Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807024026/si2015sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807024026/si2015Isup2.hkl |
CCDC reference: 651358
Crystals of (I) were prepared by a recently described method (Kopel et al., 2007). Safety note: Caution! Perchlorate salts of metal complexes with organic ligands are potentially explosive. Even a small amount of these materials should be handled with great caution.
The measurement of low-angle reflection (112) was affected by shielding by the beam stopper, therefore this reflection was removed from further calculations. A part of pmdien ligand (namely atoms C4, C5, N4, C9 and C10) has been refined as disordered between two positions [the site occupancy factors refined to 0.792 (6) and 0.208 (6)] defined by approx. 25–40° angular rotation of disordered fragment around the Cu—N4 bond. All H atoms were located in a difference map and refined using the riding model with C–H distances of 0.98 (Cmethyl) and 0.99 Å (CH2), and with Uiso(H) values of 1.2Ueq(CH2) or 1.5Ueq(Cmethyl).
This paper relates to our preceeding contributions describing X-ray structures of transition metal complexes bearing variously deprotonated trithiocyanuric acid (ttcHn, n = 0–3) (see e.g. Marek et al., 2007).
The molecular structure of the title compound, (I), is depicted in Fig. 1. The structure consists of a trinuclear CuII cation and three perchlorate anions. The three CuII metal centres are related by the body-diagonal threefold symmetry along [111] and bridged by an essentially planar [out-of-plane (C3N3) deviation is -0.009 (4) Å for C1 atom and 0.006 (3) Å for N1 atom (Brandenburg, 2006)] trithiocyanurate(3-) anion (ttc). Each CuII ion adopts a considerably distorted trigonal bipyramidal geometry (τ = 0.62) (Addison et al., 1984) and is bonded by three N atoms of pmdien, and one S and one N atoms of the ttc ligand. For comparison, ZnII ions in similar recently published trinuclear Zn complex (II) (Marek et al., 2007) have τ=0.82. A different degree of the polyhedron deformation in (I) as compared to (II) can be also seen from the metal-S distances which differ significantly (Cu—S = 2.4824 (11) and Zn—S = 2.3793 (8) Å). The separation of Cu···Cu = 5.9235 (5) Å, while the distance of Zn···Zn = 6.0283 (5) Å in (II) and the Ru···Ru distances in a similar, but nonsymmetrical, trinuclear Ru complex bridged by the ttc (Kar et al., 2004) are in the range of 5.838 (3)—5.894 (2) Å. The bond distances Cu—N are in the range of 2.073 (3)—2.118 (3) Å. The bond length C1—S = 1.705 (4) Å in (I), while the average value of a double C=S bond is 1.655 (11) Å (Cambridge Structural Database Version 5.27.1; Allen, 2002).
Mutual orientation of dinuclear cations and perchlorate anions causes the formation of the spherical voids in the crystal structure of (I) (Fig. 2). These cavities are in the distance of 3.84 Å from S1, and their volume is 63 (6) Å3 (Spek, 2003). There is no evidence for presence of any molecules of the crystal water neither in peaks of difference electron density, nor in results of FT—IR spectroscopy (Kopel et al., 2007). The secondary structure of the title compound (I) is stabilized by variety of interactions of the type C—H···O, connecting the cation and perchlorate anions [see Fig. 3 and Table 1 with the list prepared by PARST(Nardelli, 1995) and cut-off value H···A=2.7 Å). These non classic hydrogen bonds (the term from Spek, 2003) could be probably classified as weak hydrogen bonds (using terminology of Desiraju, 1996).
