Literature DB >> 21200494

A nearly planar arrangement of ions in 4,4'-bipiperidinium tetra-cyanido-platinate(II) monohydrate.

Abstract

The title compound, (C(10)H(22)N(2))[Pt(CN)(4)]·H(2)O, was isolated from solution as a mol-ecular salt. The compound contains discrete 4,4'-bipiperidinium cations and tetra-cyano-platinate(II) anions that are involved in a hydrogen-bonding network with one water mol-ecule of hydration. The structure differs from that of the similar acetonitrile solvate, (C(10)H(22)N(2))[Pt(CN)(4)]·2CH(3)CN, 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.

Entities: CellLine Chemical Disease Gene Species

Year: 2007 PMID： 21200494 PMCID： PMC2915084 DOI： 10.1107/S1600536807064835

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

Related literature

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 ▶). For the acetonitrile solvate, with a contrasting arrangement of the ions, see Crawford et al. (2004 ▶).

Experimental

Crystal data

(C10H22N2)[Pt(CN)4]·H2O M = 487.48 Orthorhombic, a = 9.5246 (13) Å b = 11.966 (3) Å c = 15.411 (3) Å V = 1756.4 (6) Å3 Z = 4 Mo Kα radiation μ = 8.00 mm−1 T = 290 (2) K 0.63 × 0.60 × 0.40 mm

Data collection

Enraf–Nonius CAD-4 diffractometer Absorption correction: numerical (XPREP in SHELXTL; Bruker, 1998 ▶) T min = 0.014, T max = 0.104 3591 measured reflections 3233 independent reflections 3030 reflections with I > 2σ(I) R int = 0.025 3 standard reflections frequency: 120 min intensity decay: none

Refinement

R[F 2 > 2σ(F 2)] = 0.033 wR(F 2) = 0.088 S = 1.10 3233 reflections 201 parameters H-atom parameters constrained Δρmax = 1.74 e Å−3 Δρmin = −0.69 e Å−3 Absolute structure: (Flack, 1983 ▶), 1371 Friedel pairs Flack parameter: 0.39 (10) Data collection: CAD-4-PC Software (Enraf–Nonius, 1993 ▶); cell refinement: CAD-4-PC Software; 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 ▶). Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807064835/pk2073sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536807064835/pk2073Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report

(C₁₀H₂₂N₂)[Pt(CN)₄]·H₂O	F₀₀₀ = 944
M_r = 487.48	D_x = 1.843 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 25 reflections
a = 9.5246 (13) Å	θ = 8.2–11.7º
b = 11.966 (3) Å	µ = 8.00 mm⁻¹
c = 15.411 (3) Å	T = 290 (2) K
V = 1756.4 (6) Å³	Rectangular prism, colorless
Z = 4	0.63 × 0.60 × 0.40 mm

Enraf–Nonius CAD-4 diffractometer	R_int = 0.025
Radiation source: fine-focus sealed tube	θ_max = 25.4º
Monochromator: graphite	θ_min = 2.2º
T = 290(2) K	h = 0→11
θ/2θ scans	k = 0→14
Absorption correction: analytical(XPREP; Bruker, 1998)	l = −18→18
T_min = 0.014, T_max = 0.104	3 standard reflections
3591 measured reflections	every 120 min
3233 independent reflections	intensity decay: none
3030 reflections with I > 2σ(I)

Refinement on F²	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0571P)² + 1.1497P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.033	(Δ/σ)_max = 0.001
wR(F²) = 0.088	Δρ_max = 1.74 e Å⁻³
S = 1.10	Δρ_min = −0.69 e Å⁻³
3233 reflections	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
201 parameters	Extinction coefficient: 0.0087 (5)
Primary atom site location: structure-invariant direct methods	Absolute structure: (Flack, 1983), 1371 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: 0.39 (10)
Hydrogen site location: inferred from neighbouring sites

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.

