3,5-Diamino-1-phenyl-1,2,4-triazolium bromide.

The title salt, C(8)H(10)N(5) (+)·Br(-), crystallizes with two independent structural units in the asymmetric unit. The two independent cations have different conformations, the triazole and phenyl rings forming dihedral angles of 32.57 (6) and 52.27 (7)°. In both cations, the amino groups are planar (the sum of the angles at the N atom of each amino group is 360°) and conjugated with the triazole ring. Inter-molecular N-H⋯N and N-H⋯Br hydrogen bonds consolidate the crystal packing.

Related literature

For the crystal structures of protonated C-amino-1,2,4-triazoles, see: Reck et al. (1982 ▶); Lynch et al. (1998 ▶, 1999 ▶); Baouab et al. (2000 ▶); Bichay et al. (2006 ▶); Guerfel et al. (2007 ▶); Matulková et al. (2007 ▶). For the crystal structure of 3,5-diamino-1,2,4-triazole, see: Starova et al. (1980 ▶). For the theoretical investigation of the protonation of C-amino-1,2,4-triazoles, see: Anders et al. (1997 ▶). For the reactions of 1-substituted 3,5-diamino-1,2,4-triazoles with electrophilic reagents, see: Steck et al. (1958 ▶); Chernyshev et al. (2005 ▶, 2008 ▶). For the use of 1-substituted 3,5-diamino-1,2,4-triazoles as building blocks in the synthesis of various derivatives of 1,2,4-triazole and fused heterocyclic systems, see: Dunstan et al. (1998 ▶); Chernyshev et al. (2006 ▶, 2009 ▶, 2010 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

C8H10N5 +·Br−

M = 256.12

Monoclinic,

a = 13.752 (2) Å

b = 7.1172 (13) Å

c = 20.394 (4) Å

β = 95.519 (3)°

V = 1986.7 (6) Å3

Z = 8

Mo Kα radiation

μ = 4.11 mm−1

T = 100 K

0.55 × 0.40 × 0.30 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.211, T max = 0.372

19484 measured reflections

4314 independent reflections

3808 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.027

wR(F 2) = 0.071

S = 1.00

4314 reflections

253 parameters

H-atom parameters constrained

Δρmax = 0.63 e Å−3

Δρmin = −0.52 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2005 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶), publCIF (Westrip, 2010 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810021318/cv2726sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810021318/cv2726Isup2.hkl

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

C8H10N5+·Br−	F(000) = 1024
Mr = 256.12	Dx = 1.713 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 568 reflections
a = 13.752 (2) Å	θ = 3–26°
b = 7.1172 (13) Å	µ = 4.11 mm−1
c = 20.394 (4) Å	T = 100 K
β = 95.519 (3)°	Plate, colourless
V = 1986.7 (6) Å3	0.55 × 0.40 × 0.30 mm
Z = 8

Bruker APEXII CCD area-detector diffractometer	4314 independent reflections
Radiation source: fine-focus sealed tube	3808 reflections with I > 2σ(I)
graphite	Rint = 0.033
ω scans	θmax = 27.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −17→17
Tmin = 0.211, Tmax = 0.372	k = −9→9
19484 measured reflections	l = −26→26

