Synthesis, structural characterization and fluorescence enhancement of chromophore-modified polyoxometalates

Intra­molecular charge transfers between π-conjugated mol­ecules and polyoxometalate (POM) clusters have been observed in donor–acceptor systems based on organic donors and inorganic POM acceptors, which unfortunately results in a general quenching of the chromophore luminescence. The development of POM–chromophore dyads that are capable of tackling the quenching process and enhancing the fluorescence intensity of such systems remains a highly challenging area of study. A family of organic–inorganic polyoxometalate hybrids, {[(n-C₄H₉)₄N]₃[(MnMo₆O₂₄){(CH₂)₃CR}₂]} [1, R = –NHCH₂C₁₄H₉, namely (anthracen-9-ylmethyl)amino; 2, R = –NHCH₂C₁₃H₉, (9H-fluoren-2-ylmethyl)amino; 3, R = –NHCH₂C₁₀H₇, (naphthalen-2-ylmethyl)amino; 4, R = –NHCH₂C₁₆H₉, (pyren-2-ylmethyl)amino], were synthesized by covalently tethering π-conjugated mol­ecules onto an Anderson cluster. The resulting POM–chromophore dyads were fully characterized by various spectroscopic techniques, single-crystal X-ray diffraction analysis and ESI–MS. The fluorescence features of these dyads were studied in detail to verify a dramatic emission enhancement that can be achieved by fine-tuning the microenvironment in solution and suppressing the intrinsic photo-induced electron-transfer process.

Computing details

For all structures, data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011). Program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a) for (1), (3); SHELXL97 (Sheldrick, 2008) for (2). Program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b) for (1), (3); SHELXL97 (Sheldrick, 2008) for (2). Molecular graphics: SHELXL2014 (Sheldrick, 2015b) for (1); WinGX (Farrugia, 2012) for (2), (3). Software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b) for (1); WinGX (Farrugia, 2012) for (2), (3).

(1)

Crystal data

(C16H36N)3[Mo6MnO24(C19H18N)2]·C2H3N	F(000) = 4744
Mr = 2303.69	Dx = 1.567 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.2871 (2) Å	Cell parameters from 23888 reflections
b = 25.6540 (3) Å	θ = 2.9–29.1°
c = 24.9018 (4) Å	µ = 0.94 mm^−1
β = 90.321 (1)°	T = 149 K
V = 9765.7 (2) Å^3	Block, yellow
Z = 4	0.1 × 0.1 × 0.1 mm

Data collection

Agilent Xcalibur Eos Gemini diffractometer	18150 independent reflections
Radiation source: fine-focus sealed tube	15046 reflections with I > 2σ(I)
Detector resolution: 16.2141 pixels mm^-1	Rint = 0.041
ω scans	θmax = 25.5°, θmin = 2.9°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	h = −18→17
Tmin = 0.98, Tmax = 1.0	k = −30→31
63584 measured reflections	l = −30→30

Refinement

Refinement on F^2	51 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.046	H-atom parameters constrained
wR(F^2) = 0.106	w = 1/[σ^2(Fo^2) + (0.0001P)^2 + 272.2739P] where P = (Fo^2 + 2Fc^2)/3
S = 0.62	(Δ/σ)max = 0.001
18150 reflections	Δρmax = 1.88 e Å^−3
1138 parameters	Δρmin = −0.81 e Å^−3

Special details

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. Refined as a 2-component twin.

