(2E)-2-[(3-Methyl-5-phen­oxy-1-phenyl-1H-pyrazol-4-yl)methyl­idene]hydrazinecarbothio­amide

Fun, H.-K.; Quah, C.K.; Shetty, S.; Kalluraya, B.; Nitinchandra

doi:10.1107/S1600536812026931

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 7| July 2012| Pages o2146-o2147

https://doi.org/10.1107/S1600536812026931

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(2E)-2-[(3-Methyl-5-phenoxy-1-phenyl-1H-pyrazol-4-yl)methylidene]hydrazinecarbothioamide

Hoong-Kun Fun,^a ^*‡ Ching Kheng Quah,^a § Shobhitha Shetty,^b Balakrishna Kalluraya ^b and Nitinchandra ^b

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri, Mangalore 574 199, India
^*Correspondence e-mail: hkfun@usm.my

(Received 11 June 2012; accepted 14 June 2012; online 20 June 2012)

In the title compound, C₁₈H₁₇N₅OS, the mean plane of the pyrazole ring [maximum deviation = 0.0031 (12) Å] forms dihedral angles of 19.6 (4) and 9.3 (5)° with the two disorder components of the N-bound benzene ring (with equal occupancies for the two orientations) and a dihedral angle of 72.58 (8)° with the C—O-bonded benzene ring. The molecule exists in a trans conformation with respect to the N=C bond [1.2792 (19) Å]. The molecular structure features an intramolecular C—H⋯O hydrogen bond, forming an S(6) ring. In the crystal, N—H⋯N and N—H⋯S hydrogen bonds result in the formation of zigzag layers lying parallel to (10-1).

Related literature

For general background to and applications of the pyrazole derivatives, see: Rai et al. (2008 ); Isloor et al. (2009 ); Girisha et al. (2010 ). For standard bond-length data, see: Allen et al. (1987 ). For the stability of the temperature controller used in the data collection, see Cosier & Glazer (1986 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For related structures, see: Fun et al. (2011a ,b ,c ).

Experimental

Crystal data

C₁₈H₁₇N₅OS
M_r = 351.43
Monoclinic, P 2₁ /n
a = 8.8280 (1) Å
b = 10.8519 (2) Å
c = 17.7353 (2) Å
β = 94.379 (1)°
V = 1694.09 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 100 K
0.29 × 0.27 × 0.22 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.942, T_max = 0.955
18467 measured reflections
4948 independent reflections
3879 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.113
S = 1.06
4948 reflections
294 parameters
216 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯N5ⁱ	0.87 (2)	2.50 (2)	3.3237 (19)	158.1 (18)
N2—H1N2⋯S1ⁱⁱ	0.89 (2)	2.56 (2)	3.4414 (13)	167.7 (17)
C13—H13A⋯O1	0.95	2.22	2.814 (12)	120
C13—H13B⋯O1	0.79	2.28	2.814 (12)	125
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x+2, -y+2, -z+2.

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812026931/hb6849sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812026931/hb6849Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812026931/hb6849Isup3.cml

checkCIF report

Comment top

Pyrazoles possess a wide variety of applications in the agrochemical and pharmaceutical industries including antibacterial (Rai et al., 2008), anti-inflammatory and analgesic (Isloor et al., 2009) activities. In view of these observations and in continuation of our search for biologically active pyrazole derivatives, we herein report the crystal structure of 3-methyl-5-phenoxy-1-phenyl-1H-pyrazole-4-carbaldehyde. Reaction of 5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde with phenol afforded 5-chloro-3-methyl-1- phenyl-1H-pyrazole-4-carbaldehyde (Girisha et al., 2010).

In the title molecule, Fig. 1, the mean plane of pyrazole ring (N4/N5/C3-C5, maximum deviation = 0.0031 (12) Å at atom N4) forms dihedral angles of 19.6 (4), 9.3 (5) and 72.58 (8)° with the three benzene rings (C12-C17, C12X-C17X and C6-C11). One of the benzene rings (C12-C17) is disordered over two positions with equal refined site-occupancies [0.50 (2) and 0.50 (2)]. The title molecule exists in a trans conformation with respect to the N3//dbC2 bond [1.2792 (19) Å]. Bond lengths (Allen et al., 1987) and angles are within normal ranges and are comparable to related structures (Fun et al., 2011a, 2011b, 2011c). The molecular structure is stabilized by intramolecular C13–H13A···O1 and C13–H13B···O1 hydrogen bonds (Table 1), which generate S(6) ring motifs (Fig. 2, Bernstein et al., 1995).