For related literature, see: Kar et al. (2004); Marek et al. (2007).
For related literature, see: Addison et al. (1984); Allen (2002); Desiraju (1996); Kopel et al. (2007).
Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: VMD 1.8.5 (Humphrey et al., 1996) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), PARST (Nardelli, 1995) and DIAMOND (Brandenburg, 2006).
[Cu3(C9H23N3)3(C3N3S3)](ClO4)3 | Dx = 1.502 Mg m−3 |
Mr = 1183.12 | Mo Kα radiation, λ = 0.71073 Å |
Cubic, P213 | Cell parameters from 29540 reflections |
Hall symbol: P 2ac 2ab 3 | θ = 2.6–31.9° |
a = 17.3590 (4) Å | µ = 1.54 mm−1 |
V = 5230.9 (2) Å3 | T = 120 K |
Z = 4 | Prism, blue |
F(000) = 2460 | 0.35 × 0.3 × 0.25 mm |
Oxford Diffraction Xcalibur2 + CCD diffractometer | 3461 independent reflections |
Radiation source: fine-focus sealed tube | 2802 reflections with I > 2σ(I) |
Enhance (Oxford Diffraction) monochromator | Rint = 0.095 |
Detector resolution: 8.3611 pixels mm-1 | θmax = 26.0°, θmin = 2.6° |
rotation method, ω–scan | h = −21→21 |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006) | k = −14→21 |
Tmin = 0.568, Tmax = 0.680 | l = −21→21 |
38778 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.072 | w = 1/[σ2(Fo2) + (0.0325P)2 + 1.P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max = 0.001 |
3460 reflections | Δρmax = 0.41 e Å−3 |
213 parameters | Δρmin = −0.38 e Å−3 |
53 restraints | Absolute structure: Flack (1983), 1556 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.050 (15) |
[Cu3(C9H23N3)3(C3N3S3)](ClO4)3 | Z = 4 |
Mr = 1183.12 | Mo Kα radiation |
Cubic, P213 | µ = 1.54 mm−1 |
a = 17.3590 (4) Å | T = 120 K |
V = 5230.9 (2) Å3 | 0.35 × 0.3 × 0.25 mm |
Oxford Diffraction Xcalibur2 + CCD diffractometer | 3461 independent reflections |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006) | 2802 reflections with I > 2σ(I) |
Tmin = 0.568, Tmax = 0.680 | Rint = 0.095 |
38778 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.072 | Δρmax = 0.41 e Å−3 |
S = 1.10 | Δρmin = −0.38 e Å−3 |
3460 reflections | Absolute structure: Flack (1983), 1556 Friedel pairs |
213 parameters | Absolute structure parameter: −0.050 (15) |
53 restraints |
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 | Occ. (<1) | |
Cu | 0.19495 (2) | 0.58035 (2) | 0.52012 (2) | 0.01962 (11) | |
Cl1 | 0.06784 (5) | 0.93216 (5) | 0.43216 (5) | 0.0264 (4) | |
Cl2 | 0.20500 (5) | 0.29500 (5) | 0.70500 (5) | 0.0288 (4) | |
Cl3 | 0.15427 (6) | 0.15427 (6) | 0.15427 (6) | 0.0304 (4) | |
O1 | 0.02855 (15) | 0.86131 (14) | 0.41485 (18) | 0.0390 (7) | |
O2 | 0.02011 (16) | 0.97989 (16) | 0.47989 (16) | 0.0502 (14) | |
O3 | 0.26501 (16) | 0.34143 (16) | 0.73923 (16) | 0.0351 (7) | |
O4 | 0.15686 (15) | 0.34314 (15) | 0.65686 (15) | 0.0336 (11) | |
O5 | 0.17414 (18) | 0.11298 (17) | 0.22363 (16) | 0.0433 (8) | |
O6 | 0.10716 (18) | 0.10716 (18) | 0.10716 (18) | 0.0575 (16) | |
S | 0.18225 (6) | 0.46540 (5) | 0.43600 (6) | 0.0289 (2) | |
N1 | 0.10373 (16) | 0.50747 (17) | 0.55558 (17) | 0.0210 (7) | |
