μ3-Dodeca­tungsto(V,VI)aluminato-κ3O:O′:O′′-tris­[aqua­bis­(ethyl­ene­diamine-κ2N,N′)copper(II)]

Lu, Y.-K.; Qu, Y.-Y.; Tian, M.-M.; Diao, C.-L.; Liu, Y.-Q.

doi:10.1107/S1600536811048288

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Pages m1778-m1779

https://doi.org/10.1107/S1600536811048288

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μ₃-Dodecatungsto(V,VI)aluminato-κ³O:O′:O′′-tris[aquabis(ethylenediamine-κ²N,N′)copper(II)]

Yu-Kun Lu,^a ^* Yuan-Yuan Qu,^b Ming-Ming Tian,^a Cheng-Lin Diao ^b and Yun-Qi Liu ^b

^aState Key Laboratory of Heavy Oil Processing, College of Science, China University of Petroleum (East China), Qingdao Shandong 266555, People's Republic of China, and ^bState Key Laboratory of Heavy Oil Processing, College of Chemical Engineering, China University of Petroleum (East China), Qingdao Shandong 266555, People's Republic of China
^*Correspondence e-mail: lyk@upc.edu.cn

(Received 10 October 2011; accepted 14 November 2011; online 19 November 2011)

The title compound, [AlCu₃W₁₂O₄₀(C₂H₈N₂)₆(H₂O)₃], was prepared under hydrothermal conditions. The Cu²⁺ ion displays an elongated octahedral geometry defined by one bridging O atom from the polyoxidoanion and a coordinated water molecule in axial positions and four N atoms of the two chelating ethylenediamine (en) ligands in equatorial positions. The one-electron reduced [AlW₁₂O₄₀]⁶⁻ anion coordinates three [Cu(en)(H₂O)]²⁺ fragments, generating a neutral tri-supported Keggin-type polyoxidometalate (POM). This tri-supported POM is located in a special position of $[\overline{3}]$ symmetry and therefore O atoms from the central AlO₄ tetrahedron are disordered over two sets of sites. Disorder is also observed for three other bridging O atoms of the POM. In the crystal, molecules are connected via N—H⋯O and O—H⋯O hydrogen bonds, forming a three-dimensional framework.

Related literature

For the isotypic V^IV and Si^IV structures, see: Lu, Cui, Chen 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_r = 3478.47
Trigonal, $[R \overline 3c ]$
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[F² > 2σ(F²)] = 0.035
wR(F²) = 0.071
S = 1.10
2220 reflections
157 parameters
H-atom parameters constrained
Δρ_max = 1.85 e Å⁻³
Δρ_min = −3.56 e Å⁻³

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) $[x+{\script{1\over 3}}, x-y+{\script{5\over 3}}, z+{\script{1\over 6}}]$ ; (ii) $[-x+{\script{2\over 3}}, -y+{\script{7\over 3}}, -z+{\script{1\over 3}}]$ ; (iii) $[x-y+1, -y+2, -z+{\script{1\over 2}}]$ .

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); molecular graphics: DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811048288/gk2416sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811048288/gk2416Isup2.hkl

checkCIF report

Comment top

There has been extensive interest in polyoxometalates (POMs), owing to their fascinating properties and great potential applications in many fields including catalysis, material science, medicine, and magnetochemistry, and their unusual structural diversities (Pope & Müller, 1991; Hill, 1998; López et al., 2001). Especially, the modified POMs, which are the decoration of polyoxoanions with various transition metal ions, organic ligands, and/or their complex moieties, can be regarded as an ideal atomic level structural model for the determination of the mechanisms of oxide-supported catalysts (Xu et al., 2000; Yuan, Li et al., 2003). Therefore, we focussed our research on the preparation of modified POMs with strong reducing reagents (Lu, Cui, Liu et al., 2009; Lu, Xu, Cui et al., 2010, Lu, Xu, Yu et al., 2010).

As shown in Fig. 1, the title compound shows a neutral tri-supported classical psedo-Keggin type structure where three [Cu(en)₂(H₂O)]²⁺ fragments are decorating the one-electron reduced heteropolyanion [AlW^VI₁₁W^VO40]^6-, which is isotypic with its V^IV and Si^IV analogue (Lu, Cui, Chen et al., 2009). The tri-supported POM is located in a special position of 3 symmetry and therefore oxygen atoms from the central AlO₄ tetrahedron are disordered over two sites. The pseudo-Keggin unit [AlW₁₂O₄₀]^6- may be viewed as a shell of {W₁₂O₃₆} encapsulating a disordered {AlO₄} moiety, present at its center and responsible for the local tetrahedral geometry (Wang et al., 2006; Yuan, Qin et al., 2009). The central Al atom is surrounded by a cube of eight oxygen (six O8 and two O9) atoms with each of them having half-occupancy due to the inversion symmetry at Al1, and the oxygens of the {AlO₄} group are covalently bonded to three different tungsten centers of the shell. All W atoms possess similar distorted octahedral geometry WO₆ defined by one terminal oxygen atom, four doubly bridging oxo-groups and one central oxygen atom. Three doubly-bridging oxo-groups are disordered over two sets of sites each (O5, O5', O6, O6', O7 and O7') with the occupancy factor assigned as 0.5. A l—O8 and Al—O9 bond lengths are 1.714 (11) and 1.81 (2), respectively, with mean bond distance 1.74 Å, in good agreement with the literature (López et al., 2001). The three classes of W—O average distances (being 1.688, 1.939 and 2.297 Å, respectively) are comparable to the corresponding distances in the similar structures (Wang et al., 2006; Yuan, Qin et al., 2009). The heteropolyanion [AlW^VI₁₁W^VO₄₀]^6- is a one-electron-reduced derivative of [AlW₁₂O₄₀]^6-, similar to other reported representatives (Lan et al., 2008; Meng et al., 2008). We consider that oxalic acid acts as reducing agent reducing W^VI to W^V in the reactions.

The most unusual structural feature of the title compound is that each of three surface bridging oxygen atoms (O4) of the polyoxoanion is coordinated to one [Cu(en)₂(H₂O)]²⁺ fragment. The Cu1 center possesses an elongated octahedral geometry defined by the bridging oxygen atom (Cu—O4, 2.718 (9) Å) from the polyoxoanion, a coordination water molecule [Cu—O1W, 2.411 (11) Å] trans to O4 atom and four N atoms from two chelating en ligands with equal Cu—N bond lengths 2.002 (9) Å. The bond lengths and angles at Cu1 are consistent with the Jahn–Teller active d⁹ electronic configuration of divalent copper. The tri-supported POMs are extended into three-dimensional supramolecular network via a combination of intermolecular N—H···O and O—H···O hydrogen bonding (Fig. 2).

Related literature top

For the isotypic V^IV and Si^IV structures, see: Lu, Cui, Chen et al. (2009). For general background to polyoxidometalates, see: Pope & Müller (1991); Hill (1998); López et al. (2001). For supported Keggin-type structures, 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 top

A mixture of Na₂WO₄.2H₂O (0.658 g, 2 mmol), CuSO₄.5H₂O (0.25 g, 1 mmol), H₂C₂O₄.2H₂O (0.189 g, 1.5 mmol), NaAlO₂ (0.10 g, 1.25 mmol) and H₂O (15 mL) was mixed and stirred for 30 min, and the pH was adjusted to 7 with en. The resulting suspension was transferred to a Teflon-lined autoclave (25 ml) and kept at 180°C for 3 days. After slow cooling to room temperature for 2 days, blue prism crystals were obtained by filtering, washing with distilled water, and drying in desiccators at ambient temperature. The yields were ca 42% based on W. Elemental analysis C₁₂H₅₄Cu₃N₁₂O₄₃AlW₁₂(3478.47): Calcd. (%): C, 4.14; H, 1.56; N, 4.83. Found: C, 4.21; H, 1.57; N, 4.94.

Structure description top

For the isotypic V^IV and Si^IV structures, see: Lu, Cui, Chen et al. (2009). For general background to polyoxidometalates, see: Pope & Müller (1991); Hill (1998); López et al. (2001). For supported Keggin-type structures, 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).

Computing details top

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

Figures top

Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level and labels shown for the asymmetric unit; the remaining part of the molecule was generated by the symmetry operations: -y, x-y, z; -x+y,-x, z; x-y, -y, 0.5-z; -x, -x+y, 0.5-z; y, x, 0.5-z. Only one position of the {AlO_4} unit and one position of the disordered O5, O6 and O7 atoms is shown. H atoms have been omitted for clarity.

Fig. 2. The crystal packing of the title compound viewed along the [001] direction with N—H···O and O—H···O hydrogen bonds displayed as dashed lines.

µ₃-Dodecatungsto(V,VI)aluminato- κ³O:O':O''-tris[aquabis(ethylenediamine- κ²N,N')copper(II)] top

Crystal data top

[AlCu₃W₁₂O₄₀(C₂H₈N₂)₆(H₂O)₃]	D_x = 4.224 Mg m⁻³
M_r = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0089P)² + 625.9202P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max = 0.001
2220 reflections	Δρ_max = 1.85 e Å⁻³
157 parameters	Δρ_min = −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)

Crystal data top

[AlCu₃W₁₂O₄₀(C₂H₈N₂)₆(H₂O)₃]	Z = 6
M_r = 3478.47	Mo Kα radiation
Trigonal, R3c	µ = 26.38 mm⁻¹
a = 17.9719 (14) Å	T = 296 K
c = 29.335 (5) Å	0.11 × 0.11 × 0.10 mm
V = 8206 (2) Å³

Data collection top

Rigaku R-AXIS RAPID diffractometer	2220 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1864 reflections with I > 2σ(I)
T_min = 0.159, T_max = 0.178	R_int = 0.071
22760 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.071	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0089P)² + 625.9202P] where P = (F_o² + 2F_c²)/3
2220 reflections	Δρ_max = 1.85 e Å⁻³
157 parameters	Δρ_min = −3.56 e Å⁻³

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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—O6^v	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—O8^iv	122.8 (8)	O7'—W2—O8ⁱⁱⁱ	85.6 (5)
O8ⁱⁱ—Al1—O9ⁱⁱ	73.4 (4)	O6^v—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—N2^v	172.2 (5)
O3—W1—O6	100.1 (4)	N2—Cu1—N1	86.2 (4)
O6'—W1—O6	22.1 (4)	N2^v—Cu1—N1	94.7 (4)
O1—W1—O4	98.8 (3)	N2—Cu1—N1^v	94.7 (4)
O3—W1—O4	161.2 (3)	N2^v—Cu1—N1^v	86.2 (4)
O6'—W1—O4	92.5 (4)	N1—Cu1—N1^v	166.4 (5)
O6—W1—O4	81.2 (4)	N2—Cu1—O1W	86.1 (3)
O1—W1—O5'	108.3 (6)	N2^v—Cu1—O1W	86.1 (3)
O3—W1—O5'	81.8 (5)	N1—Cu1—O1W	96.8 (3)
O6'—W1—O5'	140.6 (6)	N1^v—Cu1—O1W	96.8 (3)
O6—W1—O5'	158.1 (6)	N2—Cu1—O4	93.9 (3)
O4—W1—O5'	90.2 (4)	N2^v—Cu1—O4	93.9 (3)
O1—W1—O5	91.4 (5)	N1—Cu1—O4	83.2 (3)
O3—W1—O5	95.9 (4)	N1^v—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—W1^v	114.9 (4)
O5'—W1—O5	20.4 (4)	W1—O4—Cu1	122.5 (2)
O1—W1—O8ⁱⁱ	166.6 (4)	W1^v—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—W2^v	58.5 (16)
O6'—W1—O8ⁱⁱⁱ	84.3 (5)	W1—O6—W2^v	121.0 (7)
O6—W1—O8ⁱⁱⁱ	99.5 (5)	O6—O6'—W2^v	101.1 (19)
O4—W1—O8ⁱⁱⁱ	74.6 (4)	O6—O6'—W1	81.0 (19)
O5'—W1—O8ⁱⁱⁱ	58.7 (5)	W2^v—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—W2^iv	62.2 (11)
O2—W2—O5'	107.3 (6)	W2—O7—W2^iv	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—W1^iv	76.4 (10)
O7'^iv—W2—O7'	90.2 (7)	Al1—O8—W1^iv	123.7 (6)
O6'^v—W2—O7'	137.4 (6)	W1ⁱⁱ—O8—W1^iv	93.3 (4)
O2—W2—O6^v	93.7 (5)	O8ⁱ—O8—W2^iv	171.0 (3)
O5'—W2—O6^v	91.3 (6)	Al1—O8—W2^iv	115.6 (5)
O7'^iv—W2—O6^v	86.5 (6)	W1ⁱⁱ—O8—W2^iv	96.3 (4)
O6'^v—W2—O6^v	20.4 (5)	W1^iv—O8—W2^iv	96.9 (4)
O7'—W2—O6^v	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—W2^iv	118.0 (5)
O6'^v—W2—O5	92.8 (6)	W2ⁱⁱⁱ—O9—W2^iv	99.8 (6)
O7'—W2—O5	88.7 (6)	W2—O9—W2^iv	99.8 (6)
O6^v—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
O6^v—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
O6^v—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
O6^v—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)

Symmetry codes: (i) −x, −x+y, −z+1/2; (ii) y−1, x+1, −z+1/2; (iii) −x+y−1, −x+1, z; (iv) −y+1, x−y+2, z; (v) x−y+1, −y+2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O2^vi	0.85	2.25	2.856 (9)	128
N1—H1B···O5^vi	0.90	2.26	3.138 (17)	163
N1—H1B···O5′^vi	0.90	2.30	3.185 (17)	170
N2—H2A···O7^vii	0.90	2.35	3.101 (17)	141
N2—H2B···O1^v	0.90	2.11	2.956 (12)	157

Symmetry codes: (v) x−y+1, −y+2, −z+1/2; (vi) x+1/3, x−y+5/3, z+1/6; (vii) −x+2/3, −y+7/3, −z+1/3.

Experimental details

Crystal data
Chemical formula	[AlCu₃W₁₂O₄₀(C₂H₈N₂)₆(H₂O)₃]
M_r	3478.47
Crystal system, space group	Trigonal, R3c
Temperature (K)	296
a, c (Å)	17.9719 (14), 29.335 (5)
V (Å³)	8206 (2)
Z	6
Radiation type	Mo Kα
µ (mm⁻¹)	26.38
Crystal size (mm)	0.11 × 0.11 × 0.10

Data collection
Diffractometer	Rigaku R-AXIS RAPID
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.159, 0.178
No. of measured, independent and observed [I > 2σ(I)] reflections	22760, 2220, 1864
R_int	0.071
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.071, 1.10
No. of reflections	2220
No. of parameters	157
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0089P)² + 625.9202P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	1.85, −3.56

Computer programs: RAPID-AUTO (Rigaku, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999).

Hydrogen-bond geometry (Å, º) top

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) x+1/3, x−y+5/3, z+1/6; (ii) −x+2/3, −y+7/3, −z+1/3; (iii) x−y+1, −y+2, −z+1/2.

Acknowledgements

This work was supported by the Natural Science Foundation of Shandong Province (ZR2011BQ004) and the Fundamental Research Funds for the Central Universities (09CX04045A).

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