1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-aminium chloride–thio­urea (1/1)

Murtaza, S.; Hamza, M.; Tahir, M.N.

doi:10.1107/S1600536811029989

1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-aminium chloride–thiourea (1/1)

In the title compound, C₁₁H₁₄N₃O⁺·Cl⁻·CH₄N₂S, the components are connected into a two-dimensional polymeric structure parallel to (001) via N—H

Cl, N—H

O, N—H

S and C—H

S hydrogen bonds. The dihedral angle between the phenyl and 2,3-dihydro-1H-pyrazole rings is 44.96 (7)°.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536811029989/gk2395sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536811029989/gk2395Isup2.hkl Contains datablock I
	Chemical Markup Language (CML) file https://doi.org/10.1107/S1600536811029989/gk2395Isup3.cml Supplementary material

CCDC reference: 841346

checkCIF report

Key indicators

Single-crystal X-ray study
T = 296 K
Mean (C-C) = 0.003 Å
R factor = 0.039
wR factor = 0.111
Data-to-parameter ratio = 20.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings  Differ          ?
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          7
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         12
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          4

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 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

Comment top

The crystal structure of 1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol- 4-aminium 2-hydroxybenzoate (Chitradevi et al., 2009) has been published which is related to the title compound (Fig. 1).

The asymmetric unit of title compound consists of three components: 1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-aminium cation, chloride ion and thiourea molecule. In cation the phenyl ring A (C1—C6) and 2,3-dihydro-1H-pyrazole ring B (N1/N2/C7/C8/C9) are planar with r. m. s. deviations of 0.005 and 0.020 Å. The dihedral angle between A/B is 44.96 (7)°. The attached atoms O1, N3, C10 and C11 are at a distance of -0.122 (3), 0.005 (3), 0.034 (3) and 0.513 (3) Å respectively, from the mean plane of B. The thiourea molecule (S1/C12/N4/N5) is planar with r.m.s. deviations of 0.003 Å. There exist intermolecular hydrogen bonds of N–H···Cl, N–H···O, N–H···S and C–H···S types (Table 1, Fig. 2). The crystal components are connected by hydrogen bonds into infinite two dimensional polymeric network parallel to (0 0 1)

Related literature top

For the structure of 1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol- 4-aminium 2-hydroxybenzoate, see: Chitradevi et al. (2009).

Experimental top

4-Aminophenazone (0.203 g, 1.0 mmol) and thiourea (0.076 g, 1.0 mmol) were dissolved in ethanol (15 ml) and the mixture was acidified by 1 N HCl. The mixture was refluxed for one hour and solvent was evaporated on rotary evaporator to almost dryness. The crude product was recrystallized from ethanol yielding light yellow needles of the title compound.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. View of the title compound with the atom numbering scheme. The displacement ellipsoids are drawn at the 50% probability level. H-atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The partial packing (PLATON; Spek, 2009) showing hydrogen-bond interactions.

1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-aminium chloride– thiourea (1/1) top

Crystal data top

C₁₁H₁₄N₃O⁺·Cl⁻·CH₄N₂S	F(000) = 664
M_r = 315.82	D_x = 1.351 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2948 reflections
a = 9.9733 (11) Å	θ = 2.0–28.4°
b = 8.2572 (8) Å	µ = 0.38 mm⁻¹
c = 18.859 (2) Å	T = 296 K
β = 90.851 (4)°	Needle, light yellow
V = 1552.9 (3) Å³	0.30 × 0.15 × 0.14 mm
Z = 4

Data collection top

Bruker Kappa APEXII CCD diffractometer	3876 independent reflections
Radiation source: fine-focus sealed tube	2948 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
Detector resolution: 7.50 pixels mm^-1	θ_max = 28.4°, θ_min = 2.0°
ω scans	h = −13→12
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −10→6
T_min = 0.935, T_max = 0.950	l = −24→25
14413 measured reflections

