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

The asymmetric unit of the title hydrated complex salt, (C18H14N5)2[Pt(CN)4]·4H2O, consists of one 2-[2,5-bis-(pyridin-2-yl)-1H-imidazol-4-yl]pyridinium cation, half a tetra-cyanidoplatinate(II) dianion, which is located about a crystallographic inversion center, and two water mol-ecules of crystallization. The Pt(II) atom has a square-planar coordination environment, with Pt-CCN distances of 1.992 (4) and 2.000 (4) Å. In the cation, there is an N-H⋯N hydrogen bond linking adjacent pyridinium and pyridine rings in positions 4 and 5. Despite this, the organic component is non-planar, as shown by the dihedral angles of 10.3 (2), 6.60 (19) and 15.66 (18)° between the planes of the central imidazole ring and the pyridine/pyridinium substituents in the 2-, 4- and 5-positions. In the crystal, cations and anions are linked via O-H⋯O, O-H⋯N and N-H⋯O hydrogen bonds, forming a three-dimensional network. Additional π-π, C-H⋯O and C-H⋯N contacts provide stabilization to the crystal lattice.

Related literature

For the structural, magnetic, optical and electrical properties of hydrogen-bonded inorganic–organic hybrid materials, see: Anastassiadou et al. (2000 ▶); Crawford et al. (2004 ▶); Dechambenoit et al. (2006 ▶); Du et al. (2013 ▶); Lebeau & Innocenzi (2011 ▶); Maynard & Sykora (2008 ▶); Pardo et al. (2011 ▶); Sanchez et al. (2005 ▶); Wang et al. (2010 ▶); Yao et al. (2010 ▶).

Experimental

Crystal data

(C18H14N5)2[Pt(CN)4]·4H2O

M = 971.92

Monoclinic,

a = 20.958 (5) Å

b = 12.048 (3) Å

c = 15.403 (3) Å

β = 95.483 (3)°

V = 3871.6 (14) Å3

Z = 4

Mo Kα radiation

μ = 3.69 mm−1

T = 100 K

0.50 × 0.34 × 0.28 mm

Data collection

Bruker SMART CCD area detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.26, T max = 0.43

17095 measured reflections

3418 independent reflections

2726 reflections with I > 2σ(I)

R int = 0.066

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.078

S = 1.00

3418 reflections

286 parameters

8 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 3.10 e Å−3

Δρmin = −2.27 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶) and publCIF (Westrip, 2010 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813011665/su2593sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813011665/su2593Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

(C18H14N5)2[Pt(CN)4]·4H2O	F(000) = 1936
Mr = 971.92	Dx = 1.667 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 9440 reflections
a = 20.958 (5) Å	θ = 2.3–27.7°
b = 12.048 (3) Å	µ = 3.69 mm−1
c = 15.403 (3) Å	T = 100 K
β = 95.483 (3)°	Rectangular prism, yellow
V = 3871.6 (14) Å3	0.50 × 0.34 × 0.28 mm
Z = 4

Bruker SMART CCD area detector diffractometer	3418 independent reflections
Radiation source: fine-focus sealed tube	2726 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.066
phi and ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −24→24
Tmin = 0.26, Tmax = 0.43	k = −14→14
17095 measured reflections	l = −18→18

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.078	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ2(Fo2) + (0.0497P)2] where P = (Fo2 + 2Fc2)/3
3418 reflections	(Δ/σ)max < 0.001
286 parameters	Δρmax = 3.10 e Å−3
8 restraints	Δρmin = −2.27 e Å−3

Experimental. IR and TGA details for the title compound: IR(KBr, cm-1): 3406, 3385, 3268, 3100, 2129, 1661, 1596, 1501, 1447, 1235, 1139, 1096, 777, 703. TGA: Calcd. for 4H2O: 7.42. Found: 7.69% (298 - 385 K).

