Bis(μ-4-amino-3,5-dimethyl-4H-1,2,4-triazole-κN:N)bis-(dibromidozinc).

The centrosymmetric dimeric title complex, [Zn(2)Br(4)(C(4)H(8)N(4))(2)], is isotypic with its [Zn(2)Cl(4)(C(4)H(8)N(4))(2)], [Zn(2)I(4)(C(4)H(8)N(4))(2)] and [Co(2)Cl(4)(C(4)H(8)N(4))(2)] analogues. The zinc atom is bonded to two N atoms belonging to triazole bridging rings and to two terminal bromide ligands, in a geometry close to tetra-hedral. Weak N-H⋯Br hydrogen bonds, with the amine functions as donor groups, are observed in the crystal structure, forming a three-dimensional supra-molecular network.

Related literature

For background to transition metal complexes of 1,2,4-triazole derivatives, see: Liu et al. (1999 ▶). For the isotypic [Zn2Cl4(C4H8N4)2], [Zn2I4(C4H8N4)2] and [Co2Cl4(C4H8N4)2] analogues, see: Lavrenova et al. (1992 ▶); Zhang et al. (2011 ▶); Gong et al. (2009 ▶). For other related structures, see: Liu et al. (2003 ▶); Zhao et al. (2002 ▶); Yi et al. (2004 ▶); Zhang et al. (2007 ▶).

Experimental

Crystal data

[Zn2Br4(C4H8N4)2]

M = 674.67

Monoclinic,

a = 7.0344 (17) Å

b = 12.629 (3) Å

c = 11.456 (3) Å

β = 99.951 (6)°

V = 1002.4 (4) Å3

Z = 2

Mo Kα radiation

μ = 10.37 mm−1

T = 293 K

0.48 × 0.20 × 0.16 mm

Data collection

Rigaku Mercury CCD diffractometer

Absorption correction: multi-scan (REQAB; Jacobson, 1998 ▶) T min = 0.083, T max = 0.288

9580 measured reflections

1833 independent reflections

1517 reflections with I > 2σ(I)

R int = 0.054

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.148

S = 1.05

1833 reflections

110 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.69 e Å−3

Δρmin = −0.97 e Å−3

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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, global. DOI: 10.1107/S1600536811028789/bh2370sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811028789/bh2370Isup2.hkl

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

[Zn2Br4(C4H8N4)2]	F(000) = 640
Mr = 674.67	Dx = 2.235 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: -P 2ybc	Cell parameters from 2994 reflections
a = 7.0344 (17) Å	θ = 3.2–25.4°
b = 12.629 (3) Å	µ = 10.37 mm−1
c = 11.456 (3) Å	T = 293 K
β = 99.951 (6)°	Block, colourless
V = 1002.4 (4) Å3	0.48 × 0.20 × 0.16 mm
Z = 2

Rigaku Mercury CCD diffractometer	1833 independent reflections
Radiation source: fine-focus sealed tube	1517 reflections with I > 2σ(I)
graphite	Rint = 0.054
Detector resolution: 14.63 pixels mm-1	θmax = 25.3°, θmin = 3.2°
ω scans	h = −8→8
Absorption correction: multi-scan (REQAB;Jacobson, 1998)	k = −13→15
Tmin = 0.083, Tmax = 0.288	l = −13→13
9580 measured reflections

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.148	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.084P)2 + 1.6395P] where P = (Fo2 + 2Fc2)/3
1833 reflections	(Δ/σ)max < 0.001
110 parameters	Δρmax = 0.69 e Å−3
2 restraints	Δρmin = −0.97 e Å−3
0 constraints

	x	y	z	Uiso*/Ueq
Zn1	0.91275 (11)	0.89737 (6)	0.59841 (7)	0.0379 (3)
Br1	1.05816 (13)	0.72906 (7)	0.61240 (10)	0.0726 (4)
Br2	0.66056 (12)	0.91347 (7)	0.70931 (9)	0.0638 (3)
N1	0.8048 (8)	0.9248 (4)	0.4253 (5)	0.0393 (13)
N2	0.8846 (8)	0.9908 (4)	0.3485 (5)	0.0372 (13)
N3	0.6514 (8)	0.9028 (4)	0.2457 (5)	0.0386 (13)
N4	0.5184 (11)	0.8698 (6)	0.1475 (6)	0.0541 (17)
H4D	0.408 (7)	0.881 (7)	0.166 (8)	0.06 (3)*
H4E	0.520 (13)	0.803 (2)	0.161 (8)	0.06 (3)*
C1	0.7888 (10)	0.9765 (5)	0.2415 (6)	0.0381 (15)
C2	0.6619 (10)	0.8725 (5)	0.3605 (6)	0.0398 (16)
C3	0.8174 (12)	1.0313 (6)	0.1318 (6)	0.0527 (19)
H3A	0.6998	1.0660	0.0969	0.079*
H3B	0.8526	0.9805	0.0768	0.079*
H3C	0.9184	1.0828	0.1503	0.079*
C4	0.5307 (13)	0.7968 (7)	0.4037 (8)	0.063 (2)
H4A	0.6048	0.7423	0.4489	0.094*
H4B	0.4473	0.7657	0.3374	0.094*
H4C	0.4544	0.8332	0.4528	0.094*

