N'-[(4Z)-1-(3-Methyl-5-oxo-1-phenyl-4,5-di-hydro-1H-pyrazol-4-yl-idene)hex-yl]benzene-sulfono-hydrazide.

In the title compound, C22H26N4O3S, the dihedral angle between the pyrazoloneand phenyl rings is 21.73 (4)°. The benzensulfono-hydrazide group adopts a gauche conformation about the N-N vector. The C-N-N-S torsion angle is -109.88 (13)°. The mol-ecule exists as the enamine tautomeric form (C=C-NH). An intra-molecular N-H⋯O=C hydrogen bond occurs. In the crystal, mol-ecules are linked by pairs of N-H⋯O=C hydrogen bonds, forming centrosymmetric dimers.

Related literature

For the synthesis of 4-acyl-3-methyl-1-phenyl­pyrazol-5-one, see: Okafor (1983 ▶). For related studies of 4-acyl­pyrazol-5-one Schiff bases, see: Xu et al. (2008 ▶); Peng et al. (2005 ▶); Yang et al. (2007 ▶). For their ligating ability towards metal ions and their biological activity, see: Parmar & Teraiya, (2009 ▶); Bedia et al. (2006 ▶); Raman et al. (2001 ▶); Uzoukwu et al. (1996 ▶); Yang et al. (2000 ▶); Chiba et al. 1998 ▶). For their use as efficient extractants of metal ions in solution and recently as photochromic agents, see: Marchetti et al. (2005 ▶); Marchetti et al. (2000 ▶); Wu et al. (2009 ▶). For related pyrazolone derivative structures, see: Sawusch et al. (1999 ▶); Sun et al. (2007 ▶); Liu et al. (2002 ▶); Sun & Cui, (2008 ▶); Gallardo et al. (2009 ▶); Chi et al. (2010 ▶).

Experimental

Crystal data

C22H26N4O3S

M = 426.53

Monoclinic,

a = 10.8672 (8) Å

b = 14.0435 (10) Å

c = 14.3584 (10) Å

β = 104.302 (4)°

V = 2123.4 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.18 mm−1

T = 99 K

0.26 × 0.26 × 0.24 mm

Data collection

Siemens SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick 2003 ▶) T min = 0.633, T max = 0.746

25355 measured reflections

4980 independent reflections

4185 reflections with I > 2σ(I)

R int = 0.062

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.122

S = 1.11

4980 reflections

281 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.34 e Å−3

Δρmin = −0.49 e Å−3

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: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814012045/nr2051sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814012045/nr2051Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814012045/nr2051Isup3.mol

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814012045/nr2051Isup4.cml

CCDC reference: 1004998

Additional supporting information: crystallographic information; 3D view; checkCIF report

C22H26N4O3S	F(000) = 904
Mr = 426.53	Dx = 1.334 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9478 reflections
a = 10.8672 (8) Å	θ = 2–27°
b = 14.0435 (10) Å	µ = 0.18 mm−1
c = 14.3584 (10) Å	T = 99 K
β = 104.302 (4)°	Block, colourless
V = 2123.4 (3) Å3	0.26 × 0.26 × 0.24 mm
Z = 4

Siemens SMART CCD diffractometer	4980 independent reflections
Radiation source: fine-focus sealed tube	4185 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.062
Detector resolution: 512 pixels mm-1	θmax = 27.8°, θmin = 2.1°
φ and ω scans	h = −14→14
Absorption correction: multi-scan (SADABS; Sheldrick 2003)	k = −18→17
Tmin = 0.633, Tmax = 0.746	l = −18→18
25355 measured reflections

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: mixed
wR(F2) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ2(Fo2) + (0.0614P)2 + 0.5899P] where P = (Fo2 + 2Fc2)/3
4980 reflections	(Δ/σ)max = 0.002
281 parameters	Δρmax = 0.34 e Å−3
0 restraints	Δρmin = −0.49 e Å−3

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. Four low-angle reflections for which Fc differed from Fo by more than 10 σ were omitted from the refinement.

