Crystal structure of 1-(4-formyl­benzyl­idene)-4-methyl­thio­semicarbazone

Pino-Cuevas, A.; Carballo, R.; Vázquez-López, E.M.

doi:10.1107/S1600536814016407

organic compounds

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doi:10.1107/S1600536814016407

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Crystal structure of 1-(4-formylbenzylidene)-4-methylthiosemicarbazone

Arantxa Pino-Cuevas,^a Rosa Carballo ^a and Ezequiel M. Vázquez-López ^a ^*

^aDepartamento de Química Inorgánica, Facultade de Química, Edificio de Ciencias Experimentais, Universidade de Vigo, E-36310 Vigo, Galicia, Spain
^*Correspondence e-mail: ezequiel@uvigo.es

Edited by E. R. T. Tiekink, University of Malaya, Malaysia (Received 11 July 2014; accepted 15 July 2014; online 1 August 2014)

The structure of the title compound, C₁₀H₁₁N₃OS, comprises an approximately planar molecule, with the r.m.s. deviation for the 15 non-H atoms being 0.089 Å. The conformation about the imine bond is E and an intramolecular N—H⋯N hydrogen bond is evident. Molecules are linked into a supramolecular chain along the b axis by N—H⋯S hydrogen bonds.

Keywords: crystal structure; thiosemicarbazone; thiourea; hydrogen bonding.

CCDC reference: 1014062

1. Related literature

For the synthesis of the title compound, see: Jagst et al. (2005 ). For biological properties, see: Serda et al. (2012 ). For supramolecular studies of thiosemicarbazones, see: Alonso et al. (2002 ).

2. Experimental

2.1. Crystal data

C₁₀H₁₁N₃OS
M_r = 221.28
Orthorhombic, P b c a
a = 13.1231 (3) Å
b = 8.8559 (2) Å
c = 19.3702 (4) Å
V = 2251.14 (9) Å³
Z = 8
Cu Kα radiation
μ = 2.38 mm⁻¹
T = 296 K
0.14 × 0.13 × 0.05 mm

2.2. Data collection

Bruker CCD SMART 6000 diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.730, T_max = 0.898
22698 measured reflections
1986 independent reflections
1798 reflections with I > 2σ(I)
R_int = 0.046

2.3. Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.100
S = 1.08
1986 reflections
145 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯S1ⁱ	0.902 (19)	2.53 (2)	3.4154 (14)	165.6 (16)
N1—H1⋯N3	0.84 (2)	2.238 (18)	2.6467 (18)	109.9 (15)
N1—H1⋯S1ⁱⁱ	0.84 (2)	2.992 (19)	3.5401 (15)	124.6 (16)
Symmetry codes: (i) -x+2, -y+2, -z+1; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z]$ .

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Bruno et al., 2002 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1014062

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536814016407/tk5328sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814016407/tk5328Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814016407/tk5328Isup3.cml

checkCIF report

Synthesis and crystallization top

A solution of 4-methyl-3-thiosemicarbazide (392 mg, 3.72 mmol) in water (50 mL) was slowly added at 50°C to a solution of terephthaldicarboxaldehyde (500 mg, 3.73 mmol) in 100 mL water. Then the mixture was stirred at 50°C for 30 mins. Once cooled to room temperature, the yellow solid was filtered off and vacuum dried. Yellow single crystals suitable for X-ray diffraction were obtained by recrystallization from EtOH/H₂O (1:1). Yield: 91%, M. pt: 213-216 °C. IR data (KBr, cm^-1): 3368m, 3150m ν(N—H); 2838w, 2742w ν(C—H aldehyde); 1692 s ν(C═O); 1545 s, 1257m ν(C═N), 833m, 777w ν(C═S). ¹H NMR data (DMSO-d₆, ppm): 11.72 (s, 1H, N(2)—H); 10.03 (s, 1H, C(1)—H); 8.69 (s, 1H, N(2)—H); 8.11 (s, 1H, C(8)—H); 8.04 (d, 2H, J = 8.1 Hz, C(3,7)-H); 7.94 (d, 2H, J = 8.1 Hz, C(4,6)-H); 3.04 (s, 3H, C(10)—H).

Refinement top

Carbon-bound H-atoms were placed in calculated positions (C—H = 0.95–0.99 Å) and were included in the refinement in the riding model approximation, with U_iso(H) = 1.2U_eq(C). The N-bound H-atoms were located in a difference Fourier map but were refined with distance restraints N—H = 0.84 (1) and 0.90 (1) Å, and with U_iso(H) = 1.2U_eq(N).

