4-(Methyl­sulfanyl)benzaldehyde semicarbazone

The crystal packing of the title compound, C₉H₁₁N₃OS, is stabilized by two N—H...O hydrogen bonds. One of the amino H atoms is not involved in a classical hydrogen bond. The methyl group is disordered over two positions with almost equal occupancies.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.003 Å
• Disorder in main residue
• R factor = 0.054
• wR factor = 0.168
• Data-to-parameter ratio = 14.2

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT432_ALERT_2_A Short Inter X...Y Contact  C17    ..  C17     ..       2.41 Ang.

Author Response: C17 and C17' are a methyl group which is disordered over two sites.

Alert level C
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         S1
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.24
PLAT301_ALERT_3_C Main Residue  Disorder .........................       7.00 Perc.
PLAT731_ALERT_1_C Bond    Calc     0.88(3), Rep   0.886(10) ......       3.00 su-Ra
              N3   -H3A     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.88(3), Rep   0.886(10) ......       3.00 su-Ra
              N3   -H3A     1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     2.03(3), Rep   2.025(12) ......       2.50 su-Ra
              H3A  -O1      1.555   2.556

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          3

   1 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 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
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

NLO materials play an important role in the field of fibre optic communications and optical signal processing. In the last two decades, extensive research has shown that organic crystals can exhibit nonlinear optical efficiencies which are two orders of magnitude higher than those of inorganic materials. Thiosemicarbazones (TSCs) of aromatic aldehydes and ketones are widely known as carcinostatic and antimicrobial agents. Semicarbazones of substituted benzaldehydes and acetophenones were reported to be some of the potential organic NLO materials. In the present paper, we report the crystal structure of title compound, (I), C₉H₁₁N₃OS.

Related literature

For related structures, see: acetone semicarbazone and benzaldehyde semicarbazone (Naik & Palenik, 1974); 3,4-methylenedioxybenzaldehyde semicarbazone (Wang et al., 2004); 4-(methylsulfanyl)benzaldehyde thiosemicarbazone (Yathirajan et al., 2006).

For related literature, see: Fichou et al. (1988); Furnis et al. (1989); Goto et al. (1991); Tam et al. (1989); Indira et al. (2002); Vijayan et al. (2001); Ramesh Babu et al. (2002); Manivennan & Dhanushkodi (2003).

S2. Experimental

The title compound was synthesized according to the literature method (Furnis et al., 1989) with a yield of 80% and purified by recrystallization from ethanol. Crystals of (I) were grown from DMF solution by slow evaporation (m.p. 423–425 K). Analysis for C₉H₁₁N₃OS: Found (Calculated): C 51.55 (51.65); H 5.28 (5.30); N 20.15% (20.08%).

S3. Refinement

The H atoms were found in a difference map, but those bonded to C were refined using a riding model with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C) or C—H = 0.98 Å and U_iso(H) = 1.5U_eq(C_methyl). The H atoms bonded to N were refined with an N—H distance restraint of 0.88 (1) Å. The methyl group is disordered over two sites with occupation factors of 0.505 (6) and 0.495 (6).

Computing details

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. Perspective view of (I); displacement ellipsoids are at the 50% probability level (arbitrary spheres for the H atoms). One site of the disordered methyl group is shown with dashed bonds.

4-(Methylthio)benzaldehyde semicarbazone

Crystal data

C9H11N3OS	F(000) = 440
Mr = 209.27	Dx = 1.391 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5218 reflections
a = 15.1006 (19) Å	θ = 3.3–27.2°
b = 5.3082 (7) Å	µ = 0.29 mm^−1
c = 13.0746 (17) Å	T = 173 K
β = 107.494 (9)°	Block, colourless
V = 999.5 (2) Å^3	0.48 × 0.45 × 0.43 mm
Z = 4

Data collection

Stoe IPDS II two-circle diffractometer	2162 independent reflections
Radiation source: fine-focus sealed tube	1678 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.053
ω scans	θmax = 27.0°, θmin = 2.8°
Absorption correction: multi-scan [MULABS (Spek, 2003; Blessing, 1995)]	h = −19→19
Tmin = 0.872, Tmax = 0.884	k = −6→6
7445 measured reflections	l = −14→16

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.054	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.168	w = 1/[σ^2(Fo^2) + (0.0852P)^2 + 0.4974P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max < 0.001
2162 reflections	Δρmax = 0.46 e Å^−3
152 parameters	Δρmin = −0.66 e Å^−3
3 restraints	Extinction correction: SHELXL (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.087 (13)

