Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615001436/ku3148sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615001436/ku3148Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615001436/ku3148IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615001436/ku3148IIIsup4.hkl | |
Portable Document Format (PDF) file https://doi.org/10.1107/S2053229615001436/ku3148sup5.pdf |
CCDC references: 1044912; 1044911; 1044910
In recent years, dithiolate complexes have attracted considerable interest because of their technical applications as superconductors (Zou et al., 1997; Cassoux et al., 1991), pesticides (Szolnai, 1975; Geiger & Minest, 1975; Khajuria et al., 2013), resins and Q-switching dyes for IR spectroscopy (Bigoli et al., 1997; Drexhage & Mueller-Westerhoff, 1972; Yang et al., 2013), compounds with unusual magnetic properties (Coomber et al., 1996; Boudreaux & Mulay, 1976; Cerdeira et al., 2008; Cerdeira et al., 2012) and biocatalysts (Lancaster, 1988; Sellmann et al., 1996). The wide range of technical and biological applications can be attributed to the oxidation–reduction properties of dithiolate ligands. Such ligands are known as non-innocent ligands (Jörgensen, 1966; Stiefel & Karlin, 2004) and are ligands which undergo π-bonding with the metal (e.g. CO, olefins and carbenes). Some of them even have an extended π-delocalized system [e.g. cyclopentadienyl (Cp) derivatives, multi-enes and multi-enyls] and are thus capable of undergoing easy charge and spin delocalization upon oxidation or reduction of the complex. Therefore, they are by definition suspect, as they can be easily oxidized or reduced instead of the metal to which they coordinate (Jörgensen, 1966). Among the consequences of this concept in the field of coordination chemistry is the occurrence of situations in which the assignment of the oxidation state of the central metal atom is difficult, because the ligands can also undergo electron transfer and thus the `ligand oxidation state' changes. Such ligands may occur in several redox forms, e.g. O2/O2.-/O22- or NO+/NO./NO- or dithiolate and other (e.g. Kaim & Schwederski, 2010).
Recently (Walla et al., 1998; Kameníček et al., 2001, 2002; Kameníček & Mrkvová, 2003; Mrkvová et al., 2004), similar complexes of the general formula R[M(dithiole)2], where dithiole is 1-toluene-3,4-dithiole (tdt), benzene-1,2-dithiole (bdt), ethane-1,2-dithiole (ed) and maleonitrile-1,2-dithiole (mnt), M is Ni, Co and Cu, and R is Me4N, Et4N, Pr4N, Me3PhN, MePh3P and Ph4P, have been studied.
The aim of the present work was to prepare analogous complexes with different transition metals as the central atom. A comparison of the geometrical parameters of two compounds with the same formal oxidation state, i.e. (MePh3P)[CoIII(bdt)2], (I), and (MePh3P)[CuIII(bdt)2], (III), and of two compounds with the central Cu atom in different formal oxidation states, i.e. (MePh3P)2[CuII(bdt)2].2Me2SO, (II), and (III), are discussed. The redox properties of these complexes have been discussed recently (Machata et al., 2014) and it was shown that electrochemical reduction takes place predominantly on the central atom and electrochemical oxidation takes place both on the central atom and on the ligand also.
The following reagents (Sigma–Aldrich) were used for the syntheses of complexes (I)–(III): CoCl2·6H2O ≥ 98%; CuCl2·2H2O ≥ 98%; 3,6-dichlorobenzene-1,2-dithiole (bdtCl2) ≥ 95%; methyltriphenylphosphonium bromide (Me3PhP+.Br-) ≥ 98%. All solvents were obtained from mikroCHEM and were of p.a. grade.
For the preparation of (MePh3P)[CoIII(bdt)2], (I), a solution of Na (0.08 g, 3.3 mmol) in MeOH (10 ml) was added to 3,6-dichlorobenzene-1,2-dithiole (bdtCl2; 0.34 g, 1.6 mmol). To this mixture, a solution of CoCl2·6H2O (0.18 g, 0.76 mmol) in MeOH (10 ml) was added. Finally, a solution of methyltriphenylphosphonium bromide (MePh3P+.Br-; 0.57 g, 1.6 mmol) in MeOH (10 ml) was added. The resulting solution was stirred for 20 min. The complex was precipitated by the slow addition of water accompanied by vigorous stirring. The blue crystalline powder which formed (as crude product) was filtered off, washed with diethyl ether and recrystallized from acetone (yield 75%). Crystals of (I) suitable for X-ray diffraction were grown by slow evaporation of a blue solution in an acetone–methanol–toluene solvent mixture (10:1:2 ratio).
The same procedure was used for the preparation of (MePh3P)2[CuII(bdt)2].2Me2SO, (II), and (MePh3P)[CuIII(bdt)2], (III), using CuCl2·2H2O (0.13 g, 0.76 mmol) in place of CoCl2·6H2O (crude yield is 99%)[what does this relate to?]. The sample of (III) was separated from the crude product with acetone (yield 45%) and crystals suitable for X-ray diffraction were grown by slow evaporation of a green solution in an acetone–methanol–toluene solvent mixture (10:2:1 ratio). The sample of (II) (yellow crystalline powder) was insoluble in acetone (yield 44%) and crystals suitable for X-ray diffraction were grown by slow diffusion between two layers [a yellow dimethyl sulfoxide solution of a sample of (II) and H2O in a 1:3 ratio]. After crystallization, a single crystal suitable for X-ray analysis was selected.
Crystal data, data collection and structure refinement details are summarized in Table 1. The positions of all H atoms were optimized geometrically and constrained to ride on their parent atoms, with C—H = 0.95 (aromatic) or 0.98 Å (methyl) and with Uiso(H) = 1.2Ueq(C).
In each of the studied crystal structures, i.e. (I), (II) and (III), the central metal atom is on an inversion centre and is coordinated in a square-planar manner by four dithiolate donor S atoms.
CoIII complex (I) and CuIII complex (III) are isostructural and crystallize in the centrosymmetric P21/c space group (No. 14). Both structures consist of two complex anions (in special positions; the asymmetric part of the unit cell contains two halves of these anions) and one MePh3P+ cation (Figs. 1 and 2). The central metal atom is coordinated by four donor S atoms from two 3,6-dichlorobenzene-1,2-dithiolate ligands. The X-ray structure analysis of (I) and (III) confirmed a square-planar geometry of the MS4 chromophore (Table 2). The ratio of complex anion to counter-cation (1:1) results from the found stoichiometry. The expected formal oxidation state of the central metal atom of complexes (I) and (III) is +3.
For CoIII complex (I), the angle between the S2/S1/Co1 and S4/S3/Co2 planes is 83.05 (2)° and the distance between atoms Co1 and Co2 is 10.373 (6) Å. For CuIII complex (III), the corresponding angle is 83.49 (3)° and the distance between atoms Cu1 and Cu2 is 10.386 (6) Å. The M—S bond lengths for (I) are in the range 2.1570 (6)–2.1641 (6) Å and for (III) are in the range 2.1721 (6)–2.1765 (6) Å.
The values for (I) and (III) are significantly shorter than the usual reported distances for metal complexes in a +2 oxidation state. The range for CoII is from 2.19 [Cerdeira et al., 2012; Cambridge Structural Database (CSD; Groom & Allen, 2014) refcode LAYMEF] to 2.28 Å (Rao et al., 1986) and the range for CuII is from 2.26 (Cerdeira et al., 2012; CSD refcode LAYMAB) to 2.27 Å (Best et al., 1993); this fact also supports the assumption of a +3 oxidation state in these compounds (Table 2).
For comparison, in the CSD, 16 crystal structures with a square-planar arrangement around a central CoIII atom, where the M—S bond lengths range from 2.14 (Ray et al., 2005; CSD refcode MAJYUS) to 2.18 Å (Mrkvová et al., 2004; CSD refcode AWIHIX)), and for CuIII, where the M—S bond lengths range from 2.16 (Bolligarla & Das, 2011; CSD refcode OYIRUK) to 2.18 Å (Alves et al., 2004; CSD refcode EWAMOE) were found. The structures of complexes (I)/(III) and (II) are stabilized by a system of five and six intermolecular hydrogen-bond interactions, respectively (Table 3, and Figs. 4 and 5; see also Fig. 6 is in Supporting information.
CuII complex (II) crystallized in the centrosymmetric P21/n space group (No. 14). The asymmetric part of the unit cell consists of half of the centrosymmetric complex anion, one MePh3P+ cation and a dimethyl sulfoxide solvent molecule (Fig. 3). The central metal atom is coordinated in the same way as in complexes (I) and (III) (Table 2), but unlike complexes (I) and (III), the ratio of complex anion to counter-cation is 1:2 for (II). The expected formal oxidation state of the central metal atom of (II) is +2, i.e. CuII. This is supported also by the values of the interatomic distances Cu1—S1 and Cu1—S2, which are 2.2641 (2) and 2.2671 (2) Å, respectively.
