1-(5-Hydr­oxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)ethanone: a new monoclinic polymorph

Sheikh, T.U.; Khan, M.A.; Arshad, M.N.; Khan, I.U.; Stoeckli-Evans, H.

doi:10.1107/S1600536809001470

organic compounds

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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page o330

doi:10.1107/S1600536809001470

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1-(5-Hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)ethanone: a new monoclinic polymorph

Tasneem Ullah Sheikh,^a,^b Misbahul Ain Khan,^a Muhammad Nadeem Arshad,^c ^* Islam Ullah Khan ^c and Helen Stoeckli-Evans ^d

^aDepartment of Chemistry, Islamia University, Bahawalpur, Pakistan, ^bDepartment of Chemistry, Government College of Education, Afzalpur, Azad Jammu & Kashmir, Pakistan, ^cMaterials Chemistry Laboratory, Department of Chemistry, GC University, Lahore, Pakistan, and ^dInstitute of Physics, University of Neuchâtel, rue Emile-Argand 11, CH-2009 Neuchâtel, Switzerland
^*Correspondence e-mail: mnachemist@hotmail.com

(Received 9 January 2009; accepted 12 January 2009; online 17 January 2009)

The title compound, C₁₂H₁₂N₂O₂, crystallized in the monolinic space group P2₁/n, with two independent molecules (A and B) in the asymmetric unit. This is in contrast to the first monoclinic polymorph reported [Cingolani et al. (2002 ). Inorg. Chem. 41, 1151–116], which crystallized in the space group C2/c with one independent molecule per asymmetric unit. The dihedral angles between the two rings differ slightly; in molecule A it is 4.90 (11)° and in molecule B it is 16.05 (13)°. In both molecules, there is an intramolecular O—H⋯O hydrogen bond involving the hydroxyl substituent and the carbonyl O atom of the adjacent acetyl group. In the crystal structure, molecules A and B are linked via a C—H⋯N interaction. There are also some weak C—H⋯π interactions involving the phenyl ring of molecule A and H atoms of the acetyl groups of both molecules.

Related literature

For early literature on pyrazoles, see: Knorr (1883 ). For information on the pharamceutical properties of pyrazoles, see: Grimmett (1970 ). For the monoclinic C2/c polymorph of the title compound, see: Cingolani et al. (2002).

Experimental

Crystal data

C₁₂H₁₂N₂O₂
M_r = 216.24
Monoclinic, P 2₁ /n
a = 13.8735 (7) Å
b = 9.2037 (4) Å
c = 18.3702 (8) Å
β = 110.100 (2)°
V = 2202.78 (18) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 (2) K
0.34 × 0.22 × 0.16 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: none
24519 measured reflections
5500 independent reflections
2656 reflections with I > 2σ(I)
R_int = 0.047

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.149
S = 0.97
5500 reflections
292 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯O2	0.82	1.85	2.546 (2)	142
O21—H21O⋯O22	0.82	1.83	2.531 (3)	142
C8—H8⋯N22ⁱ	0.93	2.56	3.489 (3)	177
C13—H13C⋯Cg2ⁱⁱ	0.96	2.66	3.533 (3)	150
C33—H33B⋯Cg2ⁱⁱ	0.96	2.98	3.774 (3)	141
Symmetry codes: (i) x+1, y, z; (ii) -x+1, -y+1, -z+1. Cg2 is the centroid of the C6–C11 ring.

Data collection: APEX2 (Bruker, 2002 ); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809001470/wn2305sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809001470/wn2305Isup2.hkl

checkCIF report

Comment top

The history of pyrazoles began already in the late nineteenth century (Knorr, 1883). Pyrazole is isomeric with the biologically important imidazole ring system but, unlike imidazole, has fewer natural derivatives. The ring system is very stable and inert, and interest in such compounds stemmed from their applications as drugs, dyes and as anesthetics. They are also used as antioxidants in fuels but their major applications have been in the pharmaceutical (Grimmett, 1970) and agricultural industries. In view of the importance of pyrazole derivatives we have planned a systematic study of such compounds, and describe here the crystal structure of a new polymorph of the title compound.

