Sesquicaesium hemisodium tetra­cyanidoplatinate(II) sesquihydrate

Weber, A.P.; Stojanovic, M.; Pischek, M.R.; Sykora, R.E.

doi:10.1107/S1600536810032551

inorganic compounds

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Volume 66| Part 9| September 2010| Page i66

https://doi.org/10.1107/S1600536810032551

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Sesquicaesium hemisodium tetracyanidoplatinate(II) sesquihydrate

Andrew P. Weber,^a Milorad Stojanovic,^a Matthew R. Pischek ^a and Richard E. Sykora ^a ^*

^aDepartment of Chemistry, University of South Alabama, Mobile, AL 36688-0002, USA
^*Correspondence e-mail: rsykora@jaguar1.usouthal.edu

(Received 26 July 2010; accepted 12 August 2010; online 18 August 2010)

The title compound, Cs_1.5Na_0.5[Pt(CN)₄]·1.5H₂O, was isolated from solution as a salt. The tetracyanidoplatinate (TCP) anions are stacked in a linear quasi-one-dimensional arrangement along the b axis, with Pt⋯Pt interactions of 3.6321 (5) Å. The mixed alkali metal TCP contains three distinct alkali metal positions in the structure that do not show any mixed occupancy: Cs1 (site symmetry 2), Cs2 (general position) and Na1 (site symmetry $[\overline{1}]$ ). The Na⁺ ion contains an octahedral coordination environment composed of two water molecules and four N-terminal cyanides, which serve to bridge TCP anions. The Cs⁺ cations contain mono- and bicapped square-prismatic environments, where the square prisms are formed from cyanide N atoms with water molecules capping the faces. The 1.5 water molecules per formula unit are a result of two fully occupied sites, one on a general position and one on a twofold rotation axis. Weak hydrogen-bonding interactions are observed between one water molecule and terminal N-atom acceptors from TCP, while the second water molecule is not involved in hydrogen bonding.

Related literature

Crystalline TCP systems have been studied extensively for their interesting structural and spectroscopic, especially photoluminescent, properties (Holzapfel et al., 1981 ; Gliemann & Yersin, 1985 ; Stojanovic et al., 2010 ). An intrinsic factor affecting the optical properties and arrangement of TCP chains is the identity of the cations involved, and much work has been done in the systematic study of various combinations of alkali metal cations involved (Holzapfel et al., 1981). However, only one known reference of a caesium/sodium mixed alkali metal TCP, viz. NaCs[Pt(CN)₄]·1.5H₂O, exists (Bergsoe et al., 1962 ), which notes the synthesis and scintillation properties for the compound, but not any structural information.

Experimental

Crystal data

Cs_1.5Na_0.5[Pt(CN)₄]·1.5H₂O
M_r = 1074.11
Monoclinic, C 2/c
a = 17.4090 (5) Å
b = 7.2190 (1) Å
c = 18.3921 (5) Å
β = 117.858 (4)°
V = 2043.56 (11) Å³
Z = 4
Mo Kα radiation
μ = 18.99 mm⁻¹
T = 290 K
0.20 × 0.14 × 0.08 mm

Data collection

Oxford Diffraction Excalibur-E diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ) T_min = 0.471, T_max = 1.00
8164 measured reflections
1949 independent reflections
1789 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.014
wR(F²) = 0.034
S = 1.15
1949 reflections
126 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.63 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯N1ⁱ	0.85 (2)	2.37 (3)	3.154 (6)	155 (5)
O1—H1B⋯N3ⁱⁱ	0.83 (2)	2.17 (2)	2.982 (5)	166 (5)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x, -y+1, -z.