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

	x	y	z	Uiso*/Ueq
Mo1	0.99329 (3)	0.49988 (2)	0.63329 (2)	0.01616 (10)
Mo2	0.87435 (3)	0.41118 (2)	0.56407 (2)	0.01585 (10)
Mo3	1.11760 (3)	0.58878 (2)	0.57035 (2)	0.01574 (10)
Mo4	0.37145 (3)	0.91550 (2)	0.43201 (2)	0.01682 (10)
Mo5	0.35082 (3)	0.93027 (2)	0.56657 (2)	0.01618 (10)
Mo6	0.51775 (3)	0.98767 (2)	0.36493 (2)	0.01887 (11)
Mn1	1.0000	0.5000	0.5000	0.0098 (2)
Mn2	0.5000	1.0000	0.5000	0.0116 (2)
O1	1.0278 (3)	0.45195 (17)	0.67615 (16)	0.0251 (9)
O2	0.9542 (3)	0.54823 (18)	0.67348 (17)	0.0270 (10)
O3	1.1069 (2)	0.52685 (15)	0.61395 (15)	0.0174 (8)
O4	0.8827 (3)	0.47218 (16)	0.60848 (15)	0.0186 (8)
O5	0.9747 (2)	0.54970 (14)	0.55501 (15)	0.0149 (8)
O6	0.7641 (3)	0.40026 (17)	0.56555 (18)	0.0264 (9)
O7	0.9109 (2)	0.37954 (14)	0.49779 (16)	0.0185 (8)
O8	1.2272 (3)	0.60069 (16)	0.57656 (17)	0.0246 (9)
O9	1.0673 (3)	0.63391 (16)	0.61013 (17)	0.0254 (9)
O10	1.0202 (2)	0.45030 (14)	0.55681 (14)	0.0142 (8)
O11	0.8693 (2)	0.47261 (13)	0.49686 (15)	0.0119 (7)
O12	0.9186 (3)	0.36487 (16)	0.60553 (17)	0.0264 (10)
O13	0.4054 (3)	0.86157 (17)	0.39811 (17)	0.0271 (10)
O14	0.3838 (3)	0.89035 (14)	0.50453 (15)	0.0173 (8)
O15	0.2603 (3)	0.91705 (17)	0.42429 (17)	0.0268 (10)
O16	0.2406 (3)	0.93745 (16)	0.55677 (17)	0.0248 (9)
O17	0.3754 (2)	0.98829 (13)	0.49335 (15)	0.0158 (8)
O18	0.4993 (2)	0.95059 (14)	0.56529 (16)	0.0169 (8)
O19	0.3690 (3)	0.99312 (15)	0.60715 (15)	0.0185 (8)
O20	0.5484 (3)	0.93299 (18)	0.33164 (18)	0.0326 (11)
O21	0.3606 (3)	0.88288 (16)	0.61450 (17)	0.0274 (10)
O22	0.4980 (3)	1.03295 (18)	0.31641 (18)	0.0318 (11)
O23	0.3992 (3)	0.97155 (16)	0.38355 (15)	0.0200 (9)
O24	0.5165 (2)	0.94170 (14)	0.44906 (15)	0.0174 (8)
C1	1.1946 (3)	0.4856 (2)	0.5057 (2)	0.0175 (11)
H1A	1.2281	0.4892	0.5387	0.021*
H1B	1.2347	0.4894	0.4760	0.021*
C2	1.0987 (4)	0.4199 (2)	0.5538 (2)	0.0189 (12)
H2A	1.0830	0.3833	0.5543	0.023*
H2B	1.1339	0.4267	0.5856	0.023*
C3	0.8973 (4)	0.5814 (2)	0.5476 (2)	0.0191 (12)
H3A	0.9147	0.6178	0.5470	0.023*
H3B	0.8594	0.5765	0.5783	0.023*
C4	1.1549 (4)	0.4305 (2)	0.5037 (2)	0.0160 (11)
C5	1.2877 (4)	0.3842 (2)	0.4647 (2)	0.0195 (12)
H5A	1.2720	0.4075	0.4355	0.023*
H5B	1.2801	0.3487	0.4519	0.023*
C6	1.3835 (4)	0.3926 (2)	0.4789 (2)	0.0206 (12)
C7	1.4233 (4)	0.3581 (2)	0.5157 (2)	0.0233 (13)
C8	1.3774 (4)	0.3157 (2)	0.5403 (3)	0.0286 (14)
H8	1.3189	0.3102	0.5318	0.034*
C9	1.4178 (5)	0.2834 (3)	0.5759 (3)	0.0393 (17)
H9	1.3864	0.2562	0.5912	0.047*
C10	1.5071 (5)	0.2906 (3)	0.5900 (3)	0.0433 (19)
H10	1.5336	0.2685	0.6148	0.052*
C11	1.5540 (5)	0.3298 (3)	0.5671 (3)	0.0409 (18)
H11	1.6126	0.3341	0.5763	0.049*
C12	1.5147 (4)	0.3642 (3)	0.5293 (3)	0.0311 (15)
C13	1.5626 (4)	0.4033 (3)	0.5036 (3)	0.0344 (16)
H13	1.6218	0.4066	0.5115	0.041*
C14	1.5257 (4)	0.4367 (3)	0.4672 (3)	0.0312 (15)
C15	1.5757 (5)	0.4766 (3)	0.4422 (3)	0.0437 (19)
H15	1.6353	0.4787	0.4494	0.052*
C16	1.5391 (5)	0.5113 (3)	0.4083 (3)	0.046 (2)
H16	1.5735	0.5367	0.3921	0.056*
C17	1.4488 (5)	0.5090 (3)	0.3974 (3)	0.0423 (18)
H17	1.4236	0.5340	0.3751	0.051*
C18	1.3976 (5)	0.4712 (3)	0.4187 (2)	0.0299 (15)
H18	1.3385	0.4702	0.4097	0.036*
C19	1.4327 (4)	0.4326 (2)	0.4551 (2)	0.0237 (13)
C20	0.3210 (4)	1.0331 (2)	0.4837 (3)	0.0211 (13)
H20A	0.2769	1.0349	0.5115	0.025*
H20B	0.2910	1.0286	0.4496	0.025*
C21	0.5827 (4)	0.9040 (2)	0.4634 (2)	0.0220 (13)
H21A	0.6263	0.9032	0.4353	0.026*
H21B	0.5558	0.8698	0.4649	0.026*
C22	0.4337 (4)	1.0884 (2)	0.4346 (2)	0.0211 (12)
H22A	0.3998	1.0852	0.4017	0.025*
H22B	0.4611	1.1225	0.4345	0.025*
C23	0.3710 (4)	1.0853 (2)	0.4826 (2)	0.0180 (12)
C24	0.3218 (4)	1.1796 (2)	0.4748 (3)	0.0281 (14)
H24A	0.3693	1.1870	0.4503	0.034*
H24B	0.3407	1.1889	0.5108	0.034*
C25	0.2413 (4)	1.2118 (2)	0.4591 (3)	0.0284 (15)
C26	0.2253 (5)	1.2231 (3)	0.4053 (3)	0.0336 (16)
C27	0.2776 (6)	1.2040 (3)	0.3623 (3)	0.048 (2)
H27	0.3243	1.1820	0.3701	0.058*
C28	0.2609 (7)	1.2172 (4)	0.3097 (4)	0.062 (2)
