Ethyl 5-amino-1-[(4-methyl-phen-yl)sulfon-yl]-1H-pyrazole-4-carboxyl-ate.

In the title mol-ecule, C13H15N3O4S, the benzene and pyrazole rings are inclined to each other at 77.48 (3)°. Two amino H atoms are involved in bifurcated hydrogen bonds, viz. intra-molecular N-H⋯O and inter-molecular N-H⋯O(N). The inter-molecular hydrogen bonds link the mol-ecules related by translation in [100] into chains. A short distance of 3.680 (3) Å between the centroids of benzene and pyrazole rings from neighbouring mol-ecules shows the presence of π-π inter-actions, which link the hydrogen-bonded chains into layers parallel to the ab plane.

Related literature

For background details and information on the synthesis, see: Elgazwy, Ismail et al. (2012 ▶); Elgazwy, Soliman et al. (2012 ▶).

Experimental

Crystal data

C13H15N3O4S

M = 309.34

Monoclinic,

a = 6.27869 (7) Å

b = 15.43607 (12) Å

c = 15.27141 (13) Å

β = 96.2633 (9)°

V = 1471.24 (2) Å3

Z = 4

Cu Kα radiation

μ = 2.14 mm−1

T = 100 K

0.25 × 0.12 × 0.10 mm

Data collection

Oxford Diffraction Xcalibur (Atlas, Nova) diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ▶) T min = 0.800, T max = 1.000

51079 measured reflections

3043 independent reflections

3035 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.027

wR(F 2) = 0.074

S = 1.05

3043 reflections

201 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.34 e Å−3

Δρmin = −0.39 e Å−3

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP (Siemens, 1994 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813019326/cv5421sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813019326/cv5421Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813019326/cv5421Isup3.ps

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813019326/cv5421Isup5.cml

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

C13H15N3O4S	F(000) = 648
Mr = 309.34	Dx = 1.397 Mg m−3
Monoclinic, P21/n	Melting point: 408 K
Hall symbol: P 2yn	Cu Kα radiation, λ = 1.54184 Å
a = 6.27869 (7) Å	Cell parameters from 45300 reflections
b = 15.43607 (12) Å	θ = 4.1–75.6°
c = 15.27141 (13) Å	µ = 2.14 mm−1
β = 96.2633 (9)°	T = 100 K
V = 1471.24 (2) Å3	Column, colourless
Z = 4	0.25 × 0.12 × 0.10 mm

Oxford Diffraction Xcalibur (Atlas, Nova) diffractometer	3043 independent reflections
Radiation source: Nova (Cu) X-ray Source	3035 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.024
Detector resolution: 10.3543 pixels mm-1	θmax = 75.8°, θmin = 4.1°
ω scans	h = −6→7
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −19→19
Tmin = 0.800, Tmax = 1.000	l = −19→19
51079 measured reflections

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)] = 0.027	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.074	w = 1/[σ2(Fo2) + (0.0381P)2 + 0.6757P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.002
3043 reflections	Δρmax = 0.34 e Å−3
201 parameters	Δρmin = −0.39 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: 0.0050 (4)

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.Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)2.2393 (0.0028) x + 11.4616 (0.0048) y - 9.2011 (0.0057) z = 0.8382 (0.0021)* 0.0093 (0.0008) C11 * -0.0049 (0.0008) C12 * -0.0055 (0.0009) C13 * 0.0116 (0.0008) C14 * -0.0075 (0.0008) C15 * -0.0030 (0.0008) C16Rms deviation of fitted atoms = 0.0076- 1.0360 (0.0033) x + 12.4363 (0.0050) y + 8.9114 (0.0069) z = 7.4119 (0.0015)Angle to previous plane (with approximate e.s.d.) = 77.48 (0.03)* 0.0208 (0.0006) N1 * -0.0138 (0.0006) N2 * 0.0016 (0.0007) C3 * 0.0109 (0.0007) C4 * -0.0196 (0.0006) C5Rms deviation of fitted atoms = 0.0150

