A two-dimensional organic-inorganic hybrid compound, poly[(ethylenediamine)tri-μ-oxido-oxidocopper(II)molybdenum(VI)].

A new organic-inorganic two-dimensional hybrid compound, [CuMoO(4)(C(2)H(8)N(2))], has been hydro-thermally synthesized at 443 K. The unit cell contains layers composed of CuN(2)O(4) octa-hedra and MoO(4) tetra-hedra. Corner-sharing MoO(4) and CuN(2)O(4) polyhedra form CuMoO(4) bimetallic sites that are joined together through O atoms, forming an edge-sharing Cu(2)Mo(2)O(4) chain along the c axis. The one-dimensional chains are further linked through bridging O atoms that join the Cu and Mo atoms into respective chains along the b axis, thus establishing layers in the bc plane. The ethyl-enediamine ligand is coordinated to the Cu atom through its two N atoms and is oriented perpendicularly to the two-dimensional -Cu-O-Mo- layers. The average distance between adjacent layers, as calculated by consideration of the closest and furthest distances between two layers, is 8.7 Å. The oxidation states of the Mo and Cu atoms of VI and II, respectively, were confirmed by bond-valence sum calculations.

Related literature

For related literature on inorganic–organic hybrid materials, see: Gopalakrishnan (1995 ▶); Katsoulis (1998 ▶); Kresge et al. (1992 ▶). For related structures containing molybdate(VI) units, see: Cui et al. (2005 ▶); Niven et al. (1991 ▶). For the thermal behaviour of a related ethyl­enediamine-containing compound, see: Han et al. (2005 ▶). For general background, see: Brown & Altermatt (1985 ▶).

Experimental

Crystal data

[CuMoO4(C2H8N2)]

M = 283.58

Monoclinic,

a = 9.954 (4) Å

b = 9.436 (4) Å

c = 7.674 (3) Å

β = 107.734 (18)°

V = 686.6 (5) Å3

Z = 4

Mo Kα radiation

μ = 4.88 mm−1

T = 303 (2) K

0.41 × 0.06 × 0.02 mm

Data collection

Rigaku Mercury CCD diffractometer

Absorption correction: multi-scan (REQAB; Jacobson, 1998 ▶) T min = 0.678, T max = 1.000 (expected range = 0.615–0.907)

5616 measured reflections

1209 independent reflections

1098 reflections with I > 2σ(I)

R int = 0.089

Refinement

R[F 2 > 2σ(F 2)] = 0.063

wR(F 2) = 0.111

S = 1.10

1209 reflections

91 parameters

H-atom parameters constrained

Δρmax = 0.79 e Å−3

Δρmin = −0.92 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2001 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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 global, I. DOI: 10.1107/S160053680802792X/wm2192sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680802792X/wm2192Isup2.hkl

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

[CuMoO4(C2H8N2)]	F(000) = 548
Mr = 283.58	Dx = 2.743 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4208 reflections
a = 9.954 (4) Å	θ = 2.2–26.0°
b = 9.436 (4) Å	µ = 4.88 mm−1
c = 7.674 (3) Å	T = 303 K
β = 107.734 (18)°	Column, blue
V = 686.6 (5) Å3	0.41 × 0.06 × 0.02 mm
Z = 4

Rigaku Mercury CCD diffractometer	1209 independent reflections
Radiation source: Sealed Tube	1098 reflections with I > 2σ(I)
Graphite Monochromator	Rint = 0.089
Detector resolution: 14.6199 pixels mm-1	θmax = 25.0°, θmin = 3.1°
ω–scans	h = −11→11
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	k = −11→11
Tmin = 0.678, Tmax = 1.000	l = −8→9
5616 measured reflections

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.111	H-atom parameters constrained
S = 1.10	w = 1/[σ2(Fo2) + (0.0154P)2 + 14.9224P] where P = (Fo2 + 2Fc2)/3
1209 reflections	(Δ/σ)max = 0.001
91 parameters	Δρmax = 0.79 e Å−3
0 restraints	Δρmin = −0.92 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
Mo1	0.16945 (9)	0.89946 (9)	0.21937 (11)	0.0186 (3)
Cu2	−0.12230 (13)	1.03150 (13)	0.30706 (17)	0.0205 (4)
N1	−0.1618 (9)	0.8217 (9)	0.3090 (11)	0.0226 (19)
H1A	−0.1479	0.7798	0.2106	0.027*
H1B	−0.1035	0.7815	0.4103	0.027*
O1	0.0784 (7)	1.0015 (7)	0.3471 (9)	0.0212 (15)
N2	−0.3317 (9)	1.0540 (10)	0.2586 (11)	0.025 (2)
H2A	−0.3505	1.0774	0.3625	0.030*
H2B	−0.3651	1.1230	0.1758	0.030*
O2	0.3401 (7)	0.8692 (8)	0.3611 (10)	0.0299 (18)
O3	0.1771 (9)	0.9921 (8)	0.0266 (10)	0.036 (2)
O4	0.0827 (7)	0.7333 (7)	0.1511 (10)	0.0258 (16)
C2	−0.3985 (10)	0.9178 (11)	0.1886 (14)	0.024 (2)
H2C	−0.4021	0.9054	0.0630	0.029*
H2D	−0.4930	0.9145	0.1962	0.029*
C1	−0.3096 (11)	0.8039 (12)	0.3058 (16)	0.031 (3)
H1C	−0.3159	0.8100	0.4279	0.038*
H1D	−0.3433	0.7123	0.2573	0.0387*

	U11	U22	U33	U12	U13	U23
Mo1	0.0228 (5)	0.0186 (4)	0.0169 (4)	−0.0027 (4)	0.0104 (3)	−0.0023 (4)
Cu2	0.0204 (7)	0.0178 (6)	0.0233 (7)	0.0005 (5)	0.0074 (5)	0.0011 (5)
N1	0.022 (5)	0.027 (5)	0.019 (4)	−0.001 (4)	0.007 (4)	0.003 (4)
O1	0.025 (4)	0.022 (4)	0.018 (4)	0.003 (3)	0.009 (3)	−0.004 (3)
N2	0.025 (5)	0.036 (5)	0.015 (4)	−0.003 (4)	0.008 (4)	−0.004 (4)
O2	0.018 (4)	0.037 (5)	0.033 (4)	−0.001 (3)	0.006 (3)	−0.011 (4)
O3	0.055 (5)	0.035 (5)	0.023 (4)	−0.012 (4)	0.022 (4)	−0.003 (4)
O4	0.026 (4)	0.022 (4)	0.026 (4)	−0.006 (3)	0.005 (3)	−0.003 (3)
C2	0.012 (5)	0.033 (6)	0.030 (6)	−0.005 (4)	0.008 (4)	0.000 (5)
C1	0.026 (6)	0.036 (7)	0.034 (6)	0.001 (5)	0.014 (5)	0.013 (5)

Mo1—O2	1.739 (7)	N1—H1A	0.9000
Mo1—O3	1.740 (7)	N1—H1B	0.9000
Mo1—O4	1.789 (7)	N2—C2	1.471 (13)
Mo1—O1	1.803 (6)	N2—H2A	0.9000
Cu2—O1	1.947 (7)	N2—H2B	0.9000
Cu2—O4i	1.951 (7)	O4—Cu2iv	1.951 (7)
Cu2—O1Aii	2.574 (7)	C2—C1	1.505 (15)
Cu2—O3Aiii	2.460 (7)	C2—H2C	0.9600
Cu2—N2	2.014 (8)	C2—H2D	0.9600
Cu2—N1	2.020 (9)	C1—H1C	0.9600
N1—C1	1.473 (13)	C1—H1D	0.9600
O2—Mo1—O3	109.1 (4)	C2—N2—Cu2	107.6 (6)
O2—Mo1—O4	109.4 (3)	C2—N2—H2A	110.2
O3—Mo1—O4	109.5 (3)	Cu2—N2—H2A	110.2
O2—Mo1—O1	107.8 (3)	C2—N2—H2B	110.2
O3—Mo1—O1	110.7 (3)	Cu2—N2—H2B	110.2
O4—Mo1—O1	110.4 (3)	H2A—N2—H2B	108.5
O1—Cu2—O4i	88.3 (3)	Mo1—O4—Cu2iv	138.7 (4)
O1—Cu2—N2	177.3 (3)	N2—C2—C1	106.7 (9)
O4i—Cu2—N2	94.2 (3)	N2—C2—H2C	110.4
O1—Cu2—N1	92.8 (3)	C1—C2—H2C	110.4
O4i—Cu2—N1	170.2 (3)	N2—C2—H2D	110.4
N2—Cu2—N1	84.9 (3)	C1—C2—H2D	110.4
C1—N1—Cu2	107.9 (6)	H2C—C2—H2D	108.6
C1—N1—H1A	110.1	N1—C1—C2	109.3 (8)
Cu2—N1—H1A	110.1	N1—C1—H1C	109.8
C1—N1—H1B	110.1	C2—C1—H1C	109.8
Cu2—N1—H1B	110.1	N1—C1—H1D	109.8
H1A—N1—H1B	108.4	C2—C1—H1D	109.8
Mo1—O1—Cu2	130.8 (4)	H1C—C1—H1D	108.3
O1—Cu2—N1—C1	172.4 (6)	O4i—Cu2—N2—C2	170.1 (6)
O4i—Cu2—N1—C1	76 (2)	N1—Cu2—N2—C2	−19.7 (6)
N2—Cu2—N1—C1	−9.1 (7)	O2—Mo1—O4—Cu2iv	1.6 (7)
O2—Mo1—O1—Cu2	−161.3 (5)	O3—Mo1—O4—Cu2iv	121.0 (6)
O3—Mo1—O1—Cu2	79.4 (5)	O1—Mo1—O4—Cu2iv	−116.8 (6)
O4—Mo1—O1—Cu2	−42.0 (6)	Cu2—N2—C2—C1	43.7 (9)
O4i—Cu2—O1—Mo1	−133.4 (5)	Cu2—N1—C1—C2	36.0 (10)
N1—Cu2—O1—Mo1	56.3 (5)	N2—C2—C1—N1	−53.4 (11)
O1—Cu2—N2—C2	14 (7)

Table 1

Selected bond lengths (Å)

Mo1—O2	1.739 (7)
Mo1—O3	1.740 (7)
Mo1—O4	1.789 (7)
Mo1—O1	1.803 (6)
Cu2—O1	1.947 (7)
Cu2—O4i	1.951 (7)
Cu2—O1Aii	2.574 (7)
Cu2—O3Aiii	2.460 (7)
Cu2—N2	2.014 (8)
Cu2—N1	2.020 (9)

Symmetry codes: (i) ; (ii) ; (iii) .