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In the title compounds, [PtCl
2(C
3H
10N
2)], (I), [PdCl
2(C
3H
10N
2)], (II), and [Pt
2Cl
4(C
10H
26N
4)], (III), each metal atom lies in a distorted
cis-square coordination geometry. Compounds (I) and (II) are isostructural, and each complex has a mirror plane through the metal atom and the middle C atom of the propane-1,3-diamine ligand. In (III), the binuclear complex [Pt
2Cl
4(spn)] has an inversion center at the middle of the 4,9-diazadodecane-1,12-diamine (spermine, spn) ligand. The six-membered chelate rings in (III) adopt a chair form, which is unsymmetrical and less flattened than those in (I) and (II). In all three crystal structures, there are intermolecular N-H
Cl hydrogen bonds.
Supporting information
CCDC references: 605659; 605660; 605661
For the preparation of (I), propane-1,3-diamine dihydrochloride (5 mg) was dissolved in 90% (v/v) dimethylformamide (DMF)/water and added to a K2[PtCl4] (14 mg) DMF solution. Colorless platelet crystals appeared after three months on evaporation of this mixture. For the prepartion of (II), propane-1,3-diamine dihydrochloride (5 mg) was dissolved in water, and then PdCl2 (6 mg) in a 2 M NaCl aqueous solution and AgNO3 (5.8 mg) dissolved in water were added. Brown needle-like crystals appeared from this mixture within one week. For the preparation of (III), spermine phosphate (5 mg) dissolved in a 50% (v/v) DMF/1 M NaCl aqueous solution was added to K2[PtCl4] (2.6 mg) dissolved in water. Colorless platelet crystals appeared after five months on evaporation of this mixture.
All H atoms were located in difference Fourier maps, and were then placed at idealized positions and treated as riding, with C—H distances of 0.97 Å, N—H distances for the primary amine groups of 0.90 Å and for the secondary amine groups of 0.91 Å, and Uiso(H) values of 1.2Ueq(carrier atom).
For all compounds, data collection: RAPID-AUTO (Rigaku Corporation, 1998); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2005) and CRYSTALS (Watkin et al., 1996). Program(s) used to solve structure: SIR97 (Altomare et al., 1999) for (I), (II); SHELXS97 (Sheldrick, 1997) for (III). For all compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: CrystalStructure.
(I) Dichloro(propane-1,3-diamine-
κ2N,
N')platinum(II)
top
Crystal data top
[PtCl2(C3H10N2)] | F(000) = 616.00 |
Mr = 340.11 | Dx = 2.861 Mg m−3 |
Orthorhombic, Pbcm | Mo Kα radiation, λ = 0.7107 Å |
Hall symbol: -P 2c 2b | Cell parameters from 4958 reflections |
a = 8.36 (1) Å | θ = 3.1–27.4° |
b = 7.292 (8) Å | µ = 18.36 mm−1 |
c = 12.950 (5) Å | T = 296 K |
V = 789.5 (13) Å3 | Platelet, colorless |
Z = 4 | 0.20 × 0.10 × 0.05 mm |
Data collection top
Rigaku R-AXIS RAPID diffractometer | 573 reflections with F2 > 2.0σ(F2) |
Detector resolution: 10.00 pixels mm-1 | Rint = 0.020 |
