Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105041247/ob1246sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105041247/ob1246Isup2.hkl |
CCDC reference: 299616
Compound (I) was prepared using a procedure similar to that of Matsushita (1993). Golden plate-like crystals were obtained by recrystallization from an aqueous solution on slow evaporation.
A PLATON (Spek, 2003) analysis of (I) pointed out the possible presence of two additional symmetry axes, viz. a mirror plane perpendicular to the a axis and an n-glide plane perpendicular to the c axis, and suggested a proposed space group, Pmnn (No. 58). A detailed check of the reflections observed, however, indicates that the Laue class is still 2/m. The Rint value was 0.152 if the Laue class mmm was assumed. A refinement in the space group Pmnn could not be performed successfully. H atoms attached to C and N atoms were placed in geometrically calculated positions. H atoms of the phosphate ions were located at positions calculated on the basis of whether the P—O distances were long or short. As the result, the H atoms were attached to atoms O14, O23 and O24, which have longer P—O distances than the others. H atoms attached to atoms O31 and O32 of the water molecules were placed in positions satisfying their hydrogen-bonding geometry. Atom H33A of the other water molecule (O33) was also placed in a position based on the hydrogen bond between atoms O33 and O11. Atom H33B was placed in a position generated using an HFIX instruction, because the O33/H33B group does not have a hydrogen-bond acceptor. All H atoms were refined as riding (C—H = 0.97 Å, N—H = 0.90 Å and O—H = 0.82 Å), with the constraint Uiso(H) = 1.5Ueq(C,N,O). The highest peak in the difference map is located 0.94 Å from atom Pt2 and the deepest hole is located 0.86 Å from atom Pt1.
Data collection: AFC Diffractometer Control Software (Rigaku, 1987); cell refinement: AFC Diffractometer Control Software; data reduction: AFC Diffractometer Control Software and local program F2-AFC (Matsushita, 1998); program(s) used to solve structure: SHELX76 (Sheldrick, 1976); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2005); software used to prepare material for publication: SHELXL97.
[Pt2I2(C2H8N2)4](HPO4)(H2PO4)I·3H2O | F(000) = 2312 |
Mr = 1258.29 | Dx = 2.913 Mg m−3 |
Monoclinic, P21/n | Melting point: not measured K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71069 Å |
a = 14.808 (1) Å | Cell parameters from 50 reflections |
b = 16.478 (2) Å | θ = 10.0–15.0° |
c = 11.758 (1) Å | µ = 13.14 mm−1 |
β = 90.84 (1)° | T = 295 K |
V = 2868.7 (5) Å3 | Plate, gold |
Z = 4 | 0.20 × 0.20 × 0.06 mm |
Rigaku AFC-5S diffractometer | 4431 reflections with I > 2σ(I) |
Radiation source: X-ray sealed tube | Rint = 0.018 |
Graphite monochromator | θmax = 27.5°, θmin = 2.8° |
θ/2θ scans | h = −19→19 |
Absorption correction: gaussian (Coppens et al., 1965) | k = 0→21 |
Tmin = 0.127, Tmax = 0.501 | l = 0→15 |
7883 measured reflections | 3 standard reflections every 100 reflections |
6603 independent reflections | intensity decay: none |
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)] = 0.033 | H-atom parameters constrained |
wR(F2) = 0.084 | w = 1/[σ2(Fo2) + (0.044P)2 + 18.1327P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max < 0.001 |
4491 reflections | Δρmax = 2.91 e Å−3 |
314 parameters | Δρmin = −2.02 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: heavy-atom method | Extinction coefficient: 0.00064 (4) |
[Pt2I2(C2H8N2)4](HPO4)(H2PO4)I·3H2O | V = 2868.7 (5) Å3 |
Mr = 1258.29 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 14.808 (1) Å | µ = 13.14 mm−1 |
b = 16.478 (2) Å | T = 295 K |
c = 11.758 (1) Å | 0.20 × 0.20 × 0.06 mm |
β = 90.84 (1)° |
Rigaku AFC-5S diffractometer | 4431 reflections with I > 2σ(I) |
Absorption correction: gaussian (Coppens et al., 1965) | Rint = 0.018 |
Tmin = 0.127, Tmax = 0.501 | 3 standard reflections every 100 reflections |
7883 measured reflections | intensity decay: none |
6603 independent reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.084 | H-atom parameters constrained |
S = 1.10 | w = 1/[σ2(Fo2) + (0.044P)2 + 18.1327P] where P = (Fo2 + 2Fc2)/3 |
4491 reflections | Δρmax = 2.91 e Å−3 |
314 parameters | Δρmin = −2.02 e Å−3 |
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 4491 reflections with F2>0. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F. The threshold expression of F2 > 2σ(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 | ||
Pt1 | 0.24608 (2) | 0.23848 (2) | 0.11758 (3) | 0.01726 (10) | |
I1 | 0.26218 (4) | 0.21541 (5) | −0.10854 (5) | 0.02966 (16) | |
I2 | 0.22630 (4) | 0.27170 (4) | 0.34001 (5) | 0.02638 (15) | |
N11 | 0.3684 (5) | 0.2964 (6) | 0.1216 (7) | 0.0279 (19) | |
H11A | 0.4018 | 0.2787 | 0.1811 | 0.042* | |
H11B | 0.3987 | 0.2858 | 0.0574 | 0.042* | |
N12 | 0.1970 (5) | 0.3517 (5) | 0.0769 (7) | 0.0226 (17) | |
H12A | 0.1610 | 0.3485 | 0.0147 | 0.034* | |
H12B | 0.1641 | 0.3710 | 0.1347 | 0.034* | |
N13 | 0.2978 (5) | 0.1253 (5) | 0.1581 (7) | 0.0279 (19) | |
H13A | 0.3297 | 0.1060 | 0.0995 | 0.042* | |
H13B | 0.3349 | 0.1292 | 0.2191 | 0.042* | |
N14 | 0.1240 (5) | 0.1767 (5) | 0.1140 (7) | 0.0289 (19) | |
H14A | 0.0941 | 0.1850 | 0.1790 | 0.043* | |
H14B | 0.0893 | 0.1940 | 0.0554 | 0.043* | |
C11 | 0.3527 (6) | 0.3847 (6) | 0.1319 (9) | 0.030 (2) | |
H11C | 0.4063 | 0.4143 | 0.1100 | 0.045* | |
H11D | 0.3391 | 0.3985 | 0.2101 | 0.045* | |
C12 | 0.2742 (7) | 0.4070 (6) | 0.0548 (9) | 0.030 (2) | |
H12C | 0.2564 | 0.4628 | 0.0688 | 0.045* | |
H12D | 0.2920 | 0.4025 | −0.0240 | 0.045* | |
C13 | 0.2220 (7) | 0.0690 (7) | 0.1835 (10) | 0.035 (3) | |
H13C | 0.2024 | 0.0764 | 0.2611 | 0.053* | |
H13D | 0.2411 | 0.0131 | 0.1742 | 0.053* | |
C14 | 0.1456 (7) | 0.0888 (7) | 0.1005 (9) | 0.033 (2) | |
H14C | 0.1639 | 0.0777 | 0.0231 | 0.050* | |
H14D | 0.0929 | 0.0560 | 0.1168 | 0.050* | |
Pt2 | 0.24131 (2) | 0.26796 (2) | 0.61942 (3) | 0.01899 (10) | |
N21 | 0.1901 (6) | 0.3801 (5) | 0.6555 (7) | 0.0291 (19) | |
H21A | 0.1552 | 0.3974 | 0.5970 | 0.044* | |
H21B | 0.1556 | 0.3772 | 0.7177 | 0.044* | |
N22 | 0.3599 (5) | 0.3307 (6) | 0.6089 (7) | 0.030 (2) | |
H22A | 0.3932 | 0.3236 | 0.6727 | 0.045* | |
H22B | 0.3920 | 0.3128 | 0.5494 | 0.045* | |
N23 | 0.2920 (5) | 0.1555 (5) | 0.5836 (7) | 0.0266 (18) | |
H23A | 0.3254 | 0.1578 | 0.5204 | 0.040* | |
H23B | 0.3276 | 0.1384 | 0.6415 | 0.040* | |
N24 | 0.1214 (5) | 0.2084 (6) | 0.6294 (7) | 0.029 (2) | |
H24A | 0.0907 | 0.2264 | 0.6899 | 0.044* | |
H24B | 0.0879 | 0.2180 | 0.5664 | 0.044* | |
C21 | 0.2658 (7) | 0.4388 (7) | 0.6758 (9) | 0.035 (2) | |
H21C | 0.2455 | 0.4940 | 0.6626 | 0.052* | |
H21D | 0.2884 | 0.4345 | 0.7534 | 0.052* | |
C22 | 0.3376 (7) | 0.4165 (7) | 0.5940 (9) | 0.035 (3) | |
H22C | 0.3164 | 0.4262 | 0.5168 | 0.053* | |
H22D | 0.3909 | 0.4495 | 0.6078 | 0.053* | |
C23 | 0.2150 (7) | 0.0978 (7) | 0.5663 (9) | 0.036 (3) | |
H23C | 0.1953 | 0.0990 | 0.4873 | 0.054* | |
H23D | 0.2347 | 0.0431 | 0.5841 | 0.054* | |
C24 | 0.1381 (7) | 0.1205 (7) | 0.6409 (9) | 0.033 (2) | |
H24C | 0.0844 | 0.0904 | 0.6185 | 0.050* | |
H24D | 0.1527 | 0.1073 | 0.7195 | 0.050* | |
P1 | 0.49573 (14) | 0.17724 (16) | 0.3806 (2) | 0.0210 (5) | |
O11 | 0.4898 (5) | 0.2423 (5) | 0.2894 (6) | 0.0313 (17) | |
O12 | 0.5800 (4) | 0.1235 (4) | 0.3707 (6) | 0.0269 (15) | |
O13 | 0.4934 (5) | 0.2164 (5) | 0.4980 (6) | 0.0304 (16) | |
O14 | 0.4097 (4) | 0.1208 (5) | 0.3699 (7) | 0.0321 (17) | |
H14 | 0.4256 | 0.0740 | 0.3575 | 0.048* | |
P2 | 0.49812 (16) | 0.06835 (17) | 0.7320 (2) | 0.0257 (5) | |
O21 | 0.4966 (5) | 0.0655 (5) | 0.8595 (6) | 0.042 (2) | |
O22 | 0.5831 (4) | 0.0303 (5) | 0.6829 (7) | 0.0353 (18) | |
O23 | 0.4124 (4) | 0.0282 (5) | 0.6784 (8) | 0.0378 (19) | |
H23 | 0.4214 | −0.0206 | 0.6701 | 0.057* | |
O24 | 0.4909 (5) | 0.1598 (4) | 0.6972 (6) | 0.0348 (17) | |
H24 | 0.5039 | 0.1648 | 0.6301 | 0.052* | |
O31 | 0.3738 (5) | 0.0072 (5) | 0.0100 (7) | 0.0376 (18) | |
H31A | 0.4158 | −0.0160 | 0.0428 | 0.056* | |
H31B | 0.4028 | 0.0301 | −0.0394 | 0.056* | |
O32 | 0.4986 (5) | 0.2135 (7) | −0.0319 (7) | 0.053 (3) | |
H32A | 0.5082 | 0.1645 | −0.0326 | 0.080* | |
H32B | 0.4981 | 0.2389 | −0.0919 | 0.080* | |
O33 | 0.5110 (7) | 0.6022 (7) | 0.6098 (9) | 0.072 (3) | |
H33A | 0.5337 | 0.6451 | 0.6310 | 0.108* | |
H33B | 0.4604 | 0.5923 | 0.6335 | 0.108* | |
I3 | 0.49447 (5) | 0.40902 (5) | 0.85113 (7) | 0.0405 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pt1 | 0.01723 (16) | 0.0197 (2) | 0.01485 (16) | 0.00014 (13) | −0.00006 (11) | 0.00041 (15) |
I1 | 0.0309 (3) | 0.0406 (4) | 0.0174 (3) | 0.0016 (3) | 0.0000 (2) | −0.0048 (3) |
I2 | 0.0305 (3) | 0.0313 (4) | 0.0175 (3) | 0.0009 (3) | 0.0041 (2) | −0.0011 (3) |
N11 | 0.020 (4) | 0.042 (6) | 0.021 (4) | −0.010 (4) | −0.002 (3) | 0.000 (4) |
N12 | 0.021 (3) | 0.022 (4) | 0.025 (4) | 0.006 (3) | 0.003 (3) | 0.001 (4) |
N13 | 0.037 (4) | 0.021 (5) | 0.026 (4) | 0.005 (4) | −0.008 (3) | 0.004 (4) |
N14 | 0.029 (4) | 0.031 (5) | 0.027 (4) | −0.005 (4) | −0.005 (3) | 0.007 (4) |
C11 | 0.032 (5) | 0.025 (6) | 0.033 (5) | −0.014 (4) | 0.003 (4) | 0.005 (5) |
C12 | 0.045 (6) | 0.012 (5) | 0.035 (6) | 0.000 (4) | 0.001 (5) | 0.002 (4) |
C13 | 0.048 (6) | 0.018 (6) | 0.040 (6) | 0.004 (5) | −0.004 (5) | 0.006 (5) |
C14 | 0.044 (6) | 0.024 (6) | 0.033 (6) | −0.016 (5) | 0.003 (5) | 0.006 (5) |
Pt2 | 0.01904 (16) | 0.0209 (2) | 0.01713 (17) | 0.00175 (14) | 0.00182 (12) | −0.00117 (16) |
N21 | 0.040 (5) | 0.022 (5) | 0.026 (4) | 0.004 (4) | 0.006 (4) | 0.005 (4) |
N22 | 0.024 (4) | 0.033 (5) | 0.033 (5) | −0.006 (4) | −0.001 (3) | −0.005 (4) |
N23 | 0.034 (4) | 0.024 (5) | 0.022 (4) | 0.003 (4) | 0.005 (3) | 0.001 (4) |
N24 | 0.017 (3) | 0.041 (6) | 0.030 (4) | 0.001 (4) | 0.000 (3) | 0.000 (4) |
C21 | 0.047 (6) | 0.023 (6) | 0.034 (6) | −0.007 (5) | 0.006 (5) | −0.005 (5) |
C22 | 0.044 (6) | 0.030 (6) | 0.032 (6) | −0.016 (5) | −0.002 (5) | 0.001 (5) |
C23 | 0.043 (6) | 0.030 (6) | 0.034 (6) | −0.003 (5) | 0.007 (5) | −0.017 (5) |
C24 | 0.041 (6) | 0.035 (7) | 0.025 (5) | −0.014 (5) | 0.010 (4) | 0.000 (5) |
P1 | 0.0211 (10) | 0.0214 (13) | 0.0204 (11) | −0.0012 (9) | −0.0006 (9) | 0.0018 (10) |
O11 | 0.037 (4) | 0.037 (5) | 0.020 (3) | −0.006 (3) | −0.002 (3) | 0.010 (3) |
O12 | 0.017 (3) | 0.026 (4) | 0.038 (4) | 0.003 (3) | 0.002 (3) | 0.000 (3) |
O13 | 0.039 (4) | 0.033 (4) | 0.020 (3) | −0.003 (3) | −0.001 (3) | −0.006 (3) |
O14 | 0.019 (3) | 0.030 (4) | 0.048 (5) | −0.001 (3) | −0.003 (3) | −0.005 (4) |
P2 | 0.0275 (12) | 0.0224 (14) | 0.0273 (13) | 0.0001 (10) | 0.0025 (10) | 0.0052 (11) |
O21 | 0.044 (4) | 0.046 (5) | 0.035 (4) | 0.007 (4) | 0.002 (3) | 0.018 (4) |
O22 | 0.029 (3) | 0.033 (4) | 0.044 (4) | −0.002 (3) | 0.013 (3) | −0.009 (4) |
O23 | 0.028 (3) | 0.020 (4) | 0.065 (5) | 0.000 (3) | −0.005 (3) | 0.001 (4) |
O24 | 0.063 (5) | 0.018 (4) | 0.024 (4) | −0.001 (4) | 0.001 (3) | 0.003 (3) |
O31 | 0.036 (4) | 0.042 (5) | 0.035 (4) | 0.005 (4) | 0.006 (3) | 0.005 (4) |
O32 | 0.044 (4) | 0.072 (7) | 0.044 (5) | 0.003 (5) | 0.003 (4) | −0.021 (5) |
O33 | 0.076 (7) | 0.058 (7) | 0.082 (8) | −0.004 (6) | 0.006 (6) | −0.021 (6) |
I3 | 0.0349 (4) | 0.0438 (5) | 0.0427 (4) | 0.0020 (3) | 0.0010 (3) | −0.0134 (4) |
Pt1—I1 | 2.6997 (7) | N22—C22 | 1.462 (14) |
Pt1—I2 | 2.6921 (7) | N22—H22A | 0.9000 |
Pt1—N11 | 2.048 (7) | N22—H22B | 0.9000 |
Pt1—N12 | 2.055 (8) | N23—C23 | 1.496 (13) |
Pt1—N13 | 2.069 (8) | N23—H23A | 0.9000 |
Pt1—N14 | 2.075 (8) | N23—H23B | 0.9000 |
Pt2—N21 | 2.044 (8) | N24—C24 | 1.475 (14) |
Pt2—N22 | 2.043 (8) | N24—H24A | 0.9000 |
Pt2—N23 | 2.045 (8) | N24—H24B | 0.9000 |
Pt2—N24 | 2.034 (8) | C21—C22 | 1.490 (14) |
Pt2—I1i | 3.3239 (8) | C21—H21C | 0.9700 |
Pt2—I2 | 3.2902 (7) | C21—H21D | 0.9700 |
N11—C11 | 1.478 (13) | C22—H22C | 0.9700 |
N11—H11A | 0.9000 | C22—H22D | 0.9700 |
N11—H11B | 0.9000 | C23—C24 | 1.496 (14) |
N12—C12 | 1.490 (12) | C23—H23C | 0.9700 |
N12—H12A | 0.9000 | C23—H23D | 0.9700 |
N12—H12B | 0.9000 | C24—H24C | 0.9700 |
N13—C13 | 1.489 (13) | C24—H24D | 0.9700 |
N13—H13A | 0.9000 | P1—O11 | 1.518 (7) |
N13—H13B | 0.9000 | P1—O12 | 1.537 (6) |
N14—C14 | 1.492 (14) | P1—O13 | 1.524 (7) |
N14—H14A | 0.9000 | P1—O14 | 1.582 (7) |
N14—H14B | 0.9000 | O14—H14 | 0.8200 |
C11—C12 | 1.509 (13) | P2—O21 | 1.500 (8) |
C11—H11C | 0.9700 | P2—O22 | 1.527 (7) |
C11—H11D | 0.9700 | P2—O23 | 1.556 (7) |
C12—H12C | 0.9700 | P2—O24 | 1.565 (8) |
C12—H12D | 0.9700 | O23—H23 | 0.8200 |
C13—C14 | 1.520 (14) | O24—H24 | 0.8200 |
C13—H13C | 0.9700 | O31—H31B | 0.8200 |
C13—H13D | 0.9700 | O31—H31A | 0.8201 |
C14—H14C | 0.9700 | O32—H32B | 0.8200 |
C14—H14D | 0.9700 | O32—H32A | 0.8205 |
N21—C21 | 1.497 (13) | O33—H33B | 0.8200 |
N21—H21A | 0.9000 | O33—H33A | 0.8201 |
N21—H21B | 0.9000 | ||
N11—Pt1—N12 | 83.8 (3) | N14—C14—H14C | 110.2 |
N11—Pt1—N13 | 95.2 (3) | C13—C14—H14C | 110.2 |
N11—Pt1—N14 | 178.4 (3) | N14—C14—H14D | 110.2 |
N12—Pt1—N13 | 179.0 (3) | C13—C14—H14D | 110.2 |
N12—Pt1—N14 | 97.8 (3) | H14C—C14—H14D | 108.5 |
N13—Pt1—N14 | 83.2 (3) | C21—N21—Pt2 | 109.7 (6) |
N11—Pt1—I1 | 89.9 (2) | C21—N21—H21A | 109.7 |
N12—Pt1—I1 | 86.3 (2) | Pt2—N21—H21A | 109.7 |
N13—Pt1—I1 | 93.6 (2) | C21—N21—H21B | 109.7 |
N14—Pt1—I1 | 90.0 (2) | Pt2—N21—H21B | 109.7 |
N11—Pt1—I2 | 89.5 (2) | H21A—N21—H21B | 108.2 |
N12—Pt1—I2 | 89.9 (2) | C22—N22—Pt2 | 107.6 (6) |
N13—Pt1—I2 | 90.3 (2) | C22—N22—H22A | 110.2 |
N14—Pt1—I2 | 90.7 (2) | Pt2—N22—H22A | 110.2 |
I1—Pt1—I2 | 176.16 (3) | C22—N22—H22B | 110.2 |
Pt1—I1—Pt2ii | 154.52 (3) | Pt2—N22—H22B | 110.2 |
Pt1—I2—Pt2 | 163.64 (3) | H22A—N22—H22B | 108.5 |
I2—Pt2—I1i | 165.88 (2) | C23—N23—Pt2 | 108.8 (6) |
N21—Pt2—N22 | 83.0 (3) | C23—N23—H23A | 109.9 |
N21—Pt2—N23 | 179.7 (3) | Pt2—N23—H23A | 109.9 |
N21—Pt2—N24 | 95.6 (3) | C23—N23—H23B | 109.9 |
N22—Pt2—N23 | 97.3 (3) | Pt2—N23—H23B | 109.9 |
N22—Pt2—N24 | 178.5 (3) | H23A—N23—H23B | 108.3 |
N23—Pt2—N24 | 84.1 (3) | C24—N24—Pt2 | 109.5 (6) |
N24—Pt2—I1i | 83.5 (2) | C24—N24—H24A | 109.8 |
N22—Pt2—I1i | 97.0 (2) | Pt2—N24—H24A | 109.8 |
N21—Pt2—I1i | 93.8 (2) | C24—N24—H24B | 109.8 |
N23—Pt2—I1i | 86.2 (2) | Pt2—N24—H24B | 109.8 |
C11—N11—Pt1 | 108.7 (6) | H24A—N24—H24B | 108.2 |
C11—N11—H11A | 109.9 | C22—C21—N21 | 106.1 (8) |
Pt1—N11—H11A | 110.0 | C22—C21—H21C | 110.5 |
C11—N11—H11B | 110.0 | N21—C21—H21C | 110.5 |
Pt1—N11—H11B | 109.9 | C22—C21—H21D | 110.5 |
H11A—N11—H11B | 108.3 | N21—C21—H21D | 110.5 |
C12—N12—Pt1 | 109.0 (5) | H21C—C21—H21D | 108.7 |
C12—N12—H12A | 109.9 | N22—C22—C21 | 108.9 (9) |
Pt1—N12—H12A | 109.9 | N22—C22—H22C | 109.9 |
C12—N12—H12B | 109.9 | C21—C22—H22C | 109.9 |
Pt1—N12—H12B | 109.9 | N22—C22—H22D | 109.9 |
H12A—N12—H12B | 108.3 | C21—C22—H22D | 109.9 |
C13—N13—Pt1 | 109.3 (6) | H22C—C22—H22D | 108.3 |
C13—N13—H13A | 109.8 | C24—C23—N23 | 110.3 (8) |
Pt1—N13—H13A | 109.8 | C24—C23—H23C | 109.6 |
C13—N13—H13B | 109.8 | N23—C23—H23C | 109.6 |
Pt1—N13—H13B | 109.8 | C24—C23—H23D | 109.6 |
H13A—N13—H13B | 108.3 | N23—C23—H23D | 109.6 |
C14—N14—Pt1 | 106.9 (6) | H23C—C23—H23D | 108.1 |
C14—N14—H14A | 110.3 | N24—C24—C23 | 108.6 (9) |
Pt1—N14—H14A | 110.3 | N24—C24—H24C | 110.0 |
C14—N14—H14B | 110.3 | C23—C24—H24C | 110.0 |
Pt1—N14—H14B | 110.3 | N24—C24—H24D | 110.0 |
H14A—N14—H14B | 108.6 | C23—C24—H24D | 110.0 |
N11—C11—C12 | 108.1 (8) | H24C—C24—H24D | 108.3 |
N11—C11—H11C | 110.1 | O11—P1—O13 | 109.8 (4) |
C12—C11—H11C | 110.1 | O11—P1—O12 | 113.1 (4) |
N11—C11—H11D | 110.1 | O13—P1—O12 | 110.0 (4) |
C12—C11—H11D | 110.1 | O11—P1—O14 | 108.7 (4) |
H11C—C11—H11D | 108.4 | O13—P1—O14 | 107.0 (4) |
N12—C12—C11 | 109.4 (8) | O12—P1—O14 | 108.0 (4) |
N12—C12—H12C | 109.8 | P1—O14—H14 | 109.5 |
C11—C12—H12C | 109.8 | O21—P2—O22 | 112.9 (4) |
N12—C12—H12D | 109.8 | O21—P2—O23 | 111.6 (5) |
C11—C12—H12D | 109.8 | O22—P2—O23 | 110.1 (4) |
H12C—C12—H12D | 108.2 | O21—P2—O24 | 106.8 (5) |
N13—C13—C14 | 107.1 (8) | O22—P2—O24 | 110.5 (5) |
N13—C13—H13C | 110.3 | O23—P2—O24 | 104.6 (4) |
C14—C13—H13C | 110.3 | P2—O23—H23 | 109.5 |
N13—C13—H13D | 110.3 | P2—O24—H24 | 109.5 |
C14—C13—H13D | 110.3 | H31B—O31—H31A | 98.4 |
H13C—C13—H13D | 108.5 | H32B—O32—H32A | 119.6 |
N14—C14—C13 | 107.4 (8) | H33B—O33—H33A | 116.1 |
Symmetry codes: (i) x, y, z+1; (ii) x, y, z−1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11A···O11 | 0.90 | 1.91 | 2.796 (10) | 170 |
N11—H11B···O32 | 0.90 | 2.18 | 2.990 (12) | 149 |
N12—H12A···O12iii | 0.90 | 2.11 | 2.987 (10) | 164 |
N12—H12B···O22iii | 0.90 | 2.10 | 2.870 (11) | 143 |
N13—H13A···O31 | 0.90 | 2.05 | 2.854 (12) | 148 |
N13—H13B···O14 | 0.90 | 2.08 | 2.972 (10) | 170 |
N14—H14A···I3iii | 0.90 | 2.96 | 3.689 (8) | 139 |
N14—H14B···O13iii | 0.90 | 2.15 | 2.937 (11) | 146 |
N21—H21A···O31iv | 0.90 | 2.24 | 3.002 (11) | 142 |
N21—H21B···O12v | 0.90 | 2.13 | 3.030 (11) | 176 |
N22—H22A···I3 | 0.90 | 2.92 | 3.686 (8) | 144 |
N22—H22B···O13 | 0.90 | 2.27 | 3.038 (11) | 143 |
N23—H23A···O14 | 0.90 | 2.26 | 3.132 (11) | 162 |
N23—H23B···O23 | 0.90 | 2.25 | 2.962 (11) | 136 |
N24—H24A···O11v | 0.90 | 1.98 | 2.846 (11) | 161 |
N24—H24B···O32v | 0.90 | 2.08 | 2.909 (11) | 153 |
O14—H14···O22vi | 0.82 | 1.79 | 2.569 (11) | 159 |
O23—H23···O12vi | 0.82 | 1.76 | 2.567 (10) | 167 |
O24—H24···O13 | 0.82 | 1.77 | 2.522 (10) | 151 |
O31—H31B···O21ii | 0.82 | 1.93 | 2.731 (10) | 165 |
O31—H31A···O21vi | 0.82 | 1.90 | 2.717 (10) | 171 |
O32—H32B···I3ii | 0.82 | 2.88 | 3.502 (12) | 134 |
O32—H32A···O21ii | 0.82 | 2.07 | 2.753 (13) | 140 |
O33—H33A···O11vii | 0.82 | 2.11 | 2.824 (13) | 145 |
Symmetry codes: (ii) x, y, z−1; (iii) x−1/2, −y+1/2, z−1/2; (iv) −x+1/2, y+1/2, −z+1/2; (v) x−1/2, −y+1/2, z+1/2; (vi) −x+1, −y, −z+1; (vii) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Pt2I2(C2H8N2)4](HPO4)(H2PO4)I·3H2O |
Mr | 1258.29 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 295 |
a, b, c (Å) | 14.808 (1), 16.478 (2), 11.758 (1) |
β (°) | 90.84 (1) |
V (Å3) | 2868.7 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 13.14 |
Crystal size (mm) | 0.20 × 0.20 × 0.06 |
Data collection | |
Diffractometer | Rigaku AFC-5S diffractometer |
Absorption correction | Gaussian (Coppens et al., 1965) |
Tmin, Tmax | 0.127, 0.501 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7883, 6603, 4431 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.084, 1.10 |
No. of reflections | 4491 |
No. of parameters | 314 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.044P)2 + 18.1327P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 2.91, −2.02 |
Computer programs: AFC Diffractometer Control Software (Rigaku, 1987), AFC Diffractometer Control Software and local program F2-AFC (Matsushita, 1998), SHELX76 (Sheldrick, 1976), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 2005), SHELXL97.
Pt1—I1 | 2.6997 (7) | Pt2—I1i | 3.3239 (8) |
Pt1—I2 | 2.6921 (7) | Pt2—I2 | 3.2902 (7) |
Pt1—N11 | 2.048 (7) | P1—O11 | 1.518 (7) |
Pt1—N12 | 2.055 (8) | P1—O12 | 1.537 (6) |
Pt1—N13 | 2.069 (8) | P1—O13 | 1.524 (7) |
Pt1—N14 | 2.075 (8) | P1—O14 | 1.582 (7) |
Pt2—N21 | 2.044 (8) | P2—O21 | 1.500 (8) |
Pt2—N22 | 2.043 (8) | P2—O22 | 1.527 (7) |
Pt2—N23 | 2.045 (8) | P2—O23 | 1.556 (7) |
Pt2—N24 | 2.034 (8) | P2—O24 | 1.565 (8) |
N11—Pt1—N12 | 83.8 (3) | N13—Pt1—I2 | 90.3 (2) |
N11—Pt1—N13 | 95.2 (3) | N14—Pt1—I2 | 90.7 (2) |
N12—Pt1—N14 | 97.8 (3) | I1—Pt1—I2 | 176.16 (3) |
N13—Pt1—N14 | 83.2 (3) | Pt1—I1—Pt2ii | 154.52 (3) |
N11—Pt1—I1 | 89.9 (2) | Pt1—I2—Pt2 | 163.64 (3) |
N12—Pt1—I1 | 86.3 (2) | I2—Pt2—I1i | 165.88 (2) |
N13—Pt1—I1 | 93.6 (2) | N21—Pt2—N22 | 83.0 (3) |
N14—Pt1—I1 | 90.0 (2) | N21—Pt2—N24 | 95.6 (3) |
N11—Pt1—I2 | 89.5 (2) | N22—Pt2—N23 | 97.3 (3) |
N12—Pt1—I2 | 89.9 (2) | N23—Pt2—N24 | 84.1 (3) |
Symmetry codes: (i) x, y, z+1; (ii) x, y, z−1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11A···O11 | 0.90 | 1.91 | 2.796 (10) | 169.9 |
N11—H11B···O32 | 0.90 | 2.18 | 2.990 (12) | 149.2 |
N12—H12A···O12iii | 0.90 | 2.11 | 2.987 (10) | 164.1 |
N12—H12B···O22iii | 0.90 | 2.10 | 2.870 (11) | 142.6 |
N13—H13A···O31 | 0.90 | 2.05 | 2.854 (12) | 148.1 |
N13—H13B···O14 | 0.90 | 2.08 | 2.972 (10) | 170.3 |
N14—H14A···I3iii | 0.90 | 2.96 | 3.689 (8) | 139.2 |
N14—H14B···O13iii | 0.90 | 2.15 | 2.937 (11) | 145.6 |
N21—H21A···O31iv | 0.90 | 2.24 | 3.002 (11) | 141.9 |
N21—H21B···O12v | 0.90 | 2.13 | 3.030 (11) | 175.9 |
N22—H22A···I3 | 0.90 | 2.92 | 3.686 (8) | 143.7 |
N22—H22B···O13 | 0.90 | 2.27 | 3.038 (11) | 142.5 |
N23—H23A···O14 | 0.90 | 2.26 | 3.132 (11) | 161.9 |
N23—H23B···O23 | 0.90 | 2.25 | 2.962 (11) | 136.0 |
N24—H24A···O11v | 0.90 | 1.98 | 2.846 (11) | 161.4 |
N24—H24B···O32v | 0.90 | 2.08 | 2.909 (11) | 153.3 |
O14—H14···O22vi | 0.82 | 1.79 | 2.569 (11) | 158.6 |
O23—H23···O12vi | 0.82 | 1.76 | 2.567 (10) | 166.8 |
O24—H24···O13 | 0.82 | 1.77 | 2.522 (10) | 150.8 |
O31—H31B···O21ii | 0.82 | 1.93 | 2.731 (10) | 164.6 |
O31—H31A···O21vi | 0.82 | 1.90 | 2.717 (10) | 170.9 |
O32—H32B···I3ii | 0.82 | 2.88 | 3.502 (12) | 134.1 |
O32—H32A···O21ii | 0.82 | 2.07 | 2.753 (13) | 140.2 |
O33—H33A···O11vii | 0.82 | 2.11 | 2.824 (13) | 145.4 |
Symmetry codes: (ii) x, y, z−1; (iii) x−1/2, −y+1/2, z−1/2; (iv) −x+1/2, y+1/2, −z+1/2; (v) x−1/2, −y+1/2, z+1/2; (vi) −x+1, −y, −z+1; (vii) −x+1, −y+1, −z+1. |
The title compound, (I), is a member of the family of one-dimensional halogen-bridged mixed-valence metal complexes, formulated as [MII(AA)2][MIVX2(AA)2]Y4 [MII/MIV = PtII/PtIV, PdII/PdIV, NiII/NiIV, PdII/PtIV and NiII/PtIV; X = Cl, Br and I; AA = NH2(CH2)2NH2 etc.; Y = ClO4−, HSO4−, X− etc.], hereafter abbreviated as MX-chain compounds, which are typical mixed-valence compounds belonging to class II in the classification by Robin & Day (1967). MX-chain compounds have been attracting much interest as a result of the one-dimensional mixed-valence electron system. Unusual physical properties, such as a remarkably dichroic intense absorption band attributed to an intervalence charge-transfer (IVCT) transition from MII to MIV in the mixed-valence state, progressive Raman scattering in resonance with the IVCT band, and photoinduced mid-gap absorption bands due to soliton and polaron formation, are characteristics of the one-dimensional mixed-valence system.
The metal–halogen distances in crystals of MX-chain compounds characterize these physical properties on the basis of the mixed-valence state. The valence ordering of the metal site in the mixed-valence state is also structurally interesting because of the relation to the soliton and polaron formation as a mismatch of the valence alternation. The present X-ray crystallographic analysis of the title compound, (I), [Pt(en)2][PtI2(en)2](HPO4)(H2PO4)I·3H2O (en is ethylenediamine), has been performed in order to gather further structural information on these MX-chain compounds.
As shown in Fig. 1, the structure of (I) is built up from columns composed of square-planar [Pt(en)2]2+ and elongated octahedral trans-[PtI2(en)2]2+ cations stacked alternately, bridged by the I atoms, along the c axis. Pt1 and Pt2 sites are assigned to PtIV and PtII, respectively. The Pt and I atoms are occupied at general sites in the unit cell, and form an infinite zigzag ···I–PtIV–I···PtII··· chain, with PtIV–I distances of 2.6997 (7) and 2.6921 (7) Å, PtII···I distances of 3.3239 (8) and 3.2902 (7) Å (Table 1).
There is no disorder of the bridging halogen atoms in (I), although the other MX-chain compounds have disordered structures. The I atoms are not located at the exact mid-point between the two adjacent Pt atoms but at a position displaced somewhat from the mid-point to the Pt1 site. The valence ordering of the Pt site in (I) belongs to one of three different classes of the order–disorder problem pointed out by Keller (1982); the structure of (I) can be regarded as a three-dimensionally valence-ordered structure. This type of valence ordering of the Pt site is rare. Five compounds belonging to this type were described in the review of Keller (1982). After published the review, the re-refinements and re-analyses for these five compounds have shown that they belong to another class, that is, one-dimensionally valence-ordered structures with the other two directions in a disordered state; these compounds are [Pt(tn)2][PtX2(tn)2](BF4)4 (tn is 1,3-propanediamine and X = Cl and Br) and [Pt(tn)2][PtBr2(tn)2](ClO4)4, re-analyzed by Cannas et al. (1983), and [Pt(en)2][PtX2(en)2](ClO4)4 (X = Cl and Br), re-analyzed by Huckett et al. (1993) and Toriumi et al. (1993). The valence ordering of the Pt site in a majority of the MX-chain compounds belongs to this one-dimensionally valence ordered structure. So far, on the other hand, a few MX-chain compounds, [Pt(tn)2][PtI2(tn)2](ClO4)4 (Cannas et al., 1984) and [Pt(NH3)4][PtI2(NH3)4](HSO4)4·2H2O (Tanaka et al., 1986), have been reported anew as belonging to the three-dimensionally valence-ordered system to which (I) belongs.
The structural parameter indicating the mixed-valence state of the Pt atom, expressed by δ = (PtIV–I)/(PtII···I), is 0.812 and 0.818 for atoms I1 and I2, respectively. These values are much smaller than those of [Pt(pn)2][PtI2(pn)2](ClO4)4 (0.937; pn is 1,2-propanediamine; Breer et al., 1978), [Pt(pn)2][PtI2(pn)2]I4 (0.940; Endres et al., 1980), [Pt(tn)2][PtI2(tn)2](ClO4)4 (0.95; Cannas et al., 1984) and [Pt(en)2][PtI2(en)2](ClO4)4 (0.919; Endres et al., 1979), and somewhat smaller than that of [Pt(NH3)4][PtI2(NH3)4](HSO4)4·2H2O (0.834; Tanaka et al., 1986).
The hydrogen bonds, listed in Table 2, stabilize the columnar structure composed only of cationic complexes, as shown in Fig. 1. A [PtII/IV(en)2] unit is bound to an adjacent Pt complex unit in the column by four hydrogen-bond linkages, NH···counter-anion(+ water molecule)···HN. There are two sets of four hydrogen-bond linkages; one is composed of N11–H···O11–P1–O13···H–N22, N12–H···O22–P2–O21···H–O31···H–N21, N13–H···O14···H–N23 and N14–H···I3···H–O32···H–N24, and the other is composed of N21–H···O12···H–N12, N22–H···I3···H–O32···H–N11, N23–H···O23–P2–O21···H–O31···H–N13 and N24–H···O11–P1–O13···H–N14. The crystal packing is further stabilized by intercolumnar hydrogen-bond linkages, as shown in Fig. 2.
As shown in Fig. 3, a cyclic tetramer structure composed of two hydrogenphosphate ions and two dihydrogenphosphate ions is formed by strong O–H···O hydrogen bonds [2.522 (10), 2.567 (10) and 2.569 (11) Å]; the O···O distances are comparable to the average values in hydrogenphosphates (2.597 Å) and dihydrogenphosphates (2.574 Å; Ferraris & Ivaldi, 1984). An MX-chain compound containing dimerized anions has already been reported; this is [Pt(NH3)4][PtBr2(NH3)4](HSO4)4 (Tanaka et al., 1982), which also has strong O–H···O hydrogen bonds [2.582 (9) Å] in the dimer. The present tetramer structure of the counter-anion is the first observation in the MX-chain compounds in our best knowledge. In addition, the tetramers form a chain structure parallel to the Pt–I chain, connected by hydrogen bonds with the water molecules (O31).