4,4'-Diazenediyldipyridinium (4-pyridyldiazen-yl)pyridinium octa-cyanidomolyb-date(V) tetra-hydrate.

The structure of the title complex, (C(10)H(10)N(4))(C(10)H(9)N(4))[Mo(CN)(8)]·4H(2)O, consists of 4,4'-diazenediyldipyridinium and (4-pyridyldiazen-yl)pyridinium cations disordered over the same site, an [Mo(CN)(8)](3-) anion and four uncoordinated water mol-ecules. The cations (crystallographic symmetry, 2) and the [Mo(CN)(8)](3-) anion (crystallographic symmetry, 222) are arranged in an alternating fashion, forming a two-dimensional layered structure through hydrogen bonds. Hydrogen bonds, π-π stacking inter-actions (shortest distance = 4.7872 Å) and van der Waals forces between adjacent layers generate a three-dimensional supra-molecular structure.

Related literature

For information on octacyanidometalate-based compounds complexes, see: Chelebaeva et al. (2008 ▶); Ikeda et al. (2005 ▶); Kosaka et al. (2007 ▶); Matoga et al. (2005 ▶); Prins et al. (2007 ▶); Przychodzeń et al. (2007 ▶); Wang et al. (2006 ▶).

Experimental

Crystal data

(C10H10N4)(C10H9N4)[Mo(CN)8]·4H2O

M = 747.60

Orthorhombic,

a = 16.259 (5) Å

b = 12.787 (4) Å

c = 15.442 (5) Å

V = 3210.5 (18) Å3

Z = 4

Mo Kα radiation

μ = 0.47 mm−1

T = 291 (2) K

0.28 × 0.26 × 0.24 mm

Data collection

Bruker APEXII diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.879, T max = 0.895

13328 measured reflections

1851 independent reflections

1540 reflections with I > 2σ(I)

R int = 0.050

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.065

S = 1.06

1851 reflections

121 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.52 e Å−3

Δρmin = −0.28 e Å−3

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

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680802494X/br2078sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680802494X/br2078Isup2.hkl

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

(C10H10N4)(C10H9N4)[Mo(CN)8]·4H2O	F000 = 1524
Mr = 747.60	Dx = 1.547 Mg m−3
Orthorhombic, Ccca	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -C 2b 2bc	Cell parameters from 13328 reflections
a = 16.259 (5) Å	θ = 2.4–27.5º
b = 12.787 (4) Å	µ = 0.47 mm−1
c = 15.442 (5) Å	T = 291 (2) K
V = 3210.5 (18) Å3	Block, pale yellow
Z = 4	0.28 × 0.26 × 0.24 mm

Bruker SMART APEX CCD diffractometer	1851 independent reflections
Radiation source: fine-focus sealed tube	1540 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.050
T = 291(2) K	θmax = 27.6º
φ and ω scans	θmin = 2.4º
Absorption correction: multi-scan(SADABS; Bruker, 2000)	h = −21→21
Tmin = 0.879, Tmax = 0.895	k = −16→16
13328 measured reflections	l = −19→16

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.065	w = 1/[σ2(Fo2) + (0.0235P)2 + 2.9147P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max < 0.001
1851 reflections	Δρmax = 0.52 e Å−3
121 parameters	Δρmin = −0.28 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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)
C1	0.39870 (13)	0.84531 (17)	0.79366 (15)	0.0382 (5)
C2	0.45460 (14)	0.83539 (19)	0.63923 (15)	0.0427 (5)
C3	0.41341 (15)	0.62509 (19)	0.31466 (17)	0.0461 (6)
C4	0.43896 (15)	0.63527 (19)	0.40018 (17)	0.0447 (6)
H4	0.4948	0.6385	0.4132	0.054*
C5	0.38109 (14)	0.64066 (18)	0.46624 (17)	0.0450 (6)
H5	0.3982	0.6474	0.5234	0.054*
C6	0.27215 (16)	0.62570 (19)	0.36140 (16)	0.0464 (6)
H6	0.2163	0.6225	0.3484	0.056*
C7	0.33002 (14)	0.62029 (19)	0.29530 (16)	0.0441 (6)
H7	0.3129	0.6135	0.2381	0.053*
Mo1	0.5000	0.7500	0.7500	0.02552 (10)
N1	0.34570 (12)	0.89415 (16)	0.81824 (14)	0.0468 (5)
N2	0.43040 (13)	0.87856 (16)	0.57871 (13)	0.0462 (5)
N3	0.29771 (12)	0.63591 (16)	0.44687 (13)	0.0437 (5)
H3A	0.262 (2)	0.639 (3)	0.488 (2)	0.052*	0.75
N4	0.46326 (12)	0.62255 (16)	0.24043 (15)	0.0495 (5)
O1	0.17847 (11)	0.59099 (14)	0.56028 (11)	0.0457 (4)
H1A	0.1323 (19)	0.593 (2)	0.535 (2)	0.069*
H1B	0.1865 (18)	0.530 (2)	0.5803 (19)	0.069*

	U11	U22	U33	U12	U13	U23
C1	0.0371 (11)	0.0422 (12)	0.0353 (12)	0.0130 (9)	−0.0141 (9)	−0.0110 (9)
C2	0.0442 (13)	0.0452 (13)	0.0387 (13)	0.0103 (10)	−0.0093 (10)	0.0096 (10)
C3	0.0477 (13)	0.0468 (14)	0.0438 (14)	0.0125 (10)	0.0088 (11)	0.0055 (11)
C4	0.0376 (11)	0.0457 (13)	0.0510 (15)	0.0007 (9)	0.0096 (11)	0.0065 (11)
C5	0.0437 (13)	0.0476 (13)	0.0436 (14)	0.0068 (10)	0.0092 (11)	0.0120 (11)
C6	0.0499 (13)	0.0449 (13)	0.0443 (14)	0.0183 (10)	0.0102 (11)	−0.0136 (10)
C7	0.0453 (13)	0.0482 (14)	0.0388 (14)	0.0139 (10)	−0.0010 (11)	0.0019 (11)
Mo1	0.02788 (16)	0.02590 (16)	0.02278 (16)	0.000	0.000	0.000
N1	0.0505 (12)	0.0483 (11)	0.0417 (12)	0.0182 (9)	−0.0095 (9)	−0.0131 (9)
N2	0.0595 (13)	0.0422 (11)	0.0371 (11)	0.0099 (9)	−0.0119 (10)	0.0020 (9)
N3	0.0438 (11)	0.0452 (11)	0.0420 (12)	0.0206 (9)	0.0038 (9)	−0.0123 (9)
N4	0.0492 (10)	0.0498 (11)	0.0496 (13)	0.0047 (9)	0.0063 (11)	−0.0067 (10)
O1	0.0429 (9)	0.0484 (10)	0.0459 (11)	0.0129 (8)	0.0064 (8)	0.0155 (8)

C1—N1	1.130 (3)	C6—H6	0.9300
C1—Mo1	2.157 (2)	C7—H7	0.9300
C2—N2	1.155 (3)	Mo1—C1i	2.157 (2)
C2—Mo1	2.159 (2)	Mo1—C1ii	2.157 (2)
C3—C7	1.390 (3)	Mo1—C1iii	2.157 (2)
C3—C4	1.391 (4)	Mo1—C2iii	2.159 (2)
C3—N4	1.404 (3)	Mo1—C2ii	2.159 (2)
C4—C5	1.389 (3)	Mo1—C2i	2.159 (2)
C4—H4	0.9300	N3—H3A	0.86 (4)
C5—N3	1.390 (3)	N4—N4iv	1.231 (4)
C5—H5	0.9300	O1—H1A	0.85 (3)
C6—N3	1.390 (3)	O1—H1B	0.85 (3)
C6—C7	1.390 (3)
N1—C1—Mo1	178.5 (2)	C1ii—Mo1—C2iii	77.12 (10)
N2—C2—Mo1	178.1 (2)	C1iii—Mo1—C2iii	72.59 (9)
C7—C3—C4	120.0 (2)	C1i—Mo1—C2	77.12 (10)
C7—C3—N4	112.7 (2)	C1—Mo1—C2	72.59 (9)
C4—C3—N4	127.2 (2)	C1ii—Mo1—C2	74.20 (9)
C5—C4—C3	120.0 (2)	C1iii—Mo1—C2	142.59 (9)
C5—C4—H4	120.0	C2iii—Mo1—C2	75.23 (13)
C3—C4—H4	120.0	C1i—Mo1—C2ii	142.59 (9)
C4—C5—N3	120.0 (2)	C1—Mo1—C2ii	74.20 (9)
C4—C5—H5	120.0	C1ii—Mo1—C2ii	72.59 (9)
N3—C5—H5	120.0	C1iii—Mo1—C2ii	77.12 (10)
N3—C6—C7	120.0 (2)	C2iii—Mo1—C2ii	140.02 (13)
N3—C6—H6	120.0	C2—Mo1—C2ii	119.25 (14)
C7—C6—H6	120.0	C1i—Mo1—C2i	72.59 (9)
C3—C7—C6	120.0 (2)	C1—Mo1—C2i	77.12 (10)
C3—C7—H7	120.0	C1ii—Mo1—C2i	142.59 (9)
C6—C7—H7	120.0	C1iii—Mo1—C2i	74.20 (9)
C1i—Mo1—C1	80.44 (12)	C2iii—Mo1—C2i	119.25 (14)
C1i—Mo1—C1ii	143.57 (12)	C2—Mo1—C2i	140.02 (13)
C1—Mo1—C1ii	111.19 (13)	C2ii—Mo1—C2i	75.23 (13)
C1i—Mo1—C1iii	111.19 (13)	C5—N3—C6	120.0 (2)
C1—Mo1—C1iii	143.57 (12)	C5—N3—H3A	120 (2)
C1ii—Mo1—C1iii	80.44 (12)	C6—N3—H3A	120 (2)
C1i—Mo1—C2iii	74.20 (9)	N4iv—N4—C3	111.4 (3)
C1—Mo1—C2iii	142.59 (9)	H1A—O1—H1B	109 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O1	0.86 (4)	1.86 (4)	2.675 (3)	157 (3)
O1—H1A···N2v	0.85 (3)	2.06 (3)	2.809 (3)	147 (3)
O1—H1B···N1vi	0.85 (3)	2.40 (3)	3.164 (3)	150 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O1	0.86 (4)	1.86 (4)	2.675 (3)	157 (3)
O1—H1A⋯N2i	0.85 (3)	2.06 (3)	2.809 (3)	147 (3)
O1—H1B⋯N1ii	0.85 (3)	2.40 (3)	3.164 (3)	150 (3)

Symmetry codes: (i) ; (ii) .