(E)-4-Octyloxybenzaldehyde thio­semicarbazone

Islam, M.A.A.A.A.; Tarafder, M.T.H.; Zakaria, C.M.; Guidolin, N.; Zangrando, E.

doi:10.1107/S1600536809054841

organic compounds

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ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page o241

doi:10.1107/S1600536809054841

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(E)-4-Octyloxybenzaldehyde thiosemicarbazone

M. A. A. A. A. Islam,^a M. T. H. Tarafder,^b ^* C. M. Zakaria,^b N. Guidolin ^c and E. Zangrando ^c

^aDepartment of Chemistry, Rajshahi University of Engineering & Technology, Rajshahi 6204, Bangladesh, ^bDepartment of Chemistry, Rajshahi University, Rajshahi 6205, Bangladesh, and ^cDipartimento di Scienze Chimiche, Via Licio Giorgieri 1, 34127 Trieste, Italy
^*Correspondence e-mail: ttofazzal@yahoo.com

(Received 24 November 2009; accepted 21 December 2009; online 24 December 2009)

In the title compound, C₁₆H₂₅N₃OS, the thiosemicarbazone group adopts an E configuration with respect to the C=N bond and is almost coplanar with the benzene ring, forming a dihedral angle of 9.3 (1)°. In the crystal packing, the molecules lie along the a axis in an antiparallel arrangement and are held in place by van der Waals interactions. As a consequence, there is relatively low anisotropic thermal motion in the terminal atoms of the n-octyl chain.

Related literature

For the related structures, see: Basuli et al. (2000 ); Narayana et al. (2007 ); Pal et al. (2002 ); Tian et al. (2002 ); Tarafder et al. (2008 ).

Experimental

Crystal data

C₁₆H₂₅N₃OS
M_r = 307.45
Triclinic, $[P \overline 1]$
a = 5.785 (2) Å
b = 7.586 (2) Å
c = 20.789 (4) Å
α = 94.74 (2)°
β = 91.85 (2)°
γ = 104.42 (3)°
V = 879.2 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.19 mm⁻¹
T = 293 K
0.42 × 0.40 × 0.14 mm

Data collection

Enraf–Nonius dip1030 image-plate diffractometer
9930 measured reflections
3226 independent reflections
2749 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.140
S = 1.04
3226 reflections
191 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: XPRESS (MacScience, 2002 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); 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, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809054841/fj2264sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809054841/fj2264Isup2.hkl

checkCIF report

Comment top

When used in coordination chemistry this molecule is potentially a bidentate ligand acting through the α- or β-nitrogen and thiolate sulfur anion forming a four- and five-membered chelate ring, respectively (Pal et al., 2002), although a behavior as monocoordinated ligand through sulfur has also been reported (Tian et al., 2002). In the crystal structure the molecules are interconnected by N—H···N and N–H···S hydrogen bonds as found in other thiosemicarbazone species (Narayana et al., 2007; Tarafder et al., 2008). The crystal structure is also stabilized by C–H···π interactions. The octyl chain presents an anti conformation with the exception of the O1—C9—C10—C11 part that has a torsion angle of -72.7 (3)°.

Related literature top

For the related structures, see: Basuli et al. (2000); Narayana et al. (2007); Pal et al. (2002); Tian et al. (2002); Tarafder et al. (2008).

Experimental top

4-n-octyloxybenzaldehyde (6.09 g, 26 mmol) was added to a hot solution of thiosemicarbazide (2.38 g, 26 mmol) in methanol (200 ml). The mixture was refluxed for 30 min and cooled down to room temperature. The product was recrystallized from dichloromethane to give colorless microcrystals. M.P. 381 K. Brilliant colorless flat rectangular shaped crystals suitable for X-ray difraction were obtained from a mixture of dichloromethane and toluene (10:5; v/v) after 5 days.