N2 | 0.26446 (17) | 0.57110 (19) | 0.61687 (17) | 0.0262 (7) | |
N3 | 0.28906 (19) | 0.63870 (18) | 0.47013 (18) | 0.0297 (8) | |
C1 | 0.1078 (2) | 0.4533 (2) | 0.4988 (2) | 0.0222 (8) | |
C2 | 0.3432 (2) | 0.5844 (3) | 0.5876 (3) | 0.0423 (11) | |
H2A | 0.3615 | 0.5375 | 0.5609 | 0.051* | |
H2B | 0.3782 | 0.5945 | 0.6314 | 0.051* | |
C3 | 0.3456 (2) | 0.6511 (3) | 0.5331 (2) | 0.0359 (10) | |
H3A | 0.3331 | 0.6993 | 0.5610 | 0.043* | |
H3B | 0.3980 | 0.6563 | 0.5112 | 0.043* | |
N4 | 0.1269 (4) | 0.6697 (5) | 0.4766 (4) | 0.0233 (11) | 0.792 (6) |
C4 | 0.2575 (5) | 0.7153 (4) | 0.4453 (3) | 0.0280 (19) | 0.792 (6) |
H4A | 0.2901 | 0.7369 | 0.4037 | 0.034* | 0.792 (6) |
H4B | 0.2585 | 0.7516 | 0.4893 | 0.034* | 0.792 (6) |
C5 | 0.1761 (3) | 0.7064 (3) | 0.4167 (3) | 0.0310 (13) | 0.792 (6) |
H5A | 0.1548 | 0.7577 | 0.4034 | 0.037* | 0.792 (6) |
H5B | 0.1758 | 0.6744 | 0.3695 | 0.037* | 0.792 (6) |
C9 | 0.1072 (4) | 0.7230 (3) | 0.5388 (4) | 0.0352 (17) | 0.792 (6) |
H9A | 0.1546 | 0.7439 | 0.5613 | 0.053* | 0.792 (6) |
H9B | 0.0780 | 0.6956 | 0.5785 | 0.053* | 0.792 (6) |
H9C | 0.0760 | 0.7653 | 0.5182 | 0.053* | 0.792 (6) |
C10 | 0.0541 (3) | 0.6435 (3) | 0.4398 (3) | 0.0379 (15) | 0.792 (6) |
H10A | 0.0292 | 0.6872 | 0.4142 | 0.057* | 0.792 (6) |
H10B | 0.0196 | 0.6226 | 0.4792 | 0.057* | 0.792 (6) |
H10C | 0.0656 | 0.6034 | 0.4017 | 0.057* | 0.792 (6) |
N4A | 0.1346 (17) | 0.673 (2) | 0.4844 (15) | 0.0233 (11) | 0.208 (6) |
C4A | 0.260 (2) | 0.7058 (18) | 0.4241 (18) | 0.0280 (19) | 0.208 (6) |
H4A1 | 0.2429 | 0.6892 | 0.3722 | 0.034* | 0.208 (6) |
H4A2 | 0.2997 | 0.7460 | 0.4186 | 0.034* | 0.208 (6) |
C5A | 0.1920 (12) | 0.7356 (11) | 0.4703 (12) | 0.0310 (13) | 0.208 (6) |
H5A1 | 0.2106 | 0.7559 | 0.5203 | 0.037* | 0.208 (6) |
H5A2 | 0.1670 | 0.7783 | 0.4421 | 0.037* | 0.208 (6) |
C9A | 0.0754 (16) | 0.7019 (16) | 0.5375 (17) | 0.0352 (17) | 0.208 (6) |
H9A1 | 0.0987 | 0.7121 | 0.5879 | 0.053* | 0.208 (6) |
H9A2 | 0.0348 | 0.6630 | 0.5432 | 0.053* | 0.208 (6) |
H9A3 | 0.0532 | 0.7495 | 0.5170 | 0.053* | 0.208 (6) |
C10A | 0.0956 (13) | 0.6583 (13) | 0.4096 (14) | 0.0379 (15) | 0.208 (6) |
H10D | 0.0762 | 0.7069 | 0.3885 | 0.057* | 0.208 (6) |
H10E | 0.0524 | 0.6228 | 0.4176 | 0.057* | 0.208 (6) |
H10F | 0.1324 | 0.6354 | 0.3735 | 0.057* | 0.208 (6) |
C6 | 0.2592 (3) | 0.4946 (3) | 0.6536 (3) | 0.0447 (12) | |
H6A | 0.2648 | 0.4545 | 0.6143 | 0.067* | |
H6B | 0.2090 | 0.4893 | 0.6788 | 0.067* | |
H6C | 0.3002 | 0.4893 | 0.6920 | 0.067* | |
C7 | 0.2447 (2) | 0.6301 (3) | 0.6766 (2) | 0.0417 (11) | |
H7A | 0.2795 | 0.6246 | 0.7207 | 0.063* | |
H7B | 0.1914 | 0.6226 | 0.6935 | 0.063* | |
H7C | 0.2503 | 0.6818 | 0.6545 | 0.063* | |
C8 | 0.3237 (3) | 0.5950 (2) | 0.4064 (2) | 0.0430 (11) | |
H8A | 0.2849 | 0.5858 | 0.3665 | 0.064* | |
H8B | 0.3429 | 0.5455 | 0.4257 | 0.064* | |
H8C | 0.3666 | 0.6245 | 0.3845 | 0.064* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu | 0.0182 (2) | 0.0188 (2) | 0.0218 (2) | −0.00134 (19) | −0.00067 (19) | 0.0043 (2) |
Cl1 | 0.0264 (4) | 0.0264 (4) | 0.0264 (4) | −0.0045 (4) | −0.0045 (4) | 0.0045 (4) |
Cl2 | 0.0288 (4) | 0.0288 (4) | 0.0288 (4) | −0.0013 (4) | 0.0013 (4) | −0.0013 (4) |
Cl3 | 0.0304 (4) | 0.0304 (4) | 0.0304 (4) | 0.0034 (5) | 0.0034 (5) | 0.0034 (5) |
