4-(5-Oxo-3-phenyl-4,5-dihydro-1H-pyrazol-1-yl)benzene­sulfonamide

Abstract

With respect to the aliphatic planar five-membered ring (r.m.s. deviation = 0.011 Å) of the title compound, C₁₅H₁₃N₃O₂S, the phenyl ring is aligned at 6.9 (1)° and the phenyl­ene ring at 2.4 (1)°, so that the three rings are nearly coplanar. The amino group has the N atom in a pyramidal geometry; the group is a hydrogen-bond donor to the sulfonyl O atom of one mol­ecule and to the ketonic O atom of another mol­ecule, resulting in the formation of a layer parallel to the bc plane.

Related literature

For the synthesis, see: Casoni (1956 ▶); Itano (1955 ▶).

Experimental

Crystal data

• C₁₅H₁₃N₃O₃S

• M _r = 315.34

• Monoclinic,

• a = 13.6794 (4) Å

• b = 13.4304 (4) Å

• c = 7.3678 (2) Å

• β = 91.055 (3)°

• V = 1353.38 (7) ų

• Z = 4

• Cu Kα radiation

• μ = 2.29 mm⁻¹

• T = 100 K

• 0.30 × 0.05 × 0.05 mm

Data collection

• Agilent SuperNova Dual diffractometer with an Atlas detector

• Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T _min = 0.546, T _max = 0.894

• 10404 measured reflections

• 2731 independent reflections

• 2444 reflections with I > 2σ(I)

• R _int = 0.041

Refinement

• R[F ² > 2σ(F ²)] = 0.041

• wR(F ²) = 0.121

• S = 1.06

• 2731 reflections

• 207 parameters

• 2 restraints

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.73 e Å⁻³

• Δρ_min = −0.51 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2010 ▶); 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: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811032879/bt5611Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H1⋯O3i	0.88 (1)	2.12 (1)	2.975 (2)	164 (2)
N3—H2⋯O2ii	0.87 (1)	2.12 (1)	2.978 (2)	168 (2)

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

We are examining the medicinal properties of phenylpyrazolones of which the 4-benzenesulfamide derivative (Scheme I) is expected to show enhanced activity. The synthesis of the compound was reported a long time ago (Casoni, 1956; Itano, 1955). With respect to the aliphatic planar five-membered ring, the phenyl ring is aligned at 6.9 (1)° and the phenylene ring at 2.4 (1)°. The amino group is hydrogen bond donor to the sulfonyl O atom of one molecule and to the ketonic O atom of another molecule to result in the formation of a layer parallel to the bc plane.

Experimental

Ethyl benzoylacetate (10 mmol) and 4-hydrazinobenzenesulfonamide hydrochloride (10 mmol) were heated in ethanol (50 ml) for 4 h; water was added to precipitate the product, which was collected and recrystallized from ethanol as brownish-orange crystals; m.p. 510–511 K.

Refinement

Carbon bound H-atoms were placed in calculated positions [C–H 0.95 to 0.98 Å, U_iso(H) 1.2–1.5U_eq(C)] and were included in the refinement in the riding model approximation.

The amino H-atoms were located in a difference Fouier map and were refined with a distance restraint of N–H 0.88±0.01 Å; their isotropic displacement parameter were freely refined.

Figures

Fig. 1.

Anisotropic displacement ellipsoid plot (Barbour, 2001) of C15H13N3O2S at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

Crystal data

C15H13N3O3S	F(000) = 656
Mr = 315.34	Dx = 1.548 Mg m−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybc	Cell parameters from 4563 reflections
a = 13.6794 (4) Å	θ = 3.2–74.4°
b = 13.4304 (4) Å	µ = 2.29 mm−1
c = 7.3678 (2) Å	T = 100 K
β = 91.055 (3)°	Prism, brown orange
V = 1353.38 (7) Å3	0.30 × 0.05 × 0.05 mm
Z = 4

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector	2731 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	2444 reflections with I > 2σ(I)
Mirror	Rint = 0.041
Detector resolution: 10.4041 pixels mm-1	θmax = 74.5°, θmin = 3.2°
ω scan	h = −17→16
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −16→16
Tmin = 0.546, Tmax = 0.894	l = −5→9
10404 measured reflections

