N′-[Bis(benzyl­sulfan­yl)methyl­idene]benzohydrazide

Tayamon, S.; Ravoof, T.B.S.A.; Tahir, M.I.M.; Crouse, K.A.; Tiekink, E.R.T.

doi:10.1107/S1600536812019472

organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Pages o1640-o1641

doi:10.1107/S1600536812019472

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ADDENDA AND ERRATA

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N′-[Bis(benzylsulfanyl)methylidene]benzohydrazide

Shahedeh Tayamon,^a Thahira Begum S. A. Ravoof,^a Mohamed Ibrahim Mohamed Tahir,^a Karen A. Crouse ^a ‡ and Edward R. T. Tiekink ^b ^*

^aDepartment of Chemistry, Universiti Putra Malaysia, 43400 Serdang, Malaysia, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 24 April 2012; accepted 1 May 2012; online 5 May 2012)

In the title hydrazonodithioate, C₂₁H₁₉N₃OS₂, the amide group is twisted out of the plane through the S₂C=N atoms: the C—N—N—C torsion angle is 139.71 (13)°. The pyridine ring forms dihedral angles of 52.96 (8) and 86.46 (8)° with the phenyl rings, and the latter are approximately orthogonal [dihedral angle = 76.42 (9)°]. Supramolecular chains sustained by N—H⋯O hydrogen bonds and propagated by glide symmetry along the c axis are found in the crystal structure. The chains are consolidated into a three-dimensional architecture by C—H⋯O and C—H⋯N interactions.

Related literature

For background to the coordination chemistry of dithiocarbazate derivatives, see: Tarafder et al. (2002 ); Ravoof et al. (2010 ). For related syntheses, see: Ali & Tarafder (1977 ); Ali et al. (2001 ); Manan et al. (2012 ). For related structures, see: Jasinski et al. (2010 ); Singh et al. (2007 ).

Experimental

Crystal data

C₂₁H₁₉N₃OS₂
M_r = 393.51
Monoclinic, P 2₁ /c
a = 11.2593 (4) Å
b = 21.2182 (7) Å
c = 8.6041 (3) Å
β = 103.678 (3)°
V = 1997.24 (12) Å³
Z = 4
Cu Kα radiation
μ = 2.54 mm⁻¹
T = 150 K
0.50 × 0.36 × 0.16 mm

Data collection

Agilent Xcaliber Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.42, T_max = 0.67
38338 measured reflections
3867 independent reflections
3715 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.097
S = 1.03
3867 reflections
247 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯O1ⁱ	0.864 (17)	1.936 (17)	2.7852 (15)	167.4 (16)
C7—H7⋯N3ⁱⁱ	0.95	2.54	3.339 (2)	142
C8—H8⋯N3ⁱⁱⁱ	0.95	2.52	3.424 (2)	158
C18—H18⋯O1ⁱ	0.95	2.53	3.365 (2)	147
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812019472/hb6755sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812019472/hb6755Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812019472/hb6755Isup3.cml

checkCIF report

Comment top

Our interest in investigating the coordination properties of ligands containing the H—N—C═S moiety (Tarafder et al., 2002; Ravoof et al., 2010) and our desire to expand the study of this class of biologically important compounds has lead us to synthesize a series of related ligands (Ali et al., 2001; Manan et al., 2012). The title compound N'-bis(benzylsulfanyl)methylidene]benzohydrazide, (I), was obtained from an attempt to prepare S-benzyl isonicotinoylcarbonohydrazonodithioate (see Experimental).

In (I), Fig. 1, the amide is twisted out of the plane through the S₂C═N atoms with the C1—N1—N2—C16 torsion angle being 139.71 (13)°. A similar twist was found in the structure of (PhCH₂S)₂C═ NN(H)C(═ O)C₆H₄OMe-4 (Jasinski et al., 2010) but a planar arrangement was observed in the structure of (PhCH₂S)₂C═NN(H)C(═O)C₆H₄OMe-2 (Singh et al., 2007). The dihedral angle between the phenyl rings is 76.42 (9)°, indicating an almost orthogonal relationship. Each of these rings forms a dihedral angle of 52.96 (8) and 86.46 (8)° with the pyridyl ring.