Refinement top

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0519P)² + 0.4062P] where P = (F_o² + 2F_c²)/3
3876 reflections	(Δ/σ)_max < 0.001
192 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₁₁H₁₄N₃O⁺·Cl⁻·CH₄N₂S	V = 1552.9 (3) Å³
M_r = 315.82	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.9733 (11) Å	µ = 0.38 mm⁻¹
b = 8.2572 (8) Å	T = 296 K
c = 18.859 (2) Å	0.30 × 0.15 × 0.14 mm
β = 90.851 (4)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	3876 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	2948 reflections with I > 2σ(I)
T_min = 0.935, T_max = 0.950	R_int = 0.032
14413 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.28 e Å⁻³
3876 reflections	Δρ_min = −0.30 e Å⁻³
192 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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

	x	y	z	U_iso*/U_eq
O1	0.02683 (12)	0.52568 (13)	0.17891 (7)	0.0429 (4)
N1	0.15623 (14)	0.67708 (15)	0.10210 (8)	0.0380 (4)
N2	0.15254 (14)	0.83360 (15)	0.07471 (8)	0.0395 (5)
N3	−0.10897 (15)	0.84880 (18)	0.20387 (9)	0.0369 (5)
C1	0.22930 (16)	0.55157 (19)	0.06724 (9)	0.0365 (5)
C2	0.2008 (2)	0.5159 (2)	−0.00289 (11)	0.0539 (7)
C3	0.2738 (2)	0.3964 (3)	−0.03623 (12)	0.0631 (8)
C4	0.3709 (2)	0.3132 (2)	0.00038 (13)	0.0568 (7)
C5	0.3968 (2)	0.3477 (3)	0.07011 (13)	0.0587 (7)
C6	0.3260 (2)	0.4689 (2)	0.10411 (11)	0.0488 (6)
C7	0.05681 (16)	0.65825 (18)	0.15067 (9)	0.0335 (5)
C8	−0.00154 (15)	0.81326 (18)	0.15630 (9)	0.0328 (4)
C9	0.05869 (16)	0.91713 (19)	0.11086 (9)	0.0360 (5)
C10	0.0318 (2)	1.0926 (2)	0.09755 (12)	0.0506 (6)
C11	0.2742 (2)	0.9003 (2)	0.04478 (12)	0.0528 (7)
S1	0.70196 (5)	0.59619 (6)	0.27908 (3)	0.0490 (2)
N4	0.76836 (16)	0.35228 (19)	0.19593 (9)	0.0531 (6)
N5	0.57194 (16)	0.3262 (2)	0.25376 (10)	0.0579 (6)
C12	0.67972 (17)	0.4139 (2)	0.24001 (10)	0.0398 (5)
Cl1	0.64868 (5)	0.01267 (5)	0.13661 (3)	0.0476 (2)
H2	0.13349	0.57146	−0.02737	0.0647*
H3	0.25677	0.37259	−0.08371	0.0758*
H3A	−0.148 (2)	0.757 (3)	0.2222 (10)	0.0554*
H3B	−0.084 (2)	0.913 (3)	0.2403 (12)	0.0554*
