5-(4-Eth-oxy-phen-yl)-3-(pyridin-2-yl)-4,5-dihydro-1H-pyrazole-1-carbothio-amide.

In the title compound, C(17)H(18)N(4)OS, a pyrazoline derivative, the pyrazoline ring adopts an envelope conformation with the C atom bonded to the benzene ring as the flap atom. The dihedral angle between the pyridine and benzene rings is 80.50 (6)°. The eth-oxy-phenyl group is approximately planar, with an r.m.s. deviation of 0.0238 (1) Å for the nine non-H atoms. In the crystal, mol-ecules are linked by N-H⋯O and N-H⋯S hydrogen bonds into a tape along the b axis. Weak C-H⋯N and C-H⋯π inter-actions are also observed.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For related literature on ring conformations, see: Cremer & Pople (1975 ▶). For related structures, see: Fun et al. (2012 ▶); Nonthason et al. (2011 ▶). For background to and applications of pyrazoline derivatives, see: Amir et al. (2008 ▶); Gong et al. (2011 ▶); Husain et al. (2008 ▶); Manna & Agrawal (2009 ▶); Özdemir et al. (2007 ▶); Sarkar et al. (2010 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C17H18N4OS

M = 326.42

Monoclinic,

a = 13.4622 (1) Å

b = 9.4175 (1) Å

c = 13.3002 (2) Å

β = 103.146 (1)°

V = 1642.01 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.21 mm−1

T = 100 K

0.34 × 0.22 × 0.20 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.934, T max = 0.960

23465 measured reflections

4784 independent reflections

3970 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.097

S = 1.03

4784 reflections

217 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.45 e Å−3

Δρmin = −0.26 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 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812006642/is5069sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812006642/is5069Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812006642/is5069Isup3.cml

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

C17H18N4OS	F(000) = 688
Mr = 326.42	Dx = 1.320 Mg m−3
Monoclinic, P21/c	Melting point = 480–481 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 13.4622 (1) Å	Cell parameters from 4784 reflections
b = 9.4175 (1) Å	θ = 1.6–30.0°
c = 13.3002 (2) Å	µ = 0.21 mm−1
β = 103.146 (1)°	T = 100 K
V = 1642.01 (3) Å3	Block, pale yellow
Z = 4	0.34 × 0.22 × 0.20 mm

Bruker APEXII CCD area-detector diffractometer	4784 independent reflections
Radiation source: sealed tube	3970 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
φ and ω scans	θmax = 30.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −18→18
Tmin = 0.934, Tmax = 0.960	k = −13→11
23465 measured reflections	l = −18→13