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)] = 0.027	Hydrogen site location: difference Fourier map
wR(F2) = 0.071	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.0375P)2 + 2.843P] where P = (Fo2 + 2Fc2)/3
4314 reflections	(Δ/σ)max = 0.001
253 parameters	Δρmax = 0.63 e Å−3
0 restraints	Δρmin = −0.52 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
Br1	0.469797 (17)	0.08357 (3)	0.629576 (11)	0.01647 (7)
Br2	0.183938 (18)	0.24667 (3)	0.647848 (11)	0.01826 (8)
N1'	0.28802 (13)	0.3108 (3)	0.40098 (9)	0.0106 (4)
N1	0.33201 (14)	0.2566 (3)	0.88547 (9)	0.0105 (4)
C5	0.28387 (16)	0.2595 (3)	0.82544 (11)	0.0109 (4)
C3'	0.17571 (16)	0.3375 (3)	0.46553 (11)	0.0109 (4)
N2	0.43255 (13)	0.2227 (3)	0.88259 (9)	0.0110 (4)
N2'	0.18826 (13)	0.3526 (3)	0.40275 (9)	0.0110 (4)
C3	0.44019 (16)	0.2009 (3)	0.81952 (11)	0.0112 (4)
C5'	0.33040 (16)	0.2696 (3)	0.46079 (11)	0.0108 (4)
N3	0.52349 (14)	0.1671 (3)	0.79256 (10)	0.0155 (4)
H3A	0.5776	0.1581	0.8172	0.019*
H3B	0.5228	0.1544	0.7506	0.019*
C6	0.29678 (17)	0.2856 (3)	0.94788 (11)	0.0112 (4)
C6'	0.33268 (16)	0.3120 (3)	0.34068 (11)	0.0108 (4)
N3'	0.09158 (14)	0.3663 (3)	0.49263 (10)	0.0139 (4)
H3'A	0.0397	0.3978	0.4682	0.017*
H3'B	0.0897	0.3533	0.5344	0.017*
C7'	0.41759 (17)	0.4159 (3)	0.33736 (12)	0.0141 (4)
H7'	0.4425	0.4895	0.3727	0.017*
N4'	0.26139 (14)	0.2888 (3)	0.50273 (9)	0.0106 (4)
H4'	0.2691	0.2737	0.5447	0.013*
N4	0.35127 (14)	0.2222 (3)	0.78272 (9)	0.0110 (4)
H4	0.3406	0.2134	0.7406	0.013*
C7	0.20341 (17)	0.2241 (3)	0.95945 (12)	0.0144 (5)
H7	0.1630	0.1663	0.9262	0.017*
C8'	0.46478 (17)	0.4074 (3)	0.27991 (12)	0.0168 (5)
H8'	0.5225	0.4738	0.2771	0.020*
N5	0.18967 (14)	0.2885 (3)	0.80841 (10)	0.0139 (4)
H5A	0.1508	0.3091	0.8382	0.017*
H5B	0.1674	0.2869	0.7675	0.017*
N5'	0.42386 (14)	0.2226 (3)	0.47651 (10)	0.0140 (4)
H5'A	0.4634	0.2166	0.4464	0.017*
H5'B	0.4445	0.1983	0.5168	0.017*
C8	0.17218 (18)	0.2512 (4)	1.02182 (12)	0.0189 (5)
H8	0.1098	0.2134	1.0300	0.023*
C9'	0.42605 (18)	0.3005 (4)	0.22696 (12)	0.0184 (5)
H9'	0.4585	0.2932	0.1891	0.022*
C9	0.2331 (2)	0.3340 (4)	1.07174 (12)	0.0203 (5)
H9	0.2116	0.3514	1.1132	0.024*
C10'	0.33847 (19)	0.2038 (3)	0.23038 (12)	0.0177 (5)
H10'	0.3116	0.1362	0.1940	0.021*
C10	0.32641 (19)	0.3909 (3)	1.05977 (12)	0.0184 (5)
H10	0.3677	0.4445	1.0935	0.022*
C11	0.35831 (17)	0.3681 (3)	0.99777 (11)	0.0142 (5)
H11	0.4205	0.4078	0.9897	0.017*
C11'	0.29117 (17)	0.2074 (3)	0.28729 (11)	0.0135 (4)
H11'	0.2332	0.1418	0.2899	0.016*