Computing details top

Data collection: XPRESS (MacScience, 2002); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELX97 (Sheldrick, 2008); program(s) used to refine structure: SHELX97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. ORTEP drawing (ellipsoids at the 40% probability level) of the compoud with atom-labelling scheme.

(E)-4-Octyloxybenzaldehyde thiosemicarbazone top

Crystal data top

C₁₆H₂₅N₃OS	Z = 2
M_r = 307.45	F(000) = 332
Triclinic, P1	D_x = 1.161 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.785 (2) Å	Cell parameters from 146 reflections
b = 7.586 (2) Å	θ = 3.0–18.1°
c = 20.789 (4) Å	µ = 0.19 mm⁻¹
α = 94.74 (2)°	T = 293 K
β = 91.85 (2)°	Plate, colorless
γ = 104.42 (3)°	0.42 × 0.40 × 0.14 mm
V = 879.2 (4) Å³

Data collection top

Enraf–Nonius dip1030 image-plate diffractometer	2749 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.030
Graphite monochromator	θ_max = 25.7°, θ_min = 3.6°
ϕ–scans with narrow frames	h = −7→7
9930 measured reflections	k = −9→8
3226 independent reflections	l = −25→25

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.140	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.1026P)² + 0.0242P] where P = (F_o² + 2F_c²)/3
3226 reflections	(Δ/σ)_max < 0.001
191 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₆H₂₅N₃OS	γ = 104.42 (3)°
M_r = 307.45	V = 879.2 (4) Å³
Triclinic, P1	Z = 2
a = 5.785 (2) Å	Mo Kα radiation
b = 7.586 (2) Å	µ = 0.19 mm⁻¹
c = 20.789 (4) Å	T = 293 K
α = 94.74 (2)°	0.42 × 0.40 × 0.14 mm
β = 91.85 (2)°

