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

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.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.034
• wR factor = 0.100
• Data-to-parameter ratio = 13.7

checkCIF/PLATON results

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Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S1     --  C1      ..        5.9 su
PLAT480_ALERT_4_C Long H...A H-Bond Reported H1     ..  S1      ..       2.99 Ang.
PLAT761_ALERT_1_C CIF Contains no X-H Bonds ......................     Please Check
PLAT762_ALERT_1_C CIF Contains no X-Y-H or H-Y-H Angles ..........     Please Check
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.595          4 Why ?

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) still          78 %

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   5 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   2 ALERT level G = General information/check it is not something unexpected

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. 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).

S2. 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).

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).

Computing details

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

	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

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) Å^3	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 F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0559P)^2 + 0.3598P] where P = (Fo^2 + 2Fc^2)/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)

	U^11	U^22	U^33	U^12	U^13	U^23
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···S1^i	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···S1^ii	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.