Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100014256/bj1016sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100014256/bj1016Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100014256/bj1016IIsup3.hkl |
CCDC references: 158239; 158240
Complex (I): This compound was prepared by mixing EtOH solution (50 ml) of cadmium(II) bis(O,O'-diisopropyl dithiophosphate) (0.1 mmol) and phen (0.1 mmol) with heating. After cooling to room temperature and filtration, colorless single crystals suitable for X-ray analysis were obtained on slow evaporation of the solvent. Complex (II): this complex was prepared by using iron(II) bis(O,O'-diisopropyldithiophosphate) and phen in acetone solvent using the method as in complex (I). The dark red single crystals suitable for X-ray analysis were obtained on slow evaporation of the solvent.
After checking their presence in the difference map, all H-atom positions were placed at idealized positions and were allowed to ride on their parent carbon atoms. Due to the large fraction of weak data at higher angles in (II), the 2θ maximum for (II) is limited to 50°.
For both compounds, 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).
[Cd(C6H14O2PS2)2(C12H8N2)] | F(000) = 1472 |
Mr = 719.13 | Dx = 1.459 Mg m−3 |
Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2n 2ab | Cell parameters from 6966 reflections |
a = 11.7493 (1) Å | θ = 2.0–28.3° |
b = 19.0809 (3) Å | µ = 1.05 mm−1 |
c = 14.6006 (2) Å | T = 293 K |
V = 3273.27 (7) Å3 | Block, colourless |
Z = 4 | 0.46 × 0.42 × 0.36 mm |
Siemens SMART CCD area detector diffractometer | 4054 independent reflections |
Radiation source: fine-focus sealed tube | 2965 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.078 |
Detector resolution: 8.33 pixels mm-1 | θmax = 28.4°, θmin = 2.0° |
ω scans | h = −15→12 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −16→25 |
Tmin = 0.644, Tmax = 0.704 | l = −19→18 |
21589 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)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.168 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0962P)2 + 1.5469P] where P = (Fo2 + 2Fc2)/3 |
4054 reflections | (Δ/σ)max < 0.001 |
168 parameters | Δρmax = 1.03 e Å−3 |
0 restraints | Δρmin = −1.02 e Å−3 |
[Cd(C6H14O2PS2)2(C12H8N2)] | V = 3273.27 (7) Å3 |
Mr = 719.13 | Z = 4 |
Orthorhombic, Pbcn | Mo Kα radiation |
a = 11.7493 (1) Å | µ = 1.05 mm−1 |
b = 19.0809 (3) Å | T = 293 K |
c = 14.6006 (2) Å | 0.46 × 0.42 × 0.36 mm |
Siemens SMART CCD area detector diffractometer | 4054 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 2965 reflections with I > 2σ(I) |
Tmin = 0.644, Tmax = 0.704 | Rint = 0.078 |
21589 measured reflections |
R[F2 > 2σ(F2)] = 0.054 | 0 restraints |