For (II) and (III), the interatomic CuIII—S distance is shorter than the CuII—S distance. The `non-innocent' ligands act as a reservoir of electron density and stabilize the oxidation state of the central atom. In the case of compounds (I) and (III), depopulated d-orbitals form stronger coordination bonds with the donor S atoms.
The basic driving force behind this work was to obtain suitable MIII coordination compounds in order to study the electronic structure by charge-density analysis. A chloro-substituted ligand was used to eliminate large anisotropic displacement parameters (ADPs) (Fronc et al., 2009), and also disorder. All the aims of the study, the elimination of disorder and decreasing the thermal motions were successful. Complexes were prepared with Cu in two oxidation states having the formulae (MePh3P+)n[M(bdtCl2)2]n-, where n = 1 or 2, which could be separated.
Cobalt complexes are very sensitive to oxidation under normal conditions; therefore we were not able to prepare the CoII analogue. The preparation of complexes with copper in two oxidation states shows the non-innocent character of the dithiolate ligand. The oxidation state of the central metal atom is only the formal number. It is not possible to determine the exact charge of the central atom, but only of the complex anion as a whole. The non-innocet dithiolate ligand is able to stabilize both 2+ and 3+ oxidation states.
For both compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2012); cell refinement: CrysAlis CCD (Oxford Diffraction, 2012); data reduction: CrysAlis RED (Oxford Diffraction, 2012); program(s) used to solve structure: SUPERFLIP (Palatinus, 2013), OLEX2 (Dolomanov et al., 2009) and SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 1998; Brandenburg & Berndt, 1999); software used to prepare material for publication: enCIFer (Allen et al., 2004).
(C19H18P)[Co(C6H2Cl2S2)2] | F(000) = 1528 |
Mr = 754.42 | Dx = 1.564 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 13.46050 (18) Å | Cell parameters from 17287 reflections |
b = 14.6661 (2) Å | θ = 2.1–28.3° |
c = 16.24190 (19) Å | µ = 1.20 mm−1 |
β = 91.9170 (11)° | T = 100 K |
V = 3204.57 (7) Å3 | Plate, black |
Z = 4 | 0.50 × 0.21 × 0.11 mm |
Agilent Xcalibur Ruby Gemini diffractometer | 8220 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 5470 reflections with I > 2σ(I) |
Detector resolution: 10.4340 pixels mm-1 | Rint = 0.034 |
ω scans | θmax = 29.6°, θmin = 2.1° |
Absorption correction: analytical [CrysAlis PRO (Agilent, 2013), based on expressions derived by Clark & Reid (1995)] | h = −18→18 |
Tmin = 0.746, Tmax = 0.876 | k = −20→20 |
55679 measured reflections | l = −22→22 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.041 | H-atom parameters constrained |
wR(F2) = 0.096 | w = 1/[σ2(Fo2) + (0.0372P)2 + 1.2776P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.001 |
8220 reflections | Δρmax = 0.34 e Å−3 |
373 parameters | Δρmin = −0.54 e Å−3 |
(C19H18P)[Co(C6H2Cl2S2)2] | V = 3204.57 (7) Å3 |
Mr = 754.42 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.46050 (18) Å | µ = 1.20 mm−1 |
b = 14.6661 (2) Å | T = 100 K |
c = 16.24190 (19) Å | 0.50 × 0.21 × 0.11 mm |
β = 91.9170 (11)° |
Agilent Xcalibur Ruby Gemini diffractometer | 8220 independent reflections |
Absorption correction: analytical [CrysAlis PRO (Agilent, 2013), based on expressions derived by Clark & Reid (1995)] | 5470 reflections with I > 2σ(I) |
Tmin = 0.746, Tmax = 0.876 | Rint = 0.034 |
55679 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.096 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.34 e Å−3 |
8220 reflections | Δρmin = −0.54 e Å−3 |
373 parameters |
Experimental. Absorption correction: CrysAlisPro, Agilent Technologies, Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET) (compiled Aug 2 2013,16:46:58) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.37579 (19) | 0.32542 (17) | 1.02686 (13) | 0.0555 (6) | |
C2 | 0.3446 (2) | 0.23853 (18) | 1.04915 (14) | 0.0655 (7) | |
C3 | 0.2448 (3) | 0.2156 (2) | 1.04774 (18) | 0.0834 (10) | |
H3A | 0.2249 | 0.1560 | 1.0632 | 0.100* | |
C4 | 0.1752 (3) | 0.2787 (3) | 1.02415 (19) | 0.0842 (10) | |
H4A | 0.1068 | 0.2625 | 1.0218 | 0.101* | |
C5 | 0.2035 (2) | 0.3656 (2) | 1.00366 (16) | 0.0686 (7) | |
C6 | 0.30333 (18) | 0.39155 (18) | 1.00744 (14) | 0.0558 (6) | |
C7 | 0.00292 (16) | 0.61303 (17) | 0.66224 (14) | 0.0504 (5) | |
C8 | −0.00714 (18) | 0.64114 (19) | 0.74378 (15) | 0.0603 (6) | |
C9 | 0.0203 (2) | 0.7274 (2) | 0.76871 (18) | 0.0729 (8) | |
H9A | 0.0111 | 0.7459 | 0.8240 | 0.087* | |
C10 | 0.0609 (2) | 0.7868 (2) | 0.71356 (19) | 0.0729 (8) | |
H10A | 0.0793 | 0.8466 | 0.7306 | 0.088* | |
C11 | 0.07501 (18) | 0.75932 (18) | 0.63342 (17) | 0.0609 (6) | |
C12 | 0.04567 (16) | 0.67253 (16) | 0.60650 (14) | 0.0496 (5) | |
C13 | 0.6628 (2) | 0.1266 (2) | 0.92192 (15) | 0.0716 (8) | |
H13C | 0.6411 | 0.0747 | 0.9549 | 0.086* | |
H13B | 0.6355 | 0.1831 | 0.9441 | 0.086* | |
H13A | 0.7356 | 0.1298 | 0.9241 | 0.086* | |
C14 | 0.66099 (16) | 0.20659 (16) | 0.75797 (14) | 0.0512 (6) | |
C15 | 0.70247 (18) | 0.19204 (18) | 0.68216 (15) | 0.0583 (6) | |
H15A | 0.7090 | 0.1318 | 0.6614 | 0.070* | |
C16 | 0.7344 (2) | 0.2658 (2) | 0.63676 (18) | 0.0733 (8) | |
H16A | 0.7627 | 0.2563 | 0.5846 | 0.088* | |
C17 | 0.7253 (2) | 0.3514 (2) | 0.6668 (2) | 0.0858 (10) | |
H17A | 0.7483 | 0.4015 | 0.6357 | 0.103* | |
C18 | 0.6834 (2) | 0.3668 (2) | 0.7410 (2) | 0.0891 (10) | |
H18A | 0.6766 | 0.4275 | 0.7606 | 0.107* | |
C19 | 0.6510 (2) | 0.29452 (18) | 0.78785 (19) | 0.0710 (7) | |
H19A | 0.6224 | 0.3050 | 0.8397 | 0.085* | |
C20 | 0.66827 (18) | 0.00973 (15) | 0.77625 (15) | 0.0521 (6) | |
C21 | 0.7693 (2) | −0.00720 (19) | 0.7868 (2) | 0.0739 (8) | |
H21A | 0.8103 | 0.0341 | 0.8176 | 0.089* | |
C22 | 0.8100 (2) | −0.0833 (2) | 0.7528 (2) | 0.0865 (10) | |
H22A | 0.8792 | −0.0947 | 0.7599 | 0.104* | |
C23 | 0.7512 (3) | −0.1430 (2) | 0.70863 (19) | 0.0777 (8) | |
H23A | 0.7801 | −0.1954 | 0.6847 | 0.093* | |
C24 | 0.6512 (2) | −0.12801 (19) | 0.69858 (17) | 0.0695 (7) | |
H24A | 0.6107 | −0.1706 | 0.6689 | 0.083* | |
C25 | 0.6092 (2) | −0.05115 (17) | 0.73158 (15) | 0.0586 (6) | |
H25A | 0.5401 | −0.0400 | 0.7237 | 0.070* | |
C26 | 0.48643 (16) | 0.10983 (15) | 0.81463 (13) | 0.0457 (5) | |
C27 | 0.43546 (18) | 0.08208 (18) | 0.88244 (14) | 0.0576 (6) | |
H27A | 0.4709 | 0.0628 | 0.9309 | 0.069* | |
C28 | 0.3331 (2) | 0.08229 (18) | 0.87979 (16) | 0.0630 (7) | |
H28A | 0.2981 | 0.0644 | 0.9270 | 0.076* | |
C29 | 0.28175 (18) | 0.10808 (17) | 0.80985 (16) | 0.0598 (6) | |
H29A | 0.2111 | 0.1084 | 0.8086 | 0.072* | |
C30 | 0.33155 (19) | 0.13356 (19) | 0.74149 (17) | 0.0665 (7) | |
H30A | 0.2955 | 0.1498 | 0.6924 | 0.080* | |
C31 | 0.43395 (18) | 0.13566 (18) | 0.74363 (15) | 0.0590 (6) | |
H31A | 0.4684 | 0.1548 | 0.6966 | 0.071* | |
P1 | 0.61940 (4) | 0.11228 (4) | 0.81735 (4) | 0.04795 (15) | |
S1 | 0.50157 (5) | 0.35481 (4) | 1.02323 (4) | 0.05812 (16) | |
S2 | 0.33982 (5) | 0.50367 (4) | 0.99068 (4) | 0.06089 (17) | |
S3 | −0.03600 (5) | 0.50483 (4) | 0.62858 (4) | 0.05421 (15) | |
S4 | 0.06212 (4) | 0.63607 (4) | 0.50499 (4) | 0.05287 (15) | |
Cl1 | 0.43369 (8) | 0.15912 (5) | 1.08247 (4) | 0.0888 (3) | |
Cl2 | 0.11398 (6) | 0.44362 (7) | 0.97283 (5) | 0.0941 (3) | |
Cl3 | −0.05403 (6) | 0.56667 (6) | 0.81562 (4) | 0.0842 (2) | |
Cl4 | 0.13127 (6) | 0.83333 (5) | 0.56651 (5) | 0.0821 (2) | |
Co1 | 0.5000 | 0.5000 | 1.0000 | 0.04919 (12) | |
Co2 | 0.0000 | 0.5000 | 0.5000 | 0.04427 (11) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0670 (16) | 0.0583 (15) | 0.0415 (12) | −0.0132 (12) | 0.0072 (11) | −0.0026 (10) |
C2 | 0.092 (2) | 0.0578 (16) | 0.0474 (13) | −0.0162 (14) | 0.0145 (13) | −0.0061 (11) |
C3 | 0.110 (3) | 0.072 (2) | 0.0702 (18) | −0.042 (2) | 0.0329 (18) | −0.0152 (15) |
C4 | 0.078 (2) | 0.099 (3) | 0.0778 (19) | −0.036 (2) | 0.0262 (16) | −0.0266 (18) |
C5 | 0.0584 (16) | 0.088 (2) | 0.0604 (15) | −0.0169 (15) | 0.0147 (12) | −0.0183 (14) |
C6 | 0.0521 (14) | 0.0687 (16) | 0.0471 (13) | −0.0130 (12) | 0.0087 (10) | −0.0058 (11) |
C7 | 0.0353 (12) | 0.0625 (15) | 0.0532 (13) | 0.0106 (10) | 0.0003 (10) | −0.0049 (11) |
C8 | 0.0483 (14) | 0.0758 (18) | 0.0565 (14) | 0.0121 (12) | −0.0001 (11) | −0.0081 (12) |
C9 | 0.0622 (17) | 0.090 (2) | 0.0664 (17) | 0.0132 (16) | −0.0016 (14) | −0.0241 (16) |
C10 | 0.0599 (17) | 0.0695 (19) | 0.089 (2) | 0.0104 (14) | −0.0081 (15) | −0.0289 (16) |
C11 | 0.0458 (14) | 0.0577 (16) | 0.0791 (17) | 0.0072 (11) | −0.0026 (12) | −0.0054 (13) |
C12 | 0.0367 (12) | 0.0540 (14) | 0.0581 (13) | 0.0094 (10) | −0.0008 (10) | −0.0042 (11) |
C13 | 0.0620 (17) | 0.093 (2) | 0.0590 (15) | −0.0088 (15) | −0.0107 (13) | 0.0029 (14) |
C14 | 0.0418 (12) | 0.0469 (14) | 0.0649 (15) | −0.0072 (10) | 0.0003 (11) | 0.0056 (11) |
C15 | 0.0559 (15) | 0.0585 (15) | 0.0605 (15) | −0.0105 (12) | 0.0023 (12) | 0.0070 (12) |
C16 | 0.0653 (18) | 0.076 (2) | 0.0791 (18) | −0.0064 (15) | 0.0074 (14) | 0.0236 (15) |
C17 | 0.0625 (19) | 0.069 (2) | 0.127 (3) | −0.0043 (15) | 0.0117 (18) | 0.0366 (19) |
C18 | 0.078 (2) | 0.0458 (17) | 0.144 (3) | 0.0008 (14) | 0.014 (2) | 0.0090 (18) |
C19 | 0.0641 (17) | 0.0555 (17) | 0.094 (2) | 0.0005 (13) | 0.0141 (15) | −0.0024 (14) |
C20 | 0.0483 (14) | 0.0480 (14) | 0.0602 (14) | −0.0043 (10) | 0.0049 (11) | 0.0110 (10) |
C21 | 0.0489 (15) | 0.0605 (18) | 0.112 (2) | −0.0012 (13) | −0.0011 (15) | −0.0042 (15) |
C22 | 0.0587 (18) | 0.068 (2) | 0.133 (3) | 0.0075 (15) | 0.0109 (18) | 0.0000 (19) |
C23 | 0.091 (2) | 0.0570 (17) | 0.087 (2) | 0.0100 (16) | 0.0260 (17) | 0.0069 (15) |
C24 | 0.085 (2) | 0.0588 (17) | 0.0651 (16) | −0.0088 (15) | 0.0050 (14) | −0.0014 (13) |
C25 | 0.0584 (15) | 0.0595 (16) | 0.0577 (14) | −0.0059 (12) | 0.0009 (12) | 0.0067 (12) |
C26 | 0.0435 (12) | 0.0478 (13) | 0.0461 (12) | −0.0038 (10) | 0.0028 (9) | 0.0008 (9) |
C27 | 0.0539 (15) | 0.0738 (17) | 0.0453 (13) | −0.0073 (12) | 0.0027 (11) | 0.0037 (11) |
C28 | 0.0593 (16) | 0.0719 (17) | 0.0589 (15) | −0.0136 (13) | 0.0165 (12) | −0.0053 (12) |
C29 | 0.0422 (13) | 0.0592 (15) | 0.0785 (18) | −0.0017 (11) | 0.0081 (12) | −0.0031 (13) |
C30 | 0.0502 (15) | 0.0766 (18) | 0.0720 (17) | 0.0012 (13) | −0.0064 (13) | 0.0176 (14) |
C31 | 0.0492 (14) | 0.0724 (17) | 0.0554 (14) | −0.0017 (12) | 0.0035 (11) | 0.0176 (12) |
P1 | 0.0422 (3) | 0.0521 (4) | 0.0495 (3) | −0.0062 (3) | −0.0001 (2) | 0.0046 (3) |
S1 | 0.0581 (4) | 0.0553 (4) | 0.0608 (4) | −0.0020 (3) | −0.0008 (3) | 0.0084 (3) |
S2 | 0.0474 (3) | 0.0617 (4) | 0.0736 (4) | −0.0023 (3) | 0.0016 (3) | 0.0043 (3) |
S3 | 0.0531 (4) | 0.0604 (4) | 0.0497 (3) | −0.0021 (3) | 0.0095 (3) | 0.0008 (3) |
S4 | 0.0505 (3) | 0.0519 (3) | 0.0566 (3) | −0.0002 (3) | 0.0074 (3) | 0.0028 (3) |
Cl1 | 0.1438 (8) | 0.0578 (4) | 0.0650 (4) | −0.0074 (4) | 0.0079 (4) | 0.0090 (3) |
Cl2 | 0.0500 (4) | 0.1302 (8) | 0.1024 (6) | −0.0046 (4) | 0.0057 (4) | −0.0192 (5) |
Cl3 | 0.0893 (5) | 0.1119 (6) | 0.0520 (4) | 0.0095 (5) | 0.0117 (4) | 0.0019 (4) |
Cl4 | 0.0833 (5) | 0.0558 (4) | 0.1072 (6) | −0.0054 (4) | 0.0027 (4) | 0.0015 (4) |
Co1 | 0.0456 (3) | 0.0521 (3) | 0.0498 (2) | −0.00371 (19) | 0.00065 (19) | 0.00547 (19) |
Co2 | 0.0369 (2) | 0.0493 (3) | 0.0468 (2) | 0.00353 (18) | 0.00480 (17) | 0.00160 (18) |
C1—C2 | 1.393 (3) | C17—H17A | 0.9500 |
C1—C6 | 1.404 (4) | C18—C19 | 1.384 (4) |
C1—S1 | 1.750 (3) | C18—H18A | 0.9500 |
C2—C3 | 1.385 (4) | C19—H19A | 0.9500 |
C2—Cl1 | 1.744 (3) | C20—C25 | 1.384 (3) |
C3—C4 | 1.362 (5) | C20—C21 | 1.388 (4) |
C3—H3A | 0.9500 | C20—P1 | 1.780 (3) |
C4—C5 | 1.375 (4) | C21—C22 | 1.367 (4) |
C4—H4A | 0.9500 | C21—H21A | 0.9500 |
C5—C6 | 1.396 (3) | C22—C23 | 1.367 (4) |
C5—Cl2 | 1.724 (3) | C22—H22A | 0.9500 |
C6—S2 | 1.740 (3) | C23—C24 | 1.369 (4) |
C7—C12 | 1.395 (3) | C23—H23A | 0.9500 |
C7—C8 | 1.398 (3) | C24—C25 | 1.377 (4) |
C7—S3 | 1.753 (2) | C24—H24A | 0.9500 |
C8—C9 | 1.374 (4) | C25—H25A | 0.9500 |
C8—Cl3 | 1.733 (3) | C26—C27 | 1.378 (3) |
C9—C10 | 1.376 (4) | C26—C31 | 1.385 (3) |
C9—H9A | 0.9500 | C26—P1 | 1.789 (2) |
C10—C11 | 1.381 (4) | C27—C28 | 1.376 (4) |
C10—H10A | 0.9500 | C27—H27A | 0.9500 |
C11—C12 | 1.398 (3) | C28—C29 | 1.364 (4) |
C11—Cl4 | 1.729 (3) | C28—H28A | 0.9500 |
C12—S4 | 1.754 (2) | C29—C30 | 1.368 (4) |
C13—P1 | 1.790 (2) | C29—H29A | 0.9500 |
C13—H13C | 0.9800 | C30—C31 | 1.378 (3) |
C13—H13B | 0.9800 | C30—H30A | 0.9500 |
C13—H13A | 0.9800 | C31—H31A | 0.9500 |
C14—C15 | 1.385 (3) | S1—Co1 | 2.1625 (6) |
C14—C19 | 1.386 (4) | S2—Co1 | 2.1570 (6) |
C14—P1 | 1.787 (2) | S3—Co2 | 2.1607 (6) |
C15—C16 | 1.385 (3) | S4—Co2 | 2.1642 (6) |
C15—H15A | 0.9500 | Co1—S2i | 2.1570 (7) |
C16—C17 | 1.354 (4) | Co1—S1i | 2.1625 (6) |
C16—H16A | 0.9500 | Co2—S3ii | 2.1607 (6) |
C17—C18 | 1.367 (5) | Co2—S4ii | 2.1642 (6) |
C2—C1—C6 | 118.5 (2) | C14—C19—H19A | 120.5 |
C2—C1—S1 | 122.3 (2) | C25—C20—C21 | 119.5 (2) |
C6—C1—S1 | 119.21 (18) | C25—C20—P1 | 121.91 (19) |
C3—C2—C1 | 121.2 (3) | C21—C20—P1 | 118.5 (2) |
C3—C2—Cl1 | 120.0 (2) | C22—C21—C20 | 120.0 (3) |
C1—C2—Cl1 | 118.8 (2) | C22—C21—H21A | 120.0 |
C4—C3—C2 | 119.9 (3) | C20—C21—H21A | 120.0 |
C4—C3—H3A | 120.1 | C23—C22—C21 | 120.1 (3) |
C2—C3—H3A | 120.1 | C23—C22—H22A | 119.9 |
C3—C4—C5 | 120.3 (3) | C21—C22—H22A | 119.9 |
C3—C4—H4A | 119.9 | C22—C23—C24 | 120.6 (3) |
C5—C4—H4A | 119.9 | C22—C23—H23A | 119.7 |
C4—C5—C6 | 121.1 (3) | C24—C23—H23A | 119.7 |
C4—C5—Cl2 | 119.3 (2) | C23—C24—C25 | 120.0 (3) |
C6—C5—Cl2 | 119.6 (2) | C23—C24—H24A | 120.0 |
C5—C6—C1 | 118.8 (2) | C25—C24—H24A | 120.0 |
C5—C6—S2 | 121.8 (2) | C24—C25—C20 | 119.7 (3) |
C1—C6—S2 | 119.36 (18) | C24—C25—H25A | 120.1 |
C12—C7—C8 | 119.0 (2) | C20—C25—H25A | 120.1 |
C12—C7—S3 | 119.30 (17) | C27—C26—C31 | 119.5 (2) |
C8—C7—S3 | 121.7 (2) | C27—C26—P1 | 120.69 (17) |
C9—C8—C7 | 121.1 (3) | C31—C26—P1 | 119.80 (17) |
C9—C8—Cl3 | 118.8 (2) | C28—C27—C26 | 119.9 (2) |
C7—C8—Cl3 | 120.1 (2) | C28—C27—H27A | 120.0 |
C8—C9—C10 | 120.0 (3) | C26—C27—H27A | 120.0 |
C8—C9—H9A | 120.0 | C29—C28—C27 | 120.4 (2) |
C10—C9—H9A | 120.0 | C29—C28—H28A | 119.8 |
C9—C10—C11 | 119.9 (3) | C27—C28—H28A | 119.8 |
C9—C10—H10A | 120.0 | C28—C29—C30 | 120.2 (2) |
C11—C10—H10A | 120.0 | C28—C29—H29A | 119.9 |
C10—C11—C12 | 120.9 (3) | C30—C29—H29A | 119.9 |
C10—C11—Cl4 | 119.1 (2) | C29—C30—C31 | 120.2 (2) |
C12—C11—Cl4 | 120.0 (2) | C29—C30—H30A | 119.9 |
C7—C12—C11 | 119.0 (2) | C31—C30—H30A | 119.9 |
C7—C12—S4 | 119.13 (18) | C30—C31—C26 | 119.8 (2) |
C11—C12—S4 | 121.9 (2) | C30—C31—H31A | 120.1 |
P1—C13—H13C | 109.5 | C26—C31—H31A | 120.1 |
P1—C13—H13B | 109.5 | C20—P1—C14 | 108.98 (11) |
H13C—C13—H13B | 109.5 | C20—P1—C26 | 110.83 (11) |
P1—C13—H13A | 109.5 | C14—P1—C26 | 109.48 (10) |
H13C—C13—H13A | 109.5 | C20—P1—C13 | 109.98 (13) |
H13B—C13—H13A | 109.5 | C14—P1—C13 | 108.86 (13) |
C15—C14—C19 | 120.1 (2) | C26—P1—C13 | 108.69 (12) |
C15—C14—P1 | 120.22 (19) | C1—S1—Co1 | 104.15 (9) |
C19—C14—P1 | 119.7 (2) | C6—S2—Co1 | 104.60 (9) |
C14—C15—C16 | 119.6 (3) | C7—S3—Co2 | 104.88 (8) |
C14—C15—H15A | 120.2 | C12—S4—Co2 | 104.80 (8) |
C16—C15—H15A | 120.2 | S2—Co1—S2i | 180.0 |
C17—C16—C15 | 119.9 (3) | S2—Co1—S1i | 87.66 (2) |
C17—C16—H16A | 120.0 | S2i—Co1—S1i | 92.34 (2) |
C15—C16—H16A | 120.0 | S2—Co1—S1 | 92.34 (2) |
C16—C17—C18 | 121.1 (3) | S2i—Co1—S1 | 87.66 (2) |
C16—C17—H17A | 119.4 | S1i—Co1—S1 | 180.0 |
C18—C17—H17A | 119.4 | S3—Co2—S3ii | 180.0 |
C17—C18—C19 | 120.3 (3) | S3—Co2—S4ii | 88.14 (2) |
C17—C18—H18A | 119.9 | S3ii—Co2—S4ii | 91.86 (2) |
C19—C18—H18A | 119.9 | S3—Co2—S4 | 91.86 (2) |
C18—C19—C14 | 119.0 (3) | S3ii—Co2—S4 | 88.14 (2) |
C18—C19—H19A | 120.5 | S4ii—Co2—S4 | 180.0 |
C6—C1—C2—C3 | 3.7 (4) | C25—C20—C21—C22 | 0.3 (4) |
S1—C1—C2—C3 | −176.85 (19) | P1—C20—C21—C22 | −177.1 (2) |
