1,5-Dimethyl-3-oxo-2-phenyl-2,3-di-hy-dro-1H-pyrazol-4-aminium 2-hydroxy-benzoate.

In the title salt, C(11)H(14)N(3)O(+)·C(7)H(5)O(3) (-), the phenyl ring of the cation is oriented at an angle of 67.0 (1)° with respect to the five-membered pyrazolone ring. The carboxyl-ate plane of the anion is twisted out from the plane of the aromatic ring at an angle of 13.7 (3)°. In the crystal, the cations form hydrogen-bonded dimers with an R(2) (2)(10) ring motif. The salicylate anion has an intra-molecular O-H⋯O hydrogen bond.

Related literature

For the biological and pharmacological importance of pyrazolone derivatives and 4-amino­anti­pyrene compounds, see: Filho et al. (1998 ▶); Jain et al. (2003 ▶); Mishra (1999 ▶); Sondhi et al. (1999 ▶); Sondhi et al. (2001 ▶). For similar hydrogen-bonded structures, see: Athimoolam & Natarajan (2006a ▶,b ▶,c ▶); Athimoolam & Rajaram (2005 ▶). For hydrogen bonding inter­actions and graph-set notations, see: Desiraju (1989 ▶); Etter et al. (1990 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

C11H14N3O+·C7H5O3 −

M = 341.36

Monoclinic,

a = 8.3182 (6) Å

b = 23.3006 (16) Å

c = 8.8503 (6) Å

β = 101.517 (1)°

V = 1680.8 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 293 K

0.24 × 0.13 × 0.12 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: none

16025 measured reflections

2959 independent reflections

2599 reflections with I > 2σ(I)

R int = 0.020

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.113

S = 1.05

2959 reflections

229 parameters

H-atom parameters constrained

Δρmax = 0.18 e Å−3

Δρmin = −0.18 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL/PC (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL/PC; molecular graphics: Mercury (Macrae et al., 2006 ▶ ) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXTL/PC.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809045760/bt5124sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809045760/bt5124Isup2.hkl

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

C11H14N3O+·C7H5O3−	F(000) = 720
Mr = 341.36	Dx = 1.349 Mg m−3Dm = 1.339 Mg m−3Dm measured by flotation technique using a liquid-mixture of xylene and carbon tetrachloride
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3884 reflections
a = 8.3182 (6) Å	θ = 2.6–23.9°
b = 23.3006 (16) Å	µ = 0.10 mm−1
c = 8.8503 (6) Å	T = 293 K
β = 101.517 (1)°	Needle, light orange
V = 1680.8 (2) Å3	0.24 × 0.13 × 0.12 mm
Z = 4

Bruker SMART APEX CCD area-detector diffractometer	2599 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.020
graphite	θmax = 25.0°, θmin = 1.8°
ω scans	h = −9→9
16025 measured reflections	k = −27→27
2959 independent reflections	l = −10→10