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
S1	0.23094 (4)	0.321249 (17)	0.345762 (16)	0.01627 (10)
O1	0.02102 (13)	0.32316 (5)	0.37347 (6)	0.02126 (19)
O2	0.41682 (14)	0.32016 (5)	0.40895 (5)	0.02177 (19)
O3	0.69858 (13)	0.55623 (5)	0.15472 (5)	0.02182 (19)
O4	0.39748 (12)	0.58590 (5)	0.06499 (5)	0.01882 (18)
N1	0.25242 (14)	0.41272 (6)	0.28744 (6)	0.01595 (19)
N2	0.06923 (14)	0.43553 (6)	0.23043 (6)	0.0178 (2)
C3	0.14389 (17)	0.48527 (7)	0.17142 (7)	0.0168 (2)
H3	0.0556	0.5119	0.1245	0.020*
C4	0.36924 (17)	0.49552 (7)	0.18436 (7)	0.0156 (2)
C5	0.43824 (17)	0.44590 (7)	0.25821 (7)	0.0156 (2)
C6	0.50665 (17)	0.54783 (7)	0.13524 (7)	0.0158 (2)
C7	0.52593 (19)	0.63686 (7)	0.01022 (7)	0.0201 (2)
H7A	0.6350	0.6000	−0.0136	0.024*
H7B	0.5999	0.6843	0.0449	0.024*
C8	0.3728 (2)	0.67306 (8)	−0.06355 (8)	0.0272 (3)
H8A	0.2989	0.6253	−0.0966	0.041*
H8B	0.4525	0.7073	−0.1031	0.041*
H8C	0.2672	0.7101	−0.0390	0.041*
C11	0.24897 (18)	0.23989 (7)	0.26731 (7)	0.0173 (2)
C12	0.07233 (19)	0.22397 (8)	0.20604 (8)	0.0219 (2)
H12	−0.0601	0.2526	0.2104	0.026*
C13	0.0935 (2)	0.16557 (8)	0.13850 (8)	0.0248 (3)
H13	−0.0258	0.1540	0.0964	0.030*
C14	0.2884 (2)	0.12352 (8)	0.13168 (8)	0.0233 (3)
C15	0.46013 (19)	0.13919 (8)	0.19509 (8)	0.0227 (2)
H15	0.5914	0.1094	0.1917	0.027*
C16	0.44368 (18)	0.19753 (8)	0.26327 (8)	0.0200 (2)
H16	0.5622	0.2083	0.3061	0.024*
C17	0.3134 (3)	0.06341 (9)	0.05575 (9)	0.0335 (3)
H17A	0.3628	0.0964	0.0070	0.050*
H17B	0.1751	0.0364	0.0362	0.050*
H17C	0.4185	0.0184	0.0747	0.050*
N3	0.63513 (16)	0.43168 (7)	0.29848 (7)	0.0214 (2)
H02	0.743 (3)	0.4452 (11)	0.2705 (11)	0.033 (4)*
H01	0.655 (3)	0.3949 (11)	0.3402 (11)	0.033 (4)*

