4,4'-(Ethene-1,2-di-yl)dipyridinium 4-[2-(pyridin-4-yl)ethen-yl]pyridinium octa-cyanidomolybdate(V) tetra-hydrate.

The crystal structure of the title compound, (C12H12N2)(C12H11N2)[Mo(CN)8]·4H2O, consists of 4,4'-(ethene-1,2-di-yl)dipyridinium and 4-[2-(pyridin-4-yl)ethen-yl]pyridinium cations disordered over the same site, an [Mo(CN)8](3-) anion and four water mol-ecules of crystallization. The eight-coordinate [Mo(CN)8](3-) unit exhibits a slightly distorted square-anti-prismatic geometry. In the structure, the cations (crystallographic symmetry, 2) and anions (crystallographic symmetry, 222) are arranged alternately by N-H⋯O and O-H⋯N hydrogen bonds, forming layers parallel to the bc plane. These layers are further linked through O-H⋯N hydrogen bonds, generating a three-dimensional supra-molecular network.

Related literature

For general background to the design and construction of multi-functional materials, see: Nowicka et al. (2012 ▶); Prins et al. (2007 ▶); Sieklucka et al. (2011 ▶); Tanase et al. (2008 ▶); Zhou et al. (2012 ▶). For related structures, see: Liu et al. (2008 ▶); Qian et al. (2009 ▶).

Experimental

Crystal data

(C12H12N2)(C12H11N2)[Mo(CN)8]·4H2O

M = 743.63

Orthorhombic,

a = 12.403 (3) Å

b = 16.534 (3) Å

c = 15.370 (3) Å

V = 3151.8 (11) Å3

Z = 4

Mo Kα radiation

μ = 0.48 mm−1

T = 291 K

0.18 × 0.15 × 0.13 mm

Data collection

Bruker SMART APEXII diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.919, T max = 0.941

6789 measured reflections

1442 independent reflections

1388 reflections with I > 2σ(I)

R int = 0.016

Refinement

R[F 2 > 2σ(F 2)] = 0.021

wR(F 2) = 0.052

S = 1.09

1442 reflections

112 parameters

H-atom parameters constrained

Δρmax = 0.28 e Å−3

Δρmin = −0.31 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813002985/rz5039sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813002985/rz5039Isup2.hkl

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

(C12H12N2)(C12H11N2)[Mo(CN)8]·4H2O	F(000) = 1524
Mr = 743.63	Dx = 1.567 Mg m−3
Orthorhombic, Ccca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2b 2bc	Cell parameters from 6602 reflections
a = 12.403 (3) Å	θ = 3.4–29.0°
b = 16.534 (3) Å	µ = 0.48 mm−1
c = 15.370 (3) Å	T = 291 K
V = 3151.8 (11) Å3	Rod, dark blue
Z = 4	0.18 × 0.15 × 0.13 mm

Bruker SMART APEXII diffractometer	1442 independent reflections
Radiation source: fine-focus sealed tube	1388 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.016
phi and ω scans	θmax = 25.3°, θmin = 3.4°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −14→14
Tmin = 0.919, Tmax = 0.941	k = −15→19
6789 measured reflections	l = −18→16

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)] = 0.021	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.052	H-atom parameters constrained
S = 1.09	w = 1/[σ2(Fo2) + (0.0237P)2 + 4.1639P] where P = (Fo2 + 2Fc2)/3
1442 reflections	(Δ/σ)max < 0.001
112 parameters	Δρmax = 0.28 e Å−3
0 restraints	Δρmin = −0.31 e Å−3

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	Occ. (<1)
Mo1	0.0000	0.2500	0.2500	0.01026 (10)
O1	0.65008 (10)	−0.07739 (7)	−0.07004 (7)	0.0222 (3)
H1A	0.7081	−0.0819	−0.0991	0.033*
H1B	0.6515	−0.1156	−0.0330	0.033*
N1	−0.15776 (12)	0.39926 (8)	0.18061 (8)	0.0217 (3)
N2	−0.12604 (11)	0.18087 (8)	0.07447 (9)	0.0214 (3)
N3	0.61502 (11)	0.04861 (9)	0.04165 (9)	0.0222 (3)
H3X	0.6177	0.0114	−0.0001	0.027*	0.75
C1	−0.10315 (12)	0.34816 (9)	0.20714 (9)	0.0153 (3)
C2	−0.08556 (13)	0.20481 (9)	0.13705 (10)	0.0153 (3)
C3	0.61146 (13)	0.12818 (10)	0.02559 (10)	0.0226 (4)
H3	0.6063	0.1466	−0.0314	0.027*
C4	0.61534 (13)	0.18237 (10)	0.09245 (10)	0.0197 (3)
H4	0.6125	0.2375	0.0809	0.024*
C5	0.62366 (12)	0.15508 (9)	0.17825 (10)	0.0171 (3)
C6	0.62332 (13)	0.07142 (10)	0.19249 (11)	0.0212 (4)
H6	0.6258	0.0511	0.2489	0.025*
C7	0.61929 (14)	0.01956 (10)	0.12305 (11)	0.0239 (4)
H7	0.6195	−0.0360	0.1324	0.029*
C8	0.62950 (13)	0.20979 (10)	0.25268 (10)	0.0177 (3)
H8	0.6335	0.1868	0.3078	0.021*

	U11	U22	U33	U12	U13	U23
Mo1	0.01259 (15)	0.00997 (14)	0.00822 (14)	0.000	0.000	0.000
O1	0.0281 (6)	0.0209 (6)	0.0175 (6)	0.0004 (5)	0.0046 (5)	−0.0005 (5)
N1	0.0279 (8)	0.0213 (7)	0.0158 (7)	0.0060 (6)	−0.0014 (6)	−0.0007 (6)
N2	0.0263 (8)	0.0205 (7)	0.0175 (7)	−0.0032 (6)	−0.0032 (6)	−0.0003 (6)
N3	0.0209 (7)	0.0244 (8)	0.0213 (7)	0.0016 (6)	0.0000 (6)	−0.0098 (6)
C1	0.0185 (8)	0.0168 (8)	0.0107 (7)	−0.0012 (6)	0.0010 (6)	−0.0029 (6)
C2	0.0168 (8)	0.0125 (8)	0.0166 (8)	−0.0007 (6)	0.0011 (7)	0.0027 (6)
C3	0.0219 (8)	0.0295 (10)	0.0164 (8)	0.0023 (7)	0.0000 (7)	−0.0004 (7)
C4	0.0222 (8)	0.0181 (8)	0.0188 (8)	0.0018 (6)	0.0005 (7)	0.0007 (6)
C5	0.0141 (7)	0.0187 (8)	0.0186 (8)	0.0013 (6)	0.0003 (6)	−0.0010 (6)
C6	0.0253 (9)	0.0193 (8)	0.0190 (8)	0.0005 (7)	−0.0006 (7)	0.0013 (6)
C7	0.0255 (9)	0.0182 (9)	0.0281 (9)	0.0005 (7)	−0.0011 (8)	−0.0028 (7)
C8	0.0184 (8)	0.0199 (8)	0.0149 (8)	0.0019 (7)	−0.0011 (6)	0.0002 (6)

Mo1—C2	2.1674 (16)	N3—C7	1.341 (2)
Mo1—C2i	2.1674 (16)	N3—H3X	0.8896
Mo1—C2ii	2.1674 (16)	C3—C4	1.364 (2)
Mo1—C2iii	2.1674 (16)	C3—H3	0.9300
Mo1—C1i	2.1690 (16)	C4—C5	1.398 (2)
Mo1—C1iii	2.1690 (16)	C4—H4	0.9300
Mo1—C1	2.1690 (16)	C5—C6	1.400 (2)
Mo1—C1ii	2.1690 (16)	C5—C8	1.460 (2)
O1—H1A	0.8501	C6—C7	1.370 (2)
O1—H1B	0.8505	C6—H6	0.9300
N1—C1	1.157 (2)	C7—H7	0.9300
N2—C2	1.155 (2)	C8—C8i	1.332 (3)
N3—C3	1.339 (2)	C8—H8	0.9300
C2—Mo1—C2i	121.37 (8)	C1iii—Mo1—C1ii	107.72 (8)
C2—Mo1—C2ii	73.57 (8)	C1—Mo1—C1ii	144.64 (8)
C2i—Mo1—C2ii	139.67 (8)	H1A—O1—H1B	105.6
C2—Mo1—C2iii	139.67 (8)	C3—N3—C7	121.66 (14)
C2i—Mo1—C2iii	73.57 (8)	C3—N3—H3X	123.2
C2ii—Mo1—C2iii	121.37 (8)	C7—N3—H3X	115.1
C2—Mo1—C1i	72.33 (5)	N1—C1—Mo1	177.01 (13)
C2i—Mo1—C1i	74.09 (6)	N2—C2—Mo1	176.36 (14)
C2ii—Mo1—C1i	142.18 (5)	N3—C3—C4	120.35 (15)
C2iii—Mo1—C1i	77.74 (6)	N3—C3—H3	119.8
C2—Mo1—C1iii	142.18 (5)	C4—C3—H3	119.8
C2i—Mo1—C1iii	77.74 (6)	C3—C4—C5	120.08 (15)
C2ii—Mo1—C1iii	72.33 (5)	C3—C4—H4	120.0
C2iii—Mo1—C1iii	74.09 (6)	C5—C4—H4	120.0
C1i—Mo1—C1iii	144.64 (8)	C4—C5—C6	117.78 (14)
C2—Mo1—C1	74.09 (6)	C4—C5—C8	122.88 (14)
C2i—Mo1—C1	72.33 (5)	C6—C5—C8	119.32 (14)
C2ii—Mo1—C1	77.74 (6)	C7—C6—C5	119.78 (15)
C2iii—Mo1—C1	142.18 (5)	C7—C6—H6	120.1
C1i—Mo1—C1	107.72 (8)	C5—C6—H6	120.1
C1iii—Mo1—C1	83.12 (8)	N3—C7—C6	120.27 (15)
C2—Mo1—C1ii	77.74 (6)	N3—C7—H7	119.9
C2i—Mo1—C1ii	142.18 (5)	C6—C7—H7	119.9
C2ii—Mo1—C1ii	74.09 (6)	C8i—C8—C5	124.74 (18)
C2iii—Mo1—C1ii	72.33 (5)	C8i—C8—H8	117.6
C1i—Mo1—C1ii	83.12 (8)	C5—C8—H8	117.6

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N1iv	0.85	2.11	2.9524 (19)	174
O1—H1B···N2v	0.85	2.00	2.8195 (18)	162
N3—H3X···O1	0.89	1.86	2.7342 (17)	166

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯N1i	0.85	2.11	2.9524 (19)	174
O1—H1B⋯N2ii	0.85	2.00	2.8195 (18)	162
N3—H3X⋯O1	0.89	1.86	2.7342 (17)	166

Symmetry codes: (i) ; (ii) .