4-Hydrazino-1-methyl­pyrazolo[3,4-d]pyrimidine

Dolzhenko, A.V.; Pastorin, G.; Dolzhenko, A.V.; Tan, G.K.; Koh, L.L.

doi:10.1107/S1600536809023952

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Pages o1720-o1721

doi:10.1107/S1600536809023952

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4-Hydrazino-1-methylpyrazolo[3,4-d]pyrimidine

Anton V. Dolzhenko,^a ^* Giorgia Pastorin,^a Anna V. Dolzhenko,^a Geok Kheng Tan ^b and Lip Lin Koh ^b

^aDepartment of Pharmacy, Faculty of Science, National University of Singapore, 18 Science Drive 4, Singapore 117543, Singapore, and ^bDepartment of Chemistry, Faculty of Science, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore
^*Correspondence e-mail: phada@nus.edu.sg

(Received 3 June 2009; accepted 22 June 2009; online 1 July 2009)

The title compound, C₆H₈N₆, crystallizes as an N—H⋯N hydrogen-bond-linked dimer of two almost identical molecules in the asymmetric unit. Both of the molecules are almost planar (rms deviations of 0.0186 and 0.0296 Å in the two molecules) and their hydrazino groups are turned towards the pyrazole rings. The dimers are arranged into chains via intermolecular N—H⋯N hydrogen bonds between the hydrazino groups and the N atoms of the pyrimidine rings of both types of the molecules, linking the molecules into a C(7) graph-set motif along [100]. The methyl groups and the N atoms of the pyrazole rings form weak C—H⋯N hydrogen bonds, which connect chains of the dimers in a C(4) motif parallel to [100].

Related literature

For recent reviews on the synthesis and biological activity of pyrazolo[3,4-d]pyrimidines, see: Caravatti et al. (2001 ); Dang (2002 ); Schenone et al. (2007 ); Schenone et al. (2008 ). The synthesis of the title compound was performed according to the procedure reported by Taylor & Loeffler (1960 ). For the crystal structure of 1-methyl-4-(2-methylhydrazino)pyrazolo[3,4-d]pyrimidine, see: Hosmane et al. (1988 ). For the graph-set analysis of hydrogen bonding, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₆H₈N₆
M_r = 164.18
Orthorhombic, P n a 2₁
a = 14.086 (4) Å
b = 3.8756 (12) Å
c = 27.271 (8) Å
V = 1488.8 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 223 K
0.58 × 0.26 × 0.10 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ) T_min = 0.943, T_max = 0.990
8939 measured reflections
1715 independent reflections
1652 reflections with I > 2σ(I)
R_int = 0.051

Refinement

R[F² > 2σ(F²)] = 0.065
wR(F²) = 0.159
S = 1.21
1715 reflections
243 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12B⋯N1ⁱ	0.97	2.65	3.297 (7)	124
C6—H6C⋯N7ⁱⁱ	0.97	2.54	3.410 (7)	150
N11—H11N⋯N4	0.85 (6)	2.11 (6)	2.948 (6)	170 (5)
N5—H5N⋯N10	0.84 (7)	2.13 (7)	2.961 (6)	170 (5)
N12—H12E⋯N9ⁱⁱⁱ	0.97 (7)	2.56 (6)	3.125 (5)	117 (4)
N12—H12D⋯N9^iv	0.91 (6)	2.24 (6)	3.125 (6)	166 (5)
N6—H6NB⋯N3^v	0.89 (7)	2.59 (6)	3.251 (6)	131 (5)
N6—H6NA⋯N3^vi	0.86 (7)	2.30 (7)	3.149 (6)	168 (7)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x+1, -y+1, z-{\script{1\over 2}}]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z]$ ; (iv) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ ; (v) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ ; (vi) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z]$ .

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/S1600536809023952/jh2082sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809023952/jh2082Isup2.hkl

checkCIF report

Comment top

The pyrazolo[3,4-d]pyrimidine heterocyclic system is known to be a bioisoster of purine. Therefore, chemistry of pyrazolo[3,4-d]pyrimidines has received significant attention, particularly for the development of new biologically active substances (Caravatti et al., 2001; Dang, 2002; Schenone et al., 2007; Schenone et al., 2008).

