3-(4-Chloro-phen-yl)-5-(4-eth-oxy-phen-yl)-4,5-dihydro-1H-pyrazole-1-carbothio-amide ethanol monosolvate.

The asymmetric unit of the title compound, C18H18ClN3OS·C2H5OH, comprises a pyrazoline derivative and an ethanol solvent mol-ecule. In the mol-ecule of the pyrazoline derivative, the pyrazole ring adopts an envelope conformation with the C atom bearing the eth-oxy-phenyl substituent as the flap. The dihedral angle between the benzene rings is 74.22 (7)°. The eth-oxy group is coplanar with the attached benzene ring [C-O-C-Cmeth-yl = 175.50 (11)° and r.m.s. deviation = 0.0459 (1) Å for the nine non-H atoms]. In the crystal, the pyrazoline mol-ecules are linked by N-H⋯Oeth-oxy hydrogen bonds into chains along the c axis and are further linked with the solvent ethanol mol-ecules by N-H⋯Oethanol and Oethanol-H⋯S hydrogen bonds. C-H⋯π inter-actions are also present.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For ring conformational analysis, see: Cremer & Pople (1975 ▶). For related structures, see: Chantrapromma et al. (2012 ▶); Nonthason et al. (2011 ▶). For background to and applications of pyrazoline derivatives, see: Bilgin et al. (1992 ▶, 1993 ▶, 1994 ▶); Gokhan et al. (2003 ▶); Ruhoglu et al. (2005 ▶); Zhang et al. (2000 ▶). For the fluorescent properties and anti­oxidant activity of pyrazoline derivatives by DPPH scavenging, see: Molyneux (2004 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C18H18ClN3OS·C2H6O

M = 405.94

Monoclinic,

a = 9.3145 (4) Å

b = 25.3673 (12) Å

c = 9.5565 (5) Å

β = 115.082 (1)°

V = 2045.12 (17) Å3

Z = 4

Mo Kα radiation

μ = 0.31 mm−1

T = 100 K

0.49 × 0.24 × 0.24 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.864, T max = 0.929

17996 measured reflections

3514 independent reflections

3228 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.027

wR(F 2) = 0.071

S = 1.06

3514 reflections

258 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.29 e Å−3

Δρmin = −0.21 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PLATON (Spek, 2009 ▶) and publCIF (Westrip, 2010 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813005369/rz5045sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813005369/rz5045Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813005369/rz5045Isup3.cml

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

C18H18ClN3OS·C2H6O	F(000) = 856
Mr = 405.94	Dx = 1.318 Mg m−3
Monoclinic, P21/c	Melting point = 406–407 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 9.3145 (4) Å	Cell parameters from 3514 reflections
b = 25.3673 (12) Å	θ = 1.6–25.0°
c = 9.5565 (5) Å	µ = 0.31 mm−1
β = 115.082 (1)°	T = 100 K
V = 2045.12 (17) Å3	Block, pale yellow
Z = 4	0.49 × 0.24 × 0.24 mm

Bruker APEXII CCD area-detector diffractometer	3514 independent reflections
Radiation source: sealed tube	3228 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
φ and ω scans	θmax = 25.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −11→10
Tmin = 0.864, Tmax = 0.929	k = −30→30
17996 measured reflections	l = −11→11

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.071	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0305P)2 + 1.0598P] where P = (Fo2 + 2Fc2)/3
3514 reflections	(Δ/σ)max = 0.001
258 parameters	Δρmax = 0.29 e Å−3
0 restraints	Δρmin = −0.21 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 120.0 (1) K.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Cl1	−0.11105 (4)	0.286557 (14)	−0.62261 (5)	0.03191 (12)
S2	0.90677 (4)	0.091862 (13)	0.20892 (4)	0.01689 (10)
O1	0.45072 (11)	0.07649 (4)	0.58383 (11)	0.0186 (2)
O2	0.89420 (12)	0.00951 (4)	0.81489 (12)	0.0234 (2)
N1	0.51075 (13)	0.15074 (4)	−0.10757 (13)	0.0156 (2)
N2	0.63750 (13)	0.13984 (4)	0.03376 (12)	0.0153 (2)
N3	0.70567 (15)	0.07278 (5)	−0.08430 (14)	0.0188 (3)
C1	0.22275 (15)	0.18609 (5)	−0.35513 (16)	0.0170 (3)
H1A	0.2529	0.1506	−0.3600	0.020*
C2	0.09364 (16)	0.20717 (5)	−0.47764 (16)	0.0191 (3)
H2A	0.0343	0.1864	−0.5663	0.023*
C3	0.05218 (16)	0.25928 (6)	−0.46868 (16)	0.0198 (3)
C4	0.13604 (16)	0.29046 (5)	−0.34122 (17)	0.0194 (3)
H4A	0.1060	0.3260	−0.3377	0.023*
C5	0.26506 (16)	0.26870 (5)	−0.21847 (16)	0.0167 (3)
H5A	0.3235	0.2896	−0.1300	0.020*
C6	0.30981 (15)	0.21648 (5)	−0.22366 (15)	0.0152 (3)
C7	0.44749 (15)	0.19435 (5)	−0.09361 (15)	0.0145 (3)
C8	0.53006 (16)	0.21960 (5)	0.06381 (15)	0.0166 (3)
H8A	0.4538	0.2289	0.1071	0.020*
H8B	0.5888	0.2516	0.0595	0.020*
C9	0.64433 (15)	0.17545 (5)	0.15886 (15)	0.0150 (3)
H9A	0.7540	0.1898	0.2160	0.018*
C10	0.59077 (15)	0.14822 (5)	0.26960 (15)	0.0144 (3)
C11	0.66466 (15)	0.15890 (5)	0.42750 (15)	0.0157 (3)
H11A	0.7516	0.1827	0.4662	0.019*
C12	0.61322 (15)	0.13533 (5)	0.52878 (15)	0.0163 (3)
H12A	0.6637	0.1434	0.6358	0.020*
C13	0.48746 (15)	0.09970 (5)	0.47389 (15)	0.0149 (3)
C14	0.41061 (16)	0.08924 (5)	0.31602 (16)	0.0183 (3)
H14A	0.3231	0.0657	0.2770	0.022*
C15	0.46348 (16)	0.11366 (5)	0.21675 (15)	0.0182 (3)
H15A	0.4109	0.1065	0.1092	0.022*
C16	0.32760 (16)	0.03716 (6)	0.53447 (16)	0.0204 (3)
H16A	0.3520	0.0088	0.4768	0.024*
H16B	0.2245	0.0531	0.4663	0.024*
C17	0.32115 (19)	0.01539 (6)	0.67807 (19)	0.0280 (3)
H17A	0.2386	−0.0117	0.6495	0.042*
H17B	0.2967	0.0439	0.7338	0.042*
H17C	0.4239	−0.0002	0.7445	0.042*
C18	0.74149 (15)	0.10126 (5)	0.04269 (15)	0.0149 (3)
C19	1.0976 (2)	0.07701 (7)	0.8804 (2)	0.0324 (4)
H19A	1.1349	0.1057	0.8353	0.049*
H19B	1.1843	0.0520	0.9323	0.049*
H19C	1.0623	0.0916	0.9555	0.049*
C20	0.96096 (18)	0.04889 (6)	0.75385 (18)	0.0272 (3)
H20A	0.8781	0.0749	0.6948	0.033*
H20B	0.9987	0.0322	0.6818	0.033*
H2N3	0.620 (2)	0.0803 (7)	−0.168 (2)	0.025 (4)*
H1N3	0.772 (2)	0.0504 (7)	−0.0899 (19)	0.023 (4)*
H1O2	0.957 (2)	−0.0164 (8)	0.835 (2)	0.044 (6)*

