5-(2-Hy­droxy­phen­yl)-3-methyl-4,5-di­hydro-1H-pyrazole-1-carbaldehyde

Cui, P.; Li, X.-L.

doi:10.1107/S1600536810031600

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 9| September 2010| Page o2351

https://doi.org/10.1107/S1600536810031600

Open

access

5-(2-Hydroxyphenyl)-3-methyl-4,5-dihydro-1H-pyrazole-1-carbaldehyde

Ping Cui ^a ^* and Xin-Long Li ^a

^aSchool of Chemistry and Chemical Engineering, Anhui University of Technology, Maanshan 243002, People's Republic of China
^*Correspondence e-mail: cui040506@163.com

(Received 30 May 2010; accepted 6 August 2010; online 18 August 2010)

In the title compound, C₁₁H₁₂N₂O₂, the dihydropyrazole and benzene rings are oriented at a dihedral angle of 68.35 (5)°. The dihydropyrazole ring is planar, with a mean deviation from the mean plane of 0.0409 Å. The crystal structure is stabilized by O—H⋯O and C—H⋯O hydrogen bonds.

Related literature

For the antibacterial bioactivity of pyrazole derivatives, see: Bekhita & Abdel-Aziem (2004 ); Tanitame et al. (2004a ,b ). For the biological properties of dihydropyrazole derivatives, see: Dmytro et al. (2009 ); Need et al. (2006 ).

Experimental

Crystal data

C₁₁H₁₂N₂O₂
M_r = 204.23
Monoclinic, P 2₁ /n
a = 7.3835 (15) Å
b = 13.454 (3) Å
c = 10.507 (2) Å
β = 106.46 (3)°
V = 1001.0 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.21 × 0.16 × 0.11 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.980, T_max = 0.990
5606 measured reflections
1957 independent reflections
1579 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.086
S = 1.08
1957 reflections
138 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1ⁱ	0.82	1.88	2.6954 (14)	175
C4—H4B⋯O1ⁱⁱ	0.97	2.48	3.4438 (16)	170
Symmetry codes: (i) -x+2, -y+1, -z+2; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810031600/ez2216sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810031600/ez2216Isup2.hkl

checkCIF report

Comment top

There has been much research interest in pyrazole derivatives due to their antibacterial bioactivities (Bekhita et al., 2004; Tanitame et al., 2004a; Tanitame et al., 2004b). Dihydropyrazole-based derivatives have shown several biological activities as CB1 antagonists and tumor necrosis inhibitors (Dmytro et al., 2009; Need et al., 2006). In this paper, we report the synthesis and crystal structure of 5-(2-hydroxyphenyl)-3-methyl-4,5-dihydropyrazole-1-carbaldehyde (I).

The title compound crystallizes in the centrosymmetric space group P2₁/n. As shown in Fig. 1, the C—N single and double bond lengths are both in the normal ranges [C5—N1 single bond is 1.4826 (15) Å, C12═N2 double bond is 1.2797 (17) Å]. The bond lengths of C3—C12 and C3—C5 are 1.5002 (17) and 1.5421 (18) Å, respectively, which indicate that they are both single bonds. The dihedral angle between the dihydropyrazole and benzene rings is 68.35 (5) °. The dihydropyrazole ring adopts a planar conformation, with a mean deviation from the mean plane of 0.0409 Å. The intermolecular O2—H2···O1 and C4—H4B···O1 hydrogen bonds connect the molecules to form a three-dimensional network (Fig. 2).

Related literature top

For the antibacterial bioactivity of pyrazole derivatives, see: Bekhita et al. (2004); Tanitame et al. (2004a,b). For the biological properties of dihydropyrazole derivatives, see: Dmytro et al. (2009); Need et al. (2006).

Experimental top

To a solution of 4-(2-hydroxyphenyl)but-3-en-2-one (0.81 g, 5 mmol) in formic acid (10 ml) was added hydrazine monohydrate (1.25 ml, 25 mmol) and the reaction mixture was refluxed for 2 h. The solvent was evaporated and cold water (30 ml) was added to the oily residue. The resultant precipitate was filtered, recrystallized from ethanol, and colorless single crystals were obtained after 1 day. Mp 155–156 °C. Analysis found: C, 64.5; H, 6.1; N, 14.0%; calculated for C₁₁H₁₂N₂O₂: C, 64.7; H, 5.9; N, 13.7%. ¹H NMR (300 MHz, CDCl₃, δ, p.p.m.): 2.19 (s, 3H, –Me), 3.10 (dd, J = 18.7 and 3.7 Hz, 1H, pyrazole), 3.39 (dd, J = 11.2 and 18.6 Hz, 1H, pyrazole), 5.67 (dd, J = 11.6 and 3.5 Hz, 1H, pyrazole), 6.89–7.26 (m, 5H, ArH and –OH), 8.63 (s, 1H, –COH).

