Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101020789/os1146sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101020789/os1146Isup2.hkl |
CCDC reference: 181987
The preparation of the title complex was divided into two steps. The first step was the preparation of Cu[(EtO)2PS2]2, which followed the method of Drew et al. (1987). Cu[(EtO)2PS2]2 was obtained as a brown solid and 5 mmol was dissolved in of ethanol (20 ml). The second step was the preparation of [CuIIen2][(EtO)2P(S)S–]2. En (10 mmol) was added with stirring to an ethanol solution of Cu[(EtO)2PS2]2. A deep-blue solution formed immediately. As the EtOH evaporated slowly, purple single crystals of [CuIIen2][(EtO)2P(S)S]2 suitable for X-ray analysis were obtained.
After checking their presence in the difference map, all H atoms were fixed geometrically and allowed to ride on their parent C and N atoms in the refinement.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).
Fig. 1. The structure of the title complex showing 50% probability displacement ellipsoids and the atom-numbering scheme. |
[Cu(C2H8N2)](C4H10O2PS2)2 | F(000) = 582 |
Mr = 554.22 | Dx = 1.426 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 14.6683 (3) Å | Cell parameters from 5321 reflections |
b = 6.9409 (1) Å | θ = 1.5–28.3° |
c = 13.5889 (1) Å | µ = 1.32 mm−1 |
β = 111.157 (1)° | T = 293 K |
V = 1290.25 (3) Å3 | Slab, purple |
Z = 2 | 0.36 × 0.14 × 0.12 mm |
Siemens SMART CCD area-detector diffractometer | 3144 independent reflections |
Radiation source: fine-focus sealed tube | 2125 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.089 |
Detector resolution: 8.33 pixels mm-1 | θmax = 28.3°, θmin = 1.5° |
ω scans | h = −19→11 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −9→9 |
Tmin = 0.649, Tmax = 0.858 | l = −15→18 |
8941 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.106 | H-atom parameters constrained |
S = 0.92 | w = 1/[σ2(Fo2) + (0.0254P)2] where P = (Fo2 + 2Fc2)/3 |
3144 reflections | (Δ/σ)max < 0.001 |
126 parameters | Δρmax = 0.55 e Å−3 |
0 restraints | Δρmin = −1.14 e Å−3 |
[Cu(C2H8N2)](C4H10O2PS2)2 | V = 1290.25 (3) Å3 |
Mr = 554.22 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.6683 (3) Å | µ = 1.32 mm−1 |
b = 6.9409 (1) Å | T = 293 K |
c = 13.5889 (1) Å | 0.36 × 0.14 × 0.12 mm |
β = 111.157 (1)° |
Siemens SMART CCD area-detector diffractometer | 3144 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 2125 reflections with I > 2σ(I) |
Tmin = 0.649, Tmax = 0.858 | Rint = 0.089 |
8941 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.106 | H-atom parameters constrained |
S = 0.92 | Δρmax = 0.55 e Å−3 |