wR(F2) = 0.168 | H-atom parameters constrained |
S = 1.07 | Δρmax = 1.03 e Å−3 |
4054 reflections | Δρmin = −1.02 e Å−3 |
168 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 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 | ||
Cd1 | 0.0000 | 0.190082 (18) | 0.2500 | 0.04888 (17) | |
P1 | −0.21444 (9) | 0.11766 (6) | 0.16000 (9) | 0.0589 (3) | |
S1 | −0.10398 (11) | 0.17045 (8) | 0.08559 (8) | 0.0776 (4) | |
S2 | −0.16992 (10) | 0.10456 (6) | 0.28886 (9) | 0.0665 (3) | |
O2 | −0.2503 (3) | 0.0454 (2) | 0.1180 (3) | 0.0931 (12) | |
O1 | −0.3345 (3) | 0.15485 (19) | 0.1671 (3) | 0.0848 (10) | |
N1 | −0.1055 (3) | 0.29127 (15) | 0.2900 (2) | 0.0477 (7) | |
C4 | −0.1800 (7) | −0.0036 (3) | 0.0699 (5) | 0.109 (2) | |
H4A | −0.1471 | 0.0213 | 0.0175 | 0.131* | |
C6 | −0.0854 (8) | −0.0346 (4) | 0.1205 (6) | 0.135 (3) | |
H6A | −0.0359 | 0.0019 | 0.1421 | 0.202* | |
H6B | −0.0437 | −0.0655 | 0.0809 | 0.202* | |
H6C | −0.1144 | −0.0606 | 0.1717 | 0.202* | |
C5 | −0.2648 (7) | −0.0557 (4) | 0.0320 (6) | 0.139 (3) | |
H5A | −0.3238 | −0.0310 | −0.0001 | 0.209* | |
H5B | −0.2975 | −0.0821 | 0.0814 | 0.209* | |
H5C | −0.2268 | −0.0870 | −0.0094 | 0.209* | |
C1 | −0.3908 (5) | 0.1841 (3) | 0.0882 (5) | 0.0900 (17) | |
H1A | −0.3414 | 0.1772 | 0.0348 | 0.108* | |
C2 | −0.4007 (11) | 0.2593 (5) | 0.1046 (9) | 0.221 (7) | |
H2A | −0.3265 | 0.2786 | 0.1156 | 0.331* | |
H2B | −0.4481 | 0.2672 | 0.1572 | 0.331* | |
H2C | −0.4340 | 0.2814 | 0.0520 | 0.331* | |
C3 | −0.4998 (6) | 0.1483 (6) | 0.0704 (8) | 0.177 (6) | |
H3A | −0.4861 | 0.0993 | 0.0603 | 0.266* | |
H3B | −0.5350 | 0.1682 | 0.0171 | 0.266* | |
H3C | −0.5492 | 0.1540 | 0.1222 | 0.266* | |
C7 | −0.0552 (3) | 0.35357 (18) | 0.2706 (2) | 0.0448 (8) | |
C8 | −0.2070 (4) | 0.2914 (2) | 0.3273 (3) | 0.0637 (10) | |
H8A | −0.2410 | 0.2487 | 0.3412 | 0.076* | |
C9 | −0.2664 (4) | 0.3533 (3) | 0.3468 (4) | 0.0751 (13) | |
H9A | −0.3387 | 0.3514 | 0.3726 | 0.090* | |
C10 | −0.2178 (4) | 0.4154 (2) | 0.3281 (3) | 0.0730 (13) | |
H10A | −0.2563 | 0.4567 | 0.3412 | 0.088* | |
C11 | −0.1098 (4) | 0.41773 (19) | 0.2890 (3) | 0.0577 (10) | |
C12 | −0.0520 (5) | 0.4815 (2) | 0.2681 (4) | 0.0785 (15) | |
H12A | −0.0876 | 0.5240 | 0.2802 | 0.118* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.0405 (2) | 0.0336 (2) | 0.0726 (3) | 0.000 | −0.00371 (16) | 0.000 |
P1 | 0.0474 (6) | 0.0508 (6) | 0.0786 (7) | −0.0086 (4) | −0.0097 (5) | −0.0022 (5) |
S1 | 0.0656 (8) | 0.1065 (10) | 0.0607 (6) | −0.0285 (7) | −0.0048 (5) | 0.0086 (6) |
S2 | 0.0655 (7) | 0.0562 (6) | 0.0778 (7) | −0.0186 (5) | 0.0021 (6) | 0.0104 (5) |
O2 | 0.085 (3) | 0.080 (2) | 0.114 (3) | −0.0264 (19) | −0.002 (2) | −0.023 (2) |
O1 | 0.059 (2) | 0.101 (3) | 0.094 (2) | 0.0079 (17) | −0.0029 (17) | 0.024 (2) |
