3-(4-Amino-phen-yl)-5-(4-meth-oxy-phen-yl)-4,5-di-hydro-1H-pyrazole-1-carbo-thio-amide.

In the mol-ecule of title pyrazoline derivative, C17H18N4OS, the pyrazole ring adopts an envelope conformation with the flap atom, which bears the meth-oxy-phenyl substituent, displaced by 0.0750 (12) Å from the plane through the other ring atoms. The two substituted benzene rings make a dihedral angle of 70.59 (6)°. The meth-oxy group is twisted slightly with respect to the attached benzene ring [Cmeth-yl-O-C-C torsion angle = -8.84 (15)°]. An intra-molecular N-H⋯N hydrogen bond occurs. In the crystal, the pyrazoline mol-ecules are linked by N-H⋯O and N-H⋯S hydrogen bonds into zigzag layers parallel to the bc plane and stacked along the a axis by π-π inter-actions with centroid-centroid distances of 3.4690 (7) and 3.5792 (7) Å. C-H⋯π inter-actions are also present.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶). For related structures, see: Fun et al. (2011 ▶); Quah et al. (2013 ▶). For background to and applications of pyrazoline derivatives, see: Gong et al. (2010 ▶); Husain et al. (2008 ▶); Khode et al. (2009 ▶); Lv et al. (2011 ▶); Sakthinathan et al. (2012 ▶); Shaharyar et al. (2010 ▶); Shoman et al. (2009 ▶). For the stability of the temperature controller, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C17H18N4OS

M = 326.42

Monoclinic,

a = 8.0052 (2) Å

b = 17.3439 (5) Å

c = 12.4588 (3) Å

β = 114.789 (1)°

V = 1570.41 (7) Å3

Z = 4

Mo Kα radiation

μ = 0.22 mm−1

T = 100 K

0.57 × 0.39 × 0.29 mm

Data collection

Bruker APEXII CCD area detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.886, T max = 0.940

23819 measured reflections

4571 independent reflections

4045 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.104

S = 1.05

4571 reflections

225 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.43 e Å−3

Δρmin = −0.26 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813018096/rz5075sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813018096/rz5075Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813018096/rz5075Isup3.cml

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

C17H18N4OS	F(000) = 688
Mr = 326.42	Dx = 1.381 Mg m−3
Monoclinic, P21/c	Melting point = 479–480 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.0052 (2) Å	Cell parameters from 4571 reflections
b = 17.3439 (5) Å	θ = 2.2–30.0°
c = 12.4588 (3) Å	µ = 0.22 mm−1
β = 114.789 (1)°	T = 100 K
V = 1570.41 (7) Å3	Block, brown
Z = 4	0.57 × 0.39 × 0.29 mm

Bruker APEXII CCD area detector diffractometer	4571 independent reflections
Radiation source: sealed tube	4045 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
φ and ω scans	θmax = 30.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −11→11
Tmin = 0.886, Tmax = 0.940	k = −24→22
23819 measured reflections	l = −17→17

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.104	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0561P)2 + 0.5572P] where P = (Fo2 + 2Fc2)/3
4571 reflections	(Δ/σ)max = 0.002
225 parameters	Δρmax = 0.43 e Å−3
0 restraints	Δρmin = −0.26 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 100.0 (1) K.