3144 reflections | Δρmin = −1.14 e Å−3 |
126 parameters |
Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 10 s covered 0.3° in ω. The crystal-to-detector distance was 4 cm and the detector swing angle was -35°. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the intensity of duplicate reflections, and was found to be negligible. |
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 | ||
Cu1 | 0.0000 | 0.5000 | 0.0000 | 0.03526 (16) | |
P1 | −0.21830 (5) | 0.17834 (10) | 0.02951 (6) | 0.02969 (18) | |
S1 | −0.11126 (6) | 0.13620 (10) | −0.02282 (6) | 0.0376 (2) | |
S2 | −0.19133 (6) | 0.31888 (11) | 0.16269 (6) | 0.0423 (2) | |
O1 | −0.30857 (15) | 0.2898 (3) | −0.05542 (15) | 0.0394 (5) | |
O2 | −0.26241 (15) | −0.0331 (3) | 0.03245 (16) | 0.0381 (5) | |
N1 | 0.03236 (19) | 0.4767 (3) | 0.15711 (18) | 0.0413 (6) | |
H1A | 0.0566 | 0.5888 | 0.1892 | 0.050* | |
H1B | −0.0218 | 0.4479 | 0.1705 | 0.050* | |
N4 | 0.1241 (2) | 0.3484 (3) | 0.0280 (2) | 0.0420 (6) | |
H4A | 0.1097 | 0.2279 | 0.0028 | 0.050* | |
H4B | 0.1608 | 0.4046 | −0.0046 | 0.050* | |
C2 | 0.1057 (3) | 0.3217 (4) | 0.1968 (3) | 0.0486 (8) | |
H2B | 0.0742 | 0.1966 | 0.1811 | 0.058* | |
H2A | 0.1383 | 0.3327 | 0.2726 | 0.058* | |
C3 | 0.1782 (3) | 0.3431 (5) | 0.1430 (3) | 0.0510 (9) | |
H3B | 0.2153 | 0.4610 | 0.1658 | 0.061* | |
H3A | 0.2234 | 0.2354 | 0.1609 | 0.061* | |
C7 | −0.3500 (3) | 0.2163 (5) | −0.1622 (2) | 0.0528 (9) | |
H7A | −0.3744 | 0.0865 | −0.1621 | 0.063* | |
H7B | −0.3007 | 0.2134 | −0.1943 | 0.063* | |
C8 | −0.4318 (3) | 0.3484 (7) | −0.2227 (3) | 0.0767 (13) | |
H8A | −0.4590 | 0.3073 | −0.2949 | 0.115* | |
H8B | −0.4073 | 0.4774 | −0.2195 | 0.115* | |
H8C | −0.4816 | 0.3452 | −0.1923 | 0.115* | |
C5 | −0.3477 (3) | −0.0558 (5) | 0.0606 (3) | 0.0540 (9) | |
H5A | −0.3992 | 0.0297 | 0.0183 | 0.065* | |
H5B | −0.3318 | −0.0231 | 0.1343 | 0.065* | |
C6 | −0.3810 (3) | −0.2565 (6) | 0.0422 (4) | 0.0790 (13) | |
H6A | −0.4420 | −0.2693 | 0.0526 | 0.119* | |
H6B | −0.3331 | −0.3390 | 0.0907 | 0.119* | |
H6C | −0.3895 | −0.2925 | −0.0288 | 0.119* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0420 (3) | 0.0313 (3) | 0.0356 (3) | 0.0067 (2) | 0.0178 (2) | −0.0020 (2) |
P1 | 0.0313 (4) | 0.0268 (3) | 0.0340 (4) | 0.0026 (3) | 0.0154 (3) | 0.0006 (3) |
S1 | 0.0373 (4) | 0.0298 (4) | 0.0547 (5) | −0.0046 (3) | 0.0273 (4) | −0.0086 (3) |
S2 | 0.0510 (5) | 0.0449 (4) | 0.0357 (4) | 0.0019 (4) | 0.0213 (4) | −0.0054 (3) |
O1 | 0.0394 (13) | 0.0429 (11) | 0.0358 (10) | 0.0125 (10) | 0.0134 (10) | 0.0038 (9) |
O2 | 0.0365 (12) | 0.0320 (10) | 0.0549 (12) | −0.0029 (9) | 0.0276 (11) | 0.0013 (9) |