Structure description top

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The crystal structure of (I), showing the atom numbering scheme and 35% probability displacement ellipsoids (arbitrary spheres for the H atoms).
	Fig. 2. The crystal packing of (I), viewed along the a axis. Hydrogen bonds are shown as dashed lines.

5-(2-Hydroxyphenyl)-3-methyl-4,5-dihydro-1H-pyrazole-1-carbaldehyde top

Crystal data top

C₁₁H₁₂N₂O₂	F(000) = 432
M_r = 204.23	D_x = 1.355 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.3835 (15) Å	Cell parameters from 972 reflections
b = 13.454 (3) Å	θ = 3.5–24.7°
c = 10.507 (2) Å	µ = 0.10 mm⁻¹
β = 106.46 (3)°	T = 293 K
V = 1001.0 (3) Å³	Block, colorless
Z = 4	0.21 × 0.16 × 0.11 mm

Data collection top

Bruker Smart APEX CCD area-detector diffractometer	1957 independent reflections
Radiation source: fine-focus sealed tube	1579 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
phi and ω scans	θ_max = 26.0°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −9→8
T_min = 0.980, T_max = 0.990	k = −16→13
5606 measured reflections	l = −12→12

Refinement top

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.086	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0484P)² + 0.0583P] where P = (F_o² + 2F_c²)/3
1957 reflections	(Δ/σ)_max < 0.001
138 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₁H₁₂N₂O₂	V = 1001.0 (3) Å³
M_r = 204.23	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.3835 (15) Å	µ = 0.10 mm⁻¹
b = 13.454 (3) Å	T = 293 K
c = 10.507 (2) Å	0.21 × 0.16 × 0.11 mm
β = 106.46 (3)°

Data collection top

Bruker Smart APEX CCD area-detector diffractometer	1957 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1579 reflections with I > 2σ(I)
T_min = 0.980, T_max = 0.990	R_int = 0.019
5606 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.086	H-atom parameters constrained
S = 1.08	Δρ_max = 0.20 e Å⁻³
1957 reflections	Δρ_min = −0.18 e Å⁻³
138 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.71057 (17)	0.62387 (9)	0.66395 (12)	0.0271 (3)
H1	0.6378	0.6593	0.5914	0.032*
C2	0.81434 (16)	0.41527 (9)	0.51386 (12)	0.0253 (3)
C3	0.7931 (2)	0.35621 (10)	0.39114 (13)	0.0350 (3)
H3A	0.7264	0.2958	0.3963	0.052*
H3B	0.9157	0.3406	0.3820	0.052*
H3C	0.7235	0.3941	0.3157	0.052*
C4	0.93391 (17)	0.38472 (9)	0.64868 (12)	0.0260 (3)
H4A	1.0670	0.3859	0.6534	0.031*
H4B	0.9004	0.3187	0.6715	0.031*
C5	0.88677 (16)	0.46406 (8)	0.74008 (11)	0.0225 (3)
H5	1.0031	0.4963	0.7925	0.027*
C6	0.77821 (16)	0.42376 (8)	0.83124 (11)	0.0215 (3)
C7	0.58407 (17)	0.42893 (9)	0.80332 (12)	0.0284 (3)
H7	0.5137	0.4564	0.7234	0.034*
C8	0.49282 (18)	0.39382 (10)	0.89242 (14)	0.0341 (3)
H8	0.3621	0.3985	0.8730	0.041*
C9	0.59650 (18)	0.35179 (10)	1.01025 (13)	0.0320 (3)
H9	0.5357	0.3294	1.0712	0.038*
C10	0.78979 (18)	0.34274 (9)	1.03825 (12)	0.0276 (3)
H10	0.8587	0.3126	1.1167	0.033*
C11	0.88131 (16)	0.37877 (8)	0.94901 (11)	0.0221 (3)
N1	0.77351 (14)	0.53492 (7)	0.64102 (9)	0.0237 (2)
N2	0.72976 (14)	0.49870 (8)	0.51056 (9)	0.0259 (3)
O1	0.74131 (13)	0.66270 (6)	0.77367 (9)	0.0335 (2)
O2	1.07147 (12)	0.37142 (7)	0.97002 (8)	0.0306 (2)
H2	1.1227	0.3625	1.0493	0.046*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0288 (6)	0.0248 (7)	0.0264 (7)	0.0022 (5)	0.0059 (5)	0.0068 (5)
C2	0.0238 (6)	0.0293 (7)	0.0251 (6)	−0.0015 (5)	0.0107 (5)	0.0023 (5)
C3	0.0377 (7)	0.0404 (8)	0.0272 (7)	0.0047 (6)	0.0099 (6)	−0.0024 (6)
C4	0.0282 (6)	0.0268 (7)	0.0248 (6)	0.0030 (5)	0.0104 (5)	0.0037 (5)
C5	0.0231 (6)	0.0216 (6)	0.0219 (6)	0.0008 (5)	0.0049 (5)	0.0044 (5)
C6	0.0266 (6)	0.0175 (6)	0.0208 (6)	−0.0009 (5)	0.0073 (5)	−0.0007 (4)
C7	0.0262 (6)	0.0293 (7)	0.0282 (7)	−0.0012 (5)	0.0051 (5)	0.0045 (5)
C8	0.0249 (6)	0.0382 (8)	0.0407 (8)	−0.0045 (5)	0.0117 (6)	0.0015 (6)
C9	0.0383 (7)	0.0324 (7)	0.0306 (7)	−0.0097 (6)	0.0183 (6)	−0.0016 (5)
C10	0.0383 (7)	0.0248 (7)	0.0203 (6)	−0.0020 (5)	0.0092 (5)	0.0012 (5)
C11	0.0264 (6)	0.0184 (6)	0.0218 (6)	0.0009 (5)	0.0074 (5)	−0.0028 (5)
N1	0.0286 (5)	0.0233 (5)	0.0188 (5)	0.0018 (4)	0.0059 (4)	0.0037 (4)
N2	0.0275 (5)	0.0306 (6)	0.0200 (5)	0.0001 (4)	0.0072 (4)	0.0026 (4)
O1	0.0418 (5)	0.0275 (5)	0.0279 (5)	0.0067 (4)	0.0047 (4)	−0.0002 (4)
O2	0.0267 (5)	0.0416 (6)	0.0228 (4)	0.0073 (4)	0.0059 (3)	0.0066 (4)

