3-Hy-droxy-2,2-bis-(1H-pyrazol-1-yl)-cyclo-penta-none.

The title compound, C(11)H(12)N(4)O(2), was unexpectedly obtained in the reaction of α,α'-disubstituted cyclo-penta-none with 1,1,3,3-tetra-meth-oxy-propane in the presence of dioxane saturated with HCl. It belongs to a previously unknown class of gem-bihetaryl ketones which may be useful for screening of new substances with biological activity. In the studied structure, the cyclo-penta-none moiety adopts an envelope conformation, with the hy-droxy-bearing C atom as the flap [deviation from basal plane = 0.643 (3) Å]. The dihedral angle between the two pyrazole rings is 80.02 (8)°. In the crystal, inversion dimers are formed via a pair of O-H⋯N hydrogen bonds.

Related literature

For the medicinal chemistry of chiral carbo- and heterocyclic substituents of pyrazole, see: Bennani et al. (2007 ▶); Srivastava et al. (2007 ▶). For the α-amination of carbonyl compounds, see: List (2002 ▶). For standard values of bond lengths in organic compounds, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C11H12N4O2

M = 232.25

Monoclinic,

a = 11.4360 (11) Å

b = 9.5925 (9) Å

c = 11.5968 (11) Å

β = 117.25 (2)°

V = 1131.0 (3) Å3

Z = 4

Ag Kα radiation

λ = 0.56085 Å

μ = 0.06 mm−1

T = 295 K

0.20 × 0.20 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

2709 measured reflections

2458 independent reflections

1723 reflections with I > 2σ(I)

R int = 0.026

1 standard reflections every 60 min intensity decay: none

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.124

S = 1.04

2458 reflections

158 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.18 e Å−3

Δρmin = −0.22 e Å−3

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812007659/yk2045sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812007659/yk2045Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812007659/yk2045Isup3.cml

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

C11H12N4O2	F(000) = 488
Mr = 232.25	Dx = 1.364 Mg m−3
Monoclinic, P21/c	Melting point = 385–386 K
Hall symbol: -P 2ybc	Ag Kα radiation, λ = 0.56085 Å
a = 11.4360 (11) Å	Cell parameters from 25 reflections
b = 9.5925 (9) Å	θ = 10.0–12.0°
c = 11.5968 (11) Å	µ = 0.06 mm−1
β = 117.25 (2)°	T = 295 K
V = 1131.0 (3) Å3	Prism, light yellow
Z = 4	0.20 × 0.20 × 0.20 mm

Enraf–Nonius CAD-4 diffractometer	Rint = 0.026
Radiation source: fine-focus sealed tube	θmax = 21.0°, θmin = 1.6°
Graphite monochromator	h = −14→12
non–profiled ω scans	k = 0→12
2709 measured reflections	l = 0→14
2458 independent reflections	1 standard reflections every 60 min
1723 reflections with I > 2σ(I)	intensity decay: none

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.124	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0634P)2 + 0.119P] where P = (Fo2 + 2Fc2)/3
2458 reflections	(Δ/σ)max < 0.001
158 parameters	Δρmax = 0.18 e Å−3
0 restraints	Δρmin = −0.22 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	0.8285 (2)	0.02907 (18)	0.22875 (18)	0.0442 (5)
O1	0.74464 (17)	−0.04122 (16)	0.23414 (15)	0.0664 (5)
C2	0.81692 (16)	0.09021 (17)	0.09920 (15)	0.0334 (4)
C3	0.96176 (17)	0.10037 (18)	0.12975 (15)	0.0366 (4)
H3	0.9944	0.0069	0.1259	0.044*
O3	0.97820 (14)	0.18725 (14)	0.04063 (13)	0.0470 (4)
H3a	1.054 (3)	0.162 (2)	0.040 (2)	0.074 (7)*
C4	1.02716 (19)	0.1504 (2)	0.26969 (17)	0.0479 (5)
H4a	1.0111	0.2490	0.2748	0.058*
H4b	1.1213	0.1343	0.3099	0.058*
C5	0.9623 (2)	0.0629 (2)	0.33416 (17)	0.0540 (5)
H5a	1.0122	−0.0216	0.3706	0.065*
H5b	0.9563	0.1150	0.4029	0.065*
N21a	0.75682 (14)	0.22639 (14)	0.08142 (13)	0.0355 (3)
N22a	0.72893 (16)	0.27771 (16)	0.17473 (15)	0.0467 (4)
C23a	0.6800 (2)	0.4024 (2)	0.1306 (2)	0.0574 (6)
H23a	0.6514	0.4639	0.1744	0.069*
C24a	0.6759 (2)	0.4315 (2)	0.0121 (2)	0.0547 (5)
H24a	0.6452	0.5123	−0.0369	0.066*
C25a	0.72630 (18)	0.31694 (19)	−0.01749 (18)	0.0442 (4)
H25a	0.7376	0.3034	−0.0912	0.053*
N21b	0.73500 (14)	0.00404 (14)	−0.01115 (13)	0.0368 (3)
N22b	0.78713 (15)	−0.10826 (15)	−0.04212 (15)	0.0428 (4)
C23b	0.6833 (2)	−0.1781 (2)	−0.1270 (2)	0.0532 (5)
H23b	0.6885	−0.2604	−0.1668	0.064*
C24b	0.5666 (2)	−0.1145 (2)	−0.1493 (2)	0.0550 (5)
H24b	0.4817	−0.1443	−0.2044	0.066*
C25b	0.60277 (18)	0.0009 (2)	−0.07340 (18)	0.0481 (5)
H25b	0.5464	0.0660	−0.0658	0.058*

