Crystal structure of S-hexyl (E)-3-(4-methoxy­benzyl­idene)di­thio­carbazate

Begum, M.S.; Howlader, M.B.H.; Miyatake, R.; Zangrando, E.; Sheikh, M.C.

doi:10.1107/S2056989015003199

organic compounds

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Volume 71| Part 3| March 2015| Page o199

doi:10.1107/S2056989015003199

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Crystal structure of S-hexyl (E)-3-(4-methoxybenzylidene)dithiocarbazate

M. S. Begum,^a ^* M. B. H. Howlader,^a R. Miyatake,^b E. Zangrando ^c and M. C. Sheikh ^d

^aDepartment of Chemistry, Rajshahi University, Rajshahi-6205, Bangladesh, ^bCenter for Environmental Conservation and Research Safety, University of Toyama, 3190 Gofuku, Toyama 930-8555, Japan, ^cDepartment of Chemical and Pharmaceutical Sciences, Via Giorgieri 1, 34127 Trieste, Italy, and ^dDepartment of Applied Chemistry, Faculty of Engineering, University of Toyama, 3190 Gofuku, Toyama, 930-8555, Japan
^*Correspondence e-mail: sabina_sust@yahoo.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 14 February 2015; accepted 15 February 2015; online 25 February 2015)

In the title compound, C₁₅H₂₂N₂OS₂, the dithiocarbazate group adopts an EE conformation with respect to the C=N bond of the benzylidene moiety. The hexyl side chain adopts an extended conformation and the C—S—C—C torsion angle is −93.36 (13)°. In the crystal, inversion dimers linked by pairs of N—H⋯S hydrogen bonds generate R₂²(8) loops.

Keywords: crystal structure; dithiocarbazate; S-containing Schiff bases; hydrogen bonding.

CCDC reference: 1044475

1. Related literature

For a related structure and background references to Schiff bases, see: Howlader et al. (2015 ).

2. Experimental

2.1. Crystal data

C₁₅H₂₂N₂OS₂
M_r = 310.47
Triclinic, $[P \overline 1]$
a = 4.55596 (8) Å
b = 12.4224 (3) Å
c = 14.9619 (3) Å
α = 75.7300 (9)°
β = 84.7599 (10)°
γ = 84.6141 (9)°
V = 814.99 (3) Å³
Z = 2
Cu Kα radiation
μ = 2.93 mm⁻¹
T = 173 K
0.29 × 0.26 × 0.17 mm

2.2. Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Rigaku, 1995 ) T_min = 0.350, T_max = 0.607
9377 measured reflections
2932 independent reflections
2385 reflections with F² > 2σ(F²)
R_int = 0.082

2.3. Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.131
S = 1.08
2932 reflections
187 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H9⋯S1ⁱ	0.92 (3)	2.51 (3)	3.3614 (18)	154 (2)
Symmetry code: (i) -x, -y+1, -z+1.

Data collection: RAPID-AUTO (Rigaku, 2010 ); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: CrystalStructure (Rigaku, 2010); software used to prepare material for publication: CrystalStructure.

Supporting information

CCDC reference: 1044475

Crystal structure: contains datablocks General, I. DOI: 10.1107/S2056989015003199/hb7372sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015003199/hb7372Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015003199/hb7372Isup3.cml

checkCIF report

Chemical context top

As part of our ongoing structural studies of S-containing Schiff bases (Howlader et al., 2015), we now describe the structure of the title compound.

Structural commentary top

The molecule of the title compound is shown in Fig. 1. The Schiff base exists in thione tautomeric form with the dithiocarbazate fragment adopting an EE configuration with respect to the C=N bond of the benzylidene moiety. The β-nitrogen and the thioketo sulphur are trans located with respect to the C(9)—N(2) bond. With the exception of the S-hexyl chain the molecule shows co-planar atoms indicating an electron delocalization within it. The bond lengths and angles are close comparable to those detected in the S-hexyl (E)-3-(4-methylbenzylidene)dithiocarbazate (Howlader et al., 2015) which differs for a methyl replacing the methoxy group -O(1)—CH₃. However a different conformation is exhibited by the hexyl chain in the two molecules likely induced by packing requirements. In fact the torsion angle S(2)—C(10)—C(11)—C(12) is of 173.99 (13) and 66.61 (1)° in the present complex and in the methyl derivative, respectively.