	x	y	z	Uiso*/Ueq
C1	0.83554 (15)	0.58407 (11)	0.46768 (11)	0.0211 (3)
H1	0.8767	0.5476	0.5222	0.025*
C2	0.84984 (16)	0.68239 (11)	0.46701 (11)	0.0245 (3)
H2	0.9005	0.7138	0.5218	0.029*
C3	0.79021 (16)	0.73473 (11)	0.38641 (11)	0.0228 (3)
H3	0.8022	0.8017	0.3859	0.027*
C4	0.71306 (15)	0.69017 (11)	0.30635 (11)	0.0210 (3)
H4	0.6717	0.7268	0.2520	0.025*
C5	0.69679 (14)	0.59246 (10)	0.30602 (10)	0.0181 (3)
H5	0.6439	0.5615	0.2519	0.022*
C6	0.75948 (14)	0.54000 (10)	0.38658 (10)	0.0162 (3)
C7	0.61260 (13)	0.32615 (10)	0.56998 (10)	0.0157 (3)
C8	0.60209 (14)	0.23025 (10)	0.52353 (10)	0.0176 (3)
H8A	0.6358	0.1815	0.5731	0.021*
H8B	0.6547	0.2290	0.4763	0.021*
C9	0.46369 (15)	0.20498 (12)	0.47215 (11)	0.0232 (3)
H9A	0.4177	0.1850	0.5204	0.028*
H9B	0.4208	0.2622	0.4389	0.028*
C10	0.45813 (16)	0.12465 (11)	0.39871 (11)	0.0232 (3)
H10A	0.5215	0.0754	0.4272	0.028*
H10B	0.3731	0.0947	0.3852	0.028*
C11	0.48371 (17)	0.15861 (12)	0.30424 (11)	0.0263 (4)
H11A	0.5695	0.1873	0.3175	0.032*
H11B	0.4214	0.2087	0.2763	0.032*
C12	0.47532 (18)	0.07856 (12)	0.23097 (12)	0.0301 (4)
H12A	0.5398	0.0302	0.2568	0.045*
H12B	0.4900	0.1045	0.1713	0.045*
H12C	0.3908	0.0495	0.2177	0.045*
C13	0.61852 (13)	0.43759 (10)	0.70637 (10)	0.0160 (3)
C14	0.61630 (14)	0.34310 (10)	0.66620 (10)	0.0162 (3)
C15	0.61461 (15)	0.27967 (11)	0.74490 (10)	0.0195 (3)
C16	0.60908 (19)	0.17333 (11)	0.74752 (12)	0.0300 (4)
H16A	0.5975	0.1527	0.8100	0.045*
H16B	0.6884	0.1468	0.7379	0.045*
H16C	0.5377	0.1508	0.6964	0.045*
C17	0.62532 (14)	0.49222 (10)	0.87539 (10)	0.0165 (3)
C18	0.58753 (15)	0.58638 (11)	0.85585 (11)	0.0201 (3)
H18	0.5581	0.6075	0.7913	0.024*
C19	0.59322 (15)	0.64913 (11)	0.93165 (11)	0.0228 (3)
H19	0.5682	0.7136	0.9186	0.027*
C20	0.63510 (15)	0.61877 (12)	1.02633 (11)	0.0241 (3)
H20	0.6370	0.6618	1.0777	0.029*
C21	0.67404 (16)	0.52526 (12)	1.04537 (11)	0.0240 (3)
H21	0.7037	0.5045	1.1100	0.029*
C22	0.67002 (15)	0.46168 (11)	0.97043 (10)	0.0203 (3)
H22	0.6975	0.3978	0.9838	0.024*
N1	0.60894 (13)	0.39080 (9)	0.41610 (9)	0.0172 (3)
N2	0.61477 (13)	0.40250 (9)	0.51387 (8)	0.0180 (3)
N3	0.61865 (12)	0.42409 (8)	0.80069 (8)	0.0170 (3)
N4	0.61620 (13)	0.32701 (9)	0.82394 (9)	0.0207 (3)
O1	0.71266 (12)	0.38720 (8)	0.28385 (8)	0.0258 (3)
O2	0.84341 (11)	0.37306 (8)	0.45227 (8)	0.0273 (3)
O3	0.61915 (10)	0.51729 (7)	0.66509 (7)	0.0181 (2)
S	0.74133 (4)	0.41560 (2)	0.38252 (2)	0.01761 (12)
H1N	0.5412 (19)	0.4172 (13)	0.3810 (14)	0.025 (5)*
H2N	0.6204 (18)	0.4578 (14)	0.5389 (13)	0.024 (5)*

	U11	U22	U33	U12	U13	U23
C1	0.0238 (8)	0.0235 (8)	0.0156 (7)	−0.0012 (6)	0.0037 (6)	0.0003 (5)
C2	0.0313 (9)	0.0239 (8)	0.0180 (7)	−0.0065 (7)	0.0057 (6)	−0.0058 (6)
C3	0.0311 (9)	0.0171 (7)	0.0235 (7)	−0.0033 (6)	0.0129 (6)	−0.0021 (6)
C4	0.0222 (8)	0.0228 (8)	0.0195 (7)	0.0011 (6)	0.0079 (6)	0.0031 (6)
C5	0.0184 (7)	0.0212 (7)	0.0148 (7)	−0.0013 (6)	0.0042 (5)	−0.0017 (5)
C6	0.0173 (7)	0.0160 (7)	0.0169 (7)	−0.0005 (5)	0.0070 (5)	−0.0020 (5)
C7	0.0134 (7)	0.0159 (7)	0.0177 (7)	0.0009 (5)	0.0038 (5)	0.0010 (5)
C8	0.0194 (7)	0.0158 (7)	0.0181 (7)	0.0001 (6)	0.0054 (5)	−0.0003 (5)
C9	0.0192 (8)	0.0274 (8)	0.0252 (8)	−0.0048 (6)	0.0094 (6)	−0.0071 (6)
C10	0.0236 (8)	0.0229 (8)	0.0248 (8)	−0.0082 (6)	0.0094 (6)	−0.0058 (6)
C11	0.0322 (9)	0.0232 (8)	0.0245 (8)	−0.0063 (7)	0.0090 (7)	−0.0037 (6)
C12	0.0331 (10)	0.0316 (9)	0.0275 (9)	−0.0071 (7)	0.0114 (7)	−0.0083 (7)
C13	0.0140 (7)	0.0180 (7)	0.0151 (6)	0.0006 (5)	0.0021 (5)	0.0011 (5)
C14	0.0163 (7)	0.0152 (7)	0.0167 (7)	0.0001 (5)	0.0031 (5)	0.0017 (5)
C15	0.0236 (8)	0.0174 (7)	0.0173 (7)	0.0012 (6)	0.0045 (6)	0.0020 (5)
C16	0.0510 (11)	0.0168 (8)	0.0233 (8)	0.0008 (7)	0.0114 (7)	0.0034 (6)
C17	0.0144 (7)	0.0203 (7)	0.0154 (7)	−0.0016 (6)	0.0045 (5)	−0.0010 (5)
C18	0.0190 (7)	0.0218 (8)	0.0183 (7)	0.0003 (6)	0.0026 (6)	−0.0007 (5)
C19	0.0209 (8)	0.0204 (7)	0.0278 (8)	−0.0008 (6)	0.0074 (6)	−0.0042 (6)
C20	0.0236 (8)	0.0293 (8)	0.0219 (7)	−0.0054 (7)	0.0105 (6)	−0.0082 (6)
C21	0.0255 (8)	0.0320 (9)	0.0157 (7)	−0.0028 (7)	0.0071 (6)	−0.0022 (6)
C22	0.0212 (7)	0.0231 (7)	0.0173 (7)	0.0002 (6)	0.0061 (6)	0.0016 (6)
N1	0.0188 (6)	0.0196 (6)	0.0128 (6)	−0.0001 (5)	0.0032 (5)	0.0010 (5)
N2	0.0265 (7)	0.0147 (6)	0.0130 (6)	0.0005 (5)	0.0054 (5)	−0.0009 (4)
N3	0.0211 (6)	0.0147 (6)	0.0147 (6)	0.0007 (5)	0.0033 (5)	0.0015 (4)
N4	0.0279 (7)	0.0154 (6)	0.0186 (6)	0.0004 (5)	0.0051 (5)	0.0030 (5)
O1	0.0366 (7)	0.0224 (6)	0.0219 (6)	−0.0032 (5)	0.0138 (5)	−0.0074 (4)
O2	0.0231 (6)	0.0224 (6)	0.0346 (6)	0.0051 (5)	0.0040 (5)	0.0048 (5)
O3	0.0217 (5)	0.0153 (5)	0.0173 (5)	0.0003 (4)	0.0046 (4)	0.0026 (4)
S	0.0203 (2)	0.01548 (19)	0.0180 (2)	0.00128 (13)	0.00662 (14)	−0.00129 (12)