Refinement

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0759P)2 + 0.5321P] where P = (Fo2 + 2Fc2)/3
2731 reflections	(Δ/σ)max = 0.001
207 parameters	Δρmax = 0.73 e Å−3
2 restraints	Δρmin = −0.51 e Å−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.91654 (3)	0.64477 (3)	0.49527 (6)	0.01653 (16)
O1	0.52785 (10)	0.32661 (11)	0.6467 (2)	0.0319 (4)
O2	0.90632 (9)	0.74972 (10)	0.46298 (18)	0.0220 (3)
O3	0.95114 (9)	0.58212 (10)	0.35168 (17)	0.0209 (3)
N2	0.46514 (11)	0.56244 (12)	0.8066 (2)	0.0203 (3)
N3	0.99249 (12)	0.63163 (12)	0.6642 (2)	0.0197 (3)
H1	1.0122 (17)	0.5704 (9)	0.682 (3)	0.028 (6)*
H2	0.9740 (16)	0.6620 (16)	0.763 (2)	0.023 (6)*
N1	0.52929 (11)	0.49471 (11)	0.7246 (2)	0.0197 (3)
C1	0.49011 (14)	0.39912 (14)	0.7147 (3)	0.0227 (4)
C2	0.39264 (14)	0.40640 (14)	0.8033 (3)	0.0224 (4)
H2A	0.3390	0.3864	0.7189	0.027*
H2B	0.3903	0.3645	0.9138	0.027*
C3	0.38673 (13)	0.51403 (14)	0.8491 (2)	0.0198 (4)
C4	0.30272 (13)	0.56293 (14)	0.9324 (2)	0.0205 (4)
C5	0.30792 (15)	0.66235 (15)	0.9877 (3)	0.0261 (4)
H5	0.3663	0.6993	0.9713	0.031*
C6	0.22764 (16)	0.70694 (16)	1.0664 (3)	0.0312 (5)
H6	0.2311	0.7745	1.1040	0.037*
C7	0.14192 (15)	0.65297 (16)	1.0905 (3)	0.0294 (5)
H7	0.0870	0.6837	1.1441	0.035*
C8	0.13695 (14)	0.55477 (17)	1.0363 (3)	0.0281 (5)
H8	0.0784	0.5181	1.0528	0.034*
C9	0.21695 (13)	0.50911 (15)	0.9577 (3)	0.0235 (4)
H9	0.2132	0.4413	0.9213	0.028*
C10	0.62051 (12)	0.52987 (13)	0.6675 (2)	0.0178 (4)
C11	0.68801 (13)	0.46447 (14)	0.5912 (2)	0.0197 (4)
H11	0.6720	0.3961	0.5759	0.024*
C12	0.77831 (13)	0.49990 (13)	0.5381 (2)	0.0184 (4)
H12	0.8246	0.4557	0.4875	0.022*
C13	0.80101 (13)	0.60030 (13)	0.5590 (2)	0.0175 (4)
C14	0.73339 (14)	0.66554 (14)	0.6338 (3)	0.0201 (4)