In the crystal (Fig.2), intermolecular N1–H1N1···N5 and N2–H1N2···S1 hydrogen bonds (Table 1) result in the formation of zigzag layers parallel to (101).

Related literature top

For general background to and applications of the pyrazole derivatives, see: Rai et al. (2008); Isloor et al. (2009); Girisha et al. (2010). For standard bond-length data, see: Allen et al. (1987). For the stability of the temperature controller used in the data collection, see Cosier & Glazer (1986). For hydrogen-bond motifs, see: Bernstein et al. (1995). For related structures, see: Fun et al. (2011a,b,c).

Experimental top

The title compound was obtained by refluxing a mixture 3-methyl-5-phenoxy-1-phenyl-1H-pyrazole-4-carbaldehyde (0.01 mol), thiosemicarbazide (0.01 mol) in ethanol (30 ml) and 3 drops of concentrated sulfuric acid for 1 h. Excess ethanol was removed from the reaction mixture under reduced pressure. The solid product obtained was filtered, washed with ethanol and dried. Pink blocks were obtained by the slow evaporation of an ethanol-N,N-dimethylformamide (DMF) (3:1) solution.

Structure description top

In the crystal (Fig.2), intermolecular N1–H1N1···N5 and N2–H1N2···S1 hydrogen bonds (Table 1) result in the formation of zigzag layers parallel to (101).

For general background to and applications of the pyrazole derivatives, see: Rai et al. (2008); Isloor et al. (2009); Girisha et al. (2010). For standard bond-length data, see: Allen et al. (1987). For the stability of the temperature controller used in the data collection, see Cosier & Glazer (1986). For hydrogen-bond motifs, see: Bernstein et al. (1995). For related structures, see: Fun et al. (2011a,b,c).

Computing details top

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

Figures top

	Fig. 1. The molecular structure of the title compound showing 50% probability displacement ellipsoids for non-H atoms. Intramolecular hydrogen bonds are shown as dashed lines.
	Fig. 2. The crystal structure of the title compound, viewed along the [101] direction. H atoms not involved in hydrogen bonds (dashed lines) have been omitted for clarity. Only one disordered component is shown.

(2E)-2-[(3-Methyl-5-phenoxy-1-phenyl-1H-pyrazol-4- yl)methylidene]hydrazinecarbothioamide top

Crystal data top

C₁₈H₁₇N₅OS	F(000) = 736
M_r = 351.43	D_x = 1.378 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5058 reflections
a = 8.8280 (1) Å	θ = 2.3–32.4°
b = 10.8519 (2) Å	µ = 0.21 mm⁻¹
c = 17.7353 (2) Å	T = 100 K
β = 94.379 (1)°	Block, pink
V = 1694.09 (4) Å³	0.29 × 0.27 × 0.22 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD diffractometer	4948 independent reflections
Radiation source: fine-focus sealed tube	3879 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
φ and ω scans	θ_max = 30.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −12→12
T_min = 0.942, T_max = 0.955	k = −15→15
18467 measured reflections	l = −22→24

Refinement top

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0482P)² + 0.7836P] where P = (F_o² + 2F_c²)/3
4948 reflections	(Δ/σ)_max = 0.001
294 parameters	Δρ_max = 0.43 e Å⁻³
216 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₈H₁₇N₅OS	V = 1694.09 (4) Å³
M_r = 351.43	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.8280 (1) Å	µ = 0.21 mm⁻¹
b = 10.8519 (2) Å	T = 100 K
c = 17.7353 (2) Å	0.29 × 0.27 × 0.22 mm
β = 94.379 (1)°

