μ(3)-Dodeca-tungsto(V,VI)aluminato-κO:O':O''-tris-[aqua-bis-(ethyl-ene-diamine-κN,N')copper(II)].

The title compound, [AlCu(3)W(12)O(40)(C(2)H(8)N(2))(6)(H(2)O)(3)], was prepared under hydro-thermal conditions. The Cu(2+) ion displays an elongated octa-hedral geometry defined by one bridging O atom from the polyoxidoanion and a coordinated water mol-ecule in axial positions and four N atoms of the two chelating ethyl-enediamine (en) ligands in equatorial positions. The one-electron reduced [AlW(12)O(40)](6-) anion coordinates three [Cu(en)(H(2)O)](2+) fragments, generating a neutral tri-supported Keggin-type polyoxidometalate (POM). This tri-supported POM is located in a special position of [Formula: see text] symmetry and therefore O atoms from the central AlO(4) tetra-hedron are disordered over two sets of sites. Disorder is also observed for three other bridging O atoms of the POM. In the crystal, mol-ecules are connected via N-H⋯O and O-H⋯O hydrogen bonds, forming a three-dimensional framework.

Related literature

For the isotypic VIV and SiIV structures, see: Lu, Cui, Chn class="Chemical">en et al. (2009 ▶). For general background to polyoxidometalates, see: Pope & Müller (1991 ▶); Hill (1998 ▶); López et al. (2001 ▶). For modified Keggin-type structures with transition metal complexes, see: Xu et al. (2000 ▶); Yuan, Li et al. (2003 ▶). For the structure and chemistry of one-electron reduced heteropolytungstate, see: Lan et al. (2008 ▶); Meng et al. (2008 ▶). For other dodeca­tungstoaluminates, see: Wang et al. (2006 ▶); Yuan, Qin et al. (2009 ▶). For polyoxidometalates prepared with strongly reducing agents, see: Lu, Cui, Liu et al. (2009 ▶); Lu, Xu & Yu (2010 ▶); Lu, Xu, Cui et al. (2010 ▶).

Experimental

Crystal data

[AlCu3W12O40(C2H8N2)6(H2O)3]

M = 3478.47

Trigonal,

a = 17.9719 (14) Å

c = 29.335 (5) Å

V = 8206 (2) Å3

Z = 6

Mo Kα radiation

μ = 26.38 mm−1

T = 296 K

0.11 × 0.11 × 0.10 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.159, T max = 0.178

22760 measured reflections

2220 independent reflections

1864 reflections with I > 2σ(I)

R int = 0.071

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.071

S = 1.10

2220 reflections

157 parameters

H-atom parameters constrained

Δρmax = 1.85 e Å−3

Δρmin = −3.56 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molen class="Chemical">cular graphics: DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811048288/gk2416sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811048288/gk2416Isup2.hkl

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

[AlCu3W12O40(C2H8N2)6(H2O)3]	Dx = 4.224 Mg m−3
Mr = 3478.47	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3c	Cell parameters from 4488 reflections
Hall symbol: -R 3 2"c	θ = 2.3–27.9°
a = 17.9719 (14) Å	µ = 26.38 mm−1
c = 29.335 (5) Å	T = 296 K
V = 8206 (2) Å3	Prism, blue
Z = 6	0.11 × 0.11 × 0.10 mm
F(000) = 9252

Rigaku R-AXIS RAPID diffractometer	2220 independent reflections
Radiation source: fine-focus sealed tube	1864 reflections with I > 2σ(I)
graphite	Rint = 0.071
Detector resolution: 10 pixels mm-1	θmax = 28.0°, θmin = 2.3°
ω scans	h = −23→23
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −23→23
Tmin = 0.159, Tmax = 0.178	l = −38→38
22760 measured reflections

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)] = 0.035	H-atom parameters constrained
wR(F2) = 0.071	w = 1/[σ2(Fo2) + (0.0089P)2 + 625.9202P] where P = (Fo2 + 2Fc2)/3
S = 1.10	(Δ/σ)max = 0.001
2220 reflections	Δρmax = 1.85 e Å−3
157 parameters	Δρmin = −3.56 e Å−3
0 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: 0.000015 (2)

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)
Al1	0.0000	1.0000	0.2500	0.0086 (12)
W1	0.12019 (2)	0.89540 (2)	0.251326 (13)	0.01398 (11)
W2	0.11116 (3)	0.99748 (3)	0.151770 (19)	0.03112 (15)
Cu1	0.38149 (11)	1.0000	0.2500	0.0250 (4)
O1	0.1553 (4)	0.8230 (4)	0.2512 (3)	0.035 (2)
O2	0.1623 (6)	0.9928 (5)	0.1054 (3)	0.035 (2)
O3	0.0000	0.8191 (5)	0.2500	0.032 (3)
O4	0.2303 (5)	1.0000	0.2500	0.021 (2)
O5	0.1345 (9)	0.9100 (9)	0.1856 (6)	0.017 (3)	0.50
O5'	0.0992 (10)	0.9148 (9)	0.1888 (5)	0.014 (3)	0.50
O6	0.1377 (9)	0.9148 (8)	0.3158 (5)	0.016 (3)	0.50
O6'	0.0980 (9)	0.9157 (9)	0.3118 (5)	0.013 (3)	0.50
O7	0.0887 (8)	1.0866 (8)	0.1188 (5)	0.016 (3)*	0.50
O7'	−0.0036 (9)	0.9157 (8)	0.1502 (5)	0.018 (3)	0.50
O8	0.0000 (8)	1.0914 (7)	0.2333 (4)	0.010 (2)	0.50
O9	0.0000	1.0000	0.1883 (7)	0.011 (4)	0.50
O1W	0.5157 (6)	1.0000	0.2500	0.039 (3)
H1W	0.5318	0.9756	0.2693	0.059*
C1	0.3609 (8)	1.0205 (8)	0.3444 (4)	0.036 (3)
H1C	0.3626	1.0033	0.3755	0.043*
H1D	0.3169	1.0365	0.3420	0.043*
C2	0.4485 (8)	1.0956 (8)	0.3305 (4)	0.037 (3)
H2C	0.4615	1.1460	0.3484	0.044*
H2D	0.4930	1.0811	0.3359	0.044*
N1	0.3427 (6)	0.9487 (6)	0.3121 (3)	0.028 (2)
H1A	0.2861	0.9102	0.3118	0.033*
H1B	0.3712	0.9218	0.3208	0.033*
N2	0.4457 (6)	1.1133 (6)	0.2820 (3)	0.031 (2)
H2A	0.4994	1.1439	0.2707	0.037*
H2B	0.4189	1.1438	0.2780	0.037*