ω scans | θmax = 27.4° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −10→10 |
Tmin = 0.152, Tmax = 0.401 | k = −9→9 |
7821 measured reflections | l = −16→16 |
945 independent reflections | |
Refinement top
Refinement on F2 | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.016 | w = 1/[σ2(Fo2) + (0.020P)2 + 0.2145P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.042 | (Δ/σ)max < 0.001 |
S = 1.10 | Δρmax = 0.88 e Å−3 |
945 reflections | Δρmin = −0.81 e Å−3 |
41 parameters | |
Crystal data top
[PtCl2(C3H10N2)] | V = 789.5 (13) Å3 |
Mr = 340.11 | Z = 4 |
Orthorhombic, Pbcm | Mo Kα radiation |
a = 8.36 (1) Å | µ = 18.36 mm−1 |
b = 7.292 (8) Å | T = 296 K |
c = 12.950 (5) Å | 0.20 × 0.10 × 0.05 mm |
Data collection top
Rigaku R-AXIS RAPID diffractometer | 945 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 573 reflections with F2 > 2.0σ(F2) |
Tmin = 0.152, Tmax = 0.401 | Rint = 0.020 |
7821 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.016 | 41 parameters |
wR(F2) = 0.042 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.88 e Å−3 |
945 reflections | Δρmin = −0.81 e Å−3 |
Special details top
Refinement. Refinement using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Pt1 | 0.00153 (3) | 0.03892 (3) | 0.2500 | 0.03543 (9) | |
Cl1 | −0.18963 (14) | 0.02167 (16) | 0.11953 (8) | 0.0531 (3) | |
N1 | 0.1680 (4) | 0.0640 (5) | 0.1357 (2) | 0.0493 (9) | |
H1A | 0.1313 | 0.0011 | 0.0808 | 0.059* | |
H1B | 0.1705 | 0.1830 | 0.1173 | 0.059* | |
C1 | 0.3349 (5) | 0.0061 (6) | 0.1527 (3) | 0.0538 (11) | |
H1C | 0.3996 | 0.0445 | 0.0944 | 0.065* | |
H1D | 0.3392 | −0.1267 | 0.1565 | 0.065* | |
C2 | 0.4035 (8) | 0.0855 (8) | 0.2500 | 0.0480 (15) | |
H2A | 0.3852 | 0.2169 | 0.2500 | 0.058* | |
H2B | 0.5182 | 0.0657 | 0.2500 | 0.058* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Pt1 | 0.03252 (13) | 0.04391 (14) | 0.02984 (11) | 0.00046 (11) | 0.000 | 0.000 |
Cl1 | 0.0438 (6) | 0.0752 (7) | 0.0401 (5) | 0.0076 (6) | −0.0049 (5) | −0.0033 (5) |
N1 | 0.041 (2) | 0.074 (2) | 0.0328 (18) | −0.0058 (18) | 0.0020 (15) | 0.0004 (15) |
C1 | 0.041 (3) | 0.065 (2) | 0.055 (2) | 0.001 (2) | 0.007 (2) | −0.009 (2) |
C2 | 0.033 (4) | 0.054 (3) | 0.057 (3) | −0.001 (3) | 0.000 | 0.000 |
Geometric parameters (Å, º) top
Pt1—N1 | 2.040 (3) | C1—C2 | 1.501 (5) |
Pt1—Cl1 | 2.3295 (17) | C1—H1C | 0.9700 |
N1—C1 | 1.475 (6) | C1—H1D | 0.9700 |
N1—H1A | 0.9000 | C2—H2A | 0.9700 |
N1—H1B | 0.9000 | C2—H2B | 0.9700 |
| | | |
N1—Pt1—N1i | 93.0 (2) | N1—C1—C2 | 112.1 (4) |
N1—Pt1—Cl1 | 86.98 (13) | N1—C1—H1C | 109.2 |
N1i—Pt1—Cl1 | 177.94 (10) | C2—C1—H1C | 109.2 |
N1—Pt1—Cl1i | 177.94 (10) | N1—C1—H1D | 109.2 |
N1i—Pt1—Cl1i | 86.98 (13) | C2—C1—H1D | 109.2 |
Cl1—Pt1—Cl1i | 92.99 (9) | H1C—C1—H1D | 107.9 |
C1—N1—Pt1 | 120.8 (3) | C1—C2—C1i | 114.2 (5) |
