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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807023239/hb2410sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807023239/hb2410Isup2.hkl
Contains datablock I

CCDC reference: 651771

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

Comment top

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 top

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).

Experimental top

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%).

Refinement top

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 Uiso(H) = 1.2Ueq(C) or C—H = 0.98 Å and Uiso(H) = 1.5Ueq(Cmethyl). 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).

Structure description top

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.

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).

Computing details top

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 top
[Figure 1] 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 top
Crystal data top
C9H11N3OSF(000) = 440
Mr = 209.27Dx = 1.391 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5218 reflections
a = 15.1006 (19) Åθ = 3.3–27.2°
b = 5.3082 (7) ŵ = 0.29 mm1
c = 13.0746 (17) ÅT = 173 K
β = 107.494 (9)°Block, colourless
V = 999.5 (2) Å30.48 × 0.45 × 0.43 mm
Z = 4
Data collection top
Stoe IPDS II two-circle
diffractometer
2162 independent reflections
Radiation source: fine-focus sealed tube1678 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.053
ω scansθmax = 27.0°, θmin = 2.8°
Absorption correction: multi-scan
[MULABS (Spek, 2003; Blessing, 1995)]
h = 1919
Tmin = 0.872, Tmax = 0.884k = 66
7445 measured reflectionsl = 1416
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.054H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.168 w = 1/[σ2(Fo2) + (0.0852P)2 + 0.4974P]
where P = (Fo2 + 2Fc2)/3
S = 1.09(Δ/σ)max < 0.001
2162 reflectionsΔρmax = 0.46 e Å3
152 parametersΔρmin = 0.66 e Å3
3 restraintsExtinction correction: SHELXL (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.087 (13)
Crystal data top
C9H11N3OSV = 999.5 (2) Å3
Mr = 209.27Z = 4
Monoclinic, P21/cMo Kα radiation
a = 15.1006 (19) ŵ = 0.29 mm1
b = 5.3082 (7) ÅT = 173 K
c = 13.0746 (17) Å0.48 × 0.45 × 0.43 mm
β = 107.494 (9)°
Data collection top
Stoe IPDS II two-circle
diffractometer
2162 independent reflections
Absorption correction: multi-scan
[MULABS (Spek, 2003; Blessing, 1995)]
1678 reflections with I > 2σ(I)
Tmin = 0.872, Tmax = 0.884Rint = 0.053
7445 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0543 restraints
wR(F2) = 0.168H atoms treated by a mixture of independent and constrained refinement
S = 1.09Δρmax = 0.46 e Å3
2162 reflectionsΔρmin = 0.66 e Å3
152 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
xyzUiso*/UeqOcc. (<1)
N20.08441 (13)0.2424 (3)0.53704 (18)0.0462 (5)
H20.0655 (18)0.359 (4)0.4872 (17)0.051 (7)*
S10.42858 (5)0.66516 (12)0.32545 (8)0.0703 (4)
O10.00019 (11)0.4136 (3)0.63569 (15)0.0487 (5)
N10.13881 (12)0.0461 (3)0.52048 (17)0.0439 (5)
N30.07342 (13)0.0387 (4)0.68943 (18)0.0478 (5)
H3A0.049 (2)0.017 (7)0.7422 (19)0.075 (10)*
H3B0.1089 (17)0.078 (4)0.675 (2)0.057 (8)*
C10.15927 (14)0.0536 (4)0.4320 (2)0.0440 (6)
H10.13400.18460.38230.053*
C20.04991 (14)0.2357 (4)0.62250 (19)0.0426 (6)
C110.22026 (14)0.1332 (4)0.4052 (2)0.0424 (5)
C120.24456 (15)0.1058 (4)0.3108 (2)0.0477 (6)
H120.21820.02810.26310.057*
C130.30620 (15)0.2693 (5)0.2850 (2)0.0478 (6)
H130.32160.24690.22030.057*
C140.34570 (14)0.4670 (4)0.3542 (2)0.0451 (6)
C150.32039 (15)0.4988 (4)0.4481 (2)0.0482 (6)
H150.34610.63400.49530.058*
C160.25829 (16)0.3356 (4)0.4730 (2)0.0466 (6)
H160.24130.36110.53660.056*
C170.4761 (3)0.8650 (9)0.4225 (4)0.0513 (14)0.495 (6)
H17A0.52250.96720.40260.077*0.495 (6)
H17B0.50630.77180.48850.077*0.495 (6)
H17C0.42800.97520.43420.077*0.495 (6)
C17'0.4006 (4)0.6638 (12)0.1996 (5)0.0642 (17)0.505 (6)
H17D0.33370.69440.17010.096*0.505 (6)
H17E0.41580.49980.17490.096*0.505 (6)