Geometric parameters (Å, º) top

C1—O1	1.2269 (15)	C5—H5	0.9800
C1—N1	1.3303 (16)	C6—C7	1.3811 (17)
C1—H1	0.9300	C6—C11	1.3940 (16)
C2—N2	1.2802 (16)	C7—C8	1.3824 (19)
C2—C3	1.4846 (18)	C7—H7	0.9300
C2—C4	1.4988 (17)	C8—C9	1.3790 (19)
C3—H3A	0.9600	C8—H8	0.9300
C3—H3B	0.9600	C9—C10	1.3785 (18)
C3—H3C	0.9600	C9—H9	0.9300
C4—C5	1.5403 (17)	C10—C11	1.3892 (18)
C4—H4A	0.9700	C10—H10	0.9300
C4—H4B	0.9700	C11—O2	1.3617 (15)
C5—N1	1.4828 (14)	N1—N2	1.4034 (14)
C5—C6	1.5129 (17)	O2—H2	0.8200

O1—C1—N1	124.90 (11)	C7—C6—C11	118.90 (12)
O1—C1—H1	117.5	C7—C6—C5	123.48 (11)
N1—C1—H1	117.5	C11—C6—C5	117.62 (11)
N2—C2—C3	121.01 (11)	C6—C7—C8	120.97 (12)
N2—C2—C4	114.73 (11)	C6—C7—H7	119.5
C3—C2—C4	124.26 (11)	C8—C7—H7	119.5
C2—C3—H3A	109.5	C9—C8—C7	119.67 (12)
C2—C3—H3B	109.5	C9—C8—H8	120.2
H3A—C3—H3B	109.5	C7—C8—H8	120.2
C2—C3—H3C	109.5	C10—C9—C8	120.38 (13)
H3A—C3—H3C	109.5	C10—C9—H9	119.8
H3B—C3—H3C	109.5	C8—C9—H9	119.8
C2—C4—C5	102.86 (9)	C9—C10—C11	119.81 (12)
C2—C4—H4A	111.2	C9—C10—H10	120.1
C5—C4—H4A	111.2	C11—C10—H10	120.1
C2—C4—H4B	111.2	O2—C11—C10	122.79 (11)
C5—C4—H4B	111.2	O2—C11—C6	117.01 (11)
H4A—C4—H4B	109.1	C10—C11—C6	120.20 (11)
N1—C5—C6	112.35 (10)	C1—N1—N2	119.59 (9)
N1—C5—C4	100.95 (9)	C1—N1—C5	127.43 (10)
C6—C5—C4	113.59 (10)	N2—N1—C5	112.98 (9)
N1—C5—H5	109.9	C2—N2—N1	107.61 (9)
C6—C5—H5	109.9	C11—O2—H2	109.5
C4—C5—H5	109.9