Supramolecular features top

The crystal packing evidences the ligand molecules piled along axis a and connected in pair by N2—H···S1 hydrogen bonds (H···S = 2.51 (3) Å, N···S = 3.361 (2) Å, O–H···S angle = 154 (2)°) as shown in Fig. 2. On the other hand no appreciable π–π interaction among aromatic rings is present in the crystal packing.

Synthesis and crystallization top

To an ethanolic solution of KOH (2.81 g, 0.05 mol) hydrazine hydrate (2.50 g, 0.05 mol, 99%) was added and the mixture was stirred at 273 K. To this solution carbon disulfide (3.81 g, 0.05 mol) was added dropwise with constant stirring for one hour. Then n-bromohexane (8.25 g, 0.05 mol) was added dropwise with vigorous stirring at 273 K for an additional hour. Finally, 4-methoxybenzaldehyde (6.81 g, 0.05 mol) in ethanol was added and the mixture refluxed for 30 min. The mixture was filtered while hot and then the filtrate was cooled to 273 K giving a precipitate of the Schiff base product. It was recrystallized from ethanol at room temperature and dried in a vacuum desiccator over anhydrous CaCl₂. Colourless blocks of the title compound were obtained by slow evaporation of an ethanol/chloroform (2:1) solution after 29 days (m.p. 369 K).

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. Hydrogen atoms were located geometrically and treated as riding atoms with C—H = 0.95–0.99 Å and U_ĩso(H) = 1.2U_eq(C). The hydrogen atom at N2 was detected on the difference Fourier map and freely refined.

Related literature top

For a related structure and background references to Schiff bases, see: Howlader et al. (2015).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2010); cell refinement: RAPID-AUTO (Rigaku, 2010); data reduction: RAPID-AUTO (Rigaku, 2010); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku, 2010); software used to prepare material for publication: CrystalStructure (Rigaku, 2010).

Figures top

	Fig. 1. ORTEP drawing (ellipsoid probability at 50%) of molecule (1).
	Fig. 2. Crystal packing of (1) showing pair of molecules connected by N—H..·S interactions (dashed lines). H atoms not involved in hydrogen bonding have been omitted.

S-Hexyl (E)-3-(4-methoxybenzylidene)dithiocarbazate top

Crystal data top

C₁₅H₂₂N₂OS₂	Z = 2
M_r = 310.47	F(000) = 332.00
Triclinic, P1	D_x = 1.265 Mg m⁻³
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54187 Å
a = 4.55596 (8) Å	Cell parameters from 8917 reflections
b = 12.4224 (3) Å	θ = 3.1–68.2°
c = 14.9619 (3) Å	µ = 2.93 mm⁻¹
α = 75.7300 (9)°	T = 173 K
β = 84.7599 (10)°	Prism, colorless
γ = 84.6141 (9)°	0.29 × 0.26 × 0.17 mm
V = 814.99 (3) Å³

Data collection top

Rigaku R-AXIS RAPID diffractometer	2385 reflections with F² > 2σ(F²)
Detector resolution: 10.000 pixels mm^-1	R_int = 0.082
ω scans	θ_max = 68.2°
Absorption correction: multi-scan (ABSCOR; Rigaku, 1995)	h = −5→5
T_min = 0.350, T_max = 0.607	k = −14→14
9377 measured reflections	l = −17→17
2932 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.131	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.070P)²] where P = (F_o² + 2F_c²)/3
2932 reflections	(Δ/σ)_max = 0.001
187 parameters	Δρ_max = 0.55 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³
Primary atom site location: structure-invariant direct methods

Crystal data top

C₁₅H₂₂N₂OS₂	γ = 84.6141 (9)°
M_r = 310.47	V = 814.99 (3) Å³
Triclinic, P1	Z = 2
a = 4.55596 (8) Å	Cu Kα radiation
b = 12.4224 (3) Å	µ = 2.93 mm⁻¹
c = 14.9619 (3) Å	T = 173 K
α = 75.7300 (9)°	0.29 × 0.26 × 0.17 mm
β = 84.7599 (10)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	2932 independent reflections
Absorption correction: multi-scan (ABSCOR; Rigaku, 1995)	2385 reflections with F² > 2σ(F²)
T_min = 0.350, T_max = 0.607	R_int = 0.082
9377 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.131	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.55 e Å⁻³
2932 reflections	Δρ_min = −0.34 e Å⁻³
187 parameters