Data collection top

Bruker SMART APEXII CCD diffractometer	4948 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	3879 reflections with I > 2σ(I)
T_min = 0.942, T_max = 0.955	R_int = 0.042
18467 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	216 restraints
wR(F²) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.43 e Å⁻³
4948 reflections	Δρ_min = −0.26 e Å⁻³
294 parameters

Special details top

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 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1	1.02274 (4)	0.97510 (4)	1.12626 (2)	0.01906 (10)
O1	0.32416 (12)	0.80260 (10)	1.01785 (6)	0.0171 (2)
N1	0.75067 (17)	0.87882 (14)	1.14880 (8)	0.0208 (3)
N2	0.78833 (15)	0.93939 (12)	1.02818 (7)	0.0168 (3)
N3	0.64788 (14)	0.89082 (12)	1.00657 (7)	0.0169 (3)
N4	0.24554 (14)	0.73854 (11)	0.89336 (7)	0.0153 (2)
N5	0.29680 (15)	0.73976 (12)	0.82182 (7)	0.0182 (3)
C1	0.84379 (17)	0.92800 (13)	1.10068 (8)	0.0160 (3)
C2	0.61467 (17)	0.88237 (14)	0.93528 (9)	0.0179 (3)
H2A	0.6840	0.9127	0.9013	0.022*
C3	0.47312 (17)	0.82734 (14)	0.90555 (8)	0.0163 (3)
C4	0.35025 (17)	0.78988 (13)	0.94386 (8)	0.0151 (3)
C5	0.43228 (18)	0.79306 (14)	0.82963 (8)	0.0183 (3)
C6	0.40260 (17)	0.72594 (14)	1.07080 (8)	0.0155 (3)
C7	0.50846 (17)	0.63938 (14)	1.05158 (8)	0.0167 (3)
H7A	0.5306	0.6288	1.0004	0.020*
C8	0.58163 (19)	0.56845 (15)	1.10841 (9)	0.0207 (3)
H8A	0.6548	0.5090	1.0961	0.025*
C9	0.5488 (2)	0.58360 (16)	1.18318 (9)	0.0250 (4)
H9A	0.5994	0.5350	1.2219	0.030*
C10	0.4411 (2)	0.67053 (17)	1.20104 (9)	0.0269 (4)
H10A	0.4180	0.6807	1.2521	0.032*
C11	0.36739 (19)	0.74238 (16)	1.14485 (9)	0.0219 (3)
H11A	0.2941	0.8018	1.1570	0.026*
C12	0.1022 (18)	0.687 (2)	0.9077 (9)	0.0163 (15)	0.50 (2)
C13	0.0307 (13)	0.7157 (11)	0.9729 (7)	0.0168 (12)	0.50 (2)
H13A	0.0743	0.7740	1.0082	0.020*	0.50 (2)
C14	−0.1050 (15)	0.6578 (12)	0.9854 (7)	0.0217 (13)	0.50 (2)
H14A	−0.1526	0.6748	1.0305	0.026*	0.50 (2)
C15	−0.1725 (12)	0.5757 (10)	0.9335 (7)	0.0263 (15)	0.50 (2)
H15A	−0.2656	0.5368	0.9431	0.032*	0.50 (2)
C16	−0.1035 (11)	0.5501 (10)	0.8673 (6)	0.0301 (15)	0.50 (2)
H16A	−0.1515	0.4966	0.8304	0.036*	0.50 (2)
C17	0.0365 (12)	0.6033 (10)	0.8553 (6)	0.0248 (15)	0.50 (2)
H17A	0.0869	0.5825	0.8116	0.030*	0.50 (2)
C12X	0.0983 (19)	0.683 (2)	0.9013 (9)	0.0186 (16)	0.50 (2)
C13X	0.0278 (15)	0.6967 (13)	0.9686 (8)	0.0259 (17)	0.50 (2)
H13B	0.0763	0.7409	1.0099	0.031*	0.50 (2)
C14X	−0.1156 (15)	0.6440 (14)	0.9742 (8)	0.0276 (16)	0.50 (2)
H14B	−0.1636	0.6502	1.0202	0.033*	0.50 (2)
C15X	−0.1871 (12)	0.5835 (11)	0.9137 (7)	0.0286 (15)	0.50 (2)
H15B	−0.2846	0.5481	0.9177	0.034*	0.50 (2)
C16X	−0.1171 (11)	0.5744 (9)	0.8473 (7)	0.0304 (14)	0.50 (2)
