catena-Poly[copper(I)-di-μ-bromido-copper(I)-bis­­[μ-4-methyl-1H-1,2,4-triazole-5(4H)-thione-κ²S:S]]

In the title coordination polymer, [CuBr(C₃H₅N₃S)]_n, the Cu^I atom adopts a tetra­hdral CuS₂Br₂ coordination geometry arising from two S-bonded 4-methyl-1H-1,2,4-triazole-3(4H)-thione ligands and two bromide ions. Both the S and Br atoms act as bridging ligands, connecting pairs of Cu^I atoms and generating chains propagating in [100]. Inter-chain N—H⋯N hydrogen bonds generate layers in the ac plane. Weak intra-chain N—H⋯Br inter­actions also occur.

Related literature

For related structures of metals coordinated by 1,2,4-triazole derivatives, see: Cingi et al. (1996); Haasnoot (2000); Kajdan et al. (2000); Menzies & Squattrito (2001); Klingele & Brooker (2003).

Experimental

Crystal data

• [CuBr(C₃H₅N₃S)]

• M_r = 258.62

• Monoclinic, P 2₁ /n

• a = 5.5781 (11) Å

• b = 12.931 (3) Å

• c = 9.810 (2) Å

• β = 97.69 (3)°

• V = 701.2 (2) ų

• Z = 4

• Mo Kα radiation

• μ = 9.02 mm⁻¹

• T = 100 K

• 0.28 × 0.12 × 0.06 mm

Data collection

• Bruker D8 CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 1998) T_min = 0.284, T_max = 0.582

• 7830 measured reflections

• 1610 independent reflections

• 1513 reflections with I > 2σ(I)

• R_int = 0.043

Refinement

• R[F² > 2σ(F²)] = 0.027

• wR(F²) = 0.056

• S = 1.16

• 1610 reflections

• 86 parameters

• 1 restraint

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.64 e Å⁻³

• Δρ_min = −0.37 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Cu1—S1	2.3124 (9)
Cu1—S1^i	2.4012 (9)
Cu1—Br1	2.4638 (7)
Cu1—Br1^ii	2.5085 (8)

Cu1—Br1—Cu1^ii	67.81 (2)
Cu1—S1—Cu1^i	73.60 (3)
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) -x, -y+2, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N2^iii	0.86 (2)	2.35 (3)	2.890 (4)	121 (3)
N1—H1⋯Br1	0.86 (2)	2.78 (2)	3.566 (3)	153 (3)
Symmetry code: (iii) -x+1, -y+2, -z+2.

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT and SHELXTL (Sheldrick, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: Mercury (Macrae et al., 2008) and publCIF (Westrip, 2010).

Supporting information

S1. Comment

1,2,4-Triazole and its derivatives are very interesting ligands because they combine the coordination geometry of both pyrazole and imidazole with regard to the arrangement of their three heteroatoms. The interest in unsubstituted and substituted 1,2,4-triazole derivatives arise from their ability to bond metal ions in a various forms. A large number of mononuclear, oligonuclear and polynuclear metal coordination compounds with 1,2,4-triazole derivatives as ligands including the coordination chemistry have been described (Cingi et al., 1996; Haasnoot, 2000; Kajdan et al., 2000; Menzies & Squattrito, 2001; Klingele & Brooker, 2003).

Herein, we report the crystal structure of the title compound. The polymeric complex of [Cu(µ₂ –Hmptrz)(µ₂-Br)]_n is isomorphous with those complex that has been report [Cu(µ₂-Hmptrz)(µ₂-I)]_n (Wang et al., 2011). The chemical structure of this complex is shown in Scheme 1. Each Cu atom is a distorted tetrahedral geometry with the angles around Cu centre atom ranging from 104.74 (3)° to 117.72 (3)° and it is coordinated by two µ₂-S donating Hmptrz molecules and two µ₂-Br atoms. The one-dimensional chain built from two type of Cu(µ₂-S)₂ and Cu(µ₂-Br)₂ unit sharing the Cu centre atoms. Each pair of µ₂-S and of µ₂-Br bridges alternate to link between two Cu centre atoms giving the linked rhomboid of Cu₂S₂ and Cu₂Br₂ core forming a 1-D chain running along a-axis. Each Cu₂S₂ rhomboid is located at nearly perpendicular position to adjacent Cu₂Br₂ rhomboid with a dihedral angle of 86.90 (4)^o between these planes. A view of the one-dimensional polymeric chain is shown in Figure 1.

The Cu···Cu distances of of Cu(µ₂-S)₂ and Cu(µ₂-Br)₂ unit are 2.8246 (9) and 2.7740 (9) Å. The latter distance is slightly shorter than the sum of van der Waals radii of Cu atoms (2.80 Å). The inter-molecular hydrogen bonds N(1)—H(1)···N(2)ⁱⁱⁱ [N(1)···N(2)ⁱⁱⁱ = 2.890 (4) Å, iii: -x + 1, -y + 2, -z + 2] between the adjacent 1-D polymeric chains are observed generating the two-dimensional sheets of supramolecular interactions running in ac-plane. The arrangement of the polymeric chains and the inter-molecular hydrogen bonds in crystal packing of this complex are shown in Figures 2 and 3, respectively.

