An inorganic–organic hybrid supra­molecular framework based on the γ-[Mo₈O₂₆]⁴⁻ cluster and cobalt complex of aspartic acid: X-ray structure and DFT study

A new inorganic–organic hybrid based on an aspartate functionalized poly­oxomolybdate, [penta­aqua­cobalt(II)]-μ-aspartate-[γ-octa­molybdate]-μ-as­partate-[penta­aqua­cobalt(II)] tetrahydrate, [Co₂(C₄H₆NO₄)₂(γ-Mo₈O₂₆)(H₂O)₁₀]·4H₂O (1), has been synthesized under hydro­thermal conditions from the reaction of an Evans–Showell-type polyoxometalate, (NH₄)₆[Co₂Mo₁₀H₄O₃₈], and L-aspartic acid. The complex exhibits a supra­molecular three-dimensional framework structure in the crystal lattice. Compound 1 was structurally characterized by elemental analyses, IR and UV–Vis (diffuse reflectance) spectroscopy and single-crystal X-ray diffraction. In this compound, aspartic acid acts as a bridge between the two Co atoms and the Mo centres, with the –CH₂COOH side chain directly linked to the Mo centre in γ-[Mo₈O₂₆]⁴⁻ and the α-carb­oxy­late side chain bound to the Co centre. Commonly, the binding of transition-metal complexes to POMs involves coordination of the metal to a terminal O atom of the POM so that 1, with a bridging ligand between Mo and Co atoms, belongs to a separate class of hybrid materials. While the starting materials are both chiral and one might expect them to form a chiral hybrid, the decomposition of the chiral Evans–Showell-type POM and its conversion to the centrosymmetric γ-octa­molybdate POM, plus the presence of two aspartate ligands centrosymmetrically placed on either side of the POM, leads to the formation of an achiral hybrid. We have studied energetically by means of density functional theory (DFT) calculations and using the Bader's `atoms-in-mol­ecules' analysis the electrostatically enhanced hydrogen bonds (EEHBs) observed in the solid state of 1, which are crucial for the formation of one-dimensional supra­molecular assemblies.

Computing details

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Bruker, 2016) and DIAMOND (Macrae et al., 2008).

[Pentaaquacobalt(III)]-µ-aspartato-[γ-octamolybdato]-µ-aspartato- [pentaaquacobalt(III)]

Crystal data

[Co2(C4H6NO4)2(Mo8O26)(H2O)10]·4H2O	F(000) = 1752
Mr = 1817.80	Dx = 2.761 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.507 (4) Å	Cell parameters from 9042 reflections
b = 12.853 (5) Å	θ = 2.5–29.9°
c = 15.795 (6) Å	µ = 3.09 mm^−1
β = 110.602 (5)°	T = 120 K
V = 2186.6 (13) Å^3	Plate, pale pink
Z = 2	0.30 × 0.17 × 0.11 mm

Data collection

Bruker SMART APEX CCD diffractometer	6170 independent reflections
Radiation source: fine-focus sealed tube	5156 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.049
Detector resolution: 8.3333 pixels mm^-1	θmax = 30.1°, θmin = 1.9°
φ and ω scans	h = −16→16
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −18→18
Tmin = 0.50, Tmax = 0.73	l = −21→21
41259 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.030	Hydrogen site location: mixed
wR(F^2) = 0.078	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0498P)^2] where P = (Fo^2 + 2Fc^2)/3
6170 reflections	(Δ/σ)max = 0.003
307 parameters	Δρmax = 2.36 e Å^−3
0 restraints	Δρmin = −1.21 e Å^−3

Special details

Experimental. The diffraction data were obtained from 3 sets of 400 frames, each of width 0.5° in ω, colllected at φ = 0.00, 90.00 and 180.00° and 2 sets of 800 frames, each of width 0.45° in φ, collected at ω = -30.00 and 210.00°. The scan time was 10 sec/frame.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. A suitable crystal of 1 was mounted on a polymer loop with a drop of heavy oil and placed in the cold nitrogen stream of a Bruker AXS SMART APEX diffractometer. A full sphere of intensity data was collected under control of the APEX3 software and reduced to F² values with SAINT. Correction for absorption and merging of equivalent reflections was accomplished with SADABS, the structure was solved by direct methods (SHELXT) and refined by full-matrix, least-squares procedures (SHELXL).

