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In this work, we demonstrate a simple approach for growing 1D (one-dimensional) inorganic chains of K(C
6H
16N)
3Mo
8O
26·H
2O polyoxometalates (POMs) from its colloidal soft-oxometalate (SOM) phase through the variation of pH. The structure is composed mainly of a 1D inorganic chain with a β-Mo
8O
264− binding node linked using K
+ via Mo—O—K linkages, which results in a cuboctahedral geometry for the K
+ ions. Crystal structure and Hirshfeld surface studies reveal the role of triethylammonium cations in restricting the growth of the 1D chain into 2D/3D (two-/three-dimensional) structures. During the nucleation process from the heterogeneous SOM phase, some of the intermolecular interactions in the dispersion phase are retained in the crystal structure, which was evidenced from residual O
O interactions. The crystallization of the species from its colloidal form as a function of pH was studied by the use of Raman spectroscopy and it was found that the increase in volume fraction of the β-Mo
8O
264− species in the crystallizing colloidal mixture with the decrease in pH is responsible for the nucleation. This was monitored by time-dependent DLS (dynamic light scattering) measurement and zeta-potential studies, revealing the co-existence of both the crystal and the colloidal forms at pH 3–2. This brings us to the conclusion that in the crystallization of POMs, the colloidal SOM phase precedes the crystalline POM phase which occurs
via a phase transition. This work could open up avenues for the study of POM formation from the stand-point of colloidal chemistry and SOMs.
Supporting information
CCDC reference: 1575935
Data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).
Tris(triethylaminium) hemi(dopentacontaoxidopotassiohexadecamolybdate)
monohydrate
top
Crystal data top
(C6H16N)3[K2Mo16O52]0.5·H2O | F(000) = 3000 |
Mr = 1547.23 | Dx = 2.413 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 25.1247 (8) Å | Cell parameters from 8571 reflections |
b = 10.7583 (3) Å | θ = 2.1–26.8° |
c = 18.5442 (5) Å | µ = 2.46 mm−1 |
β = 121.835 (3)° | T = 100 K |
V = 4258.5 (2) Å3 | Rod, clear colourless |
Z = 4 | 0.3 × 0.1 × 0.05 mm |
Data collection top
Agilent SuperNova Dual Source diffractometer with an Eos detector | 3886 independent reflections |