N1 | 0.0436 (16) | 0.0386 (14) | 0.0610 (18) | 0.0038 (12) | 0.0008 (14) | 0.0027 (14) |
C4 | 0.119 (6) | 0.087 (4) | 0.122 (5) | −0.011 (4) | 0.004 (4) | −0.046 (4) |
C6 | 0.123 (7) | 0.101 (5) | 0.181 (8) | 0.007 (5) | 0.020 (6) | −0.016 (5) |
C5 | 0.187 (9) | 0.107 (5) | 0.125 (6) | −0.055 (5) | −0.012 (6) | −0.043 (4) |
C1 | 0.064 (3) | 0.105 (4) | 0.101 (4) | 0.000 (3) | −0.021 (3) | 0.017 (3) |
C2 | 0.255 (14) | 0.119 (7) | 0.289 (15) | 0.055 (8) | −0.163 (12) | −0.006 (8) |
C3 | 0.106 (7) | 0.176 (10) | 0.249 (13) | −0.048 (6) | −0.099 (7) | 0.074 (9) |
C7 | 0.047 (2) | 0.0382 (17) | 0.0490 (18) | 0.0078 (14) | −0.0104 (15) | −0.0021 (13) |
C8 | 0.053 (2) | 0.057 (2) | 0.081 (3) | 0.0061 (18) | 0.008 (2) | 0.006 (2) |
C9 | 0.055 (3) | 0.084 (3) | 0.086 (3) | 0.023 (2) | 0.012 (2) | −0.008 (3) |
C10 | 0.076 (3) | 0.057 (3) | 0.086 (3) | 0.025 (2) | −0.008 (2) | −0.014 (2) |
C11 | 0.061 (2) | 0.0409 (19) | 0.071 (2) | 0.0124 (16) | −0.018 (2) | −0.0053 (17) |
C12 | 0.087 (3) | 0.037 (2) | 0.112 (4) | 0.012 (2) | −0.031 (3) | −0.007 (2) |
Cd1—N1 | 2.368 (3) | N1—C7 | 1.358 (5) |
Cd1—N1i | 2.368 (3) | C4—C6 | 1.459 (11) |
Cd1—S2 | 2.6402 (10) | C4—C5 | 1.512 (8) |
Cd1—S2i | 2.6402 (10) | C1—C2 | 1.458 (10) |
Cd1—S1i | 2.7194 (12) | C1—C3 | 1.474 (8) |
Cd1—S1 | 2.7194 (12) | C7—C11 | 1.408 (5) |
P1—O2 | 1.566 (4) | C7—C7i | 1.429 (8) |
P1—O1 | 1.582 (4) | C8—C9 | 1.402 (6) |
P1—S2 | 1.9688 (18) | C9—C10 | 1.342 (7) |
P1—S1 | 1.9695 (16) | C10—C11 | 1.391 (7) |
O2—C4 | 1.432 (7) | C11—C12 | 1.427 (6) |
O1—C1 | 1.442 (6) | C12—C12i | 1.331 (12) |
N1—C8 | 1.311 (5) | ||
N1—Cd1—N1i | 70.73 (15) | P1—S2—Cd1 | 85.24 (5) |
N1—Cd1—S2 | 93.16 (8) | C4—O2—P1 | 127.7 (4) |
N1i—Cd1—S2 | 162.35 (8) | C1—O1—P1 | 122.0 (4) |
N1—Cd1—S2i | 162.35 (8) | C8—N1—C7 | 118.8 (3) |
N1i—Cd1—S2i | 93.16 (8) | C8—N1—Cd1 | 125.4 (3) |
S2—Cd1—S2i | 103.65 (6) | C7—N1—Cd1 | 115.8 (2) |
N1—Cd1—S1i | 97.44 (8) | O2—C4—C6 | 117.2 (6) |
N1i—Cd1—S1i | 95.46 (9) | O2—C4—C5 | 103.2 (6) |
S2—Cd1—S1i | 93.72 (4) | C6—C4—C5 | 114.9 (6) |
S2i—Cd1—S1i | 76.40 (4) | O1—C1—C2 | 106.6 (6) |
N1—Cd1—S1 | 95.46 (9) | O1—C1—C3 | 111.1 (6) |
N1i—Cd1—S1 | 97.44 (8) | C2—C1—C3 | 114.6 (8) |
S2—Cd1—S1 | 76.40 (4) | N1—C7—C11 | 121.5 (4) |
S2i—Cd1—S1 | 93.72 (4) | N1—C7—C7i | 118.9 (2) |
S1i—Cd1—S1 | 164.16 (7) | C11—C7—C7i | 119.6 (3) |
O2—P1—O1 | 100.4 (2) | N1—C8—C9 | 122.6 (4) |
O2—P1—S2 | 109.50 (18) | C10—C9—C8 | 119.4 (4) |
O1—P1—S2 | 103.35 (15) | C9—C10—C11 | 120.0 (4) |
O2—P1—S1 | 114.28 (17) | C10—C11—C7 | 117.7 (4) |
O1—P1—S1 | 113.22 (15) | C10—C11—C12 | 123.4 (4) |
S2—P1—S1 | 114.65 (7) | C7—C11—C12 | 118.9 (4) |
P1—S1—Cd1 | 83.08 (5) | C12i—C12—C11 | 121.5 (3) |
O2—P1—S1—Cd1 | −134.76 (19) | S1—Cd1—N1—C8 | 83.1 (3) |