It crystallized in the monoclinic space group P2₁/n, with two independent molecules (A and B) per asymmetric unit (Fig. 1). This is in contrast to an earlier reported monoclinic polymorph, (Cingolani et al., 2002), which crystallized in the space group C2/c with one independent molecule per asymmetric unit. The bond distances and angles in both polymorphs are very similar. The dihedral angles between the two rings differ slightly; in molecule A it is 4.90 (11)° and in molecule B it is 16.05 (13)°. The corresponding value in the other polymorph is 5.33 (10)°.

In both molecules (A and B), there is an intramolecular O—H···O hydrogen bond involving the hydroxyl substituent and the carbonyl O atom of the adjacent acetyl group (Table 1); this feature is also present in the C2/c polymorph. In the crystal structure, molecules A and B are linked via a C—H···N interaction (Fig. 2 and Table 1). There are also some weak C—H···π interactions involving the phenyl ring (centroid Cg2) of molecule A and some H atoms of the acetyl groups of both molecules (Table 1).

Related literature top

For early literature on pyrazoles, see: Knorr (1883). For information on the pharamceutical properties of pyrazoles, see: Grimmett (1970). For the monoclinic C2/c polymorph, see: Cingolani et al. (2002). Cg2 is the centroid of the C6–C11 ring.

Experimental top

1-Phenyl-3-methyl-5-pyrazolone (7.5 g) was dissolved by heating in tetrahydrofuran (80 ml). Calcium hydroxide (12 g) was added and acetyl chloride (4 ml) was then added dropwise over a period of 1 min. The temperature increased during the first few minutes and the reaction mixture became a thick paste. This mixture was then refluxed for 30 min. The calcium complex of the title compound that had formed in the flask was decomposed by pouring the mixture into a dilute solution of HCl (100 ml). A dark brownish-red organic layer was obtained which was extracted using dichloromethane. The solvent was then removed by vacuum distillation and the solid obtained was washed with a little water and THF. Crystals of the title compound, suitable for X-ray analysis, were obtained by recrystallization from methanol/water (1:1, v:v).

Computing details top

Data collection: APEX2 (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the molecular structure of the two independent molecules (A and B), showing the displacement ellipsoids drawn at the 50% probability level and the intramolecular O—H···O hydrogen bonds as dashed lines. Hydrogen atoms are represented as spheres of arbitrary radius.
	Fig. 2. A view along the b axis of the crystal packing, showing the intramolecular O—H···H hydrogen bonds and the intermolecular C—H···N interactions as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity.

1-(5-Hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)ethanone top

Crystal data top

C₁₂H₁₂N₂O₂	F(000) = 912
M_r = 216.24	D_x = 1.304 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4106 reflections
a = 13.8735 (7) Å	θ = 2.3–22.4°
b = 9.2037 (4) Å	µ = 0.09 mm⁻¹
c = 18.3702 (8) Å	T = 296 K
β = 110.100 (2)°	Block, colorless
V = 2202.78 (18) Å³	0.34 × 0.22 × 0.16 mm
Z = 8

Data collection top

Bruker Kappa APEXII CCD diffractometer	2656 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.047
Graphite monochromator	θ_max = 28.6°, θ_min = 2.4°
ϕ and ω scans	h = −18→18
24519 measured reflections	k = −12→12
5500 independent reflections	l = −24→24

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.051	H-atom parameters constrained
wR(F²) = 0.149	w = 1/[σ²(F_o²) + (0.0571P)² + 0.4951P] where P = (F_o² + 2F_c²)/3
S = 0.97	(Δ/σ)_max = 0.001
5500 reflections	Δρ_max = 0.18 e Å⁻³
292 parameters	Δρ_min = −0.14 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0059 (9)