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. 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	0.96189 (4)	0.737361 (16)	0.23440 (3)	0.02103 (9)
O1	0.20880 (12)	0.50083 (5)	0.02032 (7)	0.02307 (18)
N1	0.56007 (13)	0.88586 (5)	0.17966 (8)	0.01819 (18)
N2	0.65454 (13)	0.82048 (5)	0.16720 (8)	0.01788 (18)
N3	−0.00793 (15)	1.16984 (6)	−0.00281 (10)	0.0223 (2)
N4	0.88104 (15)	0.85193 (6)	0.34723 (9)	0.0236 (2)
C1	0.20776 (14)	0.99640 (6)	−0.05879 (10)	0.0176 (2)
H1A	0.2020	0.9666	−0.1242	0.021*
C2	0.10060 (15)	1.06212 (6)	−0.07863 (10)	0.0183 (2)
H2A	0.0237	1.0772	−0.1573	0.022*
C3	0.10467 (15)	1.10666 (6)	0.01667 (10)	0.0181 (2)
C4	0.22393 (15)	1.08391 (6)	0.13240 (10)	0.0191 (2)
H4A	0.2304	1.1138	0.1979	0.023*
C5	0.33141 (15)	1.01856 (6)	0.15128 (10)	0.0182 (2)
H5A	0.4112	1.0042	0.2298	0.022*
C6	0.32452 (14)	0.97303 (6)	0.05611 (10)	0.0168 (2)
C7	0.43893 (14)	0.90464 (6)	0.07541 (9)	0.0165 (2)
C8	0.43688 (14)	0.85248 (6)	−0.02203 (9)	0.0169 (2)
H8A	0.4806	0.8799	−0.0751	0.020*
H8B	0.3119	0.8319	−0.0693	0.020*
C9	0.57125 (14)	0.78746 (6)	0.04662 (9)	0.0167 (2)
H9A	0.6676	0.7810	0.0160	0.020*
C10	0.47626 (14)	0.71095 (6)	0.04153 (9)	0.0163 (2)
C11	0.41276 (16)	0.68894 (7)	0.12532 (10)	0.0202 (2)
H11A	0.4310	0.7222	0.1898	0.024*
C12	0.32283 (16)	0.61881 (7)	0.11590 (10)	0.0211 (2)
H12A	0.2805	0.6045	0.1739	0.025*
C13	0.29479 (14)	0.56940 (6)	0.02121 (10)	0.0180 (2)
C14	0.35358 (16)	0.59149 (6)	−0.06472 (10)	0.0202 (2)
H14A	0.3321	0.5590	−0.1306	0.024*
C15	0.44439 (16)	0.66176 (6)	−0.05325 (10)	0.0199 (2)
H15A	0.4855	0.6764	−0.1116	0.024*
C16	0.82554 (15)	0.80698 (6)	0.25017 (10)	0.0185 (2)
C17	0.15491 (17)	0.45460 (7)	−0.08438 (11)	0.0252 (2)
H17A	0.0945	0.4075	−0.0751	0.038*
H17B	0.2641	0.4408	−0.0970	0.038*
H17C	0.0694	0.4839	−0.1526	0.038*
H1N3	−0.039 (2)	1.1943 (10)	−0.0690 (15)	0.030 (4)*
H2N3	0.007 (3)	1.1952 (11)	0.0576 (17)	0.038 (5)*
H1N4	0.992 (3)	0.8465 (11)	0.3959 (17)	0.041 (5)*
H2N4	0.810 (2)	0.8906 (10)	0.3477 (14)	0.031 (4)*

	U11	U22	U33	U12	U13	U23
S1	0.01945 (14)	0.01830 (14)	0.02342 (15)	0.00144 (9)	0.00711 (11)	0.00405 (10)
O1	0.0271 (4)	0.0168 (4)	0.0234 (4)	−0.0078 (3)	0.0088 (3)	−0.0032 (3)
N1	0.0184 (4)	0.0153 (4)	0.0204 (4)	−0.0008 (3)	0.0076 (3)	−0.0010 (3)
N2	0.0175 (4)	0.0147 (4)	0.0187 (4)	−0.0008 (3)	0.0049 (3)	−0.0012 (3)
N3	0.0288 (5)	0.0160 (4)	0.0255 (5)	0.0033 (4)	0.0146 (4)	0.0015 (4)
N4	0.0210 (5)	0.0219 (5)	0.0208 (5)	−0.0010 (4)	0.0017 (4)	−0.0021 (4)
C1	0.0182 (5)	0.0154 (5)	0.0195 (5)	−0.0025 (4)	0.0083 (4)	−0.0013 (4)
C2	0.0189 (5)	0.0164 (5)	0.0197 (5)	−0.0019 (4)	0.0082 (4)	0.0008 (4)
C3	0.0185 (5)	0.0146 (4)	0.0241 (5)	−0.0023 (4)	0.0116 (4)	0.0004 (4)
C4	0.0211 (5)	0.0180 (5)	0.0210 (5)	−0.0026 (4)	0.0115 (4)	−0.0019 (4)
C5	0.0194 (5)	0.0178 (5)	0.0183 (5)	−0.0027 (4)	0.0087 (4)	0.0002 (4)
C6	0.0172 (4)	0.0143 (4)	0.0196 (5)	−0.0024 (4)	0.0086 (4)	−0.0006 (4)
C7	0.0164 (4)	0.0149 (4)	0.0192 (5)	−0.0031 (3)	0.0086 (4)	0.0000 (4)
C8	0.0177 (4)	0.0142 (4)	0.0181 (5)	−0.0009 (3)	0.0068 (4)	−0.0001 (4)
C9	0.0163 (4)	0.0156 (4)	0.0173 (5)	−0.0016 (3)	0.0060 (4)	−0.0007 (4)
C10	0.0155 (4)	0.0139 (4)	0.0179 (5)	0.0002 (3)	0.0053 (4)	0.0003 (4)
C11	0.0228 (5)	0.0188 (5)	0.0190 (5)	−0.0045 (4)	0.0089 (4)	−0.0039 (4)
C12	0.0228 (5)	0.0223 (5)	0.0188 (5)	−0.0054 (4)	0.0094 (4)	−0.0014 (4)
C13	0.0161 (4)	0.0143 (4)	0.0204 (5)	−0.0009 (3)	0.0044 (4)	0.0004 (4)
C14	0.0239 (5)	0.0164 (5)	0.0205 (5)	−0.0010 (4)	0.0096 (4)	−0.0039 (4)
C15	0.0236 (5)	0.0171 (5)	0.0205 (5)	−0.0012 (4)	0.0108 (4)	−0.0009 (4)
C16	0.0184 (5)	0.0156 (5)	0.0192 (5)	−0.0031 (4)	0.0057 (4)	0.0028 (4)
C17	0.0284 (6)	0.0175 (5)	0.0245 (6)	−0.0053 (4)	0.0061 (5)	−0.0047 (4)