H17F0.43470.79650.17540.096*0.505 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N20.0425 (9)0.0279 (9)0.0604 (12)0.0064 (7)0.0039 (9)0.0055 (8)
S10.0441 (4)0.0384 (4)0.1218 (8)0.0049 (2)0.0148 (4)0.0032 (3)
O10.0434 (8)0.0270 (7)0.0686 (12)0.0057 (6)0.0062 (7)0.0010 (7)
N10.0352 (9)0.0267 (9)0.0601 (13)0.0011 (7)0.0002 (8)0.0003 (8)
N30.0440 (10)0.0299 (9)0.0614 (13)0.0066 (8)0.0036 (9)0.0039 (9)
C10.0347 (10)0.0293 (10)0.0572 (14)0.0016 (8)0.0027 (9)0.0030 (9)
C20.0327 (10)0.0267 (9)0.0575 (14)0.0025 (8)0.0029 (9)0.0019 (9)
C110.0318 (9)0.0286 (10)0.0562 (14)0.0048 (7)0.0027 (9)0.0006 (9)
C120.0373 (10)0.0354 (11)0.0584 (15)0.0020 (8)0.0036 (10)0.0072 (10)
C130.0415 (11)0.0406 (12)0.0540 (14)0.0052 (9)0.0031 (10)0.0035 (10)
C140.0363 (10)0.0293 (10)0.0611 (15)0.0067 (8)0.0018 (9)0.0008 (9)
C150.0452 (11)0.0290 (10)0.0605 (15)0.0003 (9)0.0009 (10)0.0058 (9)
C160.0423 (11)0.0322 (11)0.0562 (14)0.0010 (8)0.0012 (10)0.0008 (9)
C170.036 (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) top
N2—C21.368 (3)C12—C131.386 (4)
N2—N11.384 (3)C12—H120.9500
N2—H20.881 (10)C13—C141.397 (3)
S1—C17'1.571 (6)C13—H130.9500
S1—C171.644 (5)C14—C151.401 (4)
S1—C141.760 (2)C15—C161.385 (3)
O1—C21.250 (3)C15—H150.9500
N1—C11.285 (3)C16—H160.9500
N3—C21.341 (3)C17—H17A0.9800
N3—H3A0.886 (10)C17—H17B0.9800
N3—H3B0.875 (10)C17—H17C0.9800
C1—C111.466 (3)C17'—H17D0.9800
C1—H10.9500C17'—H17E0.9800
C11—C121.397 (4)C17'—H17F0.9800
C11—C161.402 (3)
C2—N2—N1119.86 (19)C12—C13—C14120.0 (2)
C2—N2—H2120.2 (19)C12—C13—H13120.0
N1—N2—H2119.3 (19)C14—C13—H13120.0
C17'—S1—C17136.8 (3)C13—C14—C15118.8 (2)
C17'—S1—C14103.7 (2)C13—C14—S1120.2 (2)
C17—S1—C14113.2 (2)C15—C14—S1120.93 (17)
C1—N1—N2115.62 (19)C16—C15—C14120.8 (2)
C2—N3—H3A121 (2)C16—C15—H15119.6
C2—N3—H3B118 (2)C14—C15—H15119.6
H3A—N3—H3B121 (3)C15—C16—C11120.5 (3)
N1—C1—C11122.2 (2)C15—C16—H16119.7
N1—C1—H1118.9C11—C16—H16119.7
C11—C1—H1118.9S1—C17—H17A109.5
O1—C2—N3123.5 (2)S1—C17—H17B109.5
O1—C2—N2119.0 (2)S1—C17—H17C109.5
N3—C2—N2117.5 (2)S1—C17'—H17D109.5
C12—C11—C16118.2 (2)S1—C17'—H17E109.5
C12—C11—C1119.5 (2)H17D—C17'—H17E109.5
C16—C11—C1122.3 (2)S1—C17'—H17F109.5
C13—C12—C11121.6 (2)H17D—C17'—H17F109.5
C13—C12—H12119.2H17E—C17'—H17F109.5
C11—C12—H12119.2
C2—N2—N1—C1172.28 (18)C12—C13—C14—S1176.68 (16)
N2—N1—C1—C11176.76 (17)C17'—S1—C14—C1329.8 (3)
N1—N2—C2—O1179.36 (18)C17—S1—C14—C13173.2 (2)
N1—N2—C2—N32.1 (3)C17'—S1—C14—C15152.3 (3)
N1—C1—C11—C12175.99 (19)C17—S1—C14—C154.7 (3)
N1—C1—C11—C161.7 (3)C13—C14—C15—C160.9 (3)
C16—C11—C12—C131.5 (3)S1—C14—C15—C16177.06 (16)
C1—C11—C12—C13176.25 (19)C14—C15—C16—C110.7 (3)
C11—C12—C13—C140.1 (3)C12—C11—C16—C151.9 (3)
C12—C13—C14—C151.3 (3)C1—C11—C16—C15175.80 (19)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O1i0.88 (1)2.02 (1)2.886 (3)169 (2)
N3—H3A···O1ii0.89 (1)2.03 (1)2.904 (3)171 (4)
Symmetry codes: (i) x, y1, z+1; (ii) x, y+1/2, z+3/2.

Experimental details

Crystal data
Chemical formulaC9H11N3OS
Mr209.27
Crystal system, space groupMonoclinic, P21/c
Temperature (K)173
a, b, c (Å)15.1006 (19), 5.3082 (7), 13.0746 (17)
β (°) 107.494 (9)
V3)999.5 (2)
Z4
Radiation typeMo Kα
µ (mm1)0.29
Crystal size (mm)0.48 × 0.45 × 0.43
Data collection
DiffractometerStoe IPDS II two-circle
Absorption correctionMulti-scan
[MULABS (Spek, 2003; Blessing, 1995)]
Tmin, Tmax0.872, 0.884
No. of measured, independent and
observed [I > 2σ(I)] reflections
7445, 2162, 1678
Rint0.053
(sin θ/λ)max1)0.638
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.054, 0.168, 1.09
No. of reflections2162
No. of parameters152
No. of restraints3
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.46, 0.66

Computer programs: X-AREA (Stoe & Cie, 2001), X-AREA, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O1i0.881 (10)2.016 (11)2.886 (3)169 (2)
N3—H3A···O1ii0.886 (10)2.025 (12)2.904 (3)171 (4)
Symmetry codes: (i) x, y1, z+1; (ii) x, y+1/2, z+3/2.
 

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