C1—C2	1.390 (2)	C12—H12C	0.9800
C1—C6	1.395 (2)	C13—O3	1.2672 (17)
C1—H1	0.9500	C13—N3	1.3672 (18)
C2—C3	1.389 (2)	C13—C14	1.4447 (19)
C2—H2	0.9500	C14—C15	1.4425 (19)
C3—C4	1.393 (2)	C15—N4	1.3118 (19)
C3—H3	0.9500	C15—C16	1.495 (2)
C4—C5	1.383 (2)	C16—H16A	0.9800
C4—H4	0.9500	C16—H16B	0.9800
C5—C6	1.398 (2)	C16—H16C	0.9800
C5—H5	0.9500	C17—C18	1.392 (2)
C6—S	1.7575 (15)	C17—C22	1.3981 (19)
C7—N2	1.3448 (18)	C17—N3	1.4258 (18)
C7—C14	1.3927 (19)	C18—C19	1.390 (2)
C7—C8	1.4947 (19)	C18—H18	0.9500
C8—C9	1.544 (2)	C19—C20	1.390 (2)
C8—H8A	0.9900	C19—H19	0.9500
C8—H8B	0.9900	C20—C21	1.386 (2)
C9—C10	1.535 (2)	C20—H20	0.9500
C9—H9A	0.9900	C21—C22	1.391 (2)
C9—H9B	0.9900	C21—H21	0.9500
C10—C11	1.527 (2)	C22—H22	0.9500
C10—H10A	0.9900	N1—N2	1.3992 (16)
C10—H10B	0.9900	N1—S	1.6632 (13)
C11—C12	1.527 (2)	N1—H1N	0.87 (2)
C11—H11A	0.9900	N2—H2N	0.85 (2)
C11—H11B	0.9900	N3—N4	1.4054 (17)
C12—H12A	0.9800	O1—S	1.4301 (11)
C12—H12B	0.9800	O2—S	1.4289 (12)
C2—C1—C6	118.63 (14)	H12B—C12—H12C	109.5
C2—C1—H1	120.7	O3—C13—N3	125.94 (13)
C6—C1—H1	120.7	O3—C13—C14	128.76 (13)
C1—C2—C3	120.11 (14)	N3—C13—C14	105.30 (12)
C1—C2—H2	119.9	C7—C14—C15	131.96 (13)
C3—C2—H2	119.9	C7—C14—C13	123.13 (13)
C2—C3—C4	120.78 (14)	C15—C14—C13	104.88 (12)
C2—C3—H3	119.6	N4—C15—C14	111.39 (13)
C4—C3—H3	119.6	N4—C15—C16	118.45 (13)
C5—C4—C3	119.92 (14)	C14—C15—C16	130.15 (13)
C5—C4—H4	120.0	C15—C16—H16A	109.5
C3—C4—H4	120.0	C15—C16—H16B	109.5
C4—C5—C6	118.95 (13)	H16A—C16—H16B	109.5
C4—C5—H5	120.5	C15—C16—H16C	109.5
C6—C5—H5	120.5	H16A—C16—H16C	109.5
C1—C6—C5	121.58 (14)	H16B—C16—H16C	109.5
C1—C6—S	120.47 (11)	C18—C17—C22	120.13 (13)
C5—C6—S	117.94 (11)	C18—C17—N3	121.88 (12)
N2—C7—C14	117.23 (13)	C22—C17—N3	117.98 (13)
N2—C7—C8	117.51 (12)	C19—C18—C17	119.38 (14)
C14—C7—C8	125.24 (13)	C19—C18—H18	120.3
C7—C8—C9	112.22 (12)	C17—C18—H18	120.3
C7—C8—H8A	109.2	C20—C19—C18	120.79 (15)
C9—C8—H8A	109.2	C20—C19—H19	119.6
C7—C8—H8B	109.2	C18—C19—H19	119.6
C9—C8—H8B	109.2	C21—C20—C19	119.60 (14)
H8A—C8—H8B	107.9	C21—C20—H20	120.2
C10—C9—C8	111.43 (13)	C19—C20—H20	120.2
C10—C9—H9A	109.3	C20—C21—C22	120.40 (14)
C8—C9—H9A	109.3	C20—C21—H21	119.8
C10—C9—H9B	109.3	C22—C21—H21	119.8
C8—C9—H9B	109.3	C21—C22—C17	119.68 (14)
H9A—C9—H9B	108.0	C21—C22—H22	120.2
C11—C10—C9	113.32 (13)	C17—C22—H22	120.2
C11—C10—H10A	108.9	N2—N1—S	115.99 (10)
