N-(1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)benzene­sulfonamide

Mol­ecules of the title compound, C₁₇H₁₇N₃O₃S, form centrosymmetric hydrogen-bonded dimers via N—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C)= 0.004 Å
• R factor = 0.054
• wR factor = 0.140
• Data-to-parameter ratio = 14.1

checkCIF/PLATON results

No syntax errors found


No errors found in this datablock

---

S1. Comment

Benzenesulfonamides are very important intermediates in the organic synthesis and were widely used for the synthesis of medicinal and pesticidal compounds (Talley et al., 2000). 4-Aminophenazone and its derivatives are also very important compounds in pharmacology and biochemistry (El-Naggar et al., 1981; Lenarcik et al., 1980). Recently we have synthesized the title compound, a new benzenesulfonamide containing the aminophenazone component and report here its crystal structure.

All bond lengths and angles have normal values. The dihedral angle between the pyrazol and the two phenyl rings are 51.23 (7)° and 30.21 (12)°, respectively. In the structure there is a N—H···O hyrogen bond (N3—H3A···O1ⁱ, i: 2 - x, 1 - y, 2 - z) it links two molecules to form a dimer (Fig. 2). It should be indicated that weak intermolecular C—H···O interactions (C3—H3···O2ⁱⁱ, C6—H6···O3ⁱⁱⁱ, C10—H10A···O2^iv and C13—H13···O2^iv, ii: 2 - x, 1 - y, 1 - z; iii: -1 + x, y, z; iv: 2 - x, -y, 2 - z) further connect the dimers.

Related literature

For related literature, see: El-Naggar, Ahmed & Badie (1981); Lenarcik et al. (1980); Talley et al. (2000).

S2. Experimental

Under nitrogen, 4-amino-1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one (2.03 g, 10 mmol) was dissolved in 50 ml CH₂Cl₂, and then Et₃N (10 mmol) and benzenesulfonyl chloride (1.77 g, 10 mmol) were added dropwise to the above solution. The resulting mixture was refluxed for 6 h. 15 ml hydrochloric acid (0.1 M) was added to the reaction mixture and then the organic layer was separated. The aqueous layer was extracted with ethyl acetate (3 X 5 ml). The combined organic layer was washed with the 10% NaHCO₃ and water. The crude product was obtained by removing the solvent in vacuo. The crude product was further purified by washing it with a solution of CH₂Cl₂ and hexane (1:1). A white solid was obtained in 92% yield (3.30 g). Colourless single crystals suitable for X-ray analysis were grown from CH₂Cl₂ and absolute ethanol (4:1) by slow evaporation of the solvent at room temperature over a period of about a week.

S3. Refinement

H atoms bonded to N atoms were located in a difference map and refined with distance restraints of N—H = 0.97 (3) Å, and with U_iso(H) = 1.2U_eq(N). Other H atoms were positioned geometrically and refined using a riding model (including free rotation about the methyl C—C bond), with C—H = 0.93–0.96 Å and with U_iso(H) = 1.2 (1.5 for methyl groups) times U_eq(C).

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms.
	Fig. 2. View of the dimer of (I) (symmetry code: (i) 2 - x, 1 - y, 2 - z)

N-(1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)benzenesulfonamide

Crystal data

C17H17N3O3S	Z = 2
Mr = 343.40	F(000) = 360
Triclinic, P1	Dx = 1.429 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.085 (3) Å	Cell parameters from 3641 reflections
b = 9.799 (3) Å	θ = 2.6–28.0°
c = 9.809 (4) Å	µ = 0.22 mm^−1
α = 70.333 (4)°	T = 291 K
β = 76.301 (2)°	Block, colourless
γ = 87.991 (5)°	0.30 × 0.26 × 0.24 mm
V = 798.0 (5) Å^3

Data collection

Bruker SMART APEX CCD area-detector diffractometer	3125 independent reflections
Radiation source: sealed tube	2676 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
φ and ω scans	θmax = 26.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −10→11
Tmin = 0.941, Tmax = 0.952	k = −12→12
8297 measured reflections	l = −12→12

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.140	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0837P)^2 + 0.1646P] where P = (Fo^2 + 2Fc^2)/3
3125 reflections	(Δ/σ)max < 0.001
222 parameters	Δρmax = 0.56 e Å^−3
0 restraints	Δρmin = −0.46 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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