The crystal packing features supramolecular chains sustained by N—H···O hydrogen bonds, Table 1, and propagated by glide symmetry along the c axis, Fig. 2. Chains are consolidated into a three-dimensional architecture by C—H···O and C—H···N interactions, Fig. 3 and Table 1.

Related literature top

For background to the coordination chemistry of dithiocarbazate derivatives, see: Tarafder et al. (2002); Ravoof et al. (2010). For related syntheses, see: Ali & Tarafder (1977); Ali et al. (2001); Manan et al. (2012). For related structures, see: Jasinski et al. (2010); Singh et al. (2007).

Experimental top

The procedure to synthesize S-benzyldithiocarbazate (Ali & Tarafder, 1977) was adapted to prepare S-benzyl isonicotinoylcarbonohydrazono dithioate by replacing hydrazine with its isonicotinic acid derivative. Potassium hydroxide (0.2 mol, 11.2 g) in absolute ethanol (70 ml) was added to a suspension of isonicotinic acid hydrazide (0.2 mol, 27.43 g) in absolute ethanol (700 ml). The pale-yellow solution was kept in an ice-salt bath and carbon disulfide (0.2 mol) was added drop-wise with constant stirring over one hour. Benzylchloride (0.2 mol, 23 ml) was then added drop-wise with vigorous stirring to the pale-orange solution obtained above. The reaction temperature was maintained below 278 K. An unidentified pale-yellow solid (33.84 g) which did not contain any benzyl substituent was filtered from the mixture. The filtrate was kept in a freezer for one week before it was used as replacement for absolute ethanol to repeat the above reaction. The final solution produced dark-yellow blocks of the title compound after storage at 268 K for 5 months. (Yield 16 g; M.pt: 369 K).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of (I) showing displacement ellipsoids at the 50% probability level.
	Fig. 2. A view of the supramolecular chain in (I) mediated by N—H···O hydrogen bonding, shown as blue dashed lines.
	Fig. 3. A view in projection down the a axis of the unit-cell contents for (I). The N—H···O, C—H···O and C—H···N interactions are shown as blue orange and brown dashed lines, respectively.

N'-[Bis(benzylsulfanyl)methylidene]benzohydrazide top

Crystal data top

C₂₁H₁₉N₃OS₂	F(000) = 824
M_r = 393.51	D_x = 1.309 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: -P 2ybc	Cell parameters from 17900 reflections
a = 11.2593 (4) Å	θ = 4–71°
b = 21.2182 (7) Å	µ = 2.54 mm⁻¹
c = 8.6041 (3) Å	T = 150 K
β = 103.678 (3)°	Block, dark yellow
V = 1997.24 (12) Å³	0.50 × 0.36 × 0.16 mm
Z = 4

Data collection top

Agilent Xcaliber Eos Gemini diffractometer	3867 independent reflections
Radiation source: fine-focus sealed tube	3715 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
Detector resolution: 16.1952 pixels mm^-1	θ_max = 71.4°, θ_min = 4.0°
ω/2θ scans	h = −13→13
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −24→26
T_min = 0.42, T_max = 0.67	l = −10→10
38338 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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0631P)² + 0.6548P] where P = (F_o² + 2F_c²)/3
3867 reflections	(Δ/σ)_max = 0.001
247 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₂₁H₁₉N₃OS₂	V = 1997.24 (12) Å³
M_r = 393.51	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 11.2593 (4) Å	µ = 2.54 mm⁻¹
b = 21.2182 (7) Å	T = 150 K
c = 8.6041 (3) Å	0.50 × 0.36 × 0.16 mm
β = 103.678 (3)°

Data collection top

Agilent Xcaliber Eos Gemini diffractometer	3867 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	3715 reflections with I > 2σ(I)
T_min = 0.42, T_max = 0.67	R_int = 0.031
38338 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.22 e Å⁻³
3867 reflections	Δρ_min = −0.32 e Å⁻³
247 parameters