N1 | 0.0425 (16) | 0.0434 (14) | 0.0406 (14) | −0.0102 (12) | 0.0182 (13) | −0.0078 (11) |
N4 | 0.0443 (16) | 0.0292 (12) | 0.0570 (16) | 0.0009 (11) | 0.0236 (14) | −0.0004 (11) |
C2 | 0.053 (2) | 0.0439 (18) | 0.0410 (17) | −0.0068 (16) | 0.0069 (16) | 0.0037 (14) |
C3 | 0.0383 (19) | 0.0412 (17) | 0.064 (2) | 0.0024 (15) | 0.0076 (18) | 0.0003 (15) |
C7 | 0.049 (2) | 0.064 (2) | 0.0410 (18) | −0.0030 (18) | 0.0111 (17) | −0.0003 (16) |
C8 | 0.048 (2) | 0.121 (4) | 0.053 (2) | 0.006 (2) | 0.007 (2) | 0.025 (2) |
C5 | 0.046 (2) | 0.060 (2) | 0.071 (2) | −0.0054 (17) | 0.039 (2) | 0.0034 (18) |
C6 | 0.053 (3) | 0.064 (2) | 0.130 (4) | −0.014 (2) | 0.045 (3) | 0.013 (3) |
Cu1—N4i | 2.016 (2) | C2—H2B | 0.9700 |
Cu1—N4 | 2.016 (2) | C2—H2A | 0.9700 |
Cu1—N1 | 2.019 (2) | C3—H3B | 0.9700 |
Cu1—N1i | 2.019 (2) | C3—H3A | 0.9700 |
P1—O1 | 1.606 (2) | C7—C8 | 1.498 (5) |
P1—O2 | 1.6098 (19) | C7—H7A | 0.9700 |
P1—S1 | 1.9652 (10) | C7—H7B | 0.9700 |
P1—S2 | 1.9664 (10) | C8—H8A | 0.9600 |
O1—C7 | 1.449 (4) | C8—H8B | 0.9600 |
O2—C5 | 1.442 (3) | C8—H8C | 0.9600 |
N1—C2 | 1.478 (4) | C5—C6 | 1.467 (5) |
N1—H1A | 0.9000 | C5—H5A | 0.9700 |
N1—H1B | 0.9000 | C5—H5B | 0.9700 |
N4—C3 | 1.477 (4) | C6—H6A | 0.9600 |
N4—H4A | 0.9000 | C6—H6B | 0.9600 |
N4—H4B | 0.9000 | C6—H6C | 0.9600 |
C2—C3 | 1.500 (5) | ||
N4i—Cu1—N4 | 180.0 | H2B—C2—H2A | 108.5 |
N4i—Cu1—N1 | 95.33 (10) | N4—C3—C2 | 108.3 (3) |
N4—Cu1—N1 | 84.67 (10) | N4—C3—H3B | 110.0 |
N4i—Cu1—N1i | 84.67 (10) | C2—C3—H3B | 110.0 |
N4—Cu1—N1i | 95.33 (10) | N4—C3—H3A | 110.0 |
N1—Cu1—N1i | 180.00 (13) | C2—C3—H3A | 110.0 |
O1—P1—O2 | 102.84 (11) | H3B—C3—H3A | 108.4 |
O1—P1—S1 | 111.76 (8) | O1—C7—C8 | 107.3 (3) |
O2—P1—S1 | 104.72 (8) | O1—C7—H7A | 110.3 |
O1—P1—S2 | 105.20 (8) | C8—C7—H7A | 110.3 |
O2—P1—S2 | 112.24 (8) | O1—C7—H7B | 110.3 |
S1—P1—S2 | 119.03 (5) | C8—C7—H7B | 110.3 |
C7—O1—P1 | 119.28 (19) | H7A—C7—H7B | 108.5 |
C5—O2—P1 | 120.08 (19) | C7—C8—H8A | 109.5 |
C2—N1—Cu1 | 107.85 (18) | C7—C8—H8B | 109.5 |
C2—N1—H1A | 110.1 | H8A—C8—H8B | 109.5 |
Cu1—N1—H1A | 110.1 | C7—C8—H8C | 109.5 |
C2—N1—H1B | 110.1 | H8A—C8—H8C | 109.5 |
Cu1—N1—H1B | 110.1 | H8B—C8—H8C | 109.5 |
H1A—N1—H1B | 108.4 | O2—C5—C6 | 109.0 (3) |
C3—N4—Cu1 | 108.47 (19) | O2—C5—H5A | 109.9 |
C3—N4—H4A | 110.0 | C6—C5—H5A | 109.9 |
Cu1—N4—H4A | 110.0 | O2—C5—H5B | 109.9 |
C3—N4—H4B | 110.0 | C6—C5—H5B | 109.9 |
Cu1—N4—H4B | 110.0 | H5A—C5—H5B | 108.3 |
H4A—N4—H4B | 108.4 | C5—C6—H6A | 109.5 |
N1—C2—C3 | 107.5 (2) | C5—C6—H6B | 109.5 |
N1—C2—H2B | 110.2 | H6A—C6—H6B | 109.5 |
C3—C2—H2B | 110.2 | C5—C6—H6C | 109.5 |
N1—C2—H2A | 110.2 | H6A—C6—H6C | 109.5 |
C3—C2—H2A | 110.2 | H6B—C6—H6C | 109.5 |
O2—P1—O1—C7 | −59.5 (2) | N1—Cu1—N4—C3 | −12.11 (19) |