	U11	U22	U33	U12	U13	U23
Br1	0.01631 (12)	0.02134 (13)	0.01186 (12)	−0.00248 (9)	0.00199 (8)	0.00081 (9)
Br2	0.02081 (13)	0.02303 (14)	0.01122 (12)	0.00564 (10)	0.00289 (9)	−0.00001 (9)
N1'	0.0066 (9)	0.0153 (9)	0.0099 (9)	−0.0003 (7)	0.0012 (7)	0.0007 (7)
N1	0.0081 (9)	0.0145 (9)	0.0089 (9)	0.0022 (7)	0.0008 (7)	−0.0006 (7)
C5	0.0112 (10)	0.0094 (10)	0.0122 (10)	−0.0009 (8)	0.0013 (8)	−0.0006 (8)
C3'	0.0107 (10)	0.0097 (10)	0.0123 (10)	−0.0016 (8)	0.0008 (8)	−0.0007 (8)
N2	0.0074 (9)	0.0150 (9)	0.0108 (9)	0.0020 (7)	0.0020 (7)	−0.0005 (7)
N2'	0.0064 (9)	0.0146 (9)	0.0122 (9)	0.0006 (7)	0.0016 (7)	0.0012 (7)
C3	0.0129 (11)	0.0092 (10)	0.0115 (10)	0.0011 (8)	0.0014 (8)	0.0000 (8)
C5'	0.0110 (10)	0.0106 (10)	0.0109 (10)	−0.0014 (8)	0.0017 (8)	−0.0001 (8)
N3	0.0117 (9)	0.0250 (11)	0.0100 (9)	0.0050 (8)	0.0028 (7)	−0.0012 (8)
C6	0.0143 (11)	0.0106 (10)	0.0090 (10)	0.0053 (8)	0.0027 (8)	0.0015 (8)
C6'	0.0117 (10)	0.0117 (10)	0.0092 (10)	0.0030 (8)	0.0023 (8)	0.0026 (8)
N3'	0.0105 (9)	0.0209 (10)	0.0106 (9)	0.0019 (8)	0.0027 (7)	−0.0005 (8)
C7'	0.0134 (11)	0.0144 (11)	0.0146 (11)	0.0005 (9)	0.0014 (8)	0.0017 (9)
N4'	0.0111 (9)	0.0139 (9)	0.0069 (9)	−0.0009 (7)	0.0012 (7)	−0.0004 (7)
N4	0.0114 (9)	0.0141 (9)	0.0076 (9)	0.0014 (7)	0.0008 (7)	−0.0005 (7)
C7	0.0120 (11)	0.0169 (11)	0.0141 (11)	0.0040 (9)	0.0008 (9)	0.0038 (9)
C8'	0.0119 (11)	0.0193 (12)	0.0197 (12)	0.0013 (9)	0.0045 (9)	0.0094 (10)
N5	0.0102 (9)	0.0214 (10)	0.0097 (9)	0.0024 (8)	−0.0009 (7)	−0.0026 (8)
N5'	0.0099 (9)	0.0212 (10)	0.0108 (9)	0.0015 (8)	−0.0002 (7)	0.0021 (8)
C8	0.0160 (12)	0.0233 (13)	0.0187 (12)	0.0094 (10)	0.0079 (9)	0.0094 (10)
C9'	0.0202 (12)	0.0225 (12)	0.0137 (11)	0.0086 (10)	0.0084 (9)	0.0073 (10)
C9	0.0297 (14)	0.0207 (12)	0.0112 (11)	0.0139 (11)	0.0065 (10)	0.0030 (9)
C10'	0.0222 (12)	0.0182 (12)	0.0126 (11)	0.0070 (10)	0.0004 (9)	−0.0006 (9)
C10	0.0268 (13)	0.0161 (12)	0.0118 (11)	0.0074 (10)	−0.0010 (9)	−0.0016 (9)
C11	0.0158 (11)	0.0121 (10)	0.0143 (11)	0.0039 (9)	−0.0003 (9)	0.0000 (9)
C11'	0.0138 (11)	0.0137 (11)	0.0130 (11)	0.0009 (9)	0.0002 (9)	0.0011 (9)