Crystal data top

C₁₂H₁₂N₂O₂	V = 2202.78 (18) Å³
M_r = 216.24	Z = 8
Monoclinic, P2₁/n	Mo Kα radiation
a = 13.8735 (7) Å	µ = 0.09 mm⁻¹
b = 9.2037 (4) Å	T = 296 K
c = 18.3702 (8) Å	0.34 × 0.22 × 0.16 mm
β = 110.100 (2)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	2656 reflections with I > 2σ(I)
24519 measured reflections	R_int = 0.047
5500 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.149	H-atom parameters constrained
S = 0.97	Δρ_max = 0.18 e Å⁻³
5500 reflections	Δρ_min = −0.14 e Å⁻³
292 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	0.66613 (12)	0.62373 (18)	−0.03281 (8)	0.0712 (6)
O2	0.53649 (13)	0.8021 (2)	−0.11913 (9)	0.0837 (7)
N1	0.62925 (12)	0.57325 (17)	0.08026 (8)	0.0485 (5)
N2	0.55538 (12)	0.61513 (18)	0.11211 (9)	0.0540 (6)
C3	0.49372 (15)	0.7059 (2)	0.06310 (11)	0.0526 (6)
C4	0.52380 (15)	0.7271 (2)	−0.00295 (10)	0.0512 (7)
C5	0.61166 (15)	0.6395 (2)	0.01114 (10)	0.0514 (7)
C6	0.70789 (14)	0.4754 (2)	0.12184 (10)	0.0480 (6)
C7	0.77805 (16)	0.4233 (3)	0.09027 (12)	0.0651 (8)
C8	0.85362 (18)	0.3279 (3)	0.13225 (13)	0.0744 (9)
C9	0.85957 (17)	0.2840 (3)	0.20516 (12)	0.0668 (8)
C10	0.78986 (16)	0.3365 (2)	0.23610 (11)	0.0617 (7)
C11	0.71414 (15)	0.4321 (2)	0.19540 (10)	0.0547 (7)
C12	0.48768 (17)	0.8096 (2)	−0.07168 (12)	0.0612 (7)
C13	0.39531 (18)	0.9041 (3)	−0.09255 (13)	0.0753 (9)
C14	0.40749 (17)	0.7731 (3)	0.08202 (13)	0.0771 (9)
O21	0.23044 (14)	0.0334 (2)	0.01074 (9)	0.0987 (8)
O22	0.18315 (17)	0.1293 (3)	−0.12625 (11)	0.1230 (10)
N21	0.11930 (13)	0.1209 (2)	0.07053 (9)	0.0632 (7)
N22	0.03141 (16)	0.2078 (3)	0.04976 (11)	0.0871 (9)
C23	0.01369 (18)	0.2479 (3)	−0.02204 (13)	0.0760 (9)
C24	0.08731 (16)	0.1905 (2)	−0.05120 (11)	0.0617 (8)
C25	0.15261 (17)	0.1086 (2)	0.01064 (12)	0.0622 (8)
C26	0.15670 (17)	0.0590 (2)	0.14600 (11)	0.0591 (7)
C27	0.2554 (2)	0.0047 (3)	0.17540 (14)	0.0830 (10)
C28	0.2890 (2)	−0.0560 (3)	0.24905 (15)	0.0940 (11)
C29	0.2273 (2)	−0.0600 (3)	0.29305 (14)	0.0882 (10)
C30	0.1312 (2)	−0.0014 (3)	0.26406 (14)	0.0818 (10)
C31	0.09504 (19)	0.0573 (3)	0.19051 (12)	0.0706 (8)
C32	0.1070 (2)	0.2010 (3)	−0.12067 (13)	0.0786 (10)
C33	0.0467 (2)	0.2899 (3)	−0.18792 (13)	0.0988 (11)
C34	−0.0776 (2)	0.3424 (4)	−0.06259 (17)	0.1267 (14)
H1O	0.64280	0.67500	−0.07140	0.1070*
H7	0.77450	0.45230	0.04090	0.0780*
H8	0.90090	0.29290	0.11090	0.0890*
H9	0.91040	0.21950	0.23310	0.0800*
H10	0.79360	0.30710	0.28550	0.0740*
H11	0.66750	0.46730	0.21730	0.0660*
H13A	0.38720	0.95360	−0.14030	0.1130*
H13B	0.40330	0.97420	−0.05220	0.1130*
H13C	0.33570	0.84560	−0.09860	0.1130*
H14A	0.34390	0.75280	0.04120	0.1160*
H14B	0.41750	0.87630	0.08720	0.1160*
H14C	0.40560	0.73360	0.12990	0.1160*
H21O	0.23880	0.04250	−0.03110	0.1480*
H27	0.29860	0.00880	0.14640	0.1000*
H28	0.35480	−0.09470	0.26880	0.1130*
