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The structures of the title compounds, [CuCl(C3H5N3S)4]Cl·H2O, (I), and [CuCl(C4H7N3S)4]Cl, (II), comprise square-pyramidal Cu centres with four N-bound organic ligands filling the base positions, a Cl atom in the apical position and a Cl- as a free counter-ion. The cation and free chloride ion in (II) have fourfold crystallographic symmetry. Hydro­gen-bonding associations from the 2-amino H atoms dominate both structures, with the principal acceptors being the chlorides, although in (I), the N4 atoms are also involved. Furthermore, (I) is a hydrate, with the water mol­ecule participating in the hydrogen-bonding network.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101009489/gg1063sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101009489/gg1063Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101009489/gg1063IIsup3.hkl
Contains datablock II

CCDC references: 173346; 173347

Comment top

2-Amino-1,3-thiazoles have many applications in both human and veterinary medicine as well as materials science (Lynch et al., 1999). The mode of action for several 2-aminothiazole derivatives depends on metal-ligand binding, such as in the case of 2-amino-4,5-dihydro-1,3-thiazole which possibly induces the transformation of tumor cells (Kubiak et al., 1983; Kubiak & Glowiak, 1984). 2-Aminothiazoles contain three donor sites available for co-ordination to a metal species, the amine N and the heterocyclic N and S atoms. However, structural studies of metal complexes containing 2-aminothiazoles have shown that the predominant point for metal attachment is to the heterocyclic N. As a derivative of 2-aminothiazoles, 2-amino-1,3,4-thiadiazoles contain two heterocyclic N atoms available for metal complexation and have been studied as corrosion inhibitors (Downie et al., 1972), for potential antiviral activity (Saramet, 1975; Tonew & Limki, 1974), and as an inhibitor of carbonic anhydrase (Pedregosa et al., 1993).

Four structural examples of metal complexes of substituted 2-amino-1,3,4-thiadiazoles are known; they display varying co-ordination geometries. The copper(I) chloride complex of 2-amino-5-methyl-1,3,4-thiadiazole (Neverov et al., 1986) forms linear polymers with planar units of two Cu atoms bridged by two thiadiazole molecules which then propagate via two bridging Cl atoms to the next Cu (Fig. 1). For the thiadiazoles in this structure, Cu atoms bind both heterocyclic N atoms. However, in the known metal(II) halide complexes of thiadiazole derivatives (Mn: Fabretti et al., 1993; Zn: Khusenov et al., 1997; Hg: Antolini et al., 1988) only one N atom is involved in metal co-ordination. In each case there are two thiadiazoles per metal and for the ZnCl2 and HgBr2 complexes the geometry is tetrahedral whereas the addition of two water molecules in the MnCl2 complex results in octahedral geometry. We have instigated a series of studies covering the syntheses of metal halide complexes of substituted 2-amino-1,3,4-thiadiazoles to determine the role, if any, of the exocyclic N atom in determining the metal co-ordination and/or the overall packing structure. If this N atom is not metal bound it is still available for hydrogen-bonding interactions if considering the presence of the 2-amino groups. For this particular study we chose to use the same thiadiazole derivative, as well as the ethyl analogue, that produced the Neverov et al. (1986) structure. However, complexation of 2-amino-5-methyl-1,3,4-thiadiazole, (I), and 2-amino-5-ethyl-1,3,4-thiadiazole, (II), with CuCl2 yielded square pyramidal Cu complexes containing four bound thiadiazoles, one bound Cl and the other in the lattice as a counter ion. Complex (I) was characterized as a hydrate. \sch

The structures of (I) and (II) are shown in Figs. 2 and 3 while selected Cu bonds for both complexes are listed in Table 1 and hydrogen-bonding geometries are given in Table 2. For any 2-aminothiazole derivative, (I) and (II) are the first examples of five-coordinate square-pyramidal geometry. In both (I) and (II) the thiadiazoles are singly bound at N3 and occupy the four square planar positions but differences between the two structures occur in the specific orientations of the organic ligands. In the structure of (I) there are four unique heterocyclics with ligand A opposing the similar orientations of groups B, C and D whereas for (II) all four thiadiazoles are symmetry related around the Cu atom. In both complexes the amino groups are orientated in the same direction as the Cu—Cl1 bond such that all, except for ligand A in (I), are involved with N—H···Cl hydrogen-bonding associations. The Cl2 atoms also participate in N—H···Cl associations but only in (I) are the N4 atoms used as hydrogen-bonding acceptors. The rotation of the A moiety in (I) is interesting because if it were orientated the same as thiadiazoles B - D then it would associate to Cl1. Instead N21A associates with O1W and N4B while the second N21B H atom, from an adjacent molecule, slots in to associate with Cl1 (Fig. 4). The availability of the N4 atoms for hydrogen bonding, combined with the presence of Cl2, creates five free acceptor elements, in comparison to the four free 2-amino H atoms, but a water molecule is still required to complete the hydrogen-bonding network; most probably because Cl2 is a multi-point hydrogen-bonding acceptor. For (II) the unique position of Cl2 satisfies the hydrogen-bonding requirements of the second 2-amino H atom; thus, in this structure all hydrogen-bonding elements are either complimented or structurally hindered (Fig. 5).