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810032551/wm2385sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810032551/wm2385Isup2.hkl

checkCIF report

Comment top

Crystalline tetracyanidoplatinate (TCP) systems have been studied extensively for their interesting structural and spectroscopic, especially photoluminescent, properties (Holzapfel et al., 1981; Gliemann & Yersin, 1985; Stojanovic et al., 2010). The title compound, Cs_1.5Na_0.5Pt(CN)₄.1.5H₂O, was obtained as an unexpected product from a reaction that was an attempt to prepare a heterometallic cyanidometalate complex containing Eu(III), TCP, and dicyanidoaurate moieties. A number of related mixed-metal cation (alkali, alkaline-earth) TCPs have been reported (Holzapfel et al., 1981; Gliemann & Yersin, 1985). However, only one known reference of a caesium/ sodium mixed-alkali metal TCP (NaCsPt(CN)₄.1.5H₂O) exists (Bergsoe et al., 1962), which notes the synthesis and scintillation properties for the compound, but not any structural information.

The structure of the title compound consists of pseudo one-dimensional chains of square-planar TCP anions tethered by Pt···Pt interactions of 3.6321 (5) Å. The platinate chains run parallel to the b axis and are bridged by ionic interactions among Cs⁺ and Na⁺ ions with the N atoms of the cyanidoplatinate, and show a loose packing of water molecules within that space. The water molecules feature weak H-bonding interactions with the N atoms of the platinate as well (Table 1). The Na⁺ ion contains a nearly regular octahedral coordination environment composed of two trans water molecules and four cyanido N atoms. Cs1 and Cs2 contain mono- and bi-capped square prismatic environments, respectively, where the slightly distorted square prisms are formed from cyanido N atoms and the capping positions are occupied by water molecules. As per each discrete TCP anion, the empirical structure of the compound contains an equivalency of 1.5 Cs⁺ as a result of the Cs1 site residing on a twofold rotation axis and Cs2 occupying a general position, 1.5 H₂O molecules due to O1 residing on a general position and the presence of O2 on a twofold rotation axis, and 0.5 Na⁺ as a result of Na1 residing on an inversion center.

The N1 and N3 sites, trans to one another on the TCP anion, are involved in H-bonding interactions to the water molecule containing O1, while the other trans pair of cyanide groups containing N2 and N4 are involved in interactions with Na⁺ (2.527 (4) and 2.541 (4) Å, respectively). The O2 water molecule interacts with Cs1 at a distance of 3.103 (6) Å, but does not engage in any meaningful H-bonding interactions.

Related literature top

CrystallineTCP systems have been studied extensively for their interesting structural and spectroscopic, especially photoluminescent, properties (Holzapfel et al., 1981; Gliemann & Yersin, 1985; Stojanovic et al., 2010). An intrinsic factor affecting the optical properties and arrangement of TCP chains is the identity of the cations involved, and much work has been done in the systematic study of various combinations of alkali metal cations involved (Holzapfel et al., 1981). However, only one known reference of a caesium/sodium mixed alkali metal TCP, viz. NaCsPt(CN)₄.1.5H₂O, exists (Bergsoe et al., 1962), which notes the synthesis and scintillation properties for the compound, but not any structural information.

Experimental top

Eu(CF₃SO₃)₃.9H₂O (98%), Na₂Pt(CN)₄ (99.95%), NaAu(CN)₂ (99.9%), and CsCl (99.9%) were used as received from Alfa Aesar. The title compound was obtained inadvertently in an attempt to produce a heterometallic cyanidometallate compound containing europium, TCP, and dicyanidoaurate. This involved the following preparation: Eu-trifluoromethanesulfonate (6.0 mg, 0.076 mmol) dissolved in 400 µl 80% CH₃CN:H₂O within a 5 ml test tube was layered with the solutions of sodium tetracyanidoplatinate (6.9 mg, 0.020 mmol) dissolved in 300 µl 80% CH₃CN:H₂O, and sodium dicyanidoaurate (2.7 mg, 0.010 mmol) dissolved in 400 µl 80% CH₃CN:H₂O. The solution was allowed to stand for 25 minutes until 1 ml caesium chloride (33.7 mg, 0.20 mmol) in 80% CH₃CN:H₂O solution was layered onto the mixture. Colorless, transparent crystals of Cs_1.5Na_0.5Pt(CN)₄.1.5H₂O were harvested from the reaction tube following slow evaporation of solvent.