S1—P1—O1—C7 | 52.3 (2) | N1i—Cu1—N4—C3 | 167.89 (19) |
S2—P1—O1—C7 | −177.2 (2) | Cu1—N1—C2—C3 | 41.7 (3) |
O1—P1—O2—C5 | −58.8 (3) | Cu1—N4—C3—C2 | 38.3 (3) |
S1—P1—O2—C5 | −175.8 (2) | N1—C2—C3—N4 | −53.3 (3) |
S2—P1—O2—C5 | 53.7 (2) | P1—O1—C7—C8 | −179.9 (2) |
N4i—Cu1—N1—C2 | 163.41 (19) | P1—O2—C5—C6 | 171.7 (3) |
N4—Cu1—N1—C2 | −16.59 (19) |
Symmetry code: (i) −x, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···S2ii | 0.90 | 2.76 | 3.599 (2) | 155 |
N1—H1B···S2 | 0.90 | 2.61 | 3.486 (3) | 165 |
N4—H4A···S1iii | 0.90 | 2.54 | 3.368 (2) | 153 |
Symmetry codes: (ii) −x, y+1/2, −z+1/2; (iii) −x, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C2H8N2)](C4H10O2PS2)2 |
Mr | 554.22 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 14.6683 (3), 6.9409 (1), 13.5889 (1) |
β (°) | 111.157 (1) |
V (Å3) | 1290.25 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.32 |
Crystal size (mm) | 0.36 × 0.14 × 0.12 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.649, 0.858 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8941, 3144, 2125 |
Rint | 0.089 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.106, 0.92 |
No. of reflections | 3144 |
No. of parameters | 126 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.55, −1.14 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).
Cu1—N4 | 2.016 (2) | O2—C5 | 1.442 (3) |
Cu1—N1 | 2.019 (2) | N1—C2 | 1.478 (4) |
P1—O1 | 1.606 (2) | N4—C3 | 1.477 (4) |
P1—O2 | 1.6098 (19) | C2—C3 | 1.500 (5) |
P1—S1 | 1.9652 (10) | C7—C8 | 1.498 (5) |
P1—S2 | 1.9664 (10) | C5—C6 | 1.467 (5) |
O1—C7 | 1.449 (4) | ||
N4i—Cu1—N1 | 95.33 (10) | O2—P1—S2 | 112.24 (8) |
N4—Cu1—N1 | 84.67 (10) | S1—P1—S2 | 119.03 (5) |
O1—P1—O2 | 102.84 (11) | C7—O1—P1 | 119.28 (19) |
O1—P1—S1 | 111.76 (8) | C5—O2—P1 | 120.08 (19) |
O2—P1—S1 | 104.72 (8) | C2—N1—Cu1 | 107.85 (18) |
O1—P1—S2 | 105.20 (8) |
Symmetry code: (i) −x, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···S2ii | 0.90 | 2.7632 | 3.599 (2) | 155 |
N1—H1B···S2 | 0.90 | 2.6089 | 3.486 (3) | 165 |
N4—H4A···S1iii | 0.90 | 2.5410 | 3.368 (2) | 153 |
Symmetry codes: (ii) −x, y+1/2, −z+1/2; (iii) −x, −y, −z. |
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Compounds of bivalent copper exhibit different coordination arrangements, some being apparently four-coordinate, whereas others are generally five- and occasionally six-coordinate. The ligand-field strength of the donors is an important factor; weaker ligands may lead to an increased coordination number (Baker et al., 1970). Usually, the donor capacity of the ligands decreases in the following order en > phen > dmp (Kudrev, 1994).