Radiation source: micro-focus sealed X-ray tube, SuperNova (Mo) X-ray Source | 3582 reflections with I > 2σ(I) |
Detector resolution: 7.9580 pixels mm-1 | Rint = 0.034 |
ω scans | θmax = 25.4°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −30→28 |
Tmin = 0.062, Tmax = 0.093 | k = −12→12 |
12607 measured reflections | l = −22→21 |
Refinement top
Refinement on F2 | Hydrogen site location: mixed |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.023 | w = 1/[σ2(Fo2) + (0.0247P)2 + 6.8377P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.056 | (Δ/σ)max = 0.002 |
S = 1.06 | Δρmax = 0.59 e Å−3 |
3886 reflections | Δρmin = −0.52 e Å−3 |
304 parameters | Extinction correction: SHELXL2016 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
43 restraints | Extinction coefficient: 0.00020 (2) |
Special details top
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. 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Mo1 | 0.60807 (2) | 0.46762 (2) | 0.48657 (2) | 0.01373 (8) | |
Mo2 | 0.45907 (2) | 0.42819 (2) | 0.39963 (2) | 0.01256 (8) | |
Mo3 | 0.43750 (2) | 0.72147 (2) | 0.40889 (2) | 0.01356 (8) | |
Mo4 | 0.58769 (2) | 0.76365 (2) | 0.49649 (2) | 0.01453 (8) | |
K1 | 0.500000 | 0.63056 (8) | 0.250000 | 0.0175 (2) | |
O6 | 0.40089 (9) | 0.55146 (18) | 0.39590 (13) | 0.0139 (4) | |
O5 | 0.53989 (9) | 0.34477 (17) | 0.45968 (13) | 0.0141 (4) | |
O7 | 0.50838 (9) | 0.82562 (18) | 0.47312 (13) | 0.0160 (4) | |
O8 | 0.64366 (9) | 0.62419 (18) | 0.53556 (13) | 0.0161 (4) | |
O2 | 0.41322 (9) | 0.29802 (18) | 0.38701 (13) | 0.0168 (4) | |
O4 | 0.63703 (9) | 0.88406 (19) | 0.55100 (14) | 0.0201 (5) | |
O13 | 0.52072 (9) | 0.58220 (18) | 0.46285 (13) | 0.0148 (4) | |
O3 | 0.37813 (9) | 0.81053 (19) | 0.39867 (13) | 0.0190 (5) | |
O11 | 0.42950 (10) | 0.72627 (18) | 0.31153 (14) | 0.0183 (5) | |
O10 | 0.44962 (9) | 0.44827 (19) | 0.30301 (13) | 0.0179 (4) | |
O1 | 0.67186 (9) | 0.37354 (19) | 0.53047 (14) | 0.0194 (5) | |
O12 | 0.57329 (10) | 0.77401 (19) | 0.39577 (14) | 0.0193 (5) | |
O9 | 0.58913 (10) | 0.48992 (19) | 0.38481 (13) | 0.0183 (4) | |
N2 | 0.25130 (12) | 0.4973 (2) | 0.15917 (17) | 0.0210 (6) | |
H1 | 0.210462 | 0.542676 | 0.127437 | 0.025* | |
C1 | 0.24871 (15) | 0.3974 (3) | 0.1006 (2) | 0.0248 (7) | |
H1A | 0.242317 | 0.436805 | 0.048327 | 0.030* | |
H1B | 0.212168 | 0.343221 | 0.084083 | 0.030* | |
C5 | 0.30166 (15) | 0.5926 (3) | 0.1824 (2) | 0.0296 (8) | |
