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

In the title compound, C(16)H(16)N(4)OS, the dihedral angle between the pyridine and benzene rings is 81.08 (6)°. The pyrazole ring makes dihedral angles of 12.36 (7) and 87.96 (6)°, respectively, with the pyridine and benzene rings. In the crystal, mol-ecules are linked by N-H⋯O and N-H⋯S hydrogen bonds and a weak C-H⋯S inter-action into a layer parallel to the ab plane. Weak C-H⋯π and π-π inter-actions [centroid-centroid distances = 3.7043 (9) and 3.8120 (7) Å] are also observed.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For a related structure, see: Fun et al. (2011 ▶). For background to and applications of pyrazoline derivatives, see: Amir et al. (2008 ▶); Bai et al. (2007 ▶); Gong et al. (2011 ▶); Husain et al. (2008 ▶); Ji & Shi (2006 ▶); Manna & Agrawal (2009 ▶); Shoman et al. (2009 ▶).

Experimental

Crystal data

C16H16N4OS

M = 312.40

Triclinic,

a = 6.2434 (2) Å

b = 9.9348 (4) Å

c = 13.6564 (6) Å

α = 107.762 (1)°

β = 99.506 (1)°

γ = 94.331 (1)°

V = 788.43 (5) Å3

Z = 2

Mo Kα radiation

μ = 0.21 mm−1

T = 297 K

0.48 × 0.34 × 0.19 mm

Data collection

Bruker SMART APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.906, T max = 0.961

19134 measured reflections

4529 independent reflections

3927 reflections with I > 2σ(I)

R int = 0.019

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.122

S = 1.05

4529 reflections

208 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.31 e Å−3

Δρmin = −0.18 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 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811050033/is5010sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811050033/is5010Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811050033/is5010Isup3.cml

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

C16H16N4OS	Z = 2
Mr = 312.40	F(000) = 328
Triclinic, P1	Dx = 1.316 Mg m−3
Hall symbol: -P 1	Melting point = 468–469 K
a = 6.2434 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.9348 (4) Å	Cell parameters from 4529 reflections
c = 13.6564 (6) Å	θ = 1.6–30.0°
α = 107.762 (1)°	µ = 0.21 mm−1
β = 99.506 (1)°	T = 297 K
γ = 94.331 (1)°	Block, yellow
V = 788.43 (5) Å3	0.48 × 0.34 × 0.19 mm

Bruker SMART APEXII CCD diffractometer	4529 independent reflections
Radiation source: fine-focus sealed tube	3927 reflections with I > 2σ(I)
graphite	Rint = 0.019
Detector resolution: 8.33 pixels mm-1	θmax = 30.0°, θmin = 1.6°
ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 2009)	k = −13→13
Tmin = 0.906, Tmax = 0.961	l = −19→18
19134 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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0685P)2 + 0.1373P] where P = (Fo2 + 2Fc2)/3
4529 reflections	(Δ/σ)max = 0.001
208 parameters	Δρmax = 0.31 e Å−3
0 restraints	Δρmin = −0.18 e Å−3

