1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-aminium bromide monohydrate.

In the title hydrated mol-ecular salt, C(11)H(14)N(3)O(+)·Br(-)·H(2)O, the Br(-) anion is split and appears as two independent half-occupied Br(-) anions on twofold rotation axes. The dihedral angle between the phenyl ring and the mean plane of the 2,3-dihydro-1H-pyrazole ring (r.m.s. devation = 0.014 Å) is 62.43 (7)°. In the crystal, the components are connected via O-H⋯Br and N-H⋯O hydrogen bonds to form a one-dimensional polymeric structure propagating along [001].

Related literature

For general background on pyrazolone derivatives, see: Casas et al. (2007 ▶); Jain et al. (2003 ▶); Zhang et al. (2008 ▶). For related structures, see: Chitradevi et al. (2009 ▶); Murtaza et al.(2011 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C11H14N3O+·Br−·H2O

M = 302.17

Monoclinic,

a = 14.9080 (19) Å

b = 15.3961 (19) Å

c = 11.1501 (14) Å

β = 93.657 (2)°

V = 2554.0 (6) Å3

Z = 8

Mo Kα radiation

μ = 3.21 mm−1

T = 296 K

0.22 × 0.20 × 0.18 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.489, T max = 0.556

11995 measured reflections

3222 independent reflections

2081 reflections with I > 2σ(I)

R int = 0.044

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.108

S = 1.04

3222 reflections

155 parameters

H-atom parameters constrained

Δρmax = 0.48 e Å−3

Δρmin = −0.40 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812023550/su2432sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812023550/su2432Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812023550/su2432Isup3.cml

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

C11H14N3O+·Br−·H2O	F(000) = 1232
Mr = 302.17	Dx = 1.572 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2078 reflections
a = 14.9080 (19) Å	θ = 2.7–23.6°
b = 15.3961 (19) Å	µ = 3.21 mm−1
c = 11.1501 (14) Å	T = 296 K
β = 93.657 (2)°	Block, yellow
V = 2554.0 (6) Å3	0.22 × 0.20 × 0.18 mm
Z = 8

Bruker SMART CCD diffractometer	3222 independent reflections
Radiation source: fine-focus sealed tube	2081 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.044
ω scans	θmax = 28.4°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −19→19
Tmin = 0.489, Tmax = 0.556	k = −20→20
11995 measured reflections	l = −14→14

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) = 0.108	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0493P)2 + 2.161P] where P = (Fo2 + 2Fc2)/3
3222 reflections	(Δ/σ)max < 0.001
155 parameters	Δρmax = 0.48 e Å−3
0 restraints	Δρmin = −0.40 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 esds 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	0.11377 (13)	0.01137 (15)	0.64912 (16)	0.0377 (6)
N1	0.24203 (15)	0.09233 (18)	0.61672 (19)	0.0346 (8)
N2	0.28247 (16)	0.12321 (17)	0.5164 (2)	0.0353 (8)
N3	0.08569 (14)	0.01740 (16)	0.38186 (18)	0.0286 (7)
C1	0.2831 (2)	0.0971 (2)	0.7361 (2)	0.0330 (9)
C2	0.2374 (2)	0.1400 (2)	0.8221 (3)	0.0437 (10)
C3	0.2752 (3)	0.1419 (3)	0.9393 (3)	0.0630 (16)
C4	0.3572 (4)	0.1054 (3)	0.9670 (3)	0.080 (2)
C5	0.4009 (3)	0.0627 (4)	0.8813 (4)	0.0781 (18)
C6	0.3637 (2)	0.0573 (3)	0.7639 (3)	0.0551 (13)
C7	0.15821 (17)	0.05670 (17)	0.4544 (2)	0.0256 (8)
C8	0.22945 (18)	0.10325 (18)	0.4178 (2)	0.0275 (8)
C9	0.2493 (2)	0.1347 (2)	0.2962 (3)	0.0391 (10)
C10	0.3605 (2)	0.1798 (2)	0.5249 (3)	0.0466 (10)
C11	0.16456 (18)	0.04939 (18)	0.5808 (2)	0.0281 (8)
Br1	0.00000	0.19903 (3)	0.25000	0.0427 (2)
Br2	0.00000	0.29956 (4)	0.75000	0.0536 (2)
O1W	−0.04198 (19)	0.14894 (18)	0.5343 (2)	0.0651 (10)
H2A	0.18260	0.16700	0.80220	0.0530*
H3A	0.24430	0.16840	0.99940	0.0760*
H3B	0.09260	0.02850	0.30470	0.0430*
H3C	0.03360	0.03920	0.40250	0.0430*
H3D	0.08620	−0.03980	0.39370	0.0430*
H4A	0.38340	0.10970	1.04480	0.0950*
H5A	0.45620	0.03670	0.90140	0.0940*
H6A	0.39310	0.02730	0.70560	0.0660*
H9A	0.30540	0.16560	0.30100	0.0590*
H9B	0.20210	0.17280	0.26610	0.0590*
H9C	0.25330	0.08610	0.24290	0.0590*
H10A	0.37780	0.19340	0.44560	0.0700*
H10B	0.40920	0.15110	0.56910	0.0700*
H10C	0.34590	0.23250	0.56550	0.0700*
H1WA	−0.02990	0.16590	0.46460	0.0780*
H1WB	−0.02990	0.18990	0.58390	0.0780*