H5A | 0.342389 | 0.549630 | 0.206001 | 0.036* | |
H5B | 0.304599 | 0.647457 | 0.227237 | 0.036* | |
C3 | 0.25554 (16) | 0.4433 (3) | 0.2373 (2) | 0.0270 (7) | |
H3A | 0.231860 | 0.364257 | 0.222124 | 0.032* | |
H3B | 0.299896 | 0.424755 | 0.280303 | 0.032* | |
C6 | 0.28980 (17) | 0.6717 (4) | 0.1076 (3) | 0.0389 (9) | |
H6A | 0.288202 | 0.618337 | 0.063712 | 0.058* | |
H6B | 0.323724 | 0.732392 | 0.126479 | 0.058* | |
H6C | 0.249821 | 0.715530 | 0.084411 | 0.058* | |
C2 | 0.30707 (16) | 0.3182 (3) | 0.1394 (2) | 0.0299 (8) | |
H2A | 0.300543 | 0.249081 | 0.101172 | 0.045* | |
H2B | 0.316062 | 0.285309 | 0.194034 | 0.045* | |
H2C | 0.342464 | 0.368815 | 0.148274 | 0.045* | |
C4 | 0.2298 (2) | 0.5311 (5) | 0.2747 (3) | 0.0530 (12) | |
H4A | 0.186605 | 0.553331 | 0.231346 | 0.079* | |
H4B | 0.255564 | 0.606480 | 0.294639 | 0.079* | |
H4C | 0.230423 | 0.490785 | 0.322551 | 0.079* | |
N1 | 0.4996 (5) | 0.0915 (3) | 0.2512 (9) | 0.0196 (7) | 0.5 |
H0AA | 0.520749 | 0.050747 | 0.224401 | 0.024* | 0.5 |
C9 | 0.4493 (8) | 0.1725 (11) | 0.1849 (8) | 0.023 (3) | 0.5 |
H0AB | 0.470038 | 0.238783 | 0.171401 | 0.027* | 0.5 |
H0AC | 0.428100 | 0.213514 | 0.210813 | 0.027* | 0.5 |
C12 | 0.4383 (5) | 0.0462 (12) | 0.3166 (6) | 0.033 (3) | 0.5 |
H3AA | 0.415218 | −0.018759 | 0.325802 | 0.050* | 0.5 |
H3AB | 0.409297 | 0.111835 | 0.280817 | 0.050* | 0.5 |
H3AC | 0.470371 | 0.081453 | 0.371312 | 0.050* | 0.5 |
C10 | 0.3986 (8) | 0.1162 (16) | 0.1011 (9) | 0.027 (3) | 0.5 |
H1AA | 0.374471 | 0.182848 | 0.060966 | 0.041* | 0.5 |
H1AB | 0.370596 | 0.065029 | 0.110690 | 0.041* | 0.5 |
H1AC | 0.418044 | 0.064341 | 0.077782 | 0.041* | 0.5 |
C11 | 0.4696 (3) | −0.0096 (5) | 0.2727 (4) | 0.0197 (12) | 0.5 |
H2AA | 0.501705 | −0.070823 | 0.310657 | 0.024* | 0.5 |
H2AB | 0.438043 | −0.053194 | 0.220312 | 0.024* | 0.5 |
C7 | 0.5474 (9) | 0.1723 (12) | 0.3207 (8) | 0.026 (3) | 0.5 |
H7A | 0.528306 | 0.218610 | 0.347644 | 0.031* | 0.5 |
H7B | 0.564362 | 0.233025 | 0.297807 | 0.031* | 0.5 |
C8 | 0.5995 (9) | 0.0882 (17) | 0.3854 (10) | 0.044 (5) | 0.5 |
H8A | 0.614089 | 0.034607 | 0.356608 | 0.066* | 0.5 |
H8B | 0.583510 | 0.036630 | 0.413540 | 0.066* | 0.5 |
H8C | 0.634356 | 0.139158 | 0.427874 | 0.066* | 0.5 |
O14 | 0.4539 (4) | 0.0437 (8) | 0.3555 (4) | 0.0306 (16) | 0.5 |
H13A | 0.447491 | 0.104527 | 0.379140 | 0.046* | 0.5 |
H13B | 0.472012 | −0.010592 | 0.394479 | 0.046* | 0.5 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Mo1 | 0.01187 (14) | 0.01594 (14) | 0.01319 (15) | 0.00013 (9) | 0.00648 (12) | −0.00076 (10) |
Mo2 | 0.01135 (14) | 0.01429 (14) | 0.01045 (15) | −0.00077 (9) | 0.00466 (12) | −0.00192 (10) |
Mo3 | 0.01196 (14) | 0.01438 (14) | 0.01315 (15) | 0.00001 (9) | 0.00580 (12) | −0.00035 (10) |
Mo4 | 0.01237 (14) | 0.01536 (14) | 0.01447 (15) | −0.00235 (9) | 0.00612 (12) | −0.00155 (10) |
K1 | 0.0190 (5) | 0.0189 (4) | 0.0159 (5) | 0.000 | 0.0100 (4) | 0.000 |
O6 | 0.0118 (10) | 0.0164 (10) | 0.0122 (11) | −0.0009 (8) | 0.0055 (9) | −0.0017 (8) |
O5 | 0.0118 (10) | 0.0153 (10) | 0.0143 (11) | −0.0008 (8) | 0.0063 (9) | −0.0028 (8) |
O7 | 0.0159 (10) | 0.0149 (10) | 0.0170 (11) | −0.0017 (8) | 0.0084 (10) | −0.0022 (9) |
O8 | 0.0115 (10) | 0.0191 (10) | 0.0158 (11) | −0.0023 (8) | 0.0060 (9) | −0.0013 (9) |
O2 | 0.0148 (10) | 0.0181 (10) | 0.0150 (11) | −0.0021 (8) | 0.0062 (10) | −0.0035 (9) |
O4 | 0.0166 (11) | 0.0198 (11) | 0.0212 (12) | −0.0036 (8) | 0.0081 (10) | −0.0033 (9) |
O13 | 0.0131 (10) | 0.0160 (10) | 0.0142 (11) | −0.0022 (8) | 0.0063 (9) | −0.0023 (8) |
O3 | 0.0168 (11) | 0.0200 (10) | 0.0208 (12) | 0.0016 (9) | 0.0105 (10) | 0.0020 (9) |
O11 | 0.0189 (11) | 0.0203 (11) | 0.0163 (12) | −0.0033 (8) | 0.0096 (10) | −0.0018 (9) |
O10 | 0.0171 (11) | 0.0212 (11) | 0.0146 (11) | −0.0017 (8) | 0.0078 (10) | −0.0015 (9) |
O1 | 0.0141 (10) | 0.0231 (11) | 0.0203 (12) | 0.0008 (8) | 0.0086 (10) | 0.0013 (9) |
O12 | 0.0186 (11) | 0.0213 (11) | 0.0194 (12) | −0.0018 (9) | 0.0109 (10) | −0.0001 (9) |
O9 | 0.0180 (11) | 0.0216 (11) | 0.0168 (12) | 0.0005 (9) | 0.0102 (10) | −0.0002 (9) |
N2 | 0.0139 (13) | 0.0219 (13) | 0.0187 (15) | 0.0026 (11) | 0.0029 (12) | 0.0001 (11) |
C1 | 0.0245 (17) | 0.0241 (16) | 0.0240 (19) | −0.0056 (13) | 0.0116 (16) | −0.0066 (14) |
C5 | 0.0182 (17) | 0.0227 (16) | 0.032 (2) | −0.0012 (13) | 0.0026 (17) | 0.0004 (15) |
C3 | 0.0192 (17) | 0.0347 (18) | 0.0180 (18) | 0.0003 (14) | 0.0035 (15) | 0.0003 (15) |
C6 | 0.0263 (19) | 0.035 (2) | 0.048 (3) | −0.0012 (16) | 0.015 (2) | 0.0095 (19) |
C2 | 0.0299 (19) | 0.0255 (17) | 0.041 (2) | 0.0010 (15) | 0.0232 (18) | 0.0001 (16) |
C4 | 0.047 (3) | 0.077 (3) | 0.027 (2) | 0.023 (2) | 0.014 (2) | −0.003 (2) |
N1 | 0.0233 (16) | 0.0191 (16) | 0.0202 (17) | 0.004 (3) | 0.0141 (14) | 0.000 (3) |
C9 | 0.022 (3) | 0.023 (4) | 0.022 (3) | 0.001 (3) | 0.011 (2) | 0.002 (3) |
C12 | 0.046 (7) | 0.028 (4) | 0.042 (7) | 0.009 (5) | 0.035 (6) | 0.012 (5) |
C10 | 0.028 (4) | 0.017 (6) | 0.028 (3) | −0.002 (5) | 0.008 (2) | 0.001 (4) |
C11 | 0.019 (3) | 0.022 (2) | 0.015 (3) | 0.003 (2) | 0.006 (3) | 0.003 (2) |
C7 | 0.032 (4) | 0.031 (4) | 0.015 (3) | −0.004 (3) | 0.013 (2) | 0.002 (3) |
C8 | 0.034 (4) | 0.030 (8) | 0.038 (6) | −0.013 (5) | −0.002 (4) | 0.007 (5) |
O14 | 0.037 (4) | 0.020 (3) | 0.041 (5) | −0.001 (3) | 0.025 (4) | −0.003 (4) |
Geometric parameters (Å, º) top
Mo1—O6i | 2.315 (2) | N2—C5 | 1.504 (4) |
Mo1—O5 | 2.0071 (19) | N2—C3 | 1.512 (4) |
Mo1—O8 | 1.899 (2) | C1—H1A | 0.9900 |
Mo1—O13 | 2.3477 (19) | C1—H1B | 0.9900 |
Mo1—O1 | 1.697 (2) | C1—C2 | 1.510 (4) |
Mo1—O9 | 1.702 (2) | C5—H5A | 0.9900 |
Mo2—O6 | 1.9477 (19) | C5—H5B | 0.9900 |
Mo2—O5 | 1.9452 (19) | C5—C6 | 1.516 (5) |
Mo2—O2 | 1.749 (2) | C3—H3A | 0.9900 |
Mo2—O13 | 2.1455 (19) | C3—H3B | 0.9900 |
Mo2—O13i | 2.325 (2) | C3—C4 | 1.506 (5) |
Mo2—O10 | 1.693 (2) | C6—H6A | 0.9800 |
Mo3—O6 | 2.0040 (19) | C6—H6B | 0.9800 |
Mo3—O5i | 2.304 (2) | C6—H6C | 0.9800 |
Mo3—O7 | 1.899 (2) | C2—H2A | 0.9800 |
Mo3—O13 | 2.3261 (19) | C2—H2B | 0.9800 |
Mo3—O3 | 1.697 (2) | C2—H2C | 0.9800 |
Mo3—O11 | 1.709 (2) | C4—H4A | 0.9800 |
Mo4—O7 | 1.9216 (19) | C4—H4B | 0.9800 |
Mo4—O8 | 1.918 (2) | C4—H4C | 0.9800 |
Mo4—O2i | 2.272 (2) | N1—H0AA | 1.0000 |
Mo4—O4 | 1.707 (2) | N1—C9 | 1.493 (4) |
Mo4—O13 | 2.4340 (19) | N1—C11 | 1.493 (4) |
Mo4—O12 | 1.708 (2) | N1—C7 | 1.493 (4) |
K1—Mo2ii | 4.0630 (5) | C9—H0AB | 0.9900 |
K1—Mo3ii | 4.1214 (3) | C9—H0AC | 0.9900 |
K1—K1ii | 0.0000 (1) | C9—C10 | 1.521 (6) |
K1—O11 | 2.763 (2) | C12—H3AA | 0.9800 |
K1—O11ii | 2.763 (2) | C12—H3AB | 0.9800 |
K1—O10 | 2.780 (2) | C12—H3AC | 0.9800 |
K1—O10ii | 2.780 (2) | C12—C11 | 1.521 (6) |
K1—O12 | 2.798 (2) | C10—H1AA | 0.9800 |
K1—O12ii | 2.798 (2) | C10—H1AB | 0.9800 |
K1—O9ii | 2.765 (2) | C10—H1AC | 0.9800 |
K1—O9 | 2.766 (2) | C11—H2AA | 0.9900 |
O6—Mo1i | 2.315 (2) | C11—H2AB | 0.9900 |
O5—Mo3i | 2.304 (2) | C7—H7A | 0.9900 |
O2—Mo4i | 2.272 (2) | C7—H7B | 0.9900 |
O13—Mo2i | 2.325 (2) | C7—C8 | 1.521 (6) |
O11—K1ii | 2.763 (2) | C8—H8A | 0.9800 |
O10—K1ii | 2.780 (2) | C8—H8B | 0.9800 |
O12—K1ii | 2.798 (2) | C8—H8C | 0.9800 |
O9—K1ii | 2.766 (2) | O14—H13A | 0.8493 |
N2—H1 | 1.0000 | O14—H13B | 0.8504 |
N2—C1 | 1.505 (4) | | |
| | | |