C1—N1—H1A | 107.1 | C1—C2—H2A | 108.7 |
Pt1—N1—H1A | 107.1 | C1i—C2—H2A | 108.7 |
C1—N1—H1B | 107.1 | C1—C2—H2B | 108.7 |
Pt1—N1—H1B | 107.1 | C1i—C2—H2B | 108.7 |
H1A—N1—H1B | 106.8 | H2A—C2—H2B | 107.6 |
| | | |
N1i—Pt1—N1—C1 | 28.3 (4) | Pt1—N1—C1—C2 | −50.5 (5) |
Cl1—Pt1—N1—C1 | −153.7 (3) | N1—C1—C2—C1i | 70.6 (6) |
Symmetry code: (i) x, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Cl1ii | 0.90 | 2.65 | 3.369 (5) | 138 |
N1—H1B···Cl1iii | 0.90 | 2.48 | 3.349 (6) | 164 |
Symmetry codes: (ii) −x, −y, −z; (iii) −x, y+1/2, z. |
(II) dichloro(propane-1,3-diamine-
κ2N,
N')palladium(II)
top
Crystal data top
[PdCl2(C3H10N2)] | F(000) = 488.00 |
Mr = 251.45 | Dx = 2.158 Mg m−3 |
Orthorhombic, Pbcm | Mo Kα radiation, λ = 0.7107 Å |
Hall symbol: -P 2c 2b | Cell parameters from 5562 reflections |
a = 8.386 (7) Å | θ = 3.2–27.4° |
b = 7.167 (5) Å | µ = 3.00 mm−1 |
c = 12.88 (1) Å | T = 296 K |
V = 774.1 (10) Å3 | Needle, brown |
Z = 4 | 0.15 × 0.05 × 0.05 mm |
Data collection top
Rigaku R-AXIS RAPID diffractometer | 650 reflections with F2 > 2.0σ(F2) |
Detector resolution: 10.00 pixels mm-1 | Rint = 0.022 |
ω scans | θmax = 27.5° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −10→10 |
Tmin = 0.645, Tmax = 0.861 | k = −9→8 |
7656 measured reflections | l = −16→16 |
923 independent reflections | |
Refinement top
Refinement on F2 | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.017 | w = 1/[σ2(Fo2) + (0.0243P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.043 | (Δ/σ)max < 0.001 |
S = 1.02 | Δρmax = 0.26 e Å−3 |
923 reflections | Δρmin = −0.60 e Å−3 |
41 parameters | |
Crystal data top
[PdCl2(C3H10N2)] | V = 774.1 (10) Å3 |
Mr = 251.45 | Z = 4 |
Orthorhombic, Pbcm | Mo Kα radiation |
a = 8.386 (7) Å | µ = 3.00 mm−1 |
b = 7.167 (5) Å | T = 296 K |
c = 12.88 (1) Å | 0.15 × 0.05 × 0.05 mm |
Data collection top
Rigaku R-AXIS RAPID diffractometer | 923 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 650 reflections with F2 > 2.0σ(F2) |
Tmin = 0.645, Tmax = 0.861 | Rint = 0.022 |
7656 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.017 | 41 parameters |
wR(F2) = 0.043 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.26 e Å−3 |
923 reflections | Δρmin = −0.60 e Å−3 |
Special details top
Refinement. Refinement using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Pd1 | 0.00708 (3) | 0.04926 (3) | 0.2500 | 0.02881 (9) | |
Cl1 | −0.18302 (7) | 0.03777 (8) | 0.11832 (5) | 0.04133 (15) | |
N1 | 0.1721 (2) | 0.0737 (2) | 0.13486 (15) | 0.0408 (4) | |
H1A | 0.1365 | 0.0060 | 0.0808 | 0.049* | |
H1B | 0.1717 | 0.1938 | 0.1144 | 0.049* | |
C1 | 0.3417 (3) | 0.0204 (3) | 0.1518 (2) | 0.0449 (6) | |
H1C | 0.4049 | 0.0617 | 0.0931 | 0.054* | |
H1D | 0.3497 | −0.1145 | 0.1558 | 0.054* | |
C2 | 0.4087 (3) | 0.1044 (5) | 0.2500 | 0.0397 (7) | |
H2A | 0.3869 | 0.2373 | 0.2500 | 0.048* | |