4.5464 (0.0079) x + 8.5127 (0.0055) y + 5.2985 (0.0085) z = 11.0166 (0.0059)

* 0.0041 (0.0014) C1 * -0.0073 (0.0017) C2 * 0.0008 (0.0018) C3 * 0.0089 (0.0018) C4 * -0.0120 (0.0018) C5 * 0.0055 (0.0016) C6

Rms deviation of fitted atoms = 0.0073

- 2.9653 (0.0085) x + 8.2368 (0.0059) y + 5.6491 (0.0083) z = 5.5778 (0.0128)

Angle to previous plane (with approximate e.s.d.) = 51.23 (0.07)

* 0.0418 (0.0012) N2 * -0.0347 (0.0012) N1 * 0.0147 (0.0012) C7 * 0.0113 (0.0012) C8 * -0.0331 (0.0013) C9

Rms deviation of fitted atoms = 0.0296

6.4582 (0.0077) x - 4.7433 (0.0095) y - 4.3399 (0.0100) z = 1.7354 (0.0208)

Angle to previous plane (with approximate e.s.d.) = 30.21 (0.12)

* -0.0014 (0.0016) C12 * 0.0066 (0.0017) C13 * -0.0061 (0.0019) C14 * 0.0004 (0.0020) C15 * 0.0048 (0.0021) C16 * -0.0042 (0.0018) C17