C6—C1—C2—Cl1 | −174.19 (17) | C20—C21—C22—C23 | −0.2 (5) |
S1—C1—C2—Cl1 | 5.2 (3) | C21—C22—C23—C24 | −0.7 (5) |
C1—C2—C3—C4 | 0.1 (4) | C22—C23—C24—C25 | 1.4 (4) |
Cl1—C2—C3—C4 | 178.0 (2) | C23—C24—C25—C20 | −1.3 (4) |
C2—C3—C4—C5 | −1.6 (4) | C21—C20—C25—C24 | 0.4 (4) |
C3—C4—C5—C6 | −0.8 (4) | P1—C20—C25—C24 | 177.73 (19) |
C3—C4—C5—Cl2 | 179.2 (2) | C31—C26—C27—C28 | −1.5 (4) |
C4—C5—C6—C1 | 4.6 (4) | P1—C26—C27—C28 | 178.76 (19) |
Cl2—C5—C6—C1 | −175.42 (18) | C26—C27—C28—C29 | 1.3 (4) |
C4—C5—C6—S2 | −174.2 (2) | C27—C28—C29—C30 | 0.3 (4) |
Cl2—C5—C6—S2 | 5.8 (3) | C28—C29—C30—C31 | −1.8 (4) |
C2—C1—C6—C5 | −5.9 (3) | C29—C30—C31—C26 | 1.5 (4) |
S1—C1—C6—C5 | 174.63 (18) | C27—C26—C31—C30 | 0.1 (4) |
C2—C1—C6—S2 | 172.86 (17) | P1—C26—C31—C30 | 179.8 (2) |
S1—C1—C6—S2 | −6.6 (3) | C25—C20—P1—C14 | −106.6 (2) |
C12—C7—C8—C9 | 2.9 (4) | C21—C20—P1—C14 | 70.7 (2) |
S3—C7—C8—C9 | −177.6 (2) | C25—C20—P1—C26 | 13.9 (2) |
C12—C7—C8—Cl3 | −176.68 (17) | C21—C20—P1—C26 | −168.7 (2) |
S3—C7—C8—Cl3 | 2.9 (3) | C25—C20—P1—C13 | 134.1 (2) |
C7—C8—C9—C10 | −1.8 (4) | C21—C20—P1—C13 | −48.5 (2) |
Cl3—C8—C9—C10 | 177.7 (2) | C15—C14—P1—C20 | 14.3 (2) |
C8—C9—C10—C11 | −0.6 (4) | C19—C14—P1—C20 | −166.2 (2) |
C9—C10—C11—C12 | 2.0 (4) | C15—C14—P1—C26 | −107.1 (2) |
C9—C10—C11—Cl4 | −177.2 (2) | C19—C14—P1—C26 | 72.5 (2) |
C8—C7—C12—C11 | −1.5 (3) | C15—C14—P1—C13 | 134.2 (2) |
S3—C7—C12—C11 | 178.93 (17) | C19—C14—P1—C13 | −46.2 (2) |
C8—C7—C12—S4 | 177.92 (17) | C27—C26—P1—C20 | 94.9 (2) |
S3—C7—C12—S4 | −1.6 (2) | C31—C26—P1—C20 | −84.8 (2) |
C10—C11—C12—C7 | −0.9 (3) | C27—C26—P1—C14 | −144.9 (2) |
Cl4—C11—C12—C7 | 178.24 (17) | C31—C26—P1—C14 | 35.4 (2) |
C10—C11—C12—S4 | 179.71 (19) | C27—C26—P1—C13 | −26.1 (2) |
Cl4—C11—C12—S4 | −1.2 (3) | C31—C26—P1—C13 | 154.2 (2) |
C19—C14—C15—C16 | 0.4 (4) | C2—C1—S1—Co1 | −173.25 (18) |
P1—C14—C15—C16 | −179.99 (19) | C6—C1—S1—Co1 | 6.2 (2) |
C14—C15—C16—C17 | 0.2 (4) | C5—C6—S2—Co1 | −177.93 (18) |
C15—C16—C17—C18 | −1.0 (5) | C1—C6—S2—Co1 | 3.3 (2) |
C16—C17—C18—C19 | 1.1 (5) | C12—C7—S3—Co2 | 0.39 (19) |
C17—C18—C19—C14 | −0.5 (5) | C8—C7—S3—Co2 | −179.15 (17) |
C15—C14—C19—C18 | −0.3 (4) | C7—C12—S4—Co2 | 1.98 (19) |
P1—C14—C19—C18 | −179.9 (2) | C11—C12—S4—Co2 | −178.60 (17) |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C27—H27A···Cl1 | 0.95 | 2.90 | 3.441 (2) | 118 |
C4—H4A···S4iii | 0.95 | 2.95 | 3.834 (3) | 154 |
C13—H13A···S4iv | 0.98 | 2.92 | 3.853 (3) | 159 |
C31—H31A···S1v | 0.95 | 2.87 | 3.726 (3) | 151 |
C29—H29A···Cl3iii | 0.95 | 2.94 | 3.674 (3) | 135 |
Symmetry codes: (iii) −x, y−1/2, −z+3/2; (iv) −x+1, y−1/2, −z+3/2; (v) x, −y+1/2, z−1/2. |
(C19H18P)2[Cu(C6H2Cl2S2)2]·2C2H6OS | F(000) = 1230 |
Mr = 1192.59 | Dx = 1.494 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 13.94737 (14) Å | Cell parameters from 70625 reflections |
b = 11.53304 (11) Å | θ = 3.0–44.9° |
c = 16.47990 (17) Å | µ = 0.95 mm−1 |
β = 90.6983 (9)° | T = 100 K |
V = 2650.69 (5) Å3 | Plate, orange |
Z = 2 | 0.53 × 0.27 × 0.02 mm |
Agilent Xcalibur Ruby Gemini diffractometer | 28120 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 15927 reflections with I > 2σ(I) |
Detector resolution: 5.2170 pixels mm-1 | Rint = 0.089 |
ω scans | θmax = 50.9°, θmin = 2.6° |
Absorption correction: analytical [CrysAlis PRO (Agilent, 2013), based on expressions derived by Clark & Reid (1995)] | h = −29→30 |
Tmin = 0.742, Tmax = 0.981 | k = −24→25 |
369672 measured reflections | l = −35→35 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.051 | H-atom parameters constrained |
wR(F2) = 0.119 | w = 1/[σ2(Fo2) + (0.050P)2 + 0.1295P] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max = 0.001 |
28120 reflections | Δρmax = 1.14 e Å−3 |
313 parameters | Δρmin = −0.39 e Å−3 |
(C19H18P)2[Cu(C6H2Cl2S2)2]·2C2H6OS | V = 2650.69 (5) Å3 |
Mr = 1192.59 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 13.94737 (14) Å | µ = 0.95 mm−1 |
b = 11.53304 (11) Å | T = 100 K |
c = 16.47990 (17) Å | 0.53 × 0.27 × 0.02 mm |
β = 90.6983 (9)° |
Agilent Xcalibur Ruby Gemini diffractometer | 28120 independent reflections |
Absorption correction: analytical [CrysAlis PRO (Agilent, 2013), based on expressions derived by Clark & Reid (1995)] | 15927 reflections with I > 2σ(I) |
Tmin = 0.742, Tmax = 0.981 | Rint = 0.089 |
369672 measured reflections |
R[F2 > 2σ(F2)] = 0.051 | 0 restraints |
wR(F2) = 0.119 | H-atom parameters constrained |
S = 1.00 | Δρmax = 1.14 e Å−3 |
28120 reflections | Δρmin = −0.39 e Å−3 |
313 parameters |
Experimental. Absorption correction: CrysAlisPro, Agilent Technologies, Version 1.171.37.27b (release 13-12-2013 CrysAlis171 .NET) (compiled Dec 13 2013,18:28:10) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.20229 (6) | 0.61969 (8) | 0.52257 (5) | 0.01411 (13) | |
C2 | 0.29896 (6) | 0.64066 (8) | 0.54208 (5) | 0.01583 (14) | |
C3 | 0.33412 (7) | 0.74906 (9) | 0.56292 (6) | 0.01856 (15) | |
H3 | 0.4001 | 0.7593 | 0.5758 | 0.022* | |
C4 | 0.27154 (7) | 0.84246 (9) | 0.56470 (6) | 0.01890 (16) | |
H4 | 0.2942 | 0.9177 | 0.5784 | 0.023* | |
C5 | 0.17525 (7) | 0.82436 (8) | 0.54620 (6) | 0.01676 (14) | |
C6 | 0.13753 (6) | 0.71535 (8) | 0.52434 (5) | 0.01444 (13) | |