	U11	U22	U33	U12	U13	U23
O1	0.0326 (10)	0.0618 (14)	0.0186 (9)	−0.0133 (10)	0.0006 (8)	0.0052 (10)
N1	0.0309 (13)	0.0554 (16)	0.0174 (10)	−0.0125 (12)	0.0004 (9)	0.0000 (11)
N2	0.0365 (14)	0.0473 (15)	0.0222 (11)	−0.0144 (11)	0.0023 (10)	0.0009 (11)
N3	0.0255 (11)	0.0427 (14)	0.0174 (10)	−0.0025 (10)	−0.0004 (8)	−0.0018 (10)
C1	0.0337 (14)	0.0450 (18)	0.0199 (13)	−0.0118 (14)	−0.0022 (11)	0.0009 (13)
C2	0.062 (2)	0.0393 (18)	0.0301 (16)	−0.0069 (16)	0.0059 (15)	−0.0011 (14)
C3	0.106 (4)	0.056 (2)	0.0272 (17)	−0.026 (2)	0.006 (2)	−0.0081 (17)
C4	0.105 (4)	0.098 (4)	0.032 (2)	−0.057 (3)	−0.026 (2)	0.014 (2)
C5	0.047 (2)	0.126 (4)	0.058 (3)	−0.022 (2)	−0.023 (2)	0.028 (3)
C6	0.0382 (18)	0.082 (3)	0.044 (2)	−0.0042 (18)	−0.0058 (15)	0.0046 (18)
C7	0.0251 (13)	0.0337 (14)	0.0180 (12)	−0.0002 (11)	0.0006 (9)	−0.0022 (11)
C8	0.0283 (14)	0.0347 (15)	0.0197 (12)	−0.0011 (12)	0.0032 (10)	0.0006 (11)
C9	0.0439 (18)	0.0505 (19)	0.0232 (13)	−0.0086 (14)	0.0043 (12)	0.0062 (14)
C10	0.0380 (17)	0.065 (2)	0.0369 (17)	−0.0226 (16)	0.0040 (13)	−0.0049 (16)
C11	0.0264 (13)	0.0388 (16)	0.0191 (12)	−0.0037 (12)	0.0011 (10)	0.0002 (12)
Br1	0.0493 (3)	0.0400 (3)	0.0371 (2)	0.0000	−0.0094 (2)	0.0000
Br2	0.0436 (3)	0.0828 (4)	0.0347 (3)	0.0000	0.0055 (2)	0.0000
O1W	0.097 (2)	0.0533 (16)	0.0461 (14)	−0.0197 (15)	0.0132 (14)	0.0000 (13)

