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The crystal structure of the title compound, C19H17ClN4OS, has been determined in order to elucidate the mol­ecular conformation. The pyrazole ring makes dihedral angles of 74.3 (3)° and 2.9 (3)° with the phenyl and tolyl rings, respectively; these two six-membered rings are twisted by 71.6 (3)° with respect to each other. The crystal packing of the title compound is stabilized by intra­molcular N—H...O and inter­molcular N—H...S hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807043541/wn2200sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807043541/wn2200Isup2.hkl
Contains datablock I

CCDC reference: 667332

Key indicators

  • Single-crystal X-ray study
  • T = 294 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.037
  • wR factor = 0.102
  • Data-to-parameter ratio = 13.4

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT150_ALERT_1_C Volume as Calculated Differs from that Given ... 3727.00 Ang-3 PLAT153_ALERT_1_C The su's on the Cell Axes are Equal (x 100000) 600 Ang. PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C16 PLAT431_ALERT_2_C Short Inter HL..A Contact Cl1 .. S1 .. 3.53 Ang.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 6 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

In this paper, the synthesis and crystal structure of the title compound is reported. The molecular structure and the atom-numbering scheme are shown in Fig.1. The pyrazole ring makes dihedral angles of 74.3 (3)° and 2.9 (3)° with the C1—C6 ring and the C13—C18 rings, respectively; these two six-membered rings are twisted by 71.6 (3)° with respect to each other. However in the similar structure, 1-(3-methoxyphenyl)-3-(4-methylbenzoyl)thiourea (Saeed et al., 2007), the dihedral angle between the two phenyl ring planes is 48.3 (1)°. All bond lengths and angles are in the normal ranges (Saeed et al., 2007; Wang et al., 2007). The crystal packing of the title compound is stabilized by intramolcular N—H···O and intermolecular N—H···S hydrogen bonds.

Related literature top

For related literature, see: Saeed & Flörke (2007); Wang et al. (2007).

Experimental top

Powdered ammonium thiocyanate (15 mmol), 5-chloro-3-methyl-1-phenylpyrazole-4-carbonyl chloride (10 mmol), PEG-400 (0.15 mmol) and acetone (25 ml) were placed in a dried round-bottomed flask containing a magnetic stirrer bar. The mixture was stirred at room temperature for 1 h, then 4-methylaniline (9.5 mmol) was added, and the mixture was stirred for 10 h. The mixture was poured into water (20 ml). The resulting solid was filtered, dried and recrystallized from DMF-EtOH to give N-(4-methylphenyl)-N'-(5-chloro-3-methyl-1-phenylpyrazol-4-yl- carbonyl)thiourea. Single crystals of the title compound were obtained by slow evaporation of a solution in DMF-EtOH (1:1, v/v).

Refinement top

H atoms bonded to N atoms were located in a difference map and refined with distance restraints of N—H = 0.83 (3) Å, and with Uiso(H) = 1.2Ueq(N). Other H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93–0.96 Å; Uiso(H) = xUeq(carrier atom) where x = 1.5 for methyl groups and 1.2 for Csp2.

Structure description top

In this paper, the synthesis and crystal structure of the title compound is reported. The molecular structure and the atom-numbering scheme are shown in Fig.1. The pyrazole ring makes dihedral angles of 74.3 (3)° and 2.9 (3)° with the C1—C6 ring and the C13—C18 rings, respectively; these two six-membered rings are twisted by 71.6 (3)° with respect to each other. However in the similar structure, 1-(3-methoxyphenyl)-3-(4-methylbenzoyl)thiourea (Saeed et al., 2007), the dihedral angle between the two phenyl ring planes is 48.3 (1)°. All bond lengths and angles are in the normal ranges (Saeed et al., 2007; Wang et al., 2007). The crystal packing of the title compound is stabilized by intramolcular N—H···O and intermolecular N—H···S hydrogen bonds.