H16B	−0.1681	0.5338	0.8052	0.036*	0.50 (2)
C17X	0.0263 (12)	0.6231 (11)	0.8405 (6)	0.0244 (15)	0.50 (2)
H17B	0.0741	0.6150	0.7946	0.029*	0.50 (2)
C18	0.5243 (2)	0.80836 (19)	0.76296 (10)	0.0300 (4)
H18A	0.4574	0.8316	0.7186	0.045*
H18B	0.5754	0.7305	0.7529	0.045*
H18C	0.6004	0.8730	0.7736	0.045*
H2N1	0.669 (2)	0.8510 (18)	1.1330 (11)	0.025 (5)*
H1N1	0.781 (2)	0.8649 (19)	1.1957 (12)	0.030 (5)*
H1N2	0.850 (2)	0.9640 (19)	0.9934 (12)	0.032 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01562 (19)	0.0281 (2)	0.01348 (17)	−0.00380 (15)	0.00110 (13)	−0.00271 (14)
O1	0.0174 (5)	0.0224 (5)	0.0119 (5)	0.0045 (4)	0.0031 (4)	0.0019 (4)
N1	0.0161 (7)	0.0320 (8)	0.0139 (6)	−0.0047 (6)	−0.0007 (5)	0.0019 (5)
N2	0.0146 (6)	0.0214 (6)	0.0144 (6)	−0.0043 (5)	0.0004 (5)	0.0009 (5)
N3	0.0129 (6)	0.0199 (6)	0.0177 (6)	−0.0019 (5)	−0.0005 (5)	0.0006 (5)
N4	0.0130 (6)	0.0199 (6)	0.0133 (6)	−0.0011 (5)	0.0022 (5)	0.0012 (5)
N5	0.0162 (6)	0.0260 (7)	0.0125 (6)	−0.0030 (5)	0.0020 (5)	0.0012 (5)
C1	0.0166 (7)	0.0167 (7)	0.0147 (7)	0.0011 (6)	0.0020 (5)	−0.0023 (5)
C2	0.0147 (7)	0.0230 (7)	0.0164 (7)	−0.0027 (6)	0.0033 (6)	0.0012 (6)
C3	0.0150 (7)	0.0209 (7)	0.0129 (6)	−0.0018 (6)	−0.0002 (5)	0.0023 (5)
C4	0.0143 (7)	0.0176 (7)	0.0136 (6)	0.0018 (5)	0.0012 (5)	0.0020 (5)
C5	0.0164 (7)	0.0234 (7)	0.0149 (7)	−0.0034 (6)	0.0008 (6)	0.0021 (6)
C6	0.0149 (7)	0.0183 (7)	0.0135 (6)	−0.0019 (5)	0.0020 (5)	0.0035 (5)
C7	0.0165 (7)	0.0194 (7)	0.0148 (7)	−0.0020 (6)	0.0039 (6)	0.0013 (5)
C8	0.0187 (8)	0.0206 (7)	0.0229 (8)	0.0009 (6)	0.0024 (6)	0.0039 (6)
C9	0.0234 (8)	0.0315 (9)	0.0200 (8)	0.0017 (7)	0.0005 (6)	0.0102 (7)
C10	0.0271 (9)	0.0397 (10)	0.0146 (7)	0.0023 (7)	0.0054 (6)	0.0069 (7)
C11	0.0204 (8)	0.0300 (8)	0.0160 (7)	0.0036 (7)	0.0062 (6)	0.0018 (6)
C12	0.011 (2)	0.016 (2)	0.021 (3)	−0.001 (2)	−0.003 (2)	−0.002 (2)
C13	0.013 (2)	0.013 (3)	0.026 (2)	−0.0041 (17)	0.0103 (18)	−0.0068 (17)
C14	0.020 (2)	0.016 (2)	0.030 (3)	−0.0049 (17)	0.006 (2)	−0.0092 (19)
C15	0.020 (3)	0.023 (2)	0.038 (3)	−0.0064 (19)	0.015 (3)	−0.009 (3)
C16	0.023 (2)	0.031 (3)	0.038 (3)	−0.014 (2)	0.007 (2)	−0.012 (2)
C17	0.020 (2)	0.029 (3)	0.026 (3)	−0.004 (2)	0.010 (2)	−0.007 (2)
C12X	0.011 (3)	0.021 (3)	0.025 (3)	−0.001 (2)	0.008 (3)	0.003 (2)
C13X	0.025 (2)	0.024 (4)	0.028 (3)	−0.004 (2)	−0.001 (2)	−0.003 (2)
C14X	0.018 (3)	0.031 (4)	0.035 (3)	−0.005 (2)	0.013 (3)	−0.003 (3)
C15X	0.016 (2)	0.031 (2)	0.040 (4)	−0.0073 (18)	0.007 (3)	−0.006 (3)
C16X	0.024 (2)	0.031 (3)	0.036 (3)	−0.006 (2)	0.009 (2)	−0.011 (2)
C17X	0.017 (2)	0.030 (3)	0.026 (3)	−0.007 (2)	0.004 (2)	−0.005 (2)
C18	0.0265 (9)	0.0471 (11)	0.0170 (8)	−0.0129 (8)	0.0061 (7)	0.0001 (7)

