N-(2-Hy­droxy­eth­yl)-5-(4-meth­oxy­phen­yl)-4H-pyrazole-3-carboxamide

Han, G.; Lv, J.; Zhu, J.; Zhou, Y.; Wu, D.

doi:10.1107/S1600536812007829

organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o901

doi:10.1107/S1600536812007829

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N-(2-Hydroxyethyl)-5-(4-methoxyphenyl)-4H-pyrazole-3-carboxamide

Guangqian Han,^a Jiaguo Lv,^b ^* Ju Zhu,^b Youjun Zhou ^b and Defeng Wu ^a ^*

^aDepartment of Pharmacognosy, School of Food Science, Fujian Agriculture and Forestry University, Fujian 350002, People's Republic of China, and ^bDepartment of Medicinal Chemistry, School of Pharmacy, Second Military Medical University, Shanghai 200433, People's Republic of China
^*Correspondence e-mail: ljg20060508@yahoo.com.cn, zi99289@yeah.net

(Received 14 February 2012; accepted 21 February 2012; online 29 February 2012)

In the title compound, C₁₃H₁₅N₃O₃, the dihedral angle between the benzene and pyrazole rings is 7.7 (1)° and the O—C—C—N torsion angle of the side chain is 74.1 (2)°. In the crystal, molecules are linked by O—H⋯O, N—H⋯O and N—H⋯N hydrogen bonds.

Related literature

For the biological activities of pyrazole derivatives, see: Qi et al. (2011 ). For a related structure, see: Shi & Xie (2011 ).

Experimental

Crystal data

C₁₃H₁₅N₃O₃
M_r = 261.28
Monoclinic, C 2/c
a = 21.82 (5) Å
b = 10.08 (2) Å
c = 12.28 (3) Å
β = 110.53 (3)°
V = 2531 (11) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.20 × 0.15 × 0.06 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.980, T_max = 0.994
5292 measured reflections
2366 independent reflections
1841 reflections with I > 2σ(I)
R_int = 0.074

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.156
S = 1.05
2366 reflections
175 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O2ⁱ	0.82	1.88	2.668 (5)	162
N3—H3B⋯N2ⁱⁱ	0.86	2.54	3.318 (7)	151
N1—H1D⋯O3ⁱⁱ	0.86	1.90	2.739 (5)	166
Symmetry codes: (i) $[x, -y, z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812007829/hb6641sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812007829/hb6641Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812007829/hb6641Isup3.cdx

Supporting information file. DOI: 10.1107/S1600536812007829/hb6641Isup4.cml

checkCIF report

Related literature top

For the biological activities of pyrazole derivatives, see: Qi et al. (2011). For a related structure, see: Shi & Xie (2011).

Experimental top

A mixture of diethyl oxalate (0.1 mol), 1-(4-methoxyphenyl)ethanone (0.05 mol) and sodium ethylate (400 ml 0.1 mol) were stirred for 8 h at room temperature. It was then poured into diluted acetic acid and was further stirred for 20 min and then filtered to give the yellow solid and dried. Then this dried solid and hydrazine (0.05 mol) in ethanol (200 ml) refluxed for 3.5 h and then stood for 8 h yielded the yellow solid. The solid (0.004 mol) subsequently was reacted with ethanolamine (20 ml) for 4 h at 80 °C in the presence of pyridine (20 ml). The mixture was then poured into ice cold water to afford the white solid. The compound was recrystallized from methanol as colourless slabs. Yield: 0.75 g, 70.7%. M. p.: 470 K.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, with 30% probability displacement ellipsoids for non-H atoms.
	Fig. 2. Hydrogen bonds in the title compound.