Data collection top

Enraf–Nonius dip1030 image-plate diffractometer	2749 reflections with I > 2σ(I)
9930 measured reflections	R_int = 0.030
3226 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.140	H-atom parameters constrained
S = 1.04	Δρ_max = 0.19 e Å⁻³
3226 reflections	Δρ_min = −0.18 e Å⁻³
191 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	1.33919 (6)	−0.29398 (5)	0.99374 (2)	0.06930 (19)
N1	1.0386 (2)	0.02579 (17)	0.89975 (6)	0.0648 (3)
N2	1.1983 (2)	−0.04336 (17)	0.93483 (6)	0.0690 (3)
H2	1.3435	0.0203	0.9421	0.083*
N3	0.9025 (2)	−0.29670 (17)	0.94909 (6)	0.0668 (3)
H3A	0.8033	−0.2489	0.9295	0.080*
H3B	0.8534	−0.4024	0.9631	0.080*
O1	0.6110 (2)	0.55328 (16)	0.73145 (6)	0.0812 (3)
C1	1.1305 (2)	−0.20768 (19)	0.95761 (7)	0.0591 (3)
C2	1.1216 (3)	0.1882 (2)	0.88465 (7)	0.0663 (4)
H2A	1.2764	0.2498	0.8995	0.080*
C3	0.9864 (3)	0.2818 (2)	0.84546 (7)	0.0630 (4)
C4	0.7501 (3)	0.2031 (2)	0.82202 (7)	0.0681 (4)
H4	0.6725	0.0867	0.8321	0.082*
C5	0.6322 (3)	0.2971 (2)	0.78409 (8)	0.0716 (4)
H5	0.4761	0.2431	0.7683	0.086*
C6	0.7444 (3)	0.4721 (2)	0.76919 (7)	0.0677 (4)
C7	0.9777 (3)	0.5528 (2)	0.79263 (7)	0.0726 (4)
H7	1.0536	0.6704	0.7833	0.087*
C8	1.0957 (3)	0.4563 (2)	0.82997 (7)	0.0698 (4)
H8	1.2526	0.5100	0.8451	0.084*
C9	0.7089 (4)	0.7404 (2)	0.72041 (9)	0.0880 (5)
H9A	0.8564	0.7529	0.6983	0.106*
H9B	0.7432	0.8161	0.7612	0.106*
C10	0.5257 (4)	0.7986 (3)	0.67937 (9)	0.0890 (5)
H10A	0.3717	0.7624	0.6982	0.107*
H10B	0.5693	0.9309	0.6805	0.107*
C11	0.5012 (4)	0.7192 (3)	0.60985 (8)	0.0811 (5)
H11A	0.4523	0.5869	0.6085	0.097*
H11B	0.6561	0.7522	0.5913	0.097*
C12	0.3221 (3)	0.7838 (3)	0.56889 (9)	0.0817 (5)
H12A	0.1660	0.7448	0.5863	0.098*
H12B	0.3662	0.9164	0.5727	0.098*
C13	0.3025 (3)	0.7155 (2)	0.49799 (9)	0.0826 (5)
H13A	0.2573	0.5828	0.4940	0.099*
H13B	0.4583	0.7543	0.4803	0.099*
C14	0.1228 (3)	0.7824 (3)	0.45814 (8)	0.0810 (5)
H14A	−0.0331	0.7420	0.4756	0.097*
H14B	0.1667	0.9150	0.4629	0.097*
C15	0.1029 (4)	0.7182 (3)	0.38689 (9)	0.0891 (5)
H15A	0.0562	0.5857	0.3819	0.107*
H15B	0.2589	0.7573	0.3693	0.107*
C16	−0.0752 (4)	0.7893 (3)	0.34816 (10)	0.0987 (6)
H16A	−0.2329	0.7416	0.3624	0.148*
H16B	−0.0710	0.7509	0.3031	0.148*
H16C	−0.0347	0.9204	0.3544	0.148*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0526 (3)	0.0696 (3)	0.0871 (3)	0.01517 (17)	−0.00582 (18)	0.02038 (19)
N1	0.0600 (7)	0.0703 (8)	0.0671 (7)	0.0211 (5)	−0.0045 (5)	0.0120 (6)
N2	0.0551 (7)	0.0706 (8)	0.0817 (8)	0.0141 (6)	−0.0097 (6)	0.0204 (6)
N3	0.0527 (6)	0.0681 (7)	0.0810 (8)	0.0158 (5)	−0.0032 (5)	0.0155 (6)
O1	0.0863 (8)	0.0834 (7)	0.0823 (7)	0.0315 (6)	−0.0029 (6)	0.0277 (6)
C1	0.0534 (7)	0.0639 (8)	0.0604 (8)	0.0158 (6)	0.0003 (6)	0.0060 (6)
C2	0.0666 (9)	0.0705 (9)	0.0627 (8)	0.0181 (7)	−0.0032 (6)	0.0120 (7)
C3	0.0680 (8)	0.0687 (8)	0.0555 (7)	0.0224 (6)	0.0007 (6)	0.0090 (6)
C4	0.0709 (9)	0.0664 (8)	0.0691 (9)	0.0191 (7)	0.0004 (7)	0.0152 (7)
C5	0.0677 (9)	0.0792 (10)	0.0713 (9)	0.0228 (7)	−0.0027 (7)	0.0159 (7)
C6	0.0774 (9)	0.0744 (9)	0.0587 (8)	0.0309 (7)	0.0027 (7)	0.0132 (7)
C7	0.0831 (10)	0.0666 (9)	0.0687 (9)	0.0177 (7)	0.0007 (7)	0.0153 (7)
C8	0.0712 (9)	0.0711 (9)	0.0662 (9)	0.0159 (7)	−0.0042 (7)	0.0102 (7)
C9	0.1125 (15)	0.0781 (11)	0.0813 (11)	0.0368 (10)	−0.0047 (10)	0.0185 (9)
C10	0.1121 (15)	0.0853 (11)	0.0837 (12)	0.0468 (11)	0.0025 (10)	0.0239 (9)
C11	0.0900 (12)	0.0816 (11)	0.0815 (11)	0.0349 (9)	0.0066 (9)	0.0225 (8)
C12	0.0882 (12)	0.0861 (11)	0.0802 (11)	0.0350 (9)	0.0053 (9)	0.0224 (9)
C13	0.0886 (12)	0.0810 (11)	0.0843 (11)	0.0299 (9)	0.0039 (9)	0.0174 (9)
C14	0.0875 (12)	0.0802 (10)	0.0797 (11)	0.0276 (9)	0.0040 (8)	0.0146 (8)
C15	0.0945 (13)	0.0900 (12)	0.0859 (12)	0.0307 (10)	−0.0021 (9)	0.0068 (9)
C16	0.1001 (14)	0.1156 (15)	0.0842 (12)	0.0372 (12)	−0.0079 (10)	0.0060 (11)