	U11	U22	U33	U12	U13	U23
S1	0.01694 (16)	0.01813 (15)	0.01412 (15)	0.00056 (9)	0.00335 (10)	0.00249 (9)
O1	0.0211 (4)	0.0234 (4)	0.0207 (4)	0.0005 (3)	0.0088 (3)	0.0033 (3)
O2	0.0227 (4)	0.0262 (4)	0.0158 (4)	−0.0007 (3)	−0.0003 (3)	0.0038 (3)
O3	0.0144 (4)	0.0265 (4)	0.0243 (4)	−0.0008 (3)	0.0014 (3)	0.0056 (3)
O4	0.0169 (4)	0.0225 (4)	0.0170 (4)	0.0001 (3)	0.0019 (3)	0.0058 (3)
N1	0.0135 (4)	0.0179 (4)	0.0166 (4)	0.0008 (3)	0.0021 (3)	0.0024 (3)
N2	0.0137 (4)	0.0199 (5)	0.0196 (5)	0.0021 (3)	0.0007 (3)	0.0024 (4)
C3	0.0157 (5)	0.0177 (5)	0.0172 (5)	0.0015 (4)	0.0022 (4)	0.0008 (4)
C4	0.0149 (5)	0.0166 (5)	0.0155 (5)	0.0013 (4)	0.0021 (4)	0.0000 (4)
C5	0.0153 (5)	0.0168 (5)	0.0150 (5)	−0.0003 (4)	0.0036 (4)	−0.0014 (4)
C6	0.0164 (5)	0.0156 (5)	0.0154 (5)	0.0023 (4)	0.0025 (4)	−0.0003 (4)
C7	0.0248 (6)	0.0183 (5)	0.0180 (5)	−0.0018 (4)	0.0065 (4)	0.0025 (4)
C8	0.0379 (7)	0.0241 (6)	0.0196 (6)	0.0024 (5)	0.0029 (5)	0.0056 (4)
C11	0.0194 (5)	0.0161 (5)	0.0168 (5)	0.0014 (4)	0.0040 (4)	0.0028 (4)
C12	0.0203 (6)	0.0217 (6)	0.0235 (6)	0.0034 (4)	0.0007 (4)	0.0006 (4)
C13	0.0291 (6)	0.0235 (6)	0.0210 (6)	0.0021 (5)	−0.0015 (5)	0.0005 (5)
C14	0.0346 (7)	0.0171 (5)	0.0194 (6)	0.0023 (5)	0.0084 (5)	0.0040 (4)
C15	0.0247 (6)	0.0191 (5)	0.0258 (6)	0.0059 (4)	0.0101 (5)	0.0063 (4)
C16	0.0188 (5)	0.0200 (5)	0.0215 (6)	0.0021 (4)	0.0033 (4)	0.0057 (4)
C17	0.0525 (9)	0.0260 (6)	0.0236 (6)	0.0062 (6)	0.0116 (6)	−0.0008 (5)
N3	0.0149 (5)	0.0295 (5)	0.0196 (5)	−0.0002 (4)	0.0011 (4)	0.0078 (4)

