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Acta Cryst. (2008). E64, m305-m306    [ doi:10.1107/S1600536808000020 ]

Diammonium bis[(2-aminoacetato-[kappa]2N,O)(2,2'-bipyridine-[kappa]2N,N')(N,N-dimethylformamide-[kappa]O)copper(II)] hexacosaoxidooctamolybdate(VI)

H. Liu, Y. Zhang and D. Yu

Abstract top

The title compound, (NH4)2[Cu(C2H4NO2)(C10H8N2)(C3H7NO)]2[Mo8O26], contains a centrosymmetric [beta]-type octamolybdate anion, two copper(II) complex cations and two ammonium ions. The CuII atom is coordinated in a square-pyramidal geometry by a 2,2'-bipyridine and a 2-aminoacetate ligands in the basal plane and by an O atom of N,N-dimethylformamide in the apical position. The anions and cations are linked by N-H...O hydrogen bonds into a three-dimensional network.

Comment top

Polymolybdates (POMs) modified by transition metal complexes have been extensively explored (Allis et al., 2004). To further explore new POMs belonging to this family, the title compound is reported here.

The title compound consists of a [Mo8O26]4- anion, two [Cu(bpy)(gly)(dmf)]+ cations and two ammonium ions (bpy = 2,2'-bipyridine, gly = 2-aminoacetate, dmf = N,N-dimethylfomamide) (Fig. 1). The [Mo8O26]4- anion in the β-type lies on an inversion center, made up of eight edge-sharing MoO6 octahedra. The CuII atom in the [Cu(bpy)(gly)(dmf)]+ cation displays a distorted square-pyramidal geometry with two N atoms from the 2,2'-bipyridine ligand and an O atom and an N atom from the 2-aminoacetate ligand in the basal plane and an O atom of N,N-dimethylfomamide in the apical position. The Mo—O, Cu—N and Cu—O distances are given in Table 1. A calculation of bond valence sum (Brown & Altermatt, 1985) indicates the oxidation states of 5.71–5.84 for the Mo atoms and 2.17 for the Cu atom, in agreement with the expected values. These anions and cations connect to each other by N—H···O hydrogen bonds (Table 2), forming a three-dimensional supramolecular network, as shown in Fig. 2.

Related literature top

For related literature, see: Allis et al. (2004); Brown & Altermatt (1985).

Experimental top

(NH4)6(Mo7O24).4H2O (1.50 g, 1.2 mmol), Cu(CH3COO)2.2H2O (0.20 g, 1.0 mmol), 2-aminoacetic acid (0.075 g, 1.0 mmol) and bpy (0.16 g, 1.0 mmol) were dissolved in 0.5 M HCl solution (15 ml) with stirring. Then the suspension was added to a dmf solution (10 ml), which was refluxed at 333 K for 3 h. After cooling to room temperature, the mixture was filtrated and transferred into a 50 ml beaker. Blue block crystals of the title compound suitable for X-ray diffraction were obtained after several days.

Refinement top

H atoms of ammonium were located in difference Fourier maps and fixed in their as-found positions (N—H = 0.90–0.98 Å) with Uiso(H) = 1.2Ueq(N). The other H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93Å (CH), 0.97Å (CH2), N—H = 0.90Å and Uiso(H) = 1.2Ueq(C,N), and with C—H = 0.96Å (CH3) and Uiso(H) = 1.5Ueq(C).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004; program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL (Bruker, 1997; molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Bruker, 1997.

