122.8 (3)	C22—C17—C18	121.4 (3)
O1—C4—C3	123.5 (3)	C22—C17—N4	119.2 (3)
N1—C4—C3	113.7 (3)	C18—C17—N4	119.4 (3)
N2—C5—N1	117.0 (3)	C17—C18—C19	118.0 (3)
N2—C5—S1	123.9 (2)	C17—C18—H18	121.0
N1—C5—S1	119.1 (2)	C19—C18—H18	121.0
C7—C6—C11	121.4 (3)	C20—C19—C18	122.1 (3)
C7—C6—N2	119.8 (4)	C20—C19—Cl4	119.3 (3)
C11—C6—N2	118.8 (3)	C18—C19—Cl4	118.7 (3)
C6—C7—C8	117.2 (4)	C21—C20—C19	118.7 (3)
C6—C7—H7	121.4	C21—C20—H20	120.7
C8—C7—H7	121.4	C19—C20—H20	120.7
C9—C8—C7	121.2 (4)	C20—C21—C22	120.6 (4)
C9—C8—Cl2	120.0 (3)	C20—C21—H21	119.7
C7—C8—Cl2	118.8 (4)	C22—C21—H21	119.7
C10—C9—C8	120.7 (4)	C17—C22—C21	119.3 (3)
C10—C9—H9	119.7	C17—C22—H22	120.3
C8—C9—H9	119.7	C21—C22—H22	120.3

Cl1—C1—C2—C3	61.8 (4)	Cl3—C12—C13—C14	−68.4 (5)
C1—C2—C3—C4	173.7 (3)	C12—C13—C14—C15	177.4 (4)
C5—N1—C4—O1	1.6 (6)	C16—N3—C15—O2	8.2 (6)
C5—N1—C4—C3	179.5 (3)	C16—N3—C15—C14	−171.1 (3)
C2—C3—C4—O1	−28.8 (5)	C13—C14—C15—O2	6.6 (5)
C2—C3—C4—N1	153.3 (3)	C13—C14—C15—N3	−174.1 (3)
C6—N2—C5—N1	177.1 (3)	C17—N4—C16—N3	177.8 (3)
C6—N2—C5—S1	−2.8 (5)	C17—N4—C16—S2	−1.4 (5)
C4—N1—C5—N2	−8.1 (5)	C15—N3—C16—N4	−1.2 (5)
C4—N1—C5—S1	171.8 (3)	C15—N3—C16—S2	178.0 (3)
C5—N2—C6—C7	95.8 (4)	C16—N4—C17—C22	113.8 (4)
C5—N2—C6—C11	−86.6 (5)	C16—N4—C17—C18	−69.3 (5)
C11—C6—C7—C8	0.2 (6)	C22—C17—C18—C19	0.0 (5)
N2—C6—C7—C8	177.8 (3)	N4—C17—C18—C19	−176.9 (3)
C6—C7—C8—C9	−0.3 (6)	C17—C18—C19—C20	−0.8 (5)
C6—C7—C8—Cl2	−178.0 (3)	C17—C18—C19—Cl4	179.3 (3)
C7—C8—C9—C10	0.4 (7)	C18—C19—C20—C21	1.0 (6)
Cl2—C8—C9—C10	178.0 (4)	Cl4—C19—C20—C21	−179.1 (3)
C8—C9—C10—C11	−0.4 (7)	C19—C20—C21—C22	−0.4 (6)
C7—C6—C11—C10	−0.2 (6)	C18—C17—C22—C21	0.5 (5)
N2—C6—C11—C10	−177.8 (4)	N4—C17—C22—C21	177.4 (3)
C9—C10—C11—C6	0.3 (7)	C20—C21—C22—C17	−0.3 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1	0.89 (4)	1.97 (4)	2.679 (4)	136 (3)
N2—H2···O2	0.89 (4)	2.37 (3)	3.089 (4)	139 (3)
N4—H4···O1	0.88 (3)	2.38 (3)	3.106 (4)	140 (3)
N4—H4···O2	0.88 (3)	1.97 (3)	2.656 (4)	134 (3)
C3—H3A···Cl1	0.97	2.80	3.184 (4)	104
N1—H1···S2ⁱ	0.88 (3)	2.57 (2)	3.425 (3)	167 (3)
N3—H3···S1ⁱⁱ	0.87 (2)	2.54 (2)	3.397 (3)	169 (3)
C3—H3B···S1ⁱⁱⁱ	0.97	2.87	3.792 (3)	160

Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x, −y+3/2, z−1/2; (iii) −x+2, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1	0.89 (4)	1.97 (4)	2.679 (4)	136 (3)
N2—H2···O2	0.89 (4)	2.37 (3)	3.089 (4)	139 (3)
N4—H4···O1	0.88 (3)	2.38 (3)	3.106 (4)	140 (3)
N4—H4···O2	0.88 (3)	1.97 (3)	2.656 (4)	134 (3)
N1—H1···S2ⁱ	0.88 (3)	2.57 (2)	3.425 (3)	167 (3)
N3—H3···S1ⁱⁱ	0.874 (18)	2.535 (16)	3.397 (3)	169 (3)
C3—H3B···S1ⁱⁱⁱ	0.97	2.87	3.792 (3)	160

Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x, −y+3/2, z−1/2; (iii) −x+2, −y+2, −z+1.

Acknowledgements

The authors thank the Ministry of Higher Education of Malaysia and both Universiti Teknologi MARA and Universiti Kebangsaan Malaysia for the research grants No. 600-RMI/DANA5/3/RIF(147/2012) and DIP-2012–11, respectively. HMA would like to thank the Ministry of Higher Education of Libya for a scholarship.

References

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