O1 | 0.0327 (16) | 0.0213 (14) | 0.0630 (19) | −0.0087 (13) | −0.0155 (16) | 0.0091 (15) |
O2 | 0.0502 (14) | 0.0502 (14) | 0.0502 (14) | 0.0107 (16) | 0.0107 (16) | −0.0107 (16) |
O3 | 0.0312 (15) | 0.0408 (17) | 0.0331 (16) | −0.0108 (14) | −0.0046 (13) | −0.0004 (14) |
O4 | 0.0336 (11) | 0.0336 (11) | 0.0336 (11) | 0.0049 (13) | −0.0049 (13) | 0.0049 (13) |
O5 | 0.0482 (19) | 0.0508 (19) | 0.0309 (16) | 0.0163 (16) | 0.0076 (14) | 0.0168 (14) |
O6 | 0.0575 (16) | 0.0575 (16) | 0.0575 (16) | −0.0089 (17) | −0.0089 (17) | −0.0089 (17) |
S | 0.0283 (5) | 0.0250 (5) | 0.0333 (6) | −0.0017 (4) | 0.0108 (4) | −0.0013 (4) |
N1 | 0.0197 (16) | 0.0210 (16) | 0.0222 (16) | 0.0015 (13) | 0.0019 (13) | −0.0016 (13) |
N2 | 0.0203 (16) | 0.0294 (18) | 0.0291 (18) | 0.0009 (15) | 0.0012 (14) | 0.0085 (15) |
N3 | 0.035 (2) | 0.0268 (17) | 0.0276 (18) | −0.0007 (15) | −0.0019 (16) | 0.0042 (15) |
C1 | 0.023 (2) | 0.0214 (19) | 0.022 (2) | 0.0035 (16) | 0.0009 (16) | 0.0034 (16) |
C2 | 0.021 (2) | 0.068 (3) | 0.037 (2) | −0.004 (2) | −0.004 (2) | 0.013 (3) |
C3 | 0.027 (2) | 0.045 (3) | 0.035 (2) | −0.011 (2) | −0.0054 (19) | 0.009 (2) |
N4 | 0.026 (2) | 0.0246 (19) | 0.020 (2) | 0.0019 (16) | −0.0016 (19) | 0.0021 (18) |
C4 | 0.033 (2) | 0.025 (3) | 0.026 (4) | −0.005 (2) | 0.001 (3) | 0.006 (3) |
C5 | 0.038 (3) | 0.025 (3) | 0.030 (3) | 0.004 (2) | 0.008 (3) | 0.005 (2) |
C9 | 0.048 (5) | 0.028 (4) | 0.029 (3) | 0.013 (3) | −0.001 (3) | −0.001 (3) |
C10 | 0.027 (3) | 0.037 (3) | 0.049 (4) | 0.003 (3) | −0.013 (3) | 0.006 (3) |
N4A | 0.026 (2) | 0.0246 (19) | 0.020 (2) | 0.0019 (16) | −0.0016 (19) | 0.0021 (18) |
C4A | 0.033 (2) | 0.025 (3) | 0.026 (4) | −0.005 (2) | 0.001 (3) | 0.006 (3) |
C5A | 0.038 (3) | 0.025 (3) | 0.030 (3) | 0.004 (2) | 0.008 (3) | 0.005 (2) |
C9A | 0.048 (5) | 0.028 (4) | 0.029 (3) | 0.013 (3) | −0.001 (3) | −0.001 (3) |
C10A | 0.027 (3) | 0.037 (3) | 0.049 (4) | 0.003 (3) | −0.013 (3) | 0.006 (3) |
C6 | 0.039 (3) | 0.046 (3) | 0.049 (3) | 0.002 (2) | −0.010 (2) | 0.022 (2) |
C7 | 0.035 (3) | 0.065 (3) | 0.025 (2) | −0.004 (2) | −0.001 (2) | 0.000 (2) |
C8 | 0.050 (3) | 0.035 (2) | 0.044 (3) | −0.006 (2) | 0.010 (2) | −0.002 (2) |
Cu—N4A | 2.02 (4) | N4—C5 | 1.489 (8) |
Cu—S | 2.4824 (11) | C4—C5 | 1.507 (9) |
Cu—N1 | 2.118 (3) | C4—H4A | 0.9900 |
Cu—N2 | 2.074 (3) | C4—H4B | 0.9900 |
Cu—N3 | 2.109 (3) | C5—H5A | 0.9900 |
Cu—N4 | 2.091 (11) | C5—H5B | 0.9900 |
Cl1—O2 | 1.435 (5) | C9—H9A | 0.9800 |
Cl1—O1i | 1.438 (2) | C9—H9B | 0.9800 |
Cl1—O1 | 1.438 (2) | C9—H9C | 0.9800 |
Cl1—O1ii | 1.438 (2) | C10—H10A | 0.9800 |
Cl2—O3 | 1.445 (3) | C10—H10B | 0.9800 |
Cl2—O3iii | 1.445 (3) | C10—H10C | 0.9800 |
Cl2—O3iv | 1.445 (3) | N4A—C9A | 1.467 (18) |
Cl2—O4 | 1.447 (5) | N4A—C10A | 1.487 (18) |
Cl3—O6 | 1.416 (6) | N4A—C5A | 1.492 (18) |
Cl3—O5v | 1.443 (3) | C4A—C5A | 1.512 (18) |
Cl3—O5vi | 1.443 (3) | C4A—H4A1 | 0.9900 |
Cl3—O5 | 1.443 (3) | C4A—H4A2 | 0.9900 |
S—C1 | 1.705 (4) | C5A—H5A1 | 0.9900 |
N1—C1iv | 1.346 (4) | C5A—H5A2 | 0.9900 |
N1—C1 | 1.364 (5) | C9A—H9A1 | 0.9800 |
N2—C6 | 1.475 (5) | C9A—H9A2 | 0.9800 |
N2—C2 | 1.476 (5) | C9A—H9A3 | 0.9800 |
N2—C7 | 1.497 (5) | C10A—H10D | 0.9800 |
N3—C8 | 1.470 (5) | C10A—H10E | 0.9800 |
N3—C3 | 1.484 (5) | C10A—H10F | 0.9800 |
N3—C4 | 1.502 (6) | C6—H6A | 0.9800 |
N3—C4A | 1.503 (17) | C6—H6B | 0.9800 |