H29	0.25040	−0.10200	0.34210	0.1060*
H30	0.08950	−0.00120	0.29430	0.0980*
H31	0.02910	0.09560	0.17120	0.0850*
H33A	0.06630	0.26630	−0.23180	0.1480*
H33B	0.05960	0.39110	−0.17560	0.1480*
H33C	−0.02510	0.27020	−0.20000	0.1480*
H34A	−0.11410	0.36330	−0.02790	0.1910*
H34B	−0.12220	0.29250	−0.10740	0.1910*
H34C	−0.05460	0.43150	−0.07830	0.1910*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0762 (10)	0.0911 (12)	0.0547 (8)	0.0196 (9)	0.0331 (8)	0.0127 (8)
O2	0.0920 (12)	0.1028 (14)	0.0569 (9)	0.0153 (10)	0.0262 (9)	0.0176 (8)
N1	0.0489 (9)	0.0560 (10)	0.0417 (8)	0.0082 (8)	0.0170 (7)	−0.0040 (7)
N2	0.0520 (10)	0.0624 (11)	0.0501 (9)	0.0100 (9)	0.0207 (8)	−0.0060 (8)
C3	0.0503 (11)	0.0557 (12)	0.0498 (10)	0.0059 (10)	0.0145 (9)	−0.0072 (10)
C4	0.0511 (12)	0.0513 (12)	0.0461 (10)	0.0036 (10)	0.0101 (9)	−0.0066 (9)
C5	0.0543 (12)	0.0567 (12)	0.0429 (10)	−0.0004 (10)	0.0165 (9)	−0.0060 (9)
C6	0.0478 (11)	0.0500 (11)	0.0460 (10)	0.0046 (9)	0.0157 (9)	−0.0041 (9)
C7	0.0678 (14)	0.0804 (16)	0.0544 (11)	0.0209 (13)	0.0305 (11)	0.0094 (11)
C8	0.0685 (15)	0.0919 (18)	0.0725 (14)	0.0327 (14)	0.0366 (12)	0.0133 (13)
C9	0.0623 (14)	0.0737 (15)	0.0630 (13)	0.0189 (12)	0.0199 (11)	0.0076 (11)
C10	0.0686 (14)	0.0690 (14)	0.0478 (10)	0.0116 (12)	0.0203 (10)	0.0043 (10)
C11	0.0574 (12)	0.0613 (13)	0.0498 (10)	0.0076 (11)	0.0239 (9)	−0.0034 (9)
C12	0.0645 (14)	0.0599 (13)	0.0499 (11)	−0.0007 (11)	0.0078 (11)	−0.0041 (10)
C13	0.0745 (16)	0.0677 (15)	0.0679 (14)	0.0120 (13)	0.0041 (12)	0.0042 (11)
C14	0.0697 (15)	0.0915 (18)	0.0737 (14)	0.0268 (14)	0.0293 (12)	−0.0001 (13)
O21	0.0956 (13)	0.1380 (17)	0.0771 (11)	0.0562 (12)	0.0485 (10)	0.0161 (11)
O22	0.1323 (17)	0.178 (2)	0.0862 (12)	0.0505 (16)	0.0727 (13)	0.0229 (13)
N21	0.0616 (11)	0.0788 (13)	0.0554 (10)	0.0240 (10)	0.0282 (9)	0.0052 (9)
N22	0.0824 (14)	0.1190 (18)	0.0700 (12)	0.0519 (13)	0.0393 (11)	0.0221 (12)
C23	0.0722 (15)	0.0956 (18)	0.0634 (13)	0.0270 (14)	0.0275 (12)	0.0125 (13)
C24	0.0601 (13)	0.0746 (15)	0.0528 (11)	0.0049 (12)	0.0226 (10)	0.0014 (10)
C25	0.0618 (13)	0.0703 (15)	0.0607 (12)	0.0113 (12)	0.0292 (11)	−0.0019 (11)
C26	0.0674 (14)	0.0600 (13)	0.0524 (11)	0.0121 (11)	0.0239 (11)	−0.0007 (10)
C27	0.0782 (17)	0.102 (2)	0.0700 (15)	0.0283 (15)	0.0272 (13)	0.0093 (14)
C28	0.0888 (19)	0.103 (2)	0.0754 (17)	0.0238 (17)	0.0092 (16)	0.0120 (15)
C29	0.112 (2)	0.0838 (19)	0.0616 (14)	−0.0010 (17)	0.0206 (16)	0.0095 (13)
C30	0.107 (2)	0.0783 (17)	0.0679 (15)	−0.0045 (16)	0.0400 (15)	0.0041 (13)
C31	0.0774 (16)	0.0741 (15)	0.0651 (13)	0.0103 (13)	0.0306 (12)	0.0031 (12)
C32	0.0825 (17)	0.0944 (19)	0.0616 (14)	−0.0036 (15)	0.0283 (13)	−0.0008 (13)
C33	0.111 (2)	0.118 (2)	0.0601 (14)	−0.0131 (19)	0.0201 (14)	0.0143 (15)
C34	0.114 (2)	0.177 (3)	0.093 (2)	0.084 (2)	0.0405 (18)	0.042 (2)

