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Acta Cryst. (2008). E64, m138-m139    [ doi:10.1107/S1600536807064835 ]

A nearly planar arrangement of ions in 4,4'-bipiperidinium tetracyanidoplatinate(II) monohydrate

B. A. Maynard and R. E. Sykora

Abstract top

The title compound, (C10H22N2)[Pt(CN)4]·H2O, was isolated from solution as a molecular salt. The compound contains discrete 4,4'-bipiperidinium cations and tetracyanoplatinate(II) anions that are involved in a hydrogen-bonding network with one water molecule of hydration. The structure differs from that of the similar acetonitrile solvate, (C10H22N2)[Pt(CN)4]·2CH3CN, in the orientation of the ions relative to one another. The hydrate reported here contains layers of nearly parallel cations and anions with an angle between their mean planes of only 4.35 (11)°, while in the acetonitrile solvate the cations and anions are nearly perpendicular to one another (86.1° between mean planes). The crystal showed partial inversion twinning.

Comment top

The title compound, (C10H22N2)Pt(CN)4.H2O, was obtained as an unexpected product during a reaction that attempted to prepare a praseodymium tetracyanoplatinate incorporating 4,4'-bipiperidine.

The structure of (I) consists of separated 4,4'-bipiperidinium dications and tetracyanoplatinate anions, additionally one water molecule of crystallization is also present. Fig. 1 shows an illustration of the units of the structure along with the atomic labeling scheme. The 4,4'-bipiperidinium cations and tetracyanoplatinate anions lie in approximately the ab crystallographic planes and contain multiple hydrogen bonding interactions as can be seen in Fig. 2. Each of the approximately square planar anions is hydrogen bonded to four cations and each cation is also hydrogen bonded to four anions. See Table 1 for bond distances and angles of these hydrogen bonding interactions. The mean plane that passes through the 4,4'-bipiperidinium cation makes an angle of 4.35 (11)° with the mean plane of the tetracyanoplatinate anion in the structure, illustrating the nearly parallel nature of these groups relative to one another. Small cavities in these two dimensional planes are filled with water molecules that hydrogen bond within the plane to N1 and N3 atoms of the tetracyanoplatinate anions. Additional hydrogen bonding interactions are also present between the water molecules in one plane and H5A atoms of neighboring planes. See Table 1 for details of these H-bonding interactions.

Several major structural differences exist between I and the previously reported (C10H22N2)Pt(CN)4.2CH3CN, II (Crawford et al., 2004). While compound I contains a nearly parallel arrangement of the cations and anions, the 4,4'-bipiperidinium cations in II are nearly perpendicular to the tetracyanoplatinate anions. The angle between the mean planes formed by the two groups in II is 86.1°. This packing arrangement of the cations and anions in II leaves relatively large holes in the structure that accommodate acetonitrile solvate molecules. In I, the smallercavities contain water molecules.

Related literature top

Organic dications such as 4,4'-bipyridinium and 4,4'-bipiperidinium have been shown to be successful in crystallizing a number of square-planar metallate anions, and a large number of salts containing these two ions have been reported (Lewis & Orpen, 1998; Angeloni & Orpen, 2001; Crawford et al., 2004). The acetonitrile solvate (C10H22N2)Pt(CN)4.2CH3CN, (II) (Crawford et al., 2004), is very similar in formulation to the title compound, (C10H22N2)Pt(CN)4.H2O, (I). The main structural difference in these two compounds is the orientation of the cations and anions relative to one another. In (I), the 4,4'-bipiperidinium cations are nearly planar with the tetracyanoplatinate anions, while in (II) the cations and anions are nearly perpendicular to one another. The packing arrangements lead to different sized cavities that accommodate water in (I) and acetonitrile in II.