Related literature top

For the synthesis of the title compound, see: Jagst et al. (2005). For biological properties, see: Serda et al. (2012). For supramolecular studies of thiosemicarbazones, see: Alonso et al. (2002).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007; data reduction: SAINT (Bruker, 2007; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Bruno et al., 2002); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the title compound showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level.
	Fig. 2. View of supramolecular chain formed by N—H···S interactions (dashed lines).

1-[(4-formylbenzylidene)amino]-3-methylthiourea top

Crystal data top

C₁₀H₁₁N₃OS	F(000) = 928
M_r = 221.28	D_x = 1.306 Mg m⁻³
Orthorhombic, Pbca	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 9894 reflections
a = 13.1231 (3) Å	θ = 4.6–66.6°
b = 8.8559 (2) Å	µ = 2.38 mm⁻¹
c = 19.3702 (4) Å	T = 296 K
V = 2251.14 (9) Å³	Plate, yellow
Z = 8	0.14 × 0.13 × 0.05 mm

Data collection top

Bruker CCD SMART 6000 diffractometer	1986 independent reflections
Radiation source: fine-focus sealed tube	1798 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
ϕ and ω scans	θ_max = 66.6°, θ_min = 4.6°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −15→15
T_min = 0.730, T_max = 0.898	k = −10→10
22698 measured reflections	l = −22→22

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0559P)² + 0.3598P] where P = (F_o² + 2F_c²)/3
1986 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₁₀H₁₁N₃OS	V = 2251.14 (9) Å³
M_r = 221.28	Z = 8
Orthorhombic, Pbca	Cu Kα radiation
a = 13.1231 (3) Å	µ = 2.38 mm⁻¹
b = 8.8559 (2) Å	T = 296 K
c = 19.3702 (4) Å	0.14 × 0.13 × 0.05 mm

Data collection top

Bruker CCD SMART 6000 diffractometer	1986 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	1798 reflections with I > 2σ(I)
T_min = 0.730, T_max = 0.898	R_int = 0.046
22698 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.21 e Å⁻³
1986 reflections	Δρ_min = −0.16 e Å⁻³
145 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
S1	0.90393 (3)	1.04683 (4)	0.40705 (2)	0.06222 (18)
O1	0.88220 (12)	−0.01792 (18)	0.72752 (8)	0.0921 (5)
N1	0.81376 (12)	0.78044 (16)	0.39148 (7)	0.0655 (4)
C1	0.87314 (11)	0.86850 (16)	0.42864 (8)	0.0517 (3)
N2	0.90945 (10)	0.81086 (15)	0.48868 (7)	0.0579 (3)
C2	0.92328 (12)	0.62083 (19)	0.56504 (9)	0.0605 (4)
H2	0.9617	0.6879	0.5913	0.073*
N3	0.88781 (9)	0.66473 (14)	0.50704 (7)	0.0542 (3)
C3	0.90556 (11)	0.46928 (19)	0.59137 (8)	0.0536 (4)
C4	0.93836 (15)	0.43343 (19)	0.65777 (9)	0.0678 (4)
H4	0.9707	0.5066	0.6844	0.081*
C5	0.92354 (14)	0.2913 (2)	0.68448 (9)	0.0675 (4)
H5	0.9454	0.2692	0.7290	0.081*
C6	0.87602 (11)	0.18070 (18)	0.64526 (8)	0.0554 (4)
C7	0.84324 (11)	0.21631 (18)	0.57902 (8)	0.0558 (4)
H7	0.8112	0.1429	0.5524	0.067*
C8	0.85745 (11)	0.35836 (17)	0.55224 (8)	0.0543 (4)
H8	0.8349	0.3805	0.5079	0.065*
C9	0.86069 (14)	0.0265 (2)	0.67155 (10)	0.0678 (4)
H9	0.8313	−0.0428	0.6415	0.081*
C10	0.76953 (19)	0.8229 (2)	0.32581 (10)	0.0924 (7)
H10A	0.7165	0.8957	0.3332	0.139*
H10B	0.7415	0.7351	0.3038	0.139*
H10C	0.8213	0.8660	0.2968	0.139*
H2N	0.9542 (15)	0.865 (2)	0.5138 (9)	0.075 (5)*
H1	0.8010 (15)	0.695 (2)	0.4085 (9)	0.073 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0655 (3)	0.0429 (3)	0.0782 (3)	−0.00218 (15)	−0.01004 (18)	0.00628 (16)
O1	0.1022 (10)	0.0890 (10)	0.0851 (9)	0.0013 (8)	−0.0037 (8)	0.0320 (8)
N1	0.0797 (9)	0.0507 (8)	0.0662 (8)	−0.0120 (7)	−0.0135 (7)	0.0075 (6)
C1	0.0458 (7)	0.0469 (8)	0.0622 (8)	0.0028 (6)	0.0023 (6)	0.0008 (6)
N2	0.0550 (7)	0.0479 (7)	0.0707 (8)	−0.0065 (5)	−0.0097 (6)	0.0089 (6)
C2	0.0566 (8)	0.0555 (9)	0.0693 (9)	−0.0066 (7)	−0.0097 (7)	0.0047 (7)
N3	0.0477 (6)	0.0487 (7)	0.0663 (8)	−0.0014 (5)	−0.0001 (5)	0.0069 (6)
C3	0.0468 (8)	0.0555 (10)	0.0585 (9)	0.0000 (6)	−0.0032 (6)	0.0047 (6)
C4	0.0759 (11)	0.0641 (10)	0.0635 (9)	−0.0119 (8)	−0.0176 (8)	0.0023 (7)
C5	0.0763 (10)	0.0707 (11)	0.0555 (9)	−0.0044 (8)	−0.0131 (8)	0.0106 (8)
C6	0.0504 (8)	0.0573 (9)	0.0585 (8)	0.0032 (6)	0.0018 (6)	0.0059 (7)
C7	0.0539 (8)	0.0544 (9)	0.0590 (8)	−0.0013 (6)	−0.0037 (6)	−0.0017 (7)
C8	0.0536 (8)	0.0564 (9)	0.0531 (7)	0.0013 (6)	−0.0071 (6)	0.0040 (6)
C9	0.0656 (10)	0.0653 (10)	0.0724 (10)	0.0035 (8)	0.0001 (8)	0.0122 (8)
C10	0.1231 (18)	0.0784 (12)	0.0756 (11)	−0.0277 (12)	−0.0324 (12)	0.0131 (10)

Geometric parameters (Å, º) top

S1—C1	1.6829 (15)	C3—C8	1.392 (2)
O1—C9	1.187 (2)	C3—C4	1.393 (2)
N1—C1	1.317 (2)	C4—C5	1.375 (2)
N1—C10	1.448 (2)	C5—C6	1.388 (2)
C1—N2	1.356 (2)	C6—C7	1.390 (2)
N2—N3	1.3718 (18)	C6—C9	1.471 (2)
C2—N3	1.277 (2)	C7—C8	1.373 (2)
C2—C3	1.454 (2)

C1—N1—C10	124.33 (15)	C4—C3—C2	118.99 (15)
N1—C1—N2	116.98 (14)	C5—C4—C3	120.82 (15)
N1—C1—S1	124.20 (12)	C4—C5—C6	120.26 (15)
N2—C1—S1	118.81 (12)	C5—C6—C7	118.98 (15)
C1—N2—N3	120.30 (13)	C5—C6—C9	121.80 (15)
N3—C2—C3	122.09 (15)	C7—C6—C9	119.21 (15)
C2—N3—N2	116.10 (13)	C8—C7—C6	120.97 (15)
C8—C3—C4	118.82 (15)	C7—C8—C3	120.15 (14)
C8—C3—C2	122.19 (14)	O1—C9—C6	126.24 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···S1ⁱ	0.902 (19)	2.53 (2)	3.4154 (14)	165.6 (16)
N1—H1···N3	0.84 (2)	2.238 (18)	2.6467 (18)	109.9 (15)
N1—H1···S1ⁱⁱ	0.84 (2)	2.992 (19)	3.5401 (15)	124.6 (16)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···S1ⁱ	0.902 (19)	2.53 (2)	3.4154 (14)	165.6 (16)
N1—H1···N3	0.84 (2)	2.238 (18)	2.6467 (18)	109.9 (15)
N1—H1···S1ⁱⁱ	0.84 (2)	2.992 (19)	3.5401 (15)	124.6 (16)

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

Acknowledgements

This research was supported by the European Rural Development Fund and the Spanish Ministry of Education and Science through Project CTQ2010–19386/BQU.

References

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 9| September 2014| Page o926

doi:10.1107/S1600536814016407

Open

access