Special details top

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	−0.15957 (13)	0.58111 (4)	0.61120 (3)	0.0472 (3)
S2	0.02305 (12)	0.40174 (4)	0.77974 (3)	0.0394 (2)
O1	1.3023 (4)	−0.11118 (12)	0.72987 (10)	0.0557 (5)
N1	0.4025 (4)	0.31956 (12)	0.65318 (11)	0.0372 (5)
N2	0.2334 (4)	0.41308 (13)	0.61147 (12)	0.0397 (5)
C1	1.4937 (6)	−0.16105 (19)	0.66823 (17)	0.0612 (7)
C2	1.1429 (5)	−0.01440 (15)	0.69352 (14)	0.0411 (6)
C3	0.9556 (6)	0.03120 (17)	0.75560 (14)	0.0512 (7)
C4	0.7806 (5)	0.12633 (16)	0.72645 (14)	0.0437 (6)
C5	0.7833 (5)	0.18084 (15)	0.63242 (13)	0.0360 (5)
C6	0.9755 (5)	0.13648 (16)	0.57096 (13)	0.0410 (5)
C7	1.1522 (5)	0.03933 (17)	0.60045 (14)	0.0416 (6)
C8	0.5930 (5)	0.28016 (16)	0.59886 (14)	0.0386 (5)
C9	0.0392 (5)	0.46598 (15)	0.66220 (13)	0.0361 (5)
C10	−0.2390 (5)	0.49416 (16)	0.82844 (13)	0.0383 (5)
C11	−0.0961 (5)	0.58123 (16)	0.86125 (13)	0.0380 (5)
C12	−0.3195 (5)	0.65013 (15)	0.91114 (13)	0.0371 (5)
C13	−0.1786 (5)	0.72953 (16)	0.95358 (14)	0.0389 (5)
C14	−0.3987 (5)	0.80105 (16)	1.00112 (15)	0.0443 (6)
C15	−0.2532 (5)	0.87615 (16)	1.04683 (15)	0.0478 (6)
H1	1.6361	−0.1081	0.6350	0.0734*
H2	1.3769	−0.1813	0.6238	0.0734*
H3	1.6000	−0.2281	0.7035	0.0734*
H4	0.9496	−0.0047	0.8196	0.0615*
H5	0.6555	0.1561	0.7702	0.0525*
H6	0.9861	0.1736	0.5073	0.0492*
H7	1.2792	0.0096	0.5571	0.0499*
H8	0.6098	0.3169	0.5351	0.0464*
H9	0.238 (6)	0.437 (2)	0.5482 (18)	0.066 (8)*
H10	−0.3774	0.5321	0.7812	0.0460*
H11	−0.3559	0.4493	0.8812	0.0460*
H12	0.0025	0.6316	0.8074	0.0455*
H13	0.0573	0.5440	0.9036	0.0455*
H14	−0.4602	0.6934	0.8667	0.0445*
H15	−0.4335	0.5989	0.9605	0.0445*
H16	−0.0596	0.7791	0.9044	0.0467*
H17	−0.0421	0.6859	0.9993	0.0467*
H18	−0.5293	0.8476	0.9549	0.0532*
H19	−0.5239	0.7518	1.0485	0.0532*
H20	−0.1348	0.8306	1.0959	0.0574*
H21	−0.4057	0.9225	1.0735	0.0574*
H22	−0.1251	0.9241	1.0007	0.0574*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0602 (5)	0.0390 (4)	0.0377 (4)	0.0190 (3)	−0.0040 (3)	−0.0083 (3)
S2	0.0510 (4)	0.0320 (3)	0.0342 (3)	0.0070 (3)	−0.0034 (3)	−0.0094 (2)
O1	0.0693 (12)	0.0408 (9)	0.0489 (9)	0.0207 (8)	−0.0009 (8)	−0.0058 (7)
N1	0.0397 (11)	0.0302 (9)	0.0415 (10)	0.0059 (8)	−0.0050 (8)	−0.0104 (7)
N2	0.0460 (12)	0.0356 (9)	0.0352 (10)	0.0096 (8)	−0.0016 (8)	−0.0092 (8)
C1	0.0696 (18)	0.0483 (13)	0.0608 (15)	0.0272 (13)	−0.0060 (13)	−0.0151 (11)
C2	0.0467 (14)	0.0316 (11)	0.0433 (12)	0.0069 (10)	−0.0043 (10)	−0.0091 (9)
C3	0.0699 (18)	0.0436 (12)	0.0353 (11)	0.0114 (12)	−0.0014 (11)	−0.0068 (9)
C4	0.0531 (15)	0.0405 (12)	0.0363 (11)	0.0092 (11)	0.0019 (10)	−0.0132 (9)
C5	0.0366 (13)	0.0328 (10)	0.0393 (11)	0.0018 (9)	−0.0032 (9)	−0.0115 (9)
C6	0.0461 (14)	0.0402 (11)	0.0345 (11)	0.0060 (10)	0.0003 (9)	−0.0096 (9)
C7	0.0436 (14)	0.0405 (11)	0.0399 (11)	0.0073 (10)	0.0018 (9)	−0.0140 (9)
C8	0.0422 (13)	0.0366 (11)	0.0368 (11)	0.0034 (10)	−0.0015 (9)	−0.0110 (9)
C9	0.0384 (12)	0.0292 (10)	0.0412 (11)	0.0023 (9)	−0.0026 (9)	−0.0110 (8)
C10	0.0418 (13)	0.0363 (11)	0.0363 (10)	0.0015 (10)	0.0017 (9)	−0.0112 (9)
C11	0.0404 (13)	0.0358 (10)	0.0380 (11)	0.0028 (10)	−0.0024 (9)	−0.0117 (9)
C12	0.0390 (13)	0.0329 (10)	0.0386 (11)	0.0003 (10)	0.0017 (9)	−0.0097 (9)
C13	0.0404 (13)	0.0331 (10)	0.0432 (11)	0.0019 (10)	−0.0015 (9)	−0.0115 (9)
C14	0.0461 (14)	0.0356 (11)	0.0521 (13)	−0.0006 (10)	0.0029 (11)	−0.0155 (10)
C15	0.0592 (16)	0.0336 (11)	0.0517 (13)	−0.0005 (11)	−0.0003 (11)	−0.0148 (10)