Experimental top

K2Pt(CN)4.3H2O (Alfa Aesar, 99.9%), 4,4'-bipiperidine dihydrochloride (Aldrich, 97%), and Pr(NO3)3.6H2O (Strem Chemicals, 99.9%) were used as received without further purification. K2Pt(CN)4.3H2O (1 ml, 0.14 M) in 90%:10% CH3CN:H2O was added to an CH3CN solution of Pr(NO3)3.6H2O (1 ml, 0.10 M). 4,4'-bipiperidine dihydrochloride (1 ml, 0.077 M) in CH3CN was then layered on this solution. Slow evaporation of the solvents over a period of several days resulted in colorless, prismatic crystals of the title compound.

Refinement top

H atoms of the 4,4'-bipiperidinium cation were placed in calculated positions and allowed to ride during subsequent refinement, with Uiso(H) = 1.2Ueq(C) and C—H distances of 0.97 Å for H atoms bonded to the C atoms and Uiso(H) = 1.2Ueq(N) and N—H distances of 0.90 Å for the H atoms bonded to the N atoms. The H atoms on the water molecule were not located in the difference map, but were placed in calculated positions with O—H distances of 0.85 Å and Uiso(H) = 1.2Ueq(O). The H atoms were not allowed to move during refinement. The crystal of I that was used for the diffraction study was found to be a racemic twin and therefore the refinement was carried out taking into account the inverted component.

Computing details top

Data collection: CAD-4-PC Software (Enraf–Nonius, 1993); cell refinement: CAD-4-PC Software (Enraf–Nonius, 1993); data reduction: XCAD4 (Harms & Wocadlo, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level.
[Figure 2] Fig. 2. A representation of two-dimensional layers of 4,4'-bipiperidinium cations, tetracyanoplatinate anions and water molecules found in the ab plane of (I).
4,4'-bipiperidinium tetracyanidoplatinate monohydrate top
Crystal data top
(C10H22N2)[Pt(CN)4]·H2OF000 = 944
Mr = 487.48Dx = 1.843 Mg m−3
Orthorhombic, P212121Mo Kα radiation
λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 25 reflections
a = 9.5246 (13) Åθ = 8.2–11.7º
b = 11.966 (3) ŵ = 8.00 mm−1
c = 15.411 (3) ÅT = 290 (2) K
V = 1756.4 (6) Å3Rectangular prism, colorless
Z = 40.63 × 0.60 × 0.40 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer		Rint = 0.025
Radiation source: fine-focus sealed tubeθmax = 25.4º
Monochromator: graphiteθmin = 2.2º
T = 290(2) Kh = 0→11
θ/2θ scansk = 0→14
Absorption correction: analytical
(XPREP; Bruker, 1998)		l = −18→18
Tmin = 0.014, Tmax = 0.1043 standard reflections
3591 measured reflections every 120 min
3233 independent reflections intensity decay: none
3030 reflections with I > 2σ(I)
Refinement top
Refinement on F2H-atom parameters constrained
Least-squares matrix: full  w = 1/[σ2(Fo2) + (0.0571P)2 + 1.1497P]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.033(Δ/σ)max = 0.001
wR(F2) = 0.088Δρmax = 1.74 e Å−3
S = 1.10Δρmin = −0.69 e Å−3
3233 reflectionsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
201 parametersExtinction coefficient: 0.0087 (5)
Primary atom site location: structure-invariant direct methodsAbsolute structure: (Flack, 1983), 1371 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: 0.39 (10)
Hydrogen site location: inferred from neighbouring sites
Crystal data top
(C10H22N2)[Pt(CN)4]·H2OV = 1756.4 (6) Å3
Mr = 487.48Z = 4
Orthorhombic, P212121Mo Kα
a = 9.5246 (13) ŵ = 8.00 mm−1
b = 11.966 (3) ÅT = 290 (2) K
c = 15.411 (3) Å0.63 × 0.60 × 0.40 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer		3030 reflections with I > 2σ(I)
Absorption correction: analytical
(XPREP; Bruker, 1998)		Rint = 0.025
Tmin = 0.014, Tmax = 0.1043 standard reflections
3591 measured reflections every 120 min
3233 independent reflections intensity decay: none
Refinement top
R[F2 > 2σ(F2)] = 0.033H-atom parameters constrained
wR(F2) = 0.088Δρmax = 1.74 e Å−3
S = 1.10Δρmin = −0.69 e Å−3
3233 reflectionsAbsolute structure: (Flack, 1983), 1371 Friedel pairs
201 parametersFlack parameter: 0.39 (10)
Special details top