The general conformations of the Cu complexes in (I) and (II) are such that the S atom in each thiadiazole ring faces outwards, away from the metal centre. This specific ligand orientation generates several S···Cl and S···S short contacts. In (I), the S1A···Cl2 (x, 1/2 - y, 1/2 + z) distance is 3.351 (3) Å, the S1B···Cl2 (1 - x, -1/2 + y, 1/2 - z) distance is 3.534 (3) Å, the S1C···Cl1 (x, 1/2 - y, 1/2 + z) distance is 3.476 (3) Å, and the S1A···S1D (-x, -y, 1 - z) distance is 3.465 (3) Å while the slightly longer contacts are S1A···S1B [1 - x, -y, 1 - z; 3.626 (3) Å] and S1C···S1D [-x, -y, -z; 3.760 (3) Å]. In (II), the S1···S1 (1/2 + y, 1 - x, -z) distance is 3.633 (2) Å. A CSD search (Fletcher et al., 1996) on five-coordinate Cu complexes with at least one bound Cl atom gave 315 hits, of which 286 were CuII. Of the CuII complexes, only one of these was found with four separate N-bound ligands and, similar to complexes (I) and (II), the two conformations of tetra(pyridine-N)chlorocopper(II) in tetrakis(chlorotetrapyridinecopper)dotriacontaoxo-decatungsten pyridine solvated trihydrate (Gongdu et al., 1987), were square pyramidal. Analysis of the angle between the pyridine rings and the Cu—Cl bonds gave values of 22.5 (6), 23.4 (6), 31.5 (6), 50.9 (6)° and 16.1 (6), 29.1 (6), 29.4 (6), 49.8 (6)°. For comparison, these same values in (I) and (II) are 15.9 (1), 8.6 (1), 26.0 (1), 19.9 (1) and 15.5 (2)°, respectively. Given the CSD search parameters, complexes (I) and (II) have proved to be novel in their specific molecular construction whereas complex (II) is certainly unique with respect to its existence in a high symmetry space group given the near identical similarity of the thiadiazole in complex (I).

Experimental top

Complexes (I) and (II) were prepared by mixing boiling solutions of 50/50 aqueous ethanol separately containing CuCl2 and either 2-amino-5-methyl-1,3,4-thiadiazole, (I), or 2-amino-5-ethyl-1,3,4-thiadiazole, (II). Upon cooling, the mixtures were filtered and allowed to evaporate to dryness. Crystals of (I) and (II) were separated from the resultant mass that also included crystals of the unreacted starting materials.

Refinement top

All H atoms except for the water protons were included in the refinement, at calculated positions, as riding models with C—H set to either 0.98 Å (CH3) or 0.99 Å (CH2) and N—H set to 0.88 Å. The two water protons were located on difference syntheses and both position and displacement parameters refined. The OW—H distances are 0.83 and 0.89 Å.

Computing details top

Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998) for (I); DENZO (Otwinowski and Minor, 1997) and COLLECT (Hooft, 1998) for (II). For both compounds, cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1997); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1]
[Figure 2]
[Figure 3]
[Figure 4]
Fig. 1. Schematic showing the copper(I) chloride complex of 2-amino-5-methyl-1,3,4-thiadiazole (Neverov et al., 1986).

Fig. 2. Molecular configuration and atom-numbering scheme for (I), showing 50% probability ellipsoids.

Fig. 3. Molecular configuration and atom-numbering scheme for (II), showing 50% probability ellipsoids.

Fig. 4. Packing diagram showing the unit cell for (I). Hydrogen-bonding interactions are shown as dotted lines.

Fig. 5. Packing diagram showing the unit cell, viewed down the z axis, for (II).
(I) 'tetra(2-Amino-5-methyl-1,3,4-thiadiazole-N)chlorocopper(II) chloride hydrate' top
Crystal data top
[CuCl(C3H5N3S)4]Cl·H2OF(000) = 1252
Mr = 613.15Dx = 1.623 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 12.7183 (2) ÅCell parameters from 8104 reflections
b = 15.3106 (3) Åθ = 2.9–27.5°
c = 12.8865 (2) ŵ = 1.45 mm1
β = 90.4820 (9)°T = 150 K
V = 2509.23 (7) Å3Prism, green
Z = 40.25 × 0.18 × 0.05 mm
Data collection top
Enraf Nonius KappaCCD area detector
diffractometer
5620 independent reflections
Radiation source: Enraf Nonius FR591 rotating anode4500 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.050
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.1°
Phi and ω scansh = 1615
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
k = 1919
Tmin = 0.714, Tmax = 0.931l = 1416
19695 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.039H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.105 w = 1/[σ2(Fo2) + (0.0629P)2 + 3.8292P]
where P = (Fo2 + 2Fc2)/3
S = 0.85(Δ/σ)max = 0.003
5620 reflectionsΔρmax = 0.73 e Å3
302 parametersΔρmin = 0.77 e Å3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0028 (4)
Crystal data top
[CuCl(C3H5N3S)4]Cl·H2OV = 2509.23 (7) Å3
Mr = 613.15Z = 4
Monoclinic, P21/cMo Kα radiation
a = 12.7183 (2) ŵ = 1.45 mm1
b = 15.3106 (3) ÅT = 150 K
c = 12.8865 (2) Å0.25 × 0.18 × 0.05 mm
β = 90.4820 (9)°
Data collection top
Enraf Nonius KappaCCD area detector
diffractometer
5620 independent reflections
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
4500 reflections with I > 2σ(I)
Tmin = 0.714, Tmax = 0.931Rint = 0.050
19695 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.105H atoms treated by a mixture of independent and constrained refinement
S = 0.85Δρmax = 0.73 e Å3
5620 reflectionsΔρmin = 0.77 e Å3
302 parameters
Special details top

Experimental. PLEASE NOTE cell_measurement_ fields are not relevant to area detector data, the entire data set is used to refine the cell, which is indexed from all observed reflections in a 10 degree phi range.