Geometric parameters (Å, º) top

S1—C1	1.6930 (15)	C9—H9A	0.9700
N1—C2	1.275 (2)	C9—H9B	0.9700
N1—N2	1.3863 (16)	C10—C11	1.507 (3)
N2—C1	1.341 (2)	C10—H10A	0.9700
N2—H2	0.8600	C10—H10B	0.9700
N3—C1	1.3227 (19)	C11—C12	1.518 (2)
N3—H3A	0.8600	C11—H11A	0.9700
N3—H3B	0.8600	C11—H11B	0.9700
O1—C6	1.3665 (19)	C12—C13	1.513 (3)
O1—C9	1.432 (2)	C12—H12A	0.9700
C2—C3	1.453 (2)	C12—H12B	0.9700
C2—H2A	0.9300	C13—C14	1.517 (2)
C3—C8	1.387 (2)	C13—H13A	0.9700
C3—C4	1.402 (2)	C13—H13B	0.9700
C4—C5	1.377 (2)	C14—C15	1.512 (3)
C4—H4	0.9300	C14—H14A	0.9700
C5—C6	1.390 (2)	C14—H14B	0.9700
C5—H5	0.9300	C15—C16	1.515 (3)
C6—C7	1.389 (2)	C15—H15A	0.9700
C7—C8	1.383 (2)	C15—H15B	0.9700
C7—H7	0.9300	C16—H16A	0.9600
C8—H8	0.9300	C16—H16B	0.9600
C9—C10	1.511 (3)	C16—H16C	0.9600

C2—N1—N2	114.83 (13)	C9—C10—H10A	108.7
C1—N2—N1	121.23 (12)	C11—C10—H10B	108.7
C1—N2—H2	119.4	C9—C10—H10B	108.7
N1—N2—H2	119.4	H10A—C10—H10B	107.6
C1—N3—H3A	120.0	C10—C11—C12	113.38 (15)
C1—N3—H3B	120.0	C10—C11—H11A	108.9
H3A—N3—H3B	120.0	C12—C11—H11A	108.9
C6—O1—C9	117.89 (14)	C10—C11—H11B	108.9
N3—C1—N2	117.74 (13)	C12—C11—H11B	108.9
N3—C1—S1	123.14 (12)	H11A—C11—H11B	107.7
N2—C1—S1	119.09 (11)	C13—C12—C11	114.97 (15)
N1—C2—C3	123.26 (14)	C13—C12—H12A	108.5
N1—C2—H2A	118.4	C11—C12—H12A	108.5
C3—C2—H2A	118.4	C13—C12—H12B	108.5
C8—C3—C4	118.26 (14)	C11—C12—H12B	108.5
C8—C3—C2	118.79 (14)	H12A—C12—H12B	107.5
C4—C3—C2	122.94 (15)	C12—C13—C14	113.91 (15)
C5—C4—C3	120.37 (15)	C12—C13—H13A	108.8
C5—C4—H4	119.8	C14—C13—H13A	108.8
C3—C4—H4	119.8	C12—C13—H13B	108.8
C4—C5—C6	120.57 (15)	C14—C13—H13B	108.8
C4—C5—H5	119.7	H13A—C13—H13B	107.7
C6—C5—H5	119.7	C15—C14—C13	114.88 (16)
O1—C6—C7	124.47 (15)	C15—C14—H14A	108.5
O1—C6—C5	115.77 (15)	C13—C14—H14A	108.5
C7—C6—C5	119.76 (15)	C15—C14—H14B	108.5
C8—C7—C6	119.26 (15)	C13—C14—H14B	108.5
C8—C7—H7	120.4	H14A—C14—H14B	107.5
C6—C7—H7	120.4	C14—C15—C16	113.71 (16)
C7—C8—C3	121.78 (15)	C14—C15—H15A	108.8
C7—C8—H8	119.1	C16—C15—H15A	108.8
C3—C8—H8	119.1	C14—C15—H15B	108.8
O1—C9—C10	107.53 (17)	C16—C15—H15B	108.8
O1—C9—H9A	110.2	H15A—C15—H15B	107.7
C10—C9—H9A	110.2	C15—C16—H16A	109.5
O1—C9—H9B	110.2	C15—C16—H16B	109.5
C10—C9—H9B	110.2	H16A—C16—H16B	109.5
H9A—C9—H9B	108.5	C15—C16—H16C	109.5
C11—C10—C9	114.12 (15)	H16A—C16—H16C	109.5
C11—C10—H10A	108.7	H16B—C16—H16C	109.5