For related literature, see: Saeed & Flörke (2007); Wang et al. (2007).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, with the atom numbering scheme and showing displacement ellipsoids at the 50% probability level. Hydrogen atoms have been omitted.
[Figure 2] Fig. 2. The intermolecular and intramolecular hydrogen bonds are shown as dashed lines. Hydrogen atoms not involved in hydrogen bonding have been onitted. [Symmetry code A: -x + 1/2, -y + 1/2, -z]
N-(4-Methylphenyl)-N'-(5-chloro-3-methyl-1- phenylpyrazol-4-ylcarbonyl)thiourea top
Crystal data top
C19H17ClN4OSDx = 1.372 Mg m3
Mr = 384.88Melting point: 437 K
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 14.935 (6) ÅCell parameters from 3035 reflections
b = 16.321 (6) Åθ = 2.2–25.9°
c = 15.469 (6) ŵ = 0.33 mm1
β = 98.786 (6)°T = 294 K
V = 3727 (2) Å3Prism, colourless
Z = 80.24 × 0.22 × 0.10 mm
F(000) = 1600
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer
3275 independent reflections
Radiation source: fine-focus sealed tube2512 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.028
phi and ω scansθmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1713
Tmin = 0.924, Tmax = 0.968k = 1916
7376 measured reflectionsl = 1818
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.102 w = 1/[σ2(Fo2) + (0.0444P)2 + 3.1362P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.002
3275 reflectionsΔρmax = 0.26 e Å3
244 parametersΔρmin = 0.29 e Å3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0135 (6)
Crystal data top
C19H17ClN4OSV = 3727 (2) Å3
Mr = 384.88Z = 8
Monoclinic, C2/cMo Kα radiation
a = 14.935 (6) ŵ = 0.33 mm1
b = 16.321 (6) ÅT = 294 K
c = 15.469 (6) Å0.24 × 0.22 × 0.10 mm
β = 98.786 (6)°
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer
3275 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2512 reflections with I > 2σ(I)
Tmin = 0.924, Tmax = 0.968Rint = 0.028
7376 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.102H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.26 e Å3
3275 reflectionsΔρmin = 0.29 e Å3
244 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*/Ueq
Cl10.26808 (4)0.10959 (3)0.18875 (4)0.0489 (2)
S10.25725 (4)0.37690 (4)0.04136 (5)0.0548 (2)
O10.52013 (11)0.25072 (9)0.15254 (13)0.0601 (5)
N10.38841 (11)0.00224 (10)0.15040 (11)0.0368 (4)
N20.47254 (11)0.00682 (11)0.12675 (12)0.0416 (5)
N30.36918 (12)0.25941 (11)0.10169 (13)0.0435 (5)
H3A0.3265 (16)0.2329 (15)0.0743 (16)0.052*