O1—P1—S1—Cd1 | 111.07 (17) | N1i—Cd1—N1—C7 | 0.23 (17) |
S2—P1—S1—Cd1 | −7.17 (8) | S2—Cd1—N1—C7 | −172.4 (2) |
N1—Cd1—S1—P1 | −86.94 (9) | S2i—Cd1—N1—C7 | 25.3 (5) |
N1i—Cd1—S1—P1 | −158.17 (9) | S1i—Cd1—N1—C7 | 93.4 (2) |
S2—Cd1—S1—P1 | 5.00 (6) | S1—Cd1—N1—C7 | −95.8 (2) |
S2i—Cd1—S1—P1 | 108.15 (6) | P1—O2—C4—C6 | 62.5 (9) |
S1i—Cd1—S1—P1 | 57.52 (5) | P1—O2—C4—C5 | −170.2 (5) |
O2—P1—S2—Cd1 | 137.34 (17) | P1—O1—C1—C2 | −117.2 (8) |
O1—P1—S2—Cd1 | −116.33 (15) | P1—O1—C1—C3 | 117.4 (7) |
S1—P1—S2—Cd1 | 7.36 (8) | C8—N1—C7—C11 | −0.3 (5) |
N1—Cd1—S2—P1 | 89.88 (9) | Cd1—N1—C7—C11 | 178.6 (3) |
N1i—Cd1—S2—P1 | 66.3 (3) | C8—N1—C7—C7i | −179.6 (4) |
S2i—Cd1—S2—P1 | −95.55 (6) | Cd1—N1—C7—C7i | −0.7 (5) |
S1i—Cd1—S2—P1 | −172.44 (6) | C7—N1—C8—C9 | 0.7 (7) |
S1—Cd1—S2—P1 | −4.98 (6) | Cd1—N1—C8—C9 | −178.1 (4) |
O1—P1—O2—C4 | 159.5 (6) | N1—C8—C9—C10 | −0.8 (8) |
S2—P1—O2—C4 | −92.1 (6) | C8—C9—C10—C11 | 0.4 (8) |
S1—P1—O2—C4 | 38.0 (6) | C9—C10—C11—C7 | 0.0 (7) |
O2—P1—O1—C1 | −76.7 (4) | C9—C10—C11—C12 | −179.2 (5) |
S2—P1—O1—C1 | 170.2 (4) | N1—C7—C11—C10 | 0.0 (6) |
S1—P1—O1—C1 | 45.6 (4) | C7i—C7—C11—C10 | 179.2 (4) |
N1i—Cd1—N1—C8 | 179.0 (4) | N1—C7—C11—C12 | 179.2 (4) |
S2—Cd1—N1—C8 | 6.4 (3) | C7i—C7—C11—C12 | −1.6 (7) |
S2i—Cd1—N1—C8 | −155.9 (3) | C10—C11—C12—C12i | 179.1 (6) |
S1i—Cd1—N1—C8 | −87.7 (3) | C7—C11—C12—C12i | 0.0 (9) |
Symmetry code: (i) −x, y, −z+1/2. |
[Fe(C12H8N2)(C6H14O2PS2)2] | F(000) = 1384 |
Mr = 662.58 | Dx = 1.375 Mg m−3 |
Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2n 2ab | Cell parameters from 6556 reflections |
a = 11.5761 (2) Å | θ = 2.1–28.4° |
b = 18.8015 (1) Å | µ = 0.86 mm−1 |
c = 14.7098 (2) Å | T = 293 K |
V = 3201.56 (7) Å3 | Block, dark red |
Z = 4 | 0.32 × 0.28 × 0.20 mm |
Siemens SMART CCD area detector diffractometer | 2834 independent reflections |
Radiation source: fine-focus sealed tube | 1686 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.089 |
Detector resolution: 8.33 pixels mm-1 | θmax = 25.0°, θmin = 2.1° |
ω scans | h = −7→13 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −22→13 |
Tmin = 0.770, Tmax = 0.846 | l = −12→17 |
8551 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)] = 0.074 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.127 | H-atom parameters constrained |
S = 0.97 | w = 1/[σ2(Fo2) + (0.1222P)2] where P = (Fo2 + 2Fc2)/3 |
2834 reflections | (Δ/σ)max < 0.001 |
168 parameters | Δρmax = 1.02 e Å−3 |
0 restraints | Δρmin = −0.61 e Å−3 |
[Fe(C12H8N2)(C6H14O2PS2)2] | V = 3201.56 (7) Å3 |
Mr = 662.58 | Z = 4 |
Orthorhombic, Pbcn | Mo Kα radiation |
a = 11.5761 (2) Å | µ = 0.86 mm−1 |
b = 18.8015 (1) Å | T = 293 K |
c = 14.7098 (2) Å | 0.32 × 0.28 × 0.20 mm |