Special details top

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
S1	0.58342 (3)	0.395419 (15)	0.24637 (4)	0.02644 (11)
S2	0.37808 (3)	0.403747 (16)	0.41378 (4)	0.03091 (12)
O1	0.55367 (12)	0.19229 (5)	0.45894 (12)	0.0423 (3)
N1	0.45622 (11)	0.29676 (5)	0.32219 (13)	0.0266 (2)
N2	0.53822 (10)	0.26152 (5)	0.25652 (13)	0.0246 (2)
H2N	0.5455 (15)	0.2700 (8)	0.161 (2)	0.030*
N3	0.82288 (13)	0.08675 (8)	0.1580 (2)	0.0510 (4)
C1	0.47186 (11)	0.35652 (7)	0.32465 (14)	0.0240 (3)
C2	0.58359 (14)	0.47567 (7)	0.32153 (18)	0.0316 (3)
H2A	0.5016	0.4948	0.2845	0.038*
H2B	0.6056	0.4758	0.4399	0.038*
C3	0.67684 (13)	0.51237 (7)	0.25762 (17)	0.0288 (3)
C4	0.64021 (15)	0.55501 (9)	0.1339 (2)	0.0423 (4)
H4	0.5556	0.5605	0.0867	0.051*
C5	0.72615 (19)	0.58997 (10)	0.0779 (2)	0.0525 (5)
H5	0.7001	0.6193	−0.0068	0.063*
C6	0.84883 (17)	0.58206 (9)	0.1453 (2)	0.0465 (4)
H6	0.9076	0.6057	0.1069	0.056*
C7	0.88623 (15)	0.53955 (8)	0.2688 (2)	0.0421 (4)
H7	0.9709	0.5341	0.3155	0.051*
C8	0.80055 (14)	0.50489 (7)	0.32481 (19)	0.0351 (3)
H8	0.8269	0.4758	0.4099	0.042*
C9	0.27606 (13)	0.34592 (7)	0.47123 (17)	0.0297 (3)
H9A	0.3219	0.3063	0.5034	0.036*
H9B	0.2487	0.3620	0.5651	0.036*
C10	0.16574 (13)	0.33186 (7)	0.33872 (17)	0.0308 (3)
C11	0.15710 (15)	0.27626 (9)	0.2525 (2)	0.0469 (4)
H11	0.2216	0.2463	0.2766	0.056*
C12	0.05412 (18)	0.26418 (11)	0.1306 (3)	0.0620 (6)
H12	0.0489	0.2261	0.0712	0.074*
C13	−0.04034 (18)	0.30698 (12)	0.0955 (2)	0.0582 (5)
H13	−0.1102	0.2986	0.0116	0.070*
C14	−0.03337 (18)	0.36186 (10)	0.1820 (2)	0.0555 (5)
H14	−0.0989	0.3912	0.1591	0.067*
C15	0.06947 (16)	0.37429 (8)	0.3028 (2)	0.0441 (4)
H15	0.0741	0.4124	0.3618	0.053*
C16	0.57822 (13)	0.20778 (6)	0.33232 (15)	0.0262 (3)
C17	0.66171 (12)	0.16710 (7)	0.26297 (16)	0.0277 (3)
C18	0.72075 (14)	0.18668 (8)	0.14762 (18)	0.0352 (3)
H18	0.7077	0.2277	0.1026	0.042*
C19	0.79978 (15)	0.14459 (10)	0.0994 (2)	0.0475 (4)
H19	0.8397	0.1581	0.0195	0.057*
C20	0.76652 (16)	0.06886 (9)	0.2706 (2)	0.0489 (4)
H20	0.7824	0.0278	0.3144	0.059*
C21	0.68633 (15)	0.10680 (7)	0.3272 (2)	0.0381 (4)