Related literature

For related structures of metals coordinated by 1,2,4-triazole derivatives, see: Cingi et al. (1996); Haasnoot (2000); Kajdan et al. (2000); Menzies & Squattrito (2001); Klingele & Brooker (2003).

S2. Experimental

The mixture of Hmptrz ligand (0.28 g, 2.43 mmol) and copper (I) iodide (0.15 g, 1.05 mmol) in acetronitrile solution was refluxed N₂ gas. The yellow filtrate was allowed to stand at room temperature for 2 days. The block colorless crystals of [Cu(µ₂-Hmptrz)(µ₂-Br)]_n were isolated. This complex melts and decomposes at 234–235 ^oC.

S3. Refinement

All hydrogen atoms on carbon atoms were constrained, C—H = 0.95 Å with U_iso(H) = 1.2U_eq(C) for C-sp² atoms of pyridine and phenyl rings and C—H = 0.98 Å with U_iso(H) = 1.5U_eq(C) for C-sp³ atoms of the methyl group, respectively. The hydrogen atom on N atom is located in a difference Fourier map and restrained, N—H = 0.86 Å with U_iso(H) = 1.2U_eq(N).

Computing details

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003) and SHELXTL (Sheldrick, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: Mercury (Macrae et al., 2008) and publCIF (Westrip, 2010).

Figures

	Fig. 1. A view of the 1-D polymeric chain of [Cu(µ2-Hmptrz)(µ2-Br)]n with displacement ellipsoids plotted at the 50% probability level.
	Fig. 2. The arrangement of the polymeric chains in packing of [Cu(µ2-Hmptrz)(µ2-Br)]n.
	Fig. 3. The inter-molecular hydrogen bonds generating 2-D sheet of [Cu(µ2-Hmptrz)(µ2-Br)]n.

catena-Poly[copper(I)-di-µ-bromido-copper(I)-bis[µ-4-methyl- 1H-1,2,4-triazole-5(4H)-thione-κ²S:S]]

Crystal data

[CuBr(C3H5N3S)]	F(000) = 496
Mr = 258.62	Dx = 2.450 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71074 Å
Hall symbol: -P 2yn	Cell parameters from 2999 reflections
a = 5.5781 (11) Å	θ = 2.6–27.5°
b = 12.931 (3) Å	µ = 9.02 mm^−1
c = 9.810 (2) Å	T = 100 K
β = 97.69 (3)°	Prism, colorless
V = 701.2 (2) Å^3	0.28 × 0.12 × 0.06 mm
Z = 4

Data collection

Bruker D8 CCD diffractometer	1610 independent reflections
Radiation source: sealed X-ray tube	1513 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.043
Detector resolution: 8.366 pixels mm^-1	θmax = 27.5°, θmin = 2.6°
ω scans	h = −7→7
Absorption correction: multi-scan (SADABS; Bruker, 1998)	k = −16→16
Tmin = 0.284, Tmax = 0.582	l = −12→12
7830 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.056	H atoms treated by a mixture of independent and constrained refinement
S = 1.16	w = 1/[σ^2(Fo^2) + (0.0145P)^2 + 1.2302P] where P = (Fo^2 + 2Fc^2)/3
1610 reflections	(Δ/σ)max = 0.001
86 parameters	Δρmax = 0.64 e Å^−3
1 restraint	Δρmin = −0.37 e Å^−3

Special details

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 > 2σ (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 (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.25060 (7)	0.99881 (3)	0.51220 (4)	0.01363 (11)
Br1	0.02520 (5)	1.07438 (2)	0.68746 (3)	0.01177 (9)
S1	0.52061 (14)	0.86702 (6)	0.58000 (7)	0.01143 (16)
N1	0.5464 (5)	0.9389 (2)	0.8453 (3)	0.0139 (5)
H1	0.417 (5)	0.976 (2)	0.838 (4)	0.017*
N2	0.6910 (5)	0.9341 (2)	0.9706 (3)	0.0164 (6)
N3	0.8341 (4)	0.83717 (19)	0.8149 (3)	0.0113 (5)
C1	0.6309 (5)	0.8819 (2)	0.7499 (3)	0.0115 (6)
C2	0.8636 (6)	0.8719 (2)	0.9480 (3)	0.0150 (6)
H2	0.9944	0.8528	1.0154	0.018*
C3	0.9938 (6)	0.7674 (2)	0.7517 (3)	0.0154 (6)
H3A	0.9086	0.7025	0.7263	0.023*
H3B	1.1385	0.7530	0.8173	0.023*
H3C	1.0414	0.7999	0.6692	0.023*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.01225 (19)	0.0179 (2)	0.01017 (19)	0.00017 (15)	−0.00072 (14)	−0.00002 (15)
Br1	0.01057 (15)	0.01533 (16)	0.00898 (15)	−0.00146 (11)	−0.00027 (10)	−0.00234 (11)
S1	0.0127 (4)	0.0118 (4)	0.0094 (3)	−0.0004 (3)	0.0001 (3)	−0.0016 (3)
N1	0.0140 (13)	0.0179 (14)	0.0093 (12)	0.0056 (11)	−0.0001 (10)	0.0004 (10)
N2	0.0215 (14)	0.0184 (14)	0.0081 (12)	0.0047 (12)	−0.0024 (10)	0.0004 (11)
N3	0.0116 (12)	0.0102 (12)	0.0118 (12)	0.0013 (10)	0.0005 (10)	0.0013 (10)
C1	0.0116 (14)	0.0094 (14)	0.0134 (15)	−0.0018 (11)	0.0008 (11)	0.0017 (11)
C2	0.0167 (15)	0.0165 (16)	0.0107 (14)	0.0034 (13)	−0.0020 (12)	0.0005 (12)
C3	0.0132 (15)	0.0172 (16)	0.0163 (16)	0.0052 (12)	0.0042 (12)	0.0005 (13)

Geometric parameters (Å, º)

Cu1—S1	2.3124 (9)	N1—N2	1.378 (4)
Cu1—S1^i	2.4012 (9)	N1—H1	0.862 (18)
Cu1—Br1	2.4638 (7)	N2—C2	1.296 (4)
Cu1—Br1^ii	2.5085 (8)	N3—C1	1.354 (4)
Cu1—Cu1^ii	2.7740 (9)	N3—C2	1.370 (4)
Cu1—Cu1^i	2.8246 (9)	N3—C3	1.463 (4)
Br1—Cu1^ii	2.5085 (8)	C2—H2	0.9500
S1—C1	1.708 (3)	C3—H3A	0.9800
S1—Cu1^i	2.4012 (9)	C3—H3B	0.9800
N1—C1	1.327 (4)	C3—H3C	0.9800
S1—Cu1—S1^i	106.40 (3)	C2—N3—C3	127.2 (3)
S1—Cu1—Br1	117.72 (3)	N1—C1—N3	105.0 (3)
S1^i—Cu1—Br1	108.84 (3)	N1—C1—S1	129.5 (2)
S1—Cu1—Br1^ii	104.74 (3)	N3—C1—S1	125.5 (2)
S1^i—Cu1—Br1^ii	106.25 (3)	N2—C2—N3	111.7 (3)
Br1—Cu1—Br1^ii	112.19 (2)	N2—C2—H2	124.1
Cu1—Br1—Cu1^ii	67.81 (2)	N3—C2—H2	124.1
Cu1—S1—Cu1^i	73.60 (3)	N3—C3—H3A	109.5
C1—N1—N2	112.6 (3)	N3—C3—H3B	109.5
C1—N1—H1	129 (3)	H3A—C3—H3B	109.5
N2—N1—H1	119 (3)	N3—C3—H3C	109.5
C2—N2—N1	103.6 (3)	H3A—C3—H3C	109.5
C1—N3—C2	107.1 (3)	H3B—C3—H3C	109.5
C1—N3—C3	125.7 (3)
S1—Cu1—Br1—Cu1^ii	−121.64 (4)	N2—N1—C1—N3	1.1 (3)
S1^i—Cu1—Br1—Cu1^ii	117.29 (3)	N2—N1—C1—S1	−177.6 (2)
Br1^ii—Cu1—Br1—Cu1^ii	0.0	C2—N3—C1—N1	−1.1 (3)
Cu1^i—Cu1—Br1—Cu1^ii	172.54 (4)	C3—N3—C1—N1	−179.4 (3)
S1^i—Cu1—S1—C1	93.28 (12)	C2—N3—C1—S1	177.7 (2)
Br1—Cu1—S1—C1	−29.05 (12)	C3—N3—C1—S1	−0.6 (4)
Br1^ii—Cu1—S1—C1	−154.45 (11)	Cu1—S1—C1—N1	16.7 (3)
Cu1^ii—Cu1—S1—C1	−97.63 (12)	Cu1^i—S1—C1—N1	92.2 (3)
Cu1^i—Cu1—S1—C1	93.28 (12)	Cu1—S1—C1—N3	−161.8 (2)
S1^i—Cu1—S1—Cu1^i	0.0	Cu1^i—S1—C1—N3	−86.3 (3)
Br1—Cu1—S1—Cu1^i	−122.33 (3)	N1—N2—C2—N3	−0.2 (4)
Br1^ii—Cu1—S1—Cu1^i	112.27 (3)	C1—N3—C2—N2	0.8 (4)
Cu1^ii—Cu1—S1—Cu1^i	169.09 (4)	C3—N3—C2—N2	179.1 (3)
C1—N1—N2—C2	−0.5 (4)

Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x, −y+2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N2^iii	0.86 (2)	2.35 (3)	2.890 (4)	121 (3)
N1—H1···Br1	0.86 (2)	2.78 (2)	3.566 (3)	153 (3)

Symmetry code: (iii) −x+1, −y+2, −z+2.