C1—N1iii | 1.346 (4) | C6—H6C | 0.9800 |
C2—C3 | 1.497 (6) | C7—H7A | 0.9800 |
C2—H2A | 0.9900 | C7—H7B | 0.9800 |
C2—H2B | 0.9900 | C7—H7C | 0.9800 |
C3—H3A | 0.9900 | C8—H8A | 0.9800 |
C3—H3B | 0.9900 | C8—H8B | 0.9800 |
N4—C9 | 1.463 (7) | C8—H8C | 0.9800 |
N4—C10 | 1.486 (7) | ||
N4A—Cu—N2 | 127.7 (7) | C9—N4—C10 | 108.2 (6) |
N4A—Cu—N4 | 5.2 (8) | C9—N4—C5 | 112.2 (6) |
N4A—Cu—N3 | 83.8 (7) | C10—N4—C5 | 108.6 (5) |
N2—Cu—N3 | 85.39 (12) | C9—N4—Cu | 109.5 (5) |
N4—Cu—N3 | 86.1 (2) | C10—N4—Cu | 114.1 (5) |
N4A—Cu—N1 | 100.2 (6) | C5—N4—Cu | 104.3 (5) |
N2—Cu—N1 | 98.82 (12) | N3—C4—C5 | 110.2 (6) |
N4—Cu—N1 | 97.22 (19) | N3—C4—H4A | 109.6 |
N1—Cu—S | 67.95 (8) | C5—C4—H4A | 109.6 |
N1—Cu—N3 | 170.23 (12) | N3—C4—H4B | 109.6 |
N2—Cu—N4 | 132.8 (2) | C5—C4—H4B | 109.6 |
N4A—Cu—S | 114.5 (7) | H4A—C4—H4B | 108.1 |
N2—Cu—S | 117.75 (10) | N4—C5—C4 | 110.6 (5) |
N4—Cu—S | 109.46 (18) | N4—C5—H5A | 109.5 |
N3—Cu—S | 102.29 (9) | C4—C5—H5A | 109.5 |
O2—Cl1—O1i | 109.91 (14) | N4—C5—H5B | 109.5 |
O2—Cl1—O1 | 109.91 (14) | C4—C5—H5B | 109.5 |
O1i—Cl1—O1 | 109.03 (14) | H5A—C5—H5B | 108.1 |
O2—Cl1—O1ii | 109.91 (14) | C9A—N4A—C10A | 107 (3) |
O1i—Cl1—O1ii | 109.03 (14) | C9A—N4A—C5A | 109 (2) |
O1—Cl1—O1ii | 109.03 (14) | C10A—N4A—C5A | 107 (2) |
O3—Cl2—O3iii | 109.57 (12) | C9A—N4A—Cu | 116 (2) |
O3—Cl2—O3iv | 109.57 (12) | C10A—N4A—Cu | 111 (2) |
O3iii—Cl2—O3iv | 109.57 (12) | C5A—N4A—Cu | 106 (2) |
O3—Cl2—O4 | 109.37 (12) | N3—C4A—C5A | 104.3 (15) |
O3iii—Cl2—O4 | 109.37 (12) | N3—C4A—H4A1 | 110.9 |
O3iv—Cl2—O4 | 109.37 (13) | C5A—C4A—H4A1 | 110.9 |
O6—Cl3—O5v | 109.45 (15) | N3—C4A—H4A2 | 110.9 |
O6—Cl3—O5vi | 109.45 (15) | C5A—C4A—H4A2 | 110.9 |
O5v—Cl3—O5vi | 109.49 (15) | H4A1—C4A—H4A2 | 108.9 |
O6—Cl3—O5 | 109.45 (15) | N4A—C5A—C4A | 111 (2) |
O5v—Cl3—O5 | 109.49 (15) | N4A—C5A—H5A1 | 109.4 |
O5vi—Cl3—O5 | 109.49 (15) | C4A—C5A—H5A1 | 109.4 |
C1—S—Cu | 77.88 (13) | N4A—C5A—H5A2 | 109.4 |
C1iv—N1—C1 | 117.9 (3) | C4A—C5A—H5A2 | 109.4 |
C1iv—N1—Cu | 142.5 (3) | H5A1—C5A—H5A2 | 108.0 |
C1—N1—Cu | 99.4 (2) | N4A—C9A—H9A1 | 109.5 |
C6—N2—C2 | 110.3 (3) | N4A—C9A—H9A2 | 109.5 |
C6—N2—C7 | 107.6 (3) | H9A1—C9A—H9A2 | 109.5 |
C2—N2—C7 | 110.1 (3) | N4A—C9A—H9A3 | 109.5 |
C6—N2—Cu | 112.5 (3) | H9A1—C9A—H9A3 | 109.5 |
C2—N2—Cu | 104.3 (2) | H9A2—C9A—H9A3 | 109.5 |
C7—N2—Cu | 112.0 (2) | N4A—C10A—H10D | 109.5 |
C8—N3—C3 | 111.0 (3) | N4A—C10A—H10E | 109.5 |
C8—N3—C4 | 113.0 (3) | H10D—C10A—H10E | 109.5 |
C3—N3—C4 | 108.9 (4) | N4A—C10A—H10F | 109.5 |
C8—N3—C4A | 98.0 (12) | H10D—C10A—H10F | 109.5 |
C3—N3—C4A | 120.3 (18) | H10E—C10A—H10F | 109.5 |
C8—N3—Cu | 112.3 (2) | N2—C6—H6A | 109.5 |
C3—N3—Cu | 106.2 (2) | N2—C6—H6B | 109.5 |
C4—N3—Cu | 105.2 (4) | H6A—C6—H6B | 109.5 |
C4A—N3—Cu | 109.1 (13) | N2—C6—H6C | 109.5 |
N1iii—C1—N1 | 122.1 (3) | H6A—C6—H6C | 109.5 |
N1iii—C1—S | 123.3 (3) | H6B—C6—H6C | 109.5 |
N1—C1—S | 114.6 (3) | N2—C7—H7A | 109.5 |
N2—C2—C3 | 111.4 (3) | N2—C7—H7B | 109.5 |
N2—C2—H2A | 109.4 | H7A—C7—H7B | 109.5 |
C3—C2—H2A | 109.4 | N2—C7—H7C | 109.5 |
N2—C2—H2B | 109.4 | H7A—C7—H7C | 109.5 |
C3—C2—H2B | 109.4 | H7B—C7—H7C | 109.5 |
H2A—C2—H2B | 108.0 | N3—C8—H8A | 109.5 |
N3—C3—C2 | 109.6 (3) | N3—C8—H8B | 109.5 |
N3—C3—H3A | 109.8 | H8A—C8—H8B | 109.5 |
C2—C3—H3A | 109.8 | N3—C8—H8C | 109.5 |
N3—C3—H3B | 109.8 | H8A—C8—H8C | 109.5 |