N40.42555 (14)0.38937 (11)0.12986 (14)0.0505 (5)
H4A0.4725 (18)0.3629 (16)0.1476 (17)0.061*
C10.33371 (14)0.06761 (12)0.16252 (14)0.0362 (5)
C20.26236 (16)0.08688 (15)0.09905 (17)0.0514 (6)
H20.25020.05550.04840.062*
C30.20897 (16)0.15344 (15)0.11148 (19)0.0590 (7)
H30.16000.16680.06920.071*
C40.22750 (16)0.19991 (14)0.18540 (18)0.0530 (6)
H40.19140.24490.19320.064*
C50.29946 (17)0.18026 (14)0.24817 (17)0.0529 (6)
H50.31190.21200.29850.064*
C60.35346 (15)0.11362 (13)0.23706 (15)0.0435 (5)
H60.40240.10020.27940.052*
C70.59176 (15)0.08158 (16)0.08879 (18)0.0533 (6)
H7A0.62160.02980.08610.080*
H7B0.62830.11670.12970.080*
H7C0.58310.10660.03200.080*
C80.50222 (13)0.06866 (13)0.11763 (14)0.0375 (5)
C90.43742 (13)0.12760 (12)0.13398 (14)0.0355 (5)
C100.36644 (13)0.08160 (12)0.15463 (13)0.0345 (5)
C110.44734 (14)0.21691 (13)0.13126 (14)0.0397 (5)
C120.35583 (15)0.34383 (13)0.09374 (15)0.0418 (5)
C130.43399 (15)0.47650 (13)0.12661 (15)0.0456 (6)
C140.51457 (17)0.50783 (15)0.1089 (2)0.0638 (8)
H140.56150.47270.10070.077*
C150.52592 (18)0.59178 (16)0.1034 (2)0.0632 (7)
H150.58070.61230.09110.076*
C160.45840 (17)0.64529 (14)0.11565 (16)0.0499 (6)
C170.37896 (19)0.61242 (15)0.13533 (19)0.0615 (7)
H170.33250.64760.14500.074*
C180.36606 (18)0.52902 (15)0.14119 (18)0.0586 (7)
H180.31180.50860.15490.070*
C190.4709 (2)0.73671 (15)0.1069 (2)0.0743 (9)
H19A0.49150.75980.16350.111*
H19B0.41410.76130.08270.111*
H19C0.51480.74710.06900.111*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0403 (3)0.0417 (3)0.0680 (4)0.0026 (2)0.0185 (3)0.0021 (3)
S10.0537 (4)0.0364 (3)0.0676 (4)0.0055 (3)0.0116 (3)0.0025 (3)
O10.0356 (9)0.0367 (9)0.1031 (15)0.0072 (7)0.0047 (9)0.0049 (9)
N10.0299 (9)0.0296 (9)0.0509 (11)0.0002 (7)0.0065 (8)0.0045 (8)
N20.0306 (9)0.0356 (10)0.0586 (12)0.0026 (8)0.0071 (8)0.0041 (8)
N30.0365 (10)0.0298 (10)0.0601 (13)0.0037 (8)0.0063 (9)0.0035 (9)
N40.0461 (12)0.0318 (11)0.0691 (14)0.0025 (9)0.0054 (10)0.0013 (9)
C10.0337 (11)0.0270 (10)0.0480 (13)0.0008 (8)0.0068 (9)0.0008 (9)
C20.0478 (14)0.0456 (14)0.0570 (15)0.0052 (11)0.0043 (12)0.0107 (11)
C30.0436 (14)0.0480 (15)0.0786 (19)0.0120 (11)0.0125 (13)0.0035 (13)
C40.0434 (13)0.0352 (13)0.0799 (18)0.0081 (10)0.0080 (12)0.0083 (12)
C50.0569 (15)0.0416 (13)0.0593 (16)0.0058 (11)0.0057 (12)0.0148 (11)
C60.0431 (12)0.0369 (12)0.0482 (14)0.0051 (10)0.0002 (10)0.0032 (10)
C70.0370 (12)0.0513 (14)0.0735 (18)0.0021 (11)0.0142 (12)0.0003 (13)
C80.0295 (10)0.0364 (12)0.0453 (13)0.0008 (9)0.0017 (9)0.0040 (9)