	U11	U22	U33	U12	U13	U23
C1	0.0694 (12)	0.0345 (9)	0.0456 (10)	0.0067 (9)	0.0409 (10)	0.0039 (8)
O1	0.0940 (12)	0.0587 (9)	0.0741 (10)	−0.0051 (8)	0.0623 (10)	0.0126 (8)
C2	0.0427 (9)	0.0331 (8)	0.0326 (8)	0.0013 (7)	0.0242 (7)	−0.0004 (7)
C3	0.0436 (9)	0.0355 (9)	0.0368 (9)	0.0037 (7)	0.0238 (8)	0.0013 (7)
O3	0.0464 (7)	0.0543 (8)	0.0542 (8)	0.0036 (6)	0.0350 (7)	0.0106 (6)
C4	0.0529 (12)	0.0481 (11)	0.0393 (10)	0.0043 (9)	0.0180 (9)	−0.0022 (8)
C5	0.0798 (15)	0.0514 (12)	0.0347 (10)	0.0157 (11)	0.0297 (10)	0.0068 (9)
N21a	0.0444 (8)	0.0353 (8)	0.0371 (7)	0.0049 (6)	0.0275 (6)	0.0014 (6)
N22a	0.0625 (10)	0.0443 (9)	0.0483 (9)	0.0085 (7)	0.0385 (8)	−0.0037 (7)
C23a	0.0696 (14)	0.0443 (11)	0.0681 (14)	0.0122 (10)	0.0400 (12)	−0.0082 (10)
C24a	0.0587 (13)	0.0420 (11)	0.0646 (13)	0.0100 (9)	0.0292 (11)	0.0103 (10)
C25a	0.0496 (10)	0.0450 (10)	0.0440 (10)	0.0053 (8)	0.0266 (9)	0.0084 (8)
N21b	0.0420 (8)	0.0385 (8)	0.0399 (8)	0.0002 (6)	0.0273 (7)	−0.0042 (6)
N22b	0.0503 (9)	0.0394 (8)	0.0510 (9)	0.0012 (7)	0.0338 (8)	−0.0067 (7)
C23b	0.0663 (13)	0.0465 (11)	0.0574 (12)	−0.0122 (10)	0.0373 (11)	−0.0137 (9)
C24b	0.0500 (11)	0.0651 (13)	0.0543 (11)	−0.0165 (10)	0.0279 (10)	−0.0114 (10)
C25b	0.0417 (10)	0.0581 (12)	0.0534 (11)	−0.0016 (9)	0.0293 (9)	−0.0052 (10)