	U11	U22	U33	U12	U13	U23
Cl1	0.0265 (2)	0.02200 (19)	0.0290 (2)	0.00534 (14)	−0.00589 (16)	0.00216 (15)
S2	0.01535 (17)	0.01703 (18)	0.01616 (18)	0.00211 (12)	0.00463 (14)	0.00103 (12)
O1	0.0217 (5)	0.0193 (5)	0.0151 (5)	−0.0045 (4)	0.0081 (4)	0.0002 (4)
O2	0.0202 (5)	0.0218 (5)	0.0279 (6)	0.0030 (4)	0.0099 (4)	−0.0036 (4)
N1	0.0148 (5)	0.0188 (6)	0.0127 (5)	0.0017 (4)	0.0052 (5)	0.0019 (4)
N2	0.0162 (5)	0.0172 (6)	0.0110 (5)	0.0035 (4)	0.0043 (5)	0.0007 (4)
N3	0.0180 (6)	0.0205 (6)	0.0165 (6)	0.0054 (5)	0.0059 (5)	−0.0017 (5)
C1	0.0186 (7)	0.0153 (6)	0.0190 (7)	0.0011 (5)	0.0099 (6)	0.0002 (5)
C2	0.0187 (7)	0.0199 (7)	0.0169 (7)	−0.0014 (5)	0.0058 (6)	−0.0016 (5)
C3	0.0155 (6)	0.0207 (7)	0.0194 (7)	0.0020 (5)	0.0039 (6)	0.0044 (6)
C4	0.0197 (7)	0.0150 (7)	0.0232 (7)	0.0028 (5)	0.0090 (6)	0.0012 (5)
C5	0.0176 (6)	0.0176 (7)	0.0160 (7)	−0.0005 (5)	0.0080 (6)	−0.0010 (5)
C6	0.0146 (6)	0.0178 (7)	0.0159 (7)	0.0002 (5)	0.0090 (6)	0.0024 (5)
C7	0.0165 (6)	0.0151 (6)	0.0146 (7)	−0.0005 (5)	0.0093 (5)	0.0011 (5)
C8	0.0202 (7)	0.0150 (6)	0.0144 (7)	0.0018 (5)	0.0073 (6)	0.0010 (5)
C9	0.0167 (6)	0.0150 (6)	0.0138 (6)	0.0003 (5)	0.0069 (5)	−0.0011 (5)
C10	0.0154 (6)	0.0128 (6)	0.0145 (6)	0.0036 (5)	0.0057 (5)	0.0008 (5)
C11	0.0141 (6)	0.0142 (6)	0.0167 (7)	−0.0004 (5)	0.0045 (5)	−0.0009 (5)
C12	0.0182 (6)	0.0165 (6)	0.0115 (6)	0.0012 (5)	0.0038 (5)	−0.0006 (5)
C13	0.0174 (6)	0.0139 (6)	0.0147 (7)	0.0032 (5)	0.0083 (5)	0.0023 (5)
C14	0.0170 (7)	0.0189 (7)	0.0171 (7)	−0.0039 (5)	0.0053 (6)	−0.0018 (5)
C15	0.0190 (7)	0.0216 (7)	0.0114 (6)	−0.0016 (5)	0.0038 (6)	−0.0016 (5)
C16	0.0197 (7)	0.0195 (7)	0.0232 (7)	−0.0039 (5)	0.0103 (6)	−0.0007 (6)
C17	0.0324 (8)	0.0263 (8)	0.0321 (9)	−0.0050 (6)	0.0203 (7)	0.0027 (6)
C18	0.0161 (6)	0.0145 (6)	0.0167 (7)	−0.0010 (5)	0.0096 (6)	0.0019 (5)
C19	0.0400 (9)	0.0287 (8)	0.0365 (9)	−0.0080 (7)	0.0240 (8)	−0.0059 (7)
C20	0.0263 (8)	0.0299 (8)	0.0259 (8)	0.0076 (6)	0.0116 (7)	0.0047 (6)