H28	0.2967	1.2043	0.2827	0.074*
C29	0.1905 (7)	1.2500 (4)	0.2961 (4)	0.069 (3)
H29	0.1804	1.2589	0.2604	0.083*
C30	0.1379 (6)	1.2685 (4)	0.3346 (4)	0.058 (2)
H30	0.0914	1.2900	0.3250	0.070*
C31	0.1515 (5)	1.2557 (3)	0.3906 (3)	0.0402 (18)
C32	0.0968 (5)	1.2741 (3)	0.4303 (4)	0.042 (2)
H32	0.0497	1.2951	0.4207	0.051*
C33	0.1103 (4)	1.2619 (2)	0.4845 (3)	0.0333 (17)
C34	0.0539 (4)	1.2810 (2)	0.5254 (3)	0.0362 (17)
H34	0.0075	1.3027	0.5161	0.043*
C35	0.0667 (5)	1.2683 (3)	0.5772 (4)	0.044 (2)
H35	0.0292	1.2812	0.6033	0.053*
C36	0.1374 (5)	1.2352 (3)	0.5925 (3)	0.0439 (19)
H36	0.1449	1.2259	0.6283	0.053*
C37	0.1940 (5)	1.2171 (3)	0.5549 (3)	0.0363 (17)
H37	0.2404	1.1960	0.5657	0.044*
C38	0.1843 (4)	1.2294 (2)	0.4996 (3)	0.0285 (14)
C39	0.2105 (5)	0.7388 (2)	0.4737 (2)	0.0316 (15)
H39A	0.2365	0.7047	0.4791	0.038*
H39B	0.1486	0.7337	0.4668	0.038*
C40	0.2509 (5)	0.7631 (3)	0.4244 (2)	0.0355 (16)
H40A	0.2301	0.7986	0.4208	0.043*
H40B	0.3139	0.7642	0.4290	0.043*
C41	0.2292 (5)	0.7334 (3)	0.3740 (2)	0.0400 (18)
H41A	0.1662	0.7325	0.3694	0.048*
H41B	0.2493	0.6977	0.3780	0.048*
C42	0.2700 (5)	0.7568 (3)	0.3243 (3)	0.051 (2)
H42A	0.2510	0.7922	0.3204	0.076*
H42B	0.2523	0.7371	0.2933	0.076*
H42C	0.3326	0.7559	0.3277	0.076*
C43	0.3165 (4)	0.7764 (2)	0.5397 (3)	0.0361 (17)
H43A	0.3461	0.7918	0.5092	0.043*
H43B	0.3207	0.8009	0.5692	0.043*
C44	0.3651 (4)	0.7273 (3)	0.5555 (3)	0.0419 (18)
H44A	0.3602	0.7020	0.5267	0.050*
H44B	0.3383	0.7125	0.5872	0.050*
C45	0.4611 (5)	0.7378 (4)	0.5669 (3)	0.053 (2)
H45A	0.4924	0.7049	0.5666	0.064*
H45B	0.4844	0.7592	0.5383	0.064*
C46	0.4779 (7)	0.7641 (4)	0.6188 (4)	0.078 (3)
H46A	0.4626	0.8003	0.6158	0.116*
H46B	0.5387	0.7610	0.6279	0.116*
H46C	0.4432	0.7481	0.6462	0.116*
C47	0.1729 (5)	0.7409 (3)	0.5694 (3)	0.0392 (18)
H47A	0.1134	0.7345	0.5575	0.047*
H47B	0.2008	0.7072	0.5744	0.047*
C48	0.1698 (6)	0.7684 (3)	0.6236 (3)	0.059 (3)
H48A	0.2257	0.7851	0.6303	0.070*
H48B	0.1255	0.7954	0.6222	0.070*
C49	0.1497 (6)	0.7318 (3)	0.6699 (3)	0.064 (3)
H49A	0.1369	0.7527	0.7014	0.077*
H49B	0.0973	0.7122	0.6610	0.077*
C50	0.2209 (6)	0.6939 (4)	0.6841 (3)	0.066 (2)
H50A	0.2292	0.6701	0.6549	0.098*
H50B	0.2048	0.6749	0.7157	0.098*
H50C	0.2743	0.7126	0.6908	0.098*
C51	0.1834 (4)	0.8244 (2)	0.5190 (3)	0.044 (2)
H51A	0.1892	0.8423	0.5531	0.052*
H51B	0.2186	0.8432	0.4931	0.052*
C52	0.0888 (5)	0.8274 (3)	0.5012 (4)	0.060 (3)
H52A	0.0523	0.8076	0.5256	0.072*
H52B	0.0823	0.8129	0.4655	0.072*
C53	0.0612 (7)	0.8844 (3)	0.5012 (6)	0.086 (4)
H53A	0.0652	0.8983	0.5374	0.103*
H53B	0.1001	0.9044	0.4785	0.103*
C54	−0.0295 (8)	0.8894 (6)	0.4812 (6)	0.138 (7)
H54A	−0.0347	0.8724	0.4470	0.208*
H54B	−0.0440	0.9256	0.4775	0.208*
H54C	−0.0687	0.8733	0.5062	0.208*
C55	0.3171 (4)	0.9621 (3)	0.2590 (3)	0.0335 (16)
H55A	0.3648	0.9853	0.2684	0.040*
H55B	0.3131	0.9359	0.2869	0.040*
C56	0.3392 (5)	0.9353 (3)	0.2069 (3)	0.0371 (16)
H56A	0.2893	0.9152	0.1945	0.045*
H56B	0.3527	0.9612	0.1798	0.045*
C57	0.4169 (6)	0.8996 (4)	0.2148 (4)	0.065 (3)
H57A	0.4644	0.9192	0.2311	0.078*
H57B	0.4010	0.8720	0.2395	0.078*
C58	0.4475 (8)	0.8764 (5)	0.1644 (5)	0.083 (3)
H58A	0.3983	0.8631	0.1445	0.124*
H58B	0.4873	0.8484	0.1723	0.124*
H58C	0.4768	0.9024	0.1435	0.124*
C59	0.1537 (4)	0.9588 (3)	0.2490 (3)	0.0296 (14)
H59A	0.1590	0.9435	0.2136	0.036*
H59B	0.1018	0.9806	0.2486	0.036*
C60	0.1390 (5)	0.9153 (3)	0.2887 (3)	0.0378 (17)
H60A	0.1886	0.8917	0.2883	0.045*
H60B	0.1340	0.9296	0.3246	0.045*
C61	0.0556 (5)	0.8855 (3)	0.2742 (3)	0.045 (2)
H61A	0.0066	0.9095	0.2747	0.054*
H61B	0.0609	0.8720	0.2380	0.054*
C62	0.0364 (7)	0.8403 (4)	0.3122 (4)	0.073 (3)
H62A	0.0838	0.8157	0.3111	0.110*
H62B	−0.0168	0.8233	0.3012	0.110*
H62C	0.0301	0.8533	0.3481	0.110*
C63	0.2264 (5)	1.0206 (3)	0.3125 (3)	0.0374 (17)
H63A	0.2229	0.9943	0.3403	0.045*
H63B	0.2800	1.0401	0.3184	0.045*
C64	0.1496 (5)	1.0575 (3)	0.3186 (3)	0.0436 (19)
H64A	0.0964	1.0398	0.3074	0.052*
H64B	0.1578	1.0873	0.2953	0.052*
C65	0.1396 (6)	1.0763 (4)	0.3767 (3)	0.064 (3)