Figures top
[Figure 1] Fig. 1. The structures of the anion and cation of the title compound (the ammonium ion has been omitted). Displacement ellipsoides are drawn at the 30% probability level. [Symmetry code: (i) 1 - x, 1 - y, 1 - z.]
[Figure 2] Fig. 2. Crystal packing of the title compound. The ammonium ions are drawn as ball. Dotted lines denote hydrogen bonds.
Diammonium bis[(2-aminoacetato-κ2N,O)(2,2'-bipyridine-κ2N,N')(N,N- dimethylformamide-κO)copper(II)] hexacosaoxidooctamolybdate(VI) top
Crystal data top
(NH4)2[Cu(C2H4NO2)(C10H8N2)(C3H7NO)]2[Mo8O26]Z = 1
Mr = 1953.38F000 = 946
Triclinic, P1Dx = 2.430 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 10.222 (2) ÅCell parameters from 3544 reflections
b = 10.849 (2) Åθ = 1.6–26.3º
c = 13.020 (3) ŵ = 2.70 mm−1
α = 81.82 (3)ºT = 291 (2) K
β = 69.91 (2)ºBlock, blue
γ = 81.61 (3)º0.28 × 0.20 × 0.14 mm
V = 1334.9 (5) Å3
Data collection top
Bruker SMART APEXII
diffractometer		4889 independent reflections
Radiation source: fine-focus sealed tube3591 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.071
T = 291(2) Kθmax = 25.6º
φ and ω scansθmin = 3.0º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −12→12
Tmin = 0.530, Tmax = 0.690k = −13→13
10864 measured reflectionsl = −15→14
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.046H-atom parameters constrained
wR(F2) = 0.110  w = 1/[σ2(Fo2) + (0.0226P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.99(Δ/σ)max < 0.001
4889 reflectionsΔρmax = 0.86 e Å−3
370 parametersΔρmin = −0.83 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
(NH4)2[Cu(C2H4NO2)(C10H8N2)(C3H7NO)]2[Mo8O26]γ = 81.61 (3)º
Mr = 1953.38V = 1334.9 (5) Å3
Triclinic, P1Z = 1
a = 10.222 (2) ÅMo Kα
b = 10.849 (2) ŵ = 2.70 mm−1
c = 13.020 (3) ÅT = 291 (2) K
α = 81.82 (3)º0.28 × 0.20 × 0.14 mm
β = 69.91 (2)º
Data collection top
Bruker SMART APEXII
diffractometer		4889 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		3591 reflections with I > 2σ(I)
Tmin = 0.530, Tmax = 0.690Rint = 0.071
10864 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.046370 parameters
wR(F2) = 0.110H-atom parameters constrained
S = 0.99Δρmax = 0.86 e Å−3
4889 reflectionsΔρmin = −0.83 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu0.56754 (7)0.78752 (8)0.79555 (7)0.0191 (2)
Mo10.39065 (5)0.75790 (5)0.50257 (5)0.01630 (15)
Mo20.36042 (5)0.54294 (5)0.72689 (5)0.01687 (15)
Mo30.34518 (5)0.48004 (5)0.47185 (5)0.01409 (15)
Mo40.69102 (5)0.74002 (5)0.30214 (5)0.01864 (16)
O10.3028 (4)0.8061 (4)0.4114 (4)0.0242 (11)
O20.4582 (4)0.4794 (4)0.8097 (4)0.0244 (11)
O30.5990 (4)0.7957 (4)0.2141 (4)0.0258 (11)
