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In the crystal structure of the title compound, [PtCl2(C10H9N3)]·2H2O, the square-planar platinum complexes form one-dimensional columns based on the π–π-stacking interactions between the 4-amino-2,2′-bi­pyridine ligands, where the plane-to-plane separations are 3.45 (1) and 3.47 (1) Å. The Pt...Pt distances in the column are 5.1214 (7) and 6.1648 (7) Å, suggesting no metal–metal interaction. Intermolecular hydrogen bonds are formed among the water mol­ecules, the amino groups, and the coordinated Cl atoms.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803013552/ob6260sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803013552/ob6260Isup2.hkl
Contains datablock I

CCDC reference: 217391

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.012 Å
  • H-atom completeness 70%
  • R factor = 0.046
  • wR factor = 0.085
  • Data-to-parameter ratio = 19.6

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
REFLT_03 From the CIF: _diffrn_reflns_theta_max 28.27 From the CIF: _reflns_number_total 3188 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 3436 Completeness (_total/calc) 92.78% Alert C: < 95% complete General Notes
FORMU_01 There is a discrepancy between the atom counts in the _chemical_formula_sum and the formula from the _atom_site* data. Atom count from _chemical_formula_sum:C10 H13 Cl2 N3 O2 Pt1 Atom count from the _atom_site data: C10 H9 Cl2 N3 O2 Pt1 CELLZ_01 From the CIF: _cell_formula_units_Z 4 From the CIF: _chemical_formula_sum C10 H13 Cl2 N3 O2 Pt TEST: Compare cell contents of formula and atom_site data atom Z*formula cif sites diff C 40.00 40.00 0.00 H 52.00 36.00 16.00 Cl 8.00 8.00 0.00 N 12.00 12.00 0.00 O 8.00 8.00 0.00 Pt 4.00 4.00 0.00 Difference between formula and atom_site contents detected. WARNING: H atoms missing from atom site list. Is this intentional?
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

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 ππ 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).

Experimental top

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.