	U11	U22	U33	U12	U13	U23
Zn1	0.0342 (5)	0.0373 (5)	0.0419 (5)	−0.0009 (3)	0.0058 (4)	0.0031 (3)
Br1	0.0570 (6)	0.0457 (6)	0.1112 (9)	0.0139 (4)	0.0036 (5)	0.0004 (4)
Br2	0.0528 (5)	0.0687 (6)	0.0770 (7)	−0.0005 (4)	0.0308 (5)	−0.0099 (4)
N1	0.038 (3)	0.039 (3)	0.040 (3)	−0.005 (2)	0.004 (3)	0.003 (2)
N2	0.037 (3)	0.038 (3)	0.035 (3)	−0.003 (2)	0.005 (3)	0.005 (2)
N3	0.036 (3)	0.039 (3)	0.037 (3)	−0.003 (2)	−0.002 (3)	−0.004 (2)
N4	0.053 (4)	0.058 (5)	0.048 (4)	−0.017 (4)	0.001 (3)	−0.008 (3)
C1	0.040 (4)	0.037 (4)	0.038 (4)	−0.002 (3)	0.009 (3)	0.000 (3)
C2	0.039 (3)	0.041 (4)	0.038 (4)	−0.009 (3)	0.003 (3)	0.003 (3)
C3	0.070 (5)	0.048 (5)	0.041 (4)	−0.001 (4)	0.013 (4)	0.004 (3)
C4	0.072 (6)	0.054 (5)	0.061 (5)	−0.025 (4)	0.005 (4)	0.002 (4)

Zn1—N1	2.027 (6)	N4—H4D	0.85 (2)
Zn1—N2i	2.025 (6)	N4—H4E	0.86 (2)
Zn1—Br1	2.3523 (12)	C1—C3	1.478 (10)
Zn1—Br2	2.3625 (12)	C2—C4	1.472 (10)
N1—C2	1.320 (8)	C3—H3A	0.9600
N1—N2	1.398 (8)	C3—H3B	0.9600
N2—C1	1.305 (9)	C3—H3C	0.9600
N2—Zn1i	2.025 (6)	C4—H4A	0.9600
N3—C1	1.349 (9)	C4—H4B	0.9600
N3—C2	1.359 (9)	C4—H4C	0.9600
N3—N4	1.397 (9)
N2i—Zn1—N1	107.5 (2)	N2—C1—N3	108.6 (6)
N2i—Zn1—Br1	109.56 (16)	N2—C1—C3	127.6 (6)
N1—Zn1—Br1	107.83 (17)	N3—C1—C3	123.8 (6)
N2i—Zn1—Br2	109.48 (16)	N1—C2—N3	108.2 (6)
N1—Zn1—Br2	108.79 (17)	N1—C2—C4	126.7 (6)
Br1—Zn1—Br2	113.53 (5)	N3—C2—C4	125.1 (6)
C2—N1—N2	107.1 (5)	C1—C3—H3A	109.5
C2—N1—Zn1	125.8 (5)	C1—C3—H3B	109.5
N2—N1—Zn1	126.5 (4)	H3A—C3—H3B	109.5
C1—N2—N1	108.1 (5)	C1—C3—H3C	109.5
C1—N2—Zn1i	126.9 (5)	H3A—C3—H3C	109.5
N1—N2—Zn1i	124.4 (4)	H3B—C3—H3C	109.5
C1—N3—C2	108.0 (5)	C2—C4—H4A	109.5
C1—N3—N4	124.2 (6)	C2—C4—H4B	109.5
C2—N3—N4	127.7 (6)	H4A—C4—H4B	109.5
N3—N4—H4D	105 (6)	C2—C4—H4C	109.5
N3—N4—H4E	100 (6)	H4A—C4—H4C	109.5
H4D—N4—H4E	96 (8)	H4B—C4—H4C	109.5
N2i—Zn1—N1—C2	−176.0 (6)	Zn1i—N2—C1—C3	6.4 (11)
Br1—Zn1—N1—C2	66.0 (6)	C2—N3—C1—N2	1.2 (8)
Br2—Zn1—N1—C2	−57.5 (6)	N4—N3—C1—N2	178.3 (7)
N2i—Zn1—N1—N2	14.3 (7)	C2—N3—C1—C3	−177.7 (7)
Br1—Zn1—N1—N2	−103.7 (5)	N4—N3—C1—C3	−0.7 (11)
Br2—Zn1—N1—N2	132.7 (5)	N2—N1—C2—N3	0.6 (7)
C2—N1—N2—C1	0.1 (7)	Zn1—N1—C2—N3	−170.8 (5)
Zn1—N1—N2—C1	171.5 (5)	N2—N1—C2—C4	−177.4 (8)
C2—N1—N2—Zn1i	172.1 (5)	Zn1—N1—C2—C4	11.2 (11)
Zn1—N1—N2—Zn1i	−16.6 (8)	C1—N3—C2—N1	−1.1 (8)
N1—N2—C1—N3	−0.8 (8)	N4—N3—C2—N1	−178.1 (7)
Zn1i—N2—C1—N3	−172.6 (4)	C1—N3—C2—C4	176.9 (8)
N1—N2—C1—C3	178.1 (7)	N4—N3—C2—C4	0.0 (12)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4D···Br1ii	0.85 (2)	2.80 (7)	3.428 (7)	132 (8)
N4—H4E···Br2iii	0.86 (2)	2.93 (4)	3.748 (8)	161 (8)

Zn1—N1	2.027 (6)
Zn1—N2i	2.025 (6)
Zn1—Br1	2.3523 (12)
Zn1—Br2	2.3625 (12)

N2i—Zn1—N1	107.5 (2)
N2i—Zn1—Br1	109.56 (16)
N1—Zn1—Br1	107.83 (17)
N2i—Zn1—Br2	109.48 (16)
N1—Zn1—Br2	108.79 (17)
Br1—Zn1—Br2	113.53 (5)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4D⋯Br1ii	0.85 (2)	2.80 (7)	3.428 (7)	132 (8)
N4—H4E⋯Br2iii	0.86 (2)	2.93 (4)	3.748 (8)	161 (8)

Symmetry codes: (ii) ; (iii) .