C2—C3—H3B | 109.8 | H8B—C8—H8C | 109.5 |
H3A—C3—H3B | 108.2 | ||
N4A—Cu—S—C1 | −89.2 (7) | Cu—N2—C2—C3 | 44.3 (4) |
N2—Cu—S—C1 | 90.77 (15) | C8—N3—C3—C2 | −87.9 (4) |
N4—Cu—S—C1 | −87.8 (2) | C4—N3—C3—C2 | 147.1 (4) |
N3—Cu—S—C1 | −177.99 (15) | C4A—N3—C3—C2 | 158.7 (11) |
N1—Cu—S—C1 | 2.27 (15) | Cu—N3—C3—C2 | 34.4 (4) |
N4A—Cu—N1—C1iv | −65.1 (8) | N2—C2—C3—N3 | −55.0 (5) |
N2—Cu—N1—C1iv | 66.0 (4) | N4A—Cu—N4—C9 | −39 (9) |
N4—Cu—N1—C1iv | −69.5 (4) | N2—Cu—N4—C9 | −22.4 (5) |
S—Cu—N1—C1iv | −177.6 (4) | N3—Cu—N4—C9 | −102.4 (4) |
N4A—Cu—N1—C1 | 109.6 (8) | N1—Cu—N4—C9 | 86.8 (4) |
N2—Cu—N1—C1 | −119.3 (2) | S—Cu—N4—C9 | 155.9 (4) |
N4—Cu—N1—C1 | 105.3 (3) | N4A—Cu—N4—C10 | −160 (10) |
S—Cu—N1—C1 | −2.81 (18) | N2—Cu—N4—C10 | −143.8 (4) |
N4A—Cu—N2—C6 | 143.0 (9) | N3—Cu—N4—C10 | 136.1 (5) |
N4—Cu—N2—C6 | 141.2 (3) | N1—Cu—N4—C10 | −34.7 (5) |
N3—Cu—N2—C6 | −138.4 (3) | S—Cu—N4—C10 | 34.4 (5) |
N1—Cu—N2—C6 | 32.7 (3) | N4A—Cu—N4—C5 | 81 (9) |
S—Cu—N2—C6 | −37.0 (3) | N2—Cu—N4—C5 | 97.9 (4) |
N4A—Cu—N2—C2 | −97.4 (9) | N3—Cu—N4—C5 | 17.8 (4) |
N4—Cu—N2—C2 | −99.3 (4) | N1—Cu—N4—C5 | −153.0 (4) |
N3—Cu—N2—C2 | −18.9 (3) | S—Cu—N4—C5 | −83.9 (4) |
N1—Cu—N2—C2 | 152.3 (3) | C8—N3—C4—C5 | 86.6 (5) |
S—Cu—N2—C2 | 82.6 (3) | C3—N3—C4—C5 | −149.6 (4) |
N4A—Cu—N2—C7 | 21.7 (9) | C4A—N3—C4—C5 | 71 (7) |
N4—Cu—N2—C7 | 19.8 (4) | Cu—N3—C4—C5 | −36.2 (4) |
N3—Cu—N2—C7 | 100.2 (3) | C9—N4—C5—C4 | 75.1 (8) |
N1—Cu—N2—C7 | −88.7 (3) | C10—N4—C5—C4 | −165.3 (6) |
S—Cu—N2—C7 | −158.3 (2) | Cu—N4—C5—C4 | −43.3 (5) |
N4A—Cu—N3—C8 | −118.2 (8) | N3—C4—C5—N4 | 55.8 (7) |
N2—Cu—N3—C8 | 113.1 (3) | N2—Cu—N4A—C9A | −60.9 (19) |
N4—Cu—N3—C8 | −113.4 (3) | N4—Cu—N4A—C9A | 104 (10) |
S—Cu—N3—C8 | −4.3 (3) | N3—Cu—N4A—C9A | −140.2 (18) |
N4A—Cu—N3—C3 | 120.4 (8) | N1—Cu—N4A—C9A | 48.8 (18) |
N2—Cu—N3—C3 | −8.4 (3) | S—Cu—N4A—C9A | 119.1 (17) |
N4—Cu—N3—C3 | 125.1 (3) | N2—Cu—N4A—C10A | 176.5 (12) |
S—Cu—N3—C3 | −125.8 (2) | N4—Cu—N4A—C10A | −19 (9) |
N4A—Cu—N3—C4 | 5.0 (8) | N3—Cu—N4A—C10A | 97.2 (16) |
N2—Cu—N3—C4 | −123.7 (3) | N1—Cu—N4A—C10A | −73.8 (16) |
N4—Cu—N3—C4 | 9.8 (4) | S—Cu—N4A—C10A | −3.5 (18) |
S—Cu—N3—C4 | 118.8 (3) | N2—Cu—N4A—C5A | 60.6 (19) |
N4A—Cu—N3—C4A | −10.6 (18) | N4—Cu—N4A—C5A | −135 (11) |
N2—Cu—N3—C4A | −139.4 (16) | N3—Cu—N4A—C5A | −18.7 (15) |
N4—Cu—N3—C4A | −5.9 (16) | N1—Cu—N4A—C5A | 170.3 (14) |
S—Cu—N3—C4A | 103.2 (16) | S—Cu—N4A—C5A | −119.4 (14) |
C1iv—N1—C1—N1iii | 2.1 (7) | C8—N3—C4A—C5A | 153 (2) |
Cu—N1—C1—N1iii | −174.3 (3) | C3—N3—C4A—C5A | −86 (3) |
C1iv—N1—C1—S | −179.42 (16) | C4—N3—C4A—C5A | −41 (5) |
Cu—N1—C1—S | 4.2 (3) | Cu—N3—C4A—C5A | 36 (3) |
Cu—S—C1—N1iii | 174.8 (3) | C9A—N4A—C5A—C4A | 173 (2) |
Cu—S—C1—N1 | −3.6 (2) | C10A—N4A—C5A—C4A | −72 (3) |
C6—N2—C2—C3 | 165.3 (4) | Cu—N4A—C5A—C4A | 47 (2) |
C7—N2—C2—C3 | −76.1 (4) | N3—C4A—C5A—N4A | −56 (3) |
Symmetry codes: (i) −z+1/2, −x+1, y−1/2; (ii) −y+1, z+1/2, −x+1/2; (iii) z−1/2, −x+1/2, −y+1; (iv) −y+1/2, −z+1, x+1/2; (v) y, z, x; (vi) z, x, y. |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5A···O1 | 0.99 | 2.84 | 3.713 (6) | 147 |
C5A—H5A2···O1 | 0.99 | 2.84 | 3.71 (2) | 146 |
C9—H9C···O1 | 0.98 | 2.58 | 3.501 (7) | 156 |
C3—H3A···O5iv | 0.99 | 2.55 | 3.353 (5) | 138 |
C9A—H9A3···O1 | 0.98 | 2.66 | 3.59 (3) | 157 |