H2B | 0.5235 | 0.0884 | 0.2500 | 0.048* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Pd1 | 0.02779 (13) | 0.03443 (14) | 0.02421 (13) | 0.00006 (11) | 0.000 | 0.000 |
Cl1 | 0.0348 (3) | 0.0578 (3) | 0.0314 (3) | 0.0039 (3) | −0.0055 (2) | −0.0022 (2) |
N1 | 0.0366 (10) | 0.0547 (11) | 0.0313 (11) | −0.0047 (9) | 0.0041 (8) | −0.0030 (8) |
C1 | 0.0341 (11) | 0.0548 (13) | 0.0458 (14) | 0.0018 (11) | 0.0075 (11) | −0.0061 (11) |
C2 | 0.0250 (15) | 0.0446 (17) | 0.049 (2) | −0.0032 (14) | 0.000 | 0.000 |
Geometric parameters (Å, º) top
Pd1—N1 | 2.036 (2) | C1—C2 | 1.509 (3) |
Pd1—Cl1 | 2.3296 (15) | C1—H1C | 0.9700 |
N1—C1 | 1.489 (3) | C1—H1D | 0.9700 |
N1—H1A | 0.9000 | C2—H2A | 0.9700 |
N1—H1B | 0.9000 | C2—H2B | 0.9700 |
| | | |
N1—Pd1—N1i | 93.52 (13) | N1—C1—C2 | 112.1 (2) |
N1—Pd1—Cl1 | 86.42 (9) | N1—C1—H1C | 109.2 |
N1i—Pd1—Cl1 | 177.09 (5) | C2—C1—H1C | 109.2 |
N1—Pd1—Cl1i | 177.09 (5) | N1—C1—H1D | 109.2 |
N1i—Pd1—Cl1i | 86.42 (9) | C2—C1—H1D | 109.2 |
Cl1—Pd1—Cl1i | 93.49 (8) | H1C—C1—H1D | 107.9 |
C1—N1—Pd1 | 121.34 (16) | C1—C2—C1i | 113.9 (3) |
C1—N1—H1A | 107.0 | C1—C2—H2A | 108.8 |
Pd1—N1—H1A | 107.0 | C1i—C2—H2A | 108.8 |
C1—N1—H1B | 107.0 | C1—C2—H2B | 108.8 |
Pd1—N1—H1B | 107.0 | C1i—C2—H2B | 108.8 |
H1A—N1—H1B | 106.7 | H2A—C2—H2B | 107.7 |
| | | |
N1i—Pd1—N1—C1 | 26.0 (2) | Pd1—N1—C1—C2 | −49.0 (2) |
Cl1—Pd1—N1—C1 | −156.92 (16) | N1—C1—C2—C1i | 70.6 (3) |
Symmetry code: (i) x, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Cl1ii | 0.90 | 2.61 | 3.359 (3) | 141 |
N1—H1B···Cl1iii | 0.90 | 2.47 | 3.334 (3) | 162 |
Symmetry codes: (ii) −x, −y, −z; (iii) −x, y+1/2, z. |
(III) µ-4,9-diazadodecane-1,12-diamine-
κ2N1,
N4;
κ2N9,
N12– bis[dichlorodiplatinum(II)]
top
Crystal data top
[Pt2Cl4(C10H26N4)] | F(000) = 676.00 |
Mr = 734.31 | Dx = 2.657 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.7107 Å |
Hall symbol: -P 2yn | Cell parameters from 8101 reflections |
a = 8.86 (1) Å | θ = 3.1–27.5° |
b = 8.018 (6) Å | µ = 15.80 mm−1 |
c = 12.93 (1) Å | T = 123 K |
β = 92.09 (4)° | Platelet, colorless |
V = 917.9 (14) Å3 | 0.10 × 0.10 × 0.05 mm |
Z = 2 | |
Data collection top
Rigaku R-AXIS RAPID diffractometer | 1725 reflections with F2 > 2.0σ(F2) |
Detector resolution: 10.00 pixels mm-1 | Rint = 0.040 |
ω scans | θmax = 27.5° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −11→11 |
Tmin = 0.089, Tmax = 0.455 | k = −10→10 |
9030 measured reflections | l = −16→15 |
2105 independent reflections | |
Refinement top
Refinement on F2 | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.029 | w = 1/[σ2(Fo2) + (0.0438P)2 + 0.3492P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.076 | (Δ/σ)max = 0.001 |
S = 1.05 | Δρmax = 2.61 e Å−3 |
2105 reflections | Δρmin = −2.71 e Å−3 |
92 parameters | |
Crystal data top
[Pt2Cl4(C10H26N4)] | V = 917.9 (14) Å3 |