O40.2585 (4)0.5422 (4)0.3833 (4)0.0227 (11)
O50.2406 (4)0.3680 (4)0.5603 (4)0.0211 (11)
O60.3191 (4)0.8577 (4)0.6038 (4)0.0235 (11)
O70.4909 (4)0.3616 (4)0.3840 (4)0.0172 (10)
O80.2517 (5)0.6614 (4)0.7940 (4)0.0256 (11)
O90.2357 (4)0.4195 (4)0.7536 (4)0.0223 (11)
O100.2874 (4)0.6092 (4)0.5743 (4)0.0167 (10)
O110.5653 (4)0.8223 (4)0.4285 (4)0.0192 (10)
O120.5191 (4)0.5901 (4)0.4106 (3)0.0150 (9)
O130.8335 (4)0.8205 (5)0.2580 (4)0.0282 (12)
O140.4272 (4)0.7617 (4)0.9377 (4)0.0223 (11)
O150.2086 (4)0.8280 (4)1.0374 (4)0.0247 (11)
O160.6474 (5)0.9741 (5)0.8567 (5)0.0330 (13)
N10.4294 (5)0.9213 (5)0.7618 (4)0.0186 (12)
H1A0.46240.99620.75150.022*
H1B0.41620.90840.69940.022*
N20.7255 (5)0.8036 (5)0.6548 (5)0.0195 (13)
N30.7002 (5)0.6481 (5)0.8305 (5)0.0176 (12)
N40.8488 (6)0.8849 (6)0.8898 (5)0.0257 (14)
N50.3354 (5)0.7456 (6)0.1944 (5)0.0272 (14)
HN10.34380.79030.24420.033*
HN20.33300.67040.24180.033*
HN30.25840.76930.16870.033*
HN40.39960.74290.11890.033*
C10.6771 (7)0.5713 (7)0.9239 (6)0.0281 (18)
H10.59090.58210.97910.034*
C20.7758 (6)0.4768 (6)0.9418 (5)0.0214 (15)
H20.75700.42541.00760.026*
C30.9044 (7)0.4610 (7)0.8582 (6)0.0305 (17)
H30.97190.39670.86670.037*
C40.9304 (7)0.5408 (7)0.7636 (6)0.0269 (17)
H41.01740.53280.70890.032*
C50.9663 (7)0.7332 (7)0.5632 (6)0.0243 (16)
H51.04680.68020.56200.029*
C60.9666 (7)0.8216 (8)0.4778 (7)0.037 (2)
H61.04830.82790.41790.044*
C70.8487 (7)0.9025 (6)0.4776 (6)0.0242 (15)
H70.84920.96210.41860.029*
C80.7291 (6)0.8904 (6)0.5697 (6)0.0202 (15)
H80.64890.94460.57240.024*
C90.8275 (6)0.6337 (6)0.7489 (6)0.0200 (15)
C100.8423 (6)0.7234 (6)0.6532 (5)0.0177 (14)
C110.2938 (6)0.9214 (7)0.8538 (6)0.0216 (15)
H11A0.22300.89610.82930.026*
H11B0.26351.00530.87610.026*
C120.3090 (6)0.8328 (6)0.9503 (6)0.0213 (16)
C130.7109 (7)0.9109 (7)0.9152 (7)0.0316 (19)
H140.65640.87820.98420.038*
C140.9409 (7)0.9421 (8)0.7868 (7)0.039 (2)
H14A1.03680.91440.78030.058*
H14B0.92571.03160.78630.058*
H14C0.92080.91790.72610.058*
C150.9148 (8)0.8121 (9)0.9643 (7)0.043 (2)
H15A1.01460.80490.92960.065*
H15B0.88330.73020.98250.065*
H15C0.89020.85301.03010.065*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu0.0149 (4)0.0195 (5)0.0211 (5)0.0014 (3)−0.0060 (3)0.0001 (4)
Mo10.0182 (3)0.0128 (3)0.0184 (3)0.0010 (2)−0.0078 (2)−0.0011 (2)
Mo20.0177 (3)0.0176 (3)0.0147 (3)0.0002 (2)−0.0052 (2)−0.0019 (2)
Mo30.0135 (3)0.0140 (3)0.0155 (3)−0.0008 (2)−0.0062 (2)−0.0008 (2)
Mo40.0185 (3)0.0172 (3)0.0199 (3)−0.0037 (2)−0.0073 (2)0.0036 (3)
O10.027 (2)0.023 (3)0.024 (3)0.004 (2)−0.012 (2)−0.002 (2)
O20.027 (2)0.026 (3)0.018 (3)0.001 (2)−0.006 (2)−0.003 (2)