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	Occ. (<1)
N2	0.08441 (13)	−0.2424 (3)	0.53704 (18)	0.0462 (5)
H2	0.0655 (18)	−0.359 (4)	0.4872 (17)	0.051 (7)*
S1	0.42858 (5)	0.66516 (12)	0.32545 (8)	0.0703 (4)
O1	0.00019 (11)	−0.4136 (3)	0.63569 (15)	0.0487 (5)
N1	0.13881 (12)	−0.0461 (3)	0.52048 (17)	0.0439 (5)
N3	0.07342 (13)	−0.0387 (4)	0.68943 (18)	0.0478 (5)
H3A	0.049 (2)	−0.017 (7)	0.7422 (19)	0.075 (10)*
H3B	0.1089 (17)	0.078 (4)	0.675 (2)	0.057 (8)*
C1	0.15927 (14)	−0.0536 (4)	0.4320 (2)	0.0440 (6)
H1	0.1340	−0.1846	0.3823	0.053*
C2	0.04991 (14)	−0.2357 (4)	0.62250 (19)	0.0426 (6)
C11	0.22026 (14)	0.1332 (4)	0.4052 (2)	0.0424 (5)
C12	0.24456 (15)	0.1058 (4)	0.3108 (2)	0.0477 (6)
H12	0.2182	−0.0281	0.2631	0.057*
C13	0.30620 (15)	0.2693 (5)	0.2850 (2)	0.0478 (6)
H13	0.3216	0.2469	0.2203	0.057*
C14	0.34570 (14)	0.4670 (4)	0.3542 (2)	0.0451 (6)
C15	0.32039 (15)	0.4988 (4)	0.4481 (2)	0.0482 (6)
H15	0.3461	0.6340	0.4953	0.058*
C16	0.25829 (16)	0.3356 (4)	0.4730 (2)	0.0466 (6)
H16	0.2413	0.3611	0.5366	0.056*
C17	0.4761 (3)	0.8650 (9)	0.4225 (4)	0.0513 (14)	0.495 (6)
H17A	0.5225	0.9672	0.4026	0.077*	0.495 (6)
H17B	0.5063	0.7718	0.4885	0.077*	0.495 (6)
H17C	0.4280	0.9752	0.4342	0.077*	0.495 (6)
C17'	0.4006 (4)	0.6638 (12)	0.1996 (5)	0.0642 (17)	0.505 (6)
H17D	0.3337	0.6944	0.1701	0.096*	0.505 (6)
H17E	0.4158	0.4998	0.1749	0.096*	0.505 (6)
H17F	0.4347	0.7965	0.1754	0.096*	0.505 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N2	0.0425 (9)	0.0279 (9)	0.0604 (12)	−0.0064 (7)	0.0039 (9)	−0.0055 (8)
S1	0.0441 (4)	0.0384 (4)	0.1218 (8)	−0.0049 (2)	0.0148 (4)	0.0032 (3)
O1	0.0434 (8)	0.0270 (7)	0.0686 (12)	−0.0057 (6)	0.0062 (7)	−0.0010 (7)
N1	0.0352 (9)	0.0267 (9)	0.0601 (13)	−0.0011 (7)	−0.0002 (8)	−0.0003 (8)
N3	0.0440 (10)	0.0299 (9)	0.0614 (13)	−0.0066 (8)	0.0036 (9)	−0.0039 (9)
C1	0.0347 (10)	0.0293 (10)	0.0572 (14)	0.0016 (8)	−0.0027 (9)	−0.0030 (9)
C2	0.0327 (10)	0.0267 (9)	0.0575 (14)	0.0025 (8)	−0.0029 (9)	0.0019 (9)
C11	0.0318 (9)	0.0286 (10)	0.0562 (14)	0.0048 (7)	−0.0027 (9)	0.0006 (9)
C12	0.0373 (10)	0.0354 (11)	0.0584 (15)	0.0020 (8)	−0.0036 (10)	−0.0072 (10)
C13	0.0415 (11)	0.0406 (12)	0.0540 (14)	0.0052 (9)	0.0031 (10)	−0.0035 (10)
C14	0.0363 (10)	0.0293 (10)	0.0611 (15)	0.0067 (8)	0.0018 (9)	0.0008 (9)
C15	0.0452 (11)	0.0290 (10)	0.0605 (15)	−0.0003 (9)	0.0009 (10)	−0.0058 (9)
C16	0.0423 (11)	0.0322 (11)	0.0562 (14)	0.0010 (8)	0.0012 (10)	−0.0008 (9)
C17	0.036 (2)	0.043 (3)	0.068 (3)	−0.0043 (18)	0.005 (2)	0.007 (2)
C17'	0.054 (3)	0.070 (4)	0.064 (4)	−0.014 (3)	0.011 (2)	0.012 (3)