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0417P)2 + 0.7316P] where P = (Fo2 + 2Fc2)/3
4784 reflections	(Δ/σ)max = 0.001
217 parameters	Δρmax = 0.45 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 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
S1	0.59440 (2)	0.80604 (3)	1.06339 (3)	0.01960 (9)
O1	0.68026 (7)	0.21264 (9)	0.77613 (7)	0.01893 (19)
N1	0.79666 (8)	0.91705 (11)	0.90593 (8)	0.0162 (2)
N2	0.74574 (8)	0.84262 (11)	0.96929 (8)	0.0159 (2)
N3	1.05784 (8)	0.87566 (12)	0.89934 (8)	0.0186 (2)
N4	0.61973 (9)	1.00933 (12)	0.93150 (9)	0.0214 (2)
H1N4	0.5594 (14)	1.0488 (19)	0.9404 (13)	0.033 (5)*
H2N4	0.6522 (13)	1.0458 (19)	0.8925 (14)	0.032 (5)*
C1	1.12851 (10)	0.92690 (15)	0.85186 (10)	0.0216 (3)
H1A	1.1969	0.8950	0.8749	0.026*
C2	1.10730 (10)	1.02328 (15)	0.77156 (10)	0.0228 (3)
H2A	1.1596	1.0559	0.7399	0.027*
C3	1.00762 (10)	1.07148 (15)	0.73821 (10)	0.0211 (3)
H3A	0.9908	1.1381	0.6833	0.025*
C4	0.93292 (9)	1.02150 (14)	0.78583 (10)	0.0187 (2)
H4A	0.8643	1.0528	0.7644	0.022*
C5	0.96155 (9)	0.92381 (13)	0.86619 (9)	0.0159 (2)
C6	0.88757 (9)	0.86558 (13)	0.92109 (9)	0.0153 (2)
C7	0.90988 (9)	0.75117 (13)	1.00217 (9)	0.0162 (2)
H7A	0.9520	0.7875	1.0681	0.019*
H7B	0.9445	0.6689	0.9789	0.019*
C8	0.80072 (9)	0.71273 (13)	1.01217 (9)	0.0147 (2)
H8A	0.7983	0.6995	1.0862	0.018*
C9	0.76061 (9)	0.58201 (13)	0.94880 (9)	0.0142 (2)
C10	0.68335 (9)	0.58700 (13)	0.85977 (9)	0.0167 (2)
H10A	0.6505	0.6749	0.8388	0.020*
C11	0.65281 (9)	0.46572 (13)	0.80034 (10)	0.0179 (2)
H11A	0.5992	0.4710	0.7401	0.022*
C12	0.70147 (9)	0.33741 (13)	0.83010 (9)	0.0159 (2)
C13	0.77894 (10)	0.32974 (13)	0.91996 (10)	0.0184 (2)
H13A	0.8118	0.2418	0.9409	0.022*
C14	0.80746 (9)	0.45060 (13)	0.97800 (9)	0.0180 (2)
H14A	0.8600	0.4447	1.0391	0.022*
C15	0.65479 (9)	0.89184 (13)	0.98368 (9)	0.0159 (2)
C16	0.60157 (10)	0.21507 (15)	0.68243 (11)	0.0246 (3)
H16A	0.6181	0.2859	0.6337	0.029*
H16B	0.5352	0.2406	0.6977	0.029*
C17	0.59640 (12)	0.06844 (16)	0.63618 (12)	0.0306 (3)
H17A	0.5425	0.0655	0.5728	0.046*
H17B	0.5814	−0.0008	0.6857	0.046*
H17C	0.6620	0.0453	0.6200	0.046*

	U11	U22	U33	U12	U13	U23
S1	0.02002 (15)	0.01758 (16)	0.02402 (17)	0.00250 (12)	0.01091 (12)	0.00250 (12)
O1	0.0221 (4)	0.0132 (4)	0.0194 (4)	−0.0009 (3)	0.0005 (3)	−0.0023 (3)
N1	0.0165 (5)	0.0138 (5)	0.0194 (5)	−0.0013 (4)	0.0066 (4)	0.0001 (4)
N2	0.0172 (5)	0.0121 (5)	0.0197 (5)	0.0011 (4)	0.0070 (4)	0.0016 (4)
N3	0.0160 (5)	0.0194 (6)	0.0208 (5)	0.0001 (4)	0.0048 (4)	0.0000 (4)
N4	0.0191 (5)	0.0181 (6)	0.0301 (6)	0.0044 (4)	0.0119 (5)	0.0068 (5)
C1	0.0161 (6)	0.0240 (7)	0.0258 (7)	0.0004 (5)	0.0072 (5)	−0.0014 (5)
C2	0.0230 (6)	0.0245 (7)	0.0236 (6)	−0.0037 (5)	0.0114 (5)	−0.0013 (5)
C3	0.0248 (6)	0.0207 (6)	0.0180 (6)	−0.0025 (5)	0.0054 (5)	0.0018 (5)
C4	0.0179 (6)	0.0186 (6)	0.0193 (6)	−0.0007 (5)	0.0032 (4)	0.0007 (5)
C5	0.0165 (5)	0.0145 (6)	0.0171 (5)	−0.0017 (4)	0.0046 (4)	−0.0023 (4)
C6	0.0158 (5)	0.0136 (6)	0.0165 (5)	−0.0012 (4)	0.0036 (4)	−0.0016 (4)
C7	0.0158 (5)	0.0145 (6)	0.0179 (6)	0.0005 (4)	0.0032 (4)	0.0004 (5)
C8	0.0159 (5)	0.0125 (6)	0.0162 (5)	0.0012 (4)	0.0044 (4)	0.0006 (4)
C9	0.0143 (5)	0.0130 (6)	0.0163 (5)	−0.0002 (4)	0.0055 (4)	0.0007 (4)
C10	0.0152 (5)	0.0139 (6)	0.0206 (6)	0.0023 (4)	0.0033 (4)	0.0012 (5)
C11	0.0158 (5)	0.0168 (6)	0.0193 (6)	0.0013 (5)	0.0001 (4)	−0.0005 (5)
C12	0.0165 (5)	0.0141 (6)	0.0181 (6)	−0.0021 (4)	0.0059 (4)	−0.0010 (5)
C13	0.0209 (6)	0.0129 (6)	0.0204 (6)	0.0020 (5)	0.0026 (5)	0.0025 (5)
C14	0.0207 (6)	0.0161 (6)	0.0154 (5)	0.0008 (5)	0.0005 (4)	0.0022 (5)
C15	0.0161 (5)	0.0129 (6)	0.0188 (6)	−0.0004 (4)	0.0043 (4)	−0.0032 (4)
C16	0.0219 (6)	0.0227 (7)	0.0254 (7)	−0.0008 (5)	−0.0027 (5)	−0.0057 (5)
C17	0.0315 (7)	0.0262 (8)	0.0311 (8)	−0.0015 (6)	0.0010 (6)	−0.0125 (6)