H21	0.6487	0.0921	0.4082	0.046*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.02696 (19)	0.02388 (19)	0.03094 (19)	−0.00467 (12)	0.01177 (14)	−0.00630 (12)
S2	0.0295 (2)	0.02387 (19)	0.0439 (2)	−0.00234 (12)	0.01763 (16)	−0.00832 (13)
O1	0.0760 (9)	0.0293 (6)	0.0282 (5)	0.0116 (5)	0.0256 (5)	0.0044 (4)
N1	0.0300 (6)	0.0239 (6)	0.0292 (6)	0.0011 (4)	0.0134 (5)	−0.0024 (4)
N2	0.0309 (6)	0.0230 (6)	0.0232 (5)	0.0012 (4)	0.0129 (4)	−0.0005 (4)
N3	0.0308 (7)	0.0560 (10)	0.0626 (10)	0.0119 (7)	0.0037 (7)	−0.0243 (8)
C1	0.0233 (6)	0.0253 (7)	0.0238 (6)	−0.0008 (5)	0.0067 (5)	−0.0035 (5)
C2	0.0332 (7)	0.0232 (7)	0.0420 (8)	−0.0061 (5)	0.0159 (6)	−0.0090 (6)
C3	0.0312 (7)	0.0242 (7)	0.0328 (7)	−0.0057 (5)	0.0115 (6)	−0.0065 (5)
C4	0.0343 (8)	0.0482 (10)	0.0408 (8)	−0.0068 (7)	0.0017 (6)	0.0066 (7)
C5	0.0559 (11)	0.0585 (12)	0.0407 (9)	−0.0109 (9)	0.0067 (8)	0.0181 (8)
C6	0.0450 (9)	0.0502 (10)	0.0493 (9)	−0.0164 (8)	0.0213 (8)	0.0037 (8)
C7	0.0292 (8)	0.0413 (9)	0.0567 (10)	−0.0062 (7)	0.0123 (7)	0.0017 (7)
C8	0.0325 (8)	0.0301 (8)	0.0432 (8)	−0.0020 (6)	0.0096 (6)	0.0034 (6)
C9	0.0297 (7)	0.0292 (7)	0.0340 (7)	−0.0023 (5)	0.0153 (6)	−0.0026 (6)
C10	0.0312 (7)	0.0316 (7)	0.0339 (7)	−0.0053 (6)	0.0166 (6)	−0.0028 (6)
C11	0.0328 (8)	0.0466 (10)	0.0657 (11)	−0.0076 (7)	0.0207 (8)	−0.0230 (9)
C12	0.0445 (10)	0.0750 (14)	0.0714 (13)	−0.0194 (10)	0.0237 (9)	−0.0421 (11)
C13	0.0388 (10)	0.0868 (15)	0.0471 (10)	−0.0165 (10)	0.0069 (8)	−0.0133 (10)
C14	0.0430 (10)	0.0600 (12)	0.0576 (11)	0.0036 (9)	0.0004 (8)	0.0024 (9)
C15	0.0433 (9)	0.0379 (9)	0.0487 (9)	0.0024 (7)	0.0058 (7)	−0.0035 (7)
C16	0.0341 (7)	0.0230 (7)	0.0217 (6)	−0.0012 (5)	0.0071 (5)	−0.0037 (5)
C17	0.0261 (7)	0.0296 (7)	0.0246 (6)	0.0005 (5)	0.0006 (5)	−0.0084 (5)
C18	0.0296 (7)	0.0448 (9)	0.0314 (7)	0.0052 (6)	0.0073 (6)	−0.0037 (6)
C19	0.0301 (8)	0.0687 (12)	0.0451 (9)	0.0065 (8)	0.0116 (7)	−0.0148 (9)
C20	0.0382 (9)	0.0370 (9)	0.0662 (11)	0.0098 (7)	0.0018 (8)	−0.0138 (8)
C21	0.0374 (8)	0.0283 (8)	0.0465 (9)	0.0024 (6)	0.0059 (7)	−0.0062 (6)