Geometry. Mean plane data ex SHELXL97 for molecule (I) ############################################

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

10.6836 (0.0081) x + 2.6267 (0.0170) y + 6.5416 (0.0111) z = 5.0130 (0.0047)

* 0.0164 (0.0012) S1A * -0.0187 (0.0015) C2A * 0.0123 (0.0016) N3A * 0.0048 (0.0016) N4A * -0.0148 (0.0015) C5A -0.0929 (0.0042) N21A -0.1123 (0.0048) C51A

Rms deviation of fitted atoms = 0.0142

- 2.3437 (0.0099) x + 4.1620 (0.0182) y + 12.1913 (0.0051) z = 3.1329 (0.0060)

Angle to previous plane (with approximate e.s.d.) = 67.79 (0.07)

* 0.0026 (0.0011) S1B * -0.0010 (0.0014) C2B * -0.0014 (0.0015) N3B * 0.0041 (0.0015) N4B * -0.0043 (0.0014) C5B -0.0160 (0.0043) N21B -0.0062 (0.0046) C51B

Rms deviation of fitted atoms = 0.0030

12.0023 (0.0056) x + 4.9905 (0.0188) y + 0.6237 (0.0109) z = 4.2378 (0.0013)

Angle to previous plane (with approximate e.s.d.) = 88.16 (0.07)

* 0.0045 (0.0012) S1C * -0.0016 (0.0015) C2C * -0.0028 (0.0016) N3C * 0.0076 (0.0016) N4C * -0.0077 (0.0016) C5C 0.0024 (0.0042) N21C -0.0569 (0.0053) C51C

Rms deviation of fitted atoms = 0.0054

- 0.7523 (0.0098) x - 7.6151 (0.0164) y + 11.1595 (0.0080) z = 1.7041 (0.0022)

Angle to previous plane (with approximate e.s.d.) = 80.26 (0.07)

* -0.0109 (0.0011) S1D * 0.0124 (0.0014) C2D * -0.0079 (0.0015) N3D * -0.0036 (0.0015) N4D * 0.0100 (0.0014) C5D 0.0243 (0.0040) N21D 0.0576 (0.0045) C51D