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 > 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.

	x	y	z	Uiso*/Ueq
Pt1	0.2500	0.7500	0.5000	0.01672 (10)
N1	0.96962 (15)	1.0885 (2)	0.10252 (19)	0.0173 (7)
H1'	0.973 (2)	1.1564 (9)	0.114 (3)	0.026*
N2	0.92075 (14)	0.9356 (2)	0.05054 (18)	0.0179 (7)
N3	0.87601 (18)	1.2211 (3)	−0.0001 (2)	0.0226 (8)
N4	1.09913 (14)	0.9336 (2)	0.22311 (18)	0.0171 (7)
N5	1.03998 (19)	0.7543 (2)	0.1645 (2)	0.0189 (8)
H5'	1.0631 (17)	0.798 (3)	0.196 (2)	0.028*
N6	0.31880 (15)	0.8613 (3)	0.6676 (2)	0.0256 (8)
N7	0.32877 (17)	0.9085 (3)	0.3882 (2)	0.0320 (8)
C1	0.91839 (17)	1.0457 (3)	0.0535 (2)	0.0181 (8)
C2	1.00799 (17)	1.0022 (3)	0.1331 (2)	0.0168 (8)
C3	0.97619 (18)	0.9069 (3)	0.1007 (2)	0.0170 (9)
C4	0.86797 (17)	1.1094 (3)	0.0042 (2)	0.0188 (8)
C5	0.81594 (17)	1.0555 (3)	−0.0383 (2)	0.0238 (9)
H5	0.8109	0.9777	−0.0321	0.029*
C6	0.77141 (19)	1.1165 (3)	−0.0900 (2)	0.0286 (10)
H6	0.7355	1.0812	−0.1206	0.034*
C7	0.7798 (3)	1.2285 (4)	−0.0962 (3)	0.0325 (11)
H7	0.7502	1.2718	−0.1325	0.039*
C8	0.8316 (2)	1.2785 (4)	−0.0496 (3)	0.0290 (10)
H8	0.8358	1.3568	−0.0528	0.035*
C9	1.07022 (17)	1.0222 (3)	0.1828 (2)	0.0172 (8)
C10	1.09906 (18)	1.1263 (3)	0.1866 (2)	0.0201 (8)
H10	1.0780	1.1884	0.1588	0.024*
C11	1.15875 (19)	1.1376 (3)	0.2316 (2)	0.0218 (9)
H11	1.1794	1.2079	0.2344	0.026*
C12	1.18881 (19)	1.0470 (3)	0.2727 (2)	0.0225 (9)
H12	1.2301	1.0535	0.3037	0.027*
C13	1.15672 (18)	0.9468 (3)	0.2671 (2)	0.0218 (9)
H13	1.1765	0.8842	0.2959	0.026*
C14	0.99006 (18)	0.7888 (3)	0.1090 (2)	0.0155 (8)
C15	0.95298 (19)	0.7094 (3)	0.0622 (2)	0.0196 (9)
H15	0.9177	0.7314	0.0226	0.023*
C16	0.9678 (2)	0.5986 (3)	0.0734 (3)	0.0241 (9)
H16	0.9424	0.5439	0.0420	0.029*
C17	1.01988 (19)	0.5669 (3)	0.1306 (2)	0.0230 (9)
H17	1.0306	0.4907	0.1386	0.028*
C18	1.05545 (19)	0.6473 (3)	0.1752 (2)	0.0215 (9)
H18	1.0914	0.6269	0.2141	0.026*
C19	0.29365 (18)	0.8199 (3)	0.6075 (2)	0.0204 (9)
C20	0.29937 (19)	0.8513 (3)	0.4291 (2)	0.0220 (9)
O31	0.96490 (15)	0.3159 (2)	0.1280 (2)	0.0341 (7)
H31A	0.9379 (13)	0.310 (4)	0.0842 (14)	0.051*
H32A	0.1394 (19)	0.481 (2)	0.304 (2)	0.051*
O32	0.12373 (15)	0.4241 (2)	0.27892 (18)	0.0324 (7)
H31B	0.9448 (15)	0.334 (4)	0.1704 (15)	0.049*
H32B	0.135 (2)	0.426 (3)	0.2280 (11)	0.049*