Mr = 734.31 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.86 (1) Å | µ = 15.80 mm−1 |
b = 8.018 (6) Å | T = 123 K |
c = 12.93 (1) Å | 0.10 × 0.10 × 0.05 mm |
β = 92.09 (4)° | |
Data collection top
Rigaku R-AXIS RAPID diffractometer | 2105 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 1725 reflections with F2 > 2.0σ(F2) |
Tmin = 0.089, Tmax = 0.455 | Rint = 0.040 |
9030 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.029 | 92 parameters |
wR(F2) = 0.076 | H-atom parameters constrained |
S = 1.05 | Δρmax = 2.61 e Å−3 |
2105 reflections | Δρmin = −2.71 e Å−3 |
Special details top
Refinement. Refinement using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Pt1 | 0.19858 (2) | 0.16739 (2) | 0.825909 (16) | 0.02137 (10) | |
Cl1 | 0.45049 (17) | 0.16947 (15) | 0.78547 (15) | 0.0351 (4) | |
Cl2 | 0.24417 (15) | 0.03880 (16) | 0.98396 (11) | 0.0291 (3) | |
N1 | 0.1493 (5) | 0.2662 (6) | 0.6856 (4) | 0.0283 (10) | |
H1A | 0.1190 | 0.3724 | 0.6939 | 0.034* | |
H1B | 0.2339 | 0.2682 | 0.6492 | 0.034* | |
N2 | −0.0242 (5) | 0.1749 (5) | 0.8627 (4) | 0.0226 (10) | |
H2 | −0.0321 | 0.1075 | 0.9188 | 0.027* | |
C1 | 0.0288 (8) | 0.1737 (7) | 0.6241 (5) | 0.0353 (15) | |
H1C | 0.0578 | 0.0576 | 0.6175 | 0.042* | |
H1D | 0.0184 | 0.2211 | 0.5552 | 0.042* | |
C2 | −0.1197 (7) | 0.1848 (7) | 0.6765 (5) | 0.0331 (14) | |
H2A | −0.1440 | 0.3017 | 0.6857 | 0.040* | |
H2B | −0.1974 | 0.1372 | 0.6307 | 0.040* | |
C3 | −0.1262 (6) | 0.0997 (7) | 0.7794 (5) | 0.0287 (12) | |
H3A | −0.0992 | −0.0166 | 0.7710 | 0.034* | |
H3B | −0.2294 | 0.1034 | 0.8020 | 0.034* | |
C4 | −0.0748 (7) | 0.3426 (6) | 0.8963 (5) | 0.0276 (13) | |
H4A | −0.1773 | 0.3347 | 0.9199 | 0.033* | |
H4B | −0.0755 | 0.4181 | 0.8377 | 0.033* | |
C5 | 0.0268 (6) | 0.4140 (7) | 0.9830 (5) | 0.0317 (13) | |
H5A | 0.1292 | 0.4226 | 0.9596 | 0.038* | |
H5B | 0.0276 | 0.3388 | 1.0418 | 0.038* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Pt1 | 0.02145 (14) | 0.01958 (15) | 0.02336 (16) | 0.00114 (6) | 0.00473 (9) | −0.00127 (7) |
Cl1 | 0.0241 (7) | 0.0303 (8) | 0.0515 (11) | −0.0006 (4) | 0.0121 (7) | 0.0017 (6) |
Cl2 | 0.0305 (7) | 0.0335 (7) | 0.0232 (7) | 0.0054 (5) | 0.0003 (5) | −0.0003 (5) |
N1 | 0.033 (3) | 0.026 (2) | 0.027 (3) | 0.0010 (18) | 0.014 (2) | 0.006 (2) |
N2 | 0.027 (3) | 0.020 (2) | 0.021 (3) | 0.0009 (15) | 0.005 (2) | 0.0025 (17) |
C1 | 0.045 (4) | 0.036 (4) | 0.024 (3) | 0.001 (2) | −0.001 (3) | 0.000 (2) |
C2 | 0.033 (3) | 0.033 (3) | 0.032 (4) | 0.001 (2) | −0.009 (3) | −0.003 (2) |
C3 | 0.024 (3) | 0.028 (3) | 0.034 (3) | −0.005 (2) | 0.001 (2) | −0.003 (3) |
C4 | 0.027 (3) | 0.024 (3) | 0.032 (3) | 0.0083 (18) | 0.005 (2) | −0.003 (2) |
C5 | 0.037 (3) | 0.034 (3) | 0.024 (3) | 0.010 (2) | 0.002 (2) | −0.005 (2) |
Geometric parameters (Å, º) top
Pt1—N1 | 2.013 (5) | C1—H1D | 0.9700 |
