4-{(Z)-2-[(E)-Benzyl­idenehydrazinyl­idene]-3,6-dihydro-2H-1,3,4-thia­diazin-5-yl}-3-phenyl-1,2,3-oxadiazol-3-ium-5-olate

Fun, H.-K.; Quah, C.K.; Nithinchandra; Kalluraya, B.

doi:10.1107/S1600536811010609

organic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Pages o977-o978

doi:10.1107/S1600536811010609

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4-{(Z)-2-[(E)-Benzylidenehydrazinylidene]-3,6-dihydro-2H-1,3,4-thiadiazin-5-yl}-3-phenyl-1,2,3-oxadiazol-3-ium-5-olate

Hoong-Kun Fun,^a ^*‡ Ching Kheng Quah,^a § Nithinchandra ^b and Balakrishna Kalluraya ^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 19 March 2011; accepted 22 March 2011; online 26 March 2011)

The title compound, C₁₈H₁₄N₆O₂S, exists in trans and cis configurations with respect to the two acyclic C=N bonds [bond lengths = 1.2835 (9) and 1.3049 (9) Å]. The 3,6-dihydro-2H-1,3,4-thiadiazine ring adopts a half-boat conformation. The oxadiazol-3-ium ring makes dihedral angles of 53.70 (4) and 60.26 (4)° with the two phenyl rings. In the crystal, molecules are linked via pairs of intermolecular N—H⋯N hydrogen bonds, generating R₂²(8) ring motifs, and are further linked via intermolecular C—H⋯O and C—H⋯S hydrogen bonds into a three-dimensional network. The short intermolecular distance between the oxadiazol-3-ium rings [3.4154 (4) Å] indicates the existence of a π–π interaction.

Related literature

For general background to and the biological activity of sydnone derivatives, see: Newton & Ramsden (1982 ); Wagner & Hill (1974 ); Kalluraya & Rahiman (1997 ). For the preparation, see: Kalluraya et al. (2003 ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ). For bond-length data, see: Allen et al. (1987 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For ring conformations, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₁₈H₁₄N₆O₂S
M_r = 378.41
Triclinic, $[P \overline 1]$
a = 6.8752 (2) Å
b = 10.1335 (3) Å
c = 12.7374 (4) Å
α = 78.578 (1)°
β = 88.984 (1)°
γ = 85.874 (1)°
V = 867.58 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 100 K
0.58 × 0.27 × 0.08 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.885, T_max = 0.982
29236 measured reflections
7567 independent reflections
6818 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.101
S = 1.03
7567 reflections
248 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.65 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H1N3⋯N2ⁱ	0.852 (15)	2.015 (15)	2.8664 (9)	178.3 (11)
C14—H14A⋯O2ⁱⁱ	0.93	2.58	3.2303 (10)	127
C15—H15A⋯O2ⁱⁱⁱ	0.93	2.51	3.2391 (9)	136
C18—H18A⋯S1^iv	0.93	2.84	3.7061 (8)	155
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) -x+1, -y+2, -z; (iii) x, y-1, z; (iv) x+1, y, z.

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: 10.1107/S1600536811010609/sj5123sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811010609/sj5123Isup2.hkl

checkCIF report

Comment top

Sydnones are a class of mesoionic compounds containing a 1,2,3-oxadiazole ring system. A number of sydnone derivatives have shown diverse biological activities such as anti-inflammatory, analgesic and anti-arthritic (Newton & Ramsden, 1982; Wagner & Hill, 1974) properties. Sydnones with heterocyclic substituents at the 4-position are also known to exhibit a wide range of biological properties (Kalluraya & Rahiman, 1997). Encouraged by these reports and in continuation of our research for biologically-active nitrogen-containing heterocycles, a thiadiazine moiety was introduced at the 4-position of the phenylsydnone. A series of thiadiazines were synthesized by the condensation of 4-bromoacetyl-3-arylsydnones with N'-(phenylmethylidene)carbonohydrazide. 4-Bromoacetyl-3-arylsydnones were in turn obtained by the photochemical bromination of 4-acetyl-3-arylsydnones (Kalluraya et al., 2003).

The molecular structure is shown in Fig. 1. Bond lengths (Allen et al., 1987) and angles are within normal ranges. The title compound exists in trans and cis configurations with respect to the acyclic C7═N1 and C8═N2 bonds [C7═N1 = 1.2835 (9) Å and C8═N2 = 1.3049 (9) Å]. The 3,6-dihydro-2H-1,3,4-thiadiazine ring (S1/N3/N4/C8-C10) adopts a half boat-conformation with atom C9 deviating by 0.359 (1) Å from the mean plane through the remaining atoms, puckering parameters (Cremer & Pople, 1975) Q = 0.5575 (7) Å, Θ = 108.09 (7)° and ϕ = 137.99 (7)°. The oxadiazol-3-ium ring (O1/N5/N6/C11/C12) makes dihedral angles of 53.70 (4) and 60.26 (4) ° with two phenyl rings (C1-C6 and C13-C18).

In the crystal packing (Fig. 2), the molecules are linked via pairs of intermolecular N3–H1N3···N2 hydrogen bonds (Table 1), generating R₂²(8) ring motifs (Bernstein et al., 1995) and are further linked via intermolecular C14–H14A···O2, C15–H15A···O2 and C18–H18A···S1 hydrogen bonds (Table 1) into a three-dimensional network. The crystal packing is further consolidated by π-π stacking interactions between the centroids of O1/N5/N6/C11/C12 (Cg1) rings, with Cg1···Cg1^v distance of 3.4154 (4) Å [symmetry code: (v) 2-X, 2-Y, -Z].

Related literature top

For general background to and the biological activity of sydnone derivatives, see: Newton & Ramsden (1982); Wagner & Hill (1974); Kalluraya & Rahiman (1997). For the preparation, see: Kalluraya et al. (2003). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986). For bond-length data, see: Allen et al. (1987). For hydrogen-bond motifs, see: Bernstein et al. (1995). For ring conformations, see: Cremer & Pople (1975).

Experimental top

To a solution of 4-bromoacetyl-3-(p-anisyl)sydnone (0.01 mol) and N'-(phenylmethylidene) carbonohydrazide (0.01 mol) in ethanol, catalytic amount of anhydrous sodium acetate was added. The solution was stirred at room temperature for 2 to 3 h. The solid product that separated out was filtered and dried. It was then recrystallized from ethanol. Crystals suitable for X-ray analysis were obtained from 1:2 mixtures of DMF and ethanol by slow evaporation.

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 and the atom-numbering scheme.
	Fig. 2. The crystal structure of the title compound, viewed along the a axis. H atoms not involved in hydrogen bonds (dashed lines) have been omitted for clarity.

4-{(Z)-2-[(E)-Benzylidenehydrazinylidene]-3,6-dihydro- 2H-1,3,4-thiadiazin-5-yl}-3-phenyl-1,2,3-oxadiazol-3-ium-5-olate top

Crystal data top

C₁₈H₁₄N₆O₂S	Z = 2
M_r = 378.41	F(000) = 392
Triclinic, P1	D_x = 1.449 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.8752 (2) Å	Cell parameters from 9935 reflections
b = 10.1335 (3) Å	θ = 2.9–37.5°
c = 12.7374 (4) Å	µ = 0.21 mm⁻¹
α = 78.578 (1)°	T = 100 K
β = 88.984 (1)°	Block, yellow
γ = 85.874 (1)°	0.58 × 0.27 × 0.08 mm
V = 867.58 (5) Å³

Data collection top

Bruker SMART APEXII DUO CCD area-detector diffractometer	7567 independent reflections
Radiation source: fine-focus sealed tube	6818 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ϕ and ω scans	θ_max = 35.0°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −11→11
T_min = 0.885, T_max = 0.982	k = −16→16
29236 measured reflections	l = −20→20

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0601P)² + 0.2223P] where P = (F_o² + 2F_c²)/3
7567 reflections	(Δ/σ)_max = 0.001
248 parameters	Δρ_max = 0.65 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

C₁₈H₁₄N₆O₂S	γ = 85.874 (1)°
M_r = 378.41	V = 867.58 (5) Å³
Triclinic, P1	Z = 2
a = 6.8752 (2) Å	Mo Kα radiation
b = 10.1335 (3) Å	µ = 0.21 mm⁻¹
c = 12.7374 (4) Å	T = 100 K
α = 78.578 (1)°	0.58 × 0.27 × 0.08 mm
β = 88.984 (1)°

Data collection top

Bruker SMART APEXII DUO CCD area-detector diffractometer	7567 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	6818 reflections with I > 2σ(I)
T_min = 0.885, T_max = 0.982	R_int = 0.022
29236 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.65 e Å⁻³
7567 reflections	Δρ_min = −0.37 e Å⁻³
248 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems 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
S1	0.30498 (3)	0.783931 (19)	0.313847 (14)	0.01687 (5)
O1	0.78647 (9)	1.04039 (5)	−0.06087 (4)	0.01590 (10)
O2	0.64969 (9)	1.17463 (5)	0.04865 (5)	0.01895 (11)
N1	0.14753 (10)	0.81808 (6)	0.50454 (5)	0.01503 (11)
N2	0.31270 (10)	0.89086 (6)	0.48880 (5)	0.01459 (11)
N3	0.57604 (10)	0.93168 (6)	0.37674 (5)	0.01437 (10)
N4	0.65689 (9)	0.96382 (6)	0.27631 (5)	0.01327 (10)
N5	0.83490 (10)	0.90536 (6)	−0.05820 (5)	0.01491 (11)
N6	0.78483 (9)	0.84631 (6)	0.03858 (5)	0.01194 (10)
C1	−0.17886 (12)	0.66190 (8)	0.55457 (6)	0.01753 (12)
H1A	−0.0967	0.6423	0.5001	0.021*
C2	−0.34245 (13)	0.58975 (8)	0.58220 (7)	0.02162 (14)
H2A	−0.3682	0.5208	0.5470	0.026*
C3	−0.46864 (12)	0.62002 (9)	0.66263 (7)	0.02278 (15)
H3A	−0.5789	0.5721	0.6802	0.027*
C4	−0.42941 (12)	0.72184 (8)	0.71643 (7)	0.02058 (14)
H4A	−0.5135	0.7423	0.7698	0.025*
C5	−0.26331 (11)	0.79319 (7)	0.68997 (6)	0.01674 (12)
H5A	−0.2362	0.8604	0.7267	0.020*
C6	−0.13718 (11)	0.76450 (7)	0.60870 (5)	0.01428 (11)
C7	0.03747 (11)	0.83958 (7)	0.58273 (6)	0.01507 (12)
H7A	0.0684	0.9026	0.6227	0.018*
C8	0.40347 (10)	0.87300 (7)	0.40132 (5)	0.01289 (11)
C9	0.52692 (13)	0.75797 (7)	0.23945 (6)	0.01832 (13)
H9A	0.6125	0.6886	0.2826	0.022*
H9B	0.4953	0.7268	0.1749	0.022*
C10	0.63071 (10)	0.88567 (7)	0.20958 (5)	0.01271 (11)
C11	0.70776 (10)	0.92958 (6)	0.10204 (5)	0.01202 (10)
C12	0.70589 (10)	1.06188 (7)	0.03802 (5)	0.01354 (11)
C13	0.82190 (10)	0.70199 (7)	0.06881 (5)	0.01254 (11)
C14	0.73006 (11)	0.61939 (7)	0.01353 (6)	0.01455 (11)
H14A	0.6507	0.6558	−0.0449	0.017*
C15	0.76016 (11)	0.48012 (7)	0.04823 (7)	0.01743 (13)
H15A	0.7000	0.4223	0.0128	0.021*
C16	0.87966 (12)	0.42727 (7)	0.13554 (7)	0.01914 (13)
H16A	0.8974	0.3343	0.1588	0.023*
C17	0.97311 (13)	0.51258 (8)	0.18857 (7)	0.01997 (14)
H17A	1.0547	0.4764	0.2461	0.024*
C18	0.94424 (11)	0.65205 (7)	0.15537 (6)	0.01683 (12)
H18A	1.0052	0.7101	0.1902	0.020*
H1N3	0.607 (2)	0.9855 (15)	0.4163 (12)	0.029 (3)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01861 (9)	0.02017 (9)	0.01455 (8)	−0.00900 (6)	0.00407 (6)	−0.00768 (6)
O1	0.0196 (2)	0.0137 (2)	0.0136 (2)	−0.00159 (18)	0.00192 (18)	−0.00089 (16)
O2	0.0219 (3)	0.0114 (2)	0.0231 (3)	0.00014 (18)	0.0021 (2)	−0.00294 (18)
N1	0.0161 (3)	0.0161 (2)	0.0132 (2)	−0.0050 (2)	0.00206 (19)	−0.00282 (18)
N2	0.0162 (3)	0.0164 (2)	0.0120 (2)	−0.0053 (2)	0.00244 (19)	−0.00370 (18)
N3	0.0157 (3)	0.0175 (2)	0.0113 (2)	−0.0056 (2)	0.00213 (19)	−0.00495 (18)
N4	0.0143 (2)	0.0144 (2)	0.0118 (2)	−0.00285 (18)	0.00189 (18)	−0.00367 (17)
N5	0.0180 (3)	0.0141 (2)	0.0126 (2)	−0.00152 (19)	0.00223 (19)	−0.00250 (18)
N6	0.0129 (2)	0.0116 (2)	0.0117 (2)	−0.00116 (17)	0.00069 (18)	−0.00305 (17)
C1	0.0191 (3)	0.0174 (3)	0.0166 (3)	−0.0043 (2)	−0.0004 (2)	−0.0035 (2)
C2	0.0211 (3)	0.0196 (3)	0.0245 (3)	−0.0070 (3)	−0.0030 (3)	−0.0028 (3)
C3	0.0163 (3)	0.0216 (3)	0.0282 (4)	−0.0053 (3)	−0.0003 (3)	0.0020 (3)
C4	0.0157 (3)	0.0206 (3)	0.0228 (3)	−0.0006 (2)	0.0038 (3)	0.0016 (3)
C5	0.0169 (3)	0.0153 (3)	0.0170 (3)	−0.0006 (2)	0.0025 (2)	−0.0010 (2)
C6	0.0153 (3)	0.0135 (2)	0.0135 (2)	−0.0024 (2)	0.0004 (2)	−0.0008 (2)
C7	0.0171 (3)	0.0151 (3)	0.0134 (3)	−0.0038 (2)	0.0023 (2)	−0.0029 (2)
C8	0.0150 (3)	0.0125 (2)	0.0114 (2)	−0.0027 (2)	0.0007 (2)	−0.00234 (19)
C9	0.0240 (3)	0.0139 (3)	0.0188 (3)	−0.0064 (2)	0.0084 (3)	−0.0063 (2)
C10	0.0145 (3)	0.0114 (2)	0.0126 (2)	−0.0022 (2)	0.0021 (2)	−0.00294 (19)
C11	0.0133 (3)	0.0109 (2)	0.0122 (2)	−0.00156 (19)	0.0016 (2)	−0.00314 (18)
C12	0.0138 (3)	0.0126 (2)	0.0142 (3)	−0.0017 (2)	0.0007 (2)	−0.0023 (2)
C13	0.0131 (3)	0.0111 (2)	0.0136 (2)	−0.00038 (19)	0.0008 (2)	−0.00321 (19)
C14	0.0138 (3)	0.0141 (3)	0.0168 (3)	−0.0015 (2)	0.0006 (2)	−0.0055 (2)
C15	0.0155 (3)	0.0136 (3)	0.0242 (3)	−0.0027 (2)	0.0037 (2)	−0.0061 (2)
C16	0.0182 (3)	0.0134 (3)	0.0244 (3)	0.0003 (2)	0.0049 (3)	−0.0012 (2)
C17	0.0205 (3)	0.0171 (3)	0.0203 (3)	0.0034 (2)	−0.0016 (3)	−0.0006 (2)
C18	0.0173 (3)	0.0162 (3)	0.0170 (3)	0.0009 (2)	−0.0030 (2)	−0.0037 (2)

Geometric parameters (Å, º) top

S1—C8	1.7400 (7)	C4—C5	1.3961 (11)
S1—C9	1.8126 (8)	C4—H4A	0.9300
O1—N5	1.3787 (8)	C5—C6	1.3996 (10)
O1—C12	1.4168 (9)	C5—H5A	0.9300
O2—C12	1.2120 (8)	C6—C7	1.4655 (10)
N1—C7	1.2835 (9)	C7—H7A	0.9300
N1—N2	1.3884 (9)	C9—C10	1.5022 (10)
N2—C8	1.3049 (9)	C9—H9A	0.9700
N3—C8	1.3689 (9)	C9—H9B	0.9700
N3—N4	1.3737 (8)	C10—C11	1.4567 (9)
N3—H1N3	0.852 (15)	C11—C12	1.4238 (9)
N4—C10	1.2940 (9)	C13—C14	1.3857 (10)
N5—N6	1.3110 (8)	C13—C18	1.3892 (10)
N6—C11	1.3553 (9)	C14—C15	1.3944 (10)
N6—C13	1.4418 (9)	C14—H14A	0.9300
C1—C2	1.3878 (11)	C15—C16	1.3898 (12)
C1—C6	1.4044 (10)	C15—H15A	0.9300
C1—H1A	0.9300	C16—C17	1.3940 (12)
C2—C3	1.3967 (13)	C16—H16A	0.9300
C2—H2A	0.9300	C17—C18	1.3935 (11)
C3—C4	1.3906 (13)	C17—H17A	0.9300
C3—H3A	0.9300	C18—H18A	0.9300

C8—S1—C9	96.96 (4)	N3—C8—S1	120.03 (5)
N5—O1—C12	111.40 (5)	C10—C9—S1	111.37 (5)
C7—N1—N2	115.29 (6)	C10—C9—H9A	109.4
C8—N2—N1	110.58 (6)	S1—C9—H9A	109.4
C8—N3—N4	125.97 (6)	C10—C9—H9B	109.4
C8—N3—H1N3	115.9 (11)	S1—C9—H9B	109.4
N4—N3—H1N3	111.4 (10)	H9A—C9—H9B	108.0
C10—N4—N3	118.01 (6)	N4—C10—C11	115.69 (6)
N6—N5—O1	103.91 (5)	N4—C10—C9	122.87 (6)
N5—N6—C11	115.66 (6)	C11—C10—C9	121.45 (6)
N5—N6—C13	118.02 (6)	N6—C11—C12	105.42 (6)
C11—N6—C13	126.28 (6)	N6—C11—C10	125.08 (6)
C2—C1—C6	120.13 (7)	C12—C11—C10	129.33 (6)
C2—C1—H1A	119.9	O2—C12—O1	120.16 (6)
C6—C1—H1A	119.9	O2—C12—C11	136.18 (7)
C1—C2—C3	120.37 (8)	O1—C12—C11	103.61 (5)
C1—C2—H2A	119.8	C14—C13—C18	122.93 (6)
C3—C2—H2A	119.8	C14—C13—N6	119.23 (6)
C4—C3—C2	120.01 (8)	C18—C13—N6	117.80 (6)
C4—C3—H3A	120.0	C13—C14—C15	118.00 (7)
C2—C3—H3A	120.0	C13—C14—H14A	121.0
C3—C4—C5	119.76 (8)	C15—C14—H14A	121.0
C3—C4—H4A	120.1	C16—C15—C14	120.34 (7)
C5—C4—H4A	120.1	C16—C15—H15A	119.8
C4—C5—C6	120.62 (7)	C14—C15—H15A	119.8
C4—C5—H5A	119.7	C15—C16—C17	120.51 (7)
C6—C5—H5A	119.7	C15—C16—H16A	119.7
C5—C6—C1	119.11 (7)	C17—C16—H16A	119.7
C5—C6—C7	119.85 (7)	C18—C17—C16	119.99 (7)
C1—C6—C7	121.04 (7)	C18—C17—H17A	120.0
N1—C7—C6	119.76 (6)	C16—C17—H17A	120.0
N1—C7—H7A	120.1	C13—C18—C17	118.21 (7)
C6—C7—H7A	120.1	C13—C18—H18A	120.9
N2—C8—N3	118.27 (6)	C17—C18—H18A	120.9
N2—C8—S1	121.63 (5)

C7—N1—N2—C8	−173.31 (7)	N5—N6—C11—C12	0.31 (8)
C8—N3—N4—C10	−33.94 (10)	C13—N6—C11—C12	178.09 (6)
C12—O1—N5—N6	0.31 (8)	N5—N6—C11—C10	175.83 (7)
O1—N5—N6—C11	−0.39 (8)	C13—N6—C11—C10	−6.39 (11)
O1—N5—N6—C13	−178.36 (6)	N4—C10—C11—N6	145.60 (7)
C6—C1—C2—C3	1.12 (12)	C9—C10—C11—N6	−34.74 (11)
C1—C2—C3—C4	−0.80 (13)	N4—C10—C11—C12	−39.98 (11)
C2—C3—C4—C5	−0.21 (12)	C9—C10—C11—C12	139.68 (8)
C3—C4—C5—C6	0.90 (12)	N5—O1—C12—O2	−177.78 (7)
C4—C5—C6—C1	−0.58 (11)	N5—O1—C12—C11	−0.14 (8)
C4—C5—C6—C7	−179.42 (7)	N6—C11—C12—O2	176.97 (9)
C2—C1—C6—C5	−0.43 (11)	C10—C11—C12—O2	1.70 (14)
C2—C1—C6—C7	178.40 (7)	N6—C11—C12—O1	−0.09 (7)
N2—N1—C7—C6	−177.89 (6)	C10—C11—C12—O1	−175.35 (7)
C5—C6—C7—N1	−176.39 (7)	N5—N6—C13—C14	−62.37 (9)
C1—C6—C7—N1	4.79 (11)	C11—N6—C13—C14	119.90 (8)
N1—N2—C8—N3	−176.40 (6)	N5—N6—C13—C18	119.82 (7)
N1—N2—C8—S1	6.57 (9)	C11—N6—C13—C18	−57.91 (10)
N4—N3—C8—N2	−156.39 (7)	C18—C13—C14—C15	1.16 (11)
N4—N3—C8—S1	20.70 (10)	N6—C13—C14—C15	−176.54 (6)
C9—S1—C8—N2	−164.38 (6)	C13—C14—C15—C16	−0.22 (11)
C9—S1—C8—N3	18.64 (6)	C14—C15—C16—C17	−0.92 (12)
C8—S1—C9—C10	−45.98 (6)	C15—C16—C17—C18	1.17 (12)
N3—N4—C10—C11	175.86 (6)	C14—C13—C18—C17	−0.91 (11)
N3—N4—C10—C9	−3.80 (11)	N6—C13—C18—C17	176.81 (7)
S1—C9—C10—N4	45.22 (9)	C16—C17—C18—C13	−0.27 (12)
S1—C9—C10—C11	−134.42 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1N3···N2ⁱ	0.852 (15)	2.015 (15)	2.8664 (9)	178.3 (11)
C14—H14A···O2ⁱⁱ	0.93	2.58	3.2303 (10)	127
C15—H15A···O2ⁱⁱⁱ	0.93	2.51	3.2391 (9)	136
C18—H18A···S1^iv	0.93	2.84	3.7061 (8)	155

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

Experimental details

Crystal data
Chemical formula	C₁₈H₁₄N₆O₂S
M_r	378.41
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	6.8752 (2), 10.1335 (3), 12.7374 (4)
α, β, γ (°)	78.578 (1), 88.984 (1), 85.874 (1)
V (Å³)	867.58 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.21
Crystal size (mm)	0.58 × 0.27 × 0.08

Data collection
Diffractometer	Bruker SMART APEXII DUO CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.885, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections	29236, 7567, 6818
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.807

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.101, 1.03
No. of reflections	7567
No. of parameters	248
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.65, −0.37

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
N3—H1N3···N2ⁱ	0.852 (15)	2.015 (15)	2.8664 (9)	178.3 (11)
C14—H14A···O2ⁱⁱ	0.93	2.58	3.2303 (10)	127
C15—H15A···O2ⁱⁱⁱ	0.93	2.51	3.2391 (9)	136
C18—H18A···S1^iv	0.93	2.84	3.7061 (8)	155

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

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

§Thomson Reuters ResearcherID: A-5525-2009.

Acknowledgements

HKF and CKQ thank Universiti Sains Malaysia for the Research University Grant (No. 1001/PFIZIK/811160).

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