C9—C10—H10A	108.9	N2—N1—H1N	110.8 (13)
C11—C10—H10B	108.9	S—N1—H1N	114.4 (13)
C9—C10—H10B	108.9	C7—N2—N1	120.28 (12)
H10A—C10—H10B	107.7	C7—N2—H2N	118.9 (12)
C10—C11—C12	112.91 (14)	N1—N2—H2N	120.8 (12)
C10—C11—H11A	109.0	C13—N3—N4	111.99 (11)
C12—C11—H11A	109.0	C13—N3—C17	129.76 (12)
C10—C11—H11B	109.0	N4—N3—C17	118.21 (11)
C12—C11—H11B	109.0	C15—N4—N3	106.44 (11)
H11A—C11—H11B	107.8	O2—S—O1	121.28 (7)
C11—C12—H12A	109.5	O2—S—N1	106.66 (7)
C11—C12—H12B	109.5	O1—S—N1	103.68 (7)
H12A—C12—H12B	109.5	O2—S—C6	109.33 (7)
C11—C12—H12C	109.5	O1—S—C6	107.77 (7)
H12A—C12—H12C	109.5	N1—S—C6	107.25 (7)
C6—C1—C2—C3	−0.7 (2)	C19—C20—C21—C22	−0.7 (2)
C1—C2—C3—C4	1.6 (2)	C20—C21—C22—C17	−0.6 (2)
C2—C3—C4—C5	−1.0 (2)	C18—C17—C22—C21	1.3 (2)
C3—C4—C5—C6	−0.5 (2)	N3—C17—C22—C21	−177.93 (14)
C2—C1—C6—C5	−0.8 (2)	C14—C7—N2—N1	−178.82 (13)
C2—C1—C6—S	178.44 (12)	C8—C7—N2—N1	−0.8 (2)
C4—C5—C6—C1	1.4 (2)	S—N1—N2—C7	−109.88 (13)
C4—C5—C6—S	−177.89 (11)	O3—C13—N3—N4	179.25 (13)
N2—C7—C8—C9	−81.70 (16)	C14—C13—N3—N4	−0.21 (16)
C14—C7—C8—C9	96.15 (17)	O3—C13—N3—C17	−3.2 (2)
C7—C8—C9—C10	161.28 (13)	C14—C13—N3—C17	177.32 (14)
C8—C9—C10—C11	−79.10 (17)	C18—C17—N3—C13	23.8 (2)
C9—C10—C11—C12	−178.84 (14)	C22—C17—N3—C13	−156.90 (15)
N2—C7—C14—C15	179.53 (15)	C18—C17—N3—N4	−158.75 (14)
C8—C7—C14—C15	1.7 (3)	C22—C17—N3—N4	20.50 (19)
N2—C7—C14—C13	1.9 (2)	C14—C15—N4—N3	0.16 (17)
C8—C7—C14—C13	−176.00 (13)	C16—C15—N4—N3	−178.74 (14)
O3—C13—C14—C7	−0.9 (2)	C13—N3—N4—C15	0.04 (17)
N3—C13—C14—C7	178.50 (13)	C17—N3—N4—C15	−177.81 (13)
O3—C13—C14—C15	−179.16 (14)	N2—N1—S—O2	44.46 (12)
N3—C13—C14—C15	0.29 (15)	N2—N1—S—O1	173.55 (10)
C7—C14—C15—N4	−178.27 (15)	N2—N1—S—C6	−72.59 (11)
C13—C14—C15—N4	−0.29 (17)	C1—C6—S—O2	−19.91 (14)
C7—C14—C15—C16	0.5 (3)	C5—C6—S—O2	159.37 (12)
C13—C14—C15—C16	178.45 (17)	C1—C6—S—O1	−153.56 (12)
C22—C17—C18—C19	−0.8 (2)	C5—C6—S—O1	25.72 (14)
N3—C17—C18—C19	178.44 (14)	C1—C6—S—N1	95.37 (13)
C17—C18—C19—C20	−0.5 (2)	C5—C6—S—N1	−85.35 (12)
C18—C19—C20—C21	1.3 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O3i	0.87 (2)	1.94 (2)	2.7823 (17)	165.0 (18)
N2—H2N···O3	0.85 (2)	1.998 (19)	2.6953 (16)	138.5 (17)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O3i	0.87 (2)	1.94 (2)	2.7823 (17)	165.0 (18)
N2—H2N⋯O3	0.85 (2)	1.998 (19)	2.6953 (16)	138.5 (17)

Symmetry code: (i) .