H65A	0.0980	1.1048	0.3785	0.077*
H65B	0.1954	1.0883	0.3908	0.077*
C66	0.1047 (12)	1.0267 (7)	0.4106 (7)	0.140 (6)
H66A	0.1530	1.0043	0.4194	0.209*
H66B	0.0628	1.0077	0.3894	0.209*
H66C	0.0775	1.0386	0.4430	0.209*
C67	0.2325 (5)	1.0336 (3)	0.2128 (3)	0.0322 (15)
H67A	0.2337	1.0148	0.1789	0.039*
H67B	0.1779	1.0528	0.2139	0.039*
C68	0.3072 (5)	1.0724 (3)	0.2132 (3)	0.0401 (18)
H68A	0.3624	1.0538	0.2115	0.048*
H68B	0.3063	1.0921	0.2464	0.048*
C69	0.3002 (5)	1.1095 (3)	0.1659 (3)	0.0383 (17)
H69A	0.3533	1.1301	0.1642	0.046*
H69B	0.2963	1.0893	0.1331	0.046*
C70	0.2221 (5)	1.1462 (3)	0.1683 (3)	0.0429 (19)
H70A	0.1690	1.1264	0.1660	0.064*
H70B	0.2247	1.1703	0.1389	0.064*
H70C	0.2234	1.1651	0.2016	0.064*
C71	0.2026 (5)	0.5300 (4)	0.1870 (3)	0.055 (2)
H71A	0.2001	0.5592	0.1622	0.066*
H71B	0.2503	0.5077	0.1757	0.066*
C72	0.1180 (6)	0.4995 (4)	0.1814 (4)	0.072 (3)
H72A	0.1128	0.4754	0.2112	0.086*
H72B	0.0688	0.5233	0.1827	0.086*
C73	0.1155 (9)	0.4695 (6)	0.1289 (4)	0.118 (6)
H73A	0.0568	0.4560	0.1239	0.142*
H73B	0.1266	0.4938	0.0999	0.142*
C74	0.1783 (10)	0.4250 (7)	0.1236 (7)	0.178 (11)
H74A	0.2372	0.4378	0.1260	0.266*
H74B	0.1695	0.4082	0.0895	0.266*
H74C	0.1684	0.4003	0.1519	0.266*
C75	0.2316 (6)	0.5063 (3)	0.2821 (3)	0.049 (2)
H75A	0.2427	0.5211	0.3173	0.059*
H75B	0.1750	0.4894	0.2835	0.059*
C76	0.2994 (6)	0.4646 (4)	0.2726 (5)	0.082 (3)
H76A	0.3558	0.4761	0.2862	0.098*
H76B	0.3050	0.4581	0.2344	0.098*
C77	0.2716 (10)	0.4149 (4)	0.3013 (5)	0.125 (6)
H77A	0.2470	0.4251	0.3355	0.149*
H77B	0.2245	0.3996	0.2803	0.149*
C78	0.3360 (10)	0.3735 (6)	0.3120 (8)	0.152 (7)
H78A	0.3647	0.3642	0.2792	0.227*
H78B	0.3067	0.3435	0.3263	0.227*
H78C	0.3786	0.3858	0.3375	0.227*
C79	0.1508 (6)	0.5858 (3)	0.2613 (4)	0.058 (3)
H79A	0.1646	0.5981	0.2972	0.070*
H79B	0.0979	0.5651	0.2636	0.070*
C80	0.1326 (7)	0.6324 (4)	0.2261 (6)	0.100 (4)
H80A	0.1522	0.6244	0.1901	0.120*
H80B	0.1677	0.6614	0.2391	0.120*
C81	0.0380 (7)	0.6502 (5)	0.2228 (5)	0.091 (3)
H81A	0.0291	0.6737	0.1928	0.109*
H81B	−0.0012	0.6207	0.2190	0.109*
C82	0.0243 (11)	0.6770 (5)	0.2742 (4)	0.124 (6)
H82A	0.0035	0.6526	0.3003	0.185*
H82B	−0.0182	0.7043	0.2694	0.185*
H82C	0.0785	0.6919	0.2864	0.185*
C83	0.3098 (5)	0.5802 (3)	0.2375 (3)	0.0440 (19)
H83A	0.3546	0.5557	0.2264	0.053*
H83B	0.3036	0.6059	0.2092	0.053*
C84	0.3411 (5)	0.6076 (3)	0.2878 (3)	0.052 (2)
H84A	0.3074	0.6393	0.2928	0.062*
H84B	0.3309	0.5852	0.3186	0.062*
C85	0.4362 (6)	0.6210 (4)	0.2855 (4)	0.068 (3)
H85A	0.4695	0.5894	0.2795	0.081*
H85B	0.4542	0.6352	0.3199	0.081*
C86	0.4580 (7)	0.6594 (4)	0.2424 (4)	0.086 (4)
H86A	0.4471	0.6441	0.2079	0.129*
H86B	0.5186	0.6689	0.2453	0.129*
H86C	0.4223	0.6900	0.2465	0.129*
C88	0.4542 (10)	0.1903 (5)	0.6975 (6)	0.104 (5)
H88A	0.4627	0.1652	0.7256	0.156*
H88B	0.4746	0.2238	0.7094	0.156*
H88C	0.4864	0.1799	0.6663	0.156*
C89	0.3682 (12)	0.1934 (8)	0.6850 (8)	0.161 (9)
N1	1.2276 (3)	0.39318 (19)	0.5097 (2)	0.0213 (11)
H1	1.2348	0.3767	0.5394	0.026*
N2	0.3008 (3)	1.12401 (18)	0.4728 (2)	0.0216 (11)
H2	0.2482	1.1139	0.4661	0.026*
N3	0.2208 (3)	0.76992 (19)	0.5252 (2)	0.0356 (14)
N4	0.2245 (3)	0.5511 (2)	0.2424 (2)	0.0380 (15)
N5	0.2323 (4)	0.9936 (2)	0.2585 (2)	0.0282 (12)
N6	0.2932 (14)	0.1903 (8)	0.6760 (8)	0.182 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mo1	0.0153 (2)	0.0221 (2)	0.0110 (2)	−0.00164 (19)	−0.00041 (18)	0.00061 (19)
Mo2	0.0145 (2)	0.0169 (2)	0.0161 (2)	−0.00356 (18)	−0.00020 (19)	0.00444 (19)
Mo3	0.0160 (2)	0.0153 (2)	0.0158 (2)	−0.00304 (19)	−0.00302 (19)	−0.00195 (19)
Mo4	0.0182 (2)	0.0184 (2)	0.0138 (2)	−0.00593 (19)	−0.00121 (19)	−0.00076 (19)
Mo5	0.0193 (2)	0.0147 (2)	0.0146 (2)	−0.00472 (19)	0.00278 (19)	−0.00173 (19)
Mo6	0.0223 (3)	0.0227 (3)	0.0116 (2)	−0.0074 (2)	0.00040 (19)	−0.00134 (19)
Mn1	0.0086 (5)	0.0105 (5)	0.0103 (5)	−0.0005 (4)	−0.0010 (4)	0.0015 (4)
Mn2	0.0119 (5)	0.0118 (5)	0.0110 (5)	−0.0028 (4)	−0.0004 (4)	−0.0003 (4)
