4,4-Dimethyl-3,4-dihydro­pyrido[2′,3′:3,4]pyrazolo­[1,5-a][1,3,5]triazin-2-amine ethanol monosolvate

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

doi:10.1107/S160053681005097X

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 1| January 2011| Pages o83-o84

https://doi.org/10.1107/S160053681005097X

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4,4-Dimethyl-3,4-dihydropyrido[2′,3′:3,4]pyrazolo[1,5-a][1,3,5]triazin-2-amine ethanol monosolvate¹

Anton V. Dolzhenko,^a ^*‡ Geok Kheng Tan,^b Anna V. Dolzhenko,^c Lip Lin Koh ^b 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 26 November 2010; accepted 5 December 2010; online 11 December 2010)

In the title compound, C₁₀H₁₂N₆·C₂H₅OH, the planarity of the heterocyclic system is slightly distorted at the triazine ring (r.m.s. deviation = 0.1191 Å), which adopts a conformation best described as intermediate between a flattened twisted boat and a half-boat with the tertiary Csp³ atom at the bow. In the crystal, molecules form centrosymmetric dimers connected by N⋯H—O and O⋯H—N hydrogen bonds between the amino group H atom, the ethanol solvent molecule and the triazine N atom, making an R₄⁴(12) graph-set motif. The other H atom of the amino group and the H atom on the endocyclic N atom form N⋯H—N hydrogen bonds with the N atoms of the pyrazole and pyridine rings, respectively, linking the molecules into C(7)C(7) chains with the R₂²(8) binary graph-set motif running along [010].

Related literature

For a review on the synthesis and biological activity of pyrazolo[1,5-a]triazines, see: Dolzhenko et al. (2008 ). For the synthesis, crystal structure studies and biological activity of related fused gem-dimethyl-substituted amino-1,3,5-triazines, see: Dolzhenko et al. (2007a ,b , 2009 ), Toyoda et al. (1997 ). For graph-set analysis of hydrogen bonding, see: Bernstein et al. (1995 ). For a related structure, see: Sachdeva et al. (2010 ).

Experimental

Crystal data

C₁₀H₁₂N₆·C₂H₆O
M_r = 262.32
Monoclinic, C 2/c
a = 12.1250 (19) Å
b = 13.913 (2) Å
c = 16.598 (3) Å
β = 101.683 (4)°
V = 2742.0 (7) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100 K
0.60 × 0.38 × 0.10 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ) T_min = 0.950, T_max = 0.991
9471 measured reflections
3129 independent reflections
2657 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.133
S = 1.06
3129 reflections
209 parameters
38 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5⋯N1ⁱ	0.86 (2)	2.16 (2)	3.0077 (18)	169.5 (18)
N6—H6B⋯N2ⁱ	0.90 (2)	2.08 (2)	2.9754 (18)	171.5 (18)
N6—H6A⋯O1Sⁱⁱ	0.85 (2)	2.03 (2)	2.8540 (18)	163.2 (18)
O1S—H1S⋯N4	0.87 (2)	1.93 (2)	2.7943 (17)	170 (2)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) -x+1, -y, -z+1.

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: https://doi.org/10.1107/S160053681005097X/hg2760sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681005097X/hg2760Isup2.hkl

checkCIF report

Comment top

The pyrazolo[1,5-a]triazine heterocyclic system has been recognized as a template for the construction of new potential therapeutic agents (Dolzhenko et al., 2008). However data on pyrido[2',3':3,4]pyrazolo[1,5-a][1,3,5]triazines are limited and no details on their structure are available. Herein, we report molecular and crystal structure of 4,4-dimethyl-3,4-dihydropyrido[2',3':3,4]pyrazolo[1,5-a][1,3,5]triazin-2-amine, which crystallizes with a ethanol molecule to give the title compound, C₁₀H₁₂N₆.C₂H₅OH (Fig. 1 & 2). This molecule has a close structural resemblance with some known dihydrofolate reductase inhibitors such as antimalarial drug cycloguanil and its fused analogue (Toyoda et al., 1997) (Fig. 3). Due to annular tautomerism, four tautomeric forms are theoretically possible for the compound (Fig. 4). Similarly to the previously reported (Dolzhenko et al., 2007b) related fused gem-dimethyl substituted amino-1,3,5-triazine, the compound exists in the crystal as a tautomer with the labile hydrogen atom located at the triazine nitrogen atom adjacent to the sp³ hybridized carbon atom.

The heterocyclic system is nearly planar (with r.m.s. deviation of 0.1191 Å) with a distortion at the triazine ring. The triazine ring adopts the conformation best described as an intermediate between a flatten twist boat and a half-boat with atoms C-8 and N-4 at the bow and the stern. The angle between the geminal flagpole and bowsprit methyl groups is 112.40 (14)°. The N4—C7, N5—C7 and N6—C7 bond distances are similar suggesting guanidine-like electron delocalization in the N4—N6/C7 fragment of the molecule.

In the crystal, the molecules form centrosymmetric dimers connected by the N···HO and O···HN hydrogen bonds between the amino group N6—H6A, ethanol molecule and the triazine N4 atom making a R₄⁴(12) graph-set motif (Bernstein et al., 1995). Another hydrogen atom of the amino group N6—H6B and the hydrogen atom at the endocyclic N5 atom act as hydrogen donors forming N···HN contacts with the pyrazole and pyridine N2 and N1 atoms, respectively. They arrange molecules into the running along a [010] axis C(7)C(7) chains with the R₂²(8) binary graph-set motif.

Related literature top

For a review on the synthesis and biological activity of pyrazolo[1,5-a]triazines, see: Dolzhenko et al. (2008). For the synthesis, crystal structure studies and biological activity of related fused gem-dimethyl-substituted amino-1,3,5-triazines, see: Dolzhenko et al. (2007a,b, 2009), Toyoda et al. (1997). For graph-set analysis of hydrogen bonding, see: Bernstein et al. (1995). For a related structure, see: Sachdeva et al. (2010).

Experimental top

4,4-Dimethyl-3,4-dihydropyrido[2',3':3,4]pyrazolo[1,5-a][1,3,5]triazin-2-amine was prepared by the cyclocondensation of pyrazolo[3,4-b]pyridin-3-guanidine with acetone similarly to the previously described methods (Dolzhenko et al., 2007a; Dolzhenko et al., 2009). 1H-Pyrazolo[3,4-b]pyridin-3-guanidine (0.88 g, 5.0 mmol) and piperidine (0.30 ml, 3.0 mmol) were heated in acetone (30 ml) under reflux for 10 h. After cooling, the product was filtered and washed with acetone. Yield: 0.89 g (82%). The crystals suitable for crystallographic analysis were grown by recrystallization from ethanol. m.p. 559 K.

Structure description top

For a review on the synthesis and biological activity of pyrazolo[1,5-a]triazines, see: Dolzhenko et al. (2008). For the synthesis, crystal structure studies and biological activity of related fused gem-dimethyl-substituted amino-1,3,5-triazines, see: Dolzhenko et al. (2007a,b, 2009), Toyoda et al. (1997). For graph-set analysis of hydrogen bonding, see: Bernstein et al. (1995). For a related structure, see: Sachdeva et al. (2010).

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 4,4-dimethyl-3,4-dihydropyrido[2',3':3,4]pyrazolo[1,5-a][1,3,5]triazin-2-amine ethanol solvate showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Crystal packing in the cell (view along axis c).
	Fig. 3. Dihydrofolate reductase inhibitors with dihydro-1,3,5-triazine ring.
	Fig. 4. Annular tautomerism in 4,4-dimethyl-3,4-dihydropyrido[2',3':3,4]pyrazolo[1,5-a][1,3,5]triazin-2-amine.

4,4-Dimethyl-3,4-dihydropyrido[2',3':3,4]pyrazolo[1,5-a][1,3,5]triazin- 2-amine ethanol monosolvate top

Crystal data top

C₁₀H₁₂N₆·C₂H₆O	F(000) = 1120
M_r = 262.32	D_x = 1.271 Mg m⁻³
Monoclinic, C2/c	Melting point: 559 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 12.1250 (19) Å	Cell parameters from 782 reflections
b = 13.913 (2) Å	θ = 2.7–27.3°
c = 16.598 (3) Å	µ = 0.09 mm⁻¹
β = 101.683 (4)°	T = 100 K
V = 2742.0 (7) Å³	Plate, yellow
Z = 8	0.60 × 0.38 × 0.10 mm

Data collection top

Bruker SMART APEX CCD diffractometer	3129 independent reflections
Radiation source: fine-focus sealed tube	2657 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
φ and ω scans	θ_max = 27.5°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −15→14
T_min = 0.950, T_max = 0.991	k = −18→17
9471 measured reflections	l = −18→21

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.133	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0709P)² + 1.8445P] where P = (F_o² + 2F_c²)/3
3129 reflections	(Δ/σ)_max = 0.001
209 parameters	Δρ_max = 0.37 e Å⁻³
38 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₀H₁₂N₆·C₂H₆O	V = 2742.0 (7) Å³
M_r = 262.32	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 12.1250 (19) Å	µ = 0.09 mm⁻¹
b = 13.913 (2) Å	T = 100 K
c = 16.598 (3) Å	0.60 × 0.38 × 0.10 mm
β = 101.683 (4)°

Data collection top

Bruker SMART APEX CCD diffractometer	3129 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	2657 reflections with I > 2σ(I)
T_min = 0.950, T_max = 0.991	R_int = 0.030
9471 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	38 restraints
wR(F²) = 0.133	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.37 e Å⁻³
3129 reflections	Δρ_min = −0.21 e Å⁻³
209 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	Occ. (<1)
O1S	0.49619 (10)	0.11324 (8)	0.46397 (7)	0.0285 (3)
H1S	0.5246 (18)	0.1117 (15)	0.5165 (14)	0.039 (6)*
C1S	0.5838 (2)	0.0860 (2)	0.42339 (15)	0.0384 (7)	0.781 (6)
H1SA	0.5526	0.0769	0.3640	0.046*	0.781 (6)
H1SB	0.6169	0.0243	0.4461	0.046*	0.781 (6)
C2S	0.6736 (3)	0.1618 (3)	0.4346 (2)	0.0648 (11)	0.781 (6)
H2SA	0.7335	0.1420	0.4063	0.097*	0.781 (6)
H2SB	0.7051	0.1701	0.4934	0.097*	0.781 (6)
H2SC	0.6410	0.2226	0.4114	0.097*	0.781 (6)
C1SA	0.5898 (9)	0.1503 (9)	0.4290 (6)	0.044 (2)	0.219 (6)
H1SC	0.5651	0.1572	0.3687	0.053*	0.219 (6)
H1SD	0.6120	0.2146	0.4523	0.053*	0.219 (6)
C2SA	0.6822 (14)	0.0883 (12)	0.4464 (9)	0.077 (4)	0.219 (6)
H2SD	0.7437	0.1142	0.4227	0.116*	0.219 (6)
H2SE	0.6605	0.0250	0.4226	0.116*	0.219 (6)
H2SF	0.7072	0.0823	0.5062	0.116*	0.219 (6)
N1	0.56023 (10)	0.47488 (8)	0.67409 (7)	0.0203 (3)
N2	0.67666 (10)	0.34962 (9)	0.74160 (7)	0.0205 (3)
N3	0.68205 (10)	0.25362 (8)	0.72312 (7)	0.0187 (3)
N4	0.59745 (10)	0.13025 (8)	0.63025 (7)	0.0208 (3)
N5	0.77009 (11)	0.10579 (9)	0.72296 (8)	0.0220 (3)
H5	0.8212 (17)	0.0662 (15)	0.7465 (12)	0.034 (5)*
N6	0.68817 (13)	−0.01616 (10)	0.63779 (9)	0.0302 (3)
H6A	0.6334 (17)	−0.0354 (14)	0.6007 (12)	0.028 (5)*
H6B	0.7326 (17)	−0.0588 (15)	0.6701 (12)	0.037 (5)*
C1	0.47528 (13)	0.49206 (10)	0.61227 (9)	0.0226 (3)
H1	0.4479	0.5562	0.6059	0.027*
C2	0.42132 (13)	0.42321 (11)	0.55453 (9)	0.0235 (3)
H2	0.3604	0.4420	0.5119	0.028*
C3	0.45708 (12)	0.32946 (11)	0.56021 (9)	0.0211 (3)
H3	0.4242	0.2824	0.5212	0.025*
C4	0.54476 (12)	0.30661 (10)	0.62667 (8)	0.0182 (3)
C5	0.59298 (12)	0.38088 (10)	0.68156 (8)	0.0180 (3)
C6	0.60627 (12)	0.22357 (10)	0.65668 (8)	0.0189 (3)
C7	0.68259 (13)	0.07377 (11)	0.66450 (9)	0.0220 (3)
C8	0.75702 (12)	0.18664 (10)	0.77658 (8)	0.0210 (3)
C9	0.70180 (17)	0.15481 (14)	0.84683 (10)	0.0384 (4)
H9A	0.6953	0.2100	0.8823	0.058*
H9B	0.7480	0.1049	0.8791	0.058*
H9C	0.6266	0.1291	0.8243	0.058*
C10	0.87144 (15)	0.23234 (12)	0.80702 (12)	0.0363 (4)
H10A	0.8983	0.2606	0.7604	0.055*
H10B	0.9249	0.1832	0.8332	0.055*
H10C	0.8651	0.2827	0.8471	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1S	0.0298 (6)	0.0327 (6)	0.0198 (6)	0.0020 (5)	−0.0023 (5)	−0.0027 (4)
C1S	0.0441 (15)	0.0418 (17)	0.0304 (12)	0.0038 (12)	0.0104 (10)	−0.0026 (11)
C2S	0.050 (2)	0.101 (3)	0.0473 (17)	−0.0189 (19)	0.0193 (14)	0.0019 (18)
C1SA	0.044 (5)	0.049 (6)	0.040 (4)	−0.019 (4)	0.008 (4)	0.007 (4)
C2SA	0.089 (8)	0.077 (8)	0.069 (7)	0.018 (6)	0.021 (6)	0.022 (6)
N1	0.0230 (6)	0.0168 (6)	0.0203 (6)	−0.0004 (5)	0.0025 (5)	0.0008 (5)
N2	0.0230 (6)	0.0159 (6)	0.0205 (6)	0.0006 (5)	−0.0001 (5)	−0.0021 (5)
N3	0.0195 (6)	0.0158 (6)	0.0184 (6)	0.0010 (4)	−0.0016 (5)	−0.0014 (4)
N4	0.0233 (6)	0.0164 (6)	0.0192 (6)	0.0016 (5)	−0.0042 (5)	−0.0017 (4)
N5	0.0227 (6)	0.0180 (6)	0.0217 (6)	0.0050 (5)	−0.0042 (5)	−0.0022 (5)
N6	0.0356 (8)	0.0196 (7)	0.0273 (7)	0.0063 (6)	−0.0128 (6)	−0.0040 (5)
C1	0.0255 (8)	0.0178 (7)	0.0235 (7)	0.0024 (6)	0.0027 (6)	0.0018 (6)
C2	0.0234 (7)	0.0232 (7)	0.0209 (7)	0.0015 (6)	−0.0028 (6)	0.0024 (6)
C3	0.0223 (7)	0.0213 (7)	0.0177 (7)	−0.0012 (5)	−0.0002 (5)	−0.0009 (5)
C4	0.0190 (7)	0.0170 (7)	0.0183 (7)	−0.0008 (5)	0.0029 (5)	−0.0004 (5)
C5	0.0173 (6)	0.0190 (7)	0.0177 (6)	−0.0011 (5)	0.0033 (5)	0.0001 (5)
C6	0.0185 (7)	0.0209 (7)	0.0158 (6)	−0.0005 (5)	0.0003 (5)	0.0001 (5)
C7	0.0254 (7)	0.0201 (7)	0.0182 (7)	0.0013 (6)	−0.0011 (6)	−0.0004 (5)
C8	0.0226 (7)	0.0194 (7)	0.0179 (7)	0.0046 (5)	−0.0031 (6)	−0.0015 (5)
C9	0.0475 (11)	0.0425 (10)	0.0257 (8)	0.0202 (8)	0.0088 (8)	0.0115 (7)
C10	0.0286 (9)	0.0244 (8)	0.0466 (10)	0.0042 (7)	−0.0146 (8)	−0.0081 (7)

Geometric parameters (Å, º) top

O1S—C1S	1.420 (3)	N5—C7	1.3596 (18)
O1S—C1SA	1.469 (9)	N5—C8	1.4628 (19)
O1S—H1S	0.87 (2)	N5—H5	0.86 (2)
C1S—C2S	1.500 (5)	N6—C7	1.334 (2)
C1S—H1SA	0.9900	N6—H6A	0.85 (2)
C1S—H1SB	0.9900	N6—H6B	0.90 (2)
C2S—H2SA	0.9800	C1—C2	1.418 (2)
C2S—H2SB	0.9800	C1—H1	0.9500
C2S—H2SC	0.9800	C2—C3	1.372 (2)
C1SA—C2SA	1.40 (2)	C2—H2	0.9500
C1SA—H1SC	0.9900	C3—C4	1.4047 (19)
C1SA—H1SD	0.9900	C3—H3	0.9500
C2SA—H2SD	0.9800	C4—C6	1.410 (2)
C2SA—H2SE	0.9800	C4—C5	1.4227 (19)
C2SA—H2SF	0.9800	C8—C10	1.517 (2)
N1—C1	1.3202 (19)	C8—C9	1.523 (2)
N1—C5	1.3651 (18)	C9—H9A	0.9800
N2—C5	1.3425 (18)	C9—H9B	0.9800
N2—N3	1.3749 (17)	C9—H9C	0.9800
N3—C6	1.3508 (17)	C10—H10A	0.9800
N3—C8	1.4682 (18)	C10—H10B	0.9800
N4—C7	1.3299 (19)	C10—H10C	0.9800
N4—C6	1.3678 (18)

C1S—O1S—C1SA	36.3 (5)	N1—C1—C2	125.71 (14)
C1S—O1S—H1S	106.7 (14)	N1—C1—H1	117.1
C1SA—O1S—H1S	102.9 (14)	C2—C1—H1	117.1
O1S—C1S—C2S	110.4 (3)	C3—C2—C1	119.98 (13)
O1S—C1S—H1SA	109.6	C3—C2—H2	120.0
C2S—C1S—H1SA	109.6	C1—C2—H2	120.0
O1S—C1S—H1SB	109.6	C2—C3—C4	116.60 (13)
C2S—C1S—H1SB	109.6	C2—C3—H3	121.7
H1SA—C1S—H1SB	108.1	C4—C3—H3	121.7
C1S—C2S—H2SA	109.5	C3—C4—C6	136.46 (13)
C1S—C2S—H2SB	109.5	C3—C4—C5	119.08 (13)
H2SA—C2S—H2SB	109.5	C6—C4—C5	104.45 (12)
C1S—C2S—H2SC	109.5	N2—C5—N1	122.69 (12)
H2SA—C2S—H2SC	109.5	N2—C5—C4	113.00 (12)
H2SB—C2S—H2SC	109.5	N1—C5—C4	124.30 (13)
C2SA—C1SA—O1S	110.6 (11)	N3—C6—N4	123.49 (12)
C2SA—C1SA—H1SC	109.5	N3—C6—C4	104.98 (12)
O1S—C1SA—H1SC	109.5	N4—C6—C4	131.53 (13)
C2SA—C1SA—H1SD	109.5	N4—C7—N6	119.96 (13)
O1S—C1SA—H1SD	109.5	N4—C7—N5	122.51 (14)
H1SC—C1SA—H1SD	108.1	N6—C7—N5	117.38 (13)
C1SA—C2SA—H2SD	109.5	N5—C8—N3	104.50 (11)
C1SA—C2SA—H2SE	109.5	N5—C8—C10	108.70 (13)
H2SD—C2SA—H2SE	109.5	N3—C8—C10	110.36 (13)
C1SA—C2SA—H2SF	109.5	N5—C8—C9	111.15 (13)
H2SD—C2SA—H2SF	109.5	N3—C8—C9	109.45 (12)
H2SE—C2SA—H2SF	109.5	C10—C8—C9	112.40 (14)
C1—N1—C5	114.26 (12)	C8—C9—H9A	109.5
C5—N2—N3	102.25 (11)	C8—C9—H9B	109.5
C6—N3—N2	115.31 (11)	H9A—C9—H9B	109.5
C6—N3—C8	122.17 (12)	C8—C9—H9C	109.5
N2—N3—C8	122.23 (11)	H9A—C9—H9C	109.5
C7—N4—C6	114.85 (12)	H9B—C9—H9C	109.5
C7—N5—C8	121.41 (12)	C8—C10—H10A	109.5
C7—N5—H5	120.0 (13)	C8—C10—H10B	109.5
C8—N5—H5	111.9 (13)	H10A—C10—H10B	109.5
C7—N6—H6A	116.8 (13)	C8—C10—H10C	109.5
C7—N6—H6B	118.9 (13)	H10A—C10—H10C	109.5
H6A—N6—H6B	120.5 (18)	H10B—C10—H10C	109.5