Rms deviation of fitted atoms = 0.0045

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.6807 (2)	0.4957 (2)	0.6995 (2)	0.0302 (4)
C2	0.7550 (3)	0.5468 (3)	0.5516 (3)	0.0413 (5)
H2	0.8501	0.5146	0.5192	0.050*
C3	0.6865 (3)	0.6467 (3)	0.4512 (3)	0.0526 (7)
H3	0.7363	0.6826	0.3508	0.063*
C4	0.5465 (3)	0.6932 (3)	0.4983 (3)	0.0538 (7)
H4	0.5021	0.7615	0.4302	0.065*
C5	0.4707 (3)	0.6393 (3)	0.6459 (3)	0.0490 (6)
H5	0.3738	0.6688	0.6768	0.059*
C6	0.5384 (3)	0.5413 (2)	0.7487 (3)	0.0383 (5)
H6	0.4889	0.5066	0.8492	0.046*
C7	0.8830 (2)	0.4196 (2)	0.8417 (2)	0.0288 (4)
C8	0.8730 (2)	0.3155 (2)	0.9876 (2)	0.0296 (4)
C9	0.7415 (2)	0.2332 (2)	1.0308 (2)	0.0305 (4)
C10	0.6867 (3)	0.1048 (2)	1.1652 (3)	0.0421 (5)
H10A	0.6986	0.0187	1.1385	0.063*
H10B	0.5815	0.1132	1.2074	0.063*
H10C	0.7445	0.0992	1.2371	0.063*
C11	0.5614 (3)	0.1922 (2)	0.8902 (3)	0.0388 (5)
H11A	0.6226	0.1302	0.8445	0.058*
H11B	0.5046	0.2516	0.8229	0.058*
H11C	0.4927	0.1340	0.9804	0.058*
C12	1.1464 (2)	0.0924 (2)	1.2053 (2)	0.0309 (4)
C13	1.0703 (3)	−0.0376 (2)	1.2324 (3)	0.0417 (5)
H13	1.0193	−0.0476	1.1643	0.050*
C14	1.0708 (3)	−0.1510 (3)	1.3601 (3)	0.0546 (7)
H14	1.0183	−0.2380	1.3799	0.065*
C15	1.1490 (4)	−0.1368 (3)	1.4594 (3)	0.0628 (8)
H15	1.1499	−0.2147	1.5455	0.075*
C16	1.2256 (4)	−0.0086 (4)	1.4322 (3)	0.0618 (8)
H16	1.2785	−0.0002	1.4996	0.074*
C17	1.2245 (3)	0.1080 (3)	1.3052 (3)	0.0432 (5)
H17	1.2753	0.1955	1.2869	0.052*
N1	0.7521 (2)	0.39254 (18)	0.80364 (19)	0.0310 (4)
N2	0.6594 (2)	0.28519 (18)	0.9251 (2)	0.0328 (4)
N3	0.9785 (2)	0.3078 (2)	1.0760 (2)	0.0338 (4)
H3A	0.981 (3)	0.384 (3)	1.117 (3)	0.041*
O1	0.98010 (17)	0.51793 (16)	0.76107 (17)	0.0365 (4)
O2	1.1496 (2)	0.18380 (19)	0.92410 (18)	0.0470 (4)
O3	1.25871 (18)	0.34497 (18)	1.0265 (2)	0.0458 (4)
S1	1.14382 (6)	0.24086 (5)	1.04167 (5)	0.03147 (18)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0369 (11)	0.0247 (9)	0.0314 (10)	−0.0027 (7)	−0.0159 (8)	−0.0069 (8)
C2	0.0375 (12)	0.0478 (13)	0.0339 (12)	−0.0046 (10)	−0.0065 (9)	−0.0086 (10)
C3	0.0635 (17)	0.0549 (15)	0.0322 (12)	−0.0076 (13)	−0.0170 (12)	−0.0008 (11)
C4	0.0664 (18)	0.0478 (14)	0.0497 (15)	0.0082 (12)	−0.0342 (14)	−0.0065 (12)
C5	0.0490 (14)	0.0466 (13)	0.0613 (16)	0.0158 (11)	−0.0271 (12)	−0.0227 (12)
C6	0.0403 (12)	0.0391 (11)	0.0371 (12)	0.0031 (9)	−0.0128 (9)	−0.0126 (9)
C7	0.0273 (10)	0.0279 (9)	0.0341 (10)	0.0018 (7)	−0.0091 (8)	−0.0129 (8)
C8	0.0300 (10)	0.0321 (10)	0.0287 (10)	0.0028 (8)	−0.0089 (8)	−0.0116 (8)
C9	0.0317 (10)	0.0293 (10)	0.0298 (10)	0.0040 (8)	−0.0078 (8)	−0.0093 (8)
C10	0.0444 (13)	0.0346 (11)	0.0381 (12)	−0.0008 (10)	−0.0065 (10)	−0.0025 (9)
C11	0.0360 (11)	0.0341 (11)	0.0458 (13)	−0.0061 (9)	−0.0106 (9)	−0.0115 (9)
C12	0.0262 (10)	0.0336 (10)	0.0327 (10)	0.0049 (8)	−0.0089 (8)	−0.0104 (8)
C13	0.0342 (12)	0.0386 (12)	0.0526 (14)	0.0019 (9)	−0.0129 (10)	−0.0140 (10)
C14	0.0431 (14)	0.0345 (12)	0.0687 (18)	0.0035 (10)	−0.0008 (12)	−0.0038 (12)
C15	0.0652 (19)	0.0595 (17)	0.0444 (15)	0.0221 (14)	−0.0079 (13)	0.0018 (13)
C16	0.073 (2)	0.075 (2)	0.0406 (14)	0.0200 (16)	−0.0292 (14)	−0.0141 (14)
C17	0.0441 (13)	0.0488 (13)	0.0391 (12)	0.0042 (10)	−0.0168 (10)	−0.0134 (10)
N1	0.0319 (9)	0.0278 (8)	0.0302 (9)	−0.0056 (7)	−0.0101 (7)	−0.0031 (7)
N2	0.0298 (9)	0.0278 (8)	0.0357 (10)	−0.0060 (7)	−0.0097 (7)	−0.0020 (7)
N3	0.0360 (10)	0.0370 (9)	0.0362 (10)	0.0110 (7)	−0.0164 (8)	−0.0181 (8)
O1	0.0312 (8)	0.0389 (8)	0.0364 (8)	−0.0087 (6)	−0.0061 (6)	−0.0091 (6)
O2	0.0589 (11)	0.0560 (10)	0.0328 (9)	0.0158 (8)	−0.0136 (8)	−0.0228 (8)
O3	0.0339 (9)	0.0447 (9)	0.0508 (10)	−0.0080 (7)	−0.0027 (7)	−0.0100 (7)
S1	0.0311 (3)	0.0340 (3)	0.0288 (3)	0.0027 (2)	−0.0073 (2)	−0.0100 (2)

Geometric parameters (Å, º)