Siemens SMART CCD area detector diffractometer | 2834 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 1686 reflections with I > 2σ(I) |
Tmin = 0.770, Tmax = 0.846 | Rint = 0.089 |
8551 measured reflections |
R[F2 > 2σ(F2)] = 0.074 | 0 restraints |
wR(F2) = 0.127 | H-atom parameters constrained |
S = 0.97 | Δρmax = 1.02 e Å−3 |
2834 reflections | Δρmin = −0.61 e Å−3 |
168 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 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 | ||
Fe1 | 0.0000 | 0.31194 (5) | 0.2500 | 0.0409 (4) | |
P1 | −0.20786 (13) | 0.38234 (8) | 0.33768 (12) | 0.0525 (5) | |
S1 | −0.09554 (14) | 0.32606 (10) | 0.40749 (11) | 0.0665 (6) | |
S2 | −0.15747 (14) | 0.39888 (8) | 0.21160 (11) | 0.0565 (5) | |
O1 | −0.3302 (4) | 0.3447 (2) | 0.3283 (3) | 0.0734 (13) | |
O2 | −0.2469 (5) | 0.4532 (3) | 0.3844 (4) | 0.0915 (16) | |
N1 | −0.1036 (4) | 0.2188 (2) | 0.2085 (3) | 0.0421 (11) | |
C1 | −0.3890 (6) | 0.3155 (4) | 0.4078 (5) | 0.073 (2) | |
H1A | −0.3406 | 0.3229 | 0.4616 | 0.088* | |
C2 | −0.3979 (11) | 0.2369 (5) | 0.3890 (9) | 0.172 (6) | |
H2A | −0.3219 | 0.2175 | 0.3810 | 0.258* | |
H2B | −0.4424 | 0.2294 | 0.3348 | 0.258* | |
H2C | −0.4351 | 0.2138 | 0.4394 | 0.258* | |
C3 | −0.5002 (8) | 0.3518 (6) | 0.4210 (9) | 0.170 (6) | |
H3A | −0.4869 | 0.4016 | 0.4316 | 0.254* | |
H3B | −0.5393 | 0.3316 | 0.4725 | 0.254* | |
H3C | −0.5470 | 0.3461 | 0.3677 | 0.254* | |
C4 | −0.1777 (9) | 0.5052 (5) | 0.4270 (7) | 0.111 (3) | |
H4A | −0.1413 | 0.4809 | 0.4785 | 0.133* | |
C5 | −0.2635 (9) | 0.5568 (5) | 0.4693 (7) | 0.133 (4) | |
H5A | −0.3233 | 0.5305 | 0.4997 | 0.199* | |
H5B | −0.2971 | 0.5858 | 0.4225 | 0.199* | |
H5C | −0.2243 | 0.5866 | 0.5123 | 0.199* | |
C6 | −0.0844 (9) | 0.5382 (5) | 0.3782 (7) | 0.122 (3) | |
H6A | −0.0346 | 0.5022 | 0.3538 | 0.183* | |
H6B | −0.0412 | 0.5681 | 0.4188 | 0.183* | |
H6C | −0.1151 | 0.5665 | 0.3295 | 0.183* | |
C7 | −0.0553 (5) | 0.1550 (3) | 0.2279 (3) | 0.0401 (13) | |
C8 | −0.2059 (5) | 0.2191 (3) | 0.1679 (4) | 0.0551 (16) | |
H8A | −0.2396 | 0.2626 | 0.1538 | 0.066* | |
C9 | −0.2650 (6) | 0.1570 (4) | 0.1455 (5) | 0.0695 (19) | |
H9A | −0.3362 | 0.1594 | 0.1163 | 0.083* | |
C10 | −0.2184 (6) | 0.0932 (4) | 0.1662 (5) | 0.069 (2) | |
H10A | −0.2580 | 0.0516 | 0.1524 | 0.083* | |
C11 | −0.1104 (5) | 0.0901 (3) | 0.2085 (4) | 0.0553 (17) | |
C12 | −0.0522 (6) | 0.0249 (3) | 0.2310 (6) | 0.079 (2) | |
H12A | −0.0882 | −0.0183 | 0.2187 | 0.095* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.0367 (6) | 0.0294 (6) | 0.0565 (8) | 0.000 | −0.0014 (5) | 0.000 |
P1 | 0.0440 (9) | 0.0387 (8) | 0.0749 (12) | 0.0048 (7) | 0.0108 (8) | −0.0026 (7) |
S1 | 0.0557 (10) | 0.0902 (14) | 0.0537 (10) | 0.0231 (9) | 0.0040 (8) | 0.0049 (9) |