	x	y	z	U_iso*/U_eq
Pt1	0.78147 (3)	0.08308 (3)	0.143832 (18)	0.03168 (13)
C1	0.7890 (11)	0.2485 (8)	0.1344 (5)	0.0431 (18)
C2	0.9911 (9)	0.0805 (8)	0.1605 (6)	0.042 (2)
C3	0.7736 (10)	−0.0821 (7)	0.1573 (5)	0.0381 (17)
C4	0.5765 (8)	0.0854 (8)	0.1287 (6)	0.0378 (18)
C5	0.1305 (10)	0.8253 (9)	0.1135 (7)	0.044 (2)
H5C	0.0523	0.8616	0.0846	0.053*
H5D	0.1119	0.8247	0.1754	0.053*
C6	0.1454 (11)	0.7054 (7)	0.0804 (6)	0.038 (2)
H6C	0.0598	0.6646	0.0928	0.046*
H6D	0.1580	0.7066	0.0179	0.046*
C7	0.2665 (10)	0.6462 (6)	0.1210 (6)	0.0330 (18)
H7A	0.2521	0.6462	0.1840	0.040*
C8	0.3971 (12)	0.7103 (8)	0.1024 (8)	0.048 (3)
H8A	0.4145	0.7101	0.0404	0.058*
H8B	0.4760	0.6740	0.1306	0.058*
C9	0.3868 (11)	0.8308 (8)	0.1341 (9)	0.057 (3)
H9A	0.3787	0.8315	0.1969	0.068*
H9B	0.4718	0.8707	0.1185	0.068*
C10	0.1598 (12)	0.3338 (8)	0.0928 (6)	0.037 (2)
H10A	0.0749	0.2943	0.1091	0.045*
H10B	0.1741	0.3237	0.0309	0.045*
C11	0.1436 (11)	0.4557 (7)	0.1125 (6)	0.035 (2)
H11A	0.1209	0.4648	0.1735	0.042*
H11B	0.0663	0.4857	0.0789	0.042*
C12	0.2812 (11)	0.5236 (7)	0.0912 (6)	0.0336 (17)
H12A	0.2954	0.5228	0.0283	0.040*
C13	0.4053 (10)	0.4656 (8)	0.1339 (7)	0.039 (2)
H13A	0.4914	0.5003	0.1138	0.046*
H13B	0.3997	0.4765	0.1962	0.046*
C14	0.4117 (12)	0.3420 (9)	0.1151 (7)	0.045 (3)
H14A	0.4288	0.3303	0.0537	0.053*
H14B	0.4887	0.3087	0.1472	0.053*
N1	0.7856 (10)	0.3441 (7)	0.1291 (6)	0.059 (2)
N2	1.1070 (9)	0.0788 (8)	0.1678 (8)	0.070 (3)
N3	0.7651 (10)	−0.1777 (6)	0.1673 (5)	0.0474 (19)
N4	0.4565 (10)	0.0854 (9)	0.1178 (7)	0.066 (3)
N5	0.2634 (9)	0.8885 (5)	0.0956 (6)	0.0413 (18)
H5A	0.2755	0.8949	0.0379	0.050*
H5B	0.2565	0.9578	0.1179	0.050*
N6	0.2788 (8)	0.2880 (6)	0.1401 (5)	0.0383 (15)
H6A	0.2849	0.2142	0.1296	0.046*
H6B	0.2648	0.2973	0.1974	0.046*
O1	0.2238 (9)	0.0836 (6)	0.4148 (5)	0.0655 (19)
H1A	0.2210	0.0146	0.4017	0.079*
H1B	0.2269	0.1486	0.3921	0.079*