C7 | 0.34105 (8) | 1.09430 (8) | 0.20956 (6) | 0.01920 (16) | |
H7C | 0.2987 | 1.1621 | 0.2105 | 0.023* | |
H7A | 0.3369 | 1.0572 | 0.1561 | 0.023* | |
H7B | 0.4073 | 1.1188 | 0.2203 | 0.023* | |
C14 | 0.31195 (6) | 1.06566 (8) | 0.38187 (5) | 0.01469 (13) | |
C19 | 0.23386 (7) | 1.12765 (9) | 0.41189 (6) | 0.01937 (16) | |
H19 | 0.1742 | 1.1269 | 0.3835 | 0.023* | |
C18 | 0.24419 (8) | 1.19042 (9) | 0.48363 (7) | 0.02245 (18) | |
H18 | 0.1911 | 1.2317 | 0.5048 | 0.027* | |
C17 | 0.33186 (8) | 1.19275 (9) | 0.52417 (6) | 0.02125 (17) | |
H17 | 0.3386 | 1.2359 | 0.5730 | 0.025* | |
C16 | 0.40986 (7) | 1.13242 (9) | 0.49387 (6) | 0.01938 (16) | |
H16 | 0.4697 | 1.1347 | 0.5220 | 0.023* | |
C15 | 0.40055 (7) | 1.06879 (8) | 0.42263 (6) | 0.01624 (14) | |
H15 | 0.4539 | 1.0277 | 0.4017 | 0.019* | |
C20 | 0.18635 (6) | 0.94138 (8) | 0.26401 (5) | 0.01459 (13) | |
C21 | 0.12351 (7) | 0.91080 (8) | 0.32564 (6) | 0.01723 (15) | |
H21 | 0.1410 | 0.9233 | 0.3808 | 0.021* | |
C22 | 0.03520 (7) | 0.86191 (9) | 0.30581 (6) | 0.01876 (16) | |
H22 | −0.0084 | 0.8424 | 0.3475 | 0.023* | |
C23 | 0.01069 (7) | 0.84151 (8) | 0.22516 (6) | 0.01856 (15) | |
H23 | −0.0499 | 0.8085 | 0.2118 | 0.022* | |
C24 | 0.07449 (7) | 0.86918 (9) | 0.16378 (6) | 0.01836 (15) | |
H24 | 0.0578 | 0.8535 | 0.1088 | 0.022* | |
C25 | 0.16228 (7) | 0.91950 (8) | 0.18264 (6) | 0.01664 (14) | |
H25 | 0.2057 | 0.9389 | 0.1408 | 0.020* | |
C8 | 0.38173 (6) | 0.86877 (7) | 0.28620 (5) | 0.01370 (13) | |
C9 | 0.38465 (7) | 0.79763 (8) | 0.35489 (6) | 0.01706 (15) | |
H9 | 0.3493 | 0.8179 | 0.4017 | 0.020* | |
C10 | 0.43958 (8) | 0.69716 (8) | 0.35434 (6) | 0.01997 (16) | |
H10 | 0.4425 | 0.6491 | 0.4011 | 0.024* | |
C11 | 0.49039 (8) | 0.66671 (9) | 0.28536 (6) | 0.02083 (17) | |
H11 | 0.5285 | 0.5985 | 0.2853 | 0.025* | |
C12 | 0.48535 (8) | 0.73606 (9) | 0.21662 (6) | 0.02147 (17) | |
H12 | 0.5190 | 0.7142 | 0.1693 | 0.026* | |
C13 | 0.43120 (7) | 0.83745 (8) | 0.21668 (6) | 0.01810 (15) | |
H13 | 0.4280 | 0.8849 | 0.1696 | 0.022* | |
C26 | 0.20169 (9) | 0.36221 (11) | 0.69835 (8) | 0.0297 (2) | |
H26A | 0.2387 | 0.3442 | 0.7477 | 0.036* | |
H26B | 0.2452 | 0.3886 | 0.6559 | 0.036* | |
H26C | 0.1677 | 0.2926 | 0.6798 | 0.036* | |
C27 | 0.20139 (10) | 0.58249 (12) | 0.74969 (8) | 0.0332 (3) | |
H27A | 0.2415 | 0.5528 | 0.7943 | 0.040* | |
H27B | 0.1672 | 0.6520 | 0.7677 | 0.040* | |
H27C | 0.2420 | 0.6022 | 0.7036 | 0.040* | |
O1 | 0.06658 (6) | 0.43738 (8) | 0.79518 (5) | 0.02556 (15) | |
P1 | 0.30510 (2) | 0.99367 (2) | 0.28561 (2) | 0.01329 (4) | |
S1 | 0.16153 (2) | 0.48078 (2) | 0.49861 (2) | 0.01542 (4) | |
S2 | 0.01625 (2) | 0.69557 (2) | 0.50212 (2) | 0.01693 (4) | |
S3 | 0.11665 (2) | 0.47421 (2) | 0.71961 (2) | 0.02120 (5) | |
Cl1 | 0.37970 (2) | 0.52434 (2) | 0.54206 (2) | 0.02084 (4) | |
Cl2 | 0.09886 (2) | 0.94374 (2) | 0.55149 (2) | 0.02264 (5) | |
Cu1 | 0.0000 | 0.5000 | 0.5000 | 0.01322 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0149 (3) | 0.0167 (3) | 0.0107 (3) | −0.0008 (3) | 0.0004 (2) | −0.0003 (2) |
C2 | 0.0139 (3) | 0.0197 (4) | 0.0139 (3) | −0.0009 (3) | 0.0009 (3) | 0.0015 (3) |
C3 | 0.0166 (3) | 0.0239 (4) | 0.0152 (3) | −0.0052 (3) | −0.0005 (3) | 0.0002 (3) |
C4 | 0.0212 (4) | 0.0198 (4) | 0.0157 (3) | −0.0059 (3) | 0.0014 (3) | −0.0016 (3) |
C5 | 0.0196 (4) | 0.0156 (3) | 0.0151 (3) | −0.0016 (3) | 0.0036 (3) | −0.0009 (3) |
C6 | 0.0151 (3) | 0.0152 (3) | 0.0130 (3) | −0.0003 (3) | 0.0019 (3) | 0.0003 (2) |
C7 | 0.0229 (4) | 0.0169 (4) | 0.0177 (4) | −0.0030 (3) | −0.0021 (3) | 0.0037 (3) |
C14 | 0.0166 (3) | 0.0135 (3) | 0.0140 (3) | 0.0005 (3) | −0.0014 (3) | −0.0010 (3) |
C19 | 0.0176 (4) | 0.0165 (4) | 0.0239 (4) | 0.0029 (3) | −0.0021 (3) | −0.0034 (3) |
C18 | 0.0235 (4) | 0.0176 (4) | 0.0264 (5) | 0.0025 (3) | 0.0043 (4) | −0.0058 (3) |
C17 | 0.0282 (5) | 0.0181 (4) | 0.0175 (4) | −0.0014 (3) | 0.0025 (3) | −0.0054 (3) |
C16 | 0.0217 (4) | 0.0204 (4) | 0.0159 (4) | −0.0019 (3) | −0.0029 (3) | −0.0027 (3) |
C15 | 0.0165 (3) | 0.0174 (3) | 0.0148 (3) | 0.0005 (3) | −0.0010 (3) | −0.0022 (3) |
C20 | 0.0157 (3) | 0.0138 (3) | 0.0141 (3) | −0.0001 (3) | −0.0023 (3) | −0.0001 (3) |
C21 | 0.0202 (4) | 0.0177 (4) | 0.0139 (3) | −0.0010 (3) | −0.0008 (3) | 0.0002 (3) |
C22 | 0.0189 (4) | 0.0188 (4) | 0.0186 (4) | −0.0018 (3) | 0.0011 (3) | 0.0005 (3) |
C23 | 0.0176 (4) | 0.0168 (4) | 0.0212 (4) | −0.0016 (3) | −0.0028 (3) | 0.0002 (3) |
C24 | 0.0187 (4) | 0.0198 (4) | 0.0165 (4) | −0.0009 (3) | −0.0034 (3) | −0.0022 (3) |
C25 | 0.0172 (3) | 0.0189 (4) | 0.0138 (3) | 0.0002 (3) | −0.0012 (3) | −0.0006 (3) |
C8 | 0.0152 (3) | 0.0132 (3) | 0.0127 (3) | −0.0004 (2) | −0.0015 (2) | −0.0007 (2) |
C9 | 0.0216 (4) | 0.0160 (3) | 0.0136 (3) | 0.0013 (3) | 0.0005 (3) | 0.0008 (3) |
C10 | 0.0259 (4) | 0.0154 (3) | 0.0186 (4) | 0.0018 (3) | −0.0004 (3) | 0.0024 (3) |
C11 | 0.0238 (4) | 0.0147 (3) | 0.0241 (4) | 0.0021 (3) | 0.0014 (3) | −0.0018 (3) |
C12 | 0.0252 (4) | 0.0189 (4) | 0.0204 (4) | 0.0020 (3) | 0.0053 (3) | −0.0024 (3) |
C13 | 0.0221 (4) | 0.0175 (4) | 0.0147 (3) | 0.0005 (3) | 0.0025 (3) | −0.0004 (3) |
C26 | 0.0328 (6) | 0.0295 (5) | 0.0271 (5) | 0.0115 (4) | 0.0078 (4) | 0.0027 (4) |
C27 | 0.0379 (7) | 0.0312 (6) | 0.0308 (6) | −0.0090 (5) | 0.0077 (5) | 0.0013 (5) |