O1	0.022 (2)	0.034 (2)	0.019 (2)	−0.0062 (19)	−0.0055 (17)	0.0115 (18)
O2	0.026 (2)	0.034 (2)	0.021 (2)	−0.0026 (19)	0.0024 (18)	−0.0077 (19)
O3	0.017 (2)	0.021 (2)	0.0140 (19)	−0.0002 (16)	−0.0025 (15)	−0.0026 (16)
O4	0.0163 (19)	0.027 (2)	0.0125 (19)	−0.0022 (17)	0.0016 (16)	0.0023 (16)
O5	0.0117 (18)	0.0158 (19)	0.017 (2)	0.0030 (15)	−0.0005 (15)	0.0001 (15)
O6	0.021 (2)	0.031 (2)	0.028 (2)	−0.0079 (18)	−0.0014 (18)	0.0032 (19)
O7	0.021 (2)	0.0129 (19)	0.021 (2)	−0.0024 (15)	−0.0024 (17)	0.0004 (16)
O8	0.023 (2)	0.025 (2)	0.026 (2)	−0.0066 (18)	−0.0043 (18)	−0.0008 (18)
O9	0.029 (2)	0.020 (2)	0.027 (2)	0.0009 (18)	−0.0008 (19)	−0.0053 (18)
O10	0.0129 (18)	0.0161 (18)	0.0135 (19)	0.0027 (15)	0.0023 (15)	0.0036 (15)
O11	0.0080 (17)	0.0130 (17)	0.0146 (18)	0.0021 (14)	−0.0010 (14)	0.0039 (15)
O12	0.031 (2)	0.024 (2)	0.025 (2)	−0.0042 (19)	0.0001 (19)	0.0115 (18)
O13	0.033 (2)	0.027 (2)	0.022 (2)	−0.0059 (19)	0.0046 (19)	−0.0056 (18)
O14	0.024 (2)	0.0103 (17)	0.017 (2)	−0.0028 (16)	0.0013 (17)	−0.0020 (15)
O15	0.020 (2)	0.034 (2)	0.026 (2)	−0.0050 (19)	−0.0037 (18)	0.0026 (19)
O16	0.023 (2)	0.021 (2)	0.030 (2)	−0.0032 (18)	0.0021 (18)	−0.0081 (18)
O17	0.0174 (19)	0.0110 (18)	0.019 (2)	0.0016 (15)	−0.0007 (16)	0.0002 (15)
O18	0.0152 (19)	0.0158 (18)	0.020 (2)	0.0037 (15)	−0.0025 (16)	−0.0029 (16)
O19	0.017 (2)	0.020 (2)	0.018 (2)	−0.0028 (16)	0.0049 (16)	−0.0038 (16)
O20	0.039 (3)	0.034 (3)	0.025 (2)	−0.011 (2)	0.007 (2)	−0.011 (2)
O21	0.044 (3)	0.019 (2)	0.019 (2)	−0.006 (2)	0.0042 (19)	−0.0018 (17)
O22	0.037 (3)	0.035 (3)	0.023 (2)	−0.011 (2)	−0.004 (2)	0.008 (2)
O23	0.020 (2)	0.026 (2)	0.014 (2)	−0.0039 (17)	−0.0032 (16)	−0.0014 (16)
O24	0.0169 (19)	0.0170 (19)	0.018 (2)	−0.0013 (16)	−0.0012 (16)	0.0046 (16)
C1	0.010 (2)	0.020 (3)	0.023 (3)	0.000 (2)	−0.002 (2)	−0.001 (2)
C2	0.020 (3)	0.019 (3)	0.017 (3)	0.003 (2)	0.005 (2)	0.006 (2)
C3	0.018 (3)	0.017 (3)	0.022 (3)	0.005 (2)	−0.003 (2)	−0.002 (2)
C4	0.017 (3)	0.011 (2)	0.020 (3)	0.002 (2)	0.001 (2)	0.000 (2)
C5	0.015 (3)	0.022 (3)	0.022 (3)	0.000 (2)	0.000 (2)	−0.002 (2)
C6	0.016 (3)	0.025 (3)	0.020 (3)	0.003 (2)	0.002 (2)	−0.005 (2)
C7	0.018 (3)	0.028 (3)	0.024 (3)	0.004 (2)	0.000 (2)	−0.005 (3)
C8	0.026 (3)	0.029 (3)	0.031 (3)	0.010 (3)	−0.002 (3)	−0.004 (3)
C9	0.045 (4)	0.038 (4)	0.034 (4)	0.013 (3)	−0.003 (3)	0.002 (3)
C10	0.041 (4)	0.056 (5)	0.033 (4)	0.019 (4)	−0.013 (3)	0.006 (4)
C11	0.029 (4)	0.059 (5)	0.034 (4)	0.013 (3)	−0.012 (3)	−0.008 (4)
C12	0.021 (3)	0.040 (4)	0.032 (4)	0.010 (3)	−0.005 (3)	−0.010 (3)
C13	0.016 (3)	0.045 (4)	0.042 (4)	0.000 (3)	−0.001 (3)	−0.009 (3)
C14	0.021 (3)	0.038 (4)	0.035 (4)	−0.004 (3)	0.003 (3)	−0.009 (3)
C15	0.027 (4)	0.055 (5)	0.049 (5)	−0.016 (3)	0.009 (3)	−0.014 (4)
C16	0.046 (5)	0.044 (5)	0.050 (5)	−0.020 (4)	0.016 (4)	−0.002 (4)
C17	0.054 (5)	0.032 (4)	0.041 (4)	−0.010 (4)	0.006 (4)	0.002 (3)
C18	0.032 (4)	0.037 (4)	0.021 (3)	−0.002 (3)	0.002 (3)	−0.002 (3)
C19	0.019 (3)	0.028 (3)	0.024 (3)	−0.004 (3)	0.003 (2)	−0.009 (3)
C20	0.018 (3)	0.014 (3)	0.031 (3)	0.000 (2)	−0.003 (2)	0.001 (2)
C21	0.018 (3)	0.023 (3)	0.025 (3)	0.005 (2)	−0.002 (2)	−0.001 (2)
C22	0.021 (3)	0.017 (3)	0.026 (3)	0.005 (2)	0.000 (3)	0.002 (2)
C23	0.018 (3)	0.013 (3)	0.023 (3)	0.002 (2)	−0.004 (2)	−0.001 (2)
C24	0.024 (3)	0.021 (3)	0.039 (4)	0.002 (3)	−0.006 (3)	−0.002 (3)
C25	0.023 (3)	0.015 (3)	0.048 (4)	0.000 (3)	−0.004 (3)	−0.002 (3)
C26	0.029 (4)	0.023 (3)	0.049 (4)	0.001 (3)	−0.011 (3)	−0.002 (3)
C27	0.048 (5)	0.045 (5)	0.051 (5)	0.006 (4)	−0.005 (4)	−0.009 (4)
C28	0.066 (6)	0.073 (7)	0.046 (5)	0.006 (5)	−0.003 (5)	−0.003 (5)
C29	0.066 (6)	0.093 (8)	0.048 (6)	0.006 (6)	−0.014 (5)	0.010 (5)
C30	0.052 (5)	0.054 (5)	0.068 (6)	0.011 (4)	−0.026 (5)	0.013 (5)
C31	0.039 (4)	0.023 (3)	0.058 (5)	0.003 (3)	−0.011 (4)	0.001 (3)
C32	0.030 (4)	0.019 (3)	0.077 (6)	0.003 (3)	−0.023 (4)	0.002 (4)
C33	0.022 (3)	0.011 (3)	0.067 (5)	−0.001 (2)	−0.001 (3)	−0.006 (3)
C34	0.024 (3)	0.016 (3)	0.069 (5)	0.001 (3)	−0.001 (3)	−0.011 (3)