Structure description top

CrystallineTCP systems have been studied extensively for their interesting structural and spectroscopic, especially photoluminescent, properties (Holzapfel et al., 1981; Gliemann & Yersin, 1985; Stojanovic et al., 2010). An intrinsic factor affecting the optical properties and arrangement of TCP chains is the identity of the cations involved, and much work has been done in the systematic study of various combinations of alkali metal cations involved (Holzapfel et al., 1981). However, only one known reference of a caesium/sodium mixed alkali metal TCP, viz. NaCsPt(CN)₄.1.5H₂O, exists (Bergsoe et al., 1962), which notes the synthesis and scintillation properties for the compound, but not any structural information.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The asymmetric unit of Cs_1.5Na_0.5Pt(CN)₄.1.5H₂O with the atom-numbering scheme. Displacement ellipsoids for non-hydrogen atoms are drawn at the 50% probability level.
	Fig. 2. A packing diagram for Cs_1.5Na_0.5Pt(CN)₄.1.5H₂O along the b axis illustrating the tetracyanidoplatinate stacking.

Sesquicaesium hemisodium tetracyanidoplatinate(II) sesquihydrate top

Crystal data top

Cs_1.5Na_0.5[Pt(CN)₄]·1.5H₂O	F(000) = 1864
M_r = 1074.11	D_x = 3.491 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6424 reflections
a = 17.4090 (5) Å	θ = 3.1–25.6°
b = 7.2190 (1) Å	µ = 18.99 mm⁻¹
c = 18.3921 (5) Å	T = 290 K
β = 117.858 (4)°	Prism, colorless
V = 2043.56 (11) Å³	0.20 × 0.14 × 0.08 mm
Z = 4

Data collection top

Oxford Diffraction Excalibur-E diffractometer	1949 independent reflections
Radiation source: fine-focus sealed tube	1789 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
Detector resolution: 16.0514 pixels mm^-1	θ_max = 25.7°, θ_min = 3.1°
ω scans	h = −21→21
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −8→8
T_min = 0.471, T_max = 1.00	l = −22→22
8164 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.014	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.034	w = 1/[σ²(F_o²) + (0.0147P)² + 4.0939P] where P = (F_o² + 2F_c²)/3
S = 1.15	(Δ/σ)_max = 0.002
1949 reflections	Δρ_max = 0.63 e Å⁻³
126 parameters	Δρ_min = −0.47 e Å⁻³
6 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.000819 (19)

Crystal data top

Cs_1.5Na_0.5[Pt(CN)₄]·1.5H₂O	V = 2043.56 (11) Å³
M_r = 1074.11	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 17.4090 (5) Å	µ = 18.99 mm⁻¹
b = 7.2190 (1) Å	T = 290 K
c = 18.3921 (5) Å	0.20 × 0.14 × 0.08 mm
β = 117.858 (4)°

Data collection top

Oxford Diffraction Excalibur-E diffractometer	1949 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	1789 reflections with I > 2σ(I)
T_min = 0.471, T_max = 1.00	R_int = 0.019
8164 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.014	6 restraints
wR(F²) = 0.034	H atoms treated by a mixture of independent and constrained refinement
S = 1.15	Δρ_max = 0.63 e Å⁻³
1949 reflections	Δρ_min = −0.47 e Å⁻³
126 parameters