Herein, we report the crystal structure of 4-hydrazino-1-methylpyrazolo[3,4-d]pyrimidine, which was prepared via a reaction of 4-cyano-5-[(ethoxymethylene)amino]-1-methylpyrazole with hydrazine according to Taylor and Loeffler (1960) (Fig. 1). Theoretically, the compound might be involved in tautomerism with three tautomeric forms (Fig. 2). However, only one tautomeric form, similarly to previously reported 1-methyl-4-(2-methylhydrazino)pyrazolo[3,4-d]pyrimidine (Hosmane et al., 1988), was found in the crystal.

The title compound crystallizes in asymmetric unit as a dimer of two almost identical molecules (Fig. 3). Both molecules are essentially planar except for the hydrazino groups, which are turned towards pyrazole ring making the torsion angles C2—C5—N5—N6 and C8—C11—N11—N12 equal to 4.1 (7)° and 4.0 (7)°, respectively. The geometry of the molecule as well as 1.348 (6) Å and 1.332 (5) Å distances of C5—N5 and C11—N11 bonds indicate delocalization of the electron pairs of N5 and N11 with the pyrazolo[3,4-d]pyrimidine aromatic system.

In the crystal, the dimer molecules are linked in a R²₂(8) graph-set motif (Bernstein et al., 1995) by the N—H···N hydrogen bonds (Fig. 4, Table 1). The dimers are arranged into chains via intermolecular N—H···N hydrogen bonds between the hydrazino groups and the nitrogen atoms of the pyrimidine rings of both type of the molecules linking them with symmetry-related molecules in a C(7) graph-set motif along the [100] direction. The interactions between pyrimidine rings and hydrazino groups make a R⁴₄(14) hydrogen bond motif of the fourth order. The methyl groups and the nitrogen atoms of the pyrazole rings form weak C—H···N hydrogen bonds connecting chains of the dimers in a C(4) motif parallel to the [100]) direction.

Related literature top

For recent reviews on the synthesis and biological activity of pyrazolo[3,4-d]pyrimidines, see: Caravatti et al. (2001); Dang (2002); Schenone et al. (2007); Schenone et al. (2008). The synthesis of the title compound was performed according to the procedure reported by Taylor & Loeffler (1960). For the related crystal structure, 1-methyl-4-(2-methylhydrazino)pyrazolo[3,4-d]pyrimidine, see: Hosmane et al. (1988). For the graph-set analysis of hydrogen bonding, see: Bernstein et al. (1995).

Experimental top

4-Hydrazino-1-methylpyrazolo[3,4-d]pyrimidine was synthesized by cyclocondensation of 4-cyano-5-[(ethoxymethylene)amino]-1-methylpyrazole with hydrazine according to the procedure reported by Taylor and Loeffler (1960). Single crystals suitable for crystallographic analysis were grown by recrystallization from ethanol.

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 synthesis of 4-hydrazino-1-methylpyrazolo[3,4-d]pyrimidine
	Fig. 2. The hydrazino-hydrazono tautomerism in the title compound
	Fig. 3. The molecular structure of 4-hydrazino-1-methylpyrazolo[3,4-d]pyrimidine with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 4. Molecular parking in the crystal, viewed along the b axis.

4-Hydrazino-1-methylpyrazolo[3,4-d]pyrimidine top

Crystal data top

C₆H₈N₆	D_x = 1.465 Mg m⁻³
M_r = 164.18	Melting point: 514 K
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 3657 reflections
a = 14.086 (4) Å	θ = 2.9–27.2°
b = 3.8756 (12) Å	µ = 0.10 mm⁻¹
c = 27.271 (8) Å	T = 223 K
V = 1488.8 (8) Å³	Block, colourless
Z = 8	0.58 × 0.26 × 0.10 mm
F(000) = 688

Data collection top

Bruker SMART APEX CCD diffractometer	1715 independent reflections
Radiation source: fine-focus sealed tube	1652 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.051
ϕ and ω scans	θ_max = 27.5°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −18→18
T_min = 0.943, T_max = 0.990	k = −5→4
8939 measured reflections	l = −24→35