C35	0.034 (4)	0.028 (4)	0.070 (6)	−0.002 (3)	0.011 (4)	−0.015 (4)
C36	0.046 (5)	0.039 (4)	0.046 (5)	−0.009 (4)	0.006 (4)	−0.003 (3)
C37	0.028 (4)	0.024 (3)	0.057 (5)	−0.001 (3)	−0.005 (3)	0.000 (3)
C38	0.026 (3)	0.013 (3)	0.046 (4)	−0.005 (2)	−0.005 (3)	−0.001 (3)
C39	0.034 (4)	0.020 (3)	0.040 (4)	−0.005 (3)	0.009 (3)	−0.003 (3)
C40	0.033 (4)	0.028 (3)	0.046 (4)	−0.002 (3)	0.010 (3)	0.002 (3)
C41	0.039 (4)	0.041 (4)	0.040 (4)	0.001 (3)	−0.003 (3)	0.013 (3)
C42	0.048 (5)	0.057 (5)	0.046 (5)	0.002 (4)	0.006 (4)	0.017 (4)
C43	0.036 (4)	0.027 (4)	0.045 (4)	−0.017 (3)	0.013 (3)	−0.014 (3)
C44	0.041 (4)	0.039 (4)	0.046 (5)	−0.006 (3)	0.010 (4)	0.002 (3)
C45	0.050 (5)	0.066 (6)	0.042 (5)	−0.010 (4)	0.014 (4)	−0.008 (4)
C46	0.071 (7)	0.071 (7)	0.091 (9)	−0.002 (6)	0.002 (6)	−0.003 (6)
C47	0.043 (4)	0.026 (3)	0.048 (5)	−0.016 (3)	0.021 (4)	−0.013 (3)
C48	0.073 (6)	0.041 (5)	0.061 (6)	−0.019 (4)	0.035 (5)	−0.030 (4)
C49	0.092 (7)	0.046 (5)	0.055 (6)	−0.029 (4)	0.043 (5)	−0.031 (4)
C50	0.094 (7)	0.068 (6)	0.034 (5)	−0.031 (4)	0.020 (5)	−0.018 (4)
C51	0.040 (4)	0.017 (3)	0.075 (6)	−0.008 (3)	0.016 (4)	−0.012 (3)
C52	0.040 (5)	0.040 (4)	0.100 (7)	−0.005 (4)	0.015 (5)	−0.013 (5)
C53	0.073 (7)	0.052 (5)	0.132 (10)	0.019 (5)	−0.033 (7)	−0.028 (7)
C54	0.159 (15)	0.142 (14)	0.114 (12)	0.091 (12)	−0.050 (11)	−0.037 (10)
C55	0.031 (4)	0.038 (4)	0.032 (4)	0.003 (3)	−0.013 (3)	0.000 (3)
C56	0.035 (4)	0.040 (4)	0.036 (4)	0.004 (3)	−0.001 (3)	−0.002 (3)
C57	0.062 (6)	0.070 (7)	0.062 (6)	0.026 (5)	−0.015 (5)	−0.019 (5)
C58	0.079 (8)	0.075 (8)	0.094 (9)	0.012 (6)	−0.001 (7)	−0.004 (7)
C59	0.030 (3)	0.036 (4)	0.023 (3)	−0.001 (3)	−0.007 (3)	−0.003 (3)
C60	0.054 (5)	0.036 (4)	0.024 (3)	0.003 (4)	−0.006 (3)	0.005 (3)
C61	0.052 (5)	0.038 (4)	0.045 (5)	0.003 (4)	0.017 (4)	0.009 (4)
C62	0.087 (8)	0.049 (6)	0.084 (8)	−0.002 (5)	0.023 (6)	0.020 (5)
C63	0.042 (4)	0.040 (4)	0.030 (4)	0.005 (3)	−0.020 (3)	−0.005 (3)
C64	0.042 (4)	0.050 (5)	0.038 (4)	0.013 (4)	−0.013 (3)	−0.010 (4)
C65	0.055 (6)	0.093 (7)	0.045 (5)	0.022 (5)	−0.016 (4)	−0.038 (4)
C66	0.146 (16)	0.136 (13)	0.137 (15)	−0.002 (12)	0.024 (12)	0.005 (10)
C67	0.031 (4)	0.039 (4)	0.026 (3)	−0.001 (3)	−0.011 (3)	0.003 (3)
C68	0.028 (4)	0.040 (4)	0.052 (5)	−0.002 (3)	−0.014 (3)	0.005 (4)
C69	0.035 (4)	0.033 (4)	0.046 (5)	−0.004 (3)	−0.003 (3)	0.003 (3)
C70	0.053 (5)	0.034 (4)	0.041 (4)	0.006 (4)	−0.012 (4)	0.000 (3)
C71	0.042 (5)	0.099 (7)	0.024 (4)	−0.020 (5)	0.006 (3)	0.008 (4)
C72	0.040 (5)	0.116 (9)	0.060 (6)	−0.026 (6)	0.011 (4)	0.022 (6)
C73	0.101 (10)	0.199 (17)	0.055 (7)	−0.111 (12)	−0.005 (7)	0.010 (9)
C74	0.122 (14)	0.24 (2)	0.175 (18)	−0.112 (15)	0.080 (13)	−0.125 (17)
C75	0.067 (6)	0.047 (5)	0.034 (4)	0.021 (4)	0.000 (4)	0.007 (4)
C76	0.063 (7)	0.071 (6)	0.112 (9)	0.034 (5)	−0.032 (6)	−0.033 (5)
C77	0.232 (17)	0.060 (6)	0.080 (9)	0.058 (7)	−0.066 (10)	−0.009 (5)
C78	0.129 (14)	0.102 (11)	0.22 (2)	0.050 (9)	−0.037 (14)	−0.030 (13)
C79	0.057 (5)	0.052 (5)	0.066 (6)	0.023 (4)	0.037 (5)	0.029 (4)
C80	0.095 (6)	0.076 (6)	0.128 (8)	0.016 (6)	0.021 (6)	0.049 (6)
C81	0.091 (5)	0.089 (7)	0.092 (6)	0.008 (6)	−0.004 (6)	−0.007 (5)
C82	0.205 (17)	0.118 (11)	0.049 (6)	0.043 (11)	0.041 (9)	0.042 (5)
C83	0.048 (5)	0.060 (5)	0.024 (4)	0.004 (4)	0.010 (3)	−0.012 (3)
C84	0.073 (6)	0.053 (5)	0.028 (4)	0.014 (5)	0.000 (4)	−0.008 (4)
C85	0.081 (7)	0.073 (7)	0.050 (6)	0.002 (6)	−0.004 (5)	−0.025 (5)
C86	0.069 (7)	0.115 (10)	0.076 (8)	−0.040 (7)	0.008 (6)	−0.045 (7)
C88	0.147 (14)	0.052 (7)	0.113 (11)	0.002 (8)	0.030 (10)	0.017 (7)
C89	0.094 (12)	0.22 (2)	0.165 (17)	−0.005 (13)	−0.018 (11)	0.147 (16)
N1	0.018 (2)	0.021 (2)	0.025 (3)	0.009 (2)	0.003 (2)	0.005 (2)
N2	0.012 (2)	0.017 (2)	0.036 (3)	−0.0003 (19)	−0.007 (2)	0.000 (2)
N3	0.040 (3)	0.020 (3)	0.047 (4)	−0.011 (3)	0.016 (3)	−0.011 (3)
N4	0.033 (3)	0.058 (4)	0.023 (3)	0.010 (3)	0.013 (2)	0.010 (3)
N5	0.028 (3)	0.035 (3)	0.021 (3)	0.001 (2)	−0.009 (2)	−0.001 (2)