Geometric parameters (Å, º) top

S1—C1	1.6892 (16)	C10—C11	1.388 (2)
O1—C4	1.3566 (17)	C10—H10A	0.9500
O1—C6	1.3979 (17)	C11—H11A	0.9500
N1—C1	1.340 (2)	C12—C13	1.395 (9)
N1—H2N1	0.81 (2)	C12—C17	1.395 (10)
N1—H1N1	0.87 (2)	C13—C14	1.385 (9)
N2—C1	1.3461 (19)	C13—H13A	0.9500
N2—N3	1.3746 (18)	C14—C15	1.382 (8)
N2—H1N2	0.89 (2)	C14—H14A	0.9500
N3—C2	1.2792 (19)	C15—C16	1.393 (8)
N4—C4	1.3567 (19)	C15—H15A	0.9500
N4—N5	1.3793 (17)	C16—C17	1.395 (8)
N4—C12	1.423 (13)	C16—H16A	0.9500
N4—C12X	1.447 (12)	C17—H17A	0.9500
N5—C5	1.326 (2)	C12X—C17X	1.375 (10)
C2—C3	1.448 (2)	C12X—C13X	1.395 (10)
C2—H2A	0.9500	C13X—C14X	1.400 (9)
C3—C4	1.384 (2)	C13X—H13B	0.9500
C3—C5	1.417 (2)	C14X—C15X	1.370 (8)
C5—C18	1.494 (2)	C14X—H14B	0.9500
C6—C11	1.384 (2)	C15X—C16X	1.375 (8)
C6—C7	1.386 (2)	C15X—H15B	0.9500
C7—C8	1.388 (2)	C16X—C17X	1.386 (9)
C7—H7A	0.9500	C16X—H16B	0.9500
C8—C9	1.389 (2)	C17X—H17B	0.9500
C8—H8A	0.9500	C18—H18A	0.9800
C9—C10	1.393 (2)	C18—H18B	0.9800
C9—H9A	0.9500	C18—H18C	0.9800

