1-[6-(3,5-Di-methyl-pyrazol-1-yl)-1,2,4,5-tetra-zin-3-yl]guanidin-2-ium perchlorate methanol monosolvate.

In the title solvated salt, C8H12N9 (+)·ClO4 (-)·CH3OH, the dihedral angle between the tetra-zine and pyrazole rings is 26.05 (7)°. The two N atoms bonded to the 1,2,4,5-tetra-zine ring deviate from the plane defined by its four N atoms by 0.234 (2) and 0.186 (2) Å. There is an intra-molecular N-H⋯N hydrogen bond between the protonated guanidine fragment and one of the tetra-zine N atoms. In the crystal, two cations and two perchlorate anions are connected via N-H⋯O hydrogen bonds into centrosymmetric assemblies. These assemblies are further linked into a two-dimensional network parallel to (100) via bifurcated O-H⋯(N,N) hydrogen bonds formed with the bridging methanol mol-ecules.

Related literature

For 1,2,4,5-tetra­zine heterocycles containing strained ring systems, see: Boger & Zhang (1991 ▶); Chavez et al. (2004 ▶); Saikia et al. (2009 ▶).

Experimental

Crystal data

C8H12N9 +·ClO4 −·CH4O

M = 365.76

Monoclinic,

a = 12.7906 (15) Å

b = 8.0149 (10) Å

c = 16.644 (2) Å

β = 108.305 (1)°

V = 1619.9 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.28 mm−1

T = 296 K

0.38 × 0.28 × 0.19 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2000 ▶) T min = 0.902, T max = 0.948

7710 measured reflections

2875 independent reflections

2426 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.113

S = 1.06

2875 reflections

222 parameters

H-atom parameters constrained

Δρmax = 0.24 e Å−3

Δρmin = −0.27 e Å−3

Data collection: APEX2 (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2003 ▶); 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 datablock(s) I. DOI: 10.1107/S1600536813020448/gk2585sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813020448/gk2585Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813020448/gk2585Isup3.cml

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

C8H12N9+·ClO4−·CH4O	F(000) = 760
Mr = 365.76	Dx = 1.500 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3433 reflections
a = 12.7906 (15) Å	θ = 2.6–25.8°
b = 8.0149 (10) Å	µ = 0.28 mm−1
c = 16.644 (2) Å	T = 296 K
β = 108.305 (1)°	Block, yellow
V = 1619.9 (3) Å3	0.38 × 0.28 × 0.19 mm
Z = 4

Bruker SMART APEXII CCD area-detector diffractometer	2875 independent reflections
Radiation source: fine-focus sealed tube	2426 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
phi and ω scans	θmax = 25.1°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	h = −14→15
Tmin = 0.902, Tmax = 0.948	k = −9→6
7710 measured reflections	l = −19→18

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038	H-atom parameters constrained
wR(F2) = 0.113	w = 1/[σ2(Fo2) + (0.0557P)2 + 0.5826P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max < 0.001
2875 reflections	Δρmax = 0.24 e Å−3
222 parameters	Δρmin = −0.27 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0149 (15)