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

	x	y	z	U_iso*/U_eq
Cs1	0.0000	1.18745 (7)	−0.2500	0.04903 (13)
Cs2	0.111975 (18)	0.76781 (4)	−0.017780 (19)	0.03819 (9)
Na1	0.2500	0.2500	0.0000	0.0307 (5)
Pt1	0.236863 (10)	0.51660 (2)	0.244311 (9)	0.02326 (7)
C1	0.3610 (3)	0.5200 (6)	0.3297 (3)	0.0321 (10)
C2	0.2026 (3)	0.5153 (5)	0.3330 (2)	0.0285 (9)
C3	0.1120 (3)	0.5245 (6)	0.1605 (3)	0.0298 (9)
C4	0.2736 (3)	0.5128 (5)	0.1564 (2)	0.0267 (9)
N1	0.4315 (3)	0.5232 (6)	0.3789 (3)	0.0477 (11)
N2	0.1834 (3)	0.5155 (6)	0.3851 (3)	0.0446 (10)
N3	0.0407 (3)	0.5366 (6)	0.1146 (3)	0.0465 (10)
N4	0.2955 (3)	0.5061 (5)	0.1069 (2)	0.0376 (9)
O1	0.1138 (2)	0.2401 (5)	−0.0028 (2)	0.0443 (9)
H1A	0.109 (3)	0.213 (8)	0.040 (2)	0.066*
H1B	0.070 (2)	0.289 (7)	−0.040 (2)	0.066*
O2	0.0000	0.7576 (8)	−0.2500	0.087 (2)
H2	−0.031 (5)	0.698 (5)	−0.2927 (19)	0.131*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cs1	0.0443 (2)	0.0501 (3)	0.0628 (3)	0.000	0.0335 (2)	0.000
Cs2	0.02998 (15)	0.04395 (17)	0.04217 (17)	0.00112 (12)	0.01814 (13)	0.00518 (13)
Na1	0.0286 (12)	0.0374 (13)	0.0269 (12)	−0.0005 (10)	0.0135 (10)	0.0005 (10)
Pt1	0.02326 (9)	0.02732 (10)	0.01992 (9)	−0.00030 (6)	0.01069 (7)	−0.00112 (6)
C1	0.033 (2)	0.035 (2)	0.029 (2)	−0.0009 (19)	0.016 (2)	−0.0013 (19)
C2	0.028 (2)	0.028 (2)	0.027 (2)	−0.0014 (17)	0.0107 (18)	−0.0025 (17)
C3	0.032 (2)	0.034 (2)	0.026 (2)	−0.0021 (18)	0.0149 (19)	−0.0017 (18)
C4	0.025 (2)	0.026 (2)	0.026 (2)	0.0001 (17)	0.0094 (17)	−0.0009 (17)
N1	0.031 (2)	0.059 (3)	0.043 (2)	−0.0010 (19)	0.0084 (19)	−0.003 (2)
N2	0.059 (3)	0.050 (2)	0.038 (2)	−0.004 (2)	0.033 (2)	−0.0024 (19)
N3	0.032 (2)	0.056 (3)	0.042 (2)	−0.0005 (19)	0.0088 (19)	−0.004 (2)
N4	0.043 (2)	0.044 (2)	0.034 (2)	−0.0008 (18)	0.0247 (18)	−0.0023 (17)
O1	0.0303 (16)	0.066 (2)	0.038 (2)	0.0061 (16)	0.0175 (15)	0.0116 (17)
O2	0.083 (5)	0.069 (4)	0.127 (7)	0.000	0.063 (5)	0.000

Geometric parameters (Å, º) top

Cs1—O2	3.103 (6)	Pt1—C2	1.982 (4)
Cs1—N1ⁱ	3.464 (4)	Pt1—C1	1.991 (4)
Cs2—N1ⁱⁱ	3.191 (4)	Pt1—C3	1.993 (4)
Cs2—N4ⁱ	3.227 (4)	Pt1—C4	1.996 (4)
Cs2—N3ⁱⁱⁱ	3.262 (4)	C1—N1	1.135 (6)
Cs2—N2^iv	3.316 (4)	C2—N2	1.153 (6)
Cs2—O1^v	3.420 (4)	C3—N3	1.132 (6)
Cs2—N4	3.491 (4)	C4—N4	1.141 (5)
Na1—O1	2.349 (3)	O1—H1A	0.85 (4)
Na1—N2^vi	2.527 (4)	O1—H1B	0.83 (4)
Na1—N4	2.541 (4)	O2—H2	0.84 (3)

O2—Cs1—N1ⁱ	63.96 (7)	C4—Cs2—N2^ix	63.43 (9)
O2—Cs1—N1ⁱⁱ	63.96 (7)	N1ⁱⁱ—Cs2—C3	110.04 (10)
N1ⁱ—Cs1—N1ⁱⁱ	127.93 (15)	N4ⁱ—Cs2—C3	153.14 (10)
O2—Cs1—N3^vii	124.57 (7)	N3ⁱⁱⁱ—Cs2—C3	80.06 (10)
N1ⁱ—Cs1—N3^vii	169.41 (10)	N2^iv—Cs2—C3	109.76 (10)
N1ⁱⁱ—Cs1—N3^vii	61.00 (10)	O1^v—Cs2—C3	113.80 (9)
O2—Cs1—N3^viii	124.57 (7)	N4—Cs2—C3	62.76 (9)
N1ⁱ—Cs1—N3^viii	61.00 (10)	N1^ix—Cs2—C3	61.13 (9)
N1ⁱⁱ—Cs1—N3^viii	169.41 (10)	N3—Cs2—C3	17.67 (9)
N3^vii—Cs1—N3^viii	110.86 (14)	C4—Cs2—C3	45.64 (9)
O2—Cs1—N4ⁱⁱ	67.01 (6)	N2^ix—Cs2—C3	92.48 (9)
N1ⁱ—Cs1—N4ⁱⁱ	82.40 (9)	N1ⁱⁱ—Cs2—C1^ix	89.08 (11)
N1ⁱⁱ—Cs1—N4ⁱⁱ	77.84 (9)	N4ⁱ—Cs2—C1^ix	110.29 (9)
N3^vii—Cs1—N4ⁱⁱ	106.38 (9)	N3ⁱⁱⁱ—Cs2—C1^ix	123.44 (10)
N3^viii—Cs1—N4ⁱⁱ	99.28 (9)	N2^iv—Cs2—C1^ix	151.87 (10)
O2—Cs1—N4ⁱ	67.01 (6)	O1^v—Cs2—C1^ix	56.47 (9)
N1ⁱ—Cs1—N4ⁱ	77.84 (9)	N4—Cs2—C1^ix	88.55 (9)
N1ⁱⁱ—Cs1—N4ⁱ	82.40 (9)	N1^ix—Cs2—C1^ix	17.65 (9)
N3^vii—Cs1—N4ⁱ	99.28 (9)	N3—Cs2—C1^ix	62.37 (9)
N3^viii—Cs1—N4ⁱ	106.38 (9)	C4—Cs2—C1^ix	73.70 (9)
N4ⁱⁱ—Cs1—N4ⁱ	134.02 (12)	N2^ix—Cs2—C1^ix	59.27 (9)
O2—Cs1—N2^viii	125.63 (6)	C3—Cs2—C1^ix	57.73 (9)
N1ⁱ—Cs1—N2^viii	104.50 (9)	O1—Na1—O1^x	180.00 (17)
N1ⁱⁱ—Cs1—N2^viii	105.13 (9)	O1—Na1—N2^vi	93.58 (13)
N3^vii—Cs1—N2^viii	65.76 (9)	O1^x—Na1—N2^vi	86.42 (13)
N3^viii—Cs1—N2^viii	75.49 (9)	O1—Na1—N2^iv	86.42 (13)
N4ⁱⁱ—Cs1—N2^viii	167.20 (9)	O1^x—Na1—N2^iv	93.58 (13)
N4ⁱ—Cs1—N2^viii	58.66 (9)	N2^vi—Na1—N2^iv	180.00 (16)
O2—Cs1—N2^vii	125.63 (6)	O1—Na1—N4^x	90.84 (13)
N1ⁱ—Cs1—N2^vii	105.13 (9)	O1^x—Na1—N4^x	89.16 (13)
N1ⁱⁱ—Cs1—N2^vii	104.50 (9)	N2^vi—Na1—N4^x	90.85 (13)
N3^vii—Cs1—N2^vii	75.49 (9)	N2^iv—Na1—N4^x	89.15 (13)
N3^viii—Cs1—N2^vii	65.76 (9)	O1—Na1—N4	89.16 (13)
N4ⁱⁱ—Cs1—N2^vii	58.66 (9)	O1^x—Na1—N4	90.84 (13)
N4ⁱ—Cs1—N2^vii	167.20 (9)	N2^vi—Na1—N4	89.15 (13)
N2^viii—Cs1—N2^vii	108.74 (13)	N2^iv—Na1—N4	90.85 (13)
O2—Cs1—C1ⁱⁱ	66.00 (7)	N4^x—Na1—N4	180.00 (18)
N1ⁱ—Cs1—C1ⁱⁱ	126.47 (9)	C2—Pt1—C1	89.08 (17)
N1ⁱⁱ—Cs1—C1ⁱⁱ	17.94 (9)	C2—Pt1—C3	89.86 (17)
N3^vii—Cs1—C1ⁱⁱ	63.92 (10)	C1—Pt1—C3	177.41 (17)
N3^viii—Cs1—C1ⁱⁱ	154.32 (10)	C2—Pt1—C4	178.54 (16)
N4ⁱⁱ—Cs1—C1ⁱⁱ	61.35 (9)	C1—Pt1—C4	89.91 (17)
N4ⁱ—Cs1—C1ⁱⁱ	99.31 (9)	C3—Pt1—C4	91.18 (16)
N2^viii—Cs1—C1ⁱⁱ	119.49 (9)	N1—C1—Pt1	179.2 (4)
N2^vii—Cs1—C1ⁱⁱ	88.95 (9)	N1—C1—Cs1ⁱ	70.0 (3)
O2—Cs1—C1ⁱ	66.00 (7)	Pt1—C1—Cs1ⁱ	110.74 (16)
N1ⁱ—Cs1—C1ⁱ	17.94 (9)	N1—C1—Cs2^vi	69.5 (3)
N1ⁱⁱ—Cs1—C1ⁱ	126.47 (9)	Pt1—C1—Cs2^vi	110.15 (16)
N3^vii—Cs1—C1ⁱ	154.32 (10)	Cs1ⁱ—C1—Cs2^vi	110.37 (11)
N3^viii—Cs1—C1ⁱ	63.92 (10)	N2—C2—Pt1	179.4 (4)
N4ⁱⁱ—Cs1—C1ⁱ	99.31 (9)	N2—C2—Cs1^vii	75.9 (3)
N4ⁱ—Cs1—C1ⁱ	61.35 (9)	Pt1—C2—Cs1^vii	104.31 (14)
N2^viii—Cs1—C1ⁱ	88.95 (9)	N2—C2—Cs2^vi	73.6 (3)
N2^vii—Cs1—C1ⁱ	119.49 (9)	Pt1—C2—Cs2^vi	106.10 (15)
C1ⁱⁱ—Cs1—C1ⁱ	132.01 (13)	Cs1^vii—C2—Cs2^vi	148.78 (12)
O2—Cs1—C3^viii	123.99 (6)	N3—C3—Pt1	176.8 (4)
N1ⁱ—Cs1—C3^viii	61.52 (10)	N3—C3—Cs1^vii	70.7 (3)
N1ⁱⁱ—Cs1—C3^viii	165.39 (9)	Pt1—C3—Cs1^vii	106.37 (15)
N3^vii—Cs1—C3^viii	108.55 (9)	N3—C3—Cs2	75.9 (3)
N3^viii—Cs1—C3^viii	17.71 (9)	Pt1—C3—Cs2	104.23 (15)
N4ⁱⁱ—Cs1—C3^viii	116.12 (9)	Cs1^vii—C3—Cs2	110.00 (11)
N4ⁱ—Cs1—C3^viii	89.80 (9)	N4—C4—Pt1	178.2 (4)
N2^viii—Cs1—C3^viii	60.29 (9)	N4—C4—Cs2	74.1 (3)
N2^vii—Cs1—C3^viii	81.03 (9)	Pt1—C4—Cs2	107.38 (14)
C1ⁱⁱ—Cs1—C3^viii	168.91 (9)	N4—C4—Cs1ⁱ	71.4 (3)
C1ⁱ—Cs1—C3^viii	58.23 (9)	Pt1—C4—Cs1ⁱ	107.30 (14)
N1ⁱⁱ—Cs2—N4ⁱ	92.57 (11)	Cs2—C4—Cs1ⁱ	144.19 (12)
N1ⁱⁱ—Cs2—N3ⁱⁱⁱ	70.67 (10)	C1—N1—Cs2^xi	151.8 (4)
N4ⁱ—Cs2—N3ⁱⁱⁱ	122.44 (10)	C1—N1—Cs1ⁱ	92.0 (3)
N1ⁱⁱ—Cs2—N2^iv	118.92 (11)	Cs2^xi—N1—Cs1ⁱ	93.27 (11)
N4ⁱ—Cs2—N2^iv	68.68 (9)	C1—N1—Cs2^vi	92.8 (3)
N3ⁱⁱⁱ—Cs2—N2^iv	72.87 (11)	Cs2^xi—N1—Cs2^vi	107.60 (12)