C4—O1—C6	118.51 (11)	C6—C11—C10	118.82 (15)
C1—N1—H2N1	119.9 (14)	C6—C11—H11A	120.6
C1—N1—H1N1	121.4 (14)	C10—C11—H11A	120.6
H2N1—N1—H1N1	118 (2)	C13—C12—C17	120.4 (9)
C1—N2—N3	119.05 (13)	C13—C12—N4	121.8 (8)
C1—N2—H1N2	119.5 (14)	C17—C12—N4	117.8 (9)
N3—N2—H1N2	120.2 (14)	C14—C13—C12	118.9 (8)
C2—N3—N2	115.90 (13)	C14—C13—H13A	120.6
C4—N4—N5	110.39 (12)	C12—C13—H13A	120.6
C4—N4—C12	127.8 (6)	C15—C14—C13	121.4 (8)
N5—N4—C12	121.8 (5)	C15—C14—H14A	119.3
C4—N4—C12X	132.6 (6)	C13—C14—H14A	119.3
N5—N4—C12X	117.0 (6)	C14—C15—C16	119.7 (8)
C12—N4—C12X	4.8 (10)	C14—C15—H15A	120.1
C5—N5—N4	105.35 (12)	C16—C15—H15A	120.1
N1—C1—N2	116.66 (14)	C15—C16—C17	119.7 (7)
N1—C1—S1	123.78 (12)	C15—C16—H16A	120.1
N2—C1—S1	119.56 (12)	C17—C16—H16A	120.1
N3—C2—C3	121.06 (14)	C16—C17—C12	119.8 (8)
N3—C2—H2A	119.5	C16—C17—H17A	120.1
C3—C2—H2A	119.5	C12—C17—H17A	120.1
C4—C3—C5	103.72 (13)	C17X—C12X—C13X	120.6 (10)
C4—C3—C2	129.01 (14)	C17X—C12X—N4	119.1 (9)
C5—C3—C2	127.19 (14)	C13X—C12X—N4	120.3 (9)
O1—C4—N4	121.53 (13)	C12X—C13X—C14X	119.0 (9)
O1—C4—C3	129.96 (14)	C12X—C13X—H13B	120.5
N4—C4—C3	108.46 (13)	C14X—C13X—H13B	120.5
N5—C5—C3	112.08 (14)	C15X—C14X—C13X	120.3 (9)
N5—C5—C18	120.41 (14)	C15X—C14X—H14B	119.8
C3—C5—C18	127.50 (14)	C13X—C14X—H14B	119.8
C11—C6—C7	121.69 (14)	C14X—C15X—C16X	119.7 (8)
C11—C6—O1	115.15 (13)	C14X—C15X—H15B	120.1
C7—C6—O1	123.15 (13)	C16X—C15X—H15B	120.1
C6—C7—C8	118.85 (14)	C15X—C16X—C17X	121.3 (7)
C6—C7—H7A	120.6	C15X—C16X—H16B	119.4
C8—C7—H7A	120.6	C17X—C16X—H16B	119.4
C7—C8—C9	120.55 (15)	C12X—C17X—C16X	119.0 (8)
C7—C8—H8A	119.7	C12X—C17X—H17B	120.5
C9—C8—H8A	119.7	C16X—C17X—H17B	120.5
C8—C9—C10	119.56 (15)	C5—C18—H18A	109.5
C8—C9—H9A	120.2	C5—C18—H18B	109.5
C10—C9—H9A	120.2	H18A—C18—H18B	109.5
C11—C10—C9	120.53 (15)	C5—C18—H18C	109.5
C11—C10—H10A	119.7	H18A—C18—H18C	109.5
C9—C10—H10A	119.7	H18B—C18—H18C	109.5