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	0.50444 (5)	0.19990 (4)	0.13335 (2)	0.04687 (11)
O1	1.0431 (2)	0.76342 (12)	0.12097 (10)	0.0645 (3)
N1	1.06459 (15)	0.13465 (10)	0.27835 (7)	0.03555 (19)
N2	0.88621 (16)	0.19975 (9)	0.25049 (8)	0.0376 (2)
N3	1.48004 (19)	0.27191 (11)	0.50833 (8)	0.0458 (2)
N4	0.7587 (2)	−0.00487 (12)	0.11494 (10)	0.0497 (3)
H2N4	0.873 (3)	−0.0389 (18)	0.1330 (13)	0.053 (4)*
H1N4	0.667 (3)	−0.046 (2)	0.0593 (15)	0.063 (5)*
C1	1.6684 (2)	0.24072 (15)	0.55409 (11)	0.0537 (3)
H1A	1.7341	0.3000	0.6212	0.064*
C2	1.7700 (2)	0.12711 (17)	0.50832 (13)	0.0568 (3)
H2A	1.9003	0.1101	0.5437	0.068*
C3	1.6751 (2)	0.03853 (17)	0.40878 (12)	0.0562 (3)
H3A	1.7411	−0.0389	0.3754	0.067*
C4	1.4800 (2)	0.06681 (14)	0.35939 (10)	0.0453 (3)
H4A	1.4117	0.0084	0.2924	0.054*
C5	1.38864 (18)	0.18390 (11)	0.41175 (8)	0.0354 (2)
C6	1.18371 (18)	0.22122 (11)	0.36368 (8)	0.0347 (2)
C7	1.0938 (2)	0.35789 (12)	0.40702 (9)	0.0416 (2)
H7A	1.2014	0.4399	0.4191	0.050*
H7B	1.0466	0.3630	0.4721	0.050*
C8	0.89669 (19)	0.34932 (11)	0.31893 (9)	0.0364 (2)
H8A	0.7627	0.3622	0.3474	0.044*
C9	0.93345 (18)	0.45497 (11)	0.26179 (8)	0.0349 (2)
C10	0.8047 (2)	0.56443 (13)	0.26752 (10)	0.0426 (3)
H10A	0.6907	0.5700	0.3040	0.051*
C11	0.8453 (2)	0.66491 (14)	0.21933 (11)	0.0486 (3)
H11A	0.7586	0.7379	0.2239	0.058*
C12	1.0148 (2)	0.65770 (13)	0.16395 (10)	0.0439 (3)
C13	1.1430 (2)	0.54861 (14)	0.15695 (11)	0.0468 (3)
H13A	1.2560	0.5423	0.1197	0.056*
C14	1.1009 (2)	0.44869 (13)	0.20617 (10)	0.0434 (3)
H14A	1.1875	0.3757	0.2016	0.052*
C15	0.72789 (18)	0.12674 (12)	0.16632 (9)	0.0360 (2)
C16	1.2161 (3)	0.7646 (2)	0.06553 (15)	0.0706 (5)
H16A	1.2216	0.8478	0.0437	0.106*
H16B	1.1910	0.6806	0.0050	0.106*
H16C	1.3526	0.7662	0.1104	0.106*

	U11	U22	U33	U12	U13	U23
S1	0.03741 (17)	0.05216 (19)	0.04509 (18)	0.01644 (13)	0.00125 (12)	0.00828 (13)
O1	0.0804 (8)	0.0561 (6)	0.0773 (7)	0.0238 (5)	0.0297 (6)	0.0404 (6)
N1	0.0342 (4)	0.0324 (4)	0.0385 (4)	0.0070 (3)	0.0025 (3)	0.0110 (3)
N2	0.0369 (4)	0.0315 (4)	0.0401 (5)	0.0093 (3)	0.0002 (4)	0.0083 (4)
N3	0.0493 (6)	0.0392 (5)	0.0412 (5)	0.0060 (4)	−0.0046 (4)	0.0090 (4)
N4	0.0486 (6)	0.0380 (5)	0.0484 (6)	0.0120 (4)	−0.0096 (5)	0.0021 (4)
C1	0.0516 (7)	0.0504 (7)	0.0480 (7)	0.0033 (6)	−0.0122 (6)	0.0121 (5)
C2	0.0424 (7)	0.0624 (8)	0.0618 (8)	0.0117 (6)	−0.0060 (6)	0.0222 (7)
C3	0.0487 (7)	0.0586 (8)	0.0590 (8)	0.0218 (6)	0.0059 (6)	0.0147 (6)
C4	0.0450 (6)	0.0469 (6)	0.0403 (6)	0.0131 (5)	0.0037 (5)	0.0095 (5)
C5	0.0356 (5)	0.0350 (5)	0.0356 (5)	0.0037 (4)	0.0030 (4)	0.0141 (4)
C6	0.0372 (5)	0.0325 (5)	0.0344 (5)	0.0062 (4)	0.0042 (4)	0.0119 (4)
C7	0.0509 (6)	0.0340 (5)	0.0358 (5)	0.0108 (4)	0.0008 (4)	0.0084 (4)
C8	0.0388 (5)	0.0323 (5)	0.0359 (5)	0.0096 (4)	0.0054 (4)	0.0076 (4)
C9	0.0363 (5)	0.0314 (5)	0.0345 (5)	0.0102 (4)	0.0039 (4)	0.0073 (4)
C10	0.0395 (6)	0.0425 (6)	0.0495 (6)	0.0170 (5)	0.0121 (5)	0.0160 (5)
C11	0.0509 (7)	0.0433 (6)	0.0590 (7)	0.0242 (5)	0.0132 (6)	0.0218 (6)
C12	0.0509 (7)	0.0394 (6)	0.0432 (6)	0.0109 (5)	0.0073 (5)	0.0157 (5)
C13	0.0510 (7)	0.0456 (6)	0.0492 (6)	0.0157 (5)	0.0188 (5)	0.0162 (5)
C14	0.0466 (6)	0.0399 (5)	0.0492 (6)	0.0204 (5)	0.0157 (5)	0.0157 (5)
C15	0.0347 (5)	0.0363 (5)	0.0363 (5)	0.0059 (4)	0.0045 (4)	0.0118 (4)
C16	0.0854 (12)	0.0663 (10)	0.0737 (11)	0.0083 (9)	0.0283 (9)	0.0361 (9)