Geometric parameters (Å, º)

Mn1—O5^i	1.912 (4)	C15—C16	1.346 (12)
Mn1—O5	1.912 (4)	C16—C17	1.408 (11)
Mn1—O10^i	1.928 (4)	C17—C18	1.356 (10)
Mn1—O10	1.928 (4)	C18—C19	1.445 (9)
Mn1—O11	2.120 (3)	C20—C23	1.542 (8)
Mn1—O11^i	2.120 (3)	C21—C23^ii	1.541 (8)
Mn2—O17^ii	1.934 (4)	C22—O18^ii	1.432 (6)
Mn2—O17	1.934 (4)	C22—C23	1.536 (8)
Mn2—O24	1.978 (4)	C23—N2	1.482 (7)
Mn2—O24^ii	1.978 (4)	C23—C21^ii	1.541 (8)
Mn2—O18	2.062 (4)	C24—N2	1.462 (8)
Mn2—O18^ii	2.062 (4)	C24—C25	1.531 (9)
Mo1—O1	1.710 (4)	C25—C26	1.392 (10)
Mo1—O2	1.704 (4)	C25—C38	1.412 (10)
Mo1—O3	1.933 (4)	C26—C27	1.426 (11)
Mo1—O4	1.932 (4)	C26—C31	1.448 (10)
Mo1—O5	2.347 (4)	C27—C28	1.376 (12)
Mo1—O10	2.329 (4)	C28—C29	1.407 (13)
Mo2—O6	1.709 (4)	C29—C30	1.340 (14)
Mo2—O12	1.711 (4)	C30—C31	1.449 (12)
Mo2—O4	1.920 (4)	C31—C32	1.381 (11)
Mo2—O7	1.925 (4)	C32—C33	1.401 (11)
Mo2—O11	2.300 (3)	C33—C34	1.425 (10)
Mo2—O10	2.453 (4)	C33—C38	1.452 (9)
Mo3—O9	1.709 (4)	C34—C35	1.344 (11)
Mo3—O8	1.709 (4)	C35—C36	1.425 (11)
Mo3—O7^i	1.929 (4)	C36—C37	1.360 (10)
Mo3—O3	1.932 (4)	C37—C38	1.420 (10)
Mo3—O11^i	2.308 (4)	C39—C40	1.510 (7)
Mo3—O5	2.432 (4)	C39—N3	1.519 (6)
Mo4—O13	1.703 (4)	C40—C41	1.504 (7)
Mo4—O15	1.710 (4)	C41—C42	1.514 (7)
Mo4—O14	1.926 (4)	C43—C44	1.512 (7)
Mo4—O17	2.413 (4)	C43—N3	1.513 (7)
Mo4—O23	1.926 (4)	C44—C45	1.517 (7)
Mo4—O24	2.353 (4)	C45—C46	1.478 (8)
Mo5—O21	1.710 (4)	C47—C48	1.523 (7)
Mo5—O16	1.711 (4)	C47—N3	1.521 (7)
Mo5—O19	1.922 (4)	C48—C49	1.519 (8)
Mo5—O14	1.923 (4)	C49—C50	1.501 (8)
Mo5—O18	2.329 (4)	C51—C52	1.511 (8)
Mo5—O17	2.385 (4)	C51—N3	1.518 (7)
Mo6—O22	1.702 (4)	C52—C53	1.521 (8)
Mo6—O20	1.697 (4)	C53—C54	1.476 (9)
Mo6—O23	1.919 (4)	C55—C56	1.507 (10)
Mo6—O19^ii	1.926 (4)	C55—N5	1.527 (8)
Mo6—O18^ii	2.367 (4)	C56—C57	1.511 (11)
Mo6—O24	2.404 (4)	C57—C58	1.468 (14)
O5—C3	1.446 (6)	C59—N5	1.514 (8)
O7—Mo3^i	1.929 (4)	C59—C60	1.507 (9)
O10—C2	1.434 (6)	C60—C61	1.529 (11)
O11—C1^i	1.451 (6)	C61—C62	1.526 (11)
O11—Mo3^i	2.308 (4)	C63—C64	1.515 (10)
O17—C20	1.439 (7)	C63—N5	1.517 (8)
O18—C22^ii	1.432 (6)	C64—C65	1.533 (10)
O18—Mo6^ii	2.367 (4)	C65—C66	1.621 (18)
O19—Mo6^ii	1.926 (4)	C67—C68	1.516 (10)
O24—C21	1.443 (7)	C67—N5	1.533 (8)
C1—O11^i	1.451 (6)	C68—C69	1.518 (10)
C1—C4	1.539 (7)	C69—C70	1.522 (10)
C2—C4	1.542 (7)	C71—C72	1.516 (8)
C3—C4^i	1.534 (8)	C71—N4	1.519 (7)
C4—N1	1.474 (7)	C72—C73	1.516 (9)
C4—C3^i	1.534 (8)	C73—C74	1.498 (9)
C5—N1	1.472 (7)	C75—C76	1.509 (8)
C5—C6	1.521 (8)	C75—N4	1.518 (7)
C6—C7	1.409 (9)	C76—C77	1.523 (9)
C6—C19	1.406 (8)	C77—C78	1.473 (9)
C7—C8	1.433 (9)	C79—N4	1.514 (7)
C7—C12	1.445 (9)	C79—C80	1.507 (8)
C8—C9	1.358 (9)	C80—C81	1.517 (9)
C9—C10	1.421 (11)	C81—C82	1.469 (9)
C10—C11	1.362 (11)	C83—C84	1.513 (7)
C11—C12	1.422 (10)	C83—N4	1.508 (7)
C12—C13	1.398 (10)	C84—C85	1.496 (8)
C13—C14	1.366 (10)	C85—C86	1.495 (8)
C14—C15	1.424 (10)	C88—C89	1.35 (2)
C14—C19	1.455 (9)	C89—N6	1.17 (2)
O2—Mo1—O1	105.4 (2)	Mn2—O17—Mo5	101.00 (16)
O2—Mo1—O4	98.42 (19)	C20—O17—Mo4	120.0 (3)
O1—Mo1—O4	101.63 (18)	Mn2—O17—Mo4	101.27 (15)
O2—Mo1—O3	101.79 (19)	Mo5—O17—Mo4	89.85 (12)
O1—Mo1—O3	97.95 (18)	C22^ii—O18—Mn2	115.1 (3)
O4—Mo1—O3	146.91 (15)	C22^ii—O18—Mo5	122.8 (3)
O2—Mo1—O10	160.40 (18)	Mn2—O18—Mo5	99.08 (15)
O1—Mo1—O10	93.57 (17)	C22^ii—O18—Mo6^ii	123.2 (3)
O4—Mo1—O10	72.30 (14)	Mn2—O18—Mo6^ii	99.71 (14)
O3—Mo1—O10	80.13 (14)	Mo5—O18—Mo6^ii	91.63 (13)
O2—Mo1—O5	92.88 (18)	Mo5—O19—Mo6^ii	122.1 (2)
O1—Mo1—O5	161.02 (18)	Mo6—O23—Mo4	121.6 (2)
O4—Mo1—O5	80.39 (14)	C21—O24—Mn2	116.0 (3)
O3—Mo1—O5	72.72 (14)	C21—O24—Mo4	120.8 (3)
O10—Mo1—O5	68.86 (12)	Mn2—O24—Mo4	102.03 (16)
O6—Mo2—O12	105.1 (2)	C21—O24—Mo6	122.4 (3)
O6—Mo2—O4	100.57 (19)	Mn2—O24—Mo6	100.93 (15)
O12—Mo2—O4	101.17 (19)	Mo4—O24—Mo6	89.72 (13)