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 > 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Pt10.78147 (3)0.08308 (3)0.143832 (18)0.03168 (13)
C10.7890 (11)0.2485 (8)0.1344 (5)0.0431 (18)
C20.9911 (9)0.0805 (8)0.1605 (6)0.042 (2)
C30.7736 (10)−0.0821 (7)0.1573 (5)0.0381 (17)
C40.5765 (8)0.0854 (8)0.1287 (6)0.0378 (18)
C50.1305 (10)0.8253 (9)0.1135 (7)0.044 (2)
H5C0.05230.86160.08460.053*
H5D0.11190.82470.17540.053*
C60.1454 (11)0.7054 (7)0.0804 (6)0.038 (2)
H6C0.05980.66460.09280.046*
H6D0.15800.70660.01790.046*
C70.2665 (10)0.6462 (6)0.1210 (6)0.0330 (18)
H7A0.25210.64620.18400.040*
C80.3971 (12)0.7103 (8)0.1024 (8)0.048 (3)
H8A0.41450.71010.04040.058*
H8B0.47600.67400.13060.058*
C90.3868 (11)0.8308 (8)0.1341 (9)0.057 (3)
H9A0.37870.83150.19690.068*
H9B0.47180.87070.11850.068*
C100.1598 (12)0.3338 (8)0.0928 (6)0.037 (2)
H10A0.07490.29430.10910.045*
H10B0.17410.32370.03090.045*
C110.1436 (11)0.4557 (7)0.1125 (6)0.035 (2)
H11A0.12090.46480.17350.042*
H11B0.06630.48570.07890.042*
C120.2812 (11)0.5236 (7)0.0912 (6)0.0336 (17)
H12A0.29540.52280.02830.040*
C130.4053 (10)0.4656 (8)0.1339 (7)0.039 (2)
H13A0.49140.50030.11380.046*
H13B0.39970.47650.19620.046*
C140.4117 (12)0.3420 (9)0.1151 (7)0.045 (3)
H14A0.42880.33030.05370.053*
H14B0.48870.30870.14720.053*
N10.7856 (10)0.3441 (7)0.1291 (6)0.059 (2)
N21.1070 (9)0.0788 (8)0.1678 (8)0.070 (3)
N30.7651 (10)−0.1777 (6)0.1673 (5)0.0474 (19)
N40.4565 (10)0.0854 (9)0.1178 (7)0.066 (3)
N50.2634 (9)0.8885 (5)0.0956 (6)0.0413 (18)
H5A0.27550.89490.03790.050*
H5B0.25650.95780.11790.050*
N60.2788 (8)0.2880 (6)0.1401 (5)0.0383 (15)
H6A0.28490.21420.12960.046*
H6B0.26480.29730.19740.046*
O10.2238 (9)0.0836 (6)0.4148 (5)0.0655 (19)
H1A0.22100.01460.40170.079*
H1B0.22690.14860.39210.079*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pt10.03236 (18)0.02454 (17)0.03815 (18)−0.00054 (13)0.00362 (13)0.00082 (13)
C10.051 (5)0.028 (4)0.050 (4)−0.005 (4)−0.002 (5)−0.002 (4)
C20.041 (5)0.009 (3)0.075 (6)0.006 (4)0.009 (4)0.001 (5)
C30.042 (4)0.037 (5)0.035 (3)−0.007 (5)−0.003 (4)−0.002 (4)
C40.027 (4)0.019 (3)0.067 (5)0.002 (4)0.002 (4)0.010 (5)
C50.021 (4)0.037 (5)0.075 (6)0.003 (4)0.003 (4)0.001 (4)
C60.034 (5)0.022 (4)0.058 (5)0.001 (4)−0.006 (5)−0.005 (4)
C70.034 (5)0.015 (4)0.050 (4)−0.004 (3)−0.002 (4)−0.004 (3)
C80.036 (5)0.027 (5)0.082 (7)0.003 (4)−0.002 (5)−0.005 (4)
C90.032 (5)0.031 (5)0.107 (9)−0.002 (4)−0.017 (6)−0.007 (6)
C100.037 (5)0.024 (4)0.051 (5)−0.007 (4)−0.009 (4)0.005 (4)
C110.032 (4)0.024 (4)0.050 (5)−0.002 (4)−0.002 (4)0.010 (3)
C120.031 (4)0.027 (4)0.042 (4)0.000 (4)−0.001 (4)−0.002 (3)
C130.024 (4)0.028 (4)0.064 (6)0.002 (3)−0.002 (5)−0.001 (5)
C140.032 (5)0.029 (5)0.072 (7)−0.004 (4)0.006 (4)0.000 (4)
N10.043 (4)0.035 (5)0.097 (7)−0.008 (4)0.005 (6)0.004 (4)
N20.035 (5)0.034 (4)0.140 (9)0.002 (4)0.007 (5)−0.003 (6)
N30.051 (5)0.030 (4)0.061 (5)−0.006 (4)−0.001 (4)0.007 (3)
N40.049 (5)0.030 (4)0.118 (8)0.000 (5)−0.005 (5)0.006 (6)
N50.036 (4)0.021 (4)0.067 (5)0.002 (3)−0.004 (4)0.000 (3)
N60.040 (4)0.021 (3)0.054 (4)0.003 (3)0.005 (5)0.000 (3)
O10.085 (5)0.037 (3)0.074 (5)0.008 (5)−0.007 (4)−0.005 (4)
Geometric parameters (Å, °) top
Pt1—C41.967 (8)C9—H9B0.9700
Pt1—C11.986 (9)C10—N61.455 (12)
Pt1—C31.989 (8)C10—C111.498 (14)
Pt1—C22.013 (9)C10—H10A0.9700
C1—N11.147 (12)C10—H10B0.9700
C2—N21.110 (13)C11—C121.577 (14)
C3—N31.157 (10)C11—H11A0.9700
C4—N41.155 (12)C11—H11B0.9700
C5—N51.500 (12)C12—C131.520 (14)
C5—C61.529 (13)C12—H12A0.9800
C5—H5C0.9700C13—C141.508 (13)
C5—H5D0.9700C13—H13A0.9700
C6—C71.491 (13)C13—H13B0.9700
C6—H6C0.9700C14—N61.472 (13)
C6—H6D0.9700C14—H14A0.9700
C7—C81.490 (14)C14—H14B0.9700
C7—C121.543 (10)N5—H5A0.9000
C7—H7A0.9800N5—H5B0.9000
C8—C91.526 (14)N6—H6A0.9000
C8—H8A0.9700N6—H6B0.9000
C8—H8B0.9700O1—H1A0.8503
C9—N51.487 (13)O1—H1B0.8532
C9—H9A0.9700
C4—Pt1—C190.7 (4)C11—C10—H10A109.6
C4—Pt1—C389.4 (4)N6—C10—H10B109.6
C1—Pt1—C3178.2 (3)C11—C10—H10B109.6
C4—Pt1—C2179.5 (4)H10A—C10—H10B108.1
C1—Pt1—C289.4 (4)C10—C11—C12112.0 (9)
C3—Pt1—C290.5 (4)C10—C11—H11A109.2
N1—C1—Pt1176.3 (10)C12—C11—H11A109.2
N2—C2—Pt1178.5 (10)C10—C11—H11B109.2
N3—C3—Pt1177.5 (9)C12—C11—H11B109.2
N4—C4—Pt1178.3 (10)H11A—C11—H11B107.9
N5—C5—C6109.5 (8)C13—C12—C7112.1 (8)
N5—C5—H5C109.8C13—C12—C11108.7 (7)
C6—C5—H5C109.8C7—C12—C11110.7 (8)
N5—C5—H5D109.8C13—C12—H12A108.4
C6—C5—H5D109.8C7—C12—H12A108.4
H5C—C5—H5D108.2C11—C12—H12A108.4
C7—C6—C5112.2 (8)C14—C13—C12113.4 (9)
C7—C6—H6C109.2C14—C13—H13A108.9
C5—C6—H6C109.2C12—C13—H13A108.9
C7—C6—H6D109.2C14—C13—H13B108.9
C5—C6—H6D109.2C12—C13—H13B108.9
H6C—C6—H6D107.9H13A—C13—H13B107.7
C8—C7—C6108.7 (7)N6—C14—C13110.2 (9)