S1—C15	1.6801 (11)	C5—C6	1.4657 (15)
O1—C12	1.3644 (16)	C6—C7	1.4978 (15)
O1—C16	1.419 (2)	C7—C8	1.5498 (16)
N1—C6	1.2871 (14)	C7—H7A	0.9700
N1—N2	1.3864 (12)	C7—H7B	0.9700
N2—C15	1.3536 (14)	C8—C9	1.5118 (15)
N2—C8	1.4844 (14)	C8—H8A	0.9800
N3—C1	1.3414 (17)	C9—C14	1.3846 (17)
N3—C5	1.3425 (14)	C9—C10	1.3911 (15)
N4—C15	1.3273 (15)	C10—C11	1.3825 (18)
N4—H2N4	0.847 (18)	C10—H10A	0.9300
N4—H1N4	0.84 (2)	C11—C12	1.3927 (19)
C1—C2	1.370 (2)	C11—H11A	0.9300
C1—H1A	0.9300	C12—C13	1.3848 (17)
C2—C3	1.378 (2)	C13—C14	1.3901 (18)
C2—H2A	0.9300	C13—H13A	0.9300
C3—C4	1.3834 (18)	C14—H14A	0.9300
C3—H3A	0.9300	C16—H16A	0.9600
C4—C5	1.3847 (16)	C16—H16B	0.9600
C4—H4A	0.9300	C16—H16C	0.9600
C12—O1—C16	118.84 (12)	N2—C8—C9	112.03 (9)
C6—N1—N2	107.90 (9)	N2—C8—C7	100.52 (8)
C15—N2—N1	119.54 (9)	C9—C8—C7	113.07 (9)
C15—N2—C8	127.01 (9)	N2—C8—H8A	110.3
N1—N2—C8	113.43 (8)	C9—C8—H8A	110.3
C1—N3—C5	116.48 (12)	C7—C8—H8A	110.3
C15—N4—H2N4	121.2 (11)	C14—C9—C10	118.46 (11)
C15—N4—H1N4	115.2 (13)	C14—C9—C8	120.98 (10)
H2N4—N4—H1N4	123.0 (17)	C10—C9—C8	120.52 (10)
N3—C1—C2	124.18 (13)	C11—C10—C9	120.44 (11)
N3—C1—H1A	117.9	C11—C10—H10A	119.8
C2—C1—H1A	117.9	C9—C10—H10A	119.8
C1—C2—C3	118.64 (12)	C10—C11—C12	120.53 (11)
C1—C2—H2A	120.7	C10—C11—H11A	119.7
C3—C2—H2A	120.7	C12—C11—H11A	119.7
C2—C3—C4	118.81 (13)	O1—C12—C13	124.58 (12)
C2—C3—H3A	120.6	O1—C12—C11	115.81 (11)
C4—C3—H3A	120.6	C13—C12—C11	119.60 (11)
C3—C4—C5	118.60 (12)	C12—C13—C14	119.22 (12)
C3—C4—H4A	120.7	C12—C13—H13A	120.4
C5—C4—H4A	120.7	C14—C13—H13A	120.4
N3—C5—C4	123.29 (11)	C9—C14—C13	121.75 (11)
N3—C5—C6	115.16 (10)	C9—C14—H14A	119.1
C4—C5—C6	121.54 (10)	C13—C14—H14A	119.1
N1—C6—C5	120.88 (10)	N4—C15—N2	115.95 (10)
N1—C6—C7	114.44 (10)	N4—C15—S1	123.24 (9)
C5—C6—C7	124.68 (10)	N2—C15—S1	120.78 (8)
C6—C7—C8	102.65 (9)	O1—C16—H16A	109.5
C6—C7—H7A	111.2	O1—C16—H16B	109.5