C1—N2—N3—C2	−166.48 (14)	C8—C9—C10—C11	−0.4 (3)
C4—N4—N5—C5	−0.51 (16)	C7—C6—C11—C10	0.4 (2)
C12—N4—N5—C5	−179.7 (12)	O1—C6—C11—C10	−179.52 (15)
C12X—N4—N5—C5	−179.4 (12)	C9—C10—C11—C6	0.1 (3)
N3—N2—C1—N1	−5.8 (2)	C4—N4—C12—C13	20 (3)
N3—N2—C1—S1	174.23 (10)	N5—N4—C12—C13	−161.4 (14)
N2—N3—C2—C3	177.04 (13)	C12X—N4—C12—C13	−164 (27)
N3—C2—C3—C4	7.7 (3)	C4—N4—C12—C17	−158.3 (11)
N3—C2—C3—C5	−168.53 (16)	N5—N4—C12—C17	21 (2)
C6—O1—C4—N4	107.65 (16)	C12X—N4—C12—C17	18 (23)
C6—O1—C4—C3	−75.5 (2)	C17—C12—C13—C14	1 (3)
N5—N4—C4—O1	178.07 (12)	N4—C12—C13—C14	−176.7 (16)
C12—N4—C4—O1	−2.8 (13)	C12—C13—C14—C15	−2 (2)
C12X—N4—C4—O1	−3.3 (14)	C13—C14—C15—C16	0.0 (18)
N5—N4—C4—C3	0.62 (17)	C14—C15—C16—C17	2.8 (13)
C12—N4—C4—C3	179.7 (13)	C15—C16—C17—C12	−3.7 (16)
C12X—N4—C4—C3	179.3 (14)	C13—C12—C17—C16	2 (3)
C5—C3—C4—O1	−177.63 (15)	N4—C12—C17—C16	179.6 (13)
C2—C3—C4—O1	5.5 (3)	C4—N4—C12X—C17X	−171.0 (11)
C5—C3—C4—N4	−0.45 (16)	N5—N4—C12X—C17X	8 (2)
C2—C3—C4—N4	−177.34 (15)	C12—N4—C12X—C17X	−175 (27)
N4—N5—C5—C3	0.21 (17)	C4—N4—C12X—C13X	12 (3)
N4—N5—C5—C18	178.89 (15)	N5—N4—C12X—C13X	−169.3 (15)
C4—C3—C5—N5	0.15 (18)	C12—N4—C12X—C13X	8 (23)
C2—C3—C5—N5	177.11 (15)	C17X—C12X—C13X—C14X	2 (3)
C4—C3—C5—C18	−178.41 (16)	N4—C12X—C13X—C14X	179.0 (16)
C2—C3—C5—C18	−1.5 (3)	C12X—C13X—C14X—C15X	−2 (2)
C4—O1—C6—C11	−178.56 (14)	C13X—C14X—C15X—C16X	0.2 (19)
C4—O1—C6—C7	1.5 (2)	C14X—C15X—C16X—C17X	1.3 (14)
C11—C6—C7—C8	−0.6 (2)	C13X—C12X—C17X—C16X	−1 (3)
O1—C6—C7—C8	179.31 (14)	N4—C12X—C17X—C16X	−177.6 (14)
C6—C7—C8—C9	0.3 (2)	C15X—C16X—C17X—C12X	−1.0 (17)
C7—C8—C9—C10	0.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···N5ⁱ	0.87 (2)	2.50 (2)	3.3237 (19)	158.1 (18)
N2—H1N2···S1ⁱⁱ	0.89 (2)	2.56 (2)	3.4414 (13)	167.7 (17)
C13—H13A···O1	0.95	2.22	2.814 (12)	120
C13—H13B···O1	0.79	2.28	2.814 (12)	125

Symmetry codes: (i) x+1/2, −y+3/2, z+1/2; (ii) −x+2, −y+2, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₈H₁₇N₅OS
M_r	351.43
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	8.8280 (1), 10.8519 (2), 17.7353 (2)
β (°)	94.379 (1)
V (Å³)	1694.09 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.21
Crystal size (mm)	0.29 × 0.27 × 0.22

Data collection
Diffractometer	Bruker SMART APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.942, 0.955
No. of measured, independent and observed [I > 2σ(I)] reflections	18467, 4948, 3879
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.113, 1.06
No. of reflections	4948
No. of parameters	294
No. of restraints	216
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.26

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···N5ⁱ	0.87 (2)	2.50 (2)	3.3237 (19)	158.1 (18)
N2—H1N2···S1ⁱⁱ	0.89 (2)	2.56 (2)	3.4414 (13)	167.7 (17)
C13—H13A···O1	0.95	2.22	2.814 (12)	120
C13—H13B···O1	0.79	2.28	2.814 (12)	125

Symmetry codes: (i) x+1/2, −y+3/2, z+1/2; (ii) −x+2, −y+2, −z+2.

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

§Thomson Reuters ResearcherID: A-5525-2009.

Acknowledgements

The authors thank Universiti Sains Malaysia (USM) for the Research University grant (No. 1001/PFIZIK/811160). CKQ also thanks USM for an Incentive Grant.

References

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