Geometric parameters (Å, º) top

O1—C5	1.290 (3)	C11—H11	0.9300
O2—C12	1.276 (3)	C13—H13B	0.9600
O1—H1O	0.8200	C13—H13A	0.9600
O21—C25	1.282 (3)	C13—H13C	0.9600
O22—C32	1.279 (4)	C14—H14C	0.9600
O21—H21O	0.8200	C14—H14B	0.9600
N1—C5	1.353 (2)	C14—H14A	0.9600
N1—C6	1.419 (2)	C23—C24	1.409 (3)
N1—N2	1.398 (2)	C23—C34	1.506 (4)
N2—C3	1.308 (3)	C24—C25	1.404 (3)
N21—C25	1.337 (3)	C24—C32	1.397 (3)
N21—C26	1.422 (2)	C26—C31	1.372 (3)
N21—N22	1.397 (3)	C26—C27	1.381 (4)
N22—C23	1.309 (3)	C27—C28	1.388 (4)
C3—C14	1.490 (3)	C28—C29	1.365 (4)
C3—C4	1.426 (3)	C29—C30	1.365 (4)
C4—C12	1.410 (3)	C30—C31	1.380 (3)
C4—C5	1.409 (3)	C32—C33	1.478 (3)
C6—C11	1.383 (2)	C27—H27	0.9300
C6—C7	1.379 (3)	C28—H28	0.9300
C7—C8	1.382 (4)	C29—H29	0.9300
C8—C9	1.374 (3)	C30—H30	0.9300
C9—C10	1.367 (3)	C31—H31	0.9300
C10—C11	1.377 (3)	C33—H33A	0.9600
C12—C13	1.486 (3)	C33—H33B	0.9600
C7—H7	0.9300	C33—H33C	0.9600
C8—H8	0.9300	C34—H34A	0.9600
C9—H9	0.9300	C34—H34B	0.9600
C10—H10	0.9300	C34—H34C	0.9600