Pt1—N2 | 2.047 (5) | C2—C3 | 1.499 (9) |
Pt1—Cl1 | 2.310 (3) | C2—H2A | 0.9700 |
Pt1—Cl2 | 2.312 (2) | C2—H2B | 0.9700 |
N1—C1 | 1.503 (8) | C3—H3A | 0.9700 |
N1—H1A | 0.9000 | C3—H3B | 0.9700 |
N1—H1B | 0.9000 | C4—C5 | 1.524 (8) |
N2—C4 | 1.488 (6) | C4—H4A | 0.9700 |
N2—C3 | 1.506 (7) | C4—H4B | 0.9700 |
N2—H2 | 0.9100 | C5—C5i | 1.527 (11) |
C1—C2 | 1.504 (10) | C5—H5A | 0.9700 |
C1—H1C | 0.9700 | C5—H5B | 0.9700 |
| | | |
N1—Pt1—N2 | 91.0 (2) | C3—C2—C1 | 115.8 (5) |
N1—Pt1—Cl1 | 88.44 (14) | C3—C2—H2A | 108.3 |
N2—Pt1—Cl1 | 177.87 (11) | C1—C2—H2A | 108.3 |
N1—Pt1—Cl2 | 176.04 (13) | C3—C2—H2B | 108.3 |
N2—Pt1—Cl2 | 86.94 (15) | C1—C2—H2B | 108.3 |
Cl1—Pt1—Cl2 | 93.69 (7) | H2A—C2—H2B | 107.4 |
C1—N1—Pt1 | 114.2 (3) | C2—C3—N2 | 114.3 (4) |
C1—N1—H1A | 108.7 | C2—C3—H3A | 108.7 |
Pt1—N1—H1A | 108.7 | N2—C3—H3A | 108.7 |
C1—N1—H1B | 108.7 | C2—C3—H3B | 108.7 |
Pt1—N1—H1B | 108.7 | N2—C3—H3B | 108.7 |
H1A—N1—H1B | 107.6 | H3A—C3—H3B | 107.6 |
C4—N2—C3 | 113.1 (4) | N2—C4—C5 | 112.3 (5) |
C4—N2—Pt1 | 113.4 (3) | N2—C4—H4A | 109.1 |
C3—N2—Pt1 | 112.4 (4) | C5—C4—H4A | 109.1 |
C4—N2—H2 | 105.7 | N2—C4—H4B | 109.1 |
C3—N2—H2 | 105.7 | C5—C4—H4B | 109.1 |
Pt1—N2—H2 | 105.7 | H4A—C4—H4B | 107.9 |
N1—C1—C2 | 110.4 (5) | C4—C5—C5i | 111.7 (6) |
N1—C1—H1C | 109.6 | C4—C5—H5A | 109.3 |
C2—C1—H1C | 109.6 | C5i—C5—H5A | 109.3 |
N1—C1—H1D | 109.6 | C4—C5—H5B | 109.3 |
C2—C1—H1D | 109.6 | C5i—C5—H5B | 109.3 |
H1C—C1—H1D | 108.1 | H5A—C5—H5B | 107.9 |
| | | |
N2—Pt1—N1—C1 | −53.6 (4) | N1—C1—C2—C3 | −65.7 (6) |
Cl1—Pt1—N1—C1 | 128.5 (4) | C1—C2—C3—N2 | 65.1 (7) |
N1—Pt1—N2—C4 | −80.2 (4) | C4—N2—C3—C2 | 69.7 (6) |
Cl2—Pt1—N2—C4 | 103.3 (4) | Pt1—N2—C3—C2 | −60.3 (5) |
N1—Pt1—N2—C3 | 49.7 (3) | C3—N2—C4—C5 | 178.1 (5) |
Cl2—Pt1—N2—C3 | −126.9 (3) | Pt1—N2—C4—C5 | −52.5 (6) |
Pt1—N1—C1—C2 | 65.1 (5) | N2—C4—C5—C5i | −179.9 (6) |
Symmetry code: (i) −x, −y+1, −z+2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Cl1ii | 0.90 | 2.48 | 3.376 (5) | 177 |
N1—H1B···Cl2ii | 0.90 | 2.78 | 3.261 (5) | 115 |
N2—H2···Cl2iii | 0.91 | 2.58 | 3.309 (6) | 138 |
Symmetry codes: (ii) −x+1/2, y+1/2, −z+3/2; (iii) −x, −y, −z+2. |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | [PtCl2(C3H10N2)] | [PdCl2(C3H10N2)] | [Pt2Cl4(C10H26N4)] |
Mr | 340.11 | 251.45 | 734.31 |
Crystal system, space group | Orthorhombic, Pbcm | Orthorhombic, Pbcm | Monoclinic, P21/n |
Temperature (K) | 296 | 296 | 123 |
a, b, c (Å) | 8.36 (1), 7.292 (8), 12.950 (5) | 8.386 (7), 7.167 (5), 12.88 (1) | 8.86 (1), 8.018 (6), 12.93 (1) |
α, β, γ (°) | 90, 90, 90 | 90, 90, 90 | 90, 92.09 (4), 90 |
V (Å3) | 789.5 (13) | 774.1 (10) | 917.9 (14) |
Z | 4 | 4 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 18.36 | 3.00 | 15.80 |
Crystal size (mm) | 0.20 × 0.10 × 0.05 | 0.15 × 0.05 × 0.05 | 0.10 × 0.10 × 0.05 |
|
Data collection |