S2 | 0.0543 (9) | 0.0430 (9) | 0.0723 (12) | 0.0107 (8) | −0.0042 (8) | 0.0077 (7) |
O1 | 0.050 (2) | 0.078 (3) | 0.093 (3) | −0.009 (2) | 0.003 (3) | 0.019 (3) |
O2 | 0.092 (4) | 0.059 (3) | 0.124 (4) | 0.010 (3) | 0.023 (3) | −0.019 (3) |
N1 | 0.038 (2) | 0.033 (2) | 0.055 (3) | −0.001 (2) | −0.002 (2) | 0.001 (2) |
C1 | 0.054 (4) | 0.085 (5) | 0.080 (5) | −0.002 (4) | 0.012 (4) | 0.016 (4) |
C2 | 0.189 (12) | 0.091 (7) | 0.236 (14) | −0.060 (8) | 0.110 (10) | −0.003 (8) |
C3 | 0.109 (8) | 0.152 (10) | 0.248 (15) | 0.051 (8) | 0.101 (9) | 0.081 (10) |
C4 | 0.104 (7) | 0.089 (6) | 0.140 (8) | −0.004 (6) | 0.005 (7) | −0.059 (6) |
C5 | 0.182 (10) | 0.081 (6) | 0.135 (8) | 0.021 (7) | 0.046 (7) | −0.046 (6) |
C6 | 0.108 (8) | 0.083 (6) | 0.174 (10) | 0.007 (6) | −0.004 (7) | −0.032 (7) |
C7 | 0.046 (3) | 0.029 (3) | 0.046 (3) | −0.005 (3) | 0.011 (3) | −0.003 (2) |
C8 | 0.050 (4) | 0.055 (4) | 0.061 (4) | −0.008 (3) | −0.009 (3) | 0.000 (3) |
C9 | 0.049 (4) | 0.080 (5) | 0.080 (5) | −0.021 (4) | −0.009 (4) | −0.012 (4) |
C10 | 0.069 (5) | 0.052 (4) | 0.086 (5) | −0.026 (4) | 0.007 (4) | −0.014 (3) |
C11 | 0.059 (4) | 0.035 (3) | 0.072 (4) | −0.011 (3) | 0.021 (3) | −0.009 (3) |
C12 | 0.090 (5) | 0.025 (3) | 0.123 (7) | −0.009 (3) | 0.036 (5) | −0.004 (3) |
Fe1—N1 | 2.209 (4) | N1—C7 | 1.354 (6) |
Fe1—N1i | 2.209 (4) | C1—C3 | 1.470 (10) |
Fe1—S2 | 2.513 (2) | C1—C2 | 1.506 (11) |
Fe1—S2i | 2.5127 (16) | C4—C6 | 1.438 (11) |
Fe1—S1 | 2.581 (2) | C4—C5 | 1.520 (11) |
Fe1—S1i | 2.5808 (17) | C7—C11 | 1.406 (7) |
P1—O2 | 1.566 (5) | C7—C7i | 1.435 (11) |
P1—O1 | 1.589 (4) | C8—C9 | 1.393 (8) |
P1—S1 | 1.966 (2) | C9—C10 | 1.349 (9) |
P1—S2 | 1.969 (2) | C10—C11 | 1.398 (9) |
O1—C1 | 1.460 (8) | C11—C12 | 1.438 (8) |
O2—C4 | 1.412 (9) | C12—C12i | 1.331 (15) |
N1—C8 | 1.327 (7) | ||
N1—Fe1—N1i | 75.1 (2) | P1—S2—Fe1 | 84.29 (7) |
N1—Fe1—S2 | 93.44 (11) | C1—O1—P1 | 120.9 (4) |
N1i—Fe1—S2 | 166.38 (12) | C4—O2—P1 | 128.4 (5) |
N1—Fe1—S2i | 166.38 (12) | C8—N1—C7 | 117.9 (5) |
N1i—Fe1—S2i | 93.44 (11) | C8—N1—Fe1 | 127.2 (4) |
S2—Fe1—S2i | 98.84 (8) | C7—N1—Fe1 | 114.8 (3) |
N1—Fe1—S1 | 95.56 (12) | O1—C1—C3 | 109.9 (7) |
N1i—Fe1—S1 | 93.80 (12) | O1—C1—C2 | 104.7 (6) |
S2—Fe1—S1 | 79.86 (6) | C3—C1—C2 | 114.9 (9) |
S2i—Fe1—S1 | 92.42 (6) | O2—C4—C6 | 120.2 (8) |
N1—Fe1—S1i | 93.80 (12) | O2—C4—C5 | 104.6 (8) |
N1i—Fe1—S1i | 95.56 (12) | C6—C4—C5 | 114.8 (8) |
S2—Fe1—S1i | 92.42 (6) | N1—C7—C11 | 122.6 (5) |
S2i—Fe1—S1i | 79.86 (6) | N1—C7—C7i | 117.6 (3) |
S1—Fe1—S1i | 168.19 (10) | C11—C7—C7i | 119.8 (4) |
O2—P1—O1 | 99.2 (3) | N1—C8—C9 | 122.7 (6) |
O2—P1—S1 | 114.8 (2) | C10—C9—C8 | 119.7 (6) |
O1—P1—S1 | 113.27 (19) | C9—C10—C11 | 119.7 (6) |
O2—P1—S2 | 111.4 (2) | C10—C11—C7 | 117.4 (6) |