C5—O1—H1O	110.00	H14A—C14—H14B	109.00
C25—O21—H21O	110.00	H14A—C14—H14C	110.00
N2—N1—C5	110.30 (16)	C3—C14—H14B	109.00
C5—N1—C6	130.45 (17)	C3—C14—H14C	109.00
N2—N1—C6	119.25 (14)	C3—C14—H14A	109.00
N1—N2—C3	106.75 (15)	N22—C23—C24	111.6 (2)
C25—N21—C26	130.94 (19)	N22—C23—C34	119.8 (2)
N22—N21—C26	119.17 (17)	C24—C23—C34	128.7 (2)
N22—N21—C25	109.87 (17)	C23—C24—C25	104.13 (19)
N21—N22—C23	106.3 (2)	C23—C24—C32	135.7 (2)
C4—C3—C14	129.42 (18)	C25—C24—C32	120.1 (2)
N2—C3—C14	119.48 (18)	O21—C25—C24	126.9 (2)
N2—C3—C4	111.08 (18)	N21—C25—C24	108.1 (2)
C3—C4—C5	104.66 (16)	O21—C25—N21	125.02 (19)
C3—C4—C12	135.9 (2)	N21—C26—C27	120.5 (2)
C5—C4—C12	119.44 (19)	C27—C26—C31	120.0 (2)
N1—C5—C4	107.21 (17)	N21—C26—C31	119.5 (2)
O1—C5—C4	127.25 (17)	C26—C27—C28	118.9 (2)
O1—C5—N1	125.54 (18)	C27—C28—C29	121.3 (3)
N1—C6—C11	119.18 (17)	C28—C29—C30	119.0 (2)
C7—C6—C11	119.64 (19)	C29—C30—C31	121.0 (3)
N1—C6—C7	121.18 (17)	C26—C31—C30	119.8 (2)
C6—C7—C8	119.7 (2)	O22—C32—C33	117.7 (2)
C7—C8—C9	120.7 (2)	C24—C32—C33	124.7 (2)
C8—C9—C10	119.2 (2)	O22—C32—C24	117.6 (2)
C9—C10—C11	121.10 (19)	C26—C27—H27	121.00
C6—C11—C10	119.65 (19)	C28—C27—H27	121.00
O2—C12—C13	117.93 (19)	C27—C28—H28	119.00
O2—C12—C4	118.3 (2)	C29—C28—H28	119.00
C4—C12—C13	123.8 (2)	C28—C29—H29	120.00
C8—C7—H7	120.00	C30—C29—H29	120.00
C6—C7—H7	120.00	C29—C30—H30	120.00
C9—C8—H8	120.00	C31—C30—H30	120.00
C7—C8—H8	120.00	C26—C31—H31	120.00
C10—C9—H9	120.00	C30—C31—H31	120.00
C8—C9—H9	120.00	C32—C33—H33A	110.00
C9—C10—H10	119.00	C32—C33—H33B	109.00
C11—C10—H10	119.00	C32—C33—H33C	109.00
C10—C11—H11	120.00	H33A—C33—H33B	109.00
C6—C11—H11	120.00	H33A—C33—H33C	110.00
C12—C13—H13B	109.00	H33B—C33—H33C	109.00
C12—C13—H13C	109.00	C23—C34—H34A	109.00
H13A—C13—H13C	110.00	C23—C34—H34B	109.00
C12—C13—H13A	109.00	C23—C34—H34C	109.00
H13A—C13—H13B	109.00	H34A—C34—H34B	109.00
H13B—C13—H13C	109.00	H34A—C34—H34C	110.00
H14B—C14—H14C	109.00	H34B—C34—H34C	110.00