Diffractometer | Rigaku R-AXIS RAPID diffractometer | Rigaku R-AXIS RAPID diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) | Multi-scan (ABSCOR; Higashi, 1995) | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.152, 0.401 | 0.645, 0.861 | 0.089, 0.455 |
No. of measured, independent and observed [F2 > 2.0σ(F2)] reflections | 7821, 945, 573 | 7656, 923, 650 | 9030, 2105, 1725 |
Rint | 0.020 | 0.022 | 0.040 |
(sin θ/λ)max (Å−1) | 0.648 | 0.649 | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.016, 0.042, 1.10 | 0.017, 0.043, 1.02 | 0.029, 0.076, 1.05 |
No. of reflections | 945 | 923 | 2105 |
No. of parameters | 41 | 41 | 92 |
No. of restraints | ? | ? | ? |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.88, −0.81 | 0.26, −0.60 | 2.61, −2.71 |
Selected geometric parameters (Å, º) for (I) topPt1—N1 | 2.040 (3) | Pt1—Cl1 | 2.3295 (17) |
| | | |
N1—Pt1—N1i | 93.0 (2) | Cl1—Pt1—Cl1i | 92.99 (9) |
N1—Pt1—Cl1 | 86.98 (13) | | |
| | | |
N1i—Pt1—N1—C1 | 28.3 (4) | Pt1—N1—C1—C2 | −50.5 (5) |
Symmetry code: (i) x, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Cl1ii | 0.90 | 2.65 | 3.369 (5) | 138 |
N1—H1B···Cl1iii | 0.90 | 2.48 | 3.349 (6) | 164 |
Symmetry codes: (ii) −x, −y, −z; (iii) −x, y+1/2, z. |
Selected geometric parameters (Å, º) for (II) topPd1—N1 | 2.036 (2) | Pd1—Cl1 | 2.3296 (15) |
| | | |
N1—Pd1—N1i | 93.52 (13) | N1—Pd1—Cl1i | 177.09 (5) |
N1—Pd1—Cl1 | 86.42 (9) | Cl1—Pd1—Cl1i | 93.49 (8) |
| | | |
N1i—Pd1—N1—C1 | 26.0 (2) | Pd1—N1—C1—C2 | −49.0 (2) |
Symmetry code: (i) x, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Cl1ii | 0.90 | 2.61 | 3.359 (3) | 141 |
N1—H1B···Cl1iii | 0.90 | 2.47 | 3.334 (3) | 162 |
Symmetry codes: (ii) −x, −y, −z; (iii) −x, y+1/2, z. |
Selected geometric parameters (Å, º) for (III) topPt1—N1 | 2.013 (5) | Pt1—Cl1 | 2.310 (3) |
Pt1—N2 | 2.047 (5) | Pt1—Cl2 | 2.312 (2) |
| | | |
N1—Pt1—N2 | 91.0 (2) | N2—Pt1—Cl2 | 86.94 (15) |
N1—Pt1—Cl1 | 88.44 (14) | Cl1—Pt1—Cl2 | 93.69 (7) |
| | | |
N2—Pt1—N1—C1 | −53.6 (4) | Pt1—N1—C1—C2 | 65.1 (5) |
N1—Pt1—N2—C3 | 49.7 (3) | Pt1—N2—C3—C2 | −60.3 (5) |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Cl1i | 0.90 | 2.48 | 3.376 (5) | 177 |
N1—H1B···Cl2i | 0.90 | 2.78 | 3.261 (5) | 115 |
N2—H2···Cl2ii | 0.91 | 2.58 | 3.309 (6) | 138 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) −x, −y, −z+2. |
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cis-Diamminedichloroplatinum(II) (cisplatin) is known as an anticancer agent against a wide variety of human tumors, especially testicular and ovarian cancers (Siddik, 2003; Zhang & Lippard, 2003). However, its use is limited becuase of the toxic side effects and the development of resistance in tumor cells. Therefore, it is important to design new PtII compounds with improved pharmacological properties and a broader range of anticancer activity.