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pt1	0.03236 (18)	0.02454 (17)	0.03815 (18)	−0.00054 (13)	0.00362 (13)	0.00082 (13)
C1	0.051 (5)	0.028 (4)	0.050 (4)	−0.005 (4)	−0.002 (5)	−0.002 (4)
C2	0.041 (5)	0.009 (3)	0.075 (6)	0.006 (4)	0.009 (4)	0.001 (5)
C3	0.042 (4)	0.037 (5)	0.035 (3)	−0.007 (5)	−0.003 (4)	−0.002 (4)
C4	0.027 (4)	0.019 (3)	0.067 (5)	0.002 (4)	0.002 (4)	0.010 (5)
C5	0.021 (4)	0.037 (5)	0.075 (6)	0.003 (4)	0.003 (4)	0.001 (4)
C6	0.034 (5)	0.022 (4)	0.058 (5)	0.001 (4)	−0.006 (5)	−0.005 (4)
C7	0.034 (5)	0.015 (4)	0.050 (4)	−0.004 (3)	−0.002 (4)	−0.004 (3)
C8	0.036 (5)	0.027 (5)	0.082 (7)	0.003 (4)	−0.002 (5)	−0.005 (4)
C9	0.032 (5)	0.031 (5)	0.107 (9)	−0.002 (4)	−0.017 (6)	−0.007 (6)
C10	0.037 (5)	0.024 (4)	0.051 (5)	−0.007 (4)	−0.009 (4)	0.005 (4)
C11	0.032 (4)	0.024 (4)	0.050 (5)	−0.002 (4)	−0.002 (4)	0.010 (3)
C12	0.031 (4)	0.027 (4)	0.042 (4)	0.000 (4)	−0.001 (4)	−0.002 (3)
C13	0.024 (4)	0.028 (4)	0.064 (6)	0.002 (3)	−0.002 (5)	−0.001 (5)
C14	0.032 (5)	0.029 (5)	0.072 (7)	−0.004 (4)	0.006 (4)	0.000 (4)
N1	0.043 (4)	0.035 (5)	0.097 (7)	−0.008 (4)	0.005 (6)	0.004 (4)
N2	0.035 (5)	0.034 (4)	0.140 (9)	0.002 (4)	0.007 (5)	−0.003 (6)
N3	0.051 (5)	0.030 (4)	0.061 (5)	−0.006 (4)	−0.001 (4)	0.007 (3)
N4	0.049 (5)	0.030 (4)	0.118 (8)	0.000 (5)	−0.005 (5)	0.006 (6)
N5	0.036 (4)	0.021 (4)	0.067 (5)	0.002 (3)	−0.004 (4)	0.000 (3)
N6	0.040 (4)	0.021 (3)	0.054 (4)	0.003 (3)	0.005 (5)	0.000 (3)
O1	0.085 (5)	0.037 (3)	0.074 (5)	0.008 (5)	−0.007 (4)	−0.005 (4)

Pt1—C4	1.967 (8)	C9—H9B	0.9700
Pt1—C1	1.986 (9)	C10—N6	1.455 (12)
Pt1—C3	1.989 (8)	C10—C11	1.498 (14)
Pt1—C2	2.013 (9)	C10—H10A	0.9700
C1—N1	1.147 (12)	C10—H10B	0.9700
C2—N2	1.110 (13)	C11—C12	1.577 (14)
C3—N3	1.157 (10)	C11—H11A	0.9700
C4—N4	1.155 (12)	C11—H11B	0.9700
C5—N5	1.500 (12)	C12—C13	1.520 (14)
C5—C6	1.529 (13)	C12—H12A	0.9800
C5—H5C	0.9700	C13—C14	1.508 (13)
C5—H5D	0.9700	C13—H13A	0.9700
C6—C7	1.491 (13)	C13—H13B	0.9700
C6—H6C	0.9700	C14—N6	1.472 (13)
C6—H6D	0.9700	C14—H14A	0.9700
C7—C8	1.490 (14)	C14—H14B	0.9700
C7—C12	1.543 (10)	N5—H5A	0.9000
C7—H7A	0.9800	N5—H5B	0.9000
C8—C9	1.526 (14)	N6—H6A	0.9000
C8—H8A	0.9700	N6—H6B	0.9000
C8—H8B	0.9700	O1—H1A	0.8503
C9—N5	1.487 (13)	O1—H1B	0.8532
C9—H9A	0.9700

