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The new two-dimensional coordination polymer, poly[(μ4-1-phenyl-1H-1,2,3,4-tetra­zole-5-thiol­ato)copper(I)], [Cu(C7H5N4S)]n, has been prepared under solvothermal conditions by reacting CuBr with 1-phenyl-1H-1,2,3,4-tetra­zole-5-thiol (Hptt) in an aceto­nitrile and acetone solution. In the crystal structure, each CuI ion is coordinated by two N atoms and two S atoms from four ptt ligands, and each ptt ligand links four CuI ions to form two-dimensional layers which lie parallel to the (100) plane. These layers stack along the [100] direction via van der Waals inter­actions.

Supporting information


Crystallographic Information File (CIF)
Contains datablock I


Structure factor file (CIF format)
Contains datablock I

CCDC reference: 927375

Introduction top

The synthesis and design of functional d8/d10 transition-metal complexes with a closed-shell electronic configuration have drawn enormous inter­est in recent years because of their intriguing coordination architectures and potential applications in various fields including catalysis, photochemistry, fluorescence and biological properties (Yue et al., 2008, 2010; Yam et al., 1997; Lin et al., 2010). Among these materials, CuI–metal complexes have been studied intensively because of their abundant resources, low cost and nontoxic properties compared with noble metal complexes, e.g. ReI, OsII, IrIII, RhI and PtII (Yam et al., 1999, 2002; Harvey et al., 1988; White-Morris et al., 2002). Furthermore, CuI is a favourable and fashionable ion for the construction of coordination polymers because of its highly diversified and flexible coordination number and geometry, as well as its ready coordination with various donor atoms, such as O, S, N, P and I, which facilitate the discovery of inter­esting structural motifs.

Much effort has focused on using organosulfur and organo­nitro­gen ligands as bridging units between CuI sites. For example, Cu6(btt)6 and Cu4(btt)4 (btt is 2-benzo­thia­zole­thiol) feature slightly distorted o­cta­nuclear [Cu6] and tetra­nuclear [Cu4] cores, respectively, in which all the CuI ions are coordinated by two S atoms and one N atom from three btt ligands with nearly trigonal planar coordination geometries (Yue et al., 2009). Cu3(4-pyt)3 (4-pyt is pyridine-4-thiol­ate) exhibits a three-dimensional network in which two crystallographically independent CuI ions feature nearly trigonal planar and slightly distorted tetra­hedral coordination environments (Han et al., 2009).

In recent years, complexes based on tetra­zole and its derivatives have attracted much attention due to the ligand's highly flexible coordination mode (Bai et al., 2006). We are inter­ested in the synthesis of complexes between CuI and 1-phenyl-1H-tetra­zole-5-thiol (Hptt), where both the N and S atoms act as electronic donors, about which little is known compared with other systems containing tetra­zole. Our exploratory studies led to one new complex, poly[(µ4-1-phenyl-1H-1,2,3,4-tetra­zole-5-thiol­ato)copper(I)], [Cu(ptt)]n, (I), and the synthesis and crystal structure is reported herein.

Experimental top

Synthesis and crystallization top

All analytical grade chemicals were obtained commercially and used without further purification. Elemental analyses (C, H and N) were performed using a PE2400 II elemental analyzer. Compound (I) was prepared by solvothermal methods. CuBr (0.2 mmol, 29 mg) and Hptt (0.2 mmol, 36 mg) were added to a solution (8 ml) composed of aceto­nitrile and acetone in a 1:1 ratio. The solution was sealed in a Teflon-lined stainless steel reactor. The mixture was heated at 350 K for 3 d, and then cooled to room temperature over a period of 1 d, affording a yellow solution, which was evaporated under ambient conditions to give yellow crystals of (I) (yield 54.2%, 26 mg, based on Cu). Analysis calculated for C7H5CuN4S (%): H 2.09, C 34.92, N 23.27; found: H 2.07, C 34.79, N 23.21.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms were placed in calculated positions, with C—H = 0.93 Å, and refined in the riding-model approximation, with Uiso(H) = 1.2Ueq(C).

Results and discussion top

The X-ray single-crystal diffraction study reveals that [Cu(ptt)]n (ppt is 1-phenyl-1H-1,2,3,4-tetra­zole-5-thiol­ate), (I), crystallizes in the monoclinic space group P21/c. As shown in Fig. 1, there is one crystallographically independent CuI ion and one ppt- ligand in the asymmetric unit. Each CuI ion is coordinated by two N atoms and two S atoms from four different ptt- ligands to give a distorted tetra­hedral coordination environment, which is very similar to that of [CuI(ppt)(C14H8N2S5)]ClO4.CHCl3 (Jeannin et al., 1979) [what is C14H8N2S5?]. A similar tetra­hedral coordination geometry about CuI ions has been reported in many complexes, such as [Cu4I(ptt)3(Hptt)3]4 and (Ph3P)3Cu4(mmt)4 (mmt is 5-mercapto-1-methyl-1,2,3,4-tetra­zole; Wei et al., 2009; Nöth et al., 1998). As listed in Table 2, the Cu—N and Cu—S bond lengths are comparable to those reported in the above-mentioned CuI complexes. Each ptt- ligand acts as a µ4-bridging ligand linking four CuI ions. Two adjacent N atoms in the tetra­zole unit of the ptt- ligand coordinate in a monodentate fashion to two CuI ions so that the ligand bridges these metal centres, while the S atom acts as a bridging bidentate metal linker bridging two further CuI ions. This connectivity results in the formation of two-dimensional (2D) [Cu(ptt)]n layers which lie parallel to the (100) plane (Fig. 2).

It is instructive to consider the substructures apparent within the layers. The 2D layer can be considered as being built from two halves, where each half-layer is composed of one-dimensional (1D) zigzag [Cu–S–Cu–S] chains running parallel to the [001] direction inter­linked through the 1-phenyl­tetra­zole units (Fig. 3a). Two half-layers are further inter­connected via Cu—N bonds to form the 2D [Cu(ptt)]n layer. Within the 2D layer, there is a ladder, propagating along the [010] direction, composed of alternating centrosymmetric ten-membered [Cu–S–Cu–N–N–Cu–S–Cu–N–N] rings (A type) and eight-membered [Cu–N–C–S–Cu–N–C–S] rings (B type) fused by sharing the S–Cu–N edges (Fig. 3b). Between two adjacent ladders, neighbouring ten-membered rings only share a common Cu atom and no atoms are common to two eight-membered rings. At the same time, crosslinking of the A- and B-type rings along the [001] direction leads to another series of seven-membered [Cu–N–C–S–Cu–N–N] rings (C type), which also propagate along the [010] direction by fusing with each other through the Cu1—N1 bond (Fig. 3c). The seven-membered rings are fused with adjacent eight- and ten-membered rings.

The shortest Cu···Cu distance within the [Cu(ptt)]n layer is 3.504 (3) Å for Cu1···Cu1(-x+1, -y+2, -z+1), which is longer than the sum of the van der Waals radii of two CuI atoms (2.80 Å; Bondi et al., 1964). The shortest contact between neighbouring [Cu(ptt)]n layers is the H5···H6(-x, y+1/2, -z+1/2) distance of 2.64 Å. Thus, only van der Waals inter­actions exist between the 2D [Cu(ptt)]n layers (Fig. 2).

It is inter­esting to compare the coordination modes of tetra­zole-5-thiol units. As shown in Fig. 4, the tetra­zole-5-thiol units in many reported complexes exhibit a wide variety of coordination modes: µ1-1κS (mode A), µ2-1κS:2κN (mode B), µ3-1,2κS:3κN (mode C), µ4-1,2κS:3κN:4κN' (mode D) and µ5-1,2,3κS:4κN:5κN' (mode E). For example, coordination mode A has been reported in [Cu4I(ptt)3(Hptt)3]4 and coordination mode B is found in [Zn(mmt)2]n, while the mmt ligand adopts coordination mode C in (Ph3P)3Cu4(mmt)4 and [Cd(mmt)2]n (Wei et al., 2009; Wang et al., 2008; Nöth et al., 1998). Inter­estingly, the ptt- ligand simultaneously features modes A and C in [Cu4I(ptt)3(Hptt)3]4 (Wei et al., 2009). Coordination modes D and E are found in Ag6Cl2(mmt)4[H4SiMo12O40](H2O)2 and [Ag8(mmt)4][SiW12O40].H2O, respectively (Wang et al., 2012; Yang et al., 2012). The ptt ligand in (I) adopts coordination mode D.

Related literature top

For related literature, see: Bai et al. (2006); Bondi (1964); Han et al. (2009); Harvey & Gray (1988); Jeannin et al. (1979); Lin et al. (2010); Nöth et al. (1998); Wang et al. (2008, 2012); Wei et al. (2009); White-Morris, Olmstead, Jiang & Balch (2002); Yam (2002); Yam & Lo (1999); Yam et al. (1997); Yang et al. (2012); Yue et al. (2008, 2009, 2010).