On the other hand, it is known that polyamines play an important role in the syntheses of nucleic acids and protein, in the structure of the cell membrane, and in the modulation of neurophysiological function in mammalian system (Morgan, 1999). Numerous derivatives and analogues of biogenic polyamines, spermidine [N-(3-aminopropyl)-4-aminobutylamine, spd] and spermine [N,N'-bis(3-aminopropyl)-1,4-butanediamine, spn], have been synthesized with the aim of generating a new type of anticancer drugs (Seiler, 2005). The PtII or PdII complexes of these ligands have been also synthesized, their anticancer properties tested (Teixeira et al., 2004; Marques et al., 2002; McGregor et al., 2002; Hegmans et al., 2001; Amo-Ochoa et al., 1996; Navarro-Ranninger et al., 1994, 1992) and their crystal structures analyzed (Codina et al., 1999). Among them, PtII complexes of spn have been investigated for their antiproliferative and cytotoxic effects, and have been demonstrated to display irreversible anticancer properties against Hera and HSC-3 cell lines, and growth inhibition properties against THP-1 and MOLT-3 cell lines (Teixeira et al., 2004).
The PtII or PdII complexes of propane-1,3-diamine (tn) have also been used as model anticancer agents to study the interaction with DNA (Akdi et al., 2005; Alvarez-Valdes et al., 2002; Marzilli et al., 1980). In the present study, we report the crystal structures of the title compounds, namely [PtCl2(tn)], (I), [PdCl2(tn)], (II), and [Pt2Cl4(spn)], (III).
Compounds (I) and (II) are isostructural (Fig. 1). In each complex, MII [PtII or PdII] and atom C2 of the tn ligand lie on a mirror plane. The metal atom is coordinated by two N atoms from the tn ligand and two Cl atoms, which form a slightly distorted cis-square coordination geometry. The MII atom and the four coordinated atoms are coplanar [the r.m.s. deviation of the fitted atoms is 0.016 Å for (I) and 0.022 Å for (II)]. The metal atom and the tn ligand form a six-membered chelate ring, which adopts a chair form.
The MII—Cl and MII—N bond lengths in (I) and (II) (Tables 1 and 3) are comparable to those in [PtCl2(en)] and [PdCl2(en)] (en is 1,2-ethylenediamine; Iball et al., 1975) and cis-[PtCl2(NH3)2] (Milburn & Truter, 1966) [MII—Cl = 2.288 (8)–2.333 (9) Å and MII—N = 1.95 (3)–2.08 (3) Å], although the five-membered chelate rings of the en ligands have smaller N—MII—N bond angles [73 (2)–87 (2)°] than in (I) and (II). The shortest intermolecular distances between the metal atoms are 3.646 (4) Å in (I) and 3.586 (3) Å in (II), which are considerably longer than those of the en complexes cited above [3.37–3.41 Å]; this difference may be due to the steric hindrance of the propane groups of the tn ligand.
In the crystal packing of (I) and (II), centrosymmetrically related complexes are aligned along the b axis (Fig. 2). The crystal structures are stabilized by N—H···Cl hydrogen bonds (Tables 2 and 4) between the amino groups of the tn ligand and the Cl atoms of the neighboring complexes along the b and c axes (Figs. 2 and 3), forming a lattice-like network.
In (III), the spn ligand coordinates to the two PtII atoms to form a binuclear complex (Fig. 4). Compound (III) is isostructural with the corresponding PdII complex, [Pd2Cl4(spn)] (Codina et al., 1999). A crystallographic inversion center is located at the middle of the butane chain of the spn ligand. The PtII atom is in a slightly distorted cis-square coordination geometry with two N and two Cl atoms. The PtII and four coordinated atoms are coplanar (the r.m.s. deviation of fitted atoms is 0.046 Å). The coordination bond lengths and bond angles (Table 5) are similar to those of (I). The PtII atom and the tn group of the spn ligand form a six-membered chelate ring, which adopts a chair form as in (I) and (II). However, the dihedral angles of the Pt1/N1/N2 and C1/C2/C3 planes with resepct to the N1/C1/N2/C3 plane are 46.4 (2) and 57.9 (4)°, respectively, indicating a less flattened conformation than those in (I) and (II). The corresponding dihedral angles are 24.3 (2) and 62.1 (5)° for (I), 22.2 (1) and 62.1 (3)° for (II), respectively. In addition, the torsion angles of the chelate rings (Table 5) show an unsymmetrical conformation around the PtII atom.
In the crystal packing of (III), there are intermolecular N—H···Cl hydrogen bonds (Table 6) between the primary amine groups of the spn ligand and the Cl atoms of neighboring complexes along the b axis, and between the secondary amine groups and the Cl atoms of neighboring complexes along the c axis, forming a three-dimensional network (Fig. 5).