C9A—H9A2···N1 | 0.98 | 2.96 | 3.42 (3) | 110 |
C10—H10B···N1 | 0.98 | 2.81 | 3.218 (6) | 106 |
C10A—H10D···O1 | 0.98 | 2.84 | 3.71 (2) | 148 |
C5A—H5A2···O1 | 0.99 | 2.84 | 3.71 (2) | 146 |
C5A—H5A2···O1 | 0.99 | 2.84 | 3.71 (2) | 146 |
C9A—H9A2···N1 | 0.98 | 2.96 | 3.42 (3) | 110 |
C9A—H9A3···O1 | 0.98 | 2.66 | 3.59 (3) | 157 |
C6—H6C···O3 | 0.98 | 2.76 | 3.049 (5) | 97 |
C6—H6B···O4 | 0.98 | 2.72 | 3.174 (5) | 109 |
C6—H6C···O3 | 0.98 | 2.76 | 3.049 (5) | 97 |
C6—H6B···O4 | 0.98 | 2.72 | 3.174 (5) | 109 |
C6—H6B···N1 | 0.98 | 2.83 | 3.198 (5) | 103 |
C6—H6C···O3 | 0.98 | 2.76 | 3.049 (5) | 97 |
C2—H2B···O1vii | 0.99 | 2.84 | 3.354 (5) | 113 |
C3—H3B···O1vii | 0.99 | 2.62 | 3.310 (5) | 127 |
C2—H2A···O2vii | 0.99 | 2.86 | 3.472 (4) | 121 |
C2—H2A···O2viii | 0.99 | 2.86 | 3.472 (4) | 121 |
C2—H2A···O2ix | 0.99 | 2.86 | 3.472 (4) | 121 |
C3—H3A···O5x | 0.99 | 2.57 | 3.545 (6) | 168 |
C4—H4B···O5x | 0.99 | 2.52 | 3.502 (7) | 170 |
C7—H7C···O5x | 0.98 | 2.64 | 3.615 (6) | 172 |
C9—H9A···O5x | 0.98 | 2.70 | 3.669 (7) | 170 |
C5A—H5A1···O5x | 0.99 | 2.32 | 3.28 (2) | 163 |
C7—H7C···O5iv | 0.98 | 2.91 | 3.543 (6) | 124 |
C4—H4A···O3v | 0.99 | 2.57 | 3.476 (6) | 153 |
C8—H8C···O3v | 0.98 | 2.91 | 3.519 (5) | 121 |
C5A—H5A2···O1ii | 0.99 | 2.47 | 3.247 (18) | 135 |
C9—H9C···O1ii | 0.98 | 2.93 | 3.571 (7) | 124 |
C5—H5B···O3xi | 0.99 | 2.50 | 3.350 (6) | 144 |
C10A—H10F···O3xi | 0.98 | 2.96 | 3.82 (3) | 147 |
C8—H8A···O3xi | 0.98 | 2.69 | 3.466 (5) | 137 |
C4A—H4A1···O3xi | 0.99 | 2.37 | 3.34 (4) | 166 |
C10—H10B···O6xii | 0.98 | 2.68 | 2.983 (6) | 99 |
C10A—H10E···O6xii | 0.98 | 2.82 | 3.64 (2) | 142 |
C10—H10B···O6xiii | 0.98 | 2.68 | 2.983 (6) | 99 |
C10A—H10E···O6xiii | 0.98 | 2.82 | 3.64 (2) | 142 |
C10—H10B···O6xiv | 0.98 | 2.68 | 2.983 (6) | 99 |
C10A—H10E···O6xiv | 0.98 | 2.82 | 3.64 (2) | 142 |
Symmetry codes: (ii) −y+1, z+1/2, −x+1/2; (iv) −y+1/2, −z+1, x+1/2; (v) y, z, x; (vii) x+1/2, −y+3/2, −z+1; (viii) −z+1, x+1/2, −y+3/2; (ix) −y+3/2, −z+1, x+1/2; (x) −z+1/2, −x+1, y+1/2; (xi) −x+1/2, −y+1, z−1/2; (xii) −y, z+1/2, −x+1/2; (xiii) −x, y+1/2, −z+1/2; (xiv) −z, x+1/2, −y+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cu3(C9H23N3)3(C3N3S3)](ClO4)3 |
Mr | 1183.12 |
Crystal system, space group | Cubic, P213 |
Temperature (K) | 120 |
a (Å) | 17.3590 (4) |
V (Å3) | 5230.9 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.54 |
Crystal size (mm) | 0.35 × 0.3 × 0.25 |
Data collection | |
Diffractometer | Oxford Diffraction Xcalibur2 + CCD |
Absorption correction | Multi-scan (CrysAlis RED; Oxford Diffraction, 2006) |
Tmin, Tmax | 0.568, 0.680 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 38778, 3461, 2802 |
Rint | 0.095 |
(sin θ/λ)max (Å−1) | 0.618 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.072, 1.10 |
No. of reflections | 3460 |
No. of parameters | 213 |
No. of restraints | 53 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.41, −0.38 |
Absolute structure | Flack (1983), 1556 Friedel pairs |
Absolute structure parameter | −0.050 (15) |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), CrysAlis RED, SHELXS97 (Sheldrick, 1990), VMD 1.8.5 (Humphrey et al., 1996) and DIAMOND (Brandenburg, 2006), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), PARST (Nardelli, 1995) and DIAMOND (Brandenburg, 2006).