Geometric parameters (Å, º) top

S1—C9	1.6713 (19)	C1—H1	0.980
S2—C9	1.7408 (19)	C1—H2	0.980
S2—C10	1.809 (2)	C1—H3	0.980
O1—C1	1.424 (3)	C3—H4	0.950
O1—C2	1.362 (3)	C4—H5	0.950
N1—N2	1.377 (2)	C6—H6	0.950
N1—C8	1.281 (3)	C7—H7	0.950
N2—C9	1.343 (3)	C8—H8	0.950
C2—C3	1.391 (3)	C10—H10	0.990
C2—C7	1.387 (3)	C10—H11	0.990
C3—C4	1.362 (3)	C11—H12	0.990
C4—C5	1.402 (3)	C11—H13	0.990
C5—C6	1.389 (3)	C12—H14	0.990
C5—C8	1.449 (3)	C12—H15	0.990
C6—C7	1.385 (3)	C13—H16	0.990
C10—C11	1.512 (4)	C13—H17	0.990
C11—C12	1.529 (3)	C14—H18	0.990
C12—C13	1.513 (4)	C14—H19	0.990
C13—C14	1.522 (3)	C15—H20	0.980
C14—C15	1.514 (4)	C15—H21	0.980
N2—H9	0.92 (3)	C15—H22	0.980