O6i—Mo1—O13 | 71.18 (7) | Mo2—O6—Mo3 | 109.20 (9) |
O5—Mo1—O6i | 71.43 (7) | Mo3—O6—Mo1i | 103.54 (8) |
O5—Mo1—O13 | 73.03 (7) | Mo1—O5—Mo3i | 103.82 (8) |
O8—Mo1—O6i | 83.30 (8) | Mo2—O5—Mo1 | 109.57 (9) |
O8—Mo1—O5 | 145.88 (8) | Mo2—O5—Mo3i | 110.40 (8) |
O8—Mo1—O13 | 77.39 (7) | Mo3—O7—Mo4 | 117.04 (10) |
O1—Mo1—O6i | 91.81 (9) | Mo1—O8—Mo4 | 116.54 (10) |
O1—Mo1—O5 | 101.11 (9) | Mo2—O2—Mo4i | 116.29 (10) |
O1—Mo1—O8 | 102.26 (9) | Mo1—O13—Mo4 | 85.49 (6) |
O1—Mo1—O13 | 162.96 (9) | Mo2—O13—Mo1 | 91.78 (7) |
O1—Mo1—O9 | 104.89 (10) | Mo2i—O13—Mo1 | 97.32 (7) |
O9—Mo1—O6i | 161.24 (8) | Mo2—O13—Mo2i | 103.84 (8) |
O9—Mo1—O5 | 96.57 (9) | Mo2i—O13—Mo3 | 97.44 (7) |
O9—Mo1—O8 | 101.02 (9) | Mo2—O13—Mo3 | 92.08 (7) |
O9—Mo1—O13 | 91.79 (9) | Mo2i—O13—Mo4 | 92.06 (7) |
O6—Mo2—O13i | 78.31 (8) | Mo2—O13—Mo4 | 164.09 (10) |
O6—Mo2—O13 | 78.79 (8) | Mo3—O13—Mo1 | 163.37 (10) |
O5—Mo2—O6 | 150.67 (8) | Mo3—O13—Mo4 | 86.37 (6) |
O5—Mo2—O13 | 78.97 (8) | Mo3—O11—K1 | 132.96 (11) |
O5—Mo2—O13i | 77.99 (7) | Mo3—O11—K1ii | 132.96 (11) |
O2—Mo2—O6 | 96.40 (9) | K1ii—O11—K1 | 0.00 (3) |
O2—Mo2—O5 | 97.02 (9) | Mo2—O10—K1 | 128.95 (10) |
O2—Mo2—O13i | 81.70 (8) | Mo2—O10—K1ii | 128.95 (10) |
O2—Mo2—O13 | 157.86 (9) | K1ii—O10—K1 | 0.00 (3) |
O13—Mo2—O13i | 76.16 (8) | Mo4—O12—K1 | 132.24 (10) |
O10—Mo2—O6 | 101.06 (9) | Mo4—O12—K1ii | 132.24 (10) |
O10—Mo2—O5 | 100.72 (9) | K1ii—O12—K1 | 0.00 (3) |
O10—Mo2—O2 | 104.24 (10) | Mo1—O9—K1ii | 134.34 (10) |
O10—Mo2—O13i | 174.05 (8) | Mo1—O9—K1 | 134.34 (10) |
O10—Mo2—O13 | 97.91 (9) | K1ii—O9—K1 | 0.0 |
O6—Mo3—O5i | 71.72 (7) | C1—N2—H1 | 106.5 |
O6—Mo3—O13 | 73.45 (7) | C1—N2—C3 | 111.8 (2) |
O5i—Mo3—O13 | 71.43 (7) | C5—N2—H1 | 106.5 |
O7—Mo3—O6 | 146.39 (8) | C5—N2—C1 | 113.8 (3) |
O7—Mo3—O5i | 83.84 (8) | C5—N2—C3 | 111.4 (3) |
O7—Mo3—O13 | 77.15 (8) | C3—N2—H1 | 106.5 |
O3—Mo3—O6 | 100.44 (9) | N2—C1—H1A | 108.9 |
O3—Mo3—O5i | 90.26 (8) | N2—C1—H1B | 108.9 |
O3—Mo3—O7 | 102.43 (9) | N2—C1—C2 | 113.4 (3) |
O3—Mo3—O13 | 161.67 (9) | H1A—C1—H1B | 107.7 |
O3—Mo3—O11 | 104.97 (10) | C2—C1—H1A | 108.9 |
O11—Mo3—O6 | 96.31 (9) | C2—C1—H1B | 108.9 |
O11—Mo3—O5i | 162.33 (8) | N2—C5—H5A | 109.0 |
O11—Mo3—O7 | 101.16 (9) | N2—C5—H5B | 109.0 |
O11—Mo3—O13 | 92.98 (9) | N2—C5—C6 | 113.0 (3) |
O7—Mo4—O2i | 77.66 (8) | H5A—C5—H5B | 107.8 |
O7—Mo4—O13 | 74.09 (7) | C6—C5—H5A | 109.0 |
O8—Mo4—O7 | 145.39 (8) | C6—C5—H5B | 109.0 |