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 > 2sigma(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. H-atoms attached to carbon were placed in calculated positions (C—H = 0.95 - 0.99 Å) while those attached to nitrogen and oxygen were placed in locations derived from a difference map and their coordinates adjusted to give N—H = 0.91 %A and O—H = 0.87 Å. All were included as riding contributions with isotropic displacement parameters 1.2 - 1.5 times those of the attached atoms. Residual density remote from the main molecule and attributed to partially occupied/disordered lattice water sites was removed with PLATON SQUEEZE (Spek, 2015).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Mo1	0.79282 (2)	0.56969 (2)	1.02435 (2)	0.00994 (7)
Mo2	0.70115 (2)	0.35694 (2)	1.08690 (2)	0.00876 (7)
Mo3	0.49705 (2)	0.52283 (2)	1.10597 (2)	0.00749 (6)
Mo4	0.60173 (2)	0.72713 (2)	0.87952 (2)	0.00887 (7)
Co1	0.18917 (4)	0.44228 (3)	0.31910 (3)	0.01078 (9)
O1	0.86206 (19)	0.59318 (17)	1.13777 (14)	0.0155 (4)
O2	0.7988 (2)	0.38560 (17)	1.19477 (14)	0.0149 (4)
O3	0.58767 (19)	0.54451 (16)	1.21552 (14)	0.0123 (4)
O4	0.90484 (19)	0.59807 (17)	0.97852 (14)	0.0153 (4)
O5	0.80114 (18)	0.41971 (16)	1.02516 (13)	0.0118 (4)
O6	0.7225 (2)	0.22598 (16)	1.07333 (14)	0.0138 (4)
O7	0.54432 (18)	0.35937 (15)	1.10358 (13)	0.0098 (4)
O8	0.35557 (19)	0.44970 (15)	1.11207 (13)	0.0100 (4)
O9	0.43556 (19)	0.64562 (15)	1.06560 (13)	0.0110 (4)
O10	0.62134 (18)	0.51433 (15)	1.04804 (13)	0.0089 (4)
O11	0.70039 (19)	0.70166 (16)	1.00178 (13)	0.0111 (4)
O12	0.7157 (2)	0.75252 (17)	0.83442 (14)	0.0142 (4)
O13	0.5401 (2)	0.84410 (16)	0.89096 (14)	0.0145 (4)
O14	0.49066 (19)	0.68947 (16)	0.74554 (13)	0.0118 (4)
O15	0.3257 (2)	0.79201 (17)	0.72944 (14)	0.0167 (4)
O16	0.1814 (2)	0.4784 (2)	0.52425 (16)	0.0255 (6)
O17	0.3109 (2)	0.48964 (16)	0.44731 (14)	0.0125 (4)
O18	0.3245 (2)	0.49814 (16)	0.27202 (14)	0.0144 (4)
H18A	0.342437	0.564039	0.273732	0.022*
H18B	0.318342	0.479105	0.217756	0.022*
O19	0.2843 (2)	0.29945 (16)	0.33772 (14)	0.0149 (4)
H19A	0.280802	0.261958	0.291042	0.022*
H19B	0.295604	0.254166	0.380821	0.022*
O20	0.0538 (2)	0.38929 (17)	0.36856 (14)	0.0167 (4)
H20B	0.074864	0.400761	0.426307	0.025*
H20A	0.031423	0.324268	0.362422	0.025*
O21	0.10934 (19)	0.59315 (16)	0.30624 (14)	0.0150 (4)
H21A	0.160871	0.636283	0.343265	0.022*
H21B	0.094221	0.621223	0.253306	0.022*
O22	0.0663 (2)	0.3976 (2)	0.19079 (14)	0.0228 (5)
H22A	0.075882	0.393482	0.138664	0.034*
H22B	−0.013157	0.406724	0.176977	0.034*
N1	0.4715 (2)	0.6140 (2)	0.56684 (17)	0.0142 (5)
H1A	0.438103	0.653076	0.515985	0.017*
H1B	0.517868	0.561863	0.555864	0.017*
H1C	0.520678	0.654834	0.612483	0.017*
C1	0.3770 (3)	0.7194 (2)	0.70490 (19)	0.0118 (6)
C2	0.2999 (3)	0.6574 (2)	0.6222 (2)	0.0130 (6)
H2A	0.265538	0.706082	0.570830	0.016*
H2B	0.228973	0.625930	0.634550	0.016*
C3	0.3703 (3)	0.5703 (2)	0.5933 (2)	0.0135 (6)
H3	0.407783	0.522734	0.646051	0.016*
C4	0.2803 (3)	0.5069 (2)	0.5154 (2)	0.0142 (6)
O23	0.0785 (2)	0.80053 (18)	0.64879 (16)	0.0230 (5)
H23A	0.067889	0.831696	0.597714	0.035*
H23B	0.158673	0.794431	0.673706	0.035*
O24	0.1348 (2)	0.4320 (2)	0.67953 (17)	0.0302 (6)
H24A	0.147226	0.459241	0.732424	0.045*
H24B	0.055531	0.418965	0.658424	0.045*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mo1	0.00948 (12)	0.01172 (13)	0.00803 (12)	−0.00113 (9)	0.00235 (10)	0.00058 (9)
Mo2	0.00973 (12)	0.00873 (12)	0.00733 (12)	0.00071 (9)	0.00239 (9)	0.00025 (9)
Mo3	0.00923 (12)	0.00781 (12)	0.00543 (11)	−0.00052 (9)	0.00261 (9)	−0.00046 (8)
Mo4	0.01140 (12)	0.00829 (12)	0.00699 (12)	−0.00114 (9)	0.00331 (10)	−0.00023 (9)
Co1	0.0123 (2)	0.01163 (19)	0.00849 (18)	−0.00063 (15)	0.00369 (16)	−0.00057 (15)
O1	0.0163 (11)	0.0175 (11)	0.0115 (10)	−0.0029 (9)	0.0034 (9)	−0.0007 (9)
O2	0.0163 (11)	0.0164 (11)	0.0107 (10)	−0.0025 (9)	0.0030 (9)	0.0002 (9)
O3	0.0138 (10)	0.0129 (10)	0.0101 (9)	0.0001 (8)	0.0040 (8)	0.0000 (8)
O4	0.0142 (10)	0.0187 (11)	0.0133 (10)	−0.0027 (9)	0.0054 (9)	0.0010 (9)
O5	0.0101 (10)	0.0131 (10)	0.0117 (10)	0.0007 (8)	0.0033 (8)	0.0007 (8)
O6	0.0166 (11)	0.0121 (10)	0.0126 (10)	0.0023 (8)	0.0051 (9)	0.0011 (8)
O7	0.0120 (10)	0.0088 (10)	0.0082 (9)	−0.0006 (8)	0.0031 (8)	−0.0004 (7)
O8	0.0125 (10)	0.0095 (9)	0.0085 (9)	−0.0015 (8)	0.0044 (8)	−0.0001 (8)
O9	0.0136 (10)	0.0096 (10)	0.0092 (9)	−0.0008 (8)	0.0031 (8)	−0.0010 (8)
O10	0.0076 (9)	0.0114 (9)	0.0080 (9)	−0.0015 (8)	0.0031 (8)	0.0003 (8)
O11	0.0145 (10)	0.0101 (9)	0.0085 (9)	−0.0004 (8)	0.0038 (8)	−0.0009 (8)
O12	0.0146 (10)	0.0162 (10)	0.0135 (10)	−0.0024 (8)	0.0068 (9)	−0.0001 (9)
O13	0.0183 (11)	0.0115 (10)	0.0130 (10)	−0.0012 (8)	0.0046 (9)	−0.0014 (8)
O14	0.0120 (10)	0.0149 (10)	0.0083 (9)	0.0001 (8)	0.0032 (8)	−0.0016 (8)
O15	0.0172 (11)	0.0164 (11)	0.0150 (10)	0.0015 (9)	0.0039 (9)	−0.0036 (9)
O16	0.0286 (14)	0.0340 (14)	0.0183 (12)	−0.0158 (11)	0.0136 (11)	−0.0116 (10)
O17	0.0159 (11)	0.0138 (10)	0.0076 (9)	0.0015 (8)	0.0038 (8)	−0.0013 (8)
O18	0.0224 (12)	0.0109 (10)	0.0131 (10)	−0.0017 (9)	0.0102 (9)	−0.0020 (8)
O19	0.0230 (12)	0.0111 (10)	0.0118 (10)	−0.0004 (9)	0.0074 (9)	0.0000 (8)
O20	0.0176 (11)	0.0197 (11)	0.0140 (10)	−0.0046 (9)	0.0071 (9)	−0.0030 (9)
O21	0.0161 (11)	0.0133 (10)	0.0129 (10)	−0.0021 (9)	0.0018 (9)	−0.0003 (8)
O22	0.0152 (11)	0.0407 (15)	0.0105 (10)	−0.0017 (11)	0.0019 (9)	−0.0030 (10)
N1	0.0117 (12)	0.0159 (13)	0.0132 (12)	0.0028 (10)	0.0022 (10)	−0.0028 (10)
C1	0.0159 (14)	0.0106 (13)	0.0086 (13)	0.0001 (11)	0.0041 (11)	0.0016 (11)
C2	0.0143 (14)	0.0141 (14)	0.0102 (13)	−0.0001 (11)	0.0037 (11)	−0.0040 (11)
C3	0.0135 (14)	0.0164 (15)	0.0096 (13)	0.0015 (11)	0.0028 (11)	−0.0009 (11)
C4	0.0185 (15)	0.0128 (14)	0.0111 (13)	0.0015 (12)	0.0052 (12)	0.0005 (11)
O23	0.0177 (12)	0.0223 (12)	0.0250 (12)	0.0052 (10)	0.0024 (10)	−0.0017 (10)
O24	0.0307 (15)	0.0357 (15)	0.0239 (13)	−0.0006 (12)	0.0092 (12)	−0.0025 (11)

Geometric parameters (Å, º)

Mo1—O1	1.712 (2)	Co1—O21	2.125 (2)
Mo1—O4	1.725 (2)	O14—C1	1.297 (4)
Mo1—O5	1.930 (2)	O15—C1	1.236 (3)
Mo1—O11	1.967 (2)	O16—C4	1.249 (4)
Mo1—O8^i	2.243 (2)	O17—C4	1.264 (3)
Mo1—O10	2.249 (2)	O18—H18A	0.8700
Mo1—Mo2	3.2092 (9)	O18—H18B	0.8700
Mo2—O2	1.719 (2)	O19—H19A	0.8699
Mo2—O6	1.725 (2)	O19—H19B	0.8699
Mo2—O7	1.914 (2)	O20—H20B	0.8700
Mo2—O5	1.927 (2)	O20—H20A	0.8699
Mo2—O10	2.217 (2)	O21—H21A	0.8700
Mo2—O9^i	2.369 (2)	O21—H21B	0.8701
Mo3—O3	1.700 (2)	O22—H22A	0.8699
Mo3—O9	1.755 (2)	O22—H22B	0.8699
Mo3—O8	1.911 (2)	N1—C3	1.480 (4)
Mo3—O10	1.9534 (19)	N1—H1A	0.9100
Mo3—O7	2.174 (2)	N1—H1B	0.9100
Mo3—O10^i	2.381 (2)	N1—H1C	0.9100
Mo4—O13	1.699 (2)	C1—C2	1.521 (4)
Mo4—O12	1.730 (2)	C2—C3	1.542 (4)
Mo4—O11	1.893 (2)	C2—H2A	0.9900
Mo4—O14	2.108 (2)	C2—H2B	0.9900
Mo4—O7^i	2.109 (2)	C3—C4	1.534 (4)
Mo4—O8^i	2.319 (2)	C3—H3	1.0000
Co1—O18	2.076 (2)	O23—H23A	0.8700
Co1—O20	2.087 (2)	O23—H23B	0.8700
Co1—O22	2.103 (2)	O24—H24A	0.8701
Co1—O19	2.104 (2)	O24—H24B	0.8701
Co1—O17	2.106 (2)
O1—Mo1—O4	105.10 (10)	O18—Co1—O22	94.82 (9)
O1—Mo1—O5	99.53 (10)	O20—Co1—O22	86.24 (9)
O4—Mo1—O5	99.87 (9)	O18—Co1—O19	86.16 (8)
O1—Mo1—O11	93.47 (10)	O20—Co1—O19	94.75 (9)
O4—Mo1—O11	100.24 (10)	O22—Co1—O19	92.10 (9)
O5—Mo1—O11	152.25 (9)	O18—Co1—O17	85.17 (9)
O1—Mo1—O8^i	160.31 (9)	O20—Co1—O17	93.76 (9)
O4—Mo1—O8^i	92.80 (9)	O22—Co1—O17	179.01 (9)
O5—Mo1—O8^i	85.10 (8)	O19—Co1—O17	88.89 (8)
O11—Mo1—O8^i	75.01 (8)	O18—Co1—O21	90.21 (8)
O1—Mo1—O10	89.67 (9)	O20—Co1—O21	88.81 (9)
O4—Mo1—O10	164.92 (9)	O22—Co1—O21	92.05 (9)
O5—Mo1—O10	74.18 (8)	O19—Co1—O21	174.70 (8)
O11—Mo1—O10	81.54 (8)	O17—Co1—O21	86.96 (8)
O8^i—Mo1—O10	73.07 (7)	Mo2—O5—Mo1	112.60 (10)
O1—Mo1—Mo2	84.86 (8)	Mo2—O7—Mo4^i	147.24 (11)
O4—Mo1—Mo2	133.20 (7)	Mo2—O7—Mo3	105.78 (9)
O5—Mo1—Mo2	33.67 (6)	Mo4^i—O7—Mo3	106.97 (9)
O11—Mo1—Mo2	125.12 (6)	Mo3—O8—Mo1^i	112.34 (9)
O8^i—Mo1—Mo2	88.83 (5)	Mo3—O8—Mo4^i	108.53 (9)
O10—Mo1—Mo2	43.67 (5)	Mo1^i—O8—Mo4^i	91.17 (7)
O2—Mo2—O6	105.08 (10)	Mo3—O9—Mo2^i	113.30 (9)
O2—Mo2—O7	100.33 (10)	Mo3—O10—Mo2	102.80 (8)
O6—Mo2—O7	102.45 (9)	Mo3—O10—Mo1	152.87 (11)
O2—Mo2—O5	96.51 (10)	Mo2—O10—Mo1	91.86 (7)
O6—Mo2—O5	102.05 (10)	Mo3—O10—Mo3^i	103.88 (9)
O7—Mo2—O5	145.35 (9)	Mo2—O10—Mo3^i	97.59 (8)
O2—Mo2—O10	98.14 (9)	Mo1—O10—Mo3^i	96.52 (7)
O6—Mo2—O10	156.79 (9)	Mo4—O11—Mo1	115.22 (10)
O7—Mo2—O10	72.81 (8)	C1—O14—Mo4	125.35 (18)
O5—Mo2—O10	74.98 (8)	C4—O17—Co1	125.4 (2)
O2—Mo2—O9^i	168.42 (9)	Co1—O18—H18A	121.7
O6—Mo2—O9^i	86.15 (9)	Co1—O18—H18B	116.4
O7—Mo2—O9^i	79.59 (8)	H18A—O18—H18B	103.9
O5—Mo2—O9^i	78.02 (8)	Co1—O19—H19A	119.9
O10—Mo2—O9^i	70.67 (7)	Co1—O19—H19B	128.3
O2—Mo2—Mo1	87.22 (7)	H19A—O19—H19B	104.0
O6—Mo2—Mo1	135.75 (7)	Co1—O20—H20B	111.6
O7—Mo2—Mo1	117.17 (6)	Co1—O20—H20A	120.2
O5—Mo2—Mo1	33.72 (6)	H20B—O20—H20A	104.0
O10—Mo2—Mo1	44.47 (5)	Co1—O21—H21A	110.4
O9^i—Mo2—Mo1	82.61 (5)	Co1—O21—H21B	113.8
O3—Mo3—O9	104.29 (10)	H21A—O21—H21B	103.9
O3—Mo3—O8	104.93 (9)	Co1—O22—H22A	131.5
O9—Mo3—O8	102.64 (10)	Co1—O22—H22B	119.7
O3—Mo3—O10	101.42 (9)	H22A—O22—H22B	104.1
O9—Mo3—O10	98.52 (9)	C3—N1—H1A	109.2
O8—Mo3—O10	140.63 (8)	C3—N1—H1B	110.3
O3—Mo3—O7	96.23 (9)	H1A—N1—H1B	109.4
O9—Mo3—O7	159.08 (8)	C3—N1—H1C	109.0
O8—Mo3—O7	75.43 (8)	H1A—N1—H1C	109.4
O10—Mo3—O7	73.08 (8)	H1B—N1—H1C	109.5
O3—Mo3—O10^i	176.77 (8)	O15—C1—O14	125.3 (3)
O9—Mo3—O10^i	78.27 (8)	O15—C1—C2	117.8 (3)
O8—Mo3—O10^i	76.21 (8)	O14—C1—C2	116.8 (2)
O10—Mo3—O10^i	76.13 (9)	C1—C2—C3	115.2 (3)
O7—Mo3—O10^i	81.09 (7)	C1—C2—H2A	108.5
O13—Mo4—O12	106.41 (11)	C3—C2—H2A	108.5
O13—Mo4—O11	99.65 (10)	C1—C2—H2B	108.5
O12—Mo4—O11	100.56 (10)	C3—C2—H2B	108.5
O13—Mo4—O14	100.46 (9)	H2A—C2—H2B	107.5
O12—Mo4—O14	84.81 (9)	N1—C3—C4	110.5 (2)
O11—Mo4—O14	156.75 (9)	N1—C3—C2	110.8 (2)
O13—Mo4—O7^i	94.12 (9)	C4—C3—C2	110.3 (2)
O12—Mo4—O7^i	154.84 (9)	N1—C3—H3	108.4
O11—Mo4—O7^i	89.90 (8)	C4—C3—H3	108.4
O14—Mo4—O7^i	77.14 (8)	C2—C3—H3	108.4
O13—Mo4—O8^i	161.64 (9)	O16—C4—O17	125.5 (3)
O12—Mo4—O8^i	91.85 (9)	O16—C4—C3	116.8 (3)
O11—Mo4—O8^i	74.52 (8)	O17—C4—C3	117.7 (3)
O14—Mo4—O8^i	82.75 (8)	H23A—O23—H23B	104.0
O7^i—Mo4—O8^i	68.80 (7)	H24A—O24—H24B	104.0
O18—Co1—O20	178.58 (8)
O3—Mo3—O9—Mo2^i	−178.68 (9)	Mo4—O14—C1—C2	−160.46 (19)
O8—Mo3—O9—Mo2^i	−69.44 (11)	O15—C1—C2—C3	178.1 (3)
O10—Mo3—O9—Mo2^i	77.15 (11)	O14—C1—C2—C3	−3.9 (4)
O7—Mo3—O9—Mo2^i	12.8 (3)	C1—C2—C3—N1	−62.8 (3)
O10^i—Mo3—O9—Mo2^i	3.34 (8)	C1—C2—C3—C4	174.5 (2)
O13—Mo4—O11—Mo1	179.55 (11)	Co1—O17—C4—O16	16.1 (4)
O12—Mo4—O11—Mo1	−71.59 (12)	Co1—O17—C4—C3	−162.47 (19)
O14—Mo4—O11—Mo1	30.0 (3)	N1—C3—C4—O16	−170.0 (3)
O7^i—Mo4—O11—Mo1	85.39 (11)	C2—C3—C4—O16	−47.1 (4)
O8^i—Mo4—O11—Mo1	17.40 (9)	N1—C3—C4—O17	8.7 (4)
Mo4—O14—C1—O15	17.4 (4)	C2—C3—C4—O17	131.5 (3)

Symmetry code: (i) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O18—H18A···O15^ii	0.87	1.96	2.781 (3)	156
O18—H18B···O8^iii	0.87	1.90	2.745 (3)	163
O19—H19A···O12^iv	0.87	2.00	2.800 (3)	151
O19—H19B···O11^v	0.87	1.96	2.779 (3)	157
O20—H20B···O16	0.87	1.89	2.641 (3)	144
O20—H20A···O23^vi	0.87	2.01	2.838 (3)	158
O21—H21A···O6^vii	0.87	1.90	2.772 (3)	178
O21—H21B···O23^ii	0.87	1.89	2.749 (3)	171
O22—H22A···O4^iv	0.87	1.94	2.809 (3)	173
O22—H22B···O2^viii	0.87	2.29	3.104 (3)	155
O22—H22B···O5^viii	0.87	2.60	3.258 (3)	134
N1—H1A···O6^vii	0.91	2.11	2.912 (3)	147
N1—H1B···O17^iv	0.91	2.10	2.913 (3)	149
N1—H1C···O14	0.91	2.29	2.919 (3)	126
N1—H1C···O19^iv	0.91	2.18	2.902 (3)	136
C2—H2A···O6^vii	0.99	2.34	3.134 (4)	136
C3—H3···O3^i	1.00	2.33	3.240 (4)	150
O23—H23A···O4^ix	0.87	2.32	3.024 (3)	138
O23—H23B···O15	0.87	1.81	2.679 (3)	175
O24—H24A···O1^i	0.87	2.20	2.892 (3)	137
O24—H24A···O2^i	0.87	2.28	2.992 (3)	140
O24—H24B···O21^vi	0.87	2.16	2.914 (3)	144

Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x, −y+3/2, z−1/2; (iii) x, y, z−1; (iv) −x+1, −y+1, −z+1; (v) −x+1, y−1/2, −z+3/2; (vi) −x, −y+1, −z+1; (vii) −x+1, y+1/2, −z+3/2; (viii) x−1, y, z−1; (ix) x−1, −y+3/2, z−1/2.