Cl1—C3	1.7488 (14)	C8—H8A	0.9900
S2—C18	1.6962 (13)	C8—H8B	0.9900
O1—C13	1.3685 (16)	C9—C10	1.5145 (19)
O1—C16	1.4402 (16)	C9—H9A	1.0000
O2—C20	1.4256 (19)	C10—C15	1.3863 (19)
O2—H1O2	0.85 (2)	C10—C11	1.3941 (19)
N1—C7	1.2866 (18)	C11—C12	1.385 (2)
N1—N2	1.3938 (15)	C11—H11A	0.9500
N2—C18	1.3539 (17)	C12—C13	1.3939 (19)
N2—C9	1.4782 (17)	C12—H12A	0.9500
N3—C18	1.3276 (18)	C13—C14	1.3941 (19)
N3—H2N3	0.879 (19)	C14—C15	1.387 (2)
N3—H1N3	0.856 (18)	C14—H14A	0.9500
C1—C2	1.3817 (19)	C15—H15A	0.9500
C1—C6	1.4024 (19)	C16—C17	1.504 (2)
C1—H1A	0.9500	C16—H16A	0.9900
C2—C3	1.390 (2)	C16—H16B	0.9900
C2—H2A	0.9500	C17—H17A	0.9800
C3—C4	1.383 (2)	C17—H17B	0.9800
C4—C5	1.3892 (19)	C17—H17C	0.9800
C4—H4A	0.9500	C19—C20	1.512 (2)
C5—C6	1.3958 (19)	C19—H19A	0.9800
C5—H5A	0.9500	C19—H19B	0.9800
C6—C7	1.4673 (18)	C19—H19C	0.9800
C7—C8	1.5112 (18)	C20—H20A	0.9900
C8—C9	1.5468 (18)	C20—H20B	0.9900
C13—O1—C16	118.05 (10)	C11—C10—C9	120.66 (12)
C20—O2—H1O2	104.9 (14)	C12—C11—C10	120.95 (12)
C7—N1—N2	107.89 (11)	C12—C11—H11A	119.5
C18—N2—N1	119.61 (11)	C10—C11—H11A	119.5
C18—N2—C9	127.33 (11)	C11—C12—C13	120.10 (12)
N1—N2—C9	113.00 (10)	C11—C12—H12A	119.9
C18—N3—H2N3	119.5 (11)	C13—C12—H12A	119.9
C18—N3—H1N3	120.6 (11)	O1—C13—C12	115.71 (11)
H2N3—N3—H1N3	119.2 (16)	O1—C13—C14	124.62 (12)
C2—C1—C6	120.76 (12)	C12—C13—C14	119.66 (12)
C2—C1—H1A	119.6	C15—C14—C13	119.14 (12)
C6—C1—H1A	119.6	C15—C14—H14A	120.4
C1—C2—C3	118.72 (13)	C13—C14—H14A	120.4
C1—C2—H2A	120.6	C10—C15—C14	122.03 (12)
C3—C2—H2A	120.6	C10—C15—H15A	119.0
C4—C3—C2	122.02 (13)	C14—C15—H15A	119.0
C4—C3—Cl1	118.66 (11)	O1—C16—C17	106.85 (11)
C2—C3—Cl1	119.32 (11)	O1—C16—H16A	110.4
C3—C4—C5	118.68 (13)	C17—C16—H16A	110.4
C3—C4—H4A	120.7	O1—C16—H16B	110.4
C5—C4—H4A	120.7	C17—C16—H16B	110.4
C4—C5—C6	120.77 (13)	H16A—C16—H16B	108.6
C4—C5—H5A	119.6	C16—C17—H17A	109.5
C6—C5—H5A	119.6	C16—C17—H17B	109.5
C5—C6—C1	119.05 (12)	H17A—C17—H17B	109.5
C5—C6—C7	119.99 (12)	C16—C17—H17C	109.5
C1—C6—C7	120.95 (12)	H17A—C17—H17C	109.5
N1—C7—C6	121.02 (12)	H17B—C17—H17C	109.5
N1—C7—C8	113.92 (11)	N3—C18—N2	116.09 (12)
C6—C7—C8	125.05 (11)	N3—C18—S2	123.80 (11)
C7—C8—C9	102.17 (10)	N2—C18—S2	120.11 (10)
C7—C8—H8A	111.3	C20—C19—H19A	109.5
C9—C8—H8A	111.3	C20—C19—H19B	109.5
C7—C8—H8B	111.3	H19A—C19—H19B	109.5