Geometric parameters (Å, º) top

S1—C1	1.7643 (13)	C8—H8	0.9500
S1—C2	1.8213 (14)	C9—C10	1.504 (2)
S2—C1	1.7579 (13)	C9—H9A	0.9900
S2—C9	1.8270 (14)	C9—H9B	0.9900
O1—C16	1.2304 (17)	C10—C11	1.385 (2)
N1—C1	1.2795 (18)	C10—C15	1.387 (2)
N1—N2	1.4063 (15)	C11—C12	1.391 (3)
N2—C16	1.3376 (18)	C11—H11	0.9500
N2—H2N	0.867 (18)	C12—C13	1.377 (3)
N3—C20	1.333 (3)	C12—H12	0.9500
N3—C19	1.329 (3)	C13—C14	1.374 (3)
C2—C3	1.5113 (19)	C13—H13	0.9500
C2—H2A	0.9900	C14—C15	1.386 (3)
C2—H2B	0.9900	C14—H14	0.9500
C3—C8	1.385 (2)	C15—H15	0.9500
C3—C4	1.384 (2)	C16—C17	1.5001 (18)
C4—C5	1.392 (2)	C17—C18	1.383 (2)
C4—H4	0.9500	C17—C21	1.395 (2)
C5—C6	1.376 (3)	C18—C19	1.391 (2)
C5—H5	0.9500	C18—H18	0.9500
C6—C7	1.382 (3)	C19—H19	0.9500
C6—H6	0.9500	C20—C21	1.381 (2)
C7—C8	1.387 (2)	C20—H20	0.9500
C7—H7	0.9500	C21—H21	0.9500

C1—S1—C2	104.06 (6)	S2—C9—H9B	109.0
C1—S2—C9	102.48 (7)	H9A—C9—H9B	107.8
C1—N1—N2	115.64 (11)	C11—C10—C15	118.79 (15)
C16—N2—N1	115.76 (11)	C11—C10—C9	121.06 (14)
C16—N2—H2N	123.0 (12)	C15—C10—C9	120.14 (14)
N1—N2—H2N	119.4 (11)	C10—C11—C12	120.09 (18)
C20—N3—C19	117.05 (15)	C10—C11—H11	120.0
N1—C1—S2	118.53 (10)	C12—C11—H11	120.0
N1—C1—S1	124.39 (10)	C13—C12—C11	120.47 (18)
S2—C1—S1	117.07 (8)	C13—C12—H12	119.8
C3—C2—S1	107.16 (9)	C11—C12—H12	119.8
C3—C2—H2A	110.3	C12—C13—C14	119.84 (18)
S1—C2—H2A	110.3	C12—C13—H13	120.1
C3—C2—H2B	110.3	C14—C13—H13	120.1
S1—C2—H2B	110.3	C13—C14—C15	119.87 (19)
H2A—C2—H2B	108.5	C13—C14—H14	120.1
C8—C3—C4	118.91 (14)	C15—C14—H14	120.1
C8—C3—C2	120.38 (13)	C14—C15—C10	120.92 (17)
C4—C3—C2	120.69 (13)	C14—C15—H15	119.5
C3—C4—C5	120.62 (16)	C10—C15—H15	119.5
C3—C4—H4	119.7	O1—C16—N2	122.64 (13)
C5—C4—H4	119.7	O1—C16—C17	119.44 (12)
C6—C5—C4	119.99 (16)	N2—C16—C17	117.84 (12)
C6—C5—H5	120.0	C18—C17—C21	118.39 (14)
C4—C5—H5	120.0	C18—C17—C16	124.44 (13)
C5—C6—C7	119.77 (15)	C21—C17—C16	117.05 (13)
C5—C6—H6	120.1	C17—C18—C19	118.11 (16)
C7—C6—H6	120.1	C17—C18—H18	120.9
C6—C7—C8	120.20 (16)	C19—C18—H18	120.9
C6—C7—H7	119.9	N3—C19—C18	124.13 (17)
C8—C7—H7	119.9	N3—C19—H19	117.9
C3—C8—C7	120.51 (15)	C18—C19—H19	117.9
C3—C8—H8	119.7	N3—C20—C21	123.60 (18)
C7—C8—H8	119.7	N3—C20—H20	118.2
C10—C9—S2	112.79 (10)	C21—C20—H20	118.2
C10—C9—H9A	109.0	C20—C21—C17	118.70 (17)
S2—C9—H9A	109.0	C20—C21—H21	120.7
C10—C9—H9B	109.0	C17—C21—H21	120.6

