1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-aminium chloride-thio-urea (1/1).

In the title compound, C(11)H(14)N(3)O(+)·Cl(-)·CH(4)N(2)S, 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)°.

Related literature

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

Crystal data

C11H14N3O+·Cl−·CH4N2S

M = 315.82

Monoclinic,

a = 9.9733 (11) Å

b = 8.2572 (8) Å

c = 18.859 (2) Å

β = 90.851 (4)°

V = 1552.9 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.38 mm−1

T = 296 K

0.30 × 0.15 × 0.14 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.935, T max = 0.950

14413 measured reflections

3876 independent reflections

2948 reflections with I > 2σ(I)

R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.111

S = 1.02

3876 reflections

192 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.28 e Å−3

Δρmin = −0.30 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; 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.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811029989/gk2395sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811029989/gk2395Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811029989/gk2395Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C11H14N3O+·Cl−·CH4N2S	F(000) = 664
Mr = 315.82	Dx = 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

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

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(Fo2) + (0.0519P)2 + 0.4062P] where P = (Fo2 + 2Fc2)/3
3876 reflections	(Δ/σ)max < 0.001
192 parameters	Δρmax = 0.28 e Å−3
0 restraints	Δρmin = −0.30 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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···O1iv	0.86	2.12	2.970 (2)	170
N5—H5A···Cl1	0.86	2.74	3.4956 (19)	148
N5—H5A···S1v	0.86	2.87	3.3768 (17)	120
N5—H5B···Cl1vi	0.86	2.56	3.4091 (18)	171
C10—H10B···S1vi	0.96	2.85	3.505 (2)	126

Table 1

Hydrogen-bond geometry (Å, °)

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⋯O1iv	0.86	2.12	2.970 (2)	170
N5—H5A⋯Cl1	0.86	2.74	3.4956 (19)	148
N5—H5A⋯S1v	0.86	2.87	3.3768 (17)	120
N5—H5B⋯Cl1vi	0.86	2.56	3.4091 (18)	171
C10—H10B⋯S1vi	0.96	2.85	3.505 (2)	126

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .