7-(4-Fluoro­benzyl­amino)-2-phenyl-1,2,4-triazolo[1,5-a][1,3,5]triazin-5-amine methanol disolvate

Dolzhenko, A.V.; Tan, G.K.; Koh, L.L.; Dolzhenko, A.V.; Chui, W.K.

doi:10.1107/S1600536811014176

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Pages o1183-o1184

doi:10.1107/S1600536811014176

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7-(4-Fluorobenzylamino)-2-phenyl-1,2,4-triazolo[1,5-a][1,3,5]triazin-5-amine methanol disolvate †

Anton V. Dolzhenko,^a ^*‡ Geok Kheng Tan,^b Lip Lin Koh,^b Anna V. Dolzhenko ^c and Wai Keung Chui ^d

^aSchool of Pharmacy, Faculty of Health Sciences, Curtin University of Technology, GPO Box U1987, Perth 6845, Western Australia, Australia, ^bDepartment of Chemistry, Faculty of Science, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore, ^cPerm State Pharmaceutical Academy, 2 Polevaya Street, Perm 614990, Russian Federation, and ^dDepartment of Pharmacy, Faculty of Science, National University of Singapore, 18 Science Drive 4, Singapore 117543, Singapore
^*Correspondence e-mail: anton.dolzhenko@curtin.edu.au

(Received 12 April 2011; accepted 15 April 2011; online 22 April 2011)

The 1,2,4-triazolo[1,5-a][1,3,5]triazine system in the title compound, C₁₇H₁₄FN₇·2CH₃OH, is essentially planar, with an r.m.s. deviation of 0.0215 Å. The attached phenyl ring lies almost in the mean plane of the heterocyclic core [dihedral angle = 3.56 (4)°]. In the crystal, centrosymmetric inversion dimers connected via intermolecular N—H⋯N hydrogen bonds between H atom of the primary amino group and the triazine N atom [R₂²(8) graph-set motif] form sheets parallel to (010). A second set of dimers connected via N—H⋯F hydrogen bonds between the other H atom of the primary amino group and the F atom forms an R₂²(24) graph-set motif linking the sheets. Methanol solvent molecules are packed in channels running along the [010] direction.

Related literature

For a review of the synthesis and biological activity of 1,2,4-triazolo[1,5-a][1,3,5]triazines, see: Dolzhenko et al. (2006 ). For our work on the synthesis and biological activity of 1,2,4-triazolo[1,5-a][1,3,5]triazines, see: Dolzhenko et al. (2007a ,b , 2008a ,b , 2011a ). For the crystal structures of similar 1,2,4-triazolo[1,5-a][1,3,5]triazines, see: Dolzhenko et al. (2007c ,d , 2008c , 2011b ); Gilardi (1973 ); Khankischpur et al. (2010 ). For a review on the graph-set analysis of hydrogen bonding, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₇H₁₄FN₇·2CH₄O
M_r = 399.44
Monoclinic, C 2/c
a = 27.516 (3) Å
b = 7.0091 (8) Å
c = 20.778 (3) Å
β = 104.380 (3)°
V = 3881.7 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 100 K
0.56 × 0.18 × 0.02 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ) T_min = 0.946, T_max = 0.998
11861 measured reflections
3820 independent reflections
2876 reflections with I > 2σ(I)
R_int = 0.066

Refinement

R[F² > 2σ(F²)] = 0.084
wR(F²) = 0.183
S = 1.20
3820 reflections
275 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N6—H6B⋯O2Sⁱ	0.87 (2)	2.52 (3)	3.033 (4)	118 (3)
N6—H6B⋯F1ⁱⁱ	0.87 (2)	2.48 (2)	3.307 (3)	159 (3)
N6—H6A⋯N5ⁱ	0.90 (2)	2.13 (2)	3.025 (4)	178 (3)
N7—H7N⋯O1Sⁱⁱⁱ	0.88 (2)	1.96 (2)	2.797 (4)	158 (3)
O1S—H1S⋯O2S	0.84	1.86	2.690 (3)	169
O2S—H2S⋯N2	0.84	1.91	2.731 (4)	166
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) -x+1, -y+1, -z+1; (iii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811014176/sj5125sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811014176/sj5125Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811014176/sj5125Isup3.cdx

checkCIF report

Comment top

The 1,2,4-triazolo[1,5-a]triazine heterocyclic system has been well recognized as a promising scaffold for the construction of compounds with diverse biological effects (Dolzhenko et al., 2006). In our search for potential therapeutic agents in this class of compounds we devised a number of effective methods for the preparation of 1,2,4-triazolo[1,5-a]triazines (Dolzhenko et al., 2007a,b; Dolzhenko et al., 2008a,b). The structural investigations of 1,2,4-triazolo[1,5-a]triazines include an earlier report (Gilardi, 1973) of the 5,7-bis(dimethylamino)-2-methylthio-1,2,4-triazolo[1,5-a]triazine structure, our publications regarding structures of various amino substituted 1,2,4-triazolo[1,5-a]triazines (Dolzhenko et al., 2007c,d; Dolzhenko et al., 2008c; Dolzhenko et al., 2011b), and a recent paper (Khankischpur et al., 2010) mentioning the 2-amino-5-(2-phenylethyl)[1,2,4]triazolo[1,5-a] [1,3,5]triazin-7(6H)-one structure. In continuation of our program on the synthesis and structural investigation of potentially bioactive 1,2,4-triazolo[1,5-a]triazines, we synthesized 7-(4-fluorobenzylamino)-2-phenyl-1,2,4-triazolo[1,5-a][1,3,5]triazine-5-amine using a recently developed method (Dolzhenko et al., 2008a) and report herein its molecular and crystal structure.

7-(4-Fluorobenzylamino)-2-phenyl-1,2,4-triazolo[1,5-a][1,3,5]triazine-5-amine crystallizes together with two methanol molecules (Fig. 1 & 2). The closely similar 7-dimethylamino-1,2,4-triazolo[1,5-a][1,3,5]triazin-5-amine reported earlier (Dolzhenko et al., 2008c) also crystallized in the form of a methanol solvate. The 1,2,4-triazolo[1,5-a][1,3,5]triazine heterocyclic system is essentially planar with an r.m.s. deviation of 0.0215 Å. The phenyl ring mean plane C5—C10 makes a small dihedral angle of 3.56 (4)° with the mean plane of the 1,2,4-triazolo[1,5-a][1,3,5]triazine system. The amino group nitrogen atoms N6 and N7 are located practically in the plane of the heterocyclic core with slight deviations of 0.0861 (41) Å above and 0.0663 (41) Å below the mean plane, correspondingly. The molecule is twisted at the aminomethyl bridge N7—C11 [C3—N7—C11—C12 torsion angle is 100.38 (36)°].

In the crystal, molecules of 7-(4-fluorobenzylamino)-2-phenyl-1,2,4-triazolo[1,5-a][1,3,5]triazine-5-amine form two types of centrosymmetric inversion dimers (Fig. 2). The triazine N5 atom is connected with amino group N6—H6A of a neighbouring molecule by intermolecular N–H···N hydrogen bond making R²₂(8) graph-set motif (Bernstein et al., 1995) arranging the molecules in sheets parallel to the (010) plane. A second set of dimers connected via N–H···F hydrogen bonding between the N6—H6A amino group and the F1 atom of an adjacent molecule forms a R²₂(24) graph-set motif linking the sheets. The methanol molecules are packed in channels running along the [010] direction and also participate in linking the sheets via O–H···N and N–H···O contacts.

Related literature top

For a review of the synthesis and biological activity of 1,2,4-triazolo[1,5-a][1,3,5]triazines, see: Dolzhenko et al. (2006). For our work on the synthesis and biological activity of 1,2,4-triazolo[1,5-a][1,3,5]triazines, see: Dolzhenko et al. (2007a,b, 2008a,b, 2011a). For the crystal structures of similar 1,2,4-triazolo[1,5-a][1,3,5]triazines, see: Dolzhenko et al. (2007c,d, 2008c, 2011b); Gilardi (1973); Khankischpur et al. (2010). For a review on the graph-set analysis of hydrogen bonding, see: Bernstein et al. (1995).

Experimental top

The title compound was prepared according to the previously reported general method (Dolzhenko et al., 2008a). 2-Phenyl-7-trichloromethyl-1,2,4-triazolo[1,5-a][1,3,5]triazin-5-amine (0.66 g, 2.0 mmol) was added to a solution of 4-fluorobenzylamine (0.28 ml, 2.5 mmol) in DMF (5 ml) and the mixture was heated at 70–80 °C with stirring for 3 h. After cooling, ice-cold water (40 ml) was added and the product was filtered and recrystallized from methanol.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of 7-(4-fluorobenzylamino)-2-phenyl-1,2,4-triazolo[1,5-a][1,3,5]triazine-5-amine methanol disolvate showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Crystal packing in the cell (view along axis b).

7-(4-Fluorobenzylamino)-2-phenyl-1,2,4-triazolo[1,5-a][1,3,5]triazin-5- amine methanol disolvate top

Crystal data top

C₁₇H₁₄FN₇·2CH₄O	F(000) = 1680
M_r = 399.44	D_x = 1.367 Mg m⁻³
Monoclinic, C2/c	Melting point: 523 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 27.516 (3) Å	Cell parameters from 653 reflections
b = 7.0091 (8) Å	θ = 2.8–23.5°
c = 20.778 (3) Å	µ = 0.10 mm⁻¹
β = 104.380 (3)°	T = 100 K
V = 3881.7 (8) Å³	Thin plate, colourless
Z = 8	0.56 × 0.18 × 0.02 mm

Data collection top

Bruker SMART APEX CCD diffractometer	3820 independent reflections
Radiation source: fine-focus sealed tube	2876 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.066
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −31→33
T_min = 0.946, T_max = 0.998	k = −8→8
11861 measured reflections	l = −25→25

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)] = 0.084	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.183	H atoms treated by a mixture of independent and constrained refinement
S = 1.20	w = 1/[σ²(F_o²) + (0.067P)² + 5.3197P] where P = (F_o² + 2F_c²)/3
3820 reflections	(Δ/σ)_max < 0.001
275 parameters	Δρ_max = 0.41 e Å⁻³
3 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₁₇H₁₄FN₇·2CH₄O	V = 3881.7 (8) Å³
M_r = 399.44	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 27.516 (3) Å	µ = 0.10 mm⁻¹
b = 7.0091 (8) Å	T = 100 K
c = 20.778 (3) Å	0.56 × 0.18 × 0.02 mm
β = 104.380 (3)°

Data collection top

Bruker SMART APEX CCD diffractometer	3820 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	2876 reflections with I > 2σ(I)
T_min = 0.946, T_max = 0.998	R_int = 0.066
11861 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.084	3 restraints
wR(F²) = 0.183	H atoms treated by a mixture of independent and constrained refinement
S = 1.20	Δρ_max = 0.41 e Å⁻³
3820 reflections	Δρ_min = −0.27 e Å⁻³
275 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
F1	0.55659 (7)	0.8048 (3)	0.40137 (10)	0.0281 (5)
N1	0.31099 (10)	0.1280 (4)	0.27731 (12)	0.0158 (6)
N2	0.23799 (10)	0.1664 (4)	0.30860 (13)	0.0154 (6)
N3	0.31934 (10)	0.1366 (4)	0.34551 (12)	0.0147 (6)
N4	0.36437 (10)	0.1522 (4)	0.45512 (13)	0.0167 (6)
N5	0.27356 (10)	0.1770 (4)	0.42739 (13)	0.0163 (6)
N6	0.32075 (11)	0.1989 (4)	0.53427 (14)	0.0211 (7)
H6A	0.2925 (10)	0.233 (5)	0.5459 (17)	0.025*
H6B	0.3506 (9)	0.196 (5)	0.5615 (15)	0.025*
N7	0.40528 (10)	0.1013 (4)	0.37144 (13)	0.0176 (6)
H7N	0.4053 (13)	0.084 (5)	0.3297 (10)	0.021*
C1	0.26169 (12)	0.1470 (4)	0.25817 (15)	0.0139 (7)
C2	0.27519 (12)	0.1601 (5)	0.36343 (16)	0.0162 (7)
C3	0.36411 (12)	0.1303 (5)	0.39200 (15)	0.0150 (7)
C4	0.31899 (12)	0.1752 (4)	0.46998 (15)	0.0151 (7)
C5	0.23498 (12)	0.1490 (5)	0.18730 (15)	0.0150 (7)
C6	0.18294 (12)	0.1645 (5)	0.16728 (16)	0.0187 (7)
H6	0.1641	0.1717	0.1998	0.022*
C7	0.15854 (13)	0.1694 (5)	0.10072 (16)	0.0209 (8)
H7	0.1230	0.1805	0.0876	0.025*
C8	0.18578 (13)	0.1582 (5)	0.05306 (16)	0.0205 (8)
H8	0.1690	0.1636	0.0072	0.025*
C9	0.23750 (14)	0.1392 (5)	0.07209 (16)	0.0225 (8)
H9	0.2561	0.1293	0.0394	0.027*
C10	0.26205 (13)	0.1346 (5)	0.13909 (16)	0.0189 (7)
H10	0.2975	0.1216	0.1521	0.023*
C11	0.45495 (12)	0.1136 (5)	0.41539 (16)	0.0192 (8)
H11A	0.4756	0.0075	0.4052	0.023*
H11B	0.4524	0.0969	0.4617	0.023*
C12	0.48156 (12)	0.3013 (5)	0.41021 (15)	0.0161 (7)
C13	0.52866 (12)	0.3337 (5)	0.45154 (16)	0.0196 (8)
H13	0.5439	0.2371	0.4820	0.024*
C14	0.55430 (12)	0.5031 (5)	0.44964 (16)	0.0195 (8)
H14	0.5864	0.5251	0.4787	0.023*
C15	0.53142 (13)	0.6384 (5)	0.40394 (17)	0.0209 (8)
C16	0.48547 (13)	0.6132 (5)	0.36150 (16)	0.0223 (8)
H16	0.4711	0.7092	0.3303	0.027*
C17	0.46011 (13)	0.4430 (5)	0.36504 (16)	0.0200 (8)
H17	0.4278	0.4233	0.3363	0.024*
O1S	0.07528 (9)	0.4762 (4)	0.24754 (11)	0.0271 (6)
H1S	0.0990	0.4061	0.2677	0.041*
C1S	0.12533 (14)	0.0350 (6)	0.31845 (18)	0.0310 (9)
H1S1	0.1364	−0.0167	0.3635	0.047*
H1S2	0.1395	−0.0416	0.2881	0.047*
H1S3	0.0886	0.0311	0.3041	0.047*
O2S	0.14190 (9)	0.2264 (4)	0.31791 (12)	0.0250 (6)
H2S	0.1720	0.2276	0.3160	0.037*
C2S	0.06242 (18)	0.6058 (6)	0.2930 (2)	0.0419 (11)
H2S1	0.0920	0.6315	0.3293	0.063*
H2S2	0.0359	0.5501	0.3111	0.063*
H2S3	0.0504	0.7253	0.2701	0.063*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0251 (12)	0.0258 (12)	0.0301 (11)	−0.0071 (9)	0.0004 (9)	0.0057 (10)
N1	0.0165 (15)	0.0191 (15)	0.0120 (13)	0.0012 (12)	0.0037 (11)	−0.0003 (12)
N2	0.0127 (14)	0.0177 (15)	0.0139 (13)	−0.0010 (11)	−0.0002 (11)	−0.0008 (12)
N3	0.0129 (14)	0.0170 (15)	0.0131 (13)	−0.0014 (11)	0.0011 (11)	−0.0006 (11)
N4	0.0138 (14)	0.0184 (15)	0.0163 (14)	0.0000 (11)	0.0010 (11)	−0.0006 (12)
N5	0.0143 (14)	0.0204 (16)	0.0148 (13)	0.0011 (11)	0.0048 (11)	−0.0021 (12)
N6	0.0152 (16)	0.0319 (18)	0.0147 (15)	−0.0005 (13)	0.0007 (12)	−0.0026 (13)
N7	0.0131 (14)	0.0277 (17)	0.0109 (13)	−0.0019 (12)	0.0008 (11)	−0.0006 (12)
C1	0.0154 (17)	0.0081 (16)	0.0177 (16)	−0.0018 (12)	0.0031 (13)	−0.0010 (13)
C2	0.0189 (17)	0.0117 (17)	0.0184 (17)	−0.0014 (13)	0.0052 (14)	−0.0007 (14)
C3	0.0170 (17)	0.0117 (16)	0.0158 (16)	−0.0037 (13)	0.0034 (13)	−0.0009 (13)
C4	0.0173 (17)	0.0123 (17)	0.0127 (15)	−0.0007 (13)	−0.0017 (13)	0.0002 (13)
C5	0.0202 (18)	0.0114 (16)	0.0125 (16)	−0.0012 (13)	0.0024 (13)	−0.0015 (13)
C6	0.0196 (18)	0.0182 (19)	0.0183 (17)	−0.0015 (14)	0.0048 (14)	−0.0030 (14)
C7	0.0156 (18)	0.0212 (19)	0.0219 (18)	0.0011 (14)	−0.0030 (14)	−0.0017 (15)
C8	0.028 (2)	0.0187 (19)	0.0119 (16)	0.0035 (15)	−0.0005 (14)	0.0009 (14)
C9	0.032 (2)	0.022 (2)	0.0171 (17)	0.0009 (16)	0.0130 (15)	0.0038 (15)
C10	0.0168 (17)	0.0211 (19)	0.0170 (17)	0.0009 (14)	0.0011 (14)	0.0031 (15)
C11	0.0147 (17)	0.0240 (19)	0.0183 (17)	0.0013 (14)	0.0032 (14)	0.0014 (15)
C12	0.0156 (17)	0.0228 (19)	0.0129 (15)	0.0015 (14)	0.0092 (13)	−0.0034 (14)
C13	0.0158 (17)	0.027 (2)	0.0157 (16)	0.0011 (14)	0.0030 (13)	0.0026 (15)
C14	0.0111 (17)	0.026 (2)	0.0186 (17)	−0.0029 (14)	−0.0023 (13)	0.0000 (15)
C15	0.0234 (19)	0.0201 (19)	0.0214 (17)	−0.0002 (15)	0.0099 (15)	−0.0005 (15)
C16	0.0226 (19)	0.024 (2)	0.0169 (17)	0.0037 (15)	−0.0018 (14)	0.0031 (15)
C17	0.0159 (17)	0.027 (2)	0.0162 (16)	−0.0003 (15)	0.0017 (14)	0.0002 (15)
O1S	0.0222 (14)	0.0407 (17)	0.0166 (12)	0.0037 (12)	0.0014 (10)	0.0019 (12)
C1S	0.026 (2)	0.044 (3)	0.025 (2)	−0.0040 (18)	0.0104 (17)	−0.0041 (18)
O2S	0.0158 (13)	0.0364 (16)	0.0235 (13)	0.0028 (11)	0.0062 (11)	−0.0015 (12)
C2S	0.065 (3)	0.027 (2)	0.038 (2)	0.006 (2)	0.020 (2)	0.0071 (19)

Geometric parameters (Å, º) top

F1—C15	1.364 (4)	C9—C10	1.389 (5)
N1—C1	1.322 (4)	C9—H9	0.9500
N1—N3	1.379 (3)	C10—H10	0.9500
N2—C2	1.330 (4)	C11—C12	1.523 (5)
N2—C1	1.371 (4)	C11—H11A	0.9900
N3—C3	1.364 (4)	C11—H11B	0.9900
N3—C2	1.366 (4)	C12—C13	1.384 (5)
N4—C3	1.319 (4)	C12—C17	1.393 (5)
N4—C4	1.368 (4)	C13—C14	1.387 (5)
N5—C4	1.340 (4)	C13—H13	0.9500
N5—C2	1.346 (4)	C14—C15	1.378 (5)
N6—C4	1.335 (4)	C14—H14	0.9500
N6—H6A	0.900 (18)	C15—C16	1.362 (5)
N6—H6B	0.874 (18)	C16—C17	1.393 (5)
N7—C3	1.322 (4)	C16—H16	0.9500
N7—C11	1.445 (4)	C17—H17	0.9500
N7—H7N	0.877 (18)	O1S—C2S	1.418 (5)
C1—C5	1.473 (4)	O1S—H1S	0.8400
C5—C6	1.392 (5)	C1S—O2S	1.418 (5)
C5—C10	1.393 (4)	C1S—H1S1	0.9800
C6—C7	1.380 (5)	C1S—H1S2	0.9800
C6—H6	0.9500	C1S—H1S3	0.9800
C7—C8	1.385 (5)	O2S—H2S	0.8400
C7—H7	0.9500	C2S—H2S1	0.9800
C8—C9	1.386 (5)	C2S—H2S2	0.9800
C8—H8	0.9500	C2S—H2S3	0.9800

C1—N1—N3	101.6 (2)	C9—C10—H10	119.8
C2—N2—C1	103.9 (3)	C5—C10—H10	119.8
C3—N3—C2	121.2 (3)	N7—C11—C12	113.7 (3)
C3—N3—N1	128.1 (3)	N7—C11—H11A	108.8
C2—N3—N1	110.7 (2)	C12—C11—H11A	108.8
C3—N4—C4	117.3 (3)	N7—C11—H11B	108.8
C4—N5—C2	113.4 (3)	C12—C11—H11B	108.8
C4—N6—H6A	119 (2)	H11A—C11—H11B	107.7
C4—N6—H6B	116 (2)	C13—C12—C17	118.4 (3)
H6A—N6—H6B	124 (3)	C13—C12—C11	119.4 (3)
C3—N7—C11	122.6 (3)	C17—C12—C11	122.2 (3)
C3—N7—H7N	124 (2)	C12—C13—C14	121.8 (3)
C11—N7—H7N	114 (2)	C12—C13—H13	119.1
N1—C1—N2	115.3 (3)	C14—C13—H13	119.1
N1—C1—C5	121.4 (3)	C15—C14—C13	117.4 (3)
N2—C1—C5	123.3 (3)	C15—C14—H14	121.3
N2—C2—N5	129.5 (3)	C13—C14—H14	121.3
N2—C2—N3	108.5 (3)	C16—C15—F1	119.0 (3)
N5—C2—N3	122.0 (3)	C16—C15—C14	123.3 (3)
N4—C3—N7	123.1 (3)	F1—C15—C14	117.7 (3)
N4—C3—N3	118.8 (3)	C15—C16—C17	118.3 (3)
N7—C3—N3	118.1 (3)	C15—C16—H16	120.9
N6—C4—N5	117.1 (3)	C17—C16—H16	120.9
N6—C4—N4	115.6 (3)	C12—C17—C16	120.8 (3)
N5—C4—N4	127.3 (3)	C12—C17—H17	119.6
C6—C5—C10	119.0 (3)	C16—C17—H17	119.6
C6—C5—C1	121.3 (3)	C2S—O1S—H1S	109.5
C10—C5—C1	119.7 (3)	O2S—C1S—H1S1	109.5
C7—C6—C5	120.7 (3)	O2S—C1S—H1S2	109.5
C7—C6—H6	119.7	H1S1—C1S—H1S2	109.5
C5—C6—H6	119.7	O2S—C1S—H1S3	109.5
C6—C7—C8	120.0 (3)	H1S1—C1S—H1S3	109.5
C6—C7—H7	120.0	H1S2—C1S—H1S3	109.5
C8—C7—H7	120.0	C1S—O2S—H2S	109.5
C7—C8—C9	120.1 (3)	O1S—C2S—H2S1	109.5
C7—C8—H8	120.0	O1S—C2S—H2S2	109.5
C9—C8—H8	120.0	H2S1—C2S—H2S2	109.5
C8—C9—C10	119.8 (3)	O1S—C2S—H2S3	109.5
C8—C9—H9	120.1	H2S1—C2S—H2S3	109.5
C10—C9—H9	120.1	H2S2—C2S—H2S3	109.5
C9—C10—C5	120.4 (3)

C1—N1—N3—C3	−177.9 (3)	N1—C1—C5—C6	178.5 (3)
C1—N1—N3—C2	0.0 (3)	N2—C1—C5—C6	−2.3 (5)
N3—N1—C1—N2	−0.2 (4)	N1—C1—C5—C10	−1.4 (5)
N3—N1—C1—C5	179.1 (3)	N2—C1—C5—C10	177.9 (3)
C2—N2—C1—N1	0.4 (4)	C10—C5—C6—C7	−1.3 (5)
C2—N2—C1—C5	−179.0 (3)	C1—C5—C6—C7	178.9 (3)
C1—N2—C2—N5	178.2 (3)	C5—C6—C7—C8	0.2 (5)
C1—N2—C2—N3	−0.3 (3)	C6—C7—C8—C9	1.0 (5)
C4—N5—C2—N2	−176.2 (3)	C7—C8—C9—C10	−1.1 (5)
C4—N5—C2—N3	2.2 (4)	C8—C9—C10—C5	0.0 (5)
C3—N3—C2—N2	178.3 (3)	C6—C5—C10—C9	1.2 (5)
N1—N3—C2—N2	0.2 (4)	C1—C5—C10—C9	−179.0 (3)
C3—N3—C2—N5	−0.4 (5)	C3—N7—C11—C12	−100.4 (4)
N1—N3—C2—N5	−178.4 (3)	N7—C11—C12—C13	177.6 (3)
C4—N4—C3—N7	−178.0 (3)	N7—C11—C12—C17	−2.4 (4)
C4—N4—C3—N3	1.6 (4)	C17—C12—C13—C14	1.0 (5)
C11—N7—C3—N4	−7.6 (5)	C11—C12—C13—C14	−179.0 (3)
C11—N7—C3—N3	172.8 (3)	C12—C13—C14—C15	−1.1 (5)
C2—N3—C3—N4	−1.7 (5)	C13—C14—C15—C16	0.2 (5)
N1—N3—C3—N4	176.0 (3)	C13—C14—C15—F1	−179.4 (3)
C2—N3—C3—N7	177.9 (3)	F1—C15—C16—C17	−179.6 (3)
N1—N3—C3—N7	−4.4 (5)	C14—C15—C16—C17	0.8 (5)
C2—N5—C4—N6	177.4 (3)	C13—C12—C17—C16	0.0 (5)
C2—N5—C4—N4	−2.4 (5)	C11—C12—C17—C16	−179.9 (3)
C3—N4—C4—N6	−179.3 (3)	C15—C16—C17—C12	−0.9 (5)
C3—N4—C4—N5	0.5 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N6—H6B···O2Sⁱ	0.87 (2)	2.52 (3)	3.033 (4)	118 (3)
N6—H6B···F1ⁱⁱ	0.87 (2)	2.48 (2)	3.307 (3)	159 (3)
N6—H6A···N5ⁱ	0.90 (2)	2.13 (2)	3.025 (4)	178 (3)
N7—H7N···N1	0.88 (2)	2.57 (3)	2.841 (4)	99 (2)
N7—H7N···O1Sⁱⁱⁱ	0.88 (2)	1.96 (2)	2.797 (4)	158 (3)
O1S—H1S···O2S	0.84	1.86	2.690 (3)	169
O2S—H2S···N2	0.84	1.91	2.731 (4)	166
N7—H7N···N1	0.88 (2)	2.57 (3)	2.841 (4)	99 (2)

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

Experimental details

Crystal data
Chemical formula	C₁₇H₁₄FN₇·2CH₄O
M_r	399.44
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	27.516 (3), 7.0091 (8), 20.778 (3)
β (°)	104.380 (3)
V (Å³)	3881.7 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.56 × 0.18 × 0.02

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2001)
T_min, T_max	0.946, 0.998
No. of measured, independent and observed [I > 2σ(I)] reflections	11861, 3820, 2876
R_int	0.066
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.084, 0.183, 1.20
No. of reflections	3820
No. of parameters	275
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.27

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N6—H6B···O2Sⁱ	0.874 (18)	2.52 (3)	3.033 (4)	118 (3)
N6—H6B···F1ⁱⁱ	0.874 (18)	2.48 (2)	3.307 (3)	159 (3)
N6—H6A···N5ⁱ	0.900 (18)	2.125 (19)	3.025 (4)	178 (3)
N7—H7N···N1	0.877 (18)	2.57 (3)	2.841 (4)	99 (2)
N7—H7N···O1Sⁱⁱⁱ	0.877 (18)	1.96 (2)	2.797 (4)	158 (3)
O1S—H1S···O2S	0.84	1.86	2.690 (3)	169
O2S—H2S···N2	0.84	1.91	2.731 (4)	166
N7—H7N···N1	0.877 (18)	2.57 (3)	2.841 (4)	99 (2)

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

Footnotes

†Part 19 in the series Fused heterocyclic systems with an s-triazine ring, for Part 18 see Dolzhenko et al. (2011a).

‡Thomson Reuters ResearcherID: B-1130-2008.

Acknowledgements

This work was supported by the School of Pharmacy, Curtin University of Technology, and the National Medical Research Council, Singapore (NMRC/NIG/0019/2008).

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