O1—C11	1.253 (3)	C4—C5	1.360 (7)
O1W—H1WB	0.8500	C5—C6	1.391 (6)
O1W—H1WA	0.8500	C7—C8	1.365 (4)
N1—C11	1.368 (4)	C7—C11	1.411 (3)
N1—C1	1.431 (3)	C8—C9	1.487 (4)
N1—N2	1.388 (3)	C2—H2A	0.9300
N2—C8	1.348 (3)	C3—H3A	0.9300
N2—C10	1.452 (4)	C4—H4A	0.9300
N3—C7	1.441 (3)	C5—H5A	0.9300
N3—H3C	0.8900	C6—H6A	0.9300
N3—H3D	0.8900	C9—H9B	0.9600
N3—H3B	0.8900	C9—H9C	0.9600
C1—C2	1.380 (4)	C9—H9A	0.9600
C1—C6	1.367 (5)	C10—H10C	0.9600
C2—C3	1.390 (5)	C10—H10A	0.9600
C3—C4	1.363 (7)	C10—H10B	0.9600
H1WA—O1W—H1WB	109.00	N2—C8—C7	107.6 (2)
N2—N1—C1	123.4 (2)	N1—C11—C7	104.8 (2)
N2—N1—C11	109.4 (2)	O1—C11—C7	129.8 (2)
C1—N1—C11	126.9 (2)	O1—C11—N1	125.4 (2)
N1—N2—C8	108.5 (2)	C3—C2—H2A	121.00
N1—N2—C10	122.7 (2)	C1—C2—H2A	121.00
C8—N2—C10	128.0 (2)	C2—C3—H3A	120.00
C7—N3—H3D	109.00	C4—C3—H3A	120.00
C7—N3—H3B	109.00	C5—C4—H4A	120.00
C7—N3—H3C	109.00	C3—C4—H4A	120.00
H3C—N3—H3D	110.00	C4—C5—H5A	120.00
H3B—N3—H3C	110.00	C6—C5—H5A	120.00
H3B—N3—H3D	109.00	C5—C6—H6A	121.00
N1—C1—C6	120.4 (3)	C1—C6—H6A	121.00
N1—C1—C2	118.0 (3)	C8—C9—H9A	109.00
C2—C1—C6	121.5 (3)	C8—C9—H9B	109.00
C1—C2—C3	118.4 (3)	H9A—C9—H9B	109.00
C2—C3—C4	120.6 (3)	H9A—C9—H9C	109.00
C3—C4—C5	120.2 (4)	C8—C9—H9C	110.00
C4—C5—C6	120.7 (4)	H9B—C9—H9C	109.00
C1—C6—C5	118.6 (3)	N2—C10—H10B	110.00
N3—C7—C11	121.8 (2)	N2—C10—H10C	109.00
C8—C7—C11	109.7 (2)	N2—C10—H10A	109.00
N3—C7—C8	128.5 (2)	H10A—C10—H10C	109.00
N2—C8—C9	121.9 (2)	H10B—C10—H10C	109.00
C7—C8—C9	130.3 (2)	H10A—C10—H10B	110.00
C1—N1—N2—C8	175.6 (3)	N1—C1—C2—C3	177.5 (3)
C1—N1—N2—C10	−13.9 (4)	C6—C1—C2—C3	−0.2 (5)
C11—N1—N2—C8	2.5 (3)	N1—C1—C6—C5	−179.3 (4)
C11—N1—N2—C10	173.0 (3)	C2—C1—C6—C5	−1.8 (6)
N2—N1—C1—C2	122.6 (3)	C1—C2—C3—C4	2.8 (6)
C11—N1—C1—C2	−65.5 (4)	C2—C3—C4—C5	−3.4 (7)
N2—N1—C1—C6	−59.8 (4)	C3—C4—C5—C6	1.5 (8)
C11—N1—C1—C6	112.1 (4)	C4—C5—C6—C1	1.1 (7)
N2—N1—C11—C7	−1.1 (3)	N3—C7—C8—C9	6.8 (5)
C1—N1—C11—C7	−174.0 (3)	C11—C7—C8—N2	2.1 (3)
N2—N1—C11—O1	177.5 (3)	C11—C7—C8—C9	−174.3 (3)
C1—N1—C11—O1	4.7 (5)	N3—C7—C11—O1	−0.1 (5)
C10—N2—C8—C9	4.1 (5)	N3—C7—C11—N1	178.5 (2)
C10—N2—C8—C7	−172.6 (3)	C8—C7—C11—O1	−179.2 (3)
N1—N2—C8—C9	174.0 (3)	C8—C7—C11—N1	−0.6 (3)
N1—N2—C8—C7	−2.7 (3)	N3—C7—C8—N2	−176.9 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···Br1	0.85	2.51	3.360 (2)	173
O1W—H1WB···Br2	0.85	2.52	3.371 (3)	173
N3—H3B···O1i	0.89	1.89	2.692 (3)	150
N3—H3C···O1W	0.89	2.55	3.321 (3)	146
N3—H3C···O1ii	0.89	2.37	3.004 (3)	129
N3—H3D···O1Wii	0.89	1.99	2.817 (4)	153

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯Br1	0.85	2.51	3.360 (2)	173
O1W—H1WB⋯Br2	0.85	2.52	3.371 (3)	173
N3—H3B⋯O1i	0.89	1.89	2.692 (3)	150
N3—H3C⋯O1W	0.89	2.55	3.321 (3)	146
N3—H3C⋯O1ii	0.89	2.37	3.004 (3)	129
N3—H3D⋯O1Wii	0.89	1.99	2.817 (4)	153

Symmetry codes: (i) ; (ii) .