C1SA—O1S—C1S—C2S	21.3 (7)	C8—N3—C6—C4	174.81 (13)
C1S—O1S—C1SA—C2SA	−39.4 (9)	C7—N4—C6—N3	−12.5 (2)
C5—N2—N3—C6	−1.02 (16)	C7—N4—C6—C4	168.49 (15)
C5—N2—N3—C8	−175.06 (13)	C3—C4—C6—N3	178.26 (17)
C5—N1—C1—C2	−2.2 (2)	C5—C4—C6—N3	−0.17 (15)
N1—C1—C2—C3	−0.2 (2)	C3—C4—C6—N4	−2.6 (3)
C1—C2—C3—C4	2.3 (2)	C5—C4—C6—N4	178.95 (15)
C2—C3—C4—C6	179.72 (16)	C6—N4—C7—N6	−173.68 (14)
C2—C3—C4—C5	−2.0 (2)	C6—N4—C7—N5	1.7 (2)
N3—N2—C5—N1	−177.97 (13)	C8—N5—C7—N4	26.4 (2)
N3—N2—C5—C4	0.87 (16)	C8—N5—C7—N6	−158.08 (14)
C1—N1—C5—N2	−178.85 (14)	C7—N5—C8—N3	−37.89 (18)
C1—N1—C5—C4	2.4 (2)	C7—N5—C8—C10	−155.73 (14)
C3—C4—C5—N2	−179.23 (13)	C7—N5—C8—C9	80.06 (17)
C6—C4—C5—N2	−0.46 (17)	C6—N3—C8—N5	27.26 (18)
C3—C4—C5—N1	−0.4 (2)	N2—N3—C8—N5	−159.11 (12)
C6—C4—C5—N1	178.35 (13)	C6—N3—C8—C10	143.94 (14)
N2—N3—C6—N4	−178.45 (13)	N2—N3—C8—C10	−42.42 (19)
C8—N3—C6—N4	−4.4 (2)	C6—N3—C8—C9	−91.86 (17)
N2—N3—C6—C4	0.77 (17)	N2—N3—C8—C9	81.78 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5···N1ⁱ	0.86 (2)	2.16 (2)	3.0077 (18)	169.5 (18)
N6—H6B···N2ⁱ	0.90 (2)	2.08 (2)	2.9754 (18)	171.5 (18)
N6—H6A···O1Sⁱⁱ	0.85 (2)	2.03 (2)	2.8540 (18)	163.2 (18)
O1S—H1S···N4	0.87 (2)	1.93 (2)	2.7943 (17)	170 (2)

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₂N₆·C₂H₆O
M_r	262.32
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	12.1250 (19), 13.913 (2), 16.598 (3)
β (°)	101.683 (4)
V (Å³)	2742.0 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.60 × 0.38 × 0.10

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 2001)
T_min, T_max	0.950, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	9471, 3129, 2657
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.133, 1.06
No. of reflections	3129
No. of parameters	209
No. of restraints	38
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.21

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
N5—H5···N1ⁱ	0.86 (2)	2.16 (2)	3.0077 (18)	169.5 (18)
N6—H6B···N2ⁱ	0.90 (2)	2.08 (2)	2.9754 (18)	171.5 (18)
N6—H6A···O1Sⁱⁱ	0.85 (2)	2.03 (2)	2.8540 (18)	163.2 (18)
O1S—H1S···N4	0.87 (2)	1.93 (2)	2.7943 (17)	170 (2)

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

Footnotes

¹Fused heterocyclic systems with s-triazine ring. Part 16. for part 15, see Sachdeva et al. (2010).

‡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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