C2—N1—N2—C1	175.56 (13)	O1—C6—C7—C8	−179.39 (14)
N1—N2—C1—N3	−4.3 (2)	C5—C6—C7—C8	0.7 (2)
N1—N2—C1—S1	174.08 (10)	C6—C7—C8—C3	−0.9 (2)
N2—N1—C2—C3	177.06 (12)	C4—C3—C8—C7	0.2 (2)
N1—C2—C3—C8	−177.92 (14)	C2—C3—C8—C7	179.72 (13)
N1—C2—C3—C4	1.6 (2)	C6—O1—C9—C10	−178.39 (13)
C8—C3—C4—C5	0.7 (2)	O1—C9—C10—C11	−73.0 (2)
C2—C3—C4—C5	−178.83 (13)	C9—C10—C11—C12	−178.21 (16)
C3—C4—C5—C6	−0.8 (2)	C10—C11—C12—C13	176.73 (17)
C9—O1—C6—C7	−6.4 (2)	C11—C12—C13—C14	−179.85 (15)
C9—O1—C6—C5	173.52 (14)	C12—C13—C14—C15	179.08 (16)
C4—C5—C6—O1	−179.76 (13)	C13—C14—C15—C16	−179.20 (17)
C4—C5—C6—C7	0.1 (2)

Experimental details

Crystal data
Chemical formula	C₁₆H₂₅N₃OS
M_r	307.45
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	5.785 (2), 7.586 (2), 20.789 (4)
α, β, γ (°)	94.74 (2), 91.85 (2), 104.42 (3)
V (Å³)	879.2 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.19
Crystal size (mm)	0.42 × 0.40 × 0.14

Data collection
Diffractometer	Enraf–Nonius dip1030 image-plate diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	9930, 3226, 2749
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.609

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.140, 1.04
No. of reflections	3226
No. of parameters	191
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.18

Computer programs: XPRESS (MacScience, 2002), DENZO (Otwinowski & Minor, 1997), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELX97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Acknowledgements

MAAAAI, MTHT and CMZ are grateful to Rajshahi University for the provision of laboratory facilities. MAAAAI thanks Rajshahi University of Engineering and Technology for sanctioning sabbatical leave and NG thanks MIUR, Rome (PRIN No. 2007HMTJWP_002) for a fellowship.

References

Basuli, F., Peng, S.-M. & Bhattacharya, S. (2000). Inorg. Chem. 39, 1120–1127. Web of Science CSD CrossRef PubMed CAS Google Scholar
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