O1—P1—S2 | 104.6 (2) | C10—C11—C12 | 123.9 (6) |
S1—P1—S2 | 112.40 (10) | C7—C11—C12 | 118.7 (6) |
P1—S1—Fe1 | 82.53 (7) | C12i—C12—C11 | 121.5 (4) |
O2—P1—S1—Fe1 | −137.2 (2) | S1i—Fe1—N1—C8 | −85.5 (5) |
O1—P1—S1—Fe1 | 109.9 (2) | N1i—Fe1—N1—C7 | 0.0 (3) |
S2—P1—S1—Fe1 | −8.47 (10) | S2—Fe1—N1—C7 | −172.5 (3) |
N1—Fe1—S1—P1 | −86.29 (13) | S2i—Fe1—N1—C7 | 33.1 (8) |
N1i—Fe1—S1—P1 | −161.62 (13) | S1—Fe1—N1—C7 | −92.4 (4) |
S2—Fe1—S1—P1 | 6.22 (7) | S1i—Fe1—N1—C7 | 94.8 (4) |
S2i—Fe1—S1—P1 | 104.77 (8) | P1—O1—C1—C3 | 118.6 (7) |
S1i—Fe1—S1—P1 | 55.99 (7) | P1—O1—C1—C2 | −117.5 (8) |
O2—P1—S2—Fe1 | 139.1 (2) | P1—O2—C4—C6 | 55.7 (12) |
O1—P1—S2—Fe1 | −114.64 (19) | P1—O2—C4—C5 | −173.4 (6) |
S1—P1—S2—Fe1 | 8.67 (10) | C8—N1—C7—C11 | −1.4 (8) |
N1—Fe1—S2—P1 | 88.85 (13) | Fe1—N1—C7—C11 | 178.3 (4) |
N1i—Fe1—S2—P1 | 57.0 (5) | C8—N1—C7—C7i | −179.9 (6) |
S2i—Fe1—S2—P1 | −97.08 (7) | Fe1—N1—C7—C7i | −0.1 (7) |
S1—Fe1—S2—P1 | −6.19 (7) | C7—N1—C8—C9 | 0.5 (9) |
S1i—Fe1—S2—P1 | −177.19 (7) | Fe1—N1—C8—C9 | −179.2 (5) |
O2—P1—O1—C1 | −73.0 (5) | N1—C8—C9—C10 | 0.8 (10) |
S1—P1—O1—C1 | 49.2 (5) | C8—C9—C10—C11 | −1.2 (10) |
S2—P1—O1—C1 | 171.9 (4) | C9—C10—C11—C7 | 0.3 (9) |
O1—P1—O2—C4 | 167.0 (7) | C9—C10—C11—C12 | −178.2 (7) |
S1—P1—O2—C4 | 45.9 (8) | N1—C7—C11—C10 | 1.0 (9) |
S2—P1—O2—C4 | −83.3 (8) | C7i—C7—C11—C10 | 179.5 (6) |
N1i—Fe1—N1—C8 | 179.7 (6) | N1—C7—C11—C12 | 179.6 (6) |
S2—Fe1—N1—C8 | 7.1 (5) | C7i—C7—C11—C12 | −2.0 (10) |
S2i—Fe1—N1—C8 | −147.2 (4) | C10—C11—C12—C12i | 178.1 (9) |
S1—Fe1—N1—C8 | 87.3 (5) | C7—C11—C12—C12i | −0.4 (13) |
Symmetry code: (i) −x, y, −z+1/2. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Cd(C6H14O2PS2)2(C12H8N2)] | [Fe(C12H8N2)(C6H14O2PS2)2] |
Mr | 719.13 | 662.58 |
Crystal system, space group | Orthorhombic, Pbcn | Orthorhombic, Pbcn |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 11.7493 (1), 19.0809 (3), 14.6006 (2) | 11.5761 (2), 18.8015 (1), 14.7098 (2) |
V (Å3) | 3273.27 (7) | 3201.56 (7) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.05 | 0.86 |
Crystal size (mm) | 0.46 × 0.42 × 0.36 | 0.32 × 0.28 × 0.20 |
Data collection | ||
Diffractometer | Siemens SMART CCD area detector diffractometer | Siemens SMART CCD area detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.644, 0.704 | 0.770, 0.846 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 21589, 4054, 2965 | 8551, 2834, 1686 |
Rint | 0.078 | 0.089 |
(sin θ/λ)max (Å−1) | 0.668 | 0.595 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.168, 1.07 | 0.074, 0.127, 0.97 |
No. of reflections | 4054 | 2834 |
No. of parameters | 168 | 168 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.03, −1.02 | 1.02, −0.61 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).