Geometric parameters (Å, º)

N2—C2	1.368 (3)	C12—C13	1.386 (4)
N2—N1	1.384 (3)	C12—H12	0.9500
N2—H2	0.881 (10)	C13—C14	1.397 (3)
S1—C17'	1.571 (6)	C13—H13	0.9500
S1—C17	1.644 (5)	C14—C15	1.401 (4)
S1—C14	1.760 (2)	C15—C16	1.385 (3)
O1—C2	1.250 (3)	C15—H15	0.9500
N1—C1	1.285 (3)	C16—H16	0.9500
N3—C2	1.341 (3)	C17—H17A	0.9800
N3—H3A	0.886 (10)	C17—H17B	0.9800
N3—H3B	0.875 (10)	C17—H17C	0.9800
C1—C11	1.466 (3)	C17'—H17D	0.9800
C1—H1	0.9500	C17'—H17E	0.9800
C11—C12	1.397 (4)	C17'—H17F	0.9800
C11—C16	1.402 (3)
C2—N2—N1	119.86 (19)	C12—C13—C14	120.0 (2)
C2—N2—H2	120.2 (19)	C12—C13—H13	120.0
N1—N2—H2	119.3 (19)	C14—C13—H13	120.0
C17'—S1—C17	136.8 (3)	C13—C14—C15	118.8 (2)
C17'—S1—C14	103.7 (2)	C13—C14—S1	120.2 (2)
C17—S1—C14	113.2 (2)	C15—C14—S1	120.93 (17)
C1—N1—N2	115.62 (19)	C16—C15—C14	120.8 (2)
C2—N3—H3A	121 (2)	C16—C15—H15	119.6
C2—N3—H3B	118 (2)	C14—C15—H15	119.6
H3A—N3—H3B	121 (3)	C15—C16—C11	120.5 (3)
N1—C1—C11	122.2 (2)	C15—C16—H16	119.7
N1—C1—H1	118.9	C11—C16—H16	119.7
C11—C1—H1	118.9	S1—C17—H17A	109.5
O1—C2—N3	123.5 (2)	S1—C17—H17B	109.5
O1—C2—N2	119.0 (2)	S1—C17—H17C	109.5
N3—C2—N2	117.5 (2)	S1—C17'—H17D	109.5
C12—C11—C16	118.2 (2)	S1—C17'—H17E	109.5
C12—C11—C1	119.5 (2)	H17D—C17'—H17E	109.5
C16—C11—C1	122.3 (2)	S1—C17'—H17F	109.5
C13—C12—C11	121.6 (2)	H17D—C17'—H17F	109.5
C13—C12—H12	119.2	H17E—C17'—H17F	109.5
C11—C12—H12	119.2
C2—N2—N1—C1	−172.28 (18)	C12—C13—C14—S1	176.68 (16)
N2—N1—C1—C11	−176.76 (17)	C17'—S1—C14—C13	29.8 (3)
N1—N2—C2—O1	179.36 (18)	C17—S1—C14—C13	−173.2 (2)
N1—N2—C2—N3	−2.1 (3)	C17'—S1—C14—C15	−152.3 (3)
N1—C1—C11—C12	175.99 (19)	C17—S1—C14—C15	4.7 (3)
N1—C1—C11—C16	−1.7 (3)	C13—C14—C15—C16	0.9 (3)
C16—C11—C12—C13	1.5 (3)	S1—C14—C15—C16	−177.06 (16)
C1—C11—C12—C13	−176.25 (19)	C14—C15—C16—C11	0.7 (3)
C11—C12—C13—C14	0.1 (3)	C12—C11—C16—C15	−1.9 (3)
C12—C13—C14—C15	−1.3 (3)	C1—C11—C16—C15	175.80 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1^i	0.88 (1)	2.02 (1)	2.886 (3)	169 (2)
N3—H3A···O1^ii	0.89 (1)	2.03 (1)	2.904 (3)	171 (4)

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