H14	0.7495	0.7339	0.6481	0.024*
C15	0.64299 (14)	0.63125 (14)	0.6873 (3)	0.0200 (4)
H15	0.5967	0.6759	0.7369	0.024*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
S1	0.0140 (2)	0.0175 (3)	0.0182 (3)	−0.00041 (14)	0.00381 (17)	0.00075 (14)
O1	0.0230 (7)	0.0225 (7)	0.0506 (9)	−0.0015 (6)	0.0103 (7)	−0.0049 (6)
O2	0.0202 (6)	0.0184 (7)	0.0276 (7)	−0.0010 (5)	0.0052 (5)	0.0040 (5)
O3	0.0194 (6)	0.0241 (7)	0.0194 (6)	−0.0005 (5)	0.0061 (5)	−0.0021 (5)
N2	0.0148 (7)	0.0241 (8)	0.0221 (8)	0.0014 (6)	0.0047 (6)	−0.0003 (6)
N3	0.0180 (8)	0.0205 (8)	0.0208 (8)	0.0015 (6)	0.0012 (6)	−0.0009 (6)
N1	0.0161 (7)	0.0206 (8)	0.0226 (8)	−0.0004 (6)	0.0050 (6)	−0.0023 (6)
C1	0.0194 (9)	0.0227 (10)	0.0259 (9)	−0.0017 (7)	0.0013 (7)	0.0021 (7)
C2	0.0179 (9)	0.0251 (10)	0.0242 (9)	−0.0018 (7)	0.0024 (7)	0.0015 (7)
C3	0.0168 (9)	0.0248 (9)	0.0178 (8)	−0.0014 (7)	0.0008 (7)	0.0022 (7)
C4	0.0162 (9)	0.0274 (9)	0.0179 (8)	0.0009 (7)	0.0022 (7)	0.0049 (7)
C5	0.0236 (10)	0.0259 (10)	0.0290 (10)	0.0004 (8)	0.0083 (8)	0.0056 (8)
C6	0.0326 (11)	0.0261 (10)	0.0353 (11)	0.0068 (8)	0.0120 (9)	0.0078 (8)
C7	0.0220 (10)	0.0400 (12)	0.0266 (10)	0.0123 (8)	0.0080 (8)	0.0114 (8)
C8	0.0153 (9)	0.0450 (12)	0.0241 (10)	−0.0017 (8)	0.0019 (7)	0.0068 (8)
C9	0.0180 (9)	0.0329 (10)	0.0195 (9)	−0.0034 (8)	0.0007 (7)	0.0007 (7)
C10	0.0146 (8)	0.0220 (9)	0.0170 (8)	−0.0006 (7)	0.0012 (6)	0.0019 (7)
C11	0.0190 (9)	0.0203 (9)	0.0200 (8)	−0.0009 (7)	0.0019 (7)	−0.0004 (7)
C12	0.0161 (8)	0.0193 (8)	0.0199 (9)	0.0024 (7)	0.0029 (7)	0.0004 (6)
C13	0.0141 (8)	0.0208 (9)	0.0178 (8)	−0.0012 (7)	0.0015 (6)	0.0019 (6)
C14	0.0195 (9)	0.0171 (8)	0.0240 (9)	−0.0002 (7)	0.0033 (7)	0.0000 (7)
C15	0.0177 (9)	0.0211 (9)	0.0213 (9)	0.0017 (7)	0.0029 (7)	−0.0007 (7)