C4—Pt1—C1	90.7 (4)	C11—C10—H10A	109.6
C4—Pt1—C3	89.4 (4)	N6—C10—H10B	109.6
C1—Pt1—C3	178.2 (3)	C11—C10—H10B	109.6
C4—Pt1—C2	179.5 (4)	H10A—C10—H10B	108.1
C1—Pt1—C2	89.4 (4)	C10—C11—C12	112.0 (9)
C3—Pt1—C2	90.5 (4)	C10—C11—H11A	109.2
N1—C1—Pt1	176.3 (10)	C12—C11—H11A	109.2
N2—C2—Pt1	178.5 (10)	C10—C11—H11B	109.2
N3—C3—Pt1	177.5 (9)	C12—C11—H11B	109.2
N4—C4—Pt1	178.3 (10)	H11A—C11—H11B	107.9
N5—C5—C6	109.5 (8)	C13—C12—C7	112.1 (8)
N5—C5—H5C	109.8	C13—C12—C11	108.7 (7)
C6—C5—H5C	109.8	C7—C12—C11	110.7 (8)
N5—C5—H5D	109.8	C13—C12—H12A	108.4
C6—C5—H5D	109.8	C7—C12—H12A	108.4
H5C—C5—H5D	108.2	C11—C12—H12A	108.4
C7—C6—C5	112.2 (8)	C14—C13—C12	113.4 (9)
C7—C6—H6C	109.2	C14—C13—H13A	108.9
C5—C6—H6C	109.2	C12—C13—H13A	108.9
C7—C6—H6D	109.2	C14—C13—H13B	108.9
C5—C6—H6D	109.2	C12—C13—H13B	108.9
H6C—C6—H6D	107.9	H13A—C13—H13B	107.7
C8—C7—C6	108.7 (7)	N6—C14—C13	110.2 (9)
C8—C7—C12	110.9 (8)	N6—C14—H14A	109.6
C6—C7—C12	113.4 (8)	C13—C14—H14A	109.6
C8—C7—H7A	107.9	N6—C14—H14B	109.6
C6—C7—H7A	107.9	C13—C14—H14B	109.6
C12—C7—H7A	107.9	H14A—C14—H14B	108.1
C7—C8—C9	111.8 (9)	C9—N5—C5	111.1 (7)
C7—C8—H8A	109.3	C9—N5—H5A	109.4
C9—C8—H8A	109.3	C5—N5—H5A	109.4
C7—C8—H8B	109.3	C9—N5—H5B	109.4
C9—C8—H8B	109.3	C5—N5—H5B	109.4
H8A—C8—H8B	107.9	H5A—N5—H5B	108.0
N5—C9—C8	111.2 (9)	C10—N6—C14	111.9 (7)
N5—C9—H9A	109.4	C10—N6—H6A	109.2
C8—C9—H9A	109.4	C14—N6—H6A	109.2
N5—C9—H9B	109.4	C10—N6—H6B	109.2
C8—C9—H9B	109.4	C14—N6—H6B	109.2
H9A—C9—H9B	108.0	H6A—N6—H6B	107.9
N6—C10—C11	110.2 (8)	H1A—O1—H1B	142.2
N6—C10—H10A	109.6

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5A···O1ⁱ	0.90	1.92	2.809 (12)	172
N5—H5B···N2ⁱⁱ	0.90	2.17	2.940 (12)	143
N5—H5B···N4ⁱⁱⁱ	0.90	2.44	3.008 (13)	121
N6—H6A···N4	0.90	2.25	2.976 (13)	137
N6—H6A···N2^iv	0.90	2.42	3.021 (12)	125
N6—H6B···N3^v	0.90	2.13	3.026 (12)	179
O1—H1A···N1^vi	0.85	2.10	2.946 (11)	179.4
O1—H1B···N3^v	0.85	2.27	3.125 (10)	179.6

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5A⋯O1ⁱ	0.90	1.92	2.809 (12)	172
N5—H5B⋯N2ⁱⁱ	0.90	2.17	2.940 (12)	143
N5—H5B⋯N4ⁱⁱⁱ	0.90	2.44	3.008 (13)	121
N6—H6A⋯N4	0.90	2.25	2.976 (13)	137
N6—H6A⋯N2^iv	0.90	2.42	3.021 (12)	125
N6—H6B⋯N3^v	0.90	2.13	3.026 (12)	179
O1—H1A⋯N1^vi	0.85	2.10	2.946 (11)	179
O1—H1B⋯N3^v	0.85	2.27	3.125 (10)	180

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

1 in total

1. Bis{2-[2,5-bis-(pyridin-2-yl)-1H-imidazol-4-yl]pyridinium} tetra-cyanidoplatinate(II) tetra-hydrate.

Authors: Raquel Gámez-Heredia; Rosa E Navarro; Herbert Höpfl; Adriana Cruz-Enríquez; José J Campos-Gaxiola
Journal: Acta Crystallogr Sect E Struct Rep Online Date: 2013-05-04

1 in total