	U11	U22	U33	U12	U13	U23
Al1	0.0072 (17)	0.0072 (17)	0.011 (3)	0.0036 (8)	0.000	0.000
W1	0.01112 (18)	0.00943 (17)	0.0236 (2)	0.00683 (14)	−0.00119 (14)	−0.00112 (14)
W2	0.0239 (2)	0.0154 (2)	0.0504 (3)	0.00709 (17)	0.0232 (2)	−0.00150 (19)
Cu1	0.0300 (7)	0.0256 (9)	0.0178 (9)	0.0128 (5)	0.0001 (4)	0.0001 (7)
O1	0.012 (3)	0.013 (3)	0.080 (6)	0.007 (3)	−0.003 (4)	−0.001 (4)
O2	0.056 (5)	0.023 (4)	0.022 (4)	0.017 (4)	0.013 (4)	0.003 (3)
O3	0.008 (4)	0.009 (3)	0.078 (9)	0.004 (2)	0.002 (5)	0.001 (3)
O4	0.005 (3)	0.010 (4)	0.049 (7)	0.005 (2)	−0.001 (2)	−0.003 (4)
O5	0.010 (7)	0.007 (6)	0.034 (9)	0.004 (6)	0.006 (7)	−0.001 (6)
O5'	0.015 (8)	0.015 (7)	0.009 (7)	0.005 (6)	−0.006 (6)	−0.004 (5)
O6	0.011 (7)	0.007 (6)	0.029 (8)	0.005 (6)	0.003 (6)	0.001 (5)
O6'	0.013 (7)	0.016 (7)	0.014 (7)	0.009 (6)	0.000 (6)	0.003 (5)
O7'	0.023 (7)	0.009 (6)	0.025 (8)	0.009 (6)	−0.004 (6)	0.002 (6)
O8	0.011 (5)	0.015 (6)	0.009 (5)	0.009 (5)	0.001 (6)	−0.004 (5)
O9	0.011 (6)	0.011 (6)	0.012 (10)	0.005 (3)	0.000	0.000
O1W	0.026 (4)	0.038 (7)	0.058 (8)	0.019 (3)	0.009 (3)	0.017 (6)
C1	0.044 (7)	0.062 (8)	0.022 (6)	0.042 (7)	0.001 (5)	0.001 (6)
C2	0.039 (7)	0.049 (8)	0.028 (6)	0.026 (6)	−0.014 (5)	−0.012 (6)
N1	0.025 (5)	0.040 (5)	0.024 (5)	0.020 (4)	0.002 (4)	0.002 (4)
N2	0.030 (5)	0.032 (5)	0.035 (6)	0.020 (4)	−0.008 (4)	−0.004 (4)