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.113	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0515P)2 + 0.4777P] where P = (Fo2 + 2Fc2)/3
2959 reflections	(Δ/σ)max < 0.001
229 parameters	Δρmax = 0.18 e Å−3
0 restraints	Δρmin = −0.18 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.88415 (19)	0.55024 (6)	0.81347 (17)	0.0448 (3)
C11	1.0648 (2)	0.54675 (8)	0.8259 (2)	0.0584 (4)
H11A	1.0898	0.5168	0.7597	0.088*
H11C	1.1164	0.5385	0.9306	0.088*
H11B	1.1048	0.5827	0.7955	0.088*
N2	0.81742 (15)	0.57725 (6)	0.92231 (15)	0.0484 (3)
C22	0.8940 (2)	0.62350 (8)	1.0208 (2)	0.0625 (5)
H22A	1.0071	0.6143	1.0603	0.094*
H22B	0.8383	0.6285	1.1050	0.094*
H22C	0.8874	0.6584	0.9621	0.094*
N3	0.64810 (15)	0.57811 (6)	0.86977 (15)	0.0496 (3)
C4	0.60726 (19)	0.54839 (7)	0.73428 (17)	0.0479 (4)
O4	0.46461 (14)	0.53935 (6)	0.66452 (14)	0.0662 (4)
C5	0.75999 (18)	0.53088 (6)	0.70220 (16)	0.0442 (3)
N5	0.77414 (16)	0.50034 (6)	0.56334 (14)	0.0508 (3)
H5A	0.6744	0.4926	0.5091	0.076*
H5B	0.8286	0.4677	0.5883	0.076*
H5C	0.8281	0.5219	0.5071	0.076*
C31	0.54080 (18)	0.60115 (7)	0.96225 (17)	0.0471 (4)
C32	0.4479 (2)	0.64820 (8)	0.9101 (2)	0.0619 (5)
H32	0.4516	0.6640	0.8144	0.074*
C33	0.3485 (2)	0.67208 (9)	1.0009 (3)	0.0743 (6)
H33	0.2847	0.7040	0.9661	0.089*
C34	0.3436 (2)	0.64892 (10)	1.1417 (2)	0.0697 (6)
H34	0.2785	0.6657	1.2037	0.084*
C35	0.4341 (2)	0.60110 (10)	1.1917 (2)	0.0680 (5)
H35	0.4285	0.5850	1.2867	0.082*
C36	0.5338 (2)	0.57665 (8)	1.10183 (19)	0.0588 (4)
H36	0.5952	0.5441	1.1354	0.071*
C41	0.9974 (3)	0.38422 (8)	0.5503 (2)	0.0628 (5)
C42	1.0840 (2)	0.34016 (6)	0.47447 (17)	0.0493 (4)
C43	1.2516 (2)	0.34179 (8)	0.4878 (2)	0.0653 (5)
H43	1.3123	0.3703	0.5472	0.078*
C44	1.3309 (3)	0.30161 (12)	0.4140 (3)	0.0940 (8)
H44	1.4445	0.3022	0.4255	0.113*
C45	1.2386 (5)	0.26065 (11)	0.3230 (3)	0.1051 (10)
H45	1.2907	0.2340	0.2708	0.126*
C46	1.0744 (4)	0.25848 (9)	0.3083 (3)	0.0926 (8)
H46	1.0143	0.2309	0.2452	0.111*
C47	0.9954 (3)	0.29676 (8)	0.3861 (2)	0.0652 (5)