N1'—C5'	1.333 (3)	C7'—C8'	1.394 (3)
N1'—N2'	1.408 (2)	C7'—H7'	0.9300
N1'—C6'	1.426 (3)	N4'—H4'	0.8600
N1—C5	1.335 (3)	N4—H4	0.8600
N1—N2	1.410 (3)	C7—C8	1.395 (3)
N1—C6	1.420 (3)	C7—H7	0.9300
C5—N5	1.325 (3)	C8'—C9'	1.385 (4)
C5—N4	1.358 (3)	C8'—H8'	0.9300
C3'—N2'	1.313 (3)	N5—H5A	0.8600
C3'—N3'	1.345 (3)	N5—H5B	0.8600
C3'—N4'	1.383 (3)	N5'—H5'A	0.8600
N2—C3	1.310 (3)	N5'—H5'B	0.8600
C3—N3	1.339 (3)	C8—C9	1.386 (4)
C3—N4	1.380 (3)	C8—H8	0.9300
C5'—N5'	1.337 (3)	C9'—C10'	1.395 (4)
C5'—N4'	1.344 (3)	C9'—H9'	0.9300
N3—H3A	0.8600	C9—C10	1.389 (4)
N3—H3B	0.8600	C9—H9	0.9300
C6—C11	1.389 (3)	C10'—C11'	1.384 (3)
C6—C7	1.398 (3)	C10'—H10'	0.9300
C6'—C7'	1.389 (3)	C10—C11	1.387 (3)
C6'—C11'	1.395 (3)	C10—H10	0.9300
N3'—H3'A	0.8600	C11—H11	0.9300
N3'—H3'B	0.8600	C11'—H11'	0.9300
C5'—N1'—N2'	111.37 (18)	C3'—N4'—H4'	126.5
C5'—N1'—C6'	127.14 (19)	C5—N4—C3	107.23 (18)
N2'—N1'—C6'	121.48 (17)	C5—N4—H4	126.4
C5—N1—N2	111.48 (18)	C3—N4—H4	126.4
C5—N1—C6	129.6 (2)	C8—C7—C6	118.6 (2)
N2—N1—C6	118.86 (18)	C8—C7—H7	120.7
N5—C5—N1	129.0 (2)	C6—C7—H7	120.7
N5—C5—N4	125.0 (2)	C9'—C8'—C7'	120.2 (2)
N1—C5—N4	106.04 (19)	C9'—C8'—H8'	119.9
N2'—C3'—N3'	126.0 (2)	C7'—C8'—H8'	119.9
N2'—C3'—N4'	111.76 (19)	C5—N5—H5A	120.0
N3'—C3'—N4'	122.3 (2)	C5—N5—H5B	120.0
C3—N2—N1	103.46 (17)	H5A—N5—H5B	120.0
C3'—N2'—N1'	103.15 (17)	C5'—N5'—H5'A	120.0
N2—C3—N3	125.2 (2)	C5'—N5'—H5'B	120.0
N2—C3—N4	111.75 (19)	H5'A—N5'—H5'B	120.0
N3—C3—N4	123.0 (2)	C9—C8—C7	120.8 (2)
N1'—C5'—N5'	126.9 (2)	C9—C8—H8	119.6
N1'—C5'—N4'	106.66 (19)	C7—C8—H8	119.6
N5'—C5'—N4'	126.5 (2)	C8'—C9'—C10'	120.1 (2)
C3—N3—H3A	120.0	C8'—C9'—H9'	120.0
C3—N3—H3B	120.0	C10'—C9'—H9'	120.0
H3A—N3—H3B	120.0	C8—C9—C10	119.9 (2)
C11—C6—C7	120.9 (2)	C8—C9—H9	120.1
C11—C6—N1	118.8 (2)	C10—C9—H9	120.1
C7—C6—N1	120.3 (2)	C11'—C10'—C9'	120.7 (2)
C7'—C6'—C11'	121.9 (2)	C11'—C10'—H10'	119.7
C7'—C6'—N1'	118.6 (2)	C9'—C10'—H10'	119.7
C11'—C6'—N1'	119.5 (2)	C11—C10—C9	120.3 (2)
C3'—N3'—H3'A	120.0	C11—C10—H10	119.8
C3'—N3'—H3'B	120.0	C9—C10—H10	119.8
H3'A—N3'—H3'B	120.0	C10—C11—C6	119.6 (2)
C6'—C7'—C8'	118.7 (2)	C10—C11—H11	120.2
C6'—C7'—H7'	120.7	C6—C11—H11	120.2
C8'—C7'—H7'	120.7	C10'—C11'—C6'	118.3 (2)