Rms deviation of fitted atoms = 0.0095

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.26304 (2)0.088224 (19)0.25913 (2)0.01566 (11)
Cl10.25140 (5)0.25576 (4)0.27156 (5)0.02003 (15)
Cl20.18676 (6)0.72637 (5)0.09052 (6)0.0365 (2)
S1A0.13011 (5)0.01378 (4)0.56186 (5)0.02285 (16)
C2A0.1995 (2)0.01996 (17)0.44566 (19)0.0200 (5)
N21A0.2332 (2)0.09547 (14)0.40964 (19)0.0262 (5)
H21A0.26680.09760.35030.033*
H22A0.22200.14370.44500.033*
N3A0.21017 (17)0.05756 (14)0.40184 (16)0.0193 (5)
N4A0.16010 (17)0.12479 (14)0.45547 (17)0.0203 (5)
C5A0.1142 (2)0.09743 (17)0.5383 (2)0.0211 (6)
C51A0.0494 (2)0.15447 (19)0.6065 (2)0.0277 (6)
H51A0.01970.12750.61670.035*
H52A0.04040.21180.57370.035*
H53A0.08480.16160.67380.035*
S1B0.60995 (5)0.07706 (5)0.34814 (6)0.02764 (18)
C2B0.4958 (2)0.12962 (17)0.3080 (2)0.0213 (5)
N21B0.4938 (2)0.21303 (15)0.2779 (2)0.0333 (6)
H21B0.43420.23690.25730.042*
H22B0.55200.24410.27850.042*
N3B0.41291 (17)0.07819 (14)0.30955 (17)0.0190 (5)
N4B0.43585 (17)0.00594 (14)0.34313 (17)0.0214 (5)
C5B0.5339 (2)0.01633 (17)0.3648 (2)0.0226 (6)
C51B0.5797 (2)0.10071 (19)0.4023 (2)0.0293 (6)
H51B0.60990.09250.47180.037*
H52B0.63480.11970.35470.037*
H53B0.52430.14520.40490.037*
S1C0.33157 (6)0.06330 (5)0.08539 (5)0.02568 (17)
C2C0.3014 (2)0.12063 (17)0.02716 (19)0.0189 (5)
N21C0.2675 (2)0.20309 (15)0.02633 (18)0.0267 (5)
H21C0.25350.22980.08510.033*
H22C0.25910.23080.03300.033*
N3C0.31609 (17)0.07445 (14)0.11166 (16)0.0186 (5)
N4C0.35293 (18)0.00963 (14)0.09197 (17)0.0213 (5)
C5C0.3631 (2)0.02505 (18)0.0057 (2)0.0239 (6)
C51C0.3971 (3)0.1113 (2)0.0483 (2)0.0356 (7)
H51C0.46050.10330.09000.044*
H52C0.34080.13550.09190.044*
H53C0.41240.15150.00910.044*
S1D0.08151 (5)0.04405 (5)0.17629 (5)0.02463 (17)
C2D0.0249 (2)0.10239 (17)0.2254 (2)0.0204 (5)
N21D0.01343 (19)0.17733 (15)0.27680 (18)0.0258 (5)
H21D0.06920.20580.29950.032*
H22D0.04990.19830.28800.032*
N3D0.11568 (17)0.06506 (14)0.20419 (16)0.0195 (5)
N4D0.10534 (18)0.01330 (14)0.15040 (17)0.0219 (5)
C5D0.0090 (2)0.03344 (18)0.1314 (2)0.0226 (6)
C51D0.0263 (2)0.11442 (19)0.0780 (2)0.0277 (6)
H51D0.06260.09910.01320.035*
H52D0.07440.14660.12310.035*
H53D0.03490.15100.06260.035*
O1W0.66078 (18)0.33564 (14)0.27617 (17)0.0280 (5)
H1W0.653 (3)0.382 (3)0.308 (3)0.059 (13)*
H2W0.712 (4)0.311 (3)0.311 (3)0.060 (13)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.01624 (18)0.01742 (18)0.01333 (16)0.00005 (11)0.00023 (12)0.00026 (11)
Cl10.0230 (3)0.0180 (3)0.0192 (3)0.0001 (2)0.0007 (2)0.0006 (2)
Cl20.0310 (4)0.0298 (4)0.0488 (5)0.0046 (3)0.0117 (3)0.0145 (3)
S1A0.0257 (4)0.0243 (3)0.0186 (3)0.0005 (3)0.0047 (3)0.0033 (3)
C2A0.0179 (13)0.0255 (14)0.0167 (12)0.0017 (10)0.0004 (10)0.0028 (11)
N21A0.0325 (14)0.0214 (11)0.0249 (12)0.0018 (10)0.0090 (10)0.0008 (9)
N3A0.0200 (11)0.0203 (11)0.0174 (10)0.0005 (9)0.0011 (9)0.0013 (9)
N4A0.0220 (11)0.0214 (11)0.0175 (10)0.0014 (9)0.0011 (9)0.0008 (9)
C5A0.0216 (14)0.0232 (13)0.0184 (13)0.0016 (10)0.0004 (10)0.0003 (10)
C51A0.0270 (15)0.0303 (14)0.0258 (14)0.0043 (12)0.0066 (12)0.0062 (12)
S1B0.0176 (3)0.0304 (4)0.0348 (4)0.0006 (3)0.0047 (3)0.0021 (3)
C2B0.0186 (13)0.0246 (13)0.0208 (13)0.0007 (11)0.0001 (10)0.0009 (11)
N21B0.0215 (13)0.0259 (13)0.0525 (17)0.0038 (10)0.0023 (12)0.0096 (12)
N3B0.0179 (11)0.0206 (11)0.0185 (11)0.0002 (9)0.0011 (9)0.0005 (9)
N4B0.0222 (12)0.0216 (11)0.0203 (11)0.0014 (9)0.0003 (9)0.0001 (9)
C5B0.0258 (15)0.0232 (13)0.0187 (12)0.0024 (11)0.0007 (11)0.0016 (11)
C51B0.0304 (16)0.0287 (15)0.0287 (15)0.0079 (12)0.0031 (12)0.0002 (12)
S1C0.0357 (4)0.0262 (3)0.0151 (3)0.0036 (3)0.0021 (3)0.0019 (3)
C2C0.0190 (13)0.0223 (13)0.0156 (12)0.0004 (10)0.0007 (10)0.0011 (10)
N21C0.0440 (15)0.0195 (11)0.0165 (11)0.0070 (10)0.0019 (10)0.0002 (9)
N3C0.0218 (11)0.0175 (10)0.0167 (10)0.0021 (9)0.0020 (9)0.0008 (9)
N4C0.0235 (12)0.0198 (11)0.0207 (11)0.0047 (9)0.0039 (9)0.0003 (9)