C9—S2—C10	102.71 (9)	C7—C6—H6	119.260
C1—O1—C2	117.93 (16)	C2—C7—H7	120.107
N2—N1—C8	115.16 (16)	C6—C7—H7	120.106
N1—N2—C9	120.57 (16)	N1—C8—H8	119.244
O1—C2—C3	116.35 (17)	C5—C8—H8	119.248
O1—C2—C7	124.76 (19)	S2—C10—H10	108.855
C3—C2—C7	118.89 (18)	S2—C10—H11	108.851
C2—C3—C4	121.27 (18)	C11—C10—H10	108.851
C3—C4—C5	120.7 (2)	C11—C10—H11	108.850
C4—C5—C6	117.88 (17)	H10—C10—H11	107.702
C4—C5—C8	121.99 (19)	C10—C11—H12	109.133
C6—C5—C8	120.13 (17)	C10—C11—H13	109.138
C5—C6—C7	121.48 (17)	C12—C11—H12	109.128
C2—C7—C6	119.8 (2)	C12—C11—H13	109.124
N1—C8—C5	121.51 (17)	H12—C11—H13	107.854
S2—C9—S1	126.46 (13)	C11—C12—H14	108.871
S2—C9—N2	113.32 (13)	C11—C12—H15	108.874
S1—C9—N2	120.22 (14)	C13—C12—H14	108.869
S2—C10—C11	113.57 (15)	C13—C12—H15	108.863
C10—C11—C12	112.36 (17)	H14—C12—H15	107.709
C11—C12—C13	113.50 (17)	C12—C13—H16	108.730
C12—C13—C14	114.11 (18)	C12—C13—H17	108.731
C13—C14—C15	113.33 (19)	C14—C13—H16	108.724
N1—N2—H9	120.7 (15)	C14—C13—H17	108.719
C9—N2—H9	118.5 (15)	H16—C13—H17	107.637
O1—C1—H1	109.480	C13—C14—H18	108.903
O1—C1—H2	109.467	C13—C14—H19	108.907
O1—C1—H3	109.466	C15—C14—H18	108.906
H1—C1—H2	109.470	C15—C14—H19	108.918
H1—C1—H3	109.471	H18—C14—H19	107.733
H2—C1—H3	109.473	C14—C15—H20	109.466
C2—C3—H4	119.366	C14—C15—H21	109.469
C4—C3—H4	119.363	C14—C15—H22	109.479
C3—C4—H5	119.668	H20—C15—H21	109.471
C5—C4—H5	119.669	H20—C15—H22	109.465
C5—C6—H6	119.260	H21—C15—H22	109.476

C9—S2—C10—C11	−93.36 (13)	C2—C3—C4—C5	0.4 (4)
C10—S2—C9—S1	−2.95 (18)	C3—C4—C5—C6	−1.8 (4)
C10—S2—C9—N2	177.54 (14)	C3—C4—C5—C8	178.0 (2)
C1—O1—C2—C3	179.23 (18)	C4—C5—C6—C7	2.3 (3)
C1—O1—C2—C7	0.2 (3)	C4—C5—C8—N1	−3.6 (4)
N2—N1—C8—C5	−178.88 (17)	C6—C5—C8—N1	176.24 (19)
C8—N1—N2—C9	−175.79 (17)	C8—C5—C6—C7	−177.54 (18)
N1—N2—C9—S2	−1.8 (3)	C5—C6—C7—C2	−1.3 (4)
N1—N2—C9—S1	178.61 (15)	S2—C10—C11—C12	−173.99 (10)
O1—C2—C3—C4	−178.38 (19)	C10—C11—C12—C13	173.87 (13)
O1—C2—C7—C6	178.73 (19)	C11—C12—C13—C14	178.35 (13)
C3—C2—C7—C6	−0.2 (4)	C12—C13—C14—C15	177.40 (13)
C7—C2—C3—C4	0.7 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H9···S1ⁱ	0.92 (3)	2.51 (3)	3.3614 (18)	154 (2)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H9···S1ⁱ	0.92 (3)	2.51 (3)	3.3614 (18)	154 (2)

Symmetry code: (i) −x, −y+1, −z+1.

Acknowledgements

MBHH and MSB are grateful to the Department of Chemistry, Rajshahi University, for the provision of laboratory facilities. MCS acknowledges the Department of Applied Chemistry, Toyama University, for providing funds for single-crystal X-ray analyses.

References

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ISSN: 2056-9890

Volume 71| Part 3| March 2015| Page o199

doi:10.1107/S2056989015003199

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