N-(2-Hydroxyethyl)-5-(4-methoxyphenyl)-4H-pyrazole-3-carboxamide top

Crystal data top

C₁₃H₁₅N₃O₃	D_x = 1.372 Mg m⁻³
M_r = 261.28	Melting point: 470 K
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 21.82 (5) Å	Cell parameters from 925 reflections
b = 10.08 (2) Å	θ = 3.1–26.4°
c = 12.28 (3) Å	µ = 0.10 mm⁻¹
β = 110.53 (3)°	T = 293 K
V = 2531 (11) Å³	Slab, colorless
Z = 8	0.20 × 0.15 × 0.06 mm
F(000) = 1104

Data collection top

Bruker SMART CCD diffractometer	2366 independent reflections
Radiation source: fine-focus sealed tube	1841 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.074
phi and ω scans	θ_max = 25.5°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −26→10
T_min = 0.980, T_max = 0.994	k = −12→12
5292 measured reflections	l = −13→14

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)] = 0.054	H-atom parameters constrained
wR(F²) = 0.156	w = 1/[σ²(F_o²) + (0.0917P)² + 0.0958P] whereP = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
2366 reflections	Δρ_max = 0.26 e Å⁻³
175 parameters	Δρ_min = −0.30 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: 0.0026 (8)

Crystal data top

C₁₃H₁₅N₃O₃	V = 2531 (11) Å³
M_r = 261.28	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 21.82 (5) Å	µ = 0.10 mm⁻¹
b = 10.08 (2) Å	T = 293 K
c = 12.28 (3) Å	0.20 × 0.15 × 0.06 mm
β = 110.53 (3)°