C8—C7—H7A	111.2	H16A—C16—H16B	109.5
C6—C7—H7B	111.2	O1—C16—H16C	109.5
C8—C7—H7B	111.2	H16A—C16—H16C	109.5
H7A—C7—H7B	109.2	H16B—C16—H16C	109.5
C6—N1—N2—C15	−175.98 (10)	C6—C7—C8—N2	9.45 (11)
C6—N1—N2—C8	5.41 (13)	C6—C7—C8—C9	−110.14 (10)
C5—N3—C1—C2	0.3 (2)	N2—C8—C9—C14	−50.50 (14)
N3—C1—C2—C3	0.3 (2)	C7—C8—C9—C14	62.24 (14)
C1—C2—C3—C4	−0.7 (2)	N2—C8—C9—C10	132.10 (11)
C2—C3—C4—C5	0.5 (2)	C7—C8—C9—C10	−115.16 (12)
C1—N3—C5—C4	−0.49 (19)	C14—C9—C10—C11	−0.53 (19)
C1—N3—C5—C6	−179.71 (11)	C8—C9—C10—C11	176.93 (11)
C3—C4—C5—N3	0.1 (2)	C9—C10—C11—C12	0.3 (2)
C3—C4—C5—C6	179.25 (12)	C16—O1—C12—C13	−0.5 (2)
N2—N1—C6—C5	−178.44 (9)	C16—O1—C12—C11	178.55 (14)
N2—N1—C6—C7	1.85 (13)	C10—C11—C12—O1	−178.90 (13)
N3—C5—C6—N1	−169.93 (11)	C10—C11—C12—C13	0.2 (2)
C4—C5—C6—N1	10.83 (17)	O1—C12—C13—C14	178.56 (13)
N3—C5—C6—C7	9.75 (16)	C11—C12—C13—C14	−0.5 (2)
C4—C5—C6—C7	−169.49 (11)	C10—C9—C14—C13	0.26 (19)
N1—C6—C7—C8	−7.69 (13)	C8—C9—C14—C13	−177.19 (11)
C5—C6—C7—C8	172.61 (10)	C12—C13—C14—C9	0.2 (2)
C15—N2—C8—C9	−67.76 (15)	N1—N2—C15—N4	−0.80 (16)
N1—N2—C8—C9	110.73 (10)	C8—N2—C15—N4	177.61 (11)
C15—N2—C8—C7	171.91 (11)	N1—N2—C15—S1	177.43 (8)
N1—N2—C8—C7	−9.61 (12)	C8—N2—C15—S1	−4.16 (17)

Cg3 is the centroid of the C9–C14 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N4—H2N4···O1i	0.845 (19)	2.278 (19)	3.0238 (18)	147.4 (17)
N4—H1N4···S1ii	0.839 (19)	2.603 (19)	3.4090 (13)	161.6 (18)
C14—H14A···S1iii	0.93	2.82	3.7033 (14)	158
C1—H1A···Cg3iv	0.93	2.60	3.5005 (15)	162

Table 1

Hydrogen-bond geometry (Å, °)

Cg3 is the centroid of the C9–C14 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H2N4⋯O1i	0.845 (19)	2.278 (19)	3.0238 (18)	147.4 (17)
N4—H1N4⋯S1ii	0.839 (19)	2.603 (19)	3.4090 (13)	161.6 (18)
C14—H14A⋯S1iii	0.93	2.82	3.7033 (14)	158
C1—H1A⋯Cg3iv	0.93	2.60	3.5005 (15)	162

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