C5C0.0266 (15)0.0234 (14)0.0218 (13)0.0019 (11)0.0016 (11)0.0016 (11)
C51C0.049 (2)0.0305 (16)0.0275 (16)0.0088 (14)0.0057 (14)0.0061 (13)
S1D0.0187 (3)0.0313 (4)0.0239 (3)0.0028 (3)0.0007 (3)0.0008 (3)
C2D0.0188 (13)0.0271 (13)0.0154 (12)0.0006 (11)0.0004 (10)0.0032 (11)
N21D0.0195 (12)0.0280 (12)0.0297 (13)0.0010 (9)0.0021 (10)0.0041 (10)
N3D0.0201 (11)0.0221 (11)0.0163 (10)0.0011 (9)0.0021 (9)0.0020 (9)
N4D0.0227 (12)0.0207 (11)0.0223 (11)0.0023 (9)0.0004 (9)0.0007 (9)
C5D0.0265 (15)0.0246 (13)0.0166 (12)0.0016 (11)0.0008 (11)0.0028 (11)
C51D0.0279 (15)0.0275 (14)0.0277 (15)0.0065 (12)0.0026 (12)0.0003 (12)
O1W0.0301 (12)0.0223 (11)0.0317 (11)0.0001 (9)0.0015 (9)0.0002 (9)
Geometric parameters (Å, º) top
Cu1—N3A2.019 (2)C51B—H53B0.98
Cu1—N3B2.014 (2)S1C—C2C1.741 (3)
Cu1—N3C2.033 (2)S1C—C5C1.743 (3)
Cu1—N3D2.029 (2)C2C—N3C1.310 (3)
Cu1—Cl12.5744 (7)C2C—N21C1.334 (3)
S1A—C5A1.741 (3)N21C—H21C0.88
S1A—C2A1.747 (2)N21C—H22C0.88
C2A—N21A1.318 (3)N3C—N4C1.394 (3)
C2A—N3A1.322 (3)N4C—C5C1.288 (3)
N21A—H21A0.88C5C—C51C1.495 (4)
N21A—H22A0.88C51C—H51C0.98
N3A—N4A1.396 (3)C51C—H52C0.98
N4A—C5A1.291 (3)C51C—H53C0.98
C5A—C51A1.492 (4)S1D—C2D1.737 (3)
C51A—H51A0.98S1D—C5D1.755 (3)
C51A—H52A0.98C2D—N3D1.318 (3)
C51A—H53A0.98C2D—N21D1.334 (3)
S1B—C2B1.735 (3)N21D—H21D0.88
S1B—C5B1.741 (3)N21D—H22D0.88
C2B—N3B1.316 (3)N3D—N4D1.391 (3)
C2B—N21B1.335 (4)N4D—C5D1.285 (4)
N21B—H21B0.88C5D—C51D1.486 (4)
N21B—H22B0.88C51D—H51D0.98
N3B—N4B1.389 (3)C51D—H52D0.98
N4B—C5B1.286 (4)C51D—H53D0.98
C5B—C51B1.495 (4)O1W—H1W0.83 (5)
C51B—H51B0.98O1W—H2W0.88 (5)
C51B—H52B0.98
N3A—Cu1—N3B90.57 (9)H51B—C51B—H52B109.5
N3A—Cu1—N3C160.59 (9)C5B—C51B—H53B109.5
N3A—Cu1—N3D87.91 (9)H51B—C51B—H53B109.5
N3B—Cu1—N3C88.45 (9)H52B—C51B—H53B109.5
N3B—Cu1—N3D165.44 (9)C2C—S1C—C5C87.24 (12)
N3C—Cu1—N3D88.20 (9)N3C—C2C—N21C124.1 (2)
N3A—Cu1—Cl198.94 (6)N3C—C2C—S1C112.91 (19)
N3B—Cu1—Cl196.36 (6)N21C—C2C—S1C122.95 (19)
N3C—Cu1—Cl1100.44 (6)C2C—N21C—H21C120.0
N3D—Cu1—Cl198.19 (6)C2C—N21C—H22C120.0
C5A—S1A—C2A87.85 (12)H21C—N21C—H22C120.0
N21A—C2A—N3A127.0 (2)C2C—N3C—N4C113.1 (2)
N21A—C2A—S1A121.1 (2)C2C—N3C—Cu1132.42 (18)
N3A—C2A—S1A111.83 (19)N4C—N3C—Cu1112.37 (15)
C2A—N21A—H21A120.0C5C—N4C—N3C112.6 (2)
C2A—N21A—H22A120.0N4C—C5C—C51C123.5 (3)
H21A—N21A—H22A120.0N4C—C5C—S1C114.1 (2)
C2A—N3A—N4A113.7 (2)C51C—C5C—S1C122.3 (2)
C2A—N3A—Cu1129.36 (18)C5C—C51C—H51C109.5
N4A—N3A—Cu1115.86 (16)C5C—C51C—H52C109.5
C5A—N4A—N3A112.4 (2)H51C—C51C—H52C109.5
N4A—C5A—C51A123.6 (2)C5C—C51C—H53C109.5
N4A—C5A—S1A114.1 (2)H51C—C51C—H53C109.5
C51A—C5A—S1A122.3 (2)H52C—C51C—H53C109.5
C5A—C51A—H51A109.5C2D—S1D—C5D87.48 (13)
C5A—C51A—H52A109.5N3D—C2D—N21D125.1 (3)
H51A—C51A—H52A109.5N3D—C2D—S1D112.5 (2)
C5A—C51A—H53A109.5N21D—C2D—S1D122.3 (2)
H51A—C51A—H53A109.5C2D—N21D—H21D120.0
H52A—C51A—H53A109.5C2D—N21D—H22D120.0
C2B—S1B—C5B87.35 (13)H21D—N21D—H22D120.0
N3B—C2B—N21B124.3 (3)C2D—N3D—N4D113.4 (2)
N3B—C2B—S1B112.7 (2)C2D—N3D—Cu1131.27 (19)
N21B—C2B—S1B123.0 (2)N4D—N3D—Cu1114.06 (16)
C2B—N21B—H21B120.0C5D—N4D—N3D112.8 (2)
C2B—N21B—H22B120.0N4D—C5D—C51D124.9 (3)
H21B—N21B—H22B120.0N4D—C5D—S1D113.7 (2)
C2B—N3B—N4B113.2 (2)C51D—C5D—S1D121.4 (2)
C2B—N3B—Cu1134.85 (19)C5D—C51D—H51D109.5
N4B—N3B—Cu1111.52 (16)C5D—C51D—H52D109.5
C5B—N4B—N3B112.5 (2)H51D—C51D—H52D109.5
N4B—C5B—C51B123.5 (3)C5D—C51D—H53D109.5
N4B—C5B—S1B114.2 (2)H51D—C51D—H53D109.5
C51B—C5B—S1B122.3 (2)H52D—C51D—H53D109.5
C5B—C51B—H51B109.5H1W—O1W—H2W103 (4)
C5B—C51B—H52B109.5
C5A—S1A—C2A—N21A175.9 (2)C5C—S1C—C2C—N3C0.4 (2)
C5A—S1A—C2A—N3A2.9 (2)C5C—S1C—C2C—N21C179.9 (2)
N21A—C2A—N3A—N4A176.0 (3)N21C—C2C—N3C—N4C179.3 (2)
S1A—C2A—N3A—N4A2.7 (3)S1C—C2C—N3C—N4C0.3 (3)
N21A—C2A—N3A—Cu18.7 (4)N21C—C2C—N3C—Cu118.6 (4)
S1A—C2A—N3A—Cu1170.01 (13)S1C—C2C—N3C—Cu1161.75 (15)
N3B—Cu1—N3A—C2A81.6 (2)N3B—Cu1—N3C—C2C128.1 (3)
N3D—Cu1—N3A—C2A83.9 (2)N3A—Cu1—N3C—C2C144.6 (3)
N3C—Cu1—N3A—C2A5.3 (4)N3D—Cu1—N3C—C2C66.1 (3)
Cl1—Cu1—N3A—C2A178.2 (2)Cl1—Cu1—N3C—C2C31.9 (3)
