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Acta Cryst. (2008). E64, m614-m615    [ doi:10.1107/S1600536808008234 ]

Low-temperature phase of hexaguanidinium heptamolybdate monohydrate

S. Reinoso, M. H. Dickman, A. Praetorius and U. Kortz*

Abstract top

The crystal structure of the title compound, [C(NH2)3]6[Mo7O24]·H2O, previously determined at room temperature in the monoclinic space group C2/c from Weissenberg techniques [Don & Weakley (1981). Acta Cryst. B37, 451-453], has been redetermined from low-temperature single-crystal data in the monoclinic space group P21/c. The asymmetric unit contains one heptamolybdate anion, six guanidinium cations and one water molecule of hydration. The anions and cations are linked by an extensive network of N-H...O hydrogen bonds.

Comment top

Acidification of aqueous molybdate solutions gives rise to the formation of different isopolymolybdate(VI) anions depending on the pH. The heptamolybdate anion, [Mo7O24]6-, is known to be the predominant species in neutral to moderately acidic solutions (Pope, 1983). Single crystals of the title compound, [C(NH2)3]6[Mo7O24].H2O (I), were obtained in an attempt to prepare a guanidinium salt of a dimethyltin-containing phosphomolybdate species.

Routine examination of (I) at low temperature resulted in the assignment of the monoclinic space group P21/c, with the C-centered reflections being systematically weak. However, a previous room-temperature study using Weissenberg techniques reported the structure of (I) in the monoclinic space group C2/c (Don & Weakley, 1981). Therefore, data were collected on a second crystal at room temperature, confirming the original assignment of C2/c; data were then collected on this same crystal cooled to 173 K, confirming the low-temperature assignment of P21/c. The value of Rint for the low-temperature data was 15.0%. We attribute this higher than usual value to the phase change; the value of Rint for the room-temperature data was less than 10%. The low-temperature structure consists of one [Mo7O24]6- anion, six [C(NH2)3]+ cations, and one molecule of water of hydration in the asymmetric unit (Fig. 1). The [Mo7O24]6- anion shows the well known bent arrangement of seven edge-sharing MoO6 distorted octahedra (Kortz & Pope, 1995), which can be formally derived from the parent {M10O28} decametalate framework by removal of three octahedra from the central level (Pope, 1983). The anions and the cations are linked by an extensive and intricate three-dimensional network of N—H···O hydrogen bonds involving all guanidinium –NH2 groups and all heptamolybdate terminal and bridging O atoms, with the exception of the terminal O7B and the bridging µ4-O atoms (O1M4 and O2M4).

Related literature top

For the previous determination of the title compound in the monoclinic C2/c space group, see: Don & Weakley (1981). For an example of a structurally characterized [Mo7O24]6- anion, see: Kortz & Pope (1995). For more information about isopolymolybdates and polyoxometalates in general, see: Pope (1983). For related literature, see: Farrugia (1999).

Experimental top

To an aqueous solution (30 ml) of Na2MoO4.2H2O (0.726 g) and Na2HPO4 (0.071 g) was added solid (CH3)SnCl2 (0.220 g). After stirring for 30 min at room temperature, few drops of aqueous 1M [C(NH2)3]Cl were added, and the resulting solution was left to slowly evaporate at room temperature, colorless block-like single crystals of the title compound forming in a few days.

Refinement top

The H atoms of the guanidinium cations were positioned geometrically and refined as riding. The positional parameters of the H atoms of the water molecule were calculated using the CALCOH tool of WinGX (Farrugia, 1999) and fixed during the refinment. All H atoms were refined with isotropic displacement parameters fixed at 1.2 times Ueq of their parent atoms.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: APEX2 (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. ORTEP plot of (I) showing 50% probability displacement ellipsoids.
hexaguanidinium heptamolybdate monohydrate top
Crystal data top
(C1H6N3)6[Mo7O24]·H2OF000 = 2776
Mr = 1434.12Dx = 2.531 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 7762 reflections
a = 11.9402 (6) Åθ = 2.3–29.7º
b = 15.9131 (9) ŵ = 2.37 mm−1
c = 19.8223 (13) ÅT = 173 (2) K
β = 92.312 (4)ºPrism, colourless
V = 3763.3 (4) Å30.17 × 0.17 × 0.08 mm
Z = 4
Data collection top
Bruker X8 APEXII CCD area-detector
diffractometer		15842 independent reflections
Radiation source: sealed tube9689 reflections with I > 2s(I)
Monochromator: graphiteRint = 0.150
T = 173(2) Kθmax = 34.4º
φ and ω scansθmin = 1.7º
Absorption correction: multi-scan
APEXII (Bruker, 2005)		h = −18→18
Tmin = 0.689, Tmax = 0.833k = −25→25
153838 measured reflectionsl = −31→31
Refinement top
Refinement on F2H-atom parameters constrained
Least-squares matrix: full  w = 1/[σ2(Fo2) + (0.065P)2 + 1.0536P]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.053(Δ/σ)max = 0.001
wR(F2) = 0.164Δρmax = 1.77 e Å−3
S = 1.06Δρmin = −2.32 e Å−3
15842 reflectionsExtinction correction: SHELXL
506 parametersExtinction coefficient: 0.00102 (9)
Crystal data top
(C1H6N3)6[Mo7O24]·H2OV = 3763.3 (4) Å3
Mr = 1434.12Z = 4
Monoclinic, P21/cMo Kα
a = 11.9402 (6) ŵ = 2.37 mm−1
b = 15.9131 (9) ÅT = 173 (2) K
c = 19.8223 (13) Å0.17 × 0.17 × 0.08 mm
β = 92.312 (4)º
Data collection top
Bruker X8 APEXII CCD area-detector
diffractometer		15842 independent reflections
Absorption correction: multi-scan
APEXII (Bruker, 2005)		9689 reflections with I > 2s(I)
Tmin = 0.689, Tmax = 0.833Rint = 0.150
153838 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.053506 parameters
wR(F2) = 0.164H-atom parameters constrained
S = 1.06Δρmax = 1.77 e Å−3
15842 reflectionsΔρmin = −2.32 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
xyzUiso*/Ueq
Mo10.02068 (3)0.06939 (2)0.221800 (17)0.01551 (8)
Mo20.22006 (3)0.06307 (2)0.115322 (17)0.01597 (8)
Mo30.04258 (3)0.17323 (2)0.359758 (18)0.01829 (9)
Mo40.24555 (3)0.20215 (2)0.245700 (16)0.01436 (8)
Mo50.44752 (3)0.16970 (2)0.131721 (18)0.01815 (9)
Mo60.26730 (3)0.06331 (2)0.377162 (17)0.01662 (8)
Mo70.46759 (3)0.06731 (2)0.270582 (18)0.01634 (8)
O1B−0.0700 (3)0.0900 (2)0.15428 (15)0.0235 (7)
O1A−0.0382 (3)−0.0105 (2)0.26587 (16)0.0249 (7)
O2B0.1171 (3)0.0798 (2)0.05310 (15)0.0238 (7)
O2A0.2968 (3)−0.0190 (2)0.08550 (16)0.0246 (7)
O3B−0.0348 (3)0.1000 (2)0.40054 (16)0.0270 (7)
O3A−0.0090 (3)0.2697 (2)0.38553 (16)0.0266 (7)
O5B0.5214 (3)0.0936 (2)0.09095 (16)0.0256 (7)