H3C	−0.185 (2)	0.900 (2)	0.1825 (11)	0.0554*
H4	0.41951	0.23278	−0.02225	0.0681*
H5	0.46218	0.28957	0.09489	0.0704*
H6	0.34432	0.49342	0.15140	0.0586*
H10A	0.00647	1.10791	0.04870	0.0759*
H10B	0.11123	1.15417	0.10810	0.0759*
H10C	−0.03966	1.12835	0.12730	0.0759*
H11A	0.34012	0.91528	0.08178	0.0791*
H11B	0.25437	1.00266	0.02288	0.0791*
H11C	0.30826	0.82695	0.00990	0.0791*
H4A	0.75487	0.25846	0.17735	0.0637*
H4B	0.83942	0.40608	0.18589	0.0637*
H5A	0.56147	0.23283	0.23429	0.0695*
H5B	0.51243	0.36276	0.28217	0.0695*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0447 (7)	0.0331 (6)	0.0512 (7)	0.0023 (5)	0.0121 (6)	0.0107 (5)
N1	0.0424 (8)	0.0269 (7)	0.0450 (8)	0.0047 (5)	0.0125 (7)	0.0051 (6)
N2	0.0432 (8)	0.0291 (7)	0.0466 (9)	0.0016 (6)	0.0112 (7)	0.0070 (6)
N3	0.0362 (8)	0.0326 (7)	0.0421 (9)	0.0020 (6)	0.0066 (6)	−0.0039 (6)
C1	0.0348 (8)	0.0302 (7)	0.0449 (10)	0.0017 (6)	0.0116 (7)	0.0002 (7)
C2	0.0556 (12)	0.0522 (11)	0.0538 (12)	0.0118 (9)	−0.0051 (10)	−0.0050 (9)
C3	0.0764 (15)	0.0585 (13)	0.0547 (13)	0.0047 (11)	0.0069 (11)	−0.0174 (10)
C4	0.0596 (12)	0.0352 (9)	0.0763 (15)	0.0044 (9)	0.0263 (11)	−0.0066 (9)
C5	0.0512 (12)	0.0495 (11)	0.0755 (15)	0.0192 (9)	0.0085 (11)	0.0085 (10)
C6	0.0506 (11)	0.0476 (10)	0.0483 (11)	0.0100 (8)	0.0030 (9)	0.0026 (8)
C7	0.0335 (8)	0.0326 (8)	0.0343 (8)	0.0014 (6)	0.0021 (7)	0.0020 (6)
C8	0.0318 (8)	0.0305 (7)	0.0362 (8)	0.0016 (6)	0.0025 (7)	−0.0008 (6)
C9	0.0373 (9)	0.0298 (8)	0.0410 (9)	0.0020 (6)	0.0008 (7)	0.0006 (7)
C10	0.0546 (11)	0.0319 (9)	0.0655 (13)	0.0052 (8)	0.0041 (10)	0.0057 (8)
C11	0.0569 (12)	0.0411 (10)	0.0610 (13)	−0.0050 (8)	0.0257 (10)	0.0052 (9)
S1	0.0444 (3)	0.0403 (3)	0.0627 (3)	−0.0045 (2)	0.0134 (2)	−0.0056 (2)
N4	0.0495 (9)	0.0461 (9)	0.0641 (11)	−0.0048 (7)	0.0135 (8)	−0.0113 (8)
N5	0.0479 (9)	0.0522 (10)	0.0740 (12)	−0.0143 (8)	0.0133 (9)	−0.0110 (9)
C12	0.0366 (9)	0.0402 (9)	0.0426 (10)	−0.0004 (7)	−0.0018 (7)	0.0038 (7)
Cl1	0.0445 (3)	0.0443 (3)	0.0542 (3)	0.0060 (2)	0.0050 (2)	−0.0028 (2)