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
Cl	0.71723 (4)	0.14781 (6)	0.07027 (3)	0.0510 (2)
N2	0.67200 (16)	0.7743 (2)	0.19606 (13)	0.0613 (5)
H2A	0.6775	0.8725	0.1769	0.074*
H2B	0.7265	0.7322	0.2353	0.074*
N3	0.56882 (13)	0.5343 (2)	0.19387 (11)	0.0463 (4)
H3	0.5025	0.4971	0.1807	0.056*
N1	0.49649 (15)	0.7504 (3)	0.10588 (13)	0.0639 (6)
H1A	0.5002	0.8483	0.0858	0.077*
H1B	0.4373	0.6923	0.0868	0.077*
N4	0.61470 (13)	0.2743 (2)	0.24859 (12)	0.0503 (4)
N5	0.68994 (14)	0.1634 (2)	0.28457 (12)	0.0524 (5)
N6	0.82827 (13)	0.3725 (2)	0.31430 (11)	0.0510 (4)
N7	0.75184 (14)	0.4852 (2)	0.27682 (11)	0.0516 (4)
N9	0.84660 (13)	−0.0495 (2)	0.37776 (10)	0.0468 (4)
C5	0.93968 (17)	−0.1338 (2)	0.40593 (13)	0.0473 (5)
C6	1.02667 (17)	−0.0472 (3)	0.39046 (14)	0.0544 (5)
H6	1.0995	−0.0824	0.4048	0.065*
C7	0.98545 (16)	0.0966 (3)	0.35103 (13)	0.0513 (5)
N8	0.87506 (13)	0.0947 (2)	0.34434 (10)	0.0445 (4)
O1	0.69859 (19)	0.3153 (2)	0.08793 (16)	0.0991 (7)
O2	0.61828 (13)	0.0547 (2)	0.05927 (12)	0.0742 (5)
O3	0.80093 (16)	0.0795 (3)	0.13929 (14)	0.1041 (7)
O4	0.74576 (18)	0.1425 (3)	−0.00434 (12)	0.0920 (7)
O5	0.36726 (13)	0.4239 (2)	0.10212 (12)	0.0690 (5)
H5	0.3085	0.4369	0.1114	0.103*
C1	0.58130 (17)	0.6897 (2)	0.16581 (13)	0.0455 (5)
C2	0.65001 (15)	0.4300 (2)	0.24091 (12)	0.0421 (4)
C3	0.79545 (15)	0.2160 (2)	0.31182 (12)	0.0425 (4)
C4	0.9443 (2)	−0.3002 (3)	0.44739 (16)	0.0669 (7)
H4A	0.8769	−0.3192	0.4598	0.100*
H4B	1.0050	−0.3024	0.4990	0.100*
H4C	0.9540	−0.3858	0.4100	0.100*
C8	1.0389 (2)	0.2301 (4)	0.3155 (2)	0.0821 (9)
H8A	1.0451	0.3296	0.3488	0.123*
H8B	0.9950	0.2528	0.2582	0.123*
H8C	1.1109	0.1941	0.3166	0.123*
C9	0.3592 (3)	0.2881 (5)	0.0482 (3)	0.1234 (15)
H9A	0.4295	0.2681	0.0405	0.185*
H9B	0.3056	0.3116	−0.0056	0.185*
H9C	0.3371	0.1910	0.0725	0.185*

	U11	U22	U33	U12	U13	U23
Cl	0.0464 (3)	0.0461 (3)	0.0566 (3)	−0.0045 (2)	0.0103 (2)	0.0036 (2)
N2	0.0621 (12)	0.0374 (10)	0.0784 (13)	−0.0025 (9)	0.0135 (10)	0.0134 (9)
N3	0.0380 (8)	0.0378 (9)	0.0616 (10)	0.0032 (7)	0.0136 (8)	0.0093 (8)
N1	0.0550 (11)	0.0606 (12)	0.0739 (13)	0.0101 (9)	0.0171 (9)	0.0296 (10)
N4	0.0410 (9)	0.0407 (9)	0.0675 (11)	0.0020 (7)	0.0144 (8)	0.0137 (8)
N5	0.0423 (9)	0.0399 (9)	0.0713 (12)	0.0019 (7)	0.0127 (8)	0.0140 (8)
N6	0.0429 (9)	0.0379 (9)	0.0628 (11)	0.0010 (7)	0.0033 (8)	0.0040 (8)
N7	0.0481 (10)	0.0351 (9)	0.0636 (11)	0.0008 (7)	0.0058 (8)	0.0042 (8)
N9	0.0450 (9)	0.0371 (9)	0.0537 (10)	0.0021 (7)	0.0091 (7)	0.0080 (7)
C5	0.0508 (11)	0.0380 (11)	0.0452 (11)	0.0100 (9)	0.0039 (9)	−0.0030 (8)
C6	0.0427 (11)	0.0534 (13)	0.0634 (13)	0.0130 (10)	0.0111 (10)	−0.0024 (10)
C7	0.0421 (11)	0.0551 (13)	0.0572 (12)	0.0039 (10)	0.0166 (9)	0.0007 (10)
N8	0.0400 (9)	0.0385 (9)	0.0524 (10)	0.0041 (7)	0.0109 (7)	0.0076 (7)
O1	0.1156 (17)	0.0471 (10)	0.152 (2)	−0.0112 (11)	0.0675 (16)	−0.0110 (12)
O2	0.0597 (10)	0.0659 (11)	0.0934 (13)	−0.0216 (9)	0.0188 (9)	0.0095 (9)
O3	0.0709 (12)	0.1261 (19)	0.0903 (14)	0.0117 (13)	−0.0106 (10)	0.0277 (13)
O4	0.0944 (14)	0.1182 (18)	0.0745 (12)	−0.0142 (13)	0.0424 (11)	−0.0052 (12)
O5	0.0487 (9)	0.0724 (11)	0.0892 (12)	−0.0052 (8)	0.0265 (8)	−0.0270 (9)
C1	0.0468 (11)	0.0395 (11)	0.0528 (11)	0.0085 (9)	0.0197 (9)	0.0077 (9)
C2	0.0407 (10)	0.0365 (10)	0.0489 (11)	0.0022 (8)	0.0138 (8)	0.0040 (8)
C3	0.0408 (10)	0.0387 (10)	0.0457 (10)	0.0020 (8)	0.0104 (8)	0.0064 (8)
C4	0.0700 (15)	0.0437 (12)	0.0730 (16)	0.0112 (11)	0.0026 (12)	0.0095 (11)
C8	0.0601 (15)	0.0845 (19)	0.113 (2)	0.0046 (14)	0.0429 (15)	0.0253 (17)
C9	0.090 (2)	0.142 (3)	0.149 (3)	−0.019 (2)	0.053 (2)	−0.089 (3)

Cl—O4	1.4007 (19)	N9—N8	1.381 (2)
Cl—O1	1.410 (2)	C5—C6	1.402 (3)
Cl—O3	1.4118 (19)	C5—C4	1.494 (3)
Cl—O2	1.4307 (16)	C6—C7	1.349 (3)
N2—C1	1.301 (3)	C6—H6	0.9300
N2—H2A	0.8600	C7—N8	1.381 (2)
N2—H2B	0.8600	C7—C8	1.489 (3)
N3—C1	1.357 (3)	N8—C3	1.388 (2)
N3—C2	1.371 (2)	O5—C9	1.394 (3)
N3—H3	0.8600	O5—H5	0.8200
N1—C1	1.315 (3)	C4—H4A	0.9600
N1—H1A	0.8600	C4—H4B	0.9600
N1—H1B	0.8600	C4—H4C	0.9600
N4—N5	1.309 (2)	C8—H8A	0.9600
N4—C2	1.346 (3)	C8—H8B	0.9600
N5—C3	1.349 (3)	C8—H8C	0.9600
N6—C3	1.320 (3)	C9—H9A	0.9600
N6—N7	1.333 (2)	C9—H9B	0.9600
N7—C2	1.327 (2)	C9—H9C	0.9600
N9—C5	1.320 (2)
O4—Cl—O1	108.79 (14)	N9—N8—C3	119.30 (15)
O4—Cl—O3	111.56 (14)	C7—N8—C3	129.05 (17)
O1—Cl—O3	109.53 (16)	C9—O5—H5	109.5
O4—Cl—O2	109.68 (12)	N2—C1—N1	121.56 (19)
O1—Cl—O2	108.81 (12)	N2—C1—N3	122.16 (19)
O3—Cl—O2	108.42 (13)	N1—C1—N3	116.28 (19)
C1—N2—H2A	120.0	N7—C2—N4	125.26 (17)
C1—N2—H2B	120.0	N7—C2—N3	120.94 (17)
H2A—N2—H2B	120.0	N4—C2—N3	113.76 (16)
C1—N3—C2	127.33 (17)	N6—C3—N5	125.62 (18)
C1—N3—H3	116.3	N6—C3—N8	117.78 (17)
C2—N3—H3	116.3	N5—C3—N8	116.49 (17)
C1—N1—H1A	120.0	C5—C4—H4A	109.5
C1—N1—H1B	120.0	C5—C4—H4B	109.5
H1A—N1—H1B	120.0	H4A—C4—H4B	109.5
N5—N4—C2	116.91 (16)	C5—C4—H4C	109.5
N4—N5—C3	117.09 (16)	H4A—C4—H4C	109.5
C3—N6—N7	116.75 (16)	H4B—C4—H4C	109.5
C2—N7—N6	117.18 (16)	C7—C8—H8A	109.5
C5—N9—N8	104.42 (16)	C7—C8—H8B	109.5
N9—C5—C6	111.15 (18)	H8A—C8—H8B	109.5
N9—C5—C4	121.4 (2)	C7—C8—H8C	109.5
C6—C5—C4	127.4 (2)	H8A—C8—H8C	109.5
C7—C6—C5	107.51 (18)	H8B—C8—H8C	109.5
C7—C6—H6	126.2	O5—C9—H9A	109.5
C5—C6—H6	126.2	O5—C9—H9B	109.5
C6—C7—N8	105.28 (19)	H9A—C9—H9B	109.5
C6—C7—C8	130.5 (2)	O5—C9—H9C	109.5
N8—C7—C8	124.1 (2)	H9A—C9—H9C	109.5
N9—N8—C7	111.63 (16)	H9B—C9—H9C	109.5
C2—N4—N5—C3	1.1 (3)	C2—N3—C1—N1	164.5 (2)
C3—N6—N7—C2	0.3 (3)	N6—N7—C2—N4	9.1 (3)
N8—N9—C5—C6	−0.6 (2)	N6—N7—C2—N3	−173.48 (18)
N8—N9—C5—C4	−179.98 (19)	N5—N4—C2—N7	−9.8 (3)
N9—C5—C6—C7	0.0 (3)	N5—N4—C2—N3	172.61 (18)
C4—C5—C6—C7	179.3 (2)	C1—N3—C2—N7	11.8 (3)
C5—C6—C7—N8	0.6 (2)	C1—N3—C2—N4	−170.56 (19)
C5—C6—C7—C8	−175.8 (3)	N7—N6—C3—N5	−9.0 (3)
C5—N9—N8—C7	1.0 (2)	N7—N6—C3—N8	174.88 (17)
C5—N9—N8—C3	−177.43 (17)	N4—N5—C3—N6	8.3 (3)
C6—C7—N8—N9	−1.0 (2)	N4—N5—C3—N8	−175.54 (17)
C8—C7—N8—N9	175.7 (2)	N9—N8—C3—N6	151.36 (18)
C6—C7—N8—C3	177.2 (2)	C7—N8—C3—N6	−26.8 (3)
C8—C7—N8—C3	−6.0 (4)	N9—N8—C3—N5	−25.1 (3)
C2—N3—C1—N2	−15.4 (3)	C7—N8—C3—N5	156.8 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2i	0.86	2.54	3.101 (3)	124
O5—H5···N9ii	0.82	2.05	2.866 (2)	173
O5—H5···N5ii	0.82	2.50	2.940 (2)	114
N2—H2A···O3iii	0.86	2.50	3.251 (3)	146
N2—H2A···O2iii	0.86	2.37	3.118 (3)	146
N1—H1A···O2iii	0.86	2.37	3.120 (3)	146
N3—H3···O5	0.86	1.90	2.700 (2)	153
N2—H2B···N7	0.86	2.09	2.713 (2)	129
N1—H1B···O5	0.86	2.37	3.085 (3)	140

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2i	0.86	2.54	3.101 (3)	124
O5—H5⋯N9ii	0.82	2.05	2.866 (2)	173
O5—H5⋯N5ii	0.82	2.50	2.940 (2)	114
N2—H2A⋯O3iii	0.86	2.50	3.251 (3)	146
N2—H2A⋯O2iii	0.86	2.37	3.118 (3)	146
N1—H1A⋯O2iii	0.86	2.37	3.120 (3)	146
N3—H3⋯O5	0.86	1.90	2.700 (2)	153
N2—H2B⋯N7	0.86	2.09	2.713 (2)	129
N1—H1B⋯O5	0.86	2.37	3.085 (3)	140

Symmetry codes: (i) ; (ii) ; (iii) .