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

Abstract

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.

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 ▶).

Experimental  

Crystal data  

• C₁₀H₁₁N₃OS

• M _r = 221.28

• Orthorhombic,

• a = 13.1231 (3) Å

• b = 8.8559 (2) Å

• c = 19.3702 (4) Å

• V = 2251.14 (9) ų

• Z = 8

• Cu Kα radiation

• μ = 2.38 mm⁻¹

• T = 296 K

• 0.14 × 0.13 × 0.05 mm

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

Refinement  

• R[F ² > 2σ(F ²)] = 0.034

• wR(F ²) = 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

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 ▶).

Supplementary Material

CCDC reference: 1014062

Additional supporting information: crystallographic information; 3D view; checkCIF report

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) ; (ii) .

supplementary crystallographic information

S3. Synthesis and crystallization

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).

S4. Refinement

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).

Figures

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).

Crystal data

C10H11N3OS	F(000) = 928
Mr = 221.28	Dx = 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

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

Refinement

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(Fo2) + (0.0559P)2 + 0.3598P] where P = (Fo2 + 2Fc2)/3
1986 reflections	(Δ/σ)max < 0.001
145 parameters	Δρmax = 0.21 e Å−3
0 restraints	Δρmin = −0.16 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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)

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)

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.