C90.0304 (11)0.0323 (11)0.0420 (12)0.0029 (9)0.0005 (9)0.0043 (9)
C100.0302 (10)0.0314 (11)0.0411 (12)0.0019 (9)0.0032 (9)0.0010 (9)
C110.0347 (12)0.0348 (12)0.0485 (13)0.0027 (9)0.0030 (10)0.0029 (10)
C120.0478 (13)0.0313 (11)0.0455 (13)0.0015 (10)0.0041 (10)0.0029 (10)
C130.0492 (14)0.0312 (12)0.0535 (14)0.0044 (10)0.0018 (11)0.0024 (10)
C140.0417 (14)0.0396 (14)0.107 (2)0.0002 (11)0.0025 (14)0.0073 (14)
C150.0478 (15)0.0444 (15)0.097 (2)0.0118 (12)0.0092 (14)0.0041 (14)
C160.0573 (15)0.0365 (13)0.0533 (15)0.0059 (11)0.0002 (12)0.0042 (11)
C170.0652 (17)0.0389 (14)0.085 (2)0.0006 (12)0.0254 (15)0.0131 (13)
C180.0616 (16)0.0401 (14)0.0791 (19)0.0066 (12)0.0266 (14)0.0096 (13)
C190.087 (2)0.0382 (15)0.097 (2)0.0115 (14)0.0136 (18)0.0058 (14)
Geometric parameters (Å, º) top
Cl1—C101.698 (2)C6—H60.9300
S1—C121.659 (2)C7—C81.488 (3)
O1—C111.219 (2)C7—H7A0.9600
N1—C101.340 (3)C7—H7B0.9600
N1—N21.369 (2)C7—H7C0.9600
N1—C11.431 (3)C8—C91.415 (3)
N2—C81.324 (3)C9—C101.376 (3)
N3—C111.375 (3)C9—C111.466 (3)
N3—C121.395 (3)C13—C181.373 (3)
N3—H3A0.83 (2)C13—C141.373 (3)
N4—C121.331 (3)C14—C151.385 (4)
N4—C131.429 (3)C14—H140.9300
N4—H4A0.83 (3)C15—C161.369 (4)
C1—C61.370 (3)C15—H150.9300
C1—C21.371 (3)C16—C171.378 (4)
C2—C31.378 (3)C16—C191.512 (3)
C2—H20.9300C17—C181.380 (3)
C3—C41.365 (4)C17—H170.9300
C3—H30.9300C18—H180.9300
C4—C51.372 (3)C19—H19A0.9600
C4—H40.9300C19—H19B0.9600
C5—C61.380 (3)C19—H19C0.9600
C5—H50.9300
C10—N1—N2111.03 (16)C10—C9—C8104.05 (18)
C10—N1—C1127.92 (17)C10—C9—C11129.34 (19)
N2—N1—C1120.95 (16)C8—C9—C11126.59 (19)
C8—N2—N1105.29 (16)N1—C10—C9108.24 (18)
C11—N3—C12129.08 (19)N1—C10—Cl1120.34 (15)
C11—N3—H3A116.9 (17)C9—C10—Cl1131.25 (16)
C12—N3—H3A112.4 (17)O1—C11—N3122.6 (2)
C12—N4—C13127.5 (2)O1—C11—C9122.16 (19)
C12—N4—H4A114.4 (19)N3—C11—C9115.26 (18)
C13—N4—H4A116.9 (19)N4—C12—N3114.99 (19)
C6—C1—C2121.4 (2)N4—C12—S1127.06 (17)
C6—C1—N1119.54 (19)N3—C12—S1117.95 (16)
C2—C1—N1119.06 (19)C18—C13—C14119.5 (2)
C1—C2—C3118.9 (2)C18—C13—N4123.0 (2)
C1—C2—H2120.5C14—C13—N4117.5 (2)
C3—C2—H2120.5C13—C14—C15120.0 (2)
C4—C3—C2120.5 (2)C13—C14—H14120.0
C4—C3—H3119.8C15—C14—H14120.0
C2—C3—H3119.8C16—C15—C14121.5 (2)
C3—C4—C5120.0 (2)C16—C15—H15119.2
C3—C4—H4120.0C14—C15—H15119.2
C5—C4—H4120.0C15—C16—C17117.4 (2)
C4—C5—C6120.4 (2)C15—C16—C19120.9 (2)
C4—C5—H5119.8C17—C16—C19121.7 (2)
C6—C5—H5119.8C16—C17—C18122.2 (2)
C1—C6—C5118.8 (2)C16—C17—H17118.9
C1—C6—H6120.6C18—C17—H17118.9