N3B—Cu1—N3A—N4A111.27 (18)N3B—Cu1—N3C—N4C69.74 (17)
N3D—Cu1—N3A—N4A83.21 (18)N3A—Cu1—N3C—N4C17.6 (4)
N3C—Cu1—N3A—N4A161.8 (2)N3D—Cu1—N3C—N4C96.09 (18)
Cl1—Cu1—N3A—N4A14.75 (18)Cl1—Cu1—N3C—N4C165.92 (16)
C2A—N3A—N4A—C5A0.8 (3)C2C—N3C—N4C—C5C1.1 (3)
Cu1—N3A—N4A—C5A169.91 (18)Cu1—N3C—N4C—C5C164.60 (19)
N3A—N4A—C5A—C51A176.1 (2)N3C—N4C—C5C—C51C177.4 (3)
N3A—N4A—C5A—S1A1.5 (3)N3C—N4C—C5C—S1C1.5 (3)
C2A—S1A—C5A—N4A2.5 (2)C2C—S1C—C5C—N4C1.1 (2)
C2A—S1A—C5A—C51A175.1 (2)C2C—S1C—C5C—C51C177.8 (3)
C5B—S1B—C2B—N3B0.3 (2)C5D—S1D—C2D—N3D1.9 (2)
C5B—S1B—C2B—N21B179.1 (3)C5D—S1D—C2D—N21D179.2 (2)
N21B—C2B—N3B—N4B179.5 (2)N21D—C2D—N3D—N4D179.4 (2)
S1B—C2B—N3B—N4B0.1 (3)S1D—C2D—N3D—N4D1.8 (3)
N21B—C2B—N3B—Cu18.1 (4)N21D—C2D—N3D—Cu113.1 (4)
S1B—C2B—N3B—Cu1171.21 (14)S1D—C2D—N3D—Cu1168.06 (14)
N3A—Cu1—N3B—C2B126.3 (3)N3B—Cu1—N3D—C2D145.4 (3)
N3D—Cu1—N3B—C2B149.9 (3)N3A—Cu1—N3D—C2D61.1 (2)
N3C—Cu1—N3B—C2B73.1 (3)N3C—Cu1—N3D—C2D137.9 (2)
Cl1—Cu1—N3B—C2B27.2 (3)Cl1—Cu1—N3D—C2D37.6 (2)
N3A—Cu1—N3B—N4B62.29 (17)N3B—Cu1—N3D—N4D20.9 (4)
N3D—Cu1—N3B—N4B21.6 (4)N3A—Cu1—N3D—N4D105.08 (17)
N3C—Cu1—N3B—N4B98.32 (16)N3C—Cu1—N3D—N4D55.90 (17)
Cl1—Cu1—N3B—N4B161.35 (15)Cl1—Cu1—N3D—N4D156.19 (15)
C2B—N3B—N4B—C5B0.6 (3)C2D—N3D—N4D—C5D0.4 (3)
Cu1—N3B—N4B—C5B172.80 (17)Cu1—N3D—N4D—C5D169.20 (18)
N3B—N4B—C5B—C51B179.8 (2)N3D—N4D—C5D—C51D178.1 (2)
N3B—N4B—C5B—S1B0.8 (3)N3D—N4D—C5D—S1D1.1 (3)
C2B—S1B—C5B—N4B0.6 (2)C2D—S1D—C5D—N4D1.7 (2)
C2B—S1B—C5B—C51B179.9 (2)C2D—S1D—C5D—C51D177.5 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N21A—H21A···O1Wi0.882.142.953 (3)154
N21A—H21A···N4B0.882.573.049 (3)115
N21A—H22A···Cl2ii0.882.313.134 (2)156
N21B—H21B···Cl10.882.353.152 (3)151
N21B—H22B···O1W0.881.972.835 (3)167
N21C—H21C···Cl10.882.443.269 (2)158
N21C—H22C···Cl1iii0.882.533.348 (2)155
N21C—H22C···N4Aiii0.882.553.102 (3)122
N21D—H21D···Cl10.882.473.257 (2)149
N21D—H21D···N4A0.882.623.059 (3)112
N21D—H22D···Cl2iv0.882.393.169 (2)148
O1W—H1W···N4Cv0.83 (5)2.10 (5)2.921 (3)170 (4)
O1W—H2W···Cl2i0.88 (5)2.21 (5)3.075 (3)167 (4)
Symmetry codes: (i) x+1, y1/2, z+1/2; (ii) x, y+1/2, z+1/2; (iii) x, y+1/2, z1/2; (iv) x, y1/2, z+1/2; (v) x+1, y+1/2, z+1/2.
(II) 'tetra(2-amino-5-ethyl-1,3,4-thiadiazole-N)chlorocopper(II) chloride' top
Crystal data top
[CuCl(C4H7N3S)4]ClMelting point: ? K K
Mr = 651.23Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4/nccCell parameters from 6958 reflections
a = 12.3273 (17) Åθ = 2.9–27.5°
c = 17.705 (4) ŵ = 1.35 mm1
V = 2690.5 (7) Å3T = 150 K
Z = 4Plate, green
F(000) = 13400.30 × 0.15 × 0.08 mm
Dx = 1.608 Mg m3
Data collection top
Enraf Nonius KappaCCD area detector
diffractometer
1531 independent reflections
Radiation source: Enraf Nonius FR591 rotating anode1303 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.051
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.9°
Phi and ω scansh = 1515
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
k = 1515
Tmin = 0.687, Tmax = 0.905l = 2221
15487 measured reflections
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)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.088H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0565P)2 + 0.8119P]
where P = (Fo2 + 2Fc2)/3
1531 reflections(Δ/σ)max < 0.001
84 parametersΔρmax = 0.54 e Å3
0 restraintsΔρmin = 0.65 e Å3
Crystal data top
[CuCl(C4H7N3S)4]ClZ = 4
Mr = 651.23Mo Kα radiation
Tetragonal, P4/nccµ = 1.35 mm1
a = 12.3273 (17) ÅT = 150 K
c = 17.705 (4) Å0.30 × 0.15 × 0.08 mm
V = 2690.5 (7) Å3
Data collection top
Enraf Nonius KappaCCD area detector
diffractometer
1531 independent reflections
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
1303 reflections with I > 2σ(I)
Tmin = 0.687, Tmax = 0.905Rint = 0.051
15487 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0320 restraints
wR(F2) = 0.088H-atom parameters constrained
S = 1.04Δρmax = 0.54 e Å3
1531 reflectionsΔρmin = 0.65 e Å3
84 parameters
Special details top