O30.027 (3)0.020 (3)0.029 (3)−0.002 (2)−0.012 (2)0.009 (2)
O40.019 (2)0.029 (3)0.023 (3)0.004 (2)−0.011 (2)−0.007 (2)
O50.017 (2)0.021 (3)0.027 (3)−0.0034 (19)−0.009 (2)−0.001 (2)
O60.030 (3)0.019 (3)0.024 (3)0.002 (2)−0.012 (2)−0.005 (2)
O70.021 (2)0.013 (2)0.020 (2)0.0024 (18)−0.0121 (19)0.001 (2)
O80.031 (3)0.021 (3)0.025 (3)0.003 (2)−0.012 (2)−0.005 (2)
O90.017 (2)0.025 (3)0.023 (3)0.0033 (19)−0.007 (2)−0.002 (2)
O100.017 (2)0.018 (2)0.016 (2)0.0007 (18)−0.0081 (19)−0.001 (2)
O110.022 (2)0.016 (2)0.021 (3)−0.0067 (18)−0.008 (2)0.002 (2)
O120.014 (2)0.015 (2)0.016 (2)−0.0009 (17)−0.0053 (19)0.0000 (19)
O130.026 (3)0.026 (3)0.034 (3)−0.012 (2)−0.012 (2)0.008 (2)
O140.015 (2)0.029 (3)0.016 (3)−0.0027 (19)−0.0006 (19)0.006 (2)
O150.021 (2)0.028 (3)0.023 (3)−0.002 (2)−0.006 (2)−0.002 (2)
O160.036 (3)0.031 (3)0.042 (3)−0.012 (2)−0.023 (3)0.000 (3)
N10.022 (3)0.019 (3)0.015 (3)−0.002 (2)−0.006 (2)−0.002 (3)
N20.019 (3)0.015 (3)0.027 (3)0.001 (2)−0.010 (3)−0.006 (3)
N30.020 (3)0.013 (3)0.021 (3)−0.001 (2)−0.011 (2)0.003 (3)
N40.027 (3)0.026 (3)0.024 (3)−0.010 (3)−0.007 (3)0.001 (3)
N50.029 (3)0.034 (4)0.019 (3)0.002 (3)−0.012 (3)0.004 (3)
C10.022 (3)0.026 (4)0.034 (4)0.004 (3)−0.006 (3)−0.006 (4)
C20.026 (3)0.020 (4)0.014 (3)−0.005 (3)−0.005 (3)0.010 (3)
C30.029 (4)0.032 (5)0.027 (4)0.006 (3)−0.013 (3)0.005 (4)
C40.018 (3)0.026 (4)0.029 (4)−0.001 (3)−0.001 (3)0.006 (3)
C50.020 (3)0.027 (4)0.020 (4)0.003 (3)−0.005 (3)0.006 (3)
C60.020 (4)0.042 (5)0.042 (5)−0.001 (3)−0.006 (4)0.000 (4)
C70.027 (4)0.020 (4)0.023 (4)−0.009 (3)−0.008 (3)0.012 (3)
C80.018 (3)0.015 (3)0.027 (4)0.000 (3)−0.009 (3)0.001 (3)
C90.020 (3)0.018 (4)0.023 (4)0.000 (3)−0.008 (3)−0.005 (3)
C100.020 (3)0.018 (4)0.015 (3)−0.003 (3)−0.007 (3)0.001 (3)
C110.021 (3)0.022 (4)0.022 (4)0.003 (3)−0.009 (3)−0.005 (3)
C120.022 (3)0.022 (4)0.024 (4)0.000 (3)−0.011 (3)−0.008 (3)
C130.029 (4)0.031 (5)0.040 (5)−0.008 (3)−0.013 (4)−0.011 (4)
C140.033 (4)0.046 (5)0.031 (4)−0.021 (4)0.002 (4)0.004 (4)
C150.031 (4)0.054 (6)0.038 (5)0.010 (4)−0.009 (4)−0.001 (5)
Geometric parameters (Å, °) top
Cu—O141.925 (4)N2—C101.367 (8)
Cu—O162.604 (4)N3—C11.343 (10)
Cu—N11.985 (6)N3—C91.373 (8)
Cu—N21.989 (6)N4—C131.329 (8)
Cu—N31.990 (6)N4—C151.447 (10)
Mo1—O11.705 (5)N4—C141.462 (9)
Mo1—O61.720 (4)N5—HN10.8954
Mo1—O111.896 (4)N5—HN20.9477
Mo1—O101.995 (5)N5—HN30.9466
Mo1—O122.306 (4)N5—HN40.9785
Mo1—O7i2.356 (5)C1—C21.384 (10)
Mo1—Mo33.2161 (10)C1—H10.9300
Mo2—O81.699 (4)C2—C31.395 (9)
Mo2—O21.722 (5)C2—H20.9300
Mo2—O91.897 (4)C3—C41.370 (11)
Mo2—O7i1.998 (5)C3—H30.9300
Mo2—O102.340 (4)C4—C91.390 (9)
Mo2—O12i2.346 (4)C4—H40.9300
Mo3—O41.696 (5)C5—C61.361 (12)
Mo3—O51.756 (5)C5—C101.405 (9)
Mo3—O101.960 (4)C5—H50.9300
Mo3—O71.967 (4)C6—C71.383 (10)
Mo3—O122.143 (4)C6—H60.9300
Mo3—O12i2.380 (4)C7—C81.395 (9)
Mo4—O131.693 (4)C7—H70.9300
Mo4—O31.716 (5)C8—H80.9300
Mo4—O9i1.921 (4)C9—C101.446 (10)
Mo4—O111.945 (4)C11—C121.508 (10)
Mo4—O5i2.257 (5)C11—H11A0.9700
Mo4—O122.491 (4)C11—H11B0.9700
O14—C121.307 (7)C13—H140.9300
O15—C121.242 (8)C14—H14A0.9600
O16—C131.239 (10)C14—H14B0.9600
N1—C111.488 (8)C14—H14C0.9600
N1—H1A0.9000C15—H15A0.9600
N1—H1B0.9000C15—H15B0.9600
N2—C81.342 (9)C15—H15C0.9600
O14—Cu—N185.8 (2)Mo3—O12—Mo192.51 (14)
O14—Cu—N2174.4 (2)Mo3—O12—Mo2i91.87 (13)
N1—Cu—N299.6 (2)Mo1—O12—Mo2i163.2 (2)
O14—Cu—N393.0 (2)Mo3—O12—Mo3i104.57 (19)
N1—Cu—N3177.5 (2)Mo1—O12—Mo3i97.46 (14)
N2—Cu—N381.7 (2)Mo2i—O12—Mo3i97.08 (14)
O1—Mo1—O6104.5 (2)Mo3—O12—Mo4164.8 (2)
O1—Mo1—O11101.9 (2)Mo1—O12—Mo486.10 (14)
O6—Mo1—O11100.25 (19)Mo2i—O12—Mo485.44 (13)
O1—Mo1—O1096.6 (2)Mo3i—O12—Mo490.65 (12)
O6—Mo1—O10100.2 (2)C12—O14—Cu114.8 (5)
O11—Mo1—O10147.87 (18)C11—N1—Cu110.1 (4)
O1—Mo1—O1294.64 (17)C11—N1—H1A109.6
O6—Mo1—O12160.6 (2)Cu—N1—H1A109.6
O11—Mo1—O1278.82 (16)C11—N1—H1B109.6
O10—Mo1—O1273.67 (15)Cu—N1—H1B109.6
O1—Mo1—O7i164.75 (17)H1A—N1—H1B108.2
O6—Mo1—O7i87.88 (19)C8—N2—C10119.9 (6)
O11—Mo1—O7i84.26 (18)C8—N2—Cu125.9 (4)
O10—Mo1—O7i72.04 (16)C10—N2—Cu113.9 (5)
O12—Mo1—O7i72.68 (15)C1—N3—C9119.0 (6)
O1—Mo1—Mo385.12 (15)C1—N3—Cu126.7 (4)
O6—Mo1—Mo3135.43 (17)C9—N3—Cu114.4 (5)
O11—Mo1—Mo3120.55 (12)C13—N4—C15123.2 (7)
O10—Mo1—Mo335.24 (11)C13—N4—C14119.4 (7)
O12—Mo1—Mo341.75 (10)C15—N4—C14117.1 (6)
O7i—Mo1—Mo379.76 (10)HN1—N5—HN292.1
O8—Mo2—O2105.0 (2)HN1—N5—HN3117.9
O8—Mo2—O9101.5 (2)HN2—N5—HN3117.0
O2—Mo2—O9101.2 (2)HN1—N5—HN4125.0
O8—Mo2—O7i100.7 (2)HN2—N5—HN4116.8
O2—Mo2—O7i96.4 (2)HN3—N5—HN490.7
O9—Mo2—O7i146.90 (17)N3—C1—C2122.9 (7)
O8—Mo2—O1089.67 (19)N3—C1—H1118.5
O2—Mo2—O10163.20 (16)C2—C1—H1118.5
O9—Mo2—O1083.47 (18)C1—C2—C3118.1 (7)
O7i—Mo2—O1072.36 (16)C1—C2—H2121.0
O8—Mo2—O12i161.3 (2)C3—C2—H2121.0
O2—Mo2—O12i93.45 (17)C4—C3—C2119.5 (7)
O9—Mo2—O12i77.44 (15)C4—C3—H3120.2
O7i—Mo2—O12i73.72 (15)C2—C3—H3120.2
O10—Mo2—O12i71.65 (15)C3—C4—C9120.4 (7)
O4—Mo3—O5104.9 (2)C3—C4—H4119.8
O4—Mo3—O10100.12 (19)C9—C4—H4119.8
O5—Mo3—O1096.24 (19)C6—C5—C10118.9 (7)
O4—Mo3—O7102.04 (19)C6—C5—H5120.5
O5—Mo3—O796.87 (19)C10—C5—H5120.5
O10—Mo3—O7150.32 (16)C5—C6—C7121.9 (7)
O4—Mo3—O1298.9 (2)C5—C6—H6119.1
O5—Mo3—O12156.13 (19)C7—C6—H6119.1
O10—Mo3—O1278.15 (16)C6—C7—C8117.0 (7)
O7—Mo3—O1279.11 (16)C6—C7—H7121.5
O4—Mo3—O12i174.24 (19)C8—C7—H7121.5
O5—Mo3—O12i80.71 (18)N2—C8—C7122.5 (6)
O10—Mo3—O12i77.72 (16)N2—C8—H8118.8
O7—Mo3—O12i78.29 (15)C7—C8—H8118.8
O12—Mo3—O12i75.43 (19)N3—C9—C4120.1 (7)
O4—Mo3—Mo189.45 (15)N3—C9—C10114.3 (6)
O5—Mo3—Mo1132.20 (13)C4—C9—C10125.5 (6)
O10—Mo3—Mo135.97 (13)N2—C10—C5119.9 (7)
O7—Mo3—Mo1124.84 (12)N2—C10—C9115.5 (6)
O12—Mo3—Mo145.74 (10)C5—C10—C9124.6 (6)
O12i—Mo3—Mo185.72 (10)N1—C11—C12110.5 (5)
O13—Mo4—O3105.1 (2)N1—C11—H11A109.6
O13—Mo4—O9i103.1 (2)C12—C11—H11A109.6
O3—Mo4—O9i97.9 (2)N1—C11—H11B109.6
O13—Mo4—O11104.12 (19)C12—C11—H11B109.6
O3—Mo4—O1197.0 (2)H11A—C11—H11B108.1
O9i—Mo4—O11144.2 (2)O15—C12—O14122.6 (7)
O13—Mo4—O5i91.8 (2)O15—C12—C11119.1 (6)
O3—Mo4—O5i163.15 (19)O14—C12—C11118.2 (6)
O9i—Mo4—O5i77.85 (18)O16—C13—N4126.8 (8)
O11—Mo4—O5i78.55 (18)O16—C13—H14116.6
O13—Mo4—O12161.5 (2)N4—C13—H14116.6
O3—Mo4—O1293.44 (18)N4—C14—H14A109.5
O9i—Mo4—O1273.45 (16)N4—C14—H14B109.5
O11—Mo4—O1273.35 (15)H14A—C14—H14B109.5
O5i—Mo4—O1269.71 (15)N4—C14—H14C109.5
Mo3—O5—Mo4i118.9 (2)H14A—C14—H14C109.5
Mo3—O7—Mo2i109.0 (2)H14B—C14—H14C109.5
Mo3—O7—Mo1i108.78 (19)N4—C15—H15A109.5
Mo2i—O7—Mo1i103.33 (16)N4—C15—H15B109.5
Mo2—O9—Mo4i118.6 (2)H15A—C15—H15B109.5
Mo3—O10—Mo1108.8 (2)N4—C15—H15C109.5
Mo3—O10—Mo2110.6 (2)H15A—C15—H15C109.5
Mo1—O10—Mo2104.01 (16)H15B—C15—H15C109.5
Mo1—O11—Mo4117.12 (19)
O1—Mo1—Mo3—O4−0.51 (19)O5—Mo3—O12—Mo2i99.5 (4)
O6—Mo1—Mo3—O4105.2 (3)O10—Mo3—O12—Mo2i178.02 (19)
O11—Mo1—Mo3—O4−101.5 (2)O7—Mo3—O12—Mo2i17.22 (17)
O10—Mo1—Mo3—O4108.2 (3)O12i—Mo3—O12—Mo2i97.81 (17)
O12—Mo1—Mo3—O4−103.1 (2)Mo1—Mo3—O12—Mo2i−163.8 (2)
O7i—Mo1—Mo3—O4−178.49 (17)O4—Mo3—O12—Mo3i178.77 (16)
O1—Mo1—Mo3—O5−110.3 (3)O5—Mo3—O12—Mo3i1.7 (5)
O6—Mo1—Mo3—O5−4.6 (3)O10—Mo3—O12—Mo3i80.22 (17)
O11—Mo1—Mo3—O5148.8 (3)O7—Mo3—O12—Mo3i−80.58 (18)
O10—Mo1—Mo3—O5−1.6 (3)O12i—Mo3—O12—Mo3i0.0
O12—Mo1—Mo3—O5147.1 (3)Mo1—Mo3—O12—Mo3i98.37 (17)
O7i—Mo1—Mo3—O571.7 (2)O4—Mo3—O12—Mo4−4.0 (7)
O1—Mo1—Mo3—O10−108.7 (3)O5—Mo3—O12—Mo4179.0 (5)
O6—Mo1—Mo3—O10−3.0 (3)O10—Mo3—O12—Mo4−102.5 (7)
O11—Mo1—Mo3—O10150.3 (3)O7—Mo3—O12—Mo496.7 (7)
O12—Mo1—Mo3—O10148.7 (3)O12i—Mo3—O12—Mo4177.3 (7)
O7i—Mo1—Mo3—O1073.3 (2)Mo1—Mo3—O12—Mo4−84.4 (7)
O1—Mo1—Mo3—O7103.8 (2)O1—Mo1—O12—Mo3−77.3 (2)
O6—Mo1—Mo3—O7−150.5 (3)O6—Mo1—O12—Mo392.3 (5)
O11—Mo1—Mo3—O72.9 (2)O11—Mo1—O12—Mo3−178.6 (2)
O10—Mo1—Mo3—O7−147.5 (3)O10—Mo1—O12—Mo318.19 (16)
O12—Mo1—Mo3—O71.2 (2)O7i—Mo1—O12—Mo394.00 (18)
O7i—Mo1—Mo3—O7−74.2 (2)O1—Mo1—O12—Mo2i27.7 (6)
O1—Mo1—Mo3—O12102.6 (2)O6—Mo1—O12—Mo2i−162.7 (6)
O6—Mo1—Mo3—O12−151.7 (3)O11—Mo1—O12—Mo2i−73.6 (6)
O11—Mo1—Mo3—O121.6 (2)O10—Mo1—O12—Mo2i123.2 (6)
O10—Mo1—Mo3—O12−148.7 (3)O7i—Mo1—O12—Mo2i−161.0 (6)
O7i—Mo1—Mo3—O12−75.4 (2)Mo3—Mo1—O12—Mo2i105.0 (6)
O1—Mo1—Mo3—O12i176.35 (17)O1—Mo1—O12—Mo3i177.61 (19)
O6—Mo1—Mo3—O12i−77.9 (2)O6—Mo1—O12—Mo3i−12.8 (6)
O11—Mo1—Mo3—O12i75.39 (19)O11—Mo1—O12—Mo3i76.36 (18)
O10—Mo1—Mo3—O12i−74.9 (2)O10—Mo1—O12—Mo3i−86.86 (18)
O12—Mo1—Mo3—O12i73.8 (2)O7i—Mo1—O12—Mo3i−11.05 (14)
O7i—Mo1—Mo3—O12i−1.63 (13)Mo3—Mo1—O12—Mo3i−105.0 (2)
O4—Mo3—O5—Mo4i−178.66 (19)O1—Mo1—O12—Mo487.46 (19)
O10—Mo3—O5—Mo4i−76.4 (2)O6—Mo1—O12—Mo4−102.9 (6)
O7—Mo3—O5—Mo4i76.9 (2)O11—Mo1—O12—Mo4−13.79 (16)
O12—Mo3—O5—Mo4i−1.7 (5)O10—Mo1—O12—Mo4−177.01 (17)
O12i—Mo3—O5—Mo4i0.01 (18)O7i—Mo1—O12—Mo4−101.20 (14)
Mo1—Mo3—O5—Mo4i−75.5 (3)Mo3—Mo1—O12—Mo4164.8 (2)
O4—Mo3—O7—Mo2i75.4 (2)O13—Mo4—O12—Mo3−176.3 (6)
O5—Mo3—O7—Mo2i−177.7 (2)O3—Mo4—O12—Mo32.7 (7)
O10—Mo3—O7—Mo2i−62.1 (5)O9i—Mo4—O12—Mo3−94.5 (7)
O12—Mo3—O7—Mo2i−21.57 (19)O11—Mo4—O12—Mo399.0 (7)
O12i—Mo3—O7—Mo2i−98.76 (19)O5i—Mo4—O12—Mo3−177.4 (7)
Mo1—Mo3—O7—Mo2i−22.5 (3)O13—Mo4—O12—Mo198.5 (5)
O4—Mo3—O7—Mo1i−172.6 (2)O3—Mo4—O12—Mo1−82.48 (18)
O5—Mo3—O7—Mo1i−65.7 (2)O9i—Mo4—O12—Mo1−179.72 (18)
O10—Mo3—O7—Mo1i49.9 (5)O11—Mo4—O12—Mo113.75 (16)
O12—Mo3—O7—Mo1i90.45 (19)O5i—Mo4—O12—Mo197.42 (15)
O12i—Mo3—O7—Mo1i13.26 (16)O13—Mo4—O12—Mo2i−96.0 (5)
Mo1—Mo3—O7—Mo1i89.5 (2)O3—Mo4—O12—Mo2i83.04 (17)
O8—Mo2—O9—Mo4i−178.0 (3)O9i—Mo4—O12—Mo2i−14.19 (16)
O2—Mo2—O9—Mo4i−70.0 (3)O11—Mo4—O12—Mo2i179.28 (19)
O7i—Mo2—O9—Mo4i50.9 (5)O5i—Mo4—O12—Mo2i−97.06 (15)
O10—Mo2—O9—Mo4i93.6 (3)O13—Mo4—O12—Mo3i1.1 (6)
O12i—Mo2—O9—Mo4i21.0 (3)O3—Mo4—O12—Mo3i−179.91 (16)
O4—Mo3—O10—Mo1−74.8 (2)O9i—Mo4—O12—Mo3i82.86 (17)
O5—Mo3—O10—Mo1178.8 (2)O11—Mo4—O12—Mo3i−83.68 (17)
O7—Mo3—O10—Mo163.0 (5)O5i—Mo4—O12—Mo3i−0.01 (12)
O12—Mo3—O10—Mo122.3 (2)N1—Cu—O14—C122.2 (4)
O12i—Mo3—O10—Mo199.8 (2)N3—Cu—O14—C12−175.7 (4)
O4—Mo3—O10—Mo2171.6 (2)O14—Cu—N1—C11−5.8 (4)
O5—Mo3—O10—Mo265.2 (2)N2—Cu—N1—C11175.4 (4)
O7—Mo3—O10—Mo2−50.6 (5)N1—Cu—N2—C84.3 (5)
O12—Mo3—O10—Mo2−91.3 (2)N3—Cu—N2—C8−177.9 (5)
O12i—Mo3—O10—Mo2−13.88 (16)N1—Cu—N2—C10178.2 (4)
Mo1—Mo3—O10—Mo2−113.7 (2)N3—Cu—N2—C10−3.9 (4)
O1—Mo1—O10—Mo371.8 (2)O14—Cu—N3—C12.1 (5)
O6—Mo1—O10—Mo3177.9 (2)N2—Cu—N3—C1−179.3 (5)
O11—Mo1—O10—Mo3−53.3 (4)O14—Cu—N3—C9−176.9 (4)
O12—Mo1—O10—Mo3−21.12 (18)N2—Cu—N3—C91.7 (4)
O7i—Mo1—O10—Mo3−97.8 (2)C9—N3—C1—C2−0.6 (9)
O1—Mo1—O10—Mo2−170.27 (17)Cu—N3—C1—C2−179.6 (4)
O6—Mo1—O10—Mo2−64.2 (2)N3—C1—C2—C3−0.4 (10)
O11—Mo1—O10—Mo264.6 (4)C1—C2—C3—C42.0 (10)
O12—Mo1—O10—Mo296.81 (17)C2—C3—C4—C9−2.6 (10)
O7i—Mo1—O10—Mo220.18 (13)C10—C5—C6—C70.5 (11)
Mo3—Mo1—O10—Mo2117.9 (3)C5—C6—C7—C80.7 (10)
O8—Mo2—O10—Mo3−166.0 (2)C10—N2—C8—C70.5 (9)
O2—Mo2—O10—Mo343.0 (7)Cu—N2—C8—C7174.1 (4)
O9—Mo2—O10—Mo3−64.4 (2)C6—C7—C8—N2−1.2 (9)
O7i—Mo2—O10—Mo392.7 (2)C1—N3—C9—C40.0 (8)
O12i—Mo2—O10—Mo314.51 (17)Cu—N3—C9—C4179.1 (4)
O8—Mo2—O10—Mo177.4 (2)C1—N3—C9—C10−178.5 (5)
O2—Mo2—O10—Mo1−73.7 (7)Cu—N3—C9—C100.6 (6)
O9—Mo2—O10—Mo1178.95 (18)C3—C4—C9—N31.6 (9)
O7i—Mo2—O10—Mo1−23.95 (16)C3—C4—C9—C10179.9 (6)
O12i—Mo2—O10—Mo1−102.15 (17)C8—N2—C10—C50.8 (8)
O1—Mo1—O11—Mo4−72.4 (3)Cu—N2—C10—C5−173.6 (4)
O6—Mo1—O11—Mo4−179.8 (3)C8—N2—C10—C9179.7 (5)
O10—Mo1—O11—Mo451.4 (5)Cu—N2—C10—C95.4 (6)
O12—Mo1—O11—Mo420.0 (2)C6—C5—C10—N2−1.3 (9)
O7i—Mo1—O11—Mo493.4 (3)C6—C5—C10—C9179.9 (6)
Mo3—Mo1—O11—Mo418.9 (3)N3—C9—C10—N2−4.0 (7)
O13—Mo4—O11—Mo1−179.9 (3)C4—C9—C10—N2177.7 (5)
O3—Mo4—O11—Mo172.6 (3)N3—C9—C10—C5174.9 (5)
O9i—Mo4—O11—Mo1−41.4 (4)C4—C9—C10—C5−3.4 (10)
O5i—Mo4—O11—Mo1−90.9 (3)Cu—N1—C11—C128.0 (6)
O12—Mo4—O11—Mo1−18.9 (2)Cu—O14—C12—O15−179.6 (4)
O4—Mo3—O12—Mo180.40 (18)Cu—O14—C12—C112.2 (7)
O5—Mo3—O12—Mo1−96.6 (4)N1—C11—C12—O15174.8 (5)
O10—Mo3—O12—Mo1−18.16 (17)N1—C11—C12—O14−6.9 (8)
O7—Mo3—O12—Mo1−178.96 (19)C15—N4—C13—O16178.7 (7)
O12i—Mo3—O12—Mo1−98.37 (16)C14—N4—C13—O165.2 (10)
O4—Mo3—O12—Mo2i−83.42 (18)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O3ii0.902.323.093 (7)144
N1—H1B···O60.902.012.863 (6)158
N5—HN1···O10.902.102.888 (7)146
N5—HN2···O40.952.133.028 (8)158
N5—HN3···O15iii0.951.942.761 (8)143
N5—HN4···O14iii0.982.263.132 (7)148
Symmetry codes: (ii) −x+1, −y+2, −z+1; (iii) x, y, z−1.
Table 1
Selected geometric parameters (Å) top
Cu—O141.925 (4)Mo2—O102.340 (4)
Cu—O162.604 (4)Mo2—O12i2.346 (4)
Cu—N11.985 (6)Mo3—O41.696 (5)
Cu—N21.989 (6)Mo3—O51.756 (5)
Cu—N31.990 (6)Mo3—O101.960 (4)
Mo1—O11.705 (5)Mo3—O71.967 (4)
Mo1—O61.720 (4)Mo3—O122.143 (4)
Mo1—O111.896 (4)Mo3—O12i2.380 (4)
Mo1—O101.995 (5)Mo4—O131.693 (4)
Mo1—O122.306 (4)Mo4—O31.716 (5)
Mo1—O7i2.356 (5)Mo4—O9i1.921 (4)
Mo2—O81.699 (4)Mo4—O111.945 (4)
Mo2—O21.722 (5)Mo4—O5i2.257 (5)
Mo2—O91.897 (4)Mo4—O122.491 (4)
Mo2—O7i1.998 (5)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O3ii0.902.323.093 (7)144
N1—H1B···O60.902.012.863 (6)158
N5—HN1···O10.902.102.888 (7)146
N5—HN2···O40.952.133.028 (8)158
N5—HN3···O15iii0.951.942.761 (8)143
N5—HN4···O14iii0.982.263.132 (7)148
Symmetry codes: (ii) −x+1, −y+2, −z+1; (iii) x, y, z−1.
Acknowledgements top

This work was supported financially by the National Natural Science Foundation of China (grant No. 20371010) and the State Key Laboratory for Structural Chemistry of Unstable and Stable Species in Peking University (No. 03–12).

references
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