Cu—S | 2.4824 (11) | Cu—N4 | 2.091 (11) |
Cu—N1 | 2.118 (3) | S—C1 | 1.705 (4) |
Cu—N2 | 2.074 (3) | N1—C1i | 1.346 (4) |
Cu—N3 | 2.109 (3) | N1—C1 | 1.364 (5) |
N1—Cu—S | 67.95 (8) | N2—Cu—S | 117.75 (10) |
N1—Cu—N3 | 170.23 (12) | N4—Cu—S | 109.46 (18) |
N2—Cu—N4 | 132.8 (2) |
Symmetry code: (i) −y+1/2, −z+1, x+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9C···O1 | 0.98 | 2.58 | 3.501 (7) | 155.9 |
C3—H3A···O5i | 0.99 | 2.55 | 3.353 (5) | 137.6 |
C3—H3B···O1ii | 0.99 | 2.62 | 3.310 (5) | 126.6 |
C3—H3A···O5iii | 0.99 | 2.57 | 3.545 (6) | 167.7 |
C4—H4B···O5iii | 0.99 | 2.52 | 3.502 (7) | 169.5 |
C7—H7C···O5iii | 0.98 | 2.64 | 3.615 (6) | 171.9 |
C9—H9A···O5iii | 0.98 | 2.70 | 3.669 (7) | 169.7 |
C5A—H5A1···O5iii | 0.99 | 2.32 | 3.28 (2) | 162.9 |
C4—H4A···O3iv | 0.99 | 2.57 | 3.476 (6) | 152.5 |
C5A—H5A2···O1v | 0.99 | 2.47 | 3.247 (18) | 134.7 |
C5—H5B···O3vi | 0.99 | 2.50 | 3.350 (6) | 144.0 |
C8—H8A···O3vi | 0.98 | 2.69 | 3.466 (5) | 136.6 |
C4A—H4A1···O3vi | 0.99 | 2.37 | 3.34 (4) | 165.6 |
C10—H10B···O6vii | 0.98 | 2.68 | 2.983 (6) | 98.5 |
C10—H10B···O6viii | 0.98 | 2.68 | 2.983 (6) | 98.5 |
C10—H10B···O6ix | 0.98 | 2.68 | 2.983 (6) | 98.5 |
Symmetry codes: (i) −y+1/2, −z+1, x+1/2; (ii) x+1/2, −y+3/2, −z+1; (iii) −z+1/2, −x+1, y+1/2; (iv) y, z, x; (v) −y+1, z+1/2, −x+1/2; (vi) −x+1/2, −y+1, z−1/2; (vii) −y, z+1/2, −x+1/2; (viii) −x, y+1/2, −z+1/2; (ix) −z, x+1/2, −y+1/2. |
This paper relates to our preceeding contributions describing X-ray structures of transition metal complexes bearing variously deprotonated trithiocyanuric acid (ttcHn, n = 0–3) (see e.g. Marek et al., 2007).
The molecular structure of the title compound, (I), is depicted in Fig. 1. The structure consists of a trinuclear CuII cation and three perchlorate anions. The three CuII metal centres are related by the body-diagonal threefold symmetry along [111] and bridged by an essentially planar [out-of-plane (C3N3) deviation is -0.009 (4) Å for C1 atom and 0.006 (3) Å for N1 atom (Brandenburg, 2006)] trithiocyanurate(3-) anion (ttc). Each CuII ion adopts a considerably distorted trigonal bipyramidal geometry (τ = 0.62) (Addison et al., 1984) and is bonded by three N atoms of pmdien, and one S and one N atoms of the ttc ligand. For comparison, ZnII ions in similar recently published trinuclear Zn complex (II) (Marek et al., 2007) have τ=0.82. A different degree of the polyhedron deformation in (I) as compared to (II) can be also seen from the metal-S distances which differ significantly (Cu—S = 2.4824 (11) and Zn—S = 2.3793 (8) Å). The separation of Cu···Cu = 5.9235 (5) Å, while the distance of Zn···Zn = 6.0283 (5) Å in (II) and the Ru···Ru distances in a similar, but nonsymmetrical, trinuclear Ru complex bridged by the ttc (Kar et al., 2004) are in the range of 5.838 (3)—5.894 (2) Å. The bond distances Cu—N are in the range of 2.073 (3)—2.118 (3) Å. The bond length C1—S = 1.705 (4) Å in (I), while the average value of a double C=S bond is 1.655 (11) Å (Cambridge Structural Database Version 5.27.1; Allen, 2002).
Mutual orientation of dinuclear cations and perchlorate anions causes the formation of the spherical voids in the crystal structure of (I) (Fig. 2). These cavities are in the distance of 3.84 Å from S1, and their volume is 63 (6) Å3 (Spek, 2003). There is no evidence for presence of any molecules of the crystal water neither in peaks of difference electron density, nor in results of FT—IR spectroscopy (Kopel et al., 2007). The secondary structure of the title compound (I) is stabilized by variety of interactions of the type C—H···O, connecting the cation and perchlorate anions [see Fig. 3 and Table 1 with the list prepared by PARST(Nardelli, 1995) and cut-off value H···A=2.7 Å). These non classic hydrogen bonds (the term from Spek, 2003) could be probably classified as weak hydrogen bonds (using terminology of Desiraju, 1996).