Geometric parameters (Å, °)

S1—O2	1.4358 (13)	C5—H5	0.9500
S1—O3	1.4386 (13)	C6—C7	1.393 (3)
S1—N3	1.6160 (17)	C6—H6	0.9500
S1—C13	1.7611 (18)	C7—C8	1.379 (3)
O1—C1	1.215 (2)	C7—H7	0.9500
N2—C3	1.298 (2)	C8—C9	1.390 (3)
N2—N1	1.408 (2)	C8—H8	0.9500
N3—H1	0.875 (10)	C9—H9	0.9500
N3—H2	0.873 (10)	C10—C11	1.400 (2)
N1—C1	1.393 (2)	C10—C15	1.403 (3)
N1—C10	1.406 (2)	C11—C12	1.387 (3)
C1—C2	1.499 (3)	C11—H11	0.9500
C2—C3	1.487 (3)	C12—C13	1.392 (2)
C2—H2A	0.9900	C12—H12	0.9500
C2—H2B	0.9900	C13—C14	1.395 (2)
C3—C4	1.468 (2)	C14—C15	1.384 (3)
C4—C9	1.393 (3)	C14—H14	0.9500
C4—C5	1.397 (3)	C15—H15	0.9500
C5—C6	1.387 (3)
O2—S1—O3	119.00 (8)	C5—C6—C7	120.2 (2)
O2—S1—N3	107.10 (8)	C5—C6—H6	119.9
O3—S1—N3	106.67 (8)	C7—C6—H6	119.9
O2—S1—C13	106.97 (8)	C8—C7—C6	119.86 (19)
O3—S1—C13	107.85 (8)	C8—C7—H7	120.1
N3—S1—C13	108.97 (8)	C6—C7—H7	120.1
C3—N2—N1	107.72 (15)	C7—C8—C9	120.49 (19)
S1—N3—H1	114.1 (16)	C7—C8—H8	119.8
S1—N3—H2	113.3 (16)	C9—C8—H8	119.8
H1—N3—H2	114 (2)	C8—C9—C4	119.88 (19)
C1—N1—C10	129.54 (15)	C8—C9—H9	120.1
C1—N1—N2	112.08 (14)	C4—C9—H9	120.1
C10—N1—N2	118.38 (14)	C11—C10—N1	120.35 (16)
O1—C1—N1	126.49 (17)	C11—C10—C15	120.39 (16)
O1—C1—C2	128.35 (18)	N1—C10—C15	119.26 (16)
N1—C1—C2	105.17 (16)	C12—C11—C10	119.71 (17)
C3—C2—C1	102.40 (15)	C12—C11—H11	120.1
C3—C2—H2A	111.3	C10—C11—H11	120.1
C1—C2—H2A	111.3	C11—C12—C13	119.97 (16)
C3—C2—H2B	111.3	C11—C12—H12	120.0
C1—C2—H2B	111.3	C13—C12—H12	120.0
H2A—C2—H2B	109.2	C12—C13—C14	120.26 (16)
N2—C3—C4	122.26 (17)	C12—C13—S1	119.91 (13)
N2—C3—C2	112.57 (16)	C14—C13—S1	119.81 (14)
C4—C3—C2	125.17 (16)	C15—C14—C13	120.41 (17)
C9—C4—C5	119.68 (17)	C15—C14—H14	119.8
C9—C4—C3	119.44 (17)	C13—C14—H14	119.8
C5—C4—C3	120.88 (17)	C14—C15—C10	119.25 (17)
C6—C5—C4	119.85 (19)	C14—C15—H15	120.4
C6—C5—H5	120.1	C10—C15—H15	120.4
C4—C5—H5	120.1
C3—N2—N1—C1	−0.1 (2)	C5—C4—C9—C8	0.5 (3)
C3—N2—N1—C10	−179.52 (16)	C3—C4—C9—C8	−179.92 (17)
C10—N1—C1—O1	−2.7 (3)	C1—N1—C10—C11	−1.6 (3)
N2—N1—C1—O1	177.9 (2)	N2—N1—C10—C11	177.72 (15)
C10—N1—C1—C2	177.83 (17)	C1—N1—C10—C15	178.21 (18)
N2—N1—C1—C2	−1.6 (2)	N2—N1—C10—C15	−2.4 (2)
O1—C1—C2—C3	−177.1 (2)	N1—C10—C11—C12	−178.97 (16)
N1—C1—C2—C3	2.34 (19)	C15—C10—C11—C12	1.2 (3)
N1—N2—C3—C4	−178.03 (16)	C10—C11—C12—C13	−0.7 (3)
N1—N2—C3—C2	1.7 (2)	C11—C12—C13—C14	0.2 (3)
C1—C2—C3—N2	−2.6 (2)	C11—C12—C13—S1	178.85 (14)
C1—C2—C3—C4	177.17 (17)	O2—S1—C13—C12	157.60 (15)
N2—C3—C4—C9	173.44 (17)	O3—S1—C13—C12	28.50 (17)
C2—C3—C4—C9	−6.3 (3)	N3—S1—C13—C12	−86.93 (16)
N2—C3—C4—C5	−7.0 (3)	O2—S1—C13—C14	−23.78 (17)
C2—C3—C4—C5	173.27 (18)	O3—S1—C13—C14	−152.88 (15)
C9—C4—C5—C6	−0.3 (3)	N3—S1—C13—C14	91.69 (16)
C3—C4—C5—C6	−179.88 (18)	C12—C13—C14—C15	−0.3 (3)
C4—C5—C6—C7	0.0 (3)	S1—C13—C14—C15	−178.89 (14)
C5—C6—C7—C8	0.2 (3)	C13—C14—C15—C10	0.8 (3)
C6—C7—C8—C9	0.0 (3)	C11—C10—C15—C14	−1.2 (3)
C7—C8—C9—C4	−0.4 (3)	N1—C10—C15—C14	178.94 (16)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1···O3i	0.88 (1)	2.12 (1)	2.975 (2)	164 (2)
N3—H2···O2ii	0.87 (1)	2.12 (1)	2.978 (2)	168 (2)

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