O5A0.5025 (3)0.2644 (2)0.10420 (17)0.0271 (7)
O6B0.3707 (3)0.0785 (2)0.43900 (15)0.0241 (7)
O6A0.1877 (3)−0.0173 (2)0.40575 (16)0.0269 (7)
O7B0.5567 (3)0.0861 (2)0.33821 (16)0.0248 (7)
O7A0.5255 (3)−0.0139 (2)0.22726 (17)0.0256 (7)
O120.1370 (2)0.00412 (18)0.18077 (14)0.0186 (6)
O13−0.0327 (2)0.16739 (19)0.27278 (15)0.0201 (6)
O1M40.1493 (2)0.10064 (18)0.29826 (13)0.0156 (5)
O2M40.3391 (2)0.09888 (18)0.19337 (13)0.0152 (5)
O250.3103 (2)0.16081 (19)0.08014 (14)0.0203 (6)
O340.1626 (3)0.26978 (19)0.29144 (15)0.0215 (6)
O360.1794 (2)0.16226 (19)0.41150 (14)0.0208 (6)
O450.3298 (3)0.26854 (19)0.19892 (15)0.0216 (6)
O570.5234 (2)0.16324 (19)0.21861 (15)0.0205 (6)
O670.3490 (2)0.00393 (18)0.31125 (14)0.0184 (6)
O1240.1415 (2)0.16496 (18)0.17796 (14)0.0160 (5)
O4670.3486 (2)0.16389 (18)0.31372 (14)0.0175 (6)
C1−0.1887 (4)0.2916 (3)0.5167 (3)0.0331 (11)
C20.4571 (4)0.1742 (3)−0.0860 (2)0.0231 (9)
C30.0480 (4)0.1669 (3)0.5786 (2)0.0227 (9)
C4−0.2559 (3)0.2966 (3)0.24617 (19)0.0216 (9)
C5−0.2245 (4)−0.0488 (3)0.1085 (2)0.0199 (8)
C60.2837 (4)0.0415 (3)0.6044 (2)0.0225 (9)
N11−0.2273 (4)0.2477 (3)0.4624 (3)0.0513 (14)
H11A−0.28970.21860.46430.062*
H11B−0.19000.24810.42500.062*
N120.5055 (3)0.1087 (3)−0.0551 (2)0.0288 (9)
H12A0.55970.0814−0.07440.035*
H12B0.48330.0927−0.01530.035*
N130.0031 (4)0.1011 (3)0.5475 (2)0.0308 (9)
H13A−0.05060.07260.56630.037*
H13B0.02670.08570.50790.037*
N14−0.2542 (3)0.2142 (3)0.24754 (19)0.0298 (10)
H14A−0.31540.18560.23690.036*
H14B−0.19170.18750.25910.036*
N15−0.1334 (3)−0.0878 (3)0.0894 (2)0.0275 (9)
H15A−0.1071−0.07760.04940.033*
H15B−0.0990−0.12380.11680.033*
N160.2399 (3)0.0624 (3)0.66201 (18)0.0269 (9)
H16A0.27050.10280.68690.032*
H16B0.18010.03610.67560.032*
N21−0.0947 (3)0.3375 (3)0.5144 (2)0.0349 (11)
H21A−0.07120.36670.55000.042*
H21B−0.05660.33850.47730.042*
N220.3746 (3)0.2148 (2)−0.05681 (19)0.0274 (9)
H22A0.34200.2579−0.07730.033*
H22B0.35260.1986−0.01700.033*
N230.1296 (3)0.2099 (2)0.55026 (19)0.0253 (8)
H23A0.15360.19440.51080.030*
H23B0.15960.25380.57110.030*
N24−0.1629 (3)0.3397 (2)0.2631 (2)0.0299 (9)
H24A−0.10090.31280.27510.036*
H24B−0.16380.39500.26220.036*
N25−0.2628 (3)−0.0643 (3)0.16922 (19)0.0266 (8)
H25A−0.2275−0.10020.19630.032*
H25B−0.3234−0.03860.18240.032*
N260.2384 (3)−0.0186 (2)0.5654 (2)0.0273 (8)
H26A0.1780−0.04510.57790.033*
H26B0.2687−0.03170.52700.033*
N31−0.2477 (4)0.2892 (3)0.5725 (2)0.0454 (12)
H31A−0.22520.31800.60840.054*
H31B−0.30920.25880.57340.054*
N320.4905 (4)0.1984 (3)−0.1459 (2)0.0301 (9)
H32A0.54470.1712−0.16520.036*
H32B0.45840.2418−0.16630.036*
N330.0121 (4)0.1901 (3)0.63845 (19)0.0292 (9)
H33A−0.04160.16160.65720.035*
H33B0.04200.23400.65930.035*
N34−0.3495 (3)0.3368 (2)0.2289 (2)0.0281 (9)
H34A−0.41080.30830.21830.034*
H34B−0.35040.39210.22800.034*
N35−0.2762 (3)0.0054 (2)0.06749 (19)0.0268 (8)
H35A−0.25000.01550.02740.032*
H35B−0.33690.03130.08020.032*
N360.3742 (3)0.0814 (3)0.58373 (19)0.0269 (9)
H36A0.40490.12170.60860.032*
H36B0.40340.06730.54520.032*
O1W−0.4098 (3)0.1463 (3)0.4856 (2)0.0446 (10)