S1—C15	1.6822 (13)	C7—C8	1.5483 (16)
O1—C12	1.3726 (15)	C7—H7A	0.9900
O1—C16	1.4406 (15)	C7—H7B	0.9900
N1—C6	1.2889 (15)	C8—C9	1.5201 (17)
N1—N2	1.3906 (14)	C8—H8A	1.0000
N2—C15	1.3628 (15)	C9—C10	1.3878 (16)
N2—C8	1.4756 (15)	C9—C14	1.4032 (17)
N3—C1	1.3454 (16)	C10—C11	1.3966 (17)
N3—C5	1.3492 (16)	C10—H10A	0.9500
N4—C15	1.3341 (17)	C11—C12	1.3885 (17)
N4—H1N4	0.925 (18)	C11—H11A	0.9500
N4—H2N4	0.825 (18)	C12—C13	1.3979 (17)
C1—C2	1.3810 (19)	C13—C14	1.3799 (18)
C1—H1A	0.9500	C13—H13A	0.9500
C2—C3	1.3902 (19)	C14—H14A	0.9500
C2—H2A	0.9500	C16—C17	1.5069 (19)
C3—C4	1.3871 (17)	C16—H16A	0.9900
C3—H3A	0.9500	C16—H16B	0.9900
C4—C5	1.3964 (18)	C17—H17A	0.9800
C4—H4A	0.9500	C17—H17B	0.9800
C5—C6	1.4685 (16)	C17—H17C	0.9800
C6—C7	1.5056 (17)
C12—O1—C16	117.61 (10)	N2—C8—H8A	111.0
C6—N1—N2	107.28 (10)	C9—C8—H8A	111.0
C15—N2—N1	119.74 (10)	C7—C8—H8A	111.0
C15—N2—C8	127.98 (10)	C10—C9—C14	117.94 (11)
N1—N2—C8	112.27 (9)	C10—C9—C8	123.27 (11)
C1—N3—C5	117.10 (11)	C14—C9—C8	118.69 (10)
C15—N4—H1N4	118.9 (11)	C9—C10—C11	121.48 (11)
C15—N4—H2N4	119.8 (12)	C9—C10—H10A	119.3
H1N4—N4—H2N4	121.3 (16)	C11—C10—H10A	119.3
N3—C1—C2	123.70 (12)	C12—C11—C10	119.43 (11)
N3—C1—H1A	118.2	C12—C11—H11A	120.3
C2—C1—H1A	118.2	C10—C11—H11A	120.3
C1—C2—C3	118.44 (12)	O1—C12—C11	124.56 (11)
C1—C2—H2A	120.8	O1—C12—C13	115.40 (11)
C3—C2—H2A	120.8	C11—C12—C13	120.03 (11)
C4—C3—C2	119.40 (12)	C14—C13—C12	119.62 (11)
C4—C3—H3A	120.3	C14—C13—H13A	120.2
C2—C3—H3A	120.3	C12—C13—H13A	120.2
C3—C4—C5	118.07 (12)	C13—C14—C9	121.48 (11)
C3—C4—H4A	121.0	C13—C14—H14A	119.3
C5—C4—H4A	121.0	C9—C14—H14A	119.3
N3—C5—C4	123.29 (11)	N4—C15—N2	115.59 (11)
N3—C5—C6	114.95 (11)	N4—C15—S1	124.18 (9)
C4—C5—C6	121.75 (11)	N2—C15—S1	120.24 (9)
N1—C6—C5	120.60 (11)	O1—C16—C17	107.17 (11)
N1—C6—C7	114.13 (10)	O1—C16—H16A	110.3
C5—C6—C7	125.17 (10)	C17—C16—H16A	110.3
C6—C7—C8	100.97 (9)	O1—C16—H16B	110.3
C6—C7—H7A	111.6	C17—C16—H16B	110.3
C8—C7—H7A	111.6	H16A—C16—H16B	108.5
C6—C7—H7B	111.6	C16—C17—H17A	109.5