N1ⁱⁱ—Cs2—O1^v	62.99 (9)	Cs1ⁱ—N1—Cs2^vi	121.89 (13)
N4ⁱ—Cs2—O1^v	63.17 (8)	C2—N2—Na1^ix	119.8 (3)
N3ⁱⁱⁱ—Cs2—O1^v	133.63 (9)	C2—N2—Cs2^xii	140.8 (3)
N2^iv—Cs2—O1^v	131.82 (9)	Na1^ix—N2—Cs2^xii	95.96 (12)
N1ⁱⁱ—Cs2—N4	172.46 (10)	C2—N2—Cs1^vii	86.4 (3)
N4ⁱ—Cs2—N4	94.96 (9)	Na1^ix—N2—Cs1^vii	95.09 (12)
N3ⁱⁱⁱ—Cs2—N4	104.84 (9)	Cs2^xii—N2—Cs1^vii	107.33 (11)
N2^iv—Cs2—N4	64.01 (10)	C2—N2—Cs2^vi	89.0 (3)
O1^v—Cs2—N4	121.04 (8)	Na1^ix—N2—Cs2^vi	81.26 (11)
N1ⁱⁱ—Cs2—N1^ix	72.40 (12)	Cs2^xii—N2—Cs2^vi	80.48 (9)
N4ⁱ—Cs2—N1^ix	115.65 (10)	Cs1^vii—N2—Cs2^vi	171.76 (12)
N3ⁱⁱⁱ—Cs2—N1^ix	110.69 (10)	C3—N3—Cs2ⁱⁱⁱ	133.2 (3)
N2^iv—Cs2—N1^ix	168.32 (10)	C3—N3—Cs1^vii	91.6 (3)
O1^v—Cs2—N1^ix	54.15 (9)	Cs2ⁱⁱⁱ—N3—Cs1^vii	112.71 (12)
N4—Cs2—N1^ix	104.40 (9)	C3—N3—Cs2	86.4 (3)
N1ⁱⁱ—Cs2—N3	93.85 (10)	Cs2ⁱⁱⁱ—N3—Cs2	113.08 (12)
N4ⁱ—Cs2—N3	170.13 (9)	Cs1^vii—N3—Cs2	117.54 (12)
N3ⁱⁱⁱ—Cs2—N3	66.92 (12)	C4—N4—Na1	123.3 (3)
N2^iv—Cs2—N3	114.26 (10)	C4—N4—Cs2ⁱ	144.7 (3)
O1^v—Cs2—N3	113.53 (9)	Na1—N4—Cs2ⁱ	91.37 (11)
N4—Cs2—N3	78.72 (9)	C4—N4—Cs2	87.6 (3)
N1^ix—Cs2—N3	59.58 (10)	Na1—N4—Cs2	91.55 (11)
N1ⁱⁱ—Cs2—C4	155.22 (10)	Cs2ⁱ—N4—Cs2	85.04 (9)
N4ⁱ—Cs2—C4	109.89 (10)	C4—N4—Cs1ⁱ	91.0 (3)
N3ⁱⁱⁱ—Cs2—C4	103.78 (10)	Na1—N4—Cs1ⁱ	97.36 (11)
N2^iv—Cs2—C4	80.30 (10)	Cs2ⁱ—N4—Cs1ⁱ	90.55 (9)
O1^v—Cs2—C4	117.45 (8)	Cs2—N4—Cs1ⁱ	170.16 (12)
N4—Cs2—C4	18.33 (9)	Na1—O1—Cs2^xiii	90.18 (10)
N1^ix—Cs2—C4	88.03 (9)	Na1—O1—H1A	121 (4)
N3—Cs2—C4	62.56 (9)	Cs2^xiii—O1—H1A	81 (4)
N1ⁱⁱ—Cs2—N2^ix	122.71 (10)	Na1—O1—H1B	122 (4)
N4ⁱ—Cs2—N2^ix	62.33 (9)	Cs2^xiii—O1—H1B	113 (4)
N3ⁱⁱⁱ—Cs2—N2^ix	166.50 (10)	H1A—O1—H1B	115 (4)
N2^iv—Cs2—N2^ix	99.52 (9)	Cs1—O2—Cs2^xiv	88.88 (9)
O1^v—Cs2—N2^ix	59.73 (8)	Cs1—O2—Cs2	88.88 (9)
N4—Cs2—N2^ix	61.66 (9)	Cs2^xiv—O2—Cs2	177.76 (18)
N1^ix—Cs2—N2^ix	74.63 (9)	Cs1—O2—H2	121 (3)
N3—Cs2—N2^ix	107.83 (9)	Cs2—O2—H2	147 (4)