	U11	U22	U33	U12	U13	U23
Pt1	0.01960 (15)	0.01288 (15)	0.01807 (14)	0.00058 (8)	0.00385 (8)	−0.00070 (7)
N1	0.0203 (18)	0.0123 (16)	0.0202 (16)	0.0003 (15)	0.0066 (13)	−0.0003 (14)
N2	0.0202 (18)	0.0155 (17)	0.0191 (16)	−0.0003 (14)	0.0083 (13)	0.0013 (13)
N3	0.027 (2)	0.0138 (16)	0.029 (2)	0.0015 (16)	0.0114 (15)	0.0038 (15)
N4	0.0224 (18)	0.0111 (16)	0.0184 (16)	0.0006 (14)	0.0048 (13)	0.0000 (13)
N5	0.021 (2)	0.016 (2)	0.0201 (19)	−0.0058 (14)	0.0047 (14)	−0.0014 (13)
N6	0.026 (2)	0.0281 (19)	0.0228 (18)	−0.0027 (16)	0.0053 (15)	−0.0046 (15)
N7	0.035 (2)	0.031 (2)	0.031 (2)	−0.0065 (17)	0.0077 (16)	0.0025 (16)
C1	0.019 (2)	0.018 (2)	0.0183 (19)	0.0004 (17)	0.0099 (16)	0.0001 (16)
C2	0.022 (2)	0.013 (2)	0.0169 (19)	0.0014 (17)	0.0098 (15)	0.0005 (16)
C3	0.020 (2)	0.018 (2)	0.0152 (19)	−0.0019 (17)	0.0090 (16)	0.0016 (16)
C4	0.020 (2)	0.018 (2)	0.0200 (19)	0.0058 (17)	0.0117 (16)	0.0013 (16)
C5	0.023 (2)	0.024 (2)	0.025 (2)	−0.0002 (19)	0.0073 (17)	−0.0027 (17)
C6	0.026 (2)	0.030 (2)	0.030 (2)	0.006 (2)	0.0015 (17)	−0.0021 (19)
C7	0.033 (3)	0.034 (3)	0.030 (3)	0.011 (2)	0.002 (2)	0.006 (2)
C8	0.035 (3)	0.021 (2)	0.033 (3)	0.005 (2)	0.014 (2)	0.008 (2)
C9	0.022 (2)	0.016 (2)	0.0156 (19)	0.0004 (17)	0.0100 (15)	−0.0019 (15)
C10	0.028 (2)	0.0115 (19)	0.022 (2)	0.0001 (18)	0.0067 (16)	0.0003 (16)
C11	0.025 (2)	0.015 (2)	0.026 (2)	−0.0034 (18)	0.0045 (17)	−0.0038 (17)
C12	0.026 (2)	0.019 (2)	0.022 (2)	−0.0032 (18)	0.0025 (17)	−0.0033 (17)
C13	0.028 (2)	0.017 (2)	0.021 (2)	0.0022 (18)	0.0054 (17)	0.0052 (16)
C14	0.018 (2)	0.0142 (17)	0.016 (2)	−0.0009 (18)	0.0092 (16)	0.0017 (16)
C15	0.021 (2)	0.0181 (19)	0.020 (2)	0.0000 (19)	0.0057 (16)	0.0009 (17)
C16	0.029 (2)	0.019 (2)	0.025 (2)	−0.0070 (19)	0.0061 (18)	−0.0042 (17)
C17	0.028 (2)	0.012 (2)	0.030 (2)	−0.0029 (19)	0.0095 (18)	0.0008 (17)
C18	0.025 (2)	0.018 (2)	0.023 (2)	−0.0006 (18)	0.0058 (16)	0.0064 (17)
C19	0.024 (2)	0.019 (2)	0.020 (2)	0.0026 (18)	0.0069 (17)	0.0014 (17)
C20	0.025 (2)	0.019 (2)	0.022 (2)	−0.0011 (18)	0.0024 (17)	−0.0068 (17)
O31	0.0371 (19)	0.0219 (17)	0.0444 (19)	−0.0019 (15)	0.0096 (14)	−0.0049 (15)
O32	0.046 (2)	0.0254 (16)	0.0277 (16)	−0.0057 (15)	0.0115 (14)	−0.0006 (13)