H1OW−0.45890.13300.45450.054*
H2OW−0.44190.13800.52330.054*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mo10.01223 (16)0.01668 (17)0.01772 (15)−0.00120 (12)0.00174 (12)−0.00124 (12)
Mo20.01468 (17)0.01756 (17)0.01579 (15)0.00145 (13)0.00233 (12)−0.00065 (12)
Mo30.01455 (17)0.02142 (19)0.01925 (16)−0.00144 (13)0.00494 (13)−0.00450 (13)
Mo40.01179 (16)0.01357 (16)0.01786 (15)0.00013 (12)0.00221 (12)0.00014 (12)
Mo50.01378 (17)0.01978 (19)0.02126 (17)0.00092 (13)0.00547 (13)0.00439 (13)
Mo60.01591 (17)0.01855 (18)0.01550 (15)−0.00138 (13)0.00215 (12)0.00095 (12)
Mo70.01257 (16)0.01696 (17)0.01955 (16)0.00162 (12)0.00167 (12)0.00165 (12)
O1B0.0211 (16)0.0266 (17)0.0224 (14)0.0034 (13)−0.0041 (12)0.0003 (12)
O1A0.0231 (16)0.0247 (17)0.0272 (16)−0.0041 (13)0.0043 (13)0.0016 (13)
O2B0.0231 (16)0.0286 (17)0.0196 (14)−0.0017 (13)−0.0012 (12)0.0002 (12)
O2A0.0238 (16)0.0236 (16)0.0269 (16)0.0061 (13)0.0066 (13)−0.0020 (13)
O3B0.0231 (17)0.0334 (19)0.0250 (15)−0.0062 (14)0.0072 (13)−0.0005 (14)
O3A0.0227 (16)0.0247 (17)0.0326 (17)−0.0006 (13)0.0054 (13)−0.0126 (13)
O5B0.0198 (16)0.0301 (18)0.0274 (16)0.0055 (13)0.0089 (13)0.0005 (13)
O5A0.0251 (17)0.0239 (17)0.0328 (17)−0.0002 (14)0.0080 (14)0.0125 (13)
O6B0.0224 (16)0.0309 (18)0.0191 (14)0.0006 (13)0.0009 (12)−0.0004 (12)
O6A0.0265 (17)0.0263 (17)0.0281 (16)−0.0050 (14)0.0054 (14)0.0031 (13)
O7B0.0205 (16)0.0263 (17)0.0274 (16)0.0008 (13)−0.0036 (13)0.0049 (13)
O7A0.0224 (16)0.0227 (16)0.0323 (17)0.0052 (13)0.0074 (13)0.0033 (13)
O120.0198 (15)0.0160 (14)0.0201 (13)0.0007 (11)0.0021 (11)−0.0017 (11)
O130.0118 (13)0.0249 (16)0.0239 (14)0.0013 (12)0.0040 (11)−0.0038 (12)
O1M40.0137 (14)0.0170 (14)0.0163 (12)−0.0003 (11)0.0018 (10)−0.0002 (10)
O2M40.0135 (13)0.0157 (13)0.0169 (12)0.0014 (11)0.0048 (10)0.0018 (10)
O250.0175 (15)0.0258 (16)0.0179 (13)0.0009 (12)0.0045 (11)0.0038 (11)
O340.0189 (15)0.0204 (15)0.0254 (15)0.0003 (12)0.0025 (12)−0.0039 (12)
O360.0191 (15)0.0235 (16)0.0201 (14)−0.0012 (12)0.0029 (11)−0.0057 (11)
O450.0215 (15)0.0178 (15)0.0255 (15)−0.0038 (12)0.0019 (12)0.0044 (12)
O570.0118 (13)0.0215 (16)0.0283 (15)−0.0008 (11)0.0027 (12)0.0050 (12)
O670.0171 (14)0.0159 (14)0.0225 (14)−0.0009 (11)0.0041 (11)0.0016 (11)
O1240.0144 (13)0.0164 (14)0.0174 (12)−0.0009 (11)0.0006 (10)0.0004 (10)
O4670.0151 (14)0.0194 (15)0.0179 (13)−0.0005 (11)0.0017 (11)0.0017 (11)
C10.030 (3)0.037 (3)0.032 (2)0.005 (2)−0.001 (2)−0.007 (2)
C20.021 (2)0.022 (2)0.027 (2)0.0038 (17)−0.0003 (17)−0.0043 (17)
C30.021 (2)0.021 (2)0.026 (2)0.0001 (17)0.0010 (17)0.0003 (16)
C40.023 (2)0.020 (2)0.0227 (19)−0.0002 (17)0.0064 (17)−0.0016 (16)
C50.020 (2)0.019 (2)0.0199 (18)0.0045 (16)−0.0018 (16)−0.0040 (15)
C60.027 (2)0.020 (2)0.0203 (18)−0.0015 (18)−0.0011 (17)0.0021 (16)
N110.044 (3)0.066 (4)0.044 (3)−0.018 (3)0.004 (2)−0.017 (3)
N120.029 (2)0.029 (2)0.0289 (19)0.0158 (17)0.0043 (17)0.0043 (16)
N130.037 (2)0.025 (2)0.031 (2)−0.0157 (18)0.0049 (18)−0.0070 (16)
N140.0161 (19)0.0166 (19)0.056 (3)−0.0017 (14)−0.0017 (19)0.0027 (17)
N150.027 (2)0.030 (2)0.0255 (18)0.0131 (17)0.0029 (16)−0.0001 (16)
N160.029 (2)0.032 (2)0.0203 (17)−0.0072 (17)0.0101 (15)−0.0042 (15)
N210.0174 (19)0.050 (3)0.038 (2)−0.0126 (19)0.0076 (17)−0.016 (2)
N220.029 (2)0.027 (2)0.0259 (18)0.0129 (17)0.0019 (16)0.0031 (15)
N230.028 (2)0.0222 (19)0.0256 (18)−0.0116 (16)0.0055 (16)−0.0008 (15)
N240.025 (2)0.0193 (19)0.045 (2)−0.0076 (16)0.0025 (18)−0.0027 (17)
N250.023 (2)0.034 (2)0.0229 (18)0.0077 (17)0.0041 (15)0.0004 (15)
N260.0222 (19)0.032 (2)0.0276 (19)−0.0117 (17)0.0050 (15)−0.0039 (16)
N310.043 (3)0.059 (3)0.036 (2)−0.009 (2)0.014 (2)−0.011 (2)
N320.031 (2)0.032 (2)0.0278 (19)0.0099 (18)0.0049 (17)0.0057 (17)
N330.031 (2)0.033 (2)0.0240 (18)−0.0061 (18)0.0097 (16)−0.0054 (16)
N340.025 (2)0.0180 (19)0.042 (2)0.0055 (15)0.0019 (17)0.0034 (16)
N350.025 (2)0.030 (2)0.0249 (18)0.0118 (17)0.0001 (15)−0.0004 (16)
N360.030 (2)0.028 (2)0.0230 (18)−0.0130 (17)0.0045 (16)−0.0012 (15)
O1W0.027 (2)0.058 (3)0.049 (2)−0.0094 (19)0.0001 (17)−0.016 (2)
Geometric parameters (Å, °) top
Mo1—O1A1.710 (3)C3—N131.317 (6)
Mo1—O1B1.719 (3)C3—N331.330 (6)
Mo1—O121.939 (3)C3—N231.334 (6)
Mo1—O131.978 (3)C4—N141.311 (6)
Mo1—O1M42.171 (3)C4—N341.321 (6)
Mo1—O1242.291 (3)C4—N241.336 (6)
Mo1—Mo33.1968 (5)C5—N151.320 (5)
Mo2—O2A1.714 (3)C5—N351.321 (5)
Mo2—O2B1.726 (3)C5—N251.328 (5)
Mo2—O121.910 (3)C6—N161.318 (5)
Mo2—O252.032 (3)C6—N361.332 (6)
Mo2—O2M42.136 (3)C6—N261.331 (6)
Mo2—O1242.268 (3)N11—H11A0.8800
Mo2—Mo53.2078 (5)N11—H11B0.8800
Mo3—O3B1.711 (3)N12—H12A0.8800
Mo3—O3A1.738 (3)N12—H12B0.8800
Mo3—O361.902 (3)N13—H13A0.8800
Mo3—O131.914 (3)N13—H13B0.8800
Mo3—O1M42.138 (3)N14—H14A0.8800
Mo3—Mo63.2099 (5)N14—H14B0.8800
Mo4—O341.742 (3)N15—H15A0.8800
Mo4—O451.751 (3)N15—H15B0.8800
Mo4—O1241.887 (3)N16—H16A0.8800
Mo4—O4671.889 (3)N16—H16B0.8800
Mo4—O1M42.261 (3)N21—H21A0.8800
Mo4—O2M42.262 (3)N21—H21B0.8800
Mo5—O5B1.719 (3)N22—H22A0.8800
Mo5—O5A1.740 (3)N22—H22B0.8800
Mo5—O251.901 (3)N23—H23A0.8800
Mo5—O571.916 (3)N23—H23B0.8800
Mo5—O2M42.137 (3)N24—H24A0.8800
Mo5—Mo73.1993 (5)N24—H24B0.8800
Mo6—O6A1.708 (3)N25—H25A0.8800
Mo6—O6B1.721 (3)N25—H25B0.8800
Mo6—O671.911 (3)N26—H26A0.8800
Mo6—O362.025 (3)N26—H26B0.8800
Mo6—O1M42.146 (3)N31—H31A0.8800
Mo6—O4672.277 (3)N31—H31B0.8800
Mo7—O7B1.704 (3)N32—H32A0.8800
Mo7—O7A1.713 (3)N32—H32B0.8800
Mo7—O671.941 (3)N33—H33A0.8800
Mo7—O571.973 (3)N33—H33B0.8800
Mo7—O2M42.181 (3)N34—H34A0.8800
Mo7—O4672.282 (3)N34—H34B0.8800
C1—N311.336 (6)N35—H35A0.8800
C1—N211.342 (6)N35—H35B0.8800
C1—N111.350 (7)N36—H36A0.8800
C2—N321.326 (6)N36—H36B0.8800
C2—N121.328 (5)O1W—H1OW0.8600
C2—N221.330 (6)O1W—H2OW0.8620
?···??
O1A—Mo1—O1B106.28 (16)O467—Mo6—Mo386.03 (7)
O1A—Mo1—O1297.62 (14)O7B—Mo7—O7A105.95 (16)
O1B—Mo1—O12102.41 (14)O7B—Mo7—O67101.99 (14)
O1A—Mo1—O13100.22 (14)O7A—Mo7—O6797.60 (14)
O1B—Mo1—O1392.39 (14)O7B—Mo7—O5793.52 (14)
O12—Mo1—O13152.57 (12)O7A—Mo7—O5799.81 (14)
O1A—Mo1—O1M496.18 (13)O67—Mo7—O57152.48 (12)
O1B—Mo1—O1M4154.88 (14)O7B—Mo7—O2M4155.59 (14)
O12—Mo1—O1M485.24 (11)O7A—Mo7—O2M496.25 (13)
O13—Mo1—O1M472.31 (11)O67—Mo7—O2M484.65 (11)
O1A—Mo1—O124164.91 (13)O57—Mo7—O2M472.44 (11)
O1B—Mo1—O12487.97 (13)O7B—Mo7—O46788.02 (13)
O12—Mo1—O12473.97 (11)O7A—Mo7—O467164.99 (14)
O13—Mo1—O12483.74 (11)O67—Mo7—O46773.65 (11)
O1M4—Mo1—O12470.99 (10)O57—Mo7—O46784.44 (11)
O1A—Mo1—Mo388.18 (11)O2M4—Mo7—O46771.16 (10)
O1B—Mo1—Mo3126.50 (11)O7B—Mo7—Mo5127.59 (11)
O12—Mo1—Mo3126.89 (9)O7A—Mo7—Mo588.33 (11)
O13—Mo1—Mo334.13 (9)O67—Mo7—Mo5126.26 (9)
O1M4—Mo1—Mo341.71 (7)O57—Mo7—Mo534.08 (9)
O124—Mo1—Mo387.15 (7)O2M4—Mo7—Mo541.66 (7)
O2A—Mo2—O2B104.26 (15)O467—Mo7—Mo587.32 (7)
O2A—Mo2—O1299.18 (14)Mo2—O12—Mo1114.96 (15)
O2B—Mo2—O12100.77 (14)Mo3—O13—Mo1110.45 (14)
O2A—Mo2—O2599.57 (14)Mo3—O1M4—Mo697.06 (11)
O2B—Mo2—O2590.51 (14)Mo3—O1M4—Mo195.78 (11)
O12—Mo2—O25154.96 (12)Mo6—O1M4—Mo1150.49 (15)
O2A—Mo2—O2M495.94 (13)Mo3—O1M4—Mo4101.69 (12)
O2B—Mo2—O2M4155.53 (13)Mo6—O1M4—Mo4101.69 (11)
O12—Mo2—O2M489.29 (11)Mo1—O1M4—Mo4101.56 (11)
O25—Mo2—O2M472.40 (11)Mo2—O2M4—Mo597.31 (11)
O2A—Mo2—O124166.43 (13)Mo2—O2M4—Mo7151.10 (15)
O2B—Mo2—O12489.00 (13)Mo5—O2M4—Mo795.61 (11)
O12—Mo2—O12475.04 (11)Mo2—O2M4—Mo4101.50 (11)
O25—Mo2—O12482.96 (11)Mo5—O2M4—Mo4101.59 (11)
O2M4—Mo2—O12471.98 (10)Mo7—O2M4—Mo4101.07 (11)
O2A—Mo2—Mo588.60 (11)Mo5—O25—Mo2109.26 (14)
O2B—Mo2—Mo5124.49 (11)Mo3—O36—Mo6109.60 (14)
O12—Mo2—Mo5130.65 (9)Mo5—O57—Mo7110.69 (14)
O25—Mo2—Mo534.02 (8)Mo6—O67—Mo7115.34 (15)
O2M4—Mo2—Mo541.36 (7)Mo4—O124—Mo2109.78 (13)
O124—Mo2—Mo586.20 (7)Mo4—O124—Mo1110.17 (12)
O3B—Mo3—O3A104.96 (16)Mo2—O124—Mo190.79 (10)
O3B—Mo3—O3698.70 (15)Mo4—O467—Mo6109.92 (13)
O3A—Mo3—O36103.26 (14)Mo4—O467—Mo7110.30 (13)
O3B—Mo3—O1398.61 (14)Mo6—O467—Mo791.11 (10)
O3A—Mo3—O1398.55 (14)N31—C1—N21120.9 (5)
O36—Mo3—O13147.48 (12)N31—C1—N11118.1 (5)
O3B—Mo3—O1M4104.31 (14)N21—C1—N11120.9 (5)
O3A—Mo3—O1M4150.60 (13)N32—C2—N12120.0 (4)
O36—Mo3—O1M474.87 (11)N32—C2—N22120.1 (4)
O13—Mo3—O1M474.28 (11)N12—C2—N22119.8 (4)
O3B—Mo3—Mo191.43 (11)N13—C3—N33119.9 (4)
O3A—Mo3—Mo1133.64 (11)N13—C3—N23120.1 (4)
O36—Mo3—Mo1116.92 (9)N33—C3—N23120.0 (4)
O13—Mo3—Mo135.43 (9)N14—C4—N34120.1 (4)
O1M4—Mo3—Mo142.52 (7)N14—C4—N24119.8 (4)
O3B—Mo3—Mo692.46 (12)N34—C4—N24120.1 (5)
O3A—Mo3—Mo6138.95 (11)N15—C5—N35120.1 (4)
O36—Mo3—Mo636.46 (9)N15—C5—N25119.3 (4)
O13—Mo3—Mo6115.49 (9)N35—C5—N25120.6 (4)
O1M4—Mo3—Mo641.57 (7)N16—C6—N36120.1 (4)
Mo1—Mo3—Mo681.340 (13)N16—C6—N26121.2 (4)
O34—Mo4—O45104.71 (17)N36—C6—N26118.6 (4)
O34—Mo4—O124101.08 (13)C1—N11—H11A120.0
O45—Mo4—O124100.86 (13)C1—N11—H11B120.0
O34—Mo4—O467101.26 (13)H11A—N11—H11B120.0
O45—Mo4—O467101.58 (13)C2—N12—H12A120.0
O124—Mo4—O467142.93 (14)C2—N12—H12B120.0
O34—Mo4—O1M483.76 (13)H12A—N12—H12B120.0
O45—Mo4—O1M4171.52 (13)C3—N13—H13A120.0
O124—Mo4—O1M476.79 (11)C3—N13—H13B120.0
O467—Mo4—O1M476.67 (11)H13A—N13—H13B120.0
O34—Mo4—O2M4171.58 (12)C4—N14—H14A120.0
O45—Mo4—O2M483.71 (12)C4—N14—H14B120.0
O124—Mo4—O2M476.66 (11)H14A—N14—H14B120.0
O467—Mo4—O2M476.92 (11)C5—N15—H15A120.0
O1M4—Mo4—O2M487.82 (11)C5—N15—H15B120.0
O5B—Mo5—O5A104.80 (16)H15A—N15—H15B120.0
O5B—Mo5—O2598.17 (14)C6—N16—H16A120.0
O5A—Mo5—O25102.93 (14)C6—N16—H16B120.0
O5B—Mo5—O5798.72 (14)H16A—N16—H16B120.0
O5A—Mo5—O5799.06 (15)C1—N21—H21A120.0
O25—Mo5—O57147.72 (12)C1—N21—H21B120.0
O5B—Mo5—O2M4103.37 (13)H21A—N21—H21B120.0
O5A—Mo5—O2M4151.75 (13)C2—N22—H22A120.0
O25—Mo5—O2M474.91 (11)C2—N22—H22B120.0
O57—Mo5—O2M474.52 (11)H22A—N22—H22B120.0
O5B—Mo5—Mo791.35 (11)C3—N23—H23A120.0
O5A—Mo5—Mo7134.00 (11)C3—N23—H23B120.0
O25—Mo5—Mo7117.25 (9)H23A—N23—H23B120.0
O57—Mo5—Mo735.23 (9)C4—N24—H24A120.0
O2M4—Mo5—Mo742.73 (7)C4—N24—H24B120.0
O5B—Mo5—Mo291.60 (11)H24A—N24—H24B120.0
O5A—Mo5—Mo2139.02 (11)C5—N25—H25A120.0
O25—Mo5—Mo236.72 (9)C5—N25—H25B120.0
O57—Mo5—Mo2115.50 (9)H25A—N25—H25B120.0
O2M4—Mo5—Mo241.33 (7)C6—N26—H26A120.0
Mo7—Mo5—Mo281.460 (12)C6—N26—H26B120.0
O6A—Mo6—O6B105.22 (15)H26A—N26—H26B120.0
O6A—Mo6—O6799.29 (14)C1—N31—H31A120.0
O6B—Mo6—O67100.69 (14)C1—N31—H31B120.0
O6A—Mo6—O3699.78 (15)H31A—N31—H31B120.0
O6B—Mo6—O3691.00 (14)C2—N32—H32A120.0
O67—Mo6—O36154.12 (12)C2—N32—H32B120.0
O6A—Mo6—O1M495.27 (14)H32A—N32—H32B120.0
O6B—Mo6—O1M4155.62 (14)C3—N33—H33A120.0
O67—Mo6—O1M488.66 (12)C3—N33—H33B120.0
O36—Mo6—O1M472.31 (11)H33A—N33—H33B120.0
O6A—Mo6—O467165.28 (13)C4—N34—H34A120.0
O6B—Mo6—O46789.13 (13)C4—N34—H34B120.0
O67—Mo6—O46774.30 (11)H34A—N34—H34B120.0
O36—Mo6—O46782.95 (11)C5—N35—H35A120.0
O1M4—Mo6—O46771.64 (10)C5—N35—H35B120.0
O6A—Mo6—Mo388.34 (12)H35A—N35—H35B120.0
O6B—Mo6—Mo3124.90 (11)C6—N36—H36A120.0
O67—Mo6—Mo3130.03 (9)C6—N36—H36B120.0
O36—Mo6—Mo333.93 (8)H36A—N36—H36B120.0
O1M4—Mo6—Mo341.37 (7)H1OW—O1W—H2OW105.7
?—?—?—??
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N11—H11A···O1W0.881.902.765 (6)168
N11—H11B···O3A0.882.353.091 (6)142
N12—H12A···O2Ai0.882.002.845 (5)160
N12—H12B···O5B0.882.142.903 (5)145
N13—H13A···O6Aii0.881.962.828 (5)169
N13—H13B···O3B0.882.232.930 (5)136
N14—H14B···O130.881.932.774 (4)159
N14—H14A···O57iii0.881.982.814 (4)159
N15—H15A···O2Biv0.882.032.843 (5)153
N15—H15B···O3Av0.882.132.866 (5)141
N15—H15B···O34v0.882.623.302 (5)135
N16—H16B···O1Aii0.882.132.967 (5)159
N16—H16A···O45vi0.882.182.977 (5)151
N21—H21A···O1Bvi0.882.183.006 (5)156
N21—H21A···O2Bvi0.882.402.926 (5)118
N21—H21B···O3A0.882.222.992 (5)147
N22—H22A···O36vii0.882.323.087 (5)145
N22—H22A···O467vii0.882.503.216 (5)139
N22—H22A···O6Bvii0.882.643.290 (5)131
N22—H22B···O250.882.102.977 (5)177
N23—H23A···O360.882.072.937 (5)169
N23—H23B···O25vi0.882.263.023 (5)145
N23—H23B···O124vi0.882.503.219 (5)140
N24—H24A···O130.882.453.154 (5)137
N24—H24A···O3A0.882.503.186 (5)135
N24—H24B···O12viii0.882.092.855 (5)145
N25—H25A···O34v0.882.222.990 (5)146
N25—H25B···O7Aiii0.882.082.931 (5)162
N26—H26A···O3Bii0.881.982.859 (5)175
N26—H26B···O1Wii0.882.503.084 (6)124
N26—H26B···O6A0.882.573.197 (5)129
N31—H31A···O1Bvi0.882.503.248 (6)143
N31—H31B···O5Aix0.882.383.188 (6)152
N32—H32A···N34x0.882.503.242 (6)143
N32—H32B···O467vii0.882.022.864 (5)160
N33—H33A···N24vi0.882.603.334 (6)142
N33—H33B···O124vi0.882.022.867 (5)160
N34—H34B···O67viii0.881.942.776 (5)157
N34—H34A···O57iii0.882.443.154 (5)139
N34—H34A···O5Aiii0.882.553.195 (5)131
N35—H35A···O2Aiv0.882.293.040 (5)144
N35—H35B···O5Biii0.881.982.849 (5)170
N36—H36A···O5Avi0.882.162.913 (5)144
N36—H36B···O6B0.882.132.868 (5)141
O1W—H1OW···O6Biii0.862.222.948 (5)142.0
O1W—H1OW···O7Biii0.862.443.086 (5)132.8
O1W—H2OW···O5Aix0.862.352.973 (5)129.6
Symmetry codes: (i) −x+1, −y, −z; (ii) −x, −y, −z+1; (iii) x−1, y, z; (iv) −x, −y, −z; (v) −x, y−1/2, −z+1/2; (vi) x, −y+1/2, z+1/2; (vii) x, −y+1/2, z−1/2; (viii) −x, y+1/2, −z+1/2; (ix) x−1, −y+1/2, z+1/2; (x) x+1, −y+1/2, z−1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N11—H11A···O1W0.881.902.765 (6)168
N11—H11B···O3A0.882.353.091 (6)142
N12—H12A···O2Ai0.882.002.845 (5)160
N12—H12B···O5B0.882.142.903 (5)145
N13—H13A···O6Aii0.881.962.828 (5)169
N13—H13B···O3B0.882.232.930 (5)136
N14—H14B···O130.881.932.774 (4)159
N14—H14A···O57iii0.881.982.814 (4)159
N15—H15A···O2Biv0.882.032.843 (5)153
N15—H15B···O3Av0.882.132.866 (5)141
N15—H15B···O34v0.882.623.302 (5)135
N16—H16B···O1Aii0.882.132.967 (5)159
N16—H16A···O45vi0.882.182.977 (5)151
N21—H21A···O1Bvi0.882.183.006 (5)156
N21—H21A···O2Bvi0.882.402.926 (5)118
N21—H21B···O3A0.882.222.992 (5)147
N22—H22A···O36vii0.882.323.087 (5)145
N22—H22A···O467vii0.882.503.216 (5)139
N22—H22A···O6Bvii0.882.643.290 (5)131
N22—H22B···O250.882.102.977 (5)177
N23—H23A···O360.882.072.937 (5)169
N23—H23B···O25vi0.882.263.023 (5)145
N23—H23B···O124vi0.882.503.219 (5)140
N24—H24A···O130.882.453.154 (5)137
N24—H24A···O3A0.882.503.186 (5)135
N24—H24B···O12viii0.882.092.855 (5)145
N25—H25A···O34v0.882.222.990 (5)146
N25—H25B···O7Aiii0.882.082.931 (5)162
N26—H26A···O3Bii0.881.982.859 (5)175
N26—H26B···O1Wii0.882.503.084 (6)124
N26—H26B···O6A0.882.573.197 (5)129
N31—H31A···O1Bvi0.882.503.248 (6)143
N31—H31B···O5Aix0.882.383.188 (6)152
N32—H32A···N34x0.882.503.242 (6)143
N32—H32B···O467vii0.882.022.864 (5)160
N33—H33A···N24vi0.882.603.334 (6)142
N33—H33B···O124vi0.882.022.867 (5)160
N34—H34B···O67viii0.881.942.776 (5)157
N34—H34A···O57iii0.882.443.154 (5)139
N34—H34A···O5Aiii0.882.553.195 (5)131
N35—H35A···O2Aiv0.882.293.040 (5)144
N35—H35B···O5Biii0.881.982.849 (5)170
N36—H36A···O5Avi0.882.162.913 (5)144
N36—H36B···O6B0.882.132.868 (5)141
O1W—H1OW···O6Biii0.862.222.948 (5)142.0
O1W—H1OW···O7Biii0.862.443.086 (5)132.8
O1W—H2OW···O5Aix0.862.352.973 (5)129.6
Symmetry codes: (i) −x+1, −y, −z; (ii) −x, −y, −z+1; (iii) x−1, y, z; (iv) −x, −y, −z; (v) −x, y−1/2, −z+1/2; (vi) x, −y+1/2, z+1/2; (vii) x, −y+1/2, z−1/2; (viii) −x, y+1/2, −z+1/2; (ix) x−1, −y+1/2, z+1/2; (x) x+1, −y+1/2, z−1/2.
Acknowledgements top

SR thanks Gobierno Vasco/Eusko Jaurlaritza for his postdoctoral fellowship.

references
References top

Bruker (2005). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.

Don, A. & Weakley, T. J. R. (1981). Acta Cryst. B37, 451–453.

Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.

Kortz, U. & Pope, M. T. (1995). Acta Cryst. C51, 1717–1719.

Pope, M. T. (1983). Heteropoly and Isopoly oxometalates. Berlin: Springer-Verlag.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.