O41	1.0717 (2)	0.42857 (6)	0.60326 (16)	0.0872 (5)
O42	0.8508 (2)	0.37591 (8)	0.5565 (2)	0.0980 (5)
O43	0.8319 (2)	0.29178 (8)	0.3741 (2)	0.1032 (6)
H43A	0.8004	0.3156	0.4299	0.155*

	U11	U22	U33	U12	U13	U23
C1	0.0488 (8)	0.0453 (8)	0.0415 (8)	0.0025 (6)	0.0118 (6)	−0.0012 (6)
C11	0.0492 (9)	0.0706 (11)	0.0555 (10)	0.0023 (8)	0.0105 (8)	−0.0107 (8)
N2	0.0448 (7)	0.0555 (8)	0.0444 (7)	−0.0020 (6)	0.0080 (5)	−0.0119 (6)
C22	0.0581 (10)	0.0703 (11)	0.0590 (10)	−0.0100 (8)	0.0115 (8)	−0.0230 (9)
N3	0.0436 (7)	0.0609 (8)	0.0443 (7)	0.0016 (6)	0.0088 (5)	−0.0139 (6)
C4	0.0489 (9)	0.0531 (9)	0.0406 (8)	0.0024 (7)	0.0066 (7)	−0.0087 (7)
O4	0.0479 (7)	0.0914 (9)	0.0559 (7)	0.0057 (6)	0.0025 (5)	−0.0288 (6)
C5	0.0494 (9)	0.0454 (8)	0.0383 (7)	0.0036 (6)	0.0098 (6)	−0.0049 (6)
N5	0.0518 (7)	0.0569 (8)	0.0437 (7)	0.0071 (6)	0.0095 (6)	−0.0109 (6)
C31	0.0440 (8)	0.0532 (9)	0.0450 (8)	−0.0031 (7)	0.0109 (6)	−0.0134 (7)
C32	0.0641 (11)	0.0649 (11)	0.0595 (10)	0.0077 (9)	0.0191 (8)	−0.0014 (8)
C33	0.0668 (12)	0.0720 (12)	0.0878 (15)	0.0153 (10)	0.0244 (11)	−0.0116 (11)
C34	0.0518 (10)	0.0900 (14)	0.0725 (12)	−0.0073 (10)	0.0244 (9)	−0.0326 (11)
C35	0.0634 (11)	0.0938 (15)	0.0514 (10)	−0.0145 (11)	0.0225 (9)	−0.0117 (10)
C36	0.0611 (10)	0.0660 (11)	0.0508 (9)	−0.0003 (8)	0.0149 (8)	−0.0047 (8)
C41	0.0865 (14)	0.0587 (11)	0.0490 (9)	0.0174 (10)	0.0277 (9)	0.0136 (8)
C42	0.0662 (10)	0.0418 (8)	0.0419 (8)	0.0044 (7)	0.0153 (7)	0.0065 (6)
C43	0.0689 (12)	0.0627 (11)	0.0668 (11)	0.0065 (9)	0.0199 (9)	0.0089 (9)
C44	0.0935 (17)	0.0945 (17)	0.1083 (19)	0.0351 (14)	0.0544 (15)	0.0320 (15)
C45	0.181 (3)	0.0629 (14)	0.0896 (18)	0.0378 (18)	0.071 (2)	0.0077 (13)
C46	0.165 (3)	0.0485 (11)	0.0661 (13)	0.0005 (14)	0.0285 (15)	−0.0055 (9)
C47	0.0919 (14)	0.0491 (10)	0.0537 (10)	−0.0046 (9)	0.0125 (9)	0.0113 (8)
O41	0.1512 (15)	0.0554 (8)	0.0651 (9)	0.0028 (8)	0.0456 (9)	−0.0106 (7)
O42	0.0848 (11)	0.1136 (13)	0.1090 (13)	0.0311 (9)	0.0514 (10)	0.0239 (10)
O43	0.0926 (12)	0.0962 (13)	0.1114 (14)	−0.0326 (9)	−0.0020 (10)	0.0149 (10)