Geometric parameters (Å, º) top

S1—C12	1.6891 (18)	C2—C3	1.383 (3)
O1—C7	1.2554 (19)	C3—C4	1.366 (3)
N1—C1	1.432 (2)	C4—C5	1.366 (3)
N1—C7	1.369 (2)	C5—C6	1.387 (3)
N1—N2	1.3921 (18)	C7—C8	1.411 (2)
N2—C9	1.355 (2)	C8—C9	1.359 (2)
N2—C11	1.454 (2)	C9—C10	1.494 (2)
N3—C8	1.438 (2)	C2—H2	0.9300
N3—H3B	0.90 (2)	C3—H3	0.9300
N3—H3A	0.92 (2)	C4—H4	0.9300
N3—H3C	0.952 (19)	C5—H5	0.9300
N4—C12	1.324 (2)	C6—H6	0.9300
N5—C12	1.325 (2)	C10—H10A	0.9600
N4—H4A	0.8600	C10—H10B	0.9600
N4—H4B	0.8600	C10—H10C	0.9600
N5—H5B	0.8600	C11—H11A	0.9600
N5—H5A	0.8600	C11—H11B	0.9600
C1—C2	1.380 (3)	C11—H11C	0.9600
C1—C6	1.364 (3)

N2—N1—C1	120.81 (14)	C7—C8—C9	109.79 (14)
N2—N1—C7	109.78 (12)	N3—C8—C9	127.24 (14)
C1—N1—C7	127.13 (13)	N2—C9—C8	108.13 (14)
N1—N2—C9	107.49 (13)	C8—C9—C10	129.66 (16)
N1—N2—C11	118.56 (13)	N2—C9—C10	122.19 (15)
C9—N2—C11	126.10 (13)	C1—C2—H2	120.00
H3B—N3—H3C	105.7 (18)	C3—C2—H2	120.00
C8—N3—H3C	115.0 (13)	C2—C3—H3	120.00
C8—N3—H3A	112.9 (14)	C4—C3—H3	120.00
C8—N3—H3B	113.3 (13)	C5—C4—H4	120.00
H3A—N3—H3B	108.2 (19)	C3—C4—H4	120.00
H3A—N3—H3C	100.7 (17)	C4—C5—H5	120.00
H4A—N4—H4B	120.00	C6—C5—H5	120.00
C12—N4—H4A	120.00	C5—C6—H6	120.00
C12—N4—H4B	120.00	C1—C6—H6	120.00
H5A—N5—H5B	120.00	H10B—C10—H10C	109.00
C12—N5—H5A	120.00	C9—C10—H10C	109.00
C12—N5—H5B	120.00	C9—C10—H10A	109.00
N1—C1—C6	119.27 (16)	C9—C10—H10B	109.00
C2—C1—C6	121.05 (16)	H10A—C10—H10B	110.00
N1—C1—C2	119.68 (15)	H10A—C10—H10C	109.00
C1—C2—C3	119.05 (18)	N2—C11—H11B	109.00
C2—C3—C4	120.2 (2)	N2—C11—H11A	109.00
C3—C4—C5	120.3 (2)	H11A—C11—H11C	110.00
C4—C5—C6	120.3 (2)	N2—C11—H11C	109.00
C1—C6—C5	119.10 (19)	H11A—C11—H11B	110.00
N1—C7—C8	104.54 (13)	H11B—C11—H11C	109.00
O1—C7—C8	131.16 (15)	N4—C12—N5	117.65 (16)
O1—C7—N1	124.22 (14)	S1—C12—N4	122.12 (13)
N3—C8—C7	122.97 (14)	S1—C12—N5	120.22 (14)

C1—N1—N2—C9	169.48 (14)	N1—C1—C2—C3	178.85 (17)
C1—N1—N2—C11	−39.5 (2)	C6—C1—C2—C3	−1.3 (3)
C7—N1—N2—C9	5.48 (18)	C2—C1—C6—C5	0.3 (3)
C7—N1—N2—C11	156.51 (16)	N1—C1—C6—C5	−179.83 (17)
N2—N1—C1—C2	−56.2 (2)	C1—C2—C3—C4	1.2 (3)
C7—N1—C1—C2	104.8 (2)	C2—C3—C4—C5	−0.2 (3)
N2—N1—C1—C6	123.92 (17)	C3—C4—C5—C6	−0.9 (3)
C7—N1—C1—C6	−75.1 (2)	C4—C5—C6—C1	0.8 (3)
N2—N1—C7—C8	−4.53 (18)	O1—C7—C8—N3	5.1 (3)
N2—N1—C7—O1	172.53 (15)	O1—C7—C8—C9	−174.75 (18)
C1—N1—C7—O1	9.8 (3)	N1—C7—C8—N3	−178.19 (15)
C1—N1—C7—C8	−167.26 (15)	N1—C7—C8—C9	2.02 (19)
N1—N2—C9—C10	177.29 (16)	N3—C8—C9—C10	0.0 (3)
N1—N2—C9—C8	−4.06 (18)	C7—C8—C9—N2	1.30 (19)
C11—N2—C9—C8	−152.29 (17)	C7—C8—C9—C10	179.82 (18)
C11—N2—C9—C10	29.1 (3)	N3—C8—C9—N2	−178.49 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···S1ⁱ	0.92 (2)	2.28 (2)	3.1619 (17)	159.9 (19)
N3—H3B···O1ⁱⁱ	0.90 (2)	1.87 (2)	2.764 (2)	174 (2)
N3—H3C···Cl1ⁱⁱⁱ	0.952 (19)	2.08 (2)	3.0316 (16)	180 (2)
N4—H4A···Cl1	0.86	2.41	3.2404 (17)	163
N4—H4B···O1^iv	0.86	2.12	2.970 (2)	170
N5—H5A···Cl1	0.86	2.74	3.4956 (19)	148
N5—H5A···S1^v	0.86	2.87	3.3768 (17)	120
N5—H5B···Cl1^vi	0.86	2.56	3.4091 (18)	171
C10—H10B···S1^vi	0.96	2.85	3.505 (2)	126

Symmetry codes: (i) x−1, y, z; (ii) −x, y+1/2, −z+1/2; (iii) x−1, y+1, z; (iv) x+1, y, z; (v) −x+1, y−1/2, −z+1/2; (vi) −x+1, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₄N₃O⁺·Cl⁻·CH₄N₂S
M_r	315.82
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	9.9733 (11), 8.2572 (8), 18.859 (2)
β (°)	90.851 (4)
V (Å³)	1552.9 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.38
Crystal size (mm)	0.30 × 0.15 × 0.14

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.935, 0.950
No. of measured, independent and observed [I > 2σ(I)] reflections	14413, 3876, 2948
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.111, 1.02
No. of reflections	3876
No. of parameters	192
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.30

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).