N21a—C25a	1.351 (2)	C4—C5	1.523 (3)
N21a—N22a	1.3531 (19)	C4—H4a	0.9700
N21a—C2	1.446 (2)	C4—H4b	0.9700
N22a—C23a	1.321 (2)	C5—C1	1.493 (3)
C23a—C24a	1.382 (3)	C5—H5a	0.9700
C23a—H23a	0.9300	C5—H5b	0.9700
C24a—C25a	1.356 (3)	C1—O1	1.197 (2)
C24a—H24a	0.9300	N21b—C25b	1.345 (2)
C25a—H25a	0.9300	N21b—N22b	1.3568 (18)
C2—N21b	1.449 (2)	N22b—C23b	1.325 (2)
C2—C3	1.530 (2)	C23b—C24b	1.380 (3)
C2—C1	1.561 (2)	C23b—H23b	0.9300
C3—O3	1.406 (2)	C24b—C25b	1.356 (3)
C3—C4	1.521 (2)	C24b—H24b	0.9300
C3—H3	0.9800	C25b—H25b	0.9300
O3—H3a	0.90 (3)
C25a—N21a—N22a	112.41 (14)	C3—C4—H4a	111.0
C25a—N21a—C2	128.53 (14)	C5—C4—H4a	111.0
N22a—N21a—C2	119.03 (13)	C3—C4—H4b	111.0
C23a—N22a—N21a	103.46 (15)	C5—C4—H4b	111.0
N22a—C23a—C24a	112.56 (17)	H4a—C4—H4b	109.0
N22a—C23a—H23a	123.7	C1—C5—C4	105.35 (14)
C24a—C23a—H23a	123.7	C1—C5—H5a	110.7
C25a—C24a—C23a	105.26 (17)	C4—C5—H5a	110.7
C25a—C24a—H24a	127.4	C1—C5—H5b	110.7
C23a—C24a—H24a	127.4	C4—C5—H5b	110.7
N21a—C25a—C24a	106.31 (16)	H5a—C5—H5b	108.8
N21a—C25a—H25a	126.8	O1—C1—C5	128.69 (18)
C24a—C25a—H25a	126.8	O1—C1—C2	123.02 (18)
N21a—C2—N21b	108.45 (13)	C5—C1—C2	108.04 (15)
N21a—C2—C3	111.65 (13)	C25b—N21b—N22b	111.25 (14)
N21b—C2—C3	115.74 (13)	C25b—N21b—C2	126.87 (14)
N21a—C2—C1	107.57 (12)	N22b—N21b—C2	120.12 (14)
N21b—C2—C1	111.79 (14)	C23b—N22b—N21b	104.18 (15)
C3—C2—C1	101.26 (13)	N22b—C23b—C24b	112.13 (18)
O3—C3—C4	115.56 (15)	N22b—C23b—H23b	123.9
O3—C3—C2	111.26 (14)	C24b—C23b—H23b	123.9
C4—C3—C2	102.63 (13)	C25b—C24b—C23b	104.93 (18)
O3—C3—H3	109.0	C25b—C24b—H24b	127.5
C4—C3—H3	109.0	C23b—C24b—H24b	127.5
C2—C3—H3	109.0	N21b—C25b—C24b	107.48 (17)
C3—O3—H3a	107.6 (15)	N21b—C25b—H25b	126.3
C3—C4—C5	103.75 (15)	C24b—C25b—H25b	126.3
C25a—N21a—N22a—C23a	0.1 (2)	C4—C5—C1—O1	177.50 (19)
C2—N21a—N22a—C23a	178.13 (16)	C4—C5—C1—C2	3.11 (19)
N21a—N22a—C23a—C24a	0.1 (2)	N21a—C2—C1—O1	90.9 (2)
N22a—C23a—C24a—C25a	−0.3 (3)	N21b—C2—C1—O1	−28.1 (2)
N22a—N21a—C25a—C24a	−0.3 (2)	C3—C2—C1—O1	−151.91 (18)
C2—N21a—C25a—C24a	−178.07 (16)	N21a—C2—C1—C5	−94.37 (16)
C23a—C24a—C25a—N21a	0.4 (2)	N21b—C2—C1—C5	146.68 (15)
C25a—N21a—C2—N21b	−58.2 (2)	C3—C2—C1—C5	22.86 (17)
N22a—N21a—C2—N21b	124.20 (15)	N21a—C2—N21b—C25b	−38.9 (2)
C25a—N21a—C2—C3	70.5 (2)	C3—C2—N21b—C25b	−165.28 (16)
N22a—N21a—C2—C3	−107.11 (16)	C1—C2—N21b—C25b	79.5 (2)
C25a—N21a—C2—C1	−179.25 (17)	N21a—C2—N21b—N22b	157.55 (13)
N22a—N21a—C2—C1	3.1 (2)	C3—C2—N21b—N22b	31.2 (2)
N21a—C2—C3—O3	−49.79 (17)	C1—C2—N21b—N22b	−84.02 (17)
N21b—C2—C3—O3	74.91 (18)	C25b—N21b—N22b—C23b	1.36 (19)
C1—C2—C3—O3	−164.01 (13)	C2—N21b—N22b—C23b	167.26 (15)
N21a—C2—C3—C4	74.37 (16)	N21b—N22b—C23b—C24b	−0.9 (2)
N21b—C2—C3—C4	−160.92 (14)	N22b—C23b—C24b—C25b	0.2 (2)
C1—C2—C3—C4	−39.84 (16)	N22b—N21b—C25b—C24b	−1.3 (2)
O3—C3—C4—C5	164.39 (15)	C2—N21b—C25b—C24b	−166.00 (16)
C2—C3—C4—C5	43.13 (18)	C23b—C24b—C25b—N21b	0.6 (2)
C3—C4—C5—C1	−28.36 (19)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3a···N22bi	0.90 (3)	1.88 (3)	2.781 (2)	179 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3a⋯N22bi	0.90 (3)	1.88 (3)	2.781 (2)	179 (2)

Symmetry code: (i) .