C5'—N4'—C3'	107.03 (18)	C10'—C11'—H11'	120.8
C5'—N4'—H4'	126.5	C6'—C11'—H11'	120.8
N2—N1—C5—N5	−179.4 (2)	C11'—C6'—C7'—C8'	−3.1 (3)
C6—N1—C5—N5	−0.8 (4)	N1'—C6'—C7'—C8'	175.9 (2)
N2—N1—C5—N4	1.8 (2)	N1'—C5'—N4'—C3'	1.7 (2)
C6—N1—C5—N4	−179.6 (2)	N5'—C5'—N4'—C3'	−179.7 (2)
C5—N1—N2—C3	−1.7 (2)	N2'—C3'—N4'—C5'	−1.1 (3)
C6—N1—N2—C3	179.49 (19)	N3'—C3'—N4'—C5'	179.6 (2)
N3'—C3'—N2'—N1'	179.3 (2)	N5—C5—N4—C3	−180.0 (2)
N4'—C3'—N2'—N1'	0.0 (2)	N1—C5—N4—C3	−1.1 (2)
C5'—N1'—N2'—C3'	1.2 (2)	N2—C3—N4—C5	0.0 (3)
C6'—N1'—N2'—C3'	−179.8 (2)	N3—C3—N4—C5	−178.4 (2)
N1—N2—C3—N3	179.3 (2)	C11—C6—C7—C8	1.5 (3)
N1—N2—C3—N4	1.0 (2)	N1—C6—C7—C8	178.6 (2)
N2'—N1'—C5'—N5'	179.6 (2)	C6'—C7'—C8'—C9'	1.4 (3)
C6'—N1'—C5'—N5'	0.7 (4)	C6—C7—C8—C9	−1.3 (3)
N2'—N1'—C5'—N4'	−1.8 (2)	C7'—C8'—C9'—C10'	1.3 (4)
C6'—N1'—C5'—N4'	179.2 (2)	C7—C8—C9—C10	0.0 (4)
C5—N1—C6—C11	−147.8 (2)	C8'—C9'—C10'—C11'	−2.4 (4)
N2—N1—C6—C11	30.7 (3)	C8—C9—C10—C11	1.1 (4)
C5—N1—C6—C7	35.1 (3)	C9—C10—C11—C6	−0.9 (3)
N2—N1—C6—C7	−146.4 (2)	C7—C6—C11—C10	−0.4 (3)
C5'—N1'—C6'—C7'	−52.8 (3)	N1—C6—C11—C10	−177.5 (2)
N2'—N1'—C6'—C7'	128.4 (2)	C9'—C10'—C11'—C6'	0.8 (3)
C5'—N1'—C6'—C11'	126.2 (2)	C7'—C6'—C11'—C10'	2.0 (3)
N2'—N1'—C6'—C11'	−52.6 (3)	N1'—C6'—C11'—C10'	−177.0 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N2'i	0.86	2.20	3.037 (3)	164
N3—H3B···Br1	0.86	2.56	3.387 (2)	163
N3'—H3'A···N2ii	0.86	2.34	3.046 (3)	140
N3'—H3'B···Br2	0.86	2.65	3.404 (3)	147
N4—H4···Br2	0.86	2.74	3.417 (3)	137
N4'—H4'···Br2	0.86	2.51	3.254 (3)	145
N5—H5A···Br1iii	0.86	2.69	3.369 (3)	137
N5—H5B···Br2	0.86	2.49	3.281 (3)	153
N5'—H5'A···Br1iv	0.86	2.84	3.489 (3)	133
N5'—H5'B···Br1	0.86	2.43	3.278 (3)	167

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯N2′i	0.86	2.20	3.037 (3)	164
N3—H3B⋯Br1	0.86	2.56	3.387 (2)	163
N3′—H3′A⋯N2ii	0.86	2.34	3.046 (3)	140
N3′—H3′B⋯Br2	0.86	2.65	3.404 (3)	147
N4—H4⋯Br2	0.86	2.74	3.417 (3)	137
N4′—H4′⋯Br2	0.86	2.51	3.254 (3)	145
N5—H5A⋯Br1iii	0.86	2.69	3.369 (3)	137
N5—H5B⋯Br2	0.86	2.49	3.281 (3)	153
N5′—H5′A⋯Br1iv	0.86	2.84	3.489 (3)	133
N5′—H5′B⋯Br1	0.86	2.43	3.278 (3)	167

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