Al1—O8i	1.714 (11)	W2—O7iii	2.079 (13)
Al1—O9	1.81 (2)	W2—O9	2.288 (10)
W1—O1	1.707 (7)	W2—O8iii	2.421 (11)
W1—O3	1.894 (6)	Cu1—N2	2.002 (9)
W1—O6'	1.894 (6)	Cu1—N1	2.002 (9)
W1—O6	1.921 (16)	Cu1—O1W	2.411 (11)
W1—O4	1.931 (4)	Cu1—O4	2.718 (9)
W1—O5'	1.939 (14)	O1W—H1W	0.8499
W1—O5	1.946 (17)	C1—N1	1.498 (15)
W1—O8ii	2.232 (11)	C1—C2	1.530 (17)
W1—O8iii	2.248 (12)	C1—H1C	0.9700
W2—O2	1.668 (8)	C1—H1D	0.9700
W2—O5'	1.765 (14)	C2—N2	1.465 (15)
W2—O7'iv	1.787 (13)	C2—H2C	0.9700
W2—O6'v	1.793 (14)	C2—H2D	0.9700
W2—O7'	1.840 (13)	N1—H1A	0.9000
W2—O6v	2.063 (14)	N1—H1B	0.9000
W2—O5	2.072 (15)	N2—H2A	0.9000
W2—O7	2.076 (13)	N2—H2B	0.9000
O8ii—Al1—O8i	112.2 (3)	O6'v—W2—O8iii	56.2 (5)
O8ii—Al1—O8iv	122.8 (8)	O7'—W2—O8iii	85.6 (5)
O8ii—Al1—O9ii	73.4 (4)	O6v—W2—O8iii	68.1 (5)
O9ii—Al1—O9	180.000 (2)	O5—W2—O8iii	68.2 (5)
O1—W1—O3	99.8 (4)	O7—W2—O8iii	111.0 (5)
O1—W1—O6'	110.1 (5)	O7iii—W2—O8iii	112.0 (5)
O3—W1—O6'	83.4 (5)	O9—W2—O8iii	53.0 (5)
O1—W1—O6	93.0 (5)	N2—Cu1—N2v	172.2 (5)
O3—W1—O6	100.1 (4)	N2—Cu1—N1	86.2 (4)
O6'—W1—O6	22.1 (4)	N2v—Cu1—N1	94.7 (4)
O1—W1—O4	98.8 (3)	N2—Cu1—N1v	94.7 (4)
O3—W1—O4	161.2 (3)	N2v—Cu1—N1v	86.2 (4)
O6'—W1—O4	92.5 (4)	N1—Cu1—N1v	166.4 (5)
O6—W1—O4	81.2 (4)	N2—Cu1—O1W	86.1 (3)
O1—W1—O5'	108.3 (6)	N2v—Cu1—O1W	86.1 (3)
O3—W1—O5'	81.8 (5)	N1—Cu1—O1W	96.8 (3)
O6'—W1—O5'	140.6 (6)	N1v—Cu1—O1W	96.8 (3)
O6—W1—O5'	158.1 (6)	N2—Cu1—O4	93.9 (3)
O4—W1—O5'	90.2 (4)	N2v—Cu1—O4	93.9 (3)
O1—W1—O5	91.4 (5)	N1—Cu1—O4	83.2 (3)
O3—W1—O5	95.9 (4)	N1v—Cu1—O4	83.2 (3)
O6'—W1—O5	158.3 (6)	O1W—Cu1—O4	180.000 (2)
O6—W1—O5	162.3 (6)	W1—O3—W1i	162.3 (6)
O4—W1—O5	81.2 (4)	W1—O4—W1v	114.9 (4)
O5'—W1—O5	20.4 (4)	W1—O4—Cu1	122.5 (2)
O1—W1—O8ii	166.6 (4)	W1v—O4—Cu1	122.5 (2)
O3—W1—O8ii	87.3 (4)	O5'—O5—W1	79 (2)
O6'—W1—O8ii	59.2 (5)	O5'—O5—W2	54.6 (19)
O6—W1—O8ii	74.6 (5)	W1—O5—W2	120.9 (7)
O4—W1—O8ii	75.0 (4)	O5—O5'—W2	107 (2)
O5'—W1—O8ii	83.8 (5)	O5—O5'—W1	80 (2)
O5—W1—O8ii	99.1 (5)	W2—O5'—W1	141.3 (8)
O1—W1—O8iii	164.6 (4)	O6'—O6—W1	76.9 (19)
O3—W1—O8iii	86.8 (4)	O6'—O6—W2v	58.5 (16)
O6'—W1—O8iii	84.3 (5)	W1—O6—W2v	121.0 (7)
O6—W1—O8iii	99.5 (5)	O6—O6'—W2v	101.1 (19)
O4—W1—O8iii	74.6 (4)	O6—O6'—W1	81.0 (19)
O5'—W1—O8iii	58.7 (5)	W2v—O6'—W1	140.3 (8)
O5—W1—O8iii	74.0 (5)	O7'iv—O7—W2	59.1 (11)
O8ii—W1—O8iii	25.3 (6)	O7'iv—O7—W2iv	62.2 (11)
O2—W2—O5'	107.3 (6)	W2—O7—W2iv	114.8 (7)
O2—W2—O7'iv	114.1 (5)	O7iii—O7'—W2iii	94.5 (13)
O5'—W2—O7'iv	138.6 (7)	O7iii—O7'—W2	91.4 (13)
O2—W2—O6'v	111.0 (5)	W2iii—O7'—W2	149.6 (7)
O5'—W2—O6'v	95.7 (6)	O8i—O8—Al1	73.4 (4)
O7'iv—W2—O6'v	70.1 (6)	O8i—O8—W1ii	78.3 (10)
O2—W2—O7'	111.5 (5)	Al1—O8—W1ii	124.6 (6)
O5'—W2—O7'	74.1 (6)	O8i—O8—W1iv	76.4 (10)
O7'iv—W2—O7'	90.2 (7)	Al1—O8—W1iv	123.7 (6)
O6'v—W2—O7'	137.4 (6)	W1ii—O8—W1iv	93.3 (4)
O2—W2—O6v	93.7 (5)	O8i—O8—W2iv	171.0 (3)
O5'—W2—O6v	91.3 (6)	Al1—O8—W2iv	115.6 (5)
O7'iv—W2—O6v	86.5 (6)	W1ii—O8—W2iv	96.3 (4)
O6'v—W2—O6v	20.4 (5)	W1iv—O8—W2iv	96.9 (4)
O7'—W2—O6v	153.6 (6)	Al1—O9—W2iii	118.0 (5)
O2—W2—O5	91.5 (5)	Al1—O9—W2	118.0 (5)
O5'—W2—O5	18.6 (5)	W2iii—O9—W2	99.8 (6)
O7'iv—W2—O5	152.8 (6)	Al1—O9—W2iv	118.0 (5)
O6'v—W2—O5	92.8 (6)	W2iii—O9—W2iv	99.8 (6)
O7'—W2—O5	88.7 (6)	W2—O9—W2iv	99.8 (6)
O6v—W2—O5	82.5 (6)	Cu1—O1W—H1W	126.8
O2—W2—O7	89.1 (5)	N1—C1—C2	106.1 (9)
O5'—W2—O7	161.3 (7)	N1—C1—H1C	110.5
O6'v—W2—O7	86.3 (6)	C2—C1—H1C	110.5
O7'—W2—O7	91.8 (5)	N1—C1—H1D	110.5
O6v—W2—O7	96.7 (5)	C2—C1—H1D	110.5
O5—W2—O7	179.0 (6)	H1C—C1—H1D	108.7
O2—W2—O7iii	86.7 (5)	N2—C2—C1	108.6 (9)
O5'—W2—O7iii	89.9 (6)	N2—C2—H2C	110.0
O7'iv—W2—O7iii	92.2 (5)	C1—C2—H2C	110.0
O6'v—W2—O7iii	158.7 (6)	N2—C2—H2D	110.0
O6v—W2—O7iii	178.7 (5)	C1—C2—H2D	110.0
O5—W2—O7iii	98.7 (6)	H2C—C2—H2D	108.3
O7—W2—O7iii	82.1 (7)	C1—N1—Cu1	107.7 (7)
O2—W2—O9	153.2 (6)	C1—N1—H1A	110.2
O5'—W2—O9	89.3 (6)	Cu1—N1—H1A	110.2
O7'iv—W2—O9	52.5 (5)	C1—N1—H1B	110.2
O6'v—W2—O9	87.3 (6)	Cu1—N1—H1B	110.2
O7'—W2—O9	52.1 (5)	H1A—N1—H1B	108.5
O6v—W2—O9	107.2 (6)	C2—N2—Cu1	107.4 (7)
O5—W2—O9	107.5 (5)	C2—N2—H2A	110.2
O7—W2—O9	72.2 (5)	Cu1—N2—H2A	110.2
O7iii—W2—O9	72.1 (5)	C2—N2—H2B	110.2
O2—W2—O8iii	153.7 (4)	Cu1—N2—H2B	110.2
O5'—W2—O8iii	56.7 (6)	H2A—N2—H2B	108.5
O7'iv—W2—O8iii	84.6 (6)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O2vi	0.85	2.25	2.856 (9)	128
N1—H1B···O5vi	0.90	2.26	3.138 (17)	163
N1—H1B···O5'vi	0.90	2.30	3.185 (17)	170
N2—H2A···O7vii	0.90	2.35	3.101 (17)	141
N2—H2B···O1v	0.90	2.11	2.956 (12)	157

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W⋯O2i	0.85	2.25	2.856 (9)	128
N1—H1B⋯O5i	0.90	2.26	3.138 (17)	163
N1—H1B⋯O5′i	0.90	2.30	3.185 (17)	170
N2—H2A⋯O7ii	0.90	2.35	3.101 (17)	141
N2—H2B⋯O1iii	0.90	2.11	2.956 (12)	157

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