Symmetry codes: (i) −x+1/2, −y+3/2, −z; (ii) x−1/2, −y+3/2, z−1/2; (iii) −x, −y+1, −z; (iv) x, −y+1, z−1/2; (v) x, y+1, z; (vi) −x+1/2, y−1/2, −z+1/2; (vii) −x, −y+2, −z; (viii) x, −y+2, z−1/2; (ix) −x+1/2, y+1/2, −z+1/2; (x) −x+1/2, −y+1/2, −z; (xi) x+1/2, −y+3/2, z+1/2; (xii) x, −y+1, z+1/2; (xiii) x, y−1, z; (xiv) −x, y, −z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N1^vi	0.85 (2)	2.37 (3)	3.154 (6)	155 (5)
O1—H1B···N3ⁱⁱⁱ	0.83 (2)	2.17 (2)	2.982 (5)	166 (5)

Symmetry codes: (iii) −x, −y+1, −z; (vi) −x+1/2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	Cs_1.5Na_0.5[Pt(CN)₄]·1.5H₂O
M_r	1074.11
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	290
a, b, c (Å)	17.4090 (5), 7.2190 (1), 18.3921 (5)
β (°)	117.858 (4)
V (Å³)	2043.56 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	18.99
Crystal size (mm)	0.20 × 0.14 × 0.08

Data collection
Diffractometer	Oxford Diffraction Excalibur-E
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)
T_min, T_max	0.471, 1.00
No. of measured, independent and observed [I > 2σ(I)] reflections	8164, 1949, 1789
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.610

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.014, 0.034, 1.15
No. of reflections	1949
No. of parameters	126
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.63, −0.47

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N1ⁱ	0.847 (19)	2.37 (3)	3.154 (6)	155 (5)
O1—H1B···N3ⁱⁱ	0.829 (19)	2.17 (2)	2.982 (5)	166 (5)

Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x, −y+1, −z.

Acknowledgements

The authors gratefully acknowledge the National Science Foundation for its generous support (NSF-CAREER grant to RES, grant No. CHE-0846680).

References

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