C5—C6—H6120.6C13—C18—C17119.4 (2)
C8—C7—H7A109.5C13—C18—H18120.3
C8—C7—H7B109.5C17—C18—H18120.3
H7A—C7—H7B109.5C16—C19—H19A109.5
C8—C7—H7C109.5C16—C19—H19B109.5
H7A—C7—H7C109.5H19A—C19—H19B109.5
H7B—C7—H7C109.5C16—C19—H19C109.5
N2—C8—C9111.37 (18)H19A—C19—H19C109.5
N2—C8—C7119.65 (19)H19B—C19—H19C109.5
C9—C8—C7128.9 (2)
C10—N1—N2—C80.8 (2)C11—C9—C10—N1178.5 (2)
C1—N1—N2—C8177.37 (18)C8—C9—C10—Cl1175.06 (17)
C10—N1—C1—C6107.7 (3)C11—C9—C10—Cl13.3 (4)
N2—N1—C1—C676.3 (3)C12—N3—C11—O13.0 (4)
C10—N1—C1—C272.2 (3)C12—N3—C11—C9178.1 (2)
N2—N1—C1—C2103.8 (2)C10—C9—C11—O1144.7 (2)
C6—C1—C2—C30.8 (4)C8—C9—C11—O133.4 (4)
N1—C1—C2—C3179.0 (2)C10—C9—C11—N336.4 (3)
C1—C2—C3—C40.7 (4)C8—C9—C11—N3145.5 (2)
C2—C3—C4—C50.3 (4)C13—N4—C12—N3175.1 (2)
C3—C4—C5—C60.0 (4)C13—N4—C12—S14.7 (4)
C2—C1—C6—C50.5 (4)C11—N3—C12—N49.3 (4)
N1—C1—C6—C5179.3 (2)C11—N3—C12—S1170.60 (19)
C4—C5—C6—C10.1 (4)C12—N4—C13—C1845.8 (4)
N1—N2—C8—C90.8 (2)C12—N4—C13—C14134.9 (3)
N1—N2—C8—C7177.85 (19)C18—C13—C14—C151.9 (4)
N2—C8—C9—C100.6 (2)N4—C13—C14—C15178.8 (2)
C7—C8—C9—C10177.3 (2)C13—C14—C15—C160.3 (4)
N2—C8—C9—C11179.1 (2)C14—C15—C16—C171.2 (4)
C7—C8—C9—C114.3 (4)C14—C15—C16—C19178.3 (3)
N2—N1—C10—C90.4 (2)C15—C16—C17—C181.2 (4)
C1—N1—C10—C9176.71 (19)C19—C16—C17—C18178.3 (3)
N2—N1—C10—Cl1176.19 (14)C14—C13—C18—C171.9 (4)
C1—N1—C10—Cl17.5 (3)N4—C13—C18—C17178.9 (2)
C8—C9—C10—N10.1 (2)C16—C17—C18—C130.3 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3A···S1i0.83 (2)2.70 (2)3.484 (2)158 (2)
N4—H4A···O10.83 (3)1.96 (3)2.662 (3)141 (2)
Symmetry code: (i) x+1/2, y+1/2, z.

Experimental details

Crystal data
Chemical formulaC19H17ClN4OS
Mr384.88
Crystal system, space groupMonoclinic, C2/c
Temperature (K)294
a, b, c (Å)14.935 (6), 16.321 (6), 15.469 (6)
β (°) 98.786 (6)
V3)3727 (2)
Z8
Radiation typeMo Kα
µ (mm1)0.33
Crystal size (mm)0.24 × 0.22 × 0.10
Data collection
DiffractometerBruker SMART 1K CCD area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.924, 0.968
No. of measured, independent and
observed [I > 2σ(I)] reflections
7376, 3275, 2512
Rint0.028
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.102, 1.03
No. of reflections3275
No. of parameters244
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.26, 0.29

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3A···S1i0.83 (2)2.70 (2)3.484 (2)158 (2)
N4—H4A···O10.83 (3)1.96 (3)2.662 (3)141 (2)
Symmetry code: (i) x+1/2, y+1/2, z.
 

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