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004; 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 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The structure of part of a layer in (I), showing the CuI ion, the ligand coordination and the atom-numbering scheme. In the electronic version of the paper, the C, N, S and Cu atoms are drawn as gray, blue, yellow and brown spheres, respectively. [Symmetry codes: (i) x, y-1, z; (ii) x, -y+1/2, z+1/2; (iii) -x+1, y-1/2, -z+1/2; (iv) -x+1, -y+1, -z; (v) x, -y+1/2, z-1/2; (vi) -x+1, y+1/2, -z+1/2; (vii) x, -y+3/2, z-1/2; (viii) x, -y+3/2, z+1/2; (ix) x, y+1, z; (x) -x+1, -y+1, -z+1; (xi) -x+1, -y+2, -z+1; (xii) -x+1, y+3/2, -z+1/2; (xiii) -x+1, -y+2, -z.]
[Figure 2] Fig. 2. A projection of the packing of (I) along the [010] direction, showing the layers end-on.
[Figure 3] Fig. 3. Some substructures within the [Cu(ptt)]n layer: (a) the Cu–S–Cu–S chains along [001]; (b) alternating fused type A and B rings; (c) the fused type C rings.
[Figure 4] Fig. 4. Coordination modes of the tetrazole-5-thiol unit found in the literature and in (I) (mode D).
Poly[(µ4-1-phenyl-1H-1,2,3,4-tetrazole-5-thiolato)copper(I)] top
Crystal data top
[Cu(C7H5N4S)]Z = 4
Mr = 240.75F(000) = 480
Monoclinic, P21/cDx = 1.883 Mg m3
Hall symbol: -p2ybcMo Kα radiation, λ = 0.71073 Å
a = 17.344 (15) ŵ = 2.77 mm1
b = 6.509 (5) ÅT = 293 K
c = 7.522 (6) ÅBlock, yellow
β = 90.790 (17)°0.22 × 0.16 × 0.16 mm
V = 849.1 (12) Å3
Data collection top
Bruker SMART CCD area-detector
1923 independent reflections
Radiation source: fine-focus sealed tube1534 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.063
ω scanθmax = 27.4°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
h = 2222
Tmin = 0.580, Tmax = 0.674k = 78
6033 measured reflectionsl = 99
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.133H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.064P)2 + 0.6784P]
where P = (Fo2 + 2Fc2)/3
1923 reflections(Δ/σ)max < 0.001
118 parametersΔρmax = 1.00 e Å3
0 restraintsΔρmin = 0.68 e Å3
Crystal data top
[Cu(C7H5N4S)]V = 849.1 (12) Å3
Mr = 240.75Z = 4
Monoclinic, P21/cMo Kα radiation
a = 17.344 (15) ŵ = 2.77 mm1
b = 6.509 (5) ÅT = 293 K
c = 7.522 (6) Å0.22 × 0.16 × 0.16 mm
β = 90.790 (17)°
Data collection top
Bruker SMART CCD area-detector
1923 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
1534 reflections with I > 2σ(I)
Tmin = 0.580, Tmax = 0.674Rint = 0.063
6033 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0520 restraints
wR(F2) = 0.133H-atom parameters constrained
S = 1.06Δρmax = 1.00 e Å3
1923 reflectionsΔρmin = 0.68 e Å3
118 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
Cu10.45089 (3)0.89282 (8)0.31726 (8)0.0302 (2)
S10.38690 (6)0.72397 (16)0.07158 (14)0.0249 (3)
N10.4350 (2)0.3554 (5)0.2096 (5)0.0255 (8)
N20.4019 (2)0.1840 (6)0.2784 (5)0.0280 (8)
C50.0783 (4)0.5611 (13)0.1896 (10)0.068 (2)
N40.3110 (2)0.3928 (5)0.2228 (5)0.0275 (8)
N30.3276 (2)0.2016 (6)0.2880 (6)0.0346 (9)
C10.3772 (2)0.4863 (6)0.1711 (5)0.0223 (8)
C20.2317 (3)0.4576 (8)0.2081 (7)0.0334 (10)
C30.2100 (3)0.6500 (9)0.2644 (8)0.0451 (13)
C60.1015 (4)0.3707 (11)0.1311 (10)0.0612 (18)
C70.1790 (3)0.3151 (10)0.1396 (8)0.0457 (13)
C40.1321 (4)0.7021 (12)0.2540 (9)0.0634 (19)
Atomic displacement parameters (Å2) top
Cu10.0329 (3)0.0239 (3)0.0340 (4)0.0003 (2)0.0029 (2)0.0022 (2)
S10.0342 (6)0.0193 (5)0.0211 (5)0.0015 (4)0.0017 (4)0.0004 (4)
N10.0291 (19)0.0186 (17)0.029 (2)0.0019 (14)0.0006 (16)0.0021 (15)
N20.0318 (19)0.0232 (18)0.029 (2)0.0013 (15)0.0034 (16)0.0013 (15)
C50.032 (3)0.108 (6)0.064 (5)0.013 (4)0.001 (3)0.009 (4)
N40.0265 (18)0.0229 (18)0.033 (2)0.0022 (14)0.0016 (16)0.0031 (16)
N30.037 (2)0.026 (2)0.041 (2)0.0001 (17)0.0020 (18)0.0100 (18)
C10.027 (2)0.020 (2)0.020 (2)0.0022 (16)0.0030 (16)0.0014 (16)
C20.029 (2)0.040 (3)0.031 (2)0.004 (2)0.0044 (19)0.005 (2)
C30.038 (3)0.054 (3)0.043 (3)0.014 (2)0.002 (2)0.005 (3)
C60.036 (3)0.086 (5)0.062 (4)0.015 (3)0.009 (3)0.008 (4)
C70.036 (3)0.054 (3)0.047 (3)0.006 (3)0.001 (2)0.001 (3)
C40.050 (3)0.082 (5)0.059 (4)0.034 (4)0.005 (3)0.000 (4)
Geometric parameters (Å, º) top
Cu1—N1i2.007 (4)C5—H50.9300
Cu1—N2ii2.096 (4)N4—C11.361 (5)
Cu1—S1iii2.3511 (18)N4—N31.367 (5)
Cu1—S12.4079 (18)N4—C21.442 (6)
S1—C11.728 (4)C2—C31.376 (7)
S1—Cu1iv2.3511 (18)C2—C71.395 (8)
N1—C11.344 (5)C3—C41.393 (8)
N1—N21.360 (5)C3—H30.9300
N1—Cu1v2.007 (4)C6—C71.394 (8)
N2—N31.296 (5)C6—H60.9300
N2—Cu1vi2.096 (4)C7—H70.9300
C5—C61.377 (10)C4—H40.9300
C5—C41.392 (11)
N1i—Cu1—N2ii119.61 (14)N3—N4—C2119.3 (4)
N1i—Cu1—S1iii121.32 (12)N2—N3—N4105.4 (3)
N2ii—Cu1—S1iii102.17 (11)N1—C1—N4106.5 (4)
N1i—Cu1—S1108.18 (12)N1—C1—S1125.8 (3)
N2ii—Cu1—S197.13 (12)N4—C1—S1127.7 (3)
S1iii—Cu1—S1105.02 (7)C3—C2—C7122.6 (5)
C1—S1—Cu1iv96.47 (14)C3—C2—N4120.5 (5)
C1—S1—Cu197.05 (15)C7—C2—N4116.9 (5)
Cu1iv—S1—Cu1123.67 (7)C2—C3—C4118.2 (6)
C1—N1—N2106.5 (3)C2—C3—H3120.9
C1—N1—Cu1v129.4 (3)C4—C3—H3120.9
N2—N1—Cu1v124.1 (3)C5—C6—C7120.3 (6)
N3—N2—N1112.0 (4)C5—C6—H6119.8
N3—N2—Cu1vi118.2 (3)C7—C6—H6119.8
N1—N2—Cu1vi128.5 (3)C6—C7—C2118.1 (6)
C6—C5—C4120.5 (6)C6—C7—H7121.0
C4—C5—H5119.8C5—C4—C3120.3 (7)
C1—N4—N3109.6 (4)C5—C4—H4119.9
C1—N4—C2131.0 (4)C3—C4—H4119.9
Symmetry codes: (i) x+1, y+1/2, z+1/2; (ii) x, y+1, z; (iii) x, y+3/2, z+1/2; (iv) x, y+3/2, z1/2; (v) x+1, y1/2, z+1/2; (vi) x, y1, z.