C1—C5	1.354 (2)	C33—C34	1.366 (3)
C1—N2	1.3585 (19)	C33—H33	0.9300
C1—C11	1.487 (2)	C34—C35	1.368 (3)
C11—H11A	0.9600	C34—H34	0.9300
C11—H11C	0.9600	C35—C36	1.381 (3)
C11—H11B	0.9600	C35—H35	0.9300
N2—N3	1.3924 (18)	C36—H36	0.9300
N2—C22	1.451 (2)	C41—O42	1.246 (2)
C22—H22A	0.9600	C41—O41	1.247 (2)
C22—H22B	0.9600	C41—C42	1.489 (2)
C22—H22C	0.9600	C42—C43	1.376 (3)
N3—C4	1.3675 (19)	C42—C47	1.395 (2)
N3—C31	1.4306 (19)	C43—C44	1.382 (3)
C4—O4	1.2414 (19)	C43—H43	0.9300
C4—C5	1.416 (2)	C44—C45	1.379 (4)
C5—N5	1.4450 (18)	C44—H44	0.9300
N5—H5A	0.8900	C45—C46	1.347 (4)
N5—H5B	0.8900	C45—H45	0.9300
N5—H5C	0.8900	C46—C47	1.372 (3)
C31—C32	1.367 (2)	C46—H46	0.9300
C31—C36	1.373 (2)	C47—O43	1.348 (3)
C32—C33	1.380 (3)	O43—H43A	0.8200
C32—H32	0.9300
C5—C1—N2	108.04 (13)	C31—C32—H32	120.3
C5—C1—C11	130.42 (14)	C33—C32—H32	120.3
N2—C1—C11	121.52 (13)	C34—C33—C32	120.15 (19)
C1—C11—H11A	109.5	C34—C33—H33	119.9
C1—C11—H11C	109.5	C32—C33—H33	119.9
H11A—C11—H11C	109.5	C33—C34—C35	120.15 (17)
C1—C11—H11B	109.5	C33—C34—H34	119.9
H11A—C11—H11B	109.5	C35—C34—H34	119.9
H11C—C11—H11B	109.5	C34—C35—C36	120.29 (18)
C1—N2—N3	107.41 (12)	C34—C35—H35	119.9
C1—N2—C22	125.26 (14)	C36—C35—H35	119.9
N3—N2—C22	118.91 (13)	C31—C36—C35	119.02 (18)
N2—C22—H22A	109.5	C31—C36—H36	120.5
N2—C22—H22B	109.5	C35—C36—H36	120.5
H22A—C22—H22B	109.5	O42—C41—O41	121.88 (19)
N2—C22—H22C	109.5	O42—C41—C42	118.59 (19)
H22A—C22—H22C	109.5	O41—C41—C42	119.52 (19)
H22B—C22—H22C	109.5	C43—C42—C47	118.73 (17)
C4—N3—N2	110.07 (12)	C43—C42—C41	121.05 (17)
C4—N3—C31	128.14 (13)	C47—C42—C41	120.21 (18)
N2—N3—C31	121.29 (12)	C42—C43—C44	120.8 (2)
O4—C4—N3	124.58 (14)	C42—C43—H43	119.6
O4—C4—C5	131.15 (14)	C44—C43—H43	119.6
N3—C4—C5	104.24 (13)	C45—C44—C43	118.8 (2)
C1—C5—C4	110.04 (13)	C45—C44—H44	120.6
C1—C5—N5	127.06 (14)	C43—C44—H44	120.6
C4—C5—N5	122.76 (13)	C46—C45—C44	121.2 (2)
C5—N5—H5A	109.5	C46—C45—H45	119.4
C5—N5—H5B	109.5	C44—C45—H45	119.4
H5A—N5—H5B	109.5	C45—C46—C47	120.4 (2)
C5—N5—H5C	109.5	C45—C46—H46	119.8
H5A—N5—H5C	109.5	C47—C46—H46	119.8
H5B—N5—H5C	109.5	O43—C47—C46	118.8 (2)
C32—C31—C36	120.94 (15)	O43—C47—C42	121.22 (18)
C32—C31—N3	118.89 (15)	C46—C47—C42	120.0 (2)
C36—C31—N3	120.16 (15)	C47—O43—H43A	109.5
C31—C32—C33	119.41 (18)
C5—C1—N2—N3	−4.57 (17)	C36—C31—C32—C33	1.5 (3)
C11—C1—N2—N3	174.07 (14)	N3—C31—C32—C33	−177.62 (17)
C5—C1—N2—C22	−151.94 (16)	C31—C32—C33—C34	0.2 (3)
C11—C1—N2—C22	26.7 (2)	C32—C33—C34—C35	−1.6 (3)
C1—N2—N3—C4	4.24 (17)	C33—C34—C35—C36	1.4 (3)
C22—N2—N3—C4	154.04 (15)	C32—C31—C36—C35	−1.7 (3)
C1—N2—N3—C31	176.75 (14)	N3—C31—C36—C35	177.43 (15)
C22—N2—N3—C31	−33.5 (2)	C34—C35—C36—C31	0.2 (3)
N2—N3—C4—O4	176.11 (16)	O42—C41—C42—C43	−168.40 (17)
C31—N3—C4—O4	4.2 (3)	O41—C41—C42—C43	12.8 (2)
N2—N3—C4—C5	−2.15 (17)	O42—C41—C42—C47	12.6 (2)
C31—N3—C4—C5	−174.00 (15)	O41—C41—C42—C47	−166.22 (16)
N2—C1—C5—C4	3.34 (18)	C47—C42—C43—C44	0.6 (3)
C11—C1—C5—C4	−175.14 (16)	C41—C42—C43—C44	−178.37 (17)
N2—C1—C5—N5	179.12 (14)	C42—C43—C44—C45	1.8 (3)
C11—C1—C5—N5	0.6 (3)	C43—C44—C45—C46	−1.6 (4)
O4—C4—C5—C1	−178.80 (18)	C44—C45—C46—C47	−1.0 (4)
N3—C4—C5—C1	−0.71 (18)	C45—C46—C47—O43	−177.1 (2)
O4—C4—C5—N5	5.2 (3)	C45—C46—C47—C42	3.4 (3)
N3—C4—C5—N5	−176.71 (14)	C43—C42—C47—O43	177.36 (17)
C4—N3—C31—C32	−72.0 (2)	C41—C42—C47—O43	−3.6 (2)
N2—N3—C31—C32	116.97 (17)	C43—C42—C47—C46	−3.2 (3)
C4—N3—C31—C36	108.9 (2)	C41—C42—C47—C46	175.77 (16)
N2—N3—C31—C36	−62.1 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···O4i	0.89	1.88	2.696 (2)	151
N5—H5B···O41	0.89	2.20	2.949 (2)	142
N5—H5B···O42	0.89	2.17	2.972 (2)	150
N5—H5C···O41ii	0.89	1.82	2.705 (2)	175
O43—H43A···O42	0.82	1.79	2.524 (3)	148

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5A⋯O4i	0.89	1.88	2.696 (2)	151
N5—H5B⋯O41	0.89	2.20	2.949 (2)	142
N5—H5B⋯O42	0.89	2.17	2.972 (2)	150
N5—H5C⋯O41ii	0.89	1.82	2.705 (2)	175
O43—H43A⋯O42	0.82	1.79	2.524 (3)	148

Symmetry codes: (i) ; (ii) .