Data collection top

Bruker SMART CCD diffractometer	2366 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1841 reflections with I > 2σ(I)
T_min = 0.980, T_max = 0.994	R_int = 0.074
5292 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.156	H-atom parameters constrained
S = 1.05	Δρ_max = 0.26 e Å⁻³
2366 reflections	Δρ_min = −0.30 e Å⁻³
175 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
N1	0.29642 (7)	0.24543 (15)	0.29533 (13)	0.0426 (4)
H1D	0.3331	0.2866	0.3241	0.051*
N2	0.25083 (7)	0.24377 (15)	0.34610 (13)	0.0433 (4)
N3	0.13697 (7)	0.21072 (15)	0.39238 (13)	0.0414 (4)
H3B	0.1720	0.2410	0.4441	0.050*
O1	0.44500 (7)	0.12084 (15)	−0.06540 (14)	0.0593 (5)
O2	0.09398 (6)	0.09459 (14)	0.22772 (11)	0.0526 (4)
O3	0.09522 (7)	0.10663 (15)	0.58747 (12)	0.0575 (4)
H3	0.0904	0.0361	0.6168	0.086*
C1	0.42987 (12)	0.0298 (2)	−0.15960 (19)	0.0621 (6)
H1A	0.4244	−0.0573	−0.1329	0.093*
H1B	0.4649	0.0286	−0.1898	0.093*
H1C	0.3901	0.0567	−0.2197	0.093*
C2	0.40166 (9)	0.13059 (18)	−0.00812 (17)	0.0435 (5)
C3	0.34387 (9)	0.06118 (19)	−0.03558 (17)	0.0470 (5)
H3A	0.3312	0.0034	−0.0986	0.056*
C4	0.30463 (9)	0.0776 (2)	0.03073 (18)	0.0455 (5)
H4	0.2660	0.0292	0.0120	0.055*
C5	0.32117 (8)	0.16408 (18)	0.12430 (15)	0.0387 (4)
C6	0.37895 (10)	0.23460 (19)	0.14879 (18)	0.0481 (5)
H6	0.3909	0.2949	0.2100	0.058*
C7	0.41911 (10)	0.2177 (2)	0.08479 (19)	0.0512 (6)
H7	0.4581	0.2649	0.1041	0.061*
C8	0.27897 (9)	0.17627 (17)	0.19481 (15)	0.0382 (4)
C9	0.21809 (9)	0.12518 (19)	0.17982 (16)	0.0416 (5)
H9	0.1924	0.0720	0.1192	0.050*
C10	0.20311 (8)	0.17037 (18)	0.27537 (16)	0.0386 (4)
C11	0.14091 (8)	0.15331 (17)	0.29704 (15)	0.0377 (4)
C12	0.07505 (9)	0.22326 (18)	0.41093 (16)	0.0400 (5)
H12A	0.0407	0.2374	0.3362	0.048*
H12B	0.0769	0.3015	0.4579	0.048*
C13	0.05641 (9)	0.10679 (19)	0.46890 (16)	0.0426 (5)
H13A	0.0105	0.1126	0.4600	0.051*
H13B	0.0630	0.0250	0.4329	0.051*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0394 (8)	0.0550 (10)	0.0340 (9)	−0.0095 (7)	0.0135 (7)	−0.0065 (7)
N2	0.0441 (9)	0.0540 (10)	0.0343 (9)	−0.0066 (7)	0.0169 (7)	−0.0064 (7)
N3	0.0376 (8)	0.0561 (10)	0.0301 (8)	−0.0080 (7)	0.0114 (7)	−0.0086 (7)
O1	0.0660 (10)	0.0645 (10)	0.0627 (10)	−0.0145 (7)	0.0417 (9)	−0.0168 (7)
O2	0.0388 (8)	0.0742 (10)	0.0420 (8)	−0.0095 (6)	0.0107 (6)	−0.0206 (7)
O3	0.0585 (9)	0.0622 (10)	0.0378 (8)	−0.0229 (7)	−0.0006 (7)	0.0077 (6)
C1	0.0806 (16)	0.0644 (14)	0.0562 (14)	−0.0077 (12)	0.0429 (13)	−0.0116 (11)
C2	0.0514 (11)	0.0425 (10)	0.0417 (11)	−0.0008 (8)	0.0229 (9)	0.0007 (8)
C3	0.0550 (12)	0.0480 (11)	0.0410 (11)	−0.0055 (9)	0.0205 (10)	−0.0091 (9)
C4	0.0432 (10)	0.0507 (11)	0.0427 (11)	−0.0080 (8)	0.0152 (9)	−0.0054 (9)
C5	0.0413 (10)	0.0416 (10)	0.0336 (10)	0.0009 (8)	0.0134 (8)	0.0027 (8)
C6	0.0537 (12)	0.0507 (11)	0.0441 (11)	−0.0116 (9)	0.0225 (10)	−0.0121 (9)
C7	0.0520 (12)	0.0549 (12)	0.0527 (13)	−0.0147 (9)	0.0257 (10)	−0.0094 (10)
C8	0.0418 (10)	0.0413 (9)	0.0301 (10)	−0.0004 (8)	0.0108 (8)	−0.0003 (7)
C9	0.0403 (10)	0.0514 (11)	0.0318 (10)	−0.0060 (8)	0.0110 (8)	−0.0068 (8)
C10	0.0367 (9)	0.0458 (10)	0.0320 (9)	−0.0017 (7)	0.0102 (8)	−0.0015 (8)
C11	0.0379 (10)	0.0443 (10)	0.0298 (9)	−0.0006 (8)	0.0106 (8)	−0.0013 (7)
C12	0.0388 (10)	0.0486 (11)	0.0320 (10)	0.0018 (8)	0.0118 (8)	−0.0009 (8)
C13	0.0390 (10)	0.0499 (11)	0.0355 (10)	−0.0082 (8)	0.0087 (8)	−0.0044 (8)

Geometric parameters (Å, º) top

N1—N2	1.347 (3)	C3—H3A	0.9300
N1—C8	1.351 (3)	C4—C5	1.386 (4)
N1—H1D	0.8600	C4—H4	0.9300
N2—C10	1.324 (3)	C5—C6	1.385 (4)
N3—C11	1.336 (4)	C5—C8	1.474 (3)
N3—C12	1.452 (4)	C6—C7	1.378 (4)
N3—H3B	0.8600	C6—H6	0.9300
O1—C2	1.366 (3)	C7—H7	0.9300
O1—C1	1.422 (4)	C8—C9	1.376 (4)
O2—C11	1.230 (3)	C9—C10	1.400 (4)
O3—C13	1.405 (4)	C9—H9	0.9300
O3—H3	0.8200	C10—C11	1.482 (4)
C1—H1A	0.9600	C12—C13	1.502 (4)
C1—H1B	0.9600	C12—H12A	0.9700
C1—H1C	0.9600	C12—H12B	0.9700
C2—C3	1.377 (4)	C13—H13A	0.9700
C2—C7	1.383 (4)	C13—H13B	0.9700
C3—C4	1.383 (3)