C1—C2	1.372 (3)	C11—N2	1.467 (3)
C1—C6	1.383 (3)	C11—H11A	0.9600
C1—N1	1.435 (2)	C11—H11B	0.9600
C2—C3	1.383 (3)	C11—H11C	0.9600
C2—H2	0.9300	C12—C13	1.384 (3)
C3—C4	1.364 (4)	C12—C17	1.388 (3)
C3—H3	0.9300	C12—S1	1.771 (2)
C4—C5	1.374 (4)	C13—C14	1.367 (4)
C4—H4	0.9300	C13—H13	0.9300
C5—C6	1.385 (3)	C14—C15	1.378 (5)
C5—H5	0.9300	C14—H14	0.9300
C6—H6	0.9300	C15—C16	1.372 (5)
C7—O1	1.244 (2)	C15—H15	0.9300
C7—N1	1.387 (3)	C16—C17	1.379 (4)
C7—C8	1.434 (3)	C16—H16	0.9300
C8—C9	1.362 (3)	C17—H17	0.9300
C8—N3	1.422 (3)	N1—N2	1.406 (2)
C9—N2	1.369 (3)	N3—S1	1.6246 (19)
C9—C10	1.478 (3)	N3—H3A	0.97 (3)
C10—H10A	0.9600	O2—S1	1.4313 (17)
C10—H10B	0.9600	O3—S1	1.4320 (17)
C10—H10C	0.9600
C2—C1—C6	121.0 (2)	N2—C11—H11C	109.5
C2—C1—N1	119.1 (2)	H11A—C11—H11C	109.5
C6—C1—N1	119.93 (19)	H11B—C11—H11C	109.5
C1—C2—C3	119.1 (2)	C13—C12—C17	120.7 (2)
C1—C2—H2	120.4	C13—C12—S1	119.79 (17)
C3—C2—H2	120.4	C17—C12—S1	119.47 (17)
C4—C3—C2	120.5 (2)	C14—C13—C12	119.5 (2)
C4—C3—H3	119.8	C14—C13—H13	120.2
C2—C3—H3	119.8	C12—C13—H13	120.2
C3—C4—C5	120.3 (2)	C13—C14—C15	120.1 (3)
C3—C4—H4	119.8	C13—C14—H14	119.9
C5—C4—H4	119.8	C15—C14—H14	119.9
C4—C5—C6	120.1 (3)	C16—C15—C14	120.5 (3)
C4—C5—H5	120.0	C16—C15—H15	119.8
C6—C5—H5	120.0	C14—C15—H15	119.8
C1—C6—C5	119.0 (2)	C15—C16—C17	120.3 (3)
C1—C6—H6	120.5	C15—C16—H16	119.8
C5—C6—H6	120.5	C17—C16—H16	119.8
O1—C7—N1	123.91 (19)	C16—C17—C12	118.8 (3)
O1—C7—C8	131.31 (18)	C16—C17—H17	120.6
N1—C7—C8	104.75 (16)	C12—C17—H17	120.6
C9—C8—N3	125.92 (19)	C7—N1—N2	109.51 (16)
C9—C8—C7	109.00 (17)	C7—N1—C1	125.59 (16)
N3—C8—C7	124.93 (18)	N2—N1—C1	118.18 (16)
C8—C9—N2	109.17 (17)	C9—N2—N1	107.01 (16)
C8—C9—C10	129.3 (2)	C9—N2—C11	123.24 (17)
N2—C9—C10	121.52 (19)	N1—N2—C11	116.90 (17)
C9—C10—H10A	109.5	C8—N3—S1	121.88 (14)
C9—C10—H10B	109.5	C8—N3—H3A	118.0 (15)
H10A—C10—H10B	109.5	S1—N3—H3A	111.9 (15)
C9—C10—H10C	109.5	O2—S1—O3	119.74 (11)
H10A—C10—H10C	109.5	O2—S1—N3	107.71 (10)
H10B—C10—H10C	109.5	O3—S1—N3	109.03 (10)
N2—C11—H11A	109.5	O2—S1—C12	107.54 (10)
N2—C11—H11B	109.5	O3—S1—C12	106.77 (10)
H11A—C11—H11B	109.5	N3—S1—C12	105.13 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O1^i	0.97 (3)	1.86 (3)	2.789 (2)	160 (2)

Symmetry code: (i) −x+2, −y+1, −z+2.