I | II | |
M-N1 | 2.368 (3) | 2.209 (4) |
M-S1 | 2.719 (1) | 2.581 (2) |
M-S2 | 2.640 (1) | 2.513 (2) |
P1-S1 | 1.970 (2) | 1.966 (2) |
P1-S2 | 1.969 (2) | 1.969 (2) |
N1-M-N1i | 70.73 (15) | 75.1 (2) |
S2-M-S1 | 76.40 (4) | 79.86 (6) |
M = Cd (I), Fe (II); symmetry code i: -x, y, -z+1/2 |
Metal dialkyl dithiophosphates and their derivatives have been widely employed both as antioxidant and antiwear additives in rubber and as lubricating oils (Harrison & Kikabhai, 1987; Kovtun et al., 1992). Adducts and their formation reactions have also been found useful in a wide variety of ways, such as with biological systems (Livingstone & Mihkelson, 1970). Metal complex ions of the type [M(LL)3], where LL is either 1,10-phenanthroline (phen) or a modified phen ligand, are particularly attractive species for developing new diagnostic and therapeutic agents which can recognize and cleave DNA (Barton, 1986; Naing et al., 1995). Furthermore, cadmium is often substituted in the proteins and used to aid in the determination of the coordination environment of the native metal, primarily because of the usefulness of Cd NMR. Also a series of potential models, [M(SR)x(N-donor)(4 - x)] (M = Zn, Co, Cd) have been reported for cysteine containing zinc metalloproteins (Santos et al., 1990). The original CoII(dtp)2 is easily oxidized. However, similar complexes are very stable in air. Fe(II)(dtp)2 and its adducts are also expected to have this property. The title adducts, (I) and (II), were prepared and the structures were determined so that the determination of the equilibrium constants can be done to confirm the property. \sch
In complex (I), the Cd—N bond length is comparable with the complexes of [Cd{(n-BuS2CS)2}(bipy)] [2.368 (3) Å] (Black et al., 1986). It is however shorter than those of [Cd{(Et)2NCS2}(bipy) [2.434 (6) Å] (Glinskaya et al., 1992) but longer than those of [Cd(C24H18O4)(bipy)] [2.342 (5), 2.355 (5) Å; Annan et al., 1990). The Fe—N bond length in complex (II) is comparable to those of the complex [Fe(phen)2PhCOO]2OCl2·7H2O [2.221 (4), 2.168 (3), 2.139 (3) and 2.270 (3) Å] (Li et al., 1995).
The Cd—S distances in (I) are in good agreement with [Cd(II){(Et-dtp)2}(hex)2] [2.682 (1), 2.704 (1) Å] (Shimoi et al., 1982). However, the Cd—S bond lengths are longer than those found in tetrahedral configuration, [Cd(II)(iPr-dtp)2] [2.486 (7), 2.590 (8) Å] (Lawton & Kokotailo, 1969) but shorter than those in [Cd{(iPr-dtp)2}(NMe4)] [2.659 (1), 2.777 (2) Å] (McCleverty et al., 1982). Fe—S bond distances in (II), the FeII—S distances are are longer than FeIII—S reported by Drew et al., 1986 [2.461 (2), 2.492 (2), 2.473 (2) Å].
The P—S distances in the dtp groups in (I) and (II) are nearly identical, and are intermediate between the single bond (2.09 Å) and the double bond (1.87 Å) values.
In (I), the S1—Cd1—S2 bond angle is larger than those found in [Cd{(iPr-dtp)2}(NMe4)] [74.9 (5)°] and [Cd{(Et)2NCS2}(bipy)] [67.3 (1), 68.5 (2)°]. The N1—Cd1—N1A bond angle is in good agreement with those of [Cd(phen)3](ClO4)2 [71.7 (1)°; Xiong et al., 1997]. In (II), the S1—Fe1—S2 bond angle is 79.8 (7)°. The N1—Fe1—N1a bond angle [75.1 (2)°] is similar to that of the six-coordiate compound [Fe(phen)2ph]2OCl·7H2O [75.1 (1)°; Li et al., 1995].
The coordination around Cd1 in (I) and Fe1 in (II) is a distorted octahedron with bond angles ranging from 70.7 (2) to 164.2 (1)° and 75.1 (2) to 168.2 (1)°, respectively. The central metal atom is coordinated to four S atoms from the two dtp groups and two N atoms from the 1,10-phenanthroline ligand. In both complexes, the four-membered ring formed by M1, S1, S2, and P1 atoms is almost planar. This plane and the plane through M1, N1, C7, N1A and C7A atoms make a dihedral angle of 86.5 (1) and 86.9° for (I) and (II), respectively.