Experimental details

Crystal data
Chemical formula[Cu(C7H5N4S)]
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)17.344 (15), 6.509 (5), 7.522 (6)
β (°) 90.790 (17)
V3)849.1 (12)
Radiation typeMo Kα
µ (mm1)2.77
Crystal size (mm)0.22 × 0.16 × 0.16
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.580, 0.674
No. of measured, independent and
observed [I > 2σ(I)] reflections
6033, 1923, 1534
(sin θ/λ)max1)0.648
R[F2 > 2σ(F2)], wR(F2), S 0.052, 0.133, 1.06
No. of reflections1923
No. of parameters118
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.00, 0.68

Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SAINT (Bruker, 2004, SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top
Cu1—N1i2.007 (4)Cu1—S1iii2.3511 (18)
Cu1—N2ii2.096 (4)Cu1—S12.4079 (18)
N1i—Cu1—N2ii119.61 (14)S1iii—Cu1—S1105.02 (7)
N1i—Cu1—S1iii121.32 (12)C1—S1—Cu1iv96.47 (14)
N2ii—Cu1—S1iii102.17 (11)C1—S1—Cu197.05 (15)
N1i—Cu1—S1108.18 (12)Cu1iv—S1—Cu1123.67 (7)
N2ii—Cu1—S197.13 (12)
Symmetry codes: (i) x+1, y+1/2, z+1/2; (ii) x, y+1, z; (iii) x, y+3/2, z+1/2; (iv) x, y+3/2, z1/2.

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