O1 | 0.0233 (3) | 0.0282 (4) | 0.0254 (4) | 0.0012 (3) | 0.0080 (3) | 0.0037 (3) |
P1 | 0.01548 (9) | 0.01278 (9) | 0.01158 (8) | −0.00015 (7) | −0.00208 (7) | 0.00014 (7) |
S1 | 0.01402 (8) | 0.01510 (9) | 0.01713 (9) | 0.00027 (7) | 0.00005 (7) | −0.00134 (7) |
S2 | 0.01420 (9) | 0.01562 (9) | 0.02098 (10) | 0.00077 (7) | 0.00046 (7) | 0.00093 (7) |
S3 | 0.02288 (11) | 0.02286 (11) | 0.01794 (10) | 0.00442 (9) | 0.00261 (8) | 0.00203 (8) |
Cl1 | 0.01402 (8) | 0.02486 (10) | 0.02360 (10) | 0.00159 (7) | −0.00115 (7) | 0.00282 (8) |
Cl2 | 0.02563 (11) | 0.01524 (9) | 0.02721 (12) | 0.00048 (8) | 0.00724 (9) | −0.00099 (8) |
Cu1 | 0.01290 (6) | 0.01499 (6) | 0.01177 (6) | −0.00054 (5) | 0.00042 (5) | −0.00054 (5) |
C1—C2 | 1.4033 (12) | C22—C23 | 1.3885 (14) |
C1—C6 | 1.4264 (13) | C22—H22 | 0.9500 |
C1—S1 | 1.7436 (9) | C23—C24 | 1.3924 (14) |
C2—C3 | 1.3847 (14) | C23—H23 | 0.9500 |
C2—Cl1 | 1.7516 (10) | C24—C25 | 1.3868 (13) |
C3—C4 | 1.3869 (15) | C24—H24 | 0.9500 |
C3—H3 | 0.9500 | C25—H25 | 0.9500 |
C4—C5 | 1.3894 (14) | C8—C13 | 1.3923 (13) |
C4—H4 | 0.9500 | C8—C9 | 1.3982 (12) |
C5—C6 | 1.4081 (13) | C8—P1 | 1.7936 (9) |
C5—Cl2 | 1.7437 (10) | C9—C10 | 1.3891 (13) |
C6—S2 | 1.7413 (9) | C9—H9 | 0.9500 |
C7—P1 | 1.7845 (10) | C10—C11 | 1.3919 (14) |
C7—H7C | 0.9800 | C10—H10 | 0.9500 |
C7—H7A | 0.9800 | C11—C12 | 1.3878 (15) |
C7—H7B | 0.9800 | C11—H11 | 0.9500 |
C14—C19 | 1.3983 (13) | C12—C13 | 1.3921 (14) |
C14—C15 | 1.3998 (13) | C12—H12 | 0.9500 |
C14—P1 | 1.7919 (9) | C13—H13 | 0.9500 |
C19—C18 | 1.3922 (14) | C26—S3 | 1.7912 (12) |
C19—H19 | 0.9500 | C26—H26A | 0.9800 |
C18—C17 | 1.3865 (16) | C26—H26B | 0.9800 |
C18—H18 | 0.9500 | C26—H26C | 0.9800 |
C17—C16 | 1.3893 (15) | C27—S3 | 1.7855 (14) |
C17—H17 | 0.9500 | C27—H27A | 0.9800 |
C16—C15 | 1.3893 (13) | C27—H27B | 0.9800 |
C16—H16 | 0.9500 | C27—H27C | 0.9800 |
C15—H15 | 0.9500 | O1—S3 | 1.4968 (8) |
C20—C21 | 1.3948 (13) | S1—Cu1 | 2.2641 (2) |
C20—C25 | 1.4013 (12) | S2—Cu1 | 2.2671 (2) |
C20—P1 | 1.7943 (9) | Cu1—S1i | 2.2642 (2) |
C21—C22 | 1.3900 (14) | Cu1—S2i | 2.2671 (2) |
C21—H21 | 0.9500 | ||
C2—C1—C6 | 117.96 (8) | C25—C24—C23 | 120.23 (9) |
C2—C1—S1 | 121.34 (7) | C25—C24—H24 | 119.9 |
C6—C1—S1 | 120.69 (7) | C23—C24—H24 | 119.9 |
C3—C2—C1 | 123.29 (9) | C24—C25—C20 | 119.36 (9) |
C3—C2—Cl1 | 117.76 (7) | C24—C25—H25 | 120.3 |
C1—C2—Cl1 | 118.94 (7) | C20—C25—H25 | 120.3 |
C2—C3—C4 | 119.04 (9) | C13—C8—C9 | 120.28 (8) |
C2—C3—H3 | 120.5 | C13—C8—P1 | 120.33 (7) |
C4—C3—H3 | 120.5 | C9—C8—P1 | 119.15 (7) |
C3—C4—C5 | 119.05 (9) | C10—C9—C8 | 119.66 (9) |
C3—C4—H4 | 120.5 | C10—C9—H9 | 120.2 |
C5—C4—H4 | 120.5 | C8—C9—H9 | 120.2 |
C4—C5—C6 | 123.19 (9) | C9—C10—C11 | 120.14 (9) |
C4—C5—Cl2 | 117.39 (7) | C9—C10—H10 | 119.9 |
C6—C5—Cl2 | 119.42 (7) | C11—C10—H10 | 119.9 |
C5—C6—C1 | 117.46 (8) | C12—C11—C10 | 120.00 (9) |
C5—C6—S2 | 121.98 (7) | C12—C11—H11 | 120.0 |
C1—C6—S2 | 120.54 (7) | C10—C11—H11 | 120.0 |
P1—C7—H7C | 109.5 | C11—C12—C13 | 120.37 (9) |
P1—C7—H7A | 109.5 | C11—C12—H12 | 119.8 |
H7C—C7—H7A | 109.5 | C13—C12—H12 | 119.8 |
P1—C7—H7B | 109.5 | C12—C13—C8 | 119.52 (9) |
H7C—C7—H7B | 109.5 | C12—C13—H13 | 120.2 |
H7A—C7—H7B | 109.5 | C8—C13—H13 | 120.2 |
C19—C14—C15 | 120.25 (8) | S3—C26—H26A | 109.5 |
C19—C14—P1 | 121.12 (7) | S3—C26—H26B | 109.5 |
C15—C14—P1 | 118.29 (7) | H26A—C26—H26B | 109.5 |
C18—C19—C14 | 119.57 (9) | S3—C26—H26C | 109.5 |
C18—C19—H19 | 120.2 | H26A—C26—H26C | 109.5 |
C14—C19—H19 | 120.2 | H26B—C26—H26C | 109.5 |
C17—C18—C19 | 120.04 (9) | S3—C27—H27A | 109.5 |
C17—C18—H18 | 120.0 | S3—C27—H27B | 109.5 |
C19—C18—H18 | 120.0 | H27A—C27—H27B | 109.5 |
C18—C17—C16 | 120.47 (9) | S3—C27—H27C | 109.5 |
C18—C17—H17 | 119.8 | H27A—C27—H27C | 109.5 |
C16—C17—H17 | 119.8 | H27B—C27—H27C | 109.5 |
C17—C16—C15 | 120.18 (9) | C7—P1—C14 | 107.94 (5) |
C17—C16—H16 | 119.9 | C7—P1—C8 | 110.71 (5) |
C15—C16—H16 | 119.9 | C14—P1—C8 | 110.00 (4) |
C16—C15—C14 | 119.48 (9) | C7—P1—C20 | 110.24 (5) |
C16—C15—H15 | 120.3 | C14—P1—C20 | 111.74 (4) |
C14—C15—H15 | 120.3 | C8—P1—C20 | 106.24 (4) |
C21—C20—C25 | 120.39 (8) | C1—S1—Cu1 | 103.27 (3) |
C21—C20—P1 | 121.82 (7) | C6—S2—Cu1 | 103.31 (3) |
C25—C20—P1 | 117.39 (7) | O1—S3—C27 | 106.34 (6) |
C22—C21—C20 | 119.62 (9) | O1—S3—C26 | 105.95 (5) |
C22—C21—H21 | 120.2 | C27—S3—C26 | 96.95 (7) |
C20—C21—H21 | 120.2 | S1—Cu1—S1i | 179.999 (11) |
C23—C22—C21 | 120.06 (9) | S1—Cu1—S2i | 90.100 (8) |
C23—C22—H22 | 120.0 | S1i—Cu1—S2i | 89.899 (8) |
C21—C22—H22 | 120.0 | S1—Cu1—S2 | 89.899 (8) |
C22—C23—C24 | 120.30 (9) | S1i—Cu1—S2 | 90.101 (8) |
C22—C23—H23 | 119.9 | S2i—Cu1—S2 | 180.0 |
C24—C23—H23 | 119.9 | ||
C6—C1—C2—C3 | 0.09 (13) | P1—C20—C25—C24 | 174.20 (7) |
S1—C1—C2—C3 | −178.77 (7) | C13—C8—C9—C10 | 1.95 (14) |
C6—C1—C2—Cl1 | 178.94 (6) | P1—C8—C9—C10 | 176.41 (8) |
S1—C1—C2—Cl1 | 0.08 (10) | C8—C9—C10—C11 | −0.86 (15) |
C1—C2—C3—C4 | −0.14 (14) | C9—C10—C11—C12 | −0.76 (16) |
Cl1—C2—C3—C4 | −179.00 (7) | C10—C11—C12—C13 | 1.30 (16) |
C2—C3—C4—C5 | 0.55 (14) | C11—C12—C13—C8 | −0.22 (16) |
C3—C4—C5—C6 | −0.96 (14) | C9—C8—C13—C12 | −1.41 (14) |
C3—C4—C5—Cl2 | 178.58 (7) | P1—C8—C13—C12 | −175.80 (8) |
C4—C5—C6—C1 | 0.90 (13) | C19—C14—P1—C7 | 88.84 (9) |
Cl2—C5—C6—C1 | −178.63 (6) | C15—C14—P1—C7 | −84.54 (8) |