Dialkyl dithiophosphates have extensive applications, such as antioxidants and antiwear additives in the rubber industry and in lubrication engineering (Kovtun et al., 1992; Harrison & Kikabhai, 1987), as well as flotation agents for mineral ores and solvent extraction reagents for metals (Haiduc et al., 1995; Rickelton & Boyle, 1990).
The reactions of copper(II) with the (RO)2P(S)S- ion and nitrogen base ligands have been investigated (Lawton et al., 1972; Yordanov et al., 1993; Drew et al., 1987). These copper(II) complexes can cause DNA damage in the presence of H2O2. It was reported that CuII(en)2 (en is ethylenediamine) and hydrogen peroxide at physiological conditions could cause the DNA strand to break (Ozawa et al., 1993). Additionally, CuII(en)2 complexes may be used as good catalysts for all oxidizers, and the catalytic activities for all oxidizers decreased in the order Cu > Ni> Cd >> Zn (Sinditskii et al., 1994).
In order to investigate the properties of the (EtO)2P(S)S- ion complexed with CuII(en)2, the title complex, (I), was synthesized and an X-ray crystal structure analysis undertaken.
The asymmetric unit of (I) consists one half of the complex molecule, and the unit cell contains two complexes. One half of the complex is related to the other by an inversion center at the Cu atom. The Cu atom is coordinated by four N atoms in a slightly distorted square coordination geometry. The Cu—N bond lengths are 2.016 (2) and 2.019 (2) Å, and the N—Cu—N bond angles are 84.6 (1) and 95.3 (1)°. The Cu—N values are normal for primary amines (Allen et al., 1987). The bond lengths and angles of the title complex are comparable with those in a previous report of the same complex (Pervukhina & Podbereskaya, 1985), but the structure was solved in the wrong space group, P21. However, intensity statistics, as well as systematic extinctions, clearly indicate the space group to be P21/c. The Cu—N bond lengths are in good agreement with those observed in Cu(en)[N(NO2)CH3]2 [Cu—N = 2.019 (3) Å] (Palopoli et al., 1988), while the N—Cu—N angles are slightly outside the bite-angle range for ethylenediamine in CuII complexes, typically 85–86° (Palopoli et al., 1988).
The CuII–ethylenediamine complex molecule is not planar and adopts a twisted conformation. Atoms N1, N4, C2 and C3 deviate by 0.160 (2), -0.126 (2), -0.286 (3) and 0.267 (4) Å, respectively, from the mean plane of the CuII–ethylenediamine moiety, while the dihedral angle between the Cu1/N1/C2 and Cu1/N4/C3 planes is 19.5 (2)°.
In the (EtO)2P(S)S- anion, the P atom is coordinated tetrahedrally by two S atoms and two O atoms. The bond lengths around the P atom correspond to a P═S double bond and the P—O bond of an alkoxy O atom. The angles around the P atom are in the range 102.84 (11)–119.03 (5)°, implying a distorted tetrahedral coordination geometry for the P atom. The two ethoxy groups attached to the P atoms are nearly planar and make a dihedral angle of 86.3 (2)° with one another.
The crystal structure of the title complex is built from alternating molecular layers of CuII–ethylenediamine and (EtO)2P(S)S- stacked along the c axis. Atoms S1 and S2 are involved in intermolecular interactions with the amine groups. These interactions link the molecular layers into a three-dimensional arrangement.