Experimental. PLEASE NOTE cell_measurement_ fields are not relevant to area detector data, the entire data set is used to refine the cell, which is indexed from all observed reflections in a 10 degree phi range.

Geometry. Mean plane data ex SHELXL97 for molecule (II) #############################################

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

1.2389 (0.0065) x + 11.8149 (0.0038) y - 4.7278 (0.0146) z = 2.3700(0.0034)

* -0.0031 (0.0007) S1 * 0.0015 (0.0009) C2 * 0.0012 (0.0010) N3 * -0.0045 (0.0010) N4 * 0.0049 (0.0009) C5 0.0002 (0.0029) N21 0.0308 (0.0031) C51 0.2043 (0.0039) C52

Rms deviation of fitted atoms = 0.0034

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.25000.25000.09476 (2)0.01374 (16)
Cl10.25000.25000.23604 (5)0.0180 (2)
Cl20.75000.25000.25000.0247 (2)
S10.60241 (3)0.16010 (4)0.05732 (3)0.02213 (17)
C20.49154 (14)0.19444 (14)0.11310 (10)0.0183 (4)
N210.50103 (13)0.22228 (15)0.18546 (9)0.0256 (4)
H210.44290.23890.21190.032*
H220.56540.22410.20680.032*
N30.39937 (12)0.18910 (12)0.07565 (8)0.0178 (3)
N40.41141 (12)0.15744 (11)0.00091 (8)0.0191 (3)
C50.51070 (14)0.14056 (14)0.01725 (10)0.0185 (4)
C510.54716 (16)0.10795 (15)0.09468 (10)0.0229 (4)
H510.57840.03400.09250.029*
H520.60490.15810.11180.029*
C520.45463 (18)0.10947 (18)0.15181 (10)0.0303 (5)
H530.42200.18190.15310.038*
H540.39960.05610.13710.038*
H550.48280.09130.20200.038*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.01263 (19)0.01263 (19)0.0160 (2)0.0000.0000.000
Cl10.0190 (3)0.0190 (3)0.0160 (4)0.0000.0000.000
Cl20.0204 (3)0.0204 (3)0.0335 (5)0.0018 (3)0.0000.000
S10.0151 (3)0.0277 (3)0.0236 (3)0.00169 (18)0.00121 (17)0.00118 (18)
C20.0160 (8)0.0170 (8)0.0219 (9)0.0016 (7)0.0007 (7)0.0010 (7)
N210.0166 (8)0.0392 (10)0.0211 (8)0.0006 (7)0.0001 (6)0.0042 (7)
N30.0164 (7)0.0176 (7)0.0195 (7)0.0021 (6)0.0013 (6)0.0012 (6)
N40.0200 (8)0.0191 (8)0.0183 (8)0.0018 (6)0.0007 (6)0.0012 (6)
C50.0186 (9)0.0159 (9)0.0211 (9)0.0006 (7)0.0002 (7)0.0001 (7)
C510.0260 (10)0.0216 (10)0.0211 (10)0.0025 (8)0.0038 (7)0.0012 (7)
C520.0335 (12)0.0362 (12)0.0213 (9)0.0069 (10)0.0009 (8)0.0004 (8)
Geometric parameters (Å, º) top
Cu1—N3i2.0171 (15)N21—H220.88
Cu1—N3ii2.0171 (15)N3—N41.388 (2)
Cu1—N3iii2.0171 (15)N4—C51.282 (2)
Cu1—N32.0171 (15)C5—C511.498 (2)
Cu1—Cl12.5013 (10)C51—C521.525 (3)
S1—C21.7385 (18)C51—H510.99
S1—C51.7548 (18)C51—H520.99
C2—N31.317 (2)C52—H530.98
C2—N211.331 (2)C52—H540.98
N21—H210.88C52—H550.98
N3i—Cu1—N3ii160.69 (9)C2—N3—Cu1133.19 (12)
N3i—Cu1—N3iii88.388 (14)N4—N3—Cu1111.24 (11)
N3ii—Cu1—N3iii88.387 (14)C5—N4—N3112.76 (14)
N3i—Cu1—N388.387 (14)N4—C5—C51124.02 (16)
N3ii—Cu1—N388.387 (14)N4—C5—S1113.82 (13)
N3iii—Cu1—N3160.69 (9)C51—C5—S1122.16 (13)
N3i—Cu1—Cl199.66 (4)C5—C51—C52112.30 (16)
N3ii—Cu1—Cl199.66 (4)C5—C51—H51109.1
N3iii—Cu1—Cl199.66 (4)C52—C51—H51109.1
N3—Cu1—Cl199.66 (4)C5—C51—H52109.1
C2—S1—C587.39 (8)C52—C51—H52109.1
N3—C2—N21124.96 (16)H51—C51—H52107.9
N3—C2—S1112.34 (13)C51—C52—H53109.5
N21—C2—S1122.70 (14)C51—C52—H54109.5
C2—N21—H21120.0H53—C52—H54109.5
C2—N21—H22120.0C51—C52—H55109.5
H21—N21—H22120.0H53—C52—H55109.5
C2—N3—N4113.69 (14)H54—C52—H55109.5
C5—S1—C2—N30.33 (14)N3ii—Cu1—N3—N466.82 (11)
C5—S1—C2—N21179.91 (17)N3iii—Cu1—N3—N413.66 (10)
N21—C2—N3—N4179.67 (17)Cl1—Cu1—N3—N4166.34 (10)
S1—C2—N3—N40.09 (18)C2—N3—N4—C50.6 (2)
N21—C2—N3—Cu117.7 (3)Cu1—N3—N4—C5165.87 (12)
S1—C2—N3—Cu1162.58 (10)N3—N4—C5—C51178.65 (16)
N3i—Cu1—N3—C268.84 (19)N3—N4—C5—S10.91 (18)
N3ii—Cu1—N3—C2130.20 (16)C2—S1—C5—N40.72 (14)
N3iii—Cu1—N3—C2149.32 (17)C2—S1—C5—C51178.85 (16)
Cl1—Cu1—N3—C230.68 (17)N4—C5—C51—C526.5 (3)
N3i—Cu1—N3—N494.13 (10)S1—C5—C51—C52173.03 (14)
Symmetry codes: (i) y+1/2, x, z; (ii) y, x+1/2, z; (iii) x+1/2, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N21—H21···Cl10.882.423.2396 (16)155
N21—H22···Cl20.882.423.2928 (16)171