S1—C16	1.6935 (12)	C5—H5A	0.9500
O1—C13	1.3719 (13)	C6—C7	1.4557 (15)
O1—C17	1.4349 (14)	C7—C8	1.5086 (15)
N1—C7	1.2951 (14)	C8—C9	1.5457 (15)
N1—N2	1.4072 (13)	C8—H8A	0.9900
N2—C16	1.3456 (14)	C8—H8B	0.9900
N2—C9	1.4798 (14)	C9—C10	1.5173 (14)
N3—C3	1.3744 (14)	C9—H9A	1.0000
N3—H1N3	0.866 (18)	C10—C15	1.3910 (15)
N3—H2N3	0.836 (19)	C10—C11	1.3924 (15)
N4—C16	1.3479 (15)	C11—C12	1.3931 (15)
N4—H1N4	0.85 (2)	C11—H11A	0.9500
N4—H2N4	0.882 (18)	C12—C13	1.3980 (16)
C1—C2	1.3851 (15)	C12—H12A	0.9500
C1—C6	1.4018 (15)	C13—C14	1.3918 (16)
C1—H1A	0.9500	C14—C15	1.3953 (15)
C2—C3	1.4053 (15)	C14—H14A	0.9500
C2—H2A	0.9500	C15—H15A	0.9500
C3—C4	1.4113 (16)	C17—H17A	0.9800
C4—C5	1.3822 (15)	C17—H17B	0.9800
C4—H4A	0.9500	C17—H17C	0.9800
C5—C6	1.4063 (15)
C13—O1—C17	116.77 (9)	C9—C8—H8B	111.2
C7—N1—N2	107.65 (9)	H8A—C8—H8B	109.1
C16—N2—N1	118.43 (9)	N2—C9—C10	112.67 (9)
C16—N2—C9	126.36 (10)	N2—C9—C8	101.08 (8)
N1—N2—C9	112.93 (8)	C10—C9—C8	113.24 (8)
C3—N3—H1N3	117.7 (11)	N2—C9—H9A	109.8
C3—N3—H2N3	115.2 (13)	C10—C9—H9A	109.8
H1N3—N3—H2N3	118.3 (17)	C8—C9—H9A	109.8
C16—N4—H1N4	115.4 (13)	C15—C10—C11	118.26 (10)
C16—N4—H2N4	118.4 (11)	C15—C10—C9	118.83 (10)
H1N4—N4—H2N4	124.6 (16)	C11—C10—C9	122.86 (10)
C2—C1—C6	121.20 (10)	C10—C11—C12	120.97 (10)
C2—C1—H1A	119.4	C10—C11—H11A	119.5
C6—C1—H1A	119.4	C12—C11—H11A	119.5
C1—C2—C3	120.55 (10)	C11—C12—C13	120.05 (11)
C1—C2—H2A	119.7	C11—C12—H12A	120.0
C3—C2—H2A	119.7	C13—C12—H12A	120.0
N3—C3—C2	120.53 (10)	O1—C13—C14	124.25 (10)
N3—C3—C4	121.06 (10)	O1—C13—C12	116.15 (10)
C2—C3—C4	118.40 (10)	C14—C13—C12	119.60 (10)
C5—C4—C3	120.62 (10)	C13—C14—C15	119.43 (10)
C5—C4—H4A	119.7	C13—C14—H14A	120.3
C3—C4—H4A	119.7	C15—C14—H14A	120.3
C4—C5—C6	121.02 (10)	C10—C15—C14	121.67 (10)
C4—C5—H5A	119.5	C10—C15—H15A	119.2
C6—C5—H5A	119.5	C14—C15—H15A	119.2
C1—C6—C5	118.19 (10)	N2—C16—N4	115.79 (10)
C1—C6—C7	120.55 (10)	N2—C16—S1	122.17 (9)
C5—C6—C7	121.24 (10)	N4—C16—S1	122.03 (9)
N1—C7—C6	121.70 (10)	O1—C17—H17A	109.5
N1—C7—C8	114.02 (9)	O1—C17—H17B	109.5