C1—N1—N2—C16	139.71 (13)	C9—C10—C11—C12	179.87 (16)
N2—N1—C1—S2	−176.89 (9)	C10—C11—C12—C13	−0.5 (3)
N2—N1—C1—S1	2.25 (17)	C11—C12—C13—C14	−0.5 (3)
C9—S2—C1—N1	−2.38 (12)	C12—C13—C14—C15	0.9 (3)
C9—S2—C1—S1	178.42 (7)	C13—C14—C15—C10	−0.4 (3)
C2—S1—C1—N1	−168.24 (12)	C11—C10—C15—C14	−0.6 (3)
C2—S1—C1—S2	10.91 (9)	C9—C10—C15—C14	−179.43 (16)
C1—S1—C2—C3	−179.46 (10)	N1—N2—C16—O1	−5.9 (2)
S1—C2—C3—C8	−76.56 (15)	N1—N2—C16—C17	177.46 (11)
S1—C2—C3—C4	105.00 (15)	O1—C16—C17—C18	−162.44 (15)
C8—C3—C4—C5	−0.1 (3)	N2—C16—C17—C18	14.3 (2)
C2—C3—C4—C5	178.34 (16)	O1—C16—C17—C21	13.6 (2)
C3—C4—C5—C6	0.3 (3)	N2—C16—C17—C21	−169.68 (13)
C4—C5—C6—C7	−0.3 (3)	C21—C17—C18—C19	1.3 (2)
C5—C6—C7—C8	0.1 (3)	C16—C17—C18—C19	177.25 (13)
C4—C3—C8—C7	−0.1 (2)	C20—N3—C19—C18	−0.4 (3)
C2—C3—C8—C7	−178.54 (14)	C17—C18—C19—N3	−0.5 (2)
C6—C7—C8—C3	0.1 (3)	C19—N3—C20—C21	0.4 (3)
C1—S2—C9—C10	−86.57 (11)	N3—C20—C21—C17	0.4 (3)
S2—C9—C10—C11	104.40 (15)	C18—C17—C21—C20	−1.3 (2)
S2—C9—C10—C15	−76.77 (16)	C16—C17—C21—C20	−177.54 (14)
C15—C10—C11—C12	1.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···O1ⁱ	0.864 (17)	1.936 (17)	2.7852 (15)	167.4 (16)
C7—H7···N3ⁱⁱ	0.95	2.54	3.339 (2)	142
C8—H8···N3ⁱⁱⁱ	0.95	2.52	3.424 (2)	158
C18—H18···O1ⁱ	0.95	2.53	3.365 (2)	147

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

Experimental details

Crystal data
Chemical formula	C₂₁H₁₉N₃OS₂
M_r	393.51
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	11.2593 (4), 21.2182 (7), 8.6041 (3)
β (°)	103.678 (3)
V (Å³)	1997.24 (12)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	2.54
Crystal size (mm)	0.50 × 0.36 × 0.16

Data collection
Diffractometer	Agilent Xcaliber Eos Gemini diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.42, 0.67
No. of measured, independent and observed [I > 2σ(I)] reflections	38338, 3867, 3715
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.615

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.097, 1.03
No. of reflections	3867
No. of parameters	247
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.32

Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···O1ⁱ	0.864 (17)	1.936 (17)	2.7852 (15)	167.4 (16)
C7—H7···N3ⁱⁱ	0.95	2.54	3.339 (2)	142
C8—H8···N3ⁱⁱⁱ	0.95	2.52	3.424 (2)	158
C18—H18···O1ⁱ	0.95	2.53	3.365 (2)	147

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

Footnotes

‡Additional correspondence author, e-mail: kacrouse@gmail.com.

Acknowledgements

Support for the project came from Universiti Putra Malaysia (UPM) under their Research University Grant Scheme (RUGS No. 9174000), the Malaysian Ministry of Science, Technology and Innovation (grant No. 09-02-04-0752-EA001) and the Malaysian Fundamental Research Grant Scheme (FRGS No. 01-13-11-986FR). We also thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (grant No. UM.C/HIR/MOHE/SC/12).

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