C8—C7—C12110.9 (8)N6—C14—H14A109.6
C6—C7—C12113.4 (8)C13—C14—H14A109.6
C8—C7—H7A107.9N6—C14—H14B109.6
C6—C7—H7A107.9C13—C14—H14B109.6
C12—C7—H7A107.9H14A—C14—H14B108.1
C7—C8—C9111.8 (9)C9—N5—C5111.1 (7)
C7—C8—H8A109.3C9—N5—H5A109.4
C9—C8—H8A109.3C5—N5—H5A109.4
C7—C8—H8B109.3C9—N5—H5B109.4
C9—C8—H8B109.3C5—N5—H5B109.4
H8A—C8—H8B107.9H5A—N5—H5B108.0
N5—C9—C8111.2 (9)C10—N6—C14111.9 (7)
N5—C9—H9A109.4C10—N6—H6A109.2
C8—C9—H9A109.4C14—N6—H6A109.2
N5—C9—H9B109.4C10—N6—H6B109.2
C8—C9—H9B109.4C14—N6—H6B109.2
H9A—C9—H9B108.0H6A—N6—H6B107.9
N6—C10—C11110.2 (8)H1A—O1—H1B142.2
N6—C10—H10A109.6
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N5—H5A···O1i0.901.922.809 (12)172
N5—H5B···N2ii0.902.172.940 (12)143
N5—H5B···N4iii0.902.443.008 (13)121
N6—H6A···N40.902.252.976 (13)137
N6—H6A···N2iv0.902.423.021 (12)125
N6—H6B···N3v0.902.133.026 (12)179
O1—H1A···N1vi0.852.102.946 (11)179.4
O1—H1B···N3v0.852.273.125 (10)179.6
Symmetry codes: (i) −x+1/2, −y+1, z−1/2; (ii) x−1, y+1, z; (iii) x, y+1, z; (iv) x−1, y, z; (v) −x+1, y+1/2, −z+1/2; (vi) −x+1, y−1/2, −z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N5—H5A···O1i0.901.922.809 (12)172
N5—H5B···N2ii0.902.172.940 (12)143
N5—H5B···N4iii0.902.443.008 (13)121
N6—H6A···N40.902.252.976 (13)137
N6—H6A···N2iv0.902.423.021 (12)125
N6—H6B···N3v0.902.133.026 (12)179
O1—H1A···N1vi0.852.102.946 (11)179.4
O1—H1B···N3v0.852.273.125 (10)179.6
Symmetry codes: (i) −x+1/2, −y+1, z−1/2; (ii) x−1, y+1, z; (iii) x, y+1, z; (iv) x−1, y, z; (v) −x+1, y+1/2, −z+1/2; (vi) −x+1, y−1/2, −z+1/2.
Acknowledgements top

The authors gladly acknowledge the Department of Energy and Oak Ridge National Laboratory for the loan of an Enraf–Nonius CAD-4 X-ray diffractometer.

references
References top

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Bruker (1998). SHELXTL. Version 5.1 for Windows. Bruker AXS Inc., Madison, Wisconsin, USA. XPREP?

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Enraf–Nonius (1993). CAD-4-PC Software. Version 1.2. Enraf–Nonius, Delft, The Netherlands.

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Harms, K. & Wocadlo, S. (1996). XCAD4. University of Marburg, Germany.

Lewis, G. R. & Orpen, A. G. (1998). Chem. Commun. pp. 1873–1874.

Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.

Westrip, S. P. (2007). publCIF. In preparation.