S1—O1	1.4279 (8)	C14—C15	1.3898 (18)
S1—O2	1.4311 (8)	C14—C17	1.5065 (17)
S1—N1	1.6827 (9)	C15—C16	1.3890 (17)
S1—C11	1.7478 (11)	C3—H3	0.9500
O3—C6	1.2163 (14)	C7—H7A	0.9900
O4—C6	1.3437 (13)	C7—H7B	0.9900
O4—C7	1.4546 (13)	C8—H8A	0.9800
N1—C5	1.3915 (14)	C8—H8B	0.9800
N1—N2	1.4093 (12)	C8—H8C	0.9800
N2—C3	1.3089 (14)	C12—H12	0.9500
C3—C4	1.4160 (15)	C13—H13	0.9500
C4—C5	1.3927 (15)	C15—H15	0.9500
C4—C6	1.4492 (15)	C16—H16	0.9500
C5—N3	1.3375 (14)	C17—H17A	0.9800
C7—C8	1.5067 (16)	C17—H17B	0.9800
C11—C12	1.3927 (16)	C17—H17C	0.9800
C11—C16	1.3937 (16)	N3—H02	0.865 (18)
C12—C13	1.3870 (17)	N3—H01	0.852 (18)
C13—C14	1.3990 (18)
O1—S1—O2	120.77 (5)	C15—C16—C11	118.34 (11)
O1—S1—N1	105.63 (5)	N2—C3—H3	123.3
O2—S1—N1	105.08 (5)	C4—C3—H3	123.3
O1—S1—C11	110.42 (5)	O4—C7—H7A	110.5
O2—S1—C11	110.17 (5)	C8—C7—H7A	110.5
N1—S1—C11	103.01 (5)	O4—C7—H7B	110.5
C6—O4—C7	115.40 (8)	C8—C7—H7B	110.5
C5—N1—N2	111.48 (8)	H7A—C7—H7B	108.6
C5—N1—S1	126.66 (8)	C7—C8—H8A	109.5
N2—N1—S1	115.43 (7)	C7—C8—H8B	109.5
C3—N2—N1	104.03 (9)	H8A—C8—H8B	109.5
N2—C3—C4	113.39 (10)	C7—C8—H8C	109.5
C5—C4—C3	105.62 (9)	H8A—C8—H8C	109.5
C5—C4—C6	125.13 (10)	H8B—C8—H8C	109.5
C3—C4—C6	129.22 (10)	C13—C12—H12	120.6
N3—C5—N1	123.87 (10)	C11—C12—H12	120.6
N3—C5—C4	130.76 (10)	C12—C13—H13	119.6
N1—C5—C4	105.34 (9)	C14—C13—H13	119.6
O3—C6—O4	123.66 (10)	C16—C15—H15	119.3
O3—C6—C4	124.24 (10)	C14—C15—H15	119.3
O4—C6—C4	112.10 (9)	C15—C16—H16	120.8
O4—C7—C8	106.37 (9)	C11—C16—H16	120.8
C12—C11—C16	121.71 (11)	C14—C17—H17A	109.5
C12—C11—S1	118.75 (9)	C14—C17—H17B	109.5
C16—C11—S1	119.35 (9)	H17A—C17—H17B	109.5
C13—C12—C11	118.71 (11)	C14—C17—H17C	109.5
C12—C13—C14	120.83 (11)	H17A—C17—H17C	109.5
C15—C14—C13	119.07 (11)	H17B—C17—H17C	109.5
C15—C14—C17	120.36 (12)	C5—N3—H02	117.9 (11)
C13—C14—C17	120.56 (12)	C5—N3—H01	120.2 (11)
C16—C15—C14	121.31 (11)	H02—N3—H01	118.3 (15)
O1—S1—N1—C5	169.64 (9)	C5—C4—C6—O3	−2.20 (18)
O2—S1—N1—C5	40.91 (10)	C3—C4—C6—O3	175.58 (11)
C11—S1—N1—C5	−74.48 (10)	C5—C4—C6—O4	177.48 (10)
O1—S1—N1—N2	−41.11 (9)	C3—C4—C6—O4	−4.74 (16)
O2—S1—N1—N2	−169.84 (7)	C6—O4—C7—C8	−179.98 (9)
C11—S1—N1—N2	74.78 (8)	O1—S1—C11—C12	36.77 (10)
C5—N1—N2—C3	−3.39 (12)	O2—S1—C11—C12	172.69 (9)
S1—N1—N2—C3	−157.24 (8)	N1—S1—C11—C12	−75.64 (10)
N1—N2—C3—C4	1.50 (12)	O1—S1—C11—C16	−148.21 (9)
N2—C3—C4—C5	0.83 (13)	O2—S1—C11—C16	−12.29 (11)
N2—C3—C4—C6	−177.28 (11)	N1—S1—C11—C16	99.39 (9)
N2—N1—C5—N3	−177.82 (10)	C16—C11—C12—C13	−1.26 (17)
S1—N1—C5—N3	−27.56 (16)	S1—C11—C12—C13	173.65 (9)
N2—N1—C5—C4	3.92 (12)	C11—C12—C13—C14	−0.18 (18)
S1—N1—C5—C4	154.18 (8)	C12—C13—C14—C15	1.74 (18)
C3—C4—C5—N3	179.10 (12)	C12—C13—C14—C17	−177.06 (11)
C6—C4—C5—N3	−2.68 (19)	C13—C14—C15—C16	−1.94 (17)
C3—C4—C5—N1	−2.81 (12)	C17—C14—C15—C16	176.87 (11)
C6—C4—C5—N1	175.41 (10)	C14—C15—C16—C11	0.56 (17)
C7—O4—C6—O3	2.02 (15)	C12—C11—C16—C15	1.07 (17)
C7—O4—C6—C4	−177.65 (9)	S1—C11—C16—C15	−173.81 (8)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H02···O3	0.865 (18)	2.456 (17)	2.9775 (13)	119.4 (13)
N3—H01···O2	0.852 (18)	2.237 (17)	2.8624 (13)	130.3 (14)
N3—H02···N2i	0.865 (18)	2.206 (18)	3.0216 (14)	157.1 (15)
N3—H01···O1i	0.852 (18)	2.554 (17)	3.0631 (13)	119.3 (13)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H01⋯O1i	0.852 (18)	2.554 (17)	3.0631 (13)	119.3 (13)
N3—H01⋯O2	0.852 (18)	2.237 (17)	2.8624 (13)	130.3 (14)
N3—H02⋯O3	0.865 (18)	2.456 (17)	2.9775 (13)	119.4 (13)
N3—H02⋯N2i	0.865 (18)	2.206 (18)	3.0216 (14)	157.1 (15)

Symmetry code: (i) .