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. The structure of (I), showing the atom-labeling scheme. Displacement ellipsoids are shown at the 50% probability level.
[Figure 2] Fig. 2. The crystal packing in (I), showing the one-dimensional ππ-stacking interactions (a) along the a axis and (b) along the c axis (1/4 < z < 3/4). Hydrogen bonds are not shown.
cis-Diammine(L-pyrolglutamato)platinum(II) top
Crystal data top
[PtCl2(C10H9N3)]·2H2OF(000) = 888
Mr = 473.22Dx = 2.276 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 7.3136 (6) ÅCell parameters from 2848 reflections
b = 10.1125 (9) Åθ = 2.3–23.9°
c = 18.7166 (16) ŵ = 10.54 mm1
β = 93.784 (1)°T = 293 K
V = 1381.2 (2) Å3Plate, yellow
Z = 40.36 × 0.05 × 0.02 mm
Data collection top
Bruker SMART APEX CCD-detector
diffractometer
3188 independent reflections
Radiation source: fine-focus sealed tube2165 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.061
Detector resolution: 8.366 pixels mm-1θmax = 28.3°, θmin = 2.2°
ω scansh = 99
Absorption correction: gaussian
(XPREP in SAINT; Bruker, 2001)
k = 1310
Tmin = 0.323, Tmax = 0.785l = 2324
8387 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.085H-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 parametersΔρmax = 1.81 e Å3
0 restraintsΔρmin = 0.93 e Å3
Crystal data top
[PtCl2(C10H9N3)]·2H2OV = 1381.2 (2) Å3
Mr = 473.22Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.3136 (6) ŵ = 10.54 mm1
b = 10.1125 (9) ÅT = 293 K
c = 18.7166 (16) Å0.36 × 0.05 × 0.02 mm
β = 93.784 (1)°
Data collection top
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 = 0.785Rint = 0.061
8387 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.085H-atom parameters constrained
S = 0.89Δρmax = 1.81 e Å3
3188 reflectionsΔρmin = 0.93 e Å3
163 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Pt10.29409 (4)0.82704 (3)0.435191 (17)0.04860 (13)
Cl10.3670 (4)0.7512 (3)0.32458 (12)0.0767 (7)
Cl20.2551 (4)0.6124 (2)0.46897 (14)0.0871 (8)
N20.2332 (8)0.9064 (6)0.5283 (3)0.0423 (15)
C60.2284 (10)1.0409 (8)0.5294 (4)0.0426 (19)
N10.3098 (8)1.0184 (6)0.4100 (3)0.0450 (16)
C10.3519 (11)1.0692 (9)0.3464 (5)0.057 (2)
H10.38111.01160.31010.068*
C100.1987 (11)0.8399 (8)0.5891 (5)0.055 (2)
H100.20640.74810.58930.066*
C50.2688 (9)1.1025 (8)0.4618 (4)0.0389 (18)
N30.0939 (10)1.1049 (7)0.7098 (4)0.071 (2)
H3A0.06981.06250.74790.085*
H3B0.08781.18980.70900.085*
C80.1412 (10)1.0382 (9)0.6515 (4)0.049 (2)
C40.2675 (11)1.2361 (10)0.4509 (4)0.060 (2)
H40.23921.29290.48760.072*
C70.1816 (10)1.1089 (8)0.5896 (4)0.048 (2)
H70.17671.20080.58920.057*
C90.1535 (11)0.9024 (8)0.6494 (5)0.054 (2)
H90.13040.85320.68980.064*
C20.3532 (13)1.1994 (9)0.3339 (5)0.068 (3)
H20.38491.23100.28970.082*
C30.3079 (13)1.2861 (9)0.3859 (5)0.063 (2)
H30.30471.37670.37730.076*
O10.0328 (9)0.5863 (7)0.3188 (3)0.092 (2)
O20.6555 (12)0.5285 (8)0.3772 (5)0.133 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pt10.0472 (2)0.0501 (2)0.0482 (2)0.00570 (17)0.00133 (14)0.01017 (16)
Cl10.0887 (19)0.0824 (18)0.0605 (15)0.0079 (14)0.0163 (14)0.0236 (13)
Cl20.137 (3)0.0468 (14)0.0768 (18)0.0062 (15)0.0060 (17)0.0074 (12)
N20.046 (4)0.042 (4)0.039 (4)0.004 (3)0.002 (3)0.010 (3)
C60.031 (4)0.050 (5)0.046 (5)0.000 (4)0.003 (4)0.012 (4)
N10.037 (4)0.049 (4)0.050 (4)0.003 (3)0.008 (3)0.008 (3)
C10.047 (5)0.071 (7)0.053 (6)0.001 (4)0.005 (4)0.001 (5)
C100.056 (6)0.048 (5)0.060 (6)0.004 (4)0.002 (5)0.006 (5)
C50.034 (4)0.041 (5)0.042 (5)0.003 (4)0.002 (4)0.006 (4)
N30.098 (6)0.068 (5)0.048 (5)0.003 (5)0.019 (4)0.007 (4)
C80.036 (5)0.071 (6)0.040 (5)0.003 (4)0.002 (4)0.015 (4)
C40.061 (6)0.063 (6)0.056 (6)0.001 (5)0.005 (5)0.011 (5)
C70.054 (5)0.042 (5)0.047 (5)0.005 (4)0.004 (4)0.006 (4)
C90.058 (6)0.053 (6)0.049 (5)0.004 (4)0.000 (4)0.003 (4)
C20.078 (7)0.079 (8)0.050 (6)0.014 (5)0.019 (5)0.020 (5)
C30.078 (7)0.050 (6)0.061 (6)0.002 (5)0.011 (5)0.002 (5)
O10.101 (6)0.096 (5)0.079 (5)0.000 (4)0.008 (4)0.023 (4)
O20.123 (7)0.133 (7)0.148 (8)0.027 (6)0.051 (6)0.051 (6)
Geometric parameters (Å, º) top
Pt1—N21.995 (6)C1—C21.338 (10)
Pt1—N11.997 (6)C10—C91.353 (11)
Pt1—Cl22.284 (3)C5—C41.366 (11)
Pt1—Cl12.303 (2)N3—C81.348 (9)
Pt1—Pt1i5.1214 (7)C8—C91.377 (10)
Pt1—Pt1ii6.1648 (7)C8—C71.409 (11)
Cl1—O23.197 (8)C4—C31.368 (11)
Cl1—O13.362 (7)C2—C31.368 (12)
Cl2—O2iii3.240 (8)C1—H10.9300
Cl2—Cl2iii4.335 (5)C10—H100.9300
Cl2—Cl2iv4.584 (6)N3—H3A0.8600
O2—O1v2.657 (11)N3—H3B0.8600
N2—C61.360 (9)C4—H40.9300
N2—C101.361 (10)C7—H70.9300
C6—C71.382 (10)C9—H90.9300
C6—C51.458 (10)C2—H20.9300
N1—C51.339 (9)C3—H30.9300
N1—C11.350 (10)
N2—Pt1—N180.6 (3)N3—C8—C7119.4 (8)
N2—Pt1—Cl295.8 (2)C9—C8—C7117.7 (7)
N1—Pt1—Cl2175.25 (19)C5—C4—C3120.0 (8)
N2—Pt1—Cl1175.71 (19)C6—C7—C8119.6 (8)
N1—Pt1—Cl195.1 (2)C10—C9—C8120.6 (8)
Cl2—Pt1—Cl188.45 (9)C1—C2—C3120.2 (9)
Pt1—Cl1—O298.33 (18)C2—C3—C4118.2 (8)
Pt1—Cl1—O186.65 (14)C2—C1—H1118.9
O2—Cl1—O1102.4 (2)N1—C1—H1118.9
C6—N2—C10118.3 (7)C9—C10—H10118.8
C6—N2—Pt1115.1 (5)N2—C10—H10118.8
C10—N2—Pt1126.6 (5)C8—N3—H3A120.0
N2—C6—C7121.3 (7)C8—N3—H3B120.0
N2—C6—C5114.0 (7)H3A—N3—H3B120.0
C7—C6—C5124.7 (7)C5—C4—H4120.0
C5—N1—C1118.2 (7)C3—C4—H4120.0
C5—N1—Pt1115.1 (5)C6—C7—H7120.2
C1—N1—Pt1126.6 (6)C8—C7—H7120.2
C2—C1—N1122.2 (8)C10—C9—H9119.7
C9—C10—N2122.4 (8)C8—C9—H9119.7
N1—C5—C4121.2 (7)C1—C2—H2119.9
N1—C5—C6115.2 (7)C3—C2—H2119.9
C4—C5—C6123.6 (7)C2—C3—H3120.9
N3—C8—C9122.9 (8)C4—C3—H3120.9
Cl1—Pt1—N1—C10.3 (6)N1—C5—C4—C30.2 (13)
Cl2—Pt1—N2—C104.9 (6)C6—C5—C4—C3179.7 (8)
C10—N2—C6—C72.9 (11)N2—C6—C7—C81.2 (11)
C10—N2—C6—C5179.5 (6)C5—C6—C7—C8178.5 (7)
C5—N1—C1—C20.3 (12)N3—C8—C7—C6179.4 (7)
C6—N2—C10—C92.5 (12)C9—C8—C7—C61.0 (11)
C1—N1—C5—C40.7 (11)N2—C10—C9—C80.2 (13)
C1—N1—C5—C6178.8 (6)N3—C8—C9—C10178.9 (8)
N2—C6—C5—N12.0 (9)C7—C8—C9—C101.5 (12)
C7—C6—C5—N1179.4 (7)N1—C1—C2—C31.1 (14)
N2—C6—C5—C4178.6 (7)C1—C2—C3—C42.0 (15)
C7—C6—C5—C41.1 (12)C5—C4—C3—C21.6 (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.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3B···O1ii0.862.353.194 (10)167
Symmetry code: (ii) x, y+2, z+1.