N2—C2—C4—C5	7.20 (14)	C7—C6—C11—O2	177.26 (11)
C3—C2—C4—C5	−173.35 (11)	C5—C6—C11—O2	−2.42 (15)
C2—C4—C5—N1	−8.69 (12)	C7—C6—C11—C10	−2.02 (17)
C2—C4—C5—C6	111.79 (11)	C5—C6—C11—C10	178.30 (10)
N1—C5—C6—C7	17.36 (16)	O1—C1—N1—N2	−179.59 (11)
C4—C5—C6—C7	−96.46 (14)	O1—C1—N1—C5	1.7 (2)
N1—C5—C6—C11	−162.98 (10)	C6—C5—N1—C1	66.03 (15)
C4—C5—C6—C11	83.21 (13)	C4—C5—N1—C1	−172.61 (11)
C11—C6—C7—C8	2.53 (19)	C6—C5—N1—N2	−112.71 (11)
C5—C6—C7—C8	−177.80 (12)	C4—C5—N1—N2	8.64 (12)
C6—C7—C8—C9	−0.9 (2)	C3—C2—N2—N1	178.62 (11)
C7—C8—C9—C10	−1.4 (2)	C4—C2—N2—N1	−1.92 (14)
C8—C9—C10—C11	1.87 (19)	C1—N1—N2—C2	176.47 (11)
C9—C10—C11—O2	−179.39 (11)	C5—N1—N2—C2	−4.68 (13)
C9—C10—C11—C6	−0.16 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	0.82	1.88	2.6954 (14)	175
C4—H4B···O1ⁱⁱ	0.97	2.48	3.4438 (16)	170

Symmetry codes: (i) −x+2, −y+1, −z+2; (ii) −x+3/2, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₂N₂O₂
M_r	204.23
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	7.3835 (15), 13.454 (3), 10.507 (2)
β (°)	106.46 (3)
V (Å³)	1001.0 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.21 × 0.16 × 0.11

Data collection
Diffractometer	Bruker Smart APEX CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.980, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	5606, 1957, 1579
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.086, 1.08
No. of reflections	1957
No. of parameters	138
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.18

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	0.82	1.88	2.6954 (14)	174.8
C4—H4B···O1ⁱⁱ	0.97	2.48	3.4438 (16)	169.9

Symmetry codes: (i) −x+2, −y+1, −z+2; (ii) −x+3/2, y−1/2, −z+3/2.

References

Bekhita, A. A. & Abdel-Aziem, T. (2004). Bioorg. Med. Chem. 12, 1935–1945. Web of Science PubMed Google Scholar
Bruker (2001). SAINT, SMART and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dmytro, H., Borys, Z., Olexandr, V., Lucjusz, Z., Andrzej, G. & Roman, L. (2009). Eur. J. Med. Chem. 44, 1396–1404. Web of Science PubMed Google Scholar
Need, A. B., Davis, R. J., Alexander-Chacko, J. T., Eastwood, B., Chernet, E., Phebus, L. A., Sindelar, D. K. & Nomikos, G. G. (2006). Psychopharmacology (Berlin), 184, 26–35. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tanitame, A., Oyamada, Y., Ofuji, K., Fujimoto, M., Suzuki, K., Ueda, T., Terauchi, H., Kawasaki, M., Nagai, K., Wachie, M. & Yamagishib, J. I. (2004b). Bioorg. Med. Chem. 12, 5515–5524. Web of Science CrossRef PubMed CAS Google Scholar
Tanitame, A., Oyamada, Y., Ofuji, K., Kyoya, Y., Suzuki, K., Ito, H., Kawasaki, M., Nagai, K., Wachid, M. & Yamagishi, J. I. (2004a). Bioorg. Med. Chem. Lett. 14, 2857–2862. Web of Science CrossRef PubMed CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 9| September 2010| Page o2351

https://doi.org/10.1107/S1600536810031600

Open

access