Experimental details

(I)(II)
Crystal data
Chemical formula[CuCl(C3H5N3S)4]Cl·H2O[CuCl(C4H7N3S)4]Cl
Mr613.15651.23
Crystal system, space groupMonoclinic, P21/cTetragonal, P4/ncc
Temperature (K)150150
a, b, c (Å)12.7183 (2), 15.3106 (3), 12.8865 (2)12.3273 (17), 12.3273 (17), 17.705 (4)
α, β, γ (°)90, 90.4820 (9), 9090, 90, 90
V3)2509.23 (7)2690.5 (7)
Z44
Radiation typeMo KαMo Kα
µ (mm1)1.451.35
Crystal size (mm)0.25 × 0.18 × 0.050.30 × 0.15 × 0.08
Data collection
DiffractometerEnraf Nonius KappaCCD area detector
diffractometer
Enraf Nonius KappaCCD area detector
diffractometer
Absorption correctionMulti-scan
(SORTAV; Blessing, 1995)
Multi-scan
(SORTAV; Blessing, 1995)
Tmin, Tmax0.714, 0.9310.687, 0.905
No. of measured, independent and
observed [I > 2σ(I)] reflections
19695, 5620, 4500 15487, 1531, 1303
Rint0.0500.051
(sin θ/λ)max1)0.6500.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.105, 0.85 0.032, 0.088, 1.04
No. of reflections56201531
No. of parameters30284
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.73, 0.770.54, 0.65

Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), DENZO (Otwinowski and Minor, 1997) and COLLECT (Hooft, 1998), DENZO and COLLECT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 1997), SHELXL97.

Selected bond lengths (Å) for (I) top
Cu1—N3A2.019 (2)Cu1—N3D2.029 (2)
Cu1—N3B2.014 (2)Cu1—Cl12.5744 (7)
Cu1—N3C2.033 (2)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N21A—H21A···O1Wi0.882.142.953 (3)154
N21A—H21A···N4B0.882.573.049 (3)115
N21A—H22A···Cl2ii0.882.313.134 (2)156
N21B—H21B···Cl10.882.353.152 (3)151
N21B—H22B···O1W0.881.972.835 (3)167
N21C—H21C···Cl10.882.443.269 (2)158
N21C—H22C···Cl1iii0.882.533.348 (2)155
N21C—H22C···N4Aiii0.882.553.102 (3)122
N21D—H21D···Cl10.882.473.257 (2)149
N21D—H21D···N4A0.882.623.059 (3)112
N21D—H22D···Cl2iv0.882.393.169 (2)148
O1W—H1W···N4Cv0.83 (5)2.10 (5)2.921 (3)170 (4)
O1W—H2W···Cl2i0.88 (5)2.21 (5)3.075 (3)167 (4)
Symmetry codes: (i) x+1, y1/2, z+1/2; (ii) x, y+1/2, z+1/2; (iii) x, y+1/2, z1/2; (iv) x, y1/2, z+1/2; (v) x+1, y+1/2, z+1/2.
Selected bond lengths (Å) for (II) top
Cu1—N32.0171 (15)Cu1—Cl12.5013 (10)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N21—H21···Cl10.882.423.2396 (16)155
N21—H22···Cl20.882.423.2928 (16)171
 

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