Experimental details

Crystal data
Chemical formula[PtCl2(C10H9N3)]·2H2O
Mr473.22
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)7.3136 (6), 10.1125 (9), 18.7166 (16)
β (°) 93.784 (1)
V3)1381.2 (2)
Z4
Radiation typeMo Kα
µ (mm1)10.54
Crystal size (mm)0.36 × 0.05 × 0.02
Data collection
DiffractometerBruker SMART APEX CCD-detector
diffractometer
Absorption correctionGaussian
(XPREP in SAINT; Bruker, 2001)
Tmin, Tmax0.323, 0.785
No. of measured, independent and
observed [I > 2σ(I)] reflections
8387, 3188, 2165
Rint0.061
(sin θ/λ)max1)0.666
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.085, 0.89
No. of reflections3188
No. of parameters163
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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).

Selected geometric parameters (Å, º) top
Pt1—N21.995 (6)Pt1—Pt1ii6.1648 (7)
Pt1—N11.997 (6)Cl1—O23.197 (8)
Pt1—Cl22.284 (3)Cl1—O13.362 (7)
Pt1—Cl12.303 (2)Cl2—O2iii3.240 (8)
Pt1—Pt1i5.1214 (7)O2—O1iv2.657 (11)
N2—Pt1—N180.6 (3)N2—Pt1—Cl1175.71 (19)
N2—Pt1—Cl295.8 (2)N1—Pt1—Cl195.1 (2)
N1—Pt1—Cl2175.25 (19)Cl2—Pt1—Cl188.45 (9)
Cl1—Pt1—N1—C10.3 (6)N2—C6—C5—N12.0 (9)
Cl2—Pt1—N2—C104.9 (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.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3B···O1ii0.862.353.194 (10)167
Symmetry code: (ii) x, y+2, z+1.
 

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