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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.159	H atoms treated by a mixture of independent and constrained refinement
S = 1.21	w = 1/[σ²(F_o²) + (0.0699P)² + 1.3392P] where P = (F_o² + 2F_c²)/3
1715 reflections	(Δ/σ)_max < 0.001
243 parameters	Δρ_max = 0.29 e Å⁻³
1 restraint	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₆H₈N₆	V = 1488.8 (8) Å³
M_r = 164.18	Z = 8
Orthorhombic, Pna2₁	Mo Kα radiation
a = 14.086 (4) Å	µ = 0.10 mm⁻¹
b = 3.8756 (12) Å	T = 223 K
c = 27.271 (8) Å	0.58 × 0.26 × 0.10 mm

Data collection top

Bruker SMART APEX CCD diffractometer	1715 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	1652 reflections with I > 2σ(I)
T_min = 0.943, T_max = 0.990	R_int = 0.051
8939 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	1 restraint
wR(F²) = 0.159	H atoms treated by a mixture of independent and constrained refinement
S = 1.21	Δρ_max = 0.29 e Å⁻³
1715 reflections	Δρ_min = −0.28 e Å⁻³
243 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
N1	0.4891 (3)	0.4783 (12)	0.43889 (16)	0.0351 (9)
N2	0.4203 (3)	0.6408 (11)	0.46578 (15)	0.0307 (9)
N3	0.3922 (2)	0.8124 (10)	0.54938 (15)	0.0273 (9)
N4	0.5189 (3)	0.6416 (10)	0.60298 (15)	0.0281 (8)
N5	0.6553 (3)	0.3740 (12)	0.57903 (17)	0.0321 (9)
H5N	0.668 (4)	0.343 (14)	0.609 (2)	0.030 (14)*
N6	0.7119 (3)	0.2094 (13)	0.54313 (18)	0.0348 (10)
H6NA	0.764 (5)	0.32 (2)	0.549 (3)	0.05 (2)*
H6NB	0.731 (4)	0.007 (19)	0.555 (2)	0.037 (16)*
N7	0.7580 (3)	0.6324 (11)	0.84251 (15)	0.0335 (9)
N8	0.8271 (3)	0.4576 (10)	0.81702 (14)	0.0297 (9)
N9	0.8504 (2)	0.2236 (10)	0.73690 (15)	0.0274 (9)
N10	0.7183 (3)	0.3347 (11)	0.68245 (15)	0.0281 (8)
N11	0.5809 (2)	0.5994 (12)	0.70605 (16)	0.0300 (9)
H11N	0.566 (4)	0.587 (14)	0.676 (2)	0.025 (13)*
N12	0.5243 (3)	0.7763 (12)	0.74061 (17)	0.0292 (9)
H12D	0.469 (4)	0.656 (15)	0.743 (2)	0.030 (14)*
H12E	0.518 (4)	1.019 (18)	0.732 (2)	0.037 (15)*
C1	0.5567 (3)	0.3971 (14)	0.47002 (17)	0.0310 (10)
H1	0.6128	0.2804	0.4616	0.037*
C2	0.5337 (3)	0.5087 (12)	0.51798 (17)	0.0242 (9)
C3	0.4448 (3)	0.6664 (12)	0.51286 (17)	0.0247 (9)
C4	0.4345 (3)	0.7879 (13)	0.59211 (18)	0.0280 (10)
H4	0.4016	0.8853	0.6187	0.034*
C5	0.5701 (3)	0.5040 (12)	0.56624 (17)	0.0253 (9)
C6	0.3354 (4)	0.7825 (17)	0.4417 (2)	0.0425 (13)
H6A	0.3540	0.9659	0.4195	0.064*
H6B	0.2925	0.8736	0.4663	0.064*
H6C	0.3038	0.6013	0.4234	0.064*
C9	0.7999 (3)	0.3896 (12)	0.77082 (18)	0.0242 (9)
C7	0.6873 (3)	0.6765 (13)	0.81121 (18)	0.0309 (10)
H7	0.6305	0.7923	0.8187	0.037*
C8	0.7076 (3)	0.5295 (12)	0.76570 (18)	0.0239 (9)
C10	0.8039 (3)	0.2142 (13)	0.69443 (18)	0.0282 (10)
H10	0.8367	0.1051	0.6687	0.034*
C11	0.6678 (3)	0.4953 (12)	0.71848 (16)	0.0242 (9)
C12	0.9129 (4)	0.3412 (17)	0.8420 (2)	0.0430 (14)
H12A	0.9554	0.2352	0.8184	0.065*
H12B	0.8962	0.1739	0.8670	0.065*
H12C	0.9442	0.5369	0.8571	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0288 (19)	0.046 (2)	0.031 (2)	−0.0051 (18)	0.0019 (17)	−0.0057 (19)
N2	0.0226 (18)	0.042 (2)	0.027 (2)	−0.0047 (16)	−0.0017 (15)	0.0028 (18)
N3	0.0193 (16)	0.030 (2)	0.032 (2)	0.0040 (15)	−0.0007 (16)	−0.0014 (16)
N4	0.0202 (18)	0.034 (2)	0.030 (2)	−0.0008 (15)	−0.0005 (14)	−0.0005 (17)
N5	0.0208 (17)	0.046 (3)	0.029 (2)	0.0086 (17)	−0.0004 (16)	0.0020 (19)
N6	0.0206 (19)	0.036 (3)	0.048 (3)	0.0011 (18)	0.0044 (18)	−0.001 (2)
N7	0.0301 (19)	0.039 (2)	0.031 (2)	0.0009 (18)	−0.0001 (16)	0.0056 (18)
N8	0.0227 (17)	0.035 (2)	0.031 (2)	−0.0009 (15)	−0.0055 (16)	0.0078 (17)
N9	0.0163 (16)	0.0300 (19)	0.036 (2)	−0.0027 (15)	0.0012 (15)	0.0041 (17)
N10	0.0222 (17)	0.035 (2)	0.0272 (19)	0.0039 (15)	−0.0023 (15)	0.0049 (17)
N11	0.0158 (17)	0.046 (2)	0.028 (2)	0.0042 (16)	−0.0029 (15)	−0.0013 (18)
N12	0.0126 (16)	0.036 (2)	0.039 (2)	0.0009 (16)	−0.0018 (15)	−0.0010 (19)
C1	0.023 (2)	0.043 (3)	0.027 (2)	−0.005 (2)	0.0039 (19)	0.002 (2)
C2	0.0166 (18)	0.028 (2)	0.029 (2)	−0.0044 (17)	0.0037 (16)	0.0003 (18)
C3	0.020 (2)	0.025 (2)	0.029 (2)	−0.0086 (16)	−0.0021 (17)	0.0052 (18)
C4	0.0210 (19)	0.035 (3)	0.029 (2)	0.0055 (18)	0.0048 (18)	0.0001 (18)
C5	0.0191 (17)	0.024 (2)	0.033 (2)	−0.0056 (15)	0.0011 (16)	0.0043 (17)
C6	0.032 (3)	0.058 (4)	0.037 (3)	0.001 (2)	−0.015 (2)	−0.001 (3)
C9	0.0162 (17)	0.023 (2)	0.033 (2)	−0.0034 (16)	−0.0032 (17)	0.0062 (18)
C7	0.0192 (19)	0.039 (3)	0.035 (2)	−0.0018 (18)	−0.0007 (19)	0.006 (2)
C8	0.0158 (17)	0.025 (2)	0.031 (2)	−0.0027 (15)	0.0003 (17)	0.0072 (18)
C10	0.022 (2)	0.035 (2)	0.028 (2)	−0.0029 (18)	0.0048 (18)	0.0010 (19)
C11	0.0145 (17)	0.031 (2)	0.027 (2)	−0.0012 (16)	−0.0001 (16)	0.0029 (18)
C12	0.029 (2)	0.056 (3)	0.044 (3)	0.005 (2)	−0.018 (2)	0.010 (3)

Geometric parameters (Å, º) top

N1—C1	1.314 (7)	N11—C11	1.332 (5)
N1—N2	1.369 (6)	N11—N12	1.412 (6)
N2—C3	1.333 (6)	N11—H11N	0.85 (6)
N2—C6	1.470 (6)	N12—H12D	0.91 (6)
N3—C4	1.312 (6)	N12—H12E	0.97 (7)
N3—C3	1.364 (6)	C1—C2	1.415 (7)
N4—C5	1.345 (6)	C1—H1	0.9400
N4—C4	1.350 (6)	C2—C3	1.401 (6)
N5—C5	1.348 (6)	C2—C5	1.413 (6)
N5—N6	1.415 (6)	C4—H4	0.9400
N5—H5N	0.84 (7)	C6—H6A	0.9700
N6—H6NA	0.86 (7)	C6—H6B	0.9700
N6—H6NB	0.89 (7)	C6—H6C	0.9700
N7—C7	1.322 (6)	C9—C8	1.415 (5)
N7—N8	1.375 (6)	C7—C8	1.395 (7)
N8—C9	1.343 (6)	C7—H7	0.9400
N8—C12	1.458 (6)	C8—C11	1.411 (6)
N9—C10	1.331 (6)	C10—H10	0.9400
N9—C9	1.332 (6)	C12—H12A	0.9700
N10—C10	1.334 (6)	C12—H12B	0.9700
N10—C11	1.364 (6)	C12—H12C	0.9700

C1—N1—N2	106.1 (4)	N3—C4—N4	128.7 (4)
C3—N2—N1	111.5 (4)	N3—C4—H4	115.7
C3—N2—C6	127.8 (4)	N4—C4—H4	115.7
N1—N2—C6	120.5 (4)	N4—C5—N5	115.7 (4)
C4—N3—C3	111.9 (4)	N4—C5—C2	119.6 (4)
C5—N4—C4	118.4 (4)	N5—C5—C2	124.7 (4)
C5—N5—N6	119.4 (4)	N2—C6—H6A	109.5
C5—N5—H5N	120 (4)	N2—C6—H6B	109.5
N6—N5—H5N	119 (4)	H6A—C6—H6B	109.5
N5—N6—H6NA	97 (5)	N2—C6—H6C	109.5
N5—N6—H6NB	108 (4)	H6A—C6—H6C	109.5
H6NA—N6—H6NB	97 (6)	H6B—C6—H6C	109.5
C7—N7—N8	105.7 (4)	N9—C9—N8	126.4 (4)
C9—N8—N7	111.6 (4)	N9—C9—C8	127.3 (4)
C9—N8—C12	127.8 (4)	N8—C9—C8	106.2 (4)
N7—N8—C12	120.2 (4)	N7—C7—C8	111.6 (4)
C10—N9—C9	110.8 (4)	N7—C7—H7	124.2
C10—N10—C11	117.1 (4)	C8—C7—H7	124.2
C11—N11—N12	119.7 (4)	C7—C8—C11	140.2 (4)
C11—N11—H11N	118 (3)	C7—C8—C9	104.9 (4)
N12—N11—H11N	122 (4)	C11—C8—C9	114.8 (4)
N11—N12—H12D	107 (4)	N9—C10—N10	130.4 (5)
N11—N12—H12E	111 (4)	N9—C10—H10	114.8
H12D—N12—H12E	116 (5)	N10—C10—H10	114.8
N1—C1—C2	111.0 (4)	N11—C11—N10	115.7 (4)
N1—C1—H1	124.5	N11—C11—C8	124.7 (4)
C2—C1—H1	124.5	N10—C11—C8	119.5 (4)
C3—C2—C5	115.0 (4)	N8—C12—H12A	109.5
C3—C2—C1	104.2 (4)	N8—C12—H12B	109.5
C5—C2—C1	140.7 (4)	H12A—C12—H12B	109.5
N2—C3—N3	126.4 (4)	N8—C12—H12C	109.5
N2—C3—C2	107.2 (4)	H12A—C12—H12C	109.5
N3—C3—C2	126.4 (4)	H12B—C12—H12C	109.5

C1—N1—N2—C3	1.0 (5)	C3—C2—C5—N5	−178.1 (4)
C1—N1—N2—C6	177.0 (4)	C1—C2—C5—N5	3.4 (9)
C7—N7—N8—C9	−0.8 (5)	C10—N9—C9—N8	−177.2 (4)
C7—N7—N8—C12	−175.0 (4)	C10—N9—C9—C8	2.7 (6)
N2—N1—C1—C2	−0.6 (6)	N7—N8—C9—N9	−179.8 (4)
N1—C1—C2—C3	0.1 (6)	C12—N8—C9—N9	−6.0 (7)
N1—C1—C2—C5	178.6 (5)	N7—N8—C9—C8	0.3 (5)
N1—N2—C3—N3	−179.7 (4)	C12—N8—C9—C8	174.0 (5)
C6—N2—C3—N3	4.7 (8)	N8—N7—C7—C8	1.0 (6)
N1—N2—C3—C2	−0.9 (5)	N7—C7—C8—C11	−177.1 (5)
C6—N2—C3—C2	−176.6 (5)	N7—C7—C8—C9	−0.8 (6)
C4—N3—C3—N2	178.0 (4)	N9—C9—C8—C7	−179.7 (4)
C4—N3—C3—C2	−0.5 (6)	N8—C9—C8—C7	0.3 (5)
C5—C2—C3—N2	−178.5 (4)	N9—C9—C8—C11	−2.3 (7)
C1—C2—C3—N2	0.5 (5)	N8—C9—C8—C11	177.7 (4)
C5—C2—C3—N3	0.3 (6)	C9—N9—C10—N10	−1.5 (7)
C1—C2—C3—N3	179.3 (4)	C11—N10—C10—N9	0.0 (7)
C3—N3—C4—N4	−0.3 (7)	N12—N11—C11—N10	−178.3 (4)
C5—N4—C4—N3	1.3 (8)	N12—N11—C11—C8	4.0 (7)
C4—N4—C5—N5	177.5 (4)	C10—N10—C11—N11	−177.1 (4)
C4—N4—C5—C2	−1.5 (6)	C10—N10—C11—C8	0.6 (6)
N6—N5—C5—N4	176.9 (4)	C7—C8—C11—N11	−6.0 (9)
N6—N5—C5—C2	−4.1 (7)	C9—C8—C11—N11	177.9 (4)
C3—C2—C5—N4	0.8 (6)	C7—C8—C11—N10	176.4 (5)
C1—C2—C5—N4	−177.7 (6)	C9—C8—C11—N10	0.4 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12B···N1ⁱ	0.97	2.65	3.297 (7)	124
C6—H6C···N7ⁱⁱ	0.97	2.54	3.410 (7)	150
N11—H11N···N4	0.85 (6)	2.11 (6)	2.948 (6)	170 (5)
N5—H5N···N10	0.84 (7)	2.13 (7)	2.961 (6)	170 (5)
N12—H12E···N9ⁱⁱⁱ	0.97 (7)	2.56 (6)	3.125 (5)	117 (4)
N12—H12D···N9^iv	0.91 (6)	2.24 (6)	3.125 (6)	166 (5)
N6—H6NB···N3^v	0.89 (7)	2.59 (6)	3.251 (6)	131 (5)
N6—H6NA···N3^vi	0.86 (7)	2.30 (7)	3.149 (6)	168 (7)

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

Experimental details

Crystal data
Chemical formula	C₆H₈N₆
M_r	164.18
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	223
a, b, c (Å)	14.086 (4), 3.8756 (12), 27.271 (8)
V (Å³)	1488.8 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.58 × 0.26 × 0.10

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2001)
T_min, T_max	0.943, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	8939, 1715, 1652
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.159, 1.21
No. of reflections	1715
No. of parameters	243
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.28

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
C12—H12B···N1ⁱ	0.97	2.65	3.297 (7)	124.3
C6—H6C···N7ⁱⁱ	0.97	2.54	3.410 (7)	149.7
N11—H11N···N4	0.85 (6)	2.11 (6)	2.948 (6)	170 (5)
N5—H5N···N10	0.84 (7)	2.13 (7)	2.961 (6)	170 (5)
N12—H12E···N9ⁱⁱⁱ	0.97 (7)	2.56 (6)	3.125 (5)	117 (4)
N12—H12D···N9^iv	0.91 (6)	2.24 (6)	3.125 (6)	166 (5)
N6—H6NB···N3^v	0.89 (7)	2.59 (6)	3.251 (6)	131 (5)
N6—H6NA···N3^vi	0.86 (7)	2.30 (7)	3.149 (6)	168 (7)

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

Acknowledgements

This work was supported by the National Medical Research Council, Singapore (NMRC/NIG/0020/2008) and the National University of Singapore (R-148–050-091–101/133).

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