Pt1—C20	1.992 (4)	C6—C7	1.365 (5)
Pt1—C20i	1.992 (4)	C6—H6	0.9500
Pt1—C19	2.000 (4)	C7—C8	1.381 (7)
Pt1—C19i	2.000 (4)	C7—H7	0.9500
N1—C1	1.354 (5)	C8—H8	0.9500
N1—C2	1.370 (5)	C9—C10	1.391 (5)
N1—H1'	0.8400 (11)	C10—C11	1.378 (5)
N2—C1	1.328 (4)	C10—H10	0.9500
N2—C3	1.377 (5)	C11—C12	1.383 (5)
N3—C8	1.338 (6)	C11—H11	0.9500
N3—C4	1.358 (5)	C12—C13	1.381 (5)
N4—C13	1.336 (5)	C12—H12	0.9500
N4—C9	1.349 (4)	C13—H13	0.9500
N5—C18	1.336 (4)	C14—C15	1.391 (6)
N5—C14	1.351 (6)	C15—C16	1.377 (6)
N5—H5'	0.8400 (11)	C15—H15	0.9500
N6—C19	1.135 (5)	C16—C17	1.390 (6)
N7—C20	1.151 (4)	C16—H16	0.9500
C1—C4	1.459 (5)	C17—C18	1.367 (5)
C2—C3	1.396 (5)	C17—H17	0.9500
C2—C9	1.467 (5)	C18—H18	0.9500
C3—C14	1.455 (5)	O31—H31A	0.8401 (11)
C4—C5	1.380 (5)	O31—H31B	0.8400 (11)
C5—C6	1.379 (5)	O32—H32A	0.8401 (11)
C5—H5	0.9500	O32—H32B	0.8400 (11)
C20—Pt1—C20i	180.00 (17)	N3—C8—H8	118.6
C20—Pt1—C19	88.59 (15)	C7—C8—H8	118.6
C20i—Pt1—C19	91.41 (14)	N4—C9—C10	121.3 (3)
C20—Pt1—C19i	91.41 (14)	N4—C9—C2	116.6 (3)
C20i—Pt1—C19i	88.59 (15)	C10—C9—C2	122.1 (3)
C19—Pt1—C19i	180.000 (1)	C11—C10—C9	118.7 (3)
C1—N1—C2	108.2 (3)	C11—C10—H10	120.6
C1—N1—H1'	123 (3)	C9—C10—H10	120.6
C2—N1—H1'	129 (3)	C10—C11—C12	120.3 (4)
C1—N2—C3	105.3 (3)	C10—C11—H11	119.8
C8—N3—C4	117.2 (4)	C12—C11—H11	119.8
C13—N4—C9	118.9 (3)	C13—C12—C11	117.6 (4)
C18—N5—C14	122.6 (4)	C13—C12—H12	121.2
C18—N5—H5'	115 (3)	C11—C12—H12	121.2
C14—N5—H5'	123 (3)	N4—C13—C12	123.1 (3)
N2—C1—N1	111.6 (3)	N4—C13—H13	118.4
N2—C1—C4	122.3 (3)	C12—C13—H13	118.4
N1—C1—C4	125.9 (3)	N5—C14—C15	118.5 (4)
N1—C2—C3	104.9 (3)	N5—C14—C3	119.5 (4)
N1—C2—C9	121.2 (3)	C15—C14—C3	122.0 (4)
C3—C2—C9	133.8 (3)	C16—C15—C14	119.6 (4)
N2—C3—C2	110.0 (3)	C16—C15—H15	120.2
N2—C3—C14	116.5 (3)	C14—C15—H15	120.2
C2—C3—C14	133.5 (4)	C15—C16—C17	120.0 (4)
N3—C4—C5	122.6 (4)	C15—C16—H16	120.0
N3—C4—C1	117.4 (3)	C17—C16—H16	120.0
C5—C4—C1	120.0 (3)	C18—C17—C16	118.8 (4)
C6—C5—C4	118.9 (4)	C18—C17—H17	120.6
C6—C5—H5	120.5	C16—C17—H17	120.6
C4—C5—H5	120.5	N5—C18—C17	120.5 (4)
C7—C6—C5	118.8 (4)	N5—C18—H18	119.7
C7—C6—H6	120.6	C17—C18—H18	119.7
C5—C6—H6	120.6	N6—C19—Pt1	178.6 (3)
C6—C7—C8	119.6 (5)	N7—C20—Pt1	178.8 (3)
C6—C7—H7	120.2	H31A—O31—H31B	107.2 (12)
C8—C7—H7	120.2	H32A—O32—H32B	106.3 (12)
N3—C8—C7	122.7 (4)
C3—N2—C1—N1	0.4 (4)	C13—N4—C9—C10	−0.4 (5)
C3—N2—C1—C4	176.7 (3)	C13—N4—C9—C2	178.1 (3)
C2—N1—C1—N2	0.4 (4)	N1—C2—C9—N4	168.6 (3)
C2—N1—C1—C4	−175.8 (3)	C3—C2—C9—N4	−17.0 (5)
C1—N1—C2—C3	−0.9 (4)	N1—C2—C9—C10	−12.9 (5)
C1—N1—C2—C9	175.0 (3)	C3—C2—C9—C10	161.5 (4)
C1—N2—C3—C2	−1.0 (4)	N4—C9—C10—C11	1.1 (5)
C1—N2—C3—C14	179.5 (3)	C2—C9—C10—C11	−177.4 (3)
N1—C2—C3—N2	1.2 (4)	C9—C10—C11—C12	−0.7 (5)
C9—C2—C3—N2	−173.9 (3)	C10—C11—C12—C13	−0.3 (5)
N1—C2—C3—C14	−179.4 (4)	C9—N4—C13—C12	−0.7 (5)
C9—C2—C3—C14	5.5 (7)	C11—C12—C13—N4	1.0 (5)
C8—N3—C4—C5	−1.4 (5)	C18—N5—C14—C15	0.8 (6)
C8—N3—C4—C1	176.1 (3)	C18—N5—C14—C3	−179.9 (3)
N2—C1—C4—N3	−168.9 (3)	N2—C3—C14—N5	−173.1 (3)
N1—C1—C4—N3	6.9 (5)	C2—C3—C14—N5	7.4 (6)
N2—C1—C4—C5	8.7 (5)	N2—C3—C14—C15	6.1 (5)
N1—C1—C4—C5	−175.5 (3)	C2—C3—C14—C15	−173.3 (4)
N3—C4—C5—C6	2.5 (5)	N5—C14—C15—C16	0.1 (5)
C1—C4—C5—C6	−175.0 (3)	C3—C14—C15—C16	−179.1 (4)
C4—C5—C6—C7	−1.0 (6)	C14—C15—C16—C17	−0.7 (5)
C5—C6—C7—C8	−1.4 (7)	C15—C16—C17—C18	0.3 (6)
C4—N3—C8—C7	−1.1 (6)	C14—N5—C18—C17	−1.2 (6)
C6—C7—C8—N3	2.6 (7)	C16—C17—C18—N5	0.6 (6)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5′···N4	0.84	1.83	2.609 (4)	154
N1—H1′···O31ii	0.84	1.94	2.771 (4)	169
O31—H31B···O32iii	0.84	2.02	2.778 (4)	151
O32—H32A···N6i	0.84	2.12	2.937 (4)	164
O31—H31A···N3iv	0.84	2.05	2.822 (5)	152
O32—H32B···N7v	0.84	2.02	2.854 (5)	170
C6—H6···O32vi	0.95	2.68	3.564 (5)	155
C17—H17···O32vii	0.95	2.88	3.459 (5)	120
C18—H18···O32vii	0.95	2.70	3.375 (5)	129
C18—H18···N6viii	0.95	2.50	3.406 (5)	161

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5′⋯N4	0.84	1.83	2.609 (4)	154
N1—H1′⋯O31i	0.84	1.94	2.771 (4)	169
O31—H31B⋯O32ii	0.84	2.02	2.778 (4)	151
O32—H32A⋯N6iii	0.84	2.12	2.937 (4)	164
O31—H31A⋯N3iv	0.84	2.05	2.822 (5)	152
O32—H32B⋯N7v	0.84	2.02	2.854 (5)	170
C6—H6⋯O32vi	0.95	2.68	3.564 (5)	155
C17—H17⋯O32vii	0.95	2.88	3.459 (5)	120
C18—H18⋯O32vii	0.95	2.70	3.375 (5)	129
C18—H18⋯N6viii	0.95	2.50	3.406 (5)	161

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