O8—Mo4—O2i | 77.61 (8) | N2—C3—H3A | 109.3 |
O8—Mo4—O13 | 74.90 (7) | N2—C3—H3B | 109.3 |
O2i—Mo4—O13 | 69.94 (7) | H3A—C3—H3B | 107.9 |
O4—Mo4—O7 | 102.30 (9) | C4—C3—N2 | 111.7 (3) |
O4—Mo4—O8 | 102.19 (9) | C4—C3—H3A | 109.3 |
O4—Mo4—O2i | 91.54 (9) | C4—C3—H3B | 109.3 |
O4—Mo4—O13 | 161.48 (9) | C5—C6—H6A | 109.5 |
O4—Mo4—O12 | 105.47 (10) | C5—C6—H6B | 109.5 |
O12—Mo4—O7 | 97.72 (9) | C5—C6—H6C | 109.5 |
O12—Mo4—O8 | 98.88 (9) | H6A—C6—H6B | 109.5 |
O12—Mo4—O2i | 162.98 (9) | H6A—C6—H6C | 109.5 |
O12—Mo4—O13 | 93.04 (8) | H6B—C6—H6C | 109.5 |
Mo2ii—K1—Mo3ii | 46.350 (5) | C1—C2—H2A | 109.5 |
K1ii—K1—Mo2ii | 0 (8) | C1—C2—H2B | 109.5 |
K1ii—K1—Mo3ii | 0 (7) | C1—C2—H2C | 109.5 |
K1ii—K1—O11 | 0 (10) | H2A—C2—H2B | 109.5 |
K1ii—K1—O11ii | 0 (10) | H2A—C2—H2C | 109.5 |
K1ii—K1—O10 | 0 (10) | H2B—C2—H2C | 109.5 |
K1ii—K1—O10ii | 0 (10) | C3—C4—H4A | 109.5 |
K1ii—K1—O12ii | 0 (10) | C3—C4—H4B | 109.5 |
K1ii—K1—O12 | 0 (10) | C3—C4—H4C | 109.5 |
K1ii—K1—O9ii | 0 (10) | H4A—C4—H4B | 109.5 |
K1ii—K1—O9 | 0 (10) | H4A—C4—H4C | 109.5 |
O11ii—K1—Mo2ii | 57.94 (4) | H4B—C4—H4C | 109.5 |
O11—K1—Mo2ii | 158.47 (5) | C9—N1—H0AA | 106.7 |
O11—K1—Mo3ii | 140.89 (5) | C11—N1—H0AA | 106.7 |
O11ii—K1—Mo3ii | 17.66 (4) | C11—N1—C9 | 108.6 (4) |
O11—K1—O11ii | 136.23 (9) | C11—N1—C7 | 118.9 (16) |
O11—K1—O10 | 66.80 (6) | C7—N1—H0AA | 106.7 |
O11—K1—O10ii | 156.90 (7) | C7—N1—C9 | 108.5 (4) |
O11ii—K1—O10 | 156.90 (7) | N1—C9—H0AB | 107.4 |
O11ii—K1—O10ii | 66.80 (6) | N1—C9—H0AC | 107.4 |
O11—K1—O12 | 68.53 (6) | N1—C9—C10 | 119.8 (13) |
O11ii—K1—O12 | 87.41 (6) | H0AB—C9—H0AC | 106.9 |
O11ii—K1—O12ii | 68.53 (6) | C10—C9—H0AB | 107.4 |
O11—K1—O12ii | 87.41 (6) | C10—C9—H0AC | 107.4 |
O11—K1—O9 | 102.73 (6) | H3AA—C12—H3AB | 109.5 |
O11ii—K1—O9 | 100.81 (6) | H3AA—C12—H3AC | 109.5 |
O11—K1—O9ii | 100.81 (6) | H3AB—C12—H3AC | 109.5 |
O11ii—K1—O9ii | 102.73 (6) | C11—C12—H3AA | 109.5 |
O10ii—K1—Mo2ii | 18.90 (4) | C11—C12—H3AB | 109.5 |
O10—K1—Mo2ii | 100.95 (5) | C11—C12—H3AC | 109.5 |
O10ii—K1—Mo3ii | 59.89 (4) | C9—C10—H1AA | 109.5 |
O10—K1—Mo3ii | 146.78 (5) | C9—C10—H1AB | 109.5 |
O10ii—K1—O10 | 90.26 (9) | C9—C10—H1AC | 109.5 |
O10ii—K1—O12ii | 103.76 (6) | H1AA—C10—H1AB | 109.5 |
O10—K1—O12 | 103.76 (6) | H1AA—C10—H1AC | 109.5 |
O10ii—K1—O12 | 122.71 (6) | H1AB—C10—H1AC | 109.5 |
O10—K1—O12ii | 122.71 (6) | N1—C11—C12 | 109.3 (8) |
O12ii—K1—Mo2ii | 84.86 (4) | N1—C11—H2AA | 109.8 |
O12—K1—Mo2ii | 132.90 (4) | N1—C11—H2AB | 109.8 |
O12—K1—Mo3ii | 104.78 (4) | C12—C11—H2AA | 109.8 |
O12ii—K1—Mo3ii | 58.88 (4) | C12—C11—H2AB | 109.8 |
O12ii—K1—O12 | 113.05 (9) | H2AA—C11—H2AB | 108.3 |
O9—K1—Mo2ii | 87.03 (5) | N1—C7—H7A | 110.2 |
O9ii—K1—Mo2ii | 57.68 (4) | N1—C7—H7B | 110.2 |
O9ii—K1—Mo3ii | 85.16 (4) | N1—C7—C8 | 107.5 (11) |
O9—K1—Mo3ii | 110.12 (4) | H7A—C7—H7B | 108.5 |
O9—K1—O10ii | 68.35 (6) | C8—C7—H7A | 110.2 |
O9ii—K1—O10 | 68.35 (6) | C8—C7—H7B | 110.2 |
O9—K1—O10 | 66.23 (6) | C7—C8—H8A | 109.5 |
O9ii—K1—O10ii | 66.23 (6) | C7—C8—H8B | 109.5 |
O9ii—K1—O12ii | 67.79 (6) | C7—C8—H8C | 109.5 |
O9ii—K1—O12 | 168.99 (6) | H8A—C8—H8B | 109.5 |
O9—K1—O12ii | 168.99 (6) | H8A—C8—H8C | 109.5 |
O9—K1—O12 | 67.79 (6) | H8B—C8—H8C | 109.5 |
O9ii—K1—O9 | 113.66 (9) | H13A—O14—H13B | 104.6 |
Mo2—O6—Mo1i | 110.49 (9) | | |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2iii—H1iii···O4iii | 1.00 | 1.81 | 2.796 (4) | 168 |
N1iv—H0AAiv···O14iv | 1.00 | 1.90 | 2.826 (17) | 153 |
O14—H13B···O7 | 0.85 | 2.16 | 2.998 (8) | 169 |
Symmetry codes: (iii) x+1/2, −y+1/2, z−1/2; (iv) −x, y, −z+1/2. |
Bond-valence sum data topMo=O-terminal | BVS value | µ2-O (Mo-O-Mo) | BVS value |
O1 | 1.764 | O2 | 1.906 |
O3 | 1.764 | O7 | 1.982 |
O4 | 1.717 | O8 | 1.993 |
µ2-O (Mo-O-K) | BVS value | µ3-O (Mo3-O) | BVS value |
O10 | 1.956 | O5 | 2.007 |
O9 | 1.920 | O6 | 1.996 |
O12 | 1.877 | µ5-O (Mo5-O) | BVS value |
O11 | 1.890 | O13 | 1.915 |
MicroRaman spectroscopic data analysis of the reaction at varying pH 2 to 6 toppH | Mo8O264- | Mo7O246- | SOM |
2 | 241, 292, 498, 545, 620, 732, 829, 851, 895, 917, 973 | – | 952, 415, 963 |
3 | 241, 292, 498, 545, 620, 732, 829, 851, 895, 917, 973 | – | 952, 415, 963 |
4 | 725, 849, 917 | 215, 365, 561, 903 | 953, 416 |
5 | 725, 851 | 216, 365, 568, 641, 866, 903, 946 | 416 |
6 | – | 442, 547, 614, 811, 900, 945 | – |
MicroRaman spectroscopic data analysis of reaction at varying pH from 2 to 6 toppH | Mo8O264- | Mo7O246- | SOM |
2 | 241, 292, 498, 545, 620, 732, 829, 851, 895, 917, 973 | - | 952, 415, 963 |
3 | 241, 292, 498, 545, 620, 732, 829, 851, 895, 917, 973 | - | 952, 415, 963 |
4 | 725, 849, 917 | 215, 365, 561, 903 | 953, 416 |
5 | 725, 851 | 216, 365, 568, 641, 866, 903, 946 | 416 |
6 | - | 442, 547, 614, 811, 900, 945 | - |
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