C5—N1—N2—C3	−0.1 (2)	C3—C4—C5—N1	0.3 (2)
C6—N1—N2—C3	179.20 (16)	C12—C4—C5—O1	−0.2 (3)
N2—N1—C5—O1	179.96 (19)	C12—C4—C5—N1	179.92 (16)
N2—N1—C5—C4	−0.1 (2)	C3—C4—C12—O2	179.4 (2)
C6—N1—C5—O1	0.8 (3)	N1—C6—C7—C8	−179.9 (2)
C6—N1—C5—C4	−179.31 (18)	C11—C6—C7—C8	0.3 (3)
N2—N1—C6—C7	175.42 (19)	N1—C6—C11—C10	179.64 (18)
N2—N1—C6—C11	−4.7 (3)	C7—C6—C11—C10	−0.5 (3)
C5—N1—C6—C7	−5.4 (3)	C6—C7—C8—C9	0.1 (4)
C5—N1—C6—C11	174.41 (19)	C7—C8—C9—C10	−0.3 (4)
N1—N2—C3—C4	0.3 (2)	C8—C9—C10—C11	0.1 (4)
N1—N2—C3—C14	−178.50 (18)	C9—C10—C11—C6	0.4 (3)
N22—N21—C25—O21	−178.4 (2)	N22—C23—C24—C25	0.5 (3)
N22—N21—C25—C24	1.0 (2)	N22—C23—C24—C32	−177.7 (3)
C26—N21—C25—O21	−0.3 (4)	C34—C23—C24—C25	−178.6 (3)
C26—N21—C25—C24	179.2 (2)	C34—C23—C24—C32	3.1 (5)
N22—N21—C26—C27	−163.5 (2)	C23—C24—C25—O21	178.5 (2)
C25—N21—N22—C23	−0.7 (3)	C23—C24—C25—N21	−1.0 (2)
C26—N21—N22—C23	−179.1 (2)	C32—C24—C25—O21	−2.9 (3)
C25—N21—C26—C31	−163.4 (2)	C32—C24—C25—N21	177.6 (2)
N22—N21—C26—C31	14.6 (3)	C23—C24—C32—O22	−179.3 (3)
C25—N21—C26—C27	18.5 (3)	C23—C24—C32—C33	1.3 (5)
N21—N22—C23—C24	0.1 (3)	C25—C24—C32—O22	2.7 (4)
N21—N22—C23—C34	179.3 (2)	C25—C24—C32—C33	−176.8 (2)
C14—C3—C4—C5	178.3 (2)	N21—C26—C27—C28	−179.5 (2)
C14—C3—C4—C12	−1.3 (4)	C31—C26—C27—C28	2.4 (4)
N2—C3—C4—C12	−179.9 (2)	N21—C26—C31—C30	−179.4 (2)
N2—C3—C4—C5	−0.3 (2)	C27—C26—C31—C30	−1.3 (4)
C3—C4—C5—O1	−179.81 (19)	C26—C27—C28—C29	−1.4 (4)
C3—C4—C12—C13	−1.2 (4)	C27—C28—C29—C30	−0.8 (4)
C5—C4—C12—O2	−0.1 (3)	C28—C29—C30—C31	2.0 (4)
C5—C4—C12—C13	179.3 (2)	C29—C30—C31—C26	−0.9 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O2	0.82	1.85	2.546 (2)	142
O21—H21O···O22	0.82	1.83	2.531 (3)	142
C8—H8···N22ⁱ	0.93	2.56	3.489 (3)	177
C13—H13C···Cg2ⁱⁱ	0.96	2.66	3.533 (3)	150
C33—H33B···Cg2ⁱⁱ	0.96	2.98	3.774 (3)	141

Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₂N₂O₂
M_r	216.24
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	13.8735 (7), 9.2037 (4), 18.3702 (8)
β (°)	110.100 (2)
V (Å³)	2202.78 (18)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.34 × 0.22 × 0.16

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	24519, 5500, 2656
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.674

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.149, 0.97
No. of reflections	5500
No. of parameters	292
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.14

Computer programs: APEX2 (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O2	0.82	1.85	2.546 (2)	142
O21—H21O···O22	0.82	1.83	2.531 (3)	142
C8—H8···N22ⁱ	0.93	2.56	3.489 (3)	177
C13—H13C···Cg2ⁱⁱ	0.96	2.66	3.533 (3)	150
C33—H33B···Cg2ⁱⁱ	0.96	2.98	3.774 (3)	141

Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y+1, −z+1.

Acknowledgements

TUS acknowledges the Government College of Education, Afzalpur, Azad Jammu & Kashmir, for granting permission for further studies and providing laboratory facilities.

References

Bruker (2002). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cingolani, A., Effendy, Marchetti, F., Pettinari, C., Skelton, B. W. & White, A. H. (2002). Inorg. Chem. 41, 1151–1161. Web of Science CSD CrossRef PubMed CAS Google Scholar
Grimmett, M. R. (1970). Adv. Heterocycl. Chem. 12, 103–183. CrossRef CAS Google Scholar
Knorr, L. (1883). Ber. Dtsch. Chem. Ges. 16, 2593–2596. CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 65| Part 2| February 2009| Page o330

doi:10.1107/S1600536809001470

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

1-(5-Hydr­­oxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)ethanone: a new monoclinic polymorph

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

1-(5-Hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)ethanone: a new monoclinic polymorph