C8—C7—H7B	111.6	C16—C17—H17B	109.5
H7A—C7—H7B	109.4	H17A—C17—H17B	109.5
N2—C8—C9	111.92 (10)	C16—C17—H17C	109.5
N2—C8—C7	100.10 (9)	H17A—C17—H17C	109.5
C9—C8—C7	111.48 (10)	H17B—C17—H17C	109.5
C6—N1—N2—C15	167.71 (11)	C6—C7—C8—C9	97.86 (11)
C6—N1—N2—C8	−13.34 (13)	N2—C8—C9—C10	1.69 (16)
C5—N3—C1—C2	−0.8 (2)	C7—C8—C9—C10	−109.50 (13)
N3—C1—C2—C3	0.6 (2)	N2—C8—C9—C14	178.00 (10)
C1—C2—C3—C4	−0.2 (2)	C7—C8—C9—C14	66.81 (14)
C2—C3—C4—C5	0.03 (19)	C14—C9—C10—C11	−0.20 (18)
C1—N3—C5—C4	0.56 (19)	C8—C9—C10—C11	176.13 (11)
C1—N3—C5—C6	−179.50 (11)	C9—C10—C11—C12	−0.76 (18)
C3—C4—C5—N3	−0.21 (19)	C16—O1—C12—C11	−0.39 (17)
C3—C4—C5—C6	179.86 (11)	C16—O1—C12—C13	−179.50 (11)
N2—N1—C6—C5	−179.01 (10)	C10—C11—C12—O1	−177.82 (11)
N2—N1—C6—C7	−2.46 (14)	C10—C11—C12—C13	1.26 (18)
N3—C5—C6—N1	170.77 (11)	O1—C12—C13—C14	178.37 (11)
C4—C5—C6—N1	−9.29 (18)	C11—C12—C13—C14	−0.79 (18)
N3—C5—C6—C7	−5.37 (17)	C12—C13—C14—C9	−0.19 (19)
C4—C5—C6—C7	174.57 (12)	C10—C9—C14—C13	0.68 (18)
N1—C6—C7—C8	15.72 (14)	C8—C9—C14—C13	−175.83 (11)
C5—C6—C7—C8	−167.92 (11)	N1—N2—C15—N4	1.90 (17)
C15—N2—C8—C9	82.65 (15)	C8—N2—C15—N4	−176.86 (11)
N1—N2—C8—C9	−96.19 (11)	N1—N2—C15—S1	−177.84 (8)
C15—N2—C8—C7	−159.15 (12)	C8—N2—C15—S1	3.40 (17)
N1—N2—C8—C7	22.01 (12)	C12—O1—C16—C17	177.61 (11)
C6—C7—C8—N2	−20.67 (11)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H1N4···S1i	0.925 (19)	2.472 (19)	3.3803 (12)	167.3 (15)
N4—H2N4···O1ii	0.825 (18)	2.296 (18)	3.0604 (15)	154.2 (17)
C3—H3A···N3iii	0.95	2.51	3.4053 (18)	156
C2—H2A···Cg2iii	0.95	2.67	3.4401 (14)	138
C7—H7A···Cg1iv	0.99	2.69	3.4841 (13)	138

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C1–C5/N3 and C9–C14 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H1N4⋯S1i	0.925 (19)	2.472 (19)	3.3803 (12)	167.3 (15)
N4—H2N4⋯O1ii	0.825 (18)	2.296 (18)	3.0604 (15)	154.2 (17)
C3—H3A⋯N3iii	0.95	2.51	3.4053 (18)	156
C2—H2A⋯Cg2iii	0.95	2.67	3.4401 (14)	138
C7—H7A⋯Cg1iv	0.99	2.69	3.4841 (13)	138

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