4-Hydrazino-1-methyl-pyrazolo[3,4-d]pyrimidine.

The title compound, C(6)H(8)N(6), crystallizes as an N-H⋯N hydrogen-bond-linked dimer of two almost identical mol-ecules in the asymmetric unit. Both of the mol-ecules 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 inter-molecular N-H⋯N hydrogen bonds between the hydrazino groups and the N atoms of the pyrimidine rings of both types of the mol-ecules, linking the mol-ecules 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 = 164.18

Orthorhombic,

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[F 2 > 2σ(F 2)] = 0.065

wR(F 2) = 0.159

S = 1.21

1715 reflections

243 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.29 e Å−3

Δρmin = −0.28 e Å−3

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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809023952/jh2082sup1.cif

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C6H8N6	Dx = 1.465 Mg m−3
Mr = 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

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

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(Fo2) + (0.0699P)2 + 1.3392P] where P = (Fo2 + 2Fc2)/3
1715 reflections	(Δ/σ)max < 0.001
243 parameters	Δρmax = 0.29 e Å−3
1 restraint	Δρmin = −0.28 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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···N9iv	0.91 (6)	2.24 (6)	3.125 (6)	166 (5)
N6—H6NB···N3v	0.89 (7)	2.59 (6)	3.251 (6)	131 (5)
N6—H6NA···N3vi	0.86 (7)	2.30 (7)	3.149 (6)	168 (7)

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⋯N9iv	0.91 (6)	2.24 (6)	3.125 (6)	166 (5)
N6—H6NB⋯N3v	0.89 (7)	2.59 (6)	3.251 (6)	131 (5)
N6—H6NA⋯N3vi	0.86 (7)	2.30 (7)	3.149 (6)	168 (7)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .