Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803013552/ob6260sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803013552/ob6260Isup2.hkl |
CCDC reference: 217391
4-Amino-2,2'-bipyridine was prepared according to the literature method (Jones et al., 1967). The title PtII complex was prepared in the same manner as reported for [PtCl2(2,2'-bipyridine)] (Morgan & Burstall, 1963) (yield: 96%). The crystals of (I) were obtained by slow cooling of a hot aqueous solution of the complex.
All H atoms except for those of water molecules were located at their idealized positions as riding atoms (C–H = 0.93a%A and N–H = 0.86 Å). Water H atoms were not located. In the final difference Fourier synthesis, seven residual peaks in the range 1.01–1.56 e Å−3 were observed within 1.00 Å of the Pt atom.
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: KENX (Sakai, 2002); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997), TEXSAN (Molecular Structure Corporation, 2001), KENX (Sakai, 2002) and ORTEPII (Johnson, 1976).
[PtCl2(C10H9N3)]·2H2O | F(000) = 888 |
Mr = 473.22 | Dx = 2.276 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.3136 (6) Å | Cell parameters from 2848 reflections |
b = 10.1125 (9) Å | θ = 2.3–23.9° |
c = 18.7166 (16) Å | µ = 10.54 mm−1 |
β = 93.784 (1)° | T = 293 K |
V = 1381.2 (2) Å3 | Plate, yellow |
Z = 4 | 0.36 × 0.05 × 0.02 mm |
Bruker SMART APEX CCD-detector diffractometer | 3188 independent reflections |
Radiation source: fine-focus sealed tube | 2165 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.061 |
Detector resolution: 8.366 pixels mm-1 | θmax = 28.3°, θmin = 2.2° |
ω scans | h = −9→9 |
Absorption correction: gaussian (XPREP in SAINT; Bruker, 2001) | k = −13→10 |
Tmin = 0.323, Tmax = 0.785 | l = −23→24 |
8387 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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.085 | H-atom parameters constrained |
S = 0.89 | w = 1/[σ2(Fo2) + (0.0267P)2] where P = (Fo2 + 2Fc2)/3 |
3188 reflections | (Δ/σ)max = 0.001 |
163 parameters | Δρmax = 1.81 e Å−3 |
0 restraints | Δρmin = −0.93 e Å−3 |
[PtCl2(C10H9N3)]·2H2O | V = 1381.2 (2) Å3 |
Mr = 473.22 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.3136 (6) Å | µ = 10.54 mm−1 |
b = 10.1125 (9) Å | T = 293 K |
c = 18.7166 (16) Å | 0.36 × 0.05 × 0.02 mm |
β = 93.784 (1)° |
Bruker SMART APEX CCD-detector diffractometer | 3188 independent reflections |
Absorption correction: gaussian (XPREP in SAINT; Bruker, 2001) | 2165 reflections with I > 2σ(I) |
Tmin = 0.323, Tmax = 0.785 | Rint = 0.061 |
8387 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.085 | H-atom parameters constrained |
S = 0.89 | Δρmax = 1.81 e Å−3 |
3188 reflections | Δρmin = −0.93 e Å−3 |
163 parameters |
Experimental. The first 50 frames were rescanned at the end of data collection to evaluate any possible decay phenomenon. Since it was judged to be negligible, no decay correction was applied to the data. |
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. Mean-plane data from final SHELXL refinement run:- Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 6.9307 (0.0035) x − 0.2535 (0.0145) y + 4.7748 (0.0266) z = 3.8775 (0.0144) * −0.0314 (0.0026) N1 * 0.0314 (0.0026) N2 * 0.0253 (0.0021) Cl1 * −0.0253 (0.0021) Cl2 0.0290 (0.0023) Pt1 − 3.5163 (0.0087) Pt1_$2 3.4144 (0.0071) Pt1_$3 Rms deviation of fitted atoms = 0.0285 6.9184 (0.0028) x + 0.4734 (0.0172) y + 4.8239 (0.0186) z = 4.6111 (0.0233) Angle to previous plane (with approximate e.s.d.) = 4.12 (0.11) * −0.0083 (0.0055) N1 * −0.0202 (0.0055) N2 * −0.0143 (0.0055) N3 * 0.0009 (0.0066) C1 * 0.0109 (0.0081) C2 * −0.0104 (0.0075) C3 * −0.0002 (0.0074) C4 * −0.0015 (0.0066) C5 * 0.0157 (0.0066) C6 * 0.0141 (0.0067) C7 * 0.0001 (0.0069) C8 * 0.0104 (0.0070) C9 * 0.0028 (0.0064) C10 Rms deviation of fitted atoms = 0.0107 6.9295 (0.0038) x + 0.4193 (0.0257) y + 4.7521 (0.0274) z = 4.5217 (0.0320) Angle to previous plane (with approximate e.s.d.) = 0.38 (0.12) * 0.0000 (0.0044) N1 * −0.0152 (0.0055) N2 * −0.0020 (0.0054) C5 * 0.0133 (0.0064) C6 * 0.0032 (0.0056) C7 * −0.0119 (0.0058) C8 * 0.0061 (0.0063) C9 * 0.0066 (0.0056) C10 − 3.4526 (0.0059) N1_$2 − 3.4375 (0.0069) N2_$2 − 3.4507 (0.0072) C5_$2 − 3.4660 (0.0076) C6_$2 − 3.4558 (0.0071) C7_$2 − 3.4407 (0.0070) C8_$2 − 3.4587 (0.0075) C9_$2 − 3.4593 (0.0072) C10_$2 Rms deviation of fitted atoms = 0.0090 6.9338 (0.0059) x + 0.3644 (0.0406) y + 4.7305 (0.0389) z = 4.4615 (0.0554) Angle to previous plane (with approximate e.s.d.) = 0.32 (0.17) * −0.0032 (0.0054) N1 * −0.0151 (0.0055) N2 * 0.0070 (0.0059) C1 * 0.0041 (0.0061) C2 * −0.0110 (0.0062) C5 * 0.0060 (0.0060) C6 * 0.0034 (0.0055) C9 * 0.0089 (0.0059) C10 3.4735 (0.0064) N1_$3 3.4854 (0.0068) N2_$3 3.4632 (0.0080) C1_$3 3.4662 (0.0082) C2_$3 3.4813 (0.0075) C5_$3 3.4643 (0.0075) C6_$3 3.4669 (0.0074) C9_$3 3.4614 (0.0082) C10_$3 Rms deviation of fitted atoms = 0.0083 |
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 | ||
Pt1 | 0.29409 (4) | 0.82704 (3) | 0.435191 (17) | 0.04860 (13) | |
Cl1 | 0.3670 (4) | 0.7512 (3) | 0.32458 (12) | 0.0767 (7) | |
Cl2 | 0.2551 (4) | 0.6124 (2) | 0.46897 (14) | 0.0871 (8) | |
N2 | 0.2332 (8) | 0.9064 (6) | 0.5283 (3) | 0.0423 (15) | |
C6 | 0.2284 (10) | 1.0409 (8) | 0.5294 (4) | 0.0426 (19) | |
N1 | 0.3098 (8) | 1.0184 (6) | 0.4100 (3) | 0.0450 (16) | |
C1 | 0.3519 (11) | 1.0692 (9) | 0.3464 (5) | 0.057 (2) | |
H1 | 0.3811 | 1.0116 | 0.3101 | 0.068* | |
C10 | 0.1987 (11) | 0.8399 (8) | 0.5891 (5) | 0.055 (2) | |
H10 | 0.2064 | 0.7481 | 0.5893 | 0.066* | |
C5 | 0.2688 (9) | 1.1025 (8) | 0.4618 (4) | 0.0389 (18) | |
N3 | 0.0939 (10) | 1.1049 (7) | 0.7098 (4) | 0.071 (2) | |
H3A | 0.0698 | 1.0625 | 0.7479 | 0.085* | |
H3B | 0.0878 | 1.1898 | 0.7090 | 0.085* | |
C8 | 0.1412 (10) | 1.0382 (9) | 0.6515 (4) | 0.049 (2) | |
C4 | 0.2675 (11) | 1.2361 (10) | 0.4509 (4) | 0.060 (2) | |
H4 | 0.2392 | 1.2929 | 0.4876 | 0.072* | |
C7 | 0.1816 (10) | 1.1089 (8) | 0.5896 (4) | 0.048 (2) | |
H7 | 0.1767 | 1.2008 | 0.5892 | 0.057* | |
C9 | 0.1535 (11) | 0.9024 (8) | 0.6494 (5) | 0.054 (2) | |
H9 | 0.1304 | 0.8532 | 0.6898 | 0.064* | |
C2 | 0.3532 (13) | 1.1994 (9) | 0.3339 (5) | 0.068 (3) | |
H2 | 0.3849 | 1.2310 | 0.2897 | 0.082* | |
C3 | 0.3079 (13) | 1.2861 (9) | 0.3859 (5) | 0.063 (2) | |
H3 | 0.3047 | 1.3767 | 0.3773 | 0.076* | |
O1 | −0.0328 (9) | 0.5863 (7) | 0.3188 (3) | 0.092 (2) | |
O2 | 0.6555 (12) | 0.5285 (8) | 0.3772 (5) | 0.133 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pt1 | 0.0472 (2) | 0.0501 (2) | 0.0482 (2) | 0.00570 (17) | 0.00133 (14) | −0.01017 (16) |
Cl1 | 0.0887 (19) | 0.0824 (18) | 0.0605 (15) | 0.0079 (14) | 0.0163 (14) | −0.0236 (13) |
Cl2 | 0.137 (3) | 0.0468 (14) | 0.0768 (18) | 0.0062 (15) | 0.0060 (17) | −0.0074 (12) |
N2 | 0.046 (4) | 0.042 (4) | 0.039 (4) | 0.004 (3) | 0.002 (3) | −0.010 (3) |
C6 | 0.031 (4) | 0.050 (5) | 0.046 (5) | 0.000 (4) | −0.003 (4) | −0.012 (4) |
N1 | 0.037 (4) | 0.049 (4) | 0.050 (4) | 0.003 (3) | 0.008 (3) | −0.008 (3) |
C1 | 0.047 (5) | 0.071 (7) | 0.053 (6) | −0.001 (4) | 0.005 (4) | −0.001 (5) |
C10 | 0.056 (6) | 0.048 (5) | 0.060 (6) | 0.004 (4) | −0.002 (5) | 0.006 (5) |
C5 | 0.034 (4) | 0.041 (5) | 0.042 (5) | 0.003 (4) | 0.002 (4) | −0.006 (4) |
N3 | 0.098 (6) | 0.068 (5) | 0.048 (5) | 0.003 (5) | 0.019 (4) | −0.007 (4) |
C8 | 0.036 (5) | 0.071 (6) | 0.040 (5) | 0.003 (4) | 0.002 (4) | −0.015 (4) |
C4 | 0.061 (6) | 0.063 (6) | 0.056 (6) | 0.001 (5) | 0.005 (5) | −0.011 (5) |
C7 | 0.054 (5) | 0.042 (5) | 0.047 (5) | 0.005 (4) | −0.004 (4) | −0.006 (4) |
C9 | 0.058 (6) | 0.053 (6) | 0.049 (5) | 0.004 (4) | 0.000 (4) | −0.003 (4) |
C2 | 0.078 (7) | 0.079 (8) | 0.050 (6) | −0.014 (5) | 0.019 (5) | 0.020 (5) |
C3 | 0.078 (7) | 0.050 (6) | 0.061 (6) | −0.002 (5) | 0.011 (5) | 0.002 (5) |
O1 | 0.101 (6) | 0.096 (5) | 0.079 (5) | 0.000 (4) | 0.008 (4) | −0.023 (4) |
O2 | 0.123 (7) | 0.133 (7) | 0.148 (8) | 0.027 (6) | 0.051 (6) | 0.051 (6) |
Pt1—N2 | 1.995 (6) | C1—C2 | 1.338 (10) |
Pt1—N1 | 1.997 (6) | C10—C9 | 1.353 (11) |
Pt1—Cl2 | 2.284 (3) | C5—C4 | 1.366 (11) |
Pt1—Cl1 | 2.303 (2) | N3—C8 | 1.348 (9) |
Pt1—Pt1i | 5.1214 (7) | C8—C9 | 1.377 (10) |
Pt1—Pt1ii | 6.1648 (7) | C8—C7 | 1.409 (11) |
Cl1—O2 | 3.197 (8) | C4—C3 | 1.368 (11) |
Cl1—O1 | 3.362 (7) | C2—C3 | 1.368 (12) |
Cl2—O2iii | 3.240 (8) | C1—H1 | 0.9300 |
Cl2—Cl2iii | 4.335 (5) | C10—H10 | 0.9300 |
Cl2—Cl2iv | 4.584 (6) | N3—H3A | 0.8600 |
O2—O1v | 2.657 (11) | N3—H3B | 0.8600 |
N2—C6 | 1.360 (9) | C4—H4 | 0.9300 |
N2—C10 | 1.361 (10) | C7—H7 | 0.9300 |
C6—C7 | 1.382 (10) | C9—H9 | 0.9300 |
C6—C5 | 1.458 (10) | C2—H2 | 0.9300 |
N1—C5 | 1.339 (9) | C3—H3 | 0.9300 |
N1—C1 | 1.350 (10) | ||
N2—Pt1—N1 | 80.6 (3) | N3—C8—C7 | 119.4 (8) |
N2—Pt1—Cl2 | 95.8 (2) | C9—C8—C7 | 117.7 (7) |
N1—Pt1—Cl2 | 175.25 (19) | C5—C4—C3 | 120.0 (8) |
N2—Pt1—Cl1 | 175.71 (19) | C6—C7—C8 | 119.6 (8) |
N1—Pt1—Cl1 | 95.1 (2) | C10—C9—C8 | 120.6 (8) |
Cl2—Pt1—Cl1 | 88.45 (9) | C1—C2—C3 | 120.2 (9) |
Pt1—Cl1—O2 | 98.33 (18) | C2—C3—C4 | 118.2 (8) |
Pt1—Cl1—O1 | 86.65 (14) | C2—C1—H1 | 118.9 |
O2—Cl1—O1 | 102.4 (2) | N1—C1—H1 | 118.9 |
C6—N2—C10 | 118.3 (7) | C9—C10—H10 | 118.8 |
C6—N2—Pt1 | 115.1 (5) | N2—C10—H10 | 118.8 |
C10—N2—Pt1 | 126.6 (5) | C8—N3—H3A | 120.0 |
N2—C6—C7 | 121.3 (7) | C8—N3—H3B | 120.0 |
N2—C6—C5 | 114.0 (7) | H3A—N3—H3B | 120.0 |
C7—C6—C5 | 124.7 (7) | C5—C4—H4 | 120.0 |
C5—N1—C1 | 118.2 (7) | C3—C4—H4 | 120.0 |
C5—N1—Pt1 | 115.1 (5) | C6—C7—H7 | 120.2 |
C1—N1—Pt1 | 126.6 (6) | C8—C7—H7 | 120.2 |
C2—C1—N1 | 122.2 (8) | C10—C9—H9 | 119.7 |
C9—C10—N2 | 122.4 (8) | C8—C9—H9 | 119.7 |
N1—C5—C4 | 121.2 (7) | C1—C2—H2 | 119.9 |
N1—C5—C6 | 115.2 (7) | C3—C2—H2 | 119.9 |
C4—C5—C6 | 123.6 (7) | C2—C3—H3 | 120.9 |
N3—C8—C9 | 122.9 (8) | C4—C3—H3 | 120.9 |
Cl1—Pt1—N1—C1 | −0.3 (6) | N1—C5—C4—C3 | 0.2 (13) |
Cl2—Pt1—N2—C10 | 4.9 (6) | C6—C5—C4—C3 | 179.7 (8) |
C10—N2—C6—C7 | −2.9 (11) | N2—C6—C7—C8 | 1.2 (11) |
C10—N2—C6—C5 | 179.5 (6) | C5—C6—C7—C8 | 178.5 (7) |
C5—N1—C1—C2 | −0.3 (12) | N3—C8—C7—C6 | −179.4 (7) |
C6—N2—C10—C9 | 2.5 (12) | C9—C8—C7—C6 | 1.0 (11) |
C1—N1—C5—C4 | 0.7 (11) | N2—C10—C9—C8 | −0.2 (13) |
C1—N1—C5—C6 | −178.8 (6) | N3—C8—C9—C10 | 178.9 (8) |
N2—C6—C5—N1 | −2.0 (9) | C7—C8—C9—C10 | −1.5 (12) |
C7—C6—C5—N1 | −179.4 (7) | N1—C1—C2—C3 | −1.1 (14) |
N2—C6—C5—C4 | 178.6 (7) | C1—C2—C3—C4 | 2.0 (15) |
C7—C6—C5—C4 | 1.1 (12) | C5—C4—C3—C2 | −1.6 (14) |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x, −y+2, −z+1; (iii) −x+1, −y+1, −z+1; (iv) −x, −y+1, −z+1; (v) x+1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3B···O1ii | 0.86 | 2.35 | 3.194 (10) | 167 |
Symmetry code: (ii) −x, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [PtCl2(C10H9N3)]·2H2O |
Mr | 473.22 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 7.3136 (6), 10.1125 (9), 18.7166 (16) |
β (°) | 93.784 (1) |
V (Å3) | 1381.2 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 10.54 |
Crystal size (mm) | 0.36 × 0.05 × 0.02 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD-detector diffractometer |
Absorption correction | Gaussian (XPREP in SAINT; Bruker, 2001) |
Tmin, Tmax | 0.323, 0.785 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8387, 3188, 2165 |
Rint | 0.061 |
(sin θ/λ)max (Å−1) | 0.666 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.085, 0.89 |
No. of reflections | 3188 |
No. of parameters | 163 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.81, −0.93 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), TEXSAN (Molecular Structure Corporation, 2001), KENX (Sakai, 2002) and ORTEPII (Johnson, 1976).
Pt1—N2 | 1.995 (6) | Pt1—Pt1ii | 6.1648 (7) |
Pt1—N1 | 1.997 (6) | Cl1—O2 | 3.197 (8) |
Pt1—Cl2 | 2.284 (3) | Cl1—O1 | 3.362 (7) |
Pt1—Cl1 | 2.303 (2) | Cl2—O2iii | 3.240 (8) |
Pt1—Pt1i | 5.1214 (7) | O2—O1iv | 2.657 (11) |
N2—Pt1—N1 | 80.6 (3) | N2—Pt1—Cl1 | 175.71 (19) |
N2—Pt1—Cl2 | 95.8 (2) | N1—Pt1—Cl1 | 95.1 (2) |
N1—Pt1—Cl2 | 175.25 (19) | Cl2—Pt1—Cl1 | 88.45 (9) |
Cl1—Pt1—N1—C1 | −0.3 (6) | N2—C6—C5—N1 | −2.0 (9) |
Cl2—Pt1—N2—C10 | 4.9 (6) |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x, −y+2, −z+1; (iii) −x+1, −y+1, −z+1; (iv) x+1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3B···O1ii | 0.86 | 2.35 | 3.194 (10) | 167 |
Symmetry code: (ii) −x, −y+2, −z+1. |
Since we discovered that some dinuclear platinum complexes are active as catalysts in the reduction of water into molecular hydrogen (Sakai et al., 1993), continuous efforts have been made to develop bifunctional metal complexes consisting of light-harvesting centres and catalytically active centres. The title platinum compound, [PtCl2(4-amino-2,2'-bipyridine)]·2H2O, (I), has been prepared and characterized as one of precursors for our ideal systems. The amino group on the compound can be used to accommodate a photosensitizer, such as a tris(2,2'-bipyridine)ruthenium(II) derivative. In addition, this compound must be viewed as related to the yellow and red forms of [PtCl2(2,2'-bipyridine)] (Herber et al., 1994). Their difference in colour was rationally interpreted in terms of the difference in the Pt—Pt distance observed by X-ray diffraction (3.45 Å for the red form and 4.44 Å for the yellow form). The lowest energy transition was assigned as a metal-to-ligand charge transfer transition (Herber et al., 1994).
Atom Pt1 shows slight distortion toward a tetrahedral geometry (Fig. 1 and Table 1). The structure can be described that one of four coordinated atoms (i.e. Cl2) is shifted by 0.13 (1) Å from the plane defined by the rest of coordinated atoms (N1, N2 and Cl1), and the shift of Pt1 from this plane is neglibly small. The 4-amino-2,2'-bipyridine has a planar geometry with the 13-atom r.m.s. deviation of 0.011 Å. This plane is by 2.6 (2)° tilted with respect to the N1/N2/Cl1 plane.
As shown in Fig. 2, the mononuclear units stack along the a axis, in which two types of π–π stacks are achieved with the plane-to-plane separations of 3.45 (1) and 3.47 (1) Å. The Pt···Pt distances along the stack [5.1214 (7) and 6.1648 (7) Å, see Table 1] indicate that there is no metal–metal interaction in (I). There are hydrogen bonds between the Cl atoms and the water molecules (Table 1), between the water molecules,and between the amino groups and the water molecules (Table 2).