C6—C7—C8	124.19 (9)	H17A—C17—H17B	109.5
C7—C8—C9	102.83 (8)	O1—C17—H17C	109.5
C7—C8—H8A	111.2	H17A—C17—H17C	109.5
C9—C8—H8A	111.2	H17B—C17—H17C	109.5
C7—C8—H8B	111.2
C7—N1—N2—C16	155.52 (10)	N1—N2—C9—C8	12.22 (11)
C7—N1—N2—C9	−8.44 (12)	C7—C8—C9—N2	−10.76 (10)
C6—C1—C2—C3	−0.83 (16)	C7—C8—C9—C10	110.01 (9)
C1—C2—C3—N3	−176.99 (10)	N2—C9—C10—C15	−159.59 (10)
C1—C2—C3—C4	1.66 (16)	C8—C9—C10—C15	86.46 (12)
N3—C3—C4—C5	177.48 (10)	N2—C9—C10—C11	23.02 (14)
C2—C3—C4—C5	−1.17 (16)	C8—C9—C10—C11	−90.94 (12)
C3—C4—C5—C6	−0.18 (16)	C15—C10—C11—C12	1.24 (17)
C2—C1—C6—C5	−0.52 (16)	C9—C10—C11—C12	178.65 (10)
C2—C1—C6—C7	−178.81 (10)	C10—C11—C12—C13	−0.13 (17)
C4—C5—C6—C1	1.02 (16)	C17—O1—C13—C14	−8.84 (15)
C4—C5—C6—C7	179.30 (10)	C17—O1—C13—C12	171.16 (10)
N2—N1—C7—C6	−176.28 (9)	C11—C12—C13—O1	178.59 (10)
N2—N1—C7—C8	0.30 (12)	C11—C12—C13—C14	−1.41 (17)
C1—C6—C7—N1	173.53 (10)	O1—C13—C14—C15	−178.19 (10)
C5—C6—C7—N1	−4.71 (16)	C12—C13—C14—C15	1.81 (16)
C1—C6—C7—C8	−2.69 (16)	C11—C10—C15—C14	−0.84 (16)
C5—C6—C7—C8	179.07 (10)	C9—C10—C15—C14	−178.35 (10)
N1—C7—C8—C9	7.16 (12)	C13—C14—C15—C10	−0.69 (17)
C6—C7—C8—C9	−176.35 (9)	N1—N2—C16—N4	9.07 (15)
C16—N2—C9—C10	88.62 (13)	C9—N2—C16—N4	170.65 (10)
N1—N2—C9—C10	−108.95 (10)	N1—N2—C16—S1	−171.50 (8)
C16—N2—C9—C8	−150.21 (10)	C9—N2—C16—S1	−9.92 (16)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1N3···S1i	0.866 (17)	2.664 (17)	3.4559 (12)	152.5 (15)
N3—H2N3···S1ii	0.84 (2)	2.60 (2)	3.4142 (12)	164.2 (18)
N4—H2N4···N1	0.881 (17)	2.209 (16)	2.6093 (15)	107.2 (13)
N4—H2N4···O1ii	0.881 (17)	2.567 (17)	3.3022 (14)	141.5 (13)
C8—H8A···Cg2i	0.99	2.66	3.4159 (13)	133
C17—H17B···Cg3iii	0.98	2.94	3.8351 (15)	152

Table 1

Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H1N3⋯S1i	0.866 (17)	2.664 (17)	3.4559 (12)	152.5 (15)
N3—H2N3⋯S1ii	0.84 (2)	2.60 (2)	3.4142 (12)	164.2 (18)
N4—H2N4⋯N1	0.881 (17)	2.209 (16)	2.6093 (15)	107.2 (13)
N4—H2N4⋯O1ii	0.881 (17)	2.567 (17)	3.3022 (14)	141.5 (13)
C8—H8A⋯Cg2i	0.99	2.66	3.4159 (13)	133

Symmetry codes: (i) ; (ii) .