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

The title compound, C(12)H(12)N(2)O(2), crystallized in the monolinic space group P2(1)/n, with two independent mol-ecules (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 mol-ecule per asymmetric unit. The dihedral angles between the two rings differ slightly; in mol-ecule A it is 4.90 (11)° and in mol-ecule B it is 16.05 (13)°. In both mol-ecules, there is an intra-molecular O-H⋯O hydrogen bond involving the hydroxyl substituent and the carbonyl O atom of the adjacent acetyl group. In the crystal structure, mol-ecules A and B are linked via a C-H⋯N inter-action. There are also some weak C-H⋯π inter-actions involving the phenyl ring of mol-ecule A and H atoms of the acetyl groups of both mol-ecules.

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 = 216.24

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.051

wR(F 2) = 0.149

S = 0.97

5500 reflections

292 parameters

H-atom parameters constrained

Δρmax = 0.18 e Å−3

Δρmin = −0.14 e Å−3

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.

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

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

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

C12H12N2O2	F(000) = 912
Mr = 216.24	Dx = 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

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

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(Fo2) + (0.0571P)2 + 0.4951P] where P = (Fo2 + 2Fc2)/3
S = 0.97	(Δ/σ)max = 0.001
5500 reflections	Δρmax = 0.18 e Å−3
292 parameters	Δρmin = −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)

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	0.66613 (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*

	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)

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)

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

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) ; (ii) . Cg2 is the centroid of the C6–C11 ring.