C9—C8—H8B	111.3	C20—C19—H19C	109.5
H8A—C8—H8B	109.2	H19A—C19—H19C	109.5
N2—C9—C10	111.87 (10)	H19B—C19—H19C	109.5
N2—C9—C8	100.63 (10)	O2—C20—C19	111.65 (13)
C10—C9—C8	113.08 (11)	O2—C20—H20A	109.3
N2—C9—H9A	110.3	C19—C20—H20A	109.3
C10—C9—H9A	110.3	O2—C20—H20B	109.3
C8—C9—H9A	110.3	C19—C20—H20B	109.3
C15—C10—C11	118.09 (12)	H20A—C20—H20B	108.0
C15—C10—C9	121.20 (12)
C7—N1—N2—C18	−168.23 (12)	C7—C8—C9—N2	13.98 (12)
C7—N1—N2—C9	9.16 (14)	C7—C8—C9—C10	−105.49 (12)
C6—C1—C2—C3	0.5 (2)	N2—C9—C10—C15	−39.66 (16)
C1—C2—C3—C4	0.0 (2)	C8—C9—C10—C15	73.12 (15)
C1—C2—C3—Cl1	−179.93 (11)	N2—C9—C10—C11	142.87 (12)
C2—C3—C4—C5	−0.3 (2)	C8—C9—C10—C11	−104.34 (14)
Cl1—C3—C4—C5	179.57 (11)	C15—C10—C11—C12	0.53 (19)
C3—C4—C5—C6	0.3 (2)	C9—C10—C11—C12	178.07 (12)
C4—C5—C6—C1	0.1 (2)	C10—C11—C12—C13	1.0 (2)
C4—C5—C6—C7	179.33 (12)	C16—O1—C13—C12	−176.59 (11)
C2—C1—C6—C5	−0.5 (2)	C16—O1—C13—C14	2.15 (19)
C2—C1—C6—C7	−179.69 (12)	C11—C12—C13—O1	176.78 (11)
N2—N1—C7—C6	−179.82 (11)	C11—C12—C13—C14	−2.0 (2)
N2—N1—C7—C8	1.51 (15)	O1—C13—C14—C15	−177.19 (12)
C5—C6—C7—N1	−165.56 (13)	C12—C13—C14—C15	1.5 (2)
C1—C6—C7—N1	13.6 (2)	C11—C10—C15—C14	−1.1 (2)
C5—C6—C7—C8	13.0 (2)	C9—C10—C15—C14	−178.60 (12)
C1—C6—C7—C8	−167.88 (13)	C13—C14—C15—C10	0.1 (2)
N1—C7—C8—C9	−10.54 (15)	C13—O1—C16—C17	175.50 (11)
C6—C7—C8—C9	170.85 (12)	N1—N2—C18—N3	−6.07 (18)
C18—N2—C9—C10	−77.42 (16)	C9—N2—C18—N3	176.96 (12)
N1—N2—C9—C10	105.44 (12)	N1—N2—C18—S2	173.50 (9)
C18—N2—C9—C8	162.24 (12)	C9—N2—C18—S2	−3.47 (18)
N1—N2—C9—C8	−14.90 (13)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H2N3···O1i	0.879 (18)	2.225 (18)	3.0531 (16)	157.1 (17)
N3—H1N3···O2i	0.857 (19)	2.019 (19)	2.8324 (18)	158.0 (16)
O2—H1O2···S2ii	0.85 (2)	2.43 (2)	3.2340 (12)	159.1 (16)
C5—H5A···Cg2iii	0.95	2.96	3.5701 (15)	123
C8—H8A···Cg1iv	0.99	2.89	3.8543 (17)	165

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C1–C6 and C10–C15 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H2N3⋯O1i	0.879 (18)	2.225 (18)	3.0531 (16)	157.1 (17)
N3—H1N3⋯O2i	0.857 (19)	2.019 (19)	2.8324 (18)	158.0 (16)
O2—H1O2⋯S2ii	0.85 (2)	2.43 (2)	3.2340 (12)	159.1 (16)
C5—H5A⋯Cg2iii	0.95	2.96	3.5701 (15)	123
C8—H8A⋯Cg1iv	0.99	2.89	3.8543 (17)	165

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .