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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.
Supporting information
CCDC reference: 1902500
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)]
top
Crystal data top
[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) Å3 | Plate, pale pink |
Z = 2 | 0.30 × 0.17 × 0.11 mm |
Data collection top
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 top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.030 | Hydrogen site location: mixed |
wR(F2) = 0.078 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0498P)2] where P = (Fo2 + 2Fc2)/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 top
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 (Å2) top | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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—O8i | 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—O9i | 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—O10i | 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—O7i | 2.109 (2) | C3—C4 | 1.534 (4) |
Mo4—O8i | 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—O8i | 160.31 (9) | O20—Co1—O17 | 93.76 (9) |
O4—Mo1—O8i | 92.80 (9) | O22—Co1—O17 | 179.01 (9) |
O5—Mo1—O8i | 85.10 (8) | O19—Co1—O17 | 88.89 (8) |
O11—Mo1—O8i | 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) |
O8i—Mo1—O10 | 73.07 (7) | Mo2—O5—Mo1 | 112.60 (10) |
O1—Mo1—Mo2 | 84.86 (8) | Mo2—O7—Mo4i | 147.24 (11) |
O4—Mo1—Mo2 | 133.20 (7) | Mo2—O7—Mo3 | 105.78 (9) |
O5—Mo1—Mo2 | 33.67 (6) | Mo4i—O7—Mo3 | 106.97 (9) |
O11—Mo1—Mo2 | 125.12 (6) | Mo3—O8—Mo1i | 112.34 (9) |
O8i—Mo1—Mo2 | 88.83 (5) | Mo3—O8—Mo4i | 108.53 (9) |
O10—Mo1—Mo2 | 43.67 (5) | Mo1i—O8—Mo4i | 91.17 (7) |
O2—Mo2—O6 | 105.08 (10) | Mo3—O9—Mo2i | 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—Mo3i | 103.88 (9) |
O7—Mo2—O5 | 145.35 (9) | Mo2—O10—Mo3i | 97.59 (8) |
O2—Mo2—O10 | 98.14 (9) | Mo1—O10—Mo3i | 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—O9i | 168.42 (9) | Co1—O18—H18A | 121.7 |
O6—Mo2—O9i | 86.15 (9) | Co1—O18—H18B | 116.4 |
O7—Mo2—O9i | 79.59 (8) | H18A—O18—H18B | 103.9 |
O5—Mo2—O9i | 78.02 (8) | Co1—O19—H19A | 119.9 |
O10—Mo2—O9i | 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 |
O9i—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—O10i | 176.77 (8) | O15—C1—O14 | 125.3 (3) |
O9—Mo3—O10i | 78.27 (8) | O15—C1—C2 | 117.8 (3) |
O8—Mo3—O10i | 76.21 (8) | O14—C1—C2 | 116.8 (2) |
O10—Mo3—O10i | 76.13 (9) | C1—C2—C3 | 115.2 (3) |
O7—Mo3—O10i | 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—O7i | 94.12 (9) | C4—C3—C2 | 110.3 (2) |
O12—Mo4—O7i | 154.84 (9) | N1—C3—H3 | 108.4 |
O11—Mo4—O7i | 89.90 (8) | C4—C3—H3 | 108.4 |
O14—Mo4—O7i | 77.14 (8) | C2—C3—H3 | 108.4 |
O13—Mo4—O8i | 161.64 (9) | O16—C4—O17 | 125.5 (3) |
O12—Mo4—O8i | 91.85 (9) | O16—C4—C3 | 116.8 (3) |
O11—Mo4—O8i | 74.52 (8) | O17—C4—C3 | 117.7 (3) |
O14—Mo4—O8i | 82.75 (8) | H23A—O23—H23B | 104.0 |
O7i—Mo4—O8i | 68.80 (7) | H24A—O24—H24B | 104.0 |
O18—Co1—O20 | 178.58 (8) | | |
| | | |
O3—Mo3—O9—Mo2i | −178.68 (9) | Mo4—O14—C1—C2 | −160.46 (19) |
O8—Mo3—O9—Mo2i | −69.44 (11) | O15—C1—C2—C3 | 178.1 (3) |
O10—Mo3—O9—Mo2i | 77.15 (11) | O14—C1—C2—C3 | −3.9 (4) |
O7—Mo3—O9—Mo2i | 12.8 (3) | C1—C2—C3—N1 | −62.8 (3) |
O10i—Mo3—O9—Mo2i | 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) |
O7i—Mo4—O11—Mo1 | 85.39 (11) | C2—C3—C4—O16 | −47.1 (4) |
O8i—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) top
D—H···A | D—H | H···A | D···A | D—H···A |
O18—H18A···O15ii | 0.87 | 1.96 | 2.781 (3) | 156 |
O18—H18B···O8iii | 0.87 | 1.90 | 2.745 (3) | 163 |
O19—H19A···O12iv | 0.87 | 2.00 | 2.800 (3) | 151 |
O19—H19B···O11v | 0.87 | 1.96 | 2.779 (3) | 157 |
O20—H20B···O16 | 0.87 | 1.89 | 2.641 (3) | 144 |
O20—H20A···O23vi | 0.87 | 2.01 | 2.838 (3) | 158 |
O21—H21A···O6vii | 0.87 | 1.90 | 2.772 (3) | 178 |
O21—H21B···O23ii | 0.87 | 1.89 | 2.749 (3) | 171 |
O22—H22A···O4iv | 0.87 | 1.94 | 2.809 (3) | 173 |
O22—H22B···O2viii | 0.87 | 2.29 | 3.104 (3) | 155 |
O22—H22B···O5viii | 0.87 | 2.60 | 3.258 (3) | 134 |
N1—H1A···O6vii | 0.91 | 2.11 | 2.912 (3) | 147 |
N1—H1B···O17iv | 0.91 | 2.10 | 2.913 (3) | 149 |
N1—H1C···O14 | 0.91 | 2.29 | 2.919 (3) | 126 |
N1—H1C···O19iv | 0.91 | 2.18 | 2.902 (3) | 136 |
C2—H2A···O6vii | 0.99 | 2.34 | 3.134 (4) | 136 |
C3—H3···O3i | 1.00 | 2.33 | 3.240 (4) | 150 |
O23—H23A···O4ix | 0.87 | 2.32 | 3.024 (3) | 138 |
O23—H23B···O15 | 0.87 | 1.81 | 2.679 (3) | 175 |
O24—H24A···O1i | 0.87 | 2.20 | 2.892 (3) | 137 |
O24—H24A···O2i | 0.87 | 2.28 | 2.992 (3) | 140 |
O24—H24B···O21vi | 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. |
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