C4—C5—C6—S2 | 179.60 (7) | C19—C14—P1—C8 | −150.27 (8) |
Cl2—C5—C6—S2 | 0.07 (11) | C15—C14—P1—C8 | 36.35 (9) |
C2—C1—C6—C5 | −0.45 (12) | C19—C14—P1—C20 | −32.53 (9) |
S1—C1—C6—C5 | 178.43 (7) | C15—C14—P1—C20 | 154.09 (7) |
C2—C1—C6—S2 | −179.16 (6) | C13—C8—P1—C7 | −24.58 (9) |
S1—C1—C6—S2 | −0.29 (10) | C9—C8—P1—C7 | 160.97 (7) |
C15—C14—C19—C18 | −1.46 (15) | C13—C8—P1—C14 | −143.79 (7) |
P1—C14—C19—C18 | −174.71 (8) | C9—C8—P1—C14 | 41.76 (9) |
C14—C19—C18—C17 | 1.04 (16) | C13—C8—P1—C20 | 95.11 (8) |
C19—C18—C17—C16 | −0.22 (16) | C9—C8—P1—C20 | −79.34 (8) |
C18—C17—C16—C15 | −0.19 (16) | C21—C20—P1—C7 | −148.23 (8) |
C17—C16—C15—C14 | −0.23 (15) | C25—C20—P1—C7 | 38.93 (9) |
C19—C14—C15—C16 | 1.06 (14) | C21—C20—P1—C14 | −28.21 (9) |
P1—C14—C15—C16 | 174.50 (8) | C25—C20—P1—C14 | 158.96 (7) |
C25—C20—C21—C22 | −2.16 (14) | C21—C20—P1—C8 | 91.77 (8) |
P1—C20—C21—C22 | −174.79 (7) | C25—C20—P1—C8 | −81.07 (8) |
C20—C21—C22—C23 | 1.33 (15) | C2—C1—S1—Cu1 | 168.55 (6) |
C21—C22—C23—C24 | 0.39 (15) | C6—C1—S1—Cu1 | −10.28 (7) |
C22—C23—C24—C25 | −1.29 (15) | C5—C6—S2—Cu1 | −167.98 (7) |
C23—C24—C25—C20 | 0.47 (15) | C1—C6—S2—Cu1 | 10.68 (8) |
C21—C20—C25—C24 | 1.26 (14) |
Symmetry code: (i) −x, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7A···S1ii | 0.98 | 2.70 | 3.6717 (10) | 172 |
C7—H7B···O1iii | 0.98 | 2.61 | 3.4511 (14) | 144 |
C15—H15···O1iii | 0.95 | 2.40 | 3.1460 (12) | 135 |
C21—H21···Cl2 | 0.95 | 2.89 | 3.7613 (10) | 153 |
C25—H25···S1ii | 0.95 | 3.01 | 3.9546 (10) | 175 |
C26—H26B···S1 | 0.98 | 3.02 | 3.6021 (13) | 119 |
Symmetry codes: (ii) −x+1/2, y+1/2, −z+1/2; (iii) x+1/2, −y+3/2, z−1/2. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | (C19H18P)[Co(C6H2Cl2S2)2] | (C19H18P)2[Cu(C6H2Cl2S2)2]·2C2H6OS |
Mr | 754.42 | 1192.59 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/n |
Temperature (K) | 100 | 100 |
a, b, c (Å) | 13.46050 (18), 14.6661 (2), 16.24190 (19) | 13.94737 (14), 11.53304 (11), 16.47990 (17) |
β (°) | 91.9170 (11) | 90.6983 (9) |
V (Å3) | 3204.57 (7) | 2650.69 (5) |
Z | 4 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.20 | 0.95 |
Crystal size (mm) | 0.50 × 0.21 × 0.11 | 0.53 × 0.27 × 0.02 |
Data collection | ||
Diffractometer | Agilent Xcalibur Ruby Gemini diffractometer | Agilent Xcalibur Ruby Gemini diffractometer |
Absorption correction | Analytical [CrysAlis PRO (Agilent, 2013), based on expressions derived by Clark & Reid (1995)] | Analytical [CrysAlis PRO (Agilent, 2013), based on expressions derived by Clark & Reid (1995)] |
Tmin, Tmax | 0.746, 0.876 | 0.742, 0.981 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 55679, 8220, 5470 | 369672, 28120, 15927 |
Rint | 0.034 | 0.089 |
(sin θ/λ)max (Å−1) | 0.696 | 1.091 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.096, 1.01 | 0.051, 0.119, 1.00 |
No. of reflections | 8220 | 28120 |
No. of parameters | 373 | 313 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.34, −0.54 | 1.14, −0.39 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2012), CrysAlis RED (Oxford Diffraction, 2012), SUPERFLIP (Palatinus, 2013), OLEX2 (Dolomanov et al., 2009) and SHELXS97 (Sheldrick, 2008), SHELXL2013 (Sheldrick, 2015), DIAMOND (Brandenburg, 1998; Brandenburg & Berndt, 1999), enCIFer (Allen et al., 2004).
(I) | (II) | (III) | |||
S1—Co1 | 2.1625 (6) | S1—Cu1 | 2.2641 (2) | S1—Cu1 | 2.1721 (6) |
S2—Co1 | 2.1570 (6) | S2—Cu1 | 2.2671 (2) | S2—Cu1 | 2.1724 (7) |
S3—Co2 | 2.1607 (6) | - | - | S3—Cu2 | 2.1740 (6) |
S4—Co2 | 2.1642 (6) | - | - | S4—Cu2 | 2.1765 (6) |
S2—Co1—S1 | 92.34 (2) | S2—Cu1—S1 | 89.899 (8) | S2—Cu1—S1 | 92.91 (2) |
S2—Co1—S1i | 87.66 (2) | S2—Cu1—S1ii | 90.101 (8) | S2—Cu1—S1i | 87.09 (2) |
S1i—Co1—S1 | 180.0 | S1ii—Cu1—S1 | 180.0 | S1i—Cu1—S1 | 180.0 |
S2—Co1—S2i | 180.0 | S2—Cu1—S2ii | 180.0 | S2—Cu1—S2i | 180.0 |
S3—Co2—S4 | 91.86 (2) | - | - | S3—Cu2—S4 | 92.42 (2) |
S3—Co2—S4ii | 88.14 (2) | - | - | S3—Cu2—S4ii | 87.58 (2) |
S3—Co2—S3ii | 180.0 | - | - | S3—Cu2—S3ii | 180.0 |
S4—Co2—S4ii | 180.0 | - | - | S4—Cu2—S4ii | 180.0 |
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) -x, -y+1, -z+1. |
Compound | D—H···A | D—H | H···A | D···A | D—H···A |
(I) | C27—H27A···Cl1 | 0.95 | 2.90 | 3.441 (2) | 117.6 |
C29—H29A···Cl3iii | 0.95 | 2.94 | 3.674 (3) | 135.3 | |
C31—H31A···S1v | 0.95 | 2.87 | 3.726 (3) | 150.7 | |
C13—H13A···S4iv | 0.98 | 2.92 | 3.853 (3) | 158.8 | |
C4—H4A···S4iii | 0.95 | 2.95 | 3.834 (3) | 154.4 | |
(II) | C7—H7A···S1vi' | 0.98 | 2.70 | 3.672 (1) | 172.2 |
C7—H7B···O1vii | 0.98 | 2.61 | 3.4511 (14) | 143.9 | |
C15—H15···O1vii | 0.95 | 2.40 | 3.1460 (12) | 134.7 | |
C21—H21···Cl2 | 0.95 | 2.89 | 3.7613 (10) | 153.1 | |
C25—H25···S1vi | 0.95 | 3.01 | 3.9546 (10) | 175.0 | |
C26—H26B···S1 | 0.98 | 3.02 | 3.6021 (13) | 119.0 | |
(III) | C27–H27A···Cl1' | 0.95 | 2.90 | 3.456 (3) | 118.6 |
C29—H29A···Cl3iii | 0.95 | 2.94 | 3.674 (3) | 134.8 | |
C31–H31A···S1v | 0.95 | 2.88 | 3.744 (3) | 151.7 | |
C13—H13A···S4iv | 0.98 | 2.92 | 3.847 (3) | 158.4 | |
C4—H4A···S4iii | 0.95 | 2.97 | 3.854 (3) | 155.3 |
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) -x, -y+1, -z+1; (iii) -x, y-1/2, -z+3/2; (iv) -x+1, y-1/2, -z+3/2; (v) x, -y+1/2, z-1/2; (vi) -x+1/2, y+1/2, -z+1/2; (vii) x+1/2, -y+3/2, z-1/2. |