N2—N1—C8	113.55 (19)	C5—C6—H6	119.2
N2—N1—H1D	123.2	C6—C7—C2	120.2 (2)
C8—N1—H1D	123.2	C6—C7—H7	119.9
C10—N2—N1	104.0 (2)	C2—C7—H7	119.9
C11—N3—C12	121.65 (15)	N1—C8—C9	105.35 (16)
C11—N3—H3B	119.2	N1—C8—C5	123.1 (2)
C12—N3—H3B	119.2	C9—C8—C5	131.5 (2)
C2—O1—C1	117.42 (19)	C8—C9—C10	105.33 (19)
C13—O3—H3	109.5	C8—C9—H9	127.3
O1—C1—H1A	109.5	C10—C9—H9	127.3
O1—C1—H1B	109.5	N2—C10—C9	111.8 (2)
H1A—C1—H1B	109.5	N2—C10—C11	120.4 (2)
O1—C1—H1C	109.5	C9—C10—C11	127.62 (17)
H1A—C1—H1C	109.5	O2—C11—N3	121.4 (2)
H1B—C1—H1C	109.5	O2—C11—C10	121.6 (2)
O1—C2—C3	125.3 (2)	N3—C11—C10	116.86 (16)
O1—C2—C7	115.5 (2)	N3—C12—C13	115.33 (17)
C3—C2—C7	119.21 (18)	N3—C12—H12A	108.4
C2—C3—C4	119.9 (2)	C13—C12—H12A	108.4
C2—C3—H3A	120.1	N3—C12—H12B	108.4
C4—C3—H3A	120.1	C13—C12—H12B	108.4
C3—C4—C5	121.9 (2)	H12A—C12—H12B	107.5
C3—C4—H4	119.0	O3—C13—C12	109.12 (19)
C5—C4—H4	119.0	O3—C13—H13A	109.9
C6—C5—C4	117.09 (18)	C12—C13—H13A	109.9
C6—C5—C8	122.5 (2)	O3—C13—H13B	109.9
C4—C5—C8	120.3 (2)	C12—C13—H13B	109.9
C7—C6—C5	121.7 (2)	H13A—C13—H13B	108.3
C7—C6—H6	119.2

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2ⁱ	0.82	1.88	2.668 (5)	162
N3—H3B···N2ⁱⁱ	0.86	2.54	3.318 (7)	151
N1—H1D···O3ⁱⁱ	0.86	1.90	2.739 (5)	166

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₅N₃O₃
M_r	261.28
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	21.82 (5), 10.08 (2), 12.28 (3)
β (°)	110.53 (3)
V (Å³)	2531 (11)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.20 × 0.15 × 0.06

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.980, 0.994
No. of measured, independent and observed [I > 2σ(I)] reflections	5292, 2366, 1841
R_int	0.074
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.156, 1.05
No. of reflections	2366
No. of parameters	175
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.30

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), 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
O3—H3···O2ⁱ	0.82	1.88	2.668 (5)	162
N3—H3B···N2ⁱⁱ	0.86	2.54	3.318 (7)	151
N1—H1D···O3ⁱⁱ	0.86	1.90	2.739 (5)	166

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

References

Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Qi, J. J., Zhu, J., Liu, X. F., Ding, L. L., Zheng, C. H., Han, G. Q., Lv, J. G. & Zhou, Y. J. (2011). Bioorg. Med. Chem. Lett. 21, 5822–5825. Web of Science CrossRef CAS PubMed Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shi, C.-X. & Xie, Y.-M. (2011). Acta Cryst. E67, o1084. Web of Science CSD CrossRef IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o901

doi:10.1107/S1600536812007829

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