O6—Mo2—O7	103.89 (19)	O11^i—C1—C4	114.4 (4)
O12—Mo2—O7	96.26 (19)	O10—C2—C4	114.6 (4)
O4—Mo2—O7	144.99 (16)	O5—C3—C4^i	114.6 (4)
O6—Mo2—O11	95.66 (17)	N1—C4—C3^i	110.1 (4)
O12—Mo2—O11	157.92 (17)	N1—C4—C1	107.3 (4)
O4—Mo2—O11	82.10 (15)	C3^i—C4—C1	114.4 (5)
O7—Mo2—O11	70.96 (14)	N1—C4—C2	103.1 (4)
O6—Mo2—O10	164.93 (17)	C3^i—C4—C2	110.4 (5)
O12—Mo2—O10	88.40 (17)	C1—C4—C2	111.0 (5)
O4—Mo2—O10	69.61 (14)	N1—C5—C6	113.9 (5)
O7—Mo2—O10	80.87 (14)	C7—C6—C19	120.2 (6)
O11—Mo2—O10	72.13 (12)	C7—C6—C5	118.3 (5)
O9—Mo3—O8	105.7 (2)	C19—C6—C5	121.5 (5)
O9—Mo3—O7^i	97.14 (19)	C6—C7—C8	123.0 (6)
O8—Mo3—O7^i	102.73 (18)	C6—C7—C12	119.8 (6)
O9—Mo3—O3	101.04 (18)	C8—C7—C12	117.2 (6)
O8—Mo3—O3	100.50 (18)	C9—C8—C7	121.4 (7)
O7^i—Mo3—O3	145.25 (16)	C8—C9—C10	121.0 (7)
O9—Mo3—O11^i	157.51 (17)	C11—C10—C9	120.0 (7)
O8—Mo3—O11^i	95.66 (16)	C10—C11—C12	120.9 (7)
O7^i—Mo3—O11^i	70.72 (14)	C11—C12—C13	121.8 (6)
O3—Mo3—O11^i	81.63 (14)	C11—C12—C7	119.5 (7)
O9—Mo3—O5	87.93 (17)	C13—C12—C7	118.6 (6)
O8—Mo3—O5	165.29 (17)	C14—C13—C12	122.5 (6)
O7^i—Mo3—O5	80.65 (14)	C13—C14—C15	121.4 (6)
O3—Mo3—O5	70.76 (14)	C13—C14—C19	119.4 (6)
O11^i—Mo3—O5	71.73 (12)	C15—C14—C19	119.1 (7)
O13—Mo4—O15	105.6 (2)	C16—C15—C14	121.9 (7)
O13—Mo4—O14	99.44 (18)	C15—C16—C17	119.8 (7)
O15—Mo4—O14	101.86 (18)	C18—C17—C16	121.5 (8)
O13—Mo4—O23	103.14 (19)	C17—C18—C19	121.5 (7)
O15—Mo4—O23	97.72 (19)	C6—C19—C18	124.6 (6)
O14—Mo4—O23	144.77 (16)	C6—C19—C14	119.3 (6)
O13—Mo4—O24	91.86 (18)	C18—C19—C14	116.1 (6)
O15—Mo4—O24	161.55 (18)	O17—C20—C23	114.3 (4)
O14—Mo4—O24	80.74 (15)	O24—C21—C23^ii	114.5 (5)
O23—Mo4—O24	71.90 (15)	O18^ii—C22—C23	114.3 (5)
O13—Mo4—O17	159.36 (18)	N2—C23—C21^ii	110.7 (4)
O15—Mo4—O17	94.28 (17)	N2—C23—C22	107.0 (4)
O14—Mo4—O17	70.35 (14)	C21^ii—C23—C22	112.6 (5)
O23—Mo4—O17	79.28 (15)	N2—C23—C20	103.0 (4)
O24—Mo4—O17	69.18 (13)	C21^ii—C23—C20	111.3 (5)
O21—Mo5—O16	105.0 (2)	C22—C23—C20	111.7 (5)
O21—Mo5—O19	102.57 (18)	N2—C24—C25	109.9 (5)
O16—Mo5—O19	97.13 (18)	C26—C25—C38	121.0 (6)
O21—Mo5—O14	99.19 (18)	C26—C25—C24	119.7 (6)
O16—Mo5—O14	101.85 (18)	C38—C25—C24	119.3 (6)
O19—Mo5—O14	146.20 (16)	C25—C26—C27	123.7 (7)
O21—Mo5—O18	94.99 (19)	C25—C26—C31	119.7 (7)
O16—Mo5—O18	158.88 (17)	C27—C26—C31	116.7 (7)
O19—Mo5—O18	71.41 (14)	C28—C27—C26	121.9 (8)
O14—Mo5—O18	81.27 (15)	C27—C28—C29	121.0 (9)
O21—Mo5—O17	164.55 (18)	C30—C29—C28	120.0 (9)
O16—Mo5—O17	89.03 (17)	C29—C30—C31	121.7 (8)
O19—Mo5—O17	81.68 (15)	C32—C31—C30	121.8 (7)
O14—Mo5—O17	71.04 (14)	C32—C31—C26	119.5 (7)
O18—Mo5—O17	72.07 (13)	C30—C31—C26	118.7 (8)
O22—Mo6—O20	105.4 (2)	C31—C32—C33	121.7 (6)
O22—Mo6—O23	98.9 (2)	C34—C33—C32	121.7 (7)
O20—Mo6—O23	101.7 (2)	C34—C33—C38	119.0 (7)
O22—Mo6—O19^ii	103.7 (2)	C32—C33—C38	119.3 (6)
O20—Mo6—O19^ii	97.9 (2)	C35—C34—C33	121.1 (7)
O23—Mo6—O19^ii	144.72 (16)	C34—C35—C36	120.4 (7)
O22—Mo6—O18^ii	92.56 (19)	C37—C36—C35	120.3 (8)
O20—Mo6—O18^ii	160.72 (19)	C36—C37—C38	121.8 (7)
O23—Mo6—O18^ii	81.88 (15)	C25—C38—C37	124.0 (6)
O19^ii—Mo6—O18^ii	70.49 (14)	C25—C38—C33	118.8 (7)
O22—Mo6—O24	162.01 (19)	C37—C38—C33	117.2 (6)
O20—Mo6—O24	91.36 (19)	C40—C39—N3	115.3 (5)
O23—Mo6—O24	70.81 (15)	C41—C40—C39	112.3 (5)
O19^ii—Mo6—O24	79.78 (15)	C40—C41—C42	113.1 (6)
O18^ii—Mo6—O24	71.77 (13)	C44—C43—N3	116.4 (5)
O5^i—Mn1—O5	180.00 (15)	C43—C44—C45	112.0 (6)
O5^i—Mn1—O10^i	87.00 (15)	C46—C45—C44	114.1 (7)
O5—Mn1—O10^i	93.00 (15)	C48—C47—N3	115.6 (5)
O5^i—Mn1—O10	93.00 (15)	C49—C48—C47	113.2 (6)
O5—Mn1—O10	87.00 (15)	C50—C49—C48	115.4 (7)
O10^i—Mn1—O10	180.0	C52—C51—N3	115.9 (5)
O5^i—Mn1—O11	86.96 (15)	C51—C52—C53	108.4 (6)
O5—Mn1—O11	93.04 (15)	C54—C53—C52	110.1 (9)
O10^i—Mn1—O11	92.58 (14)	C56—C55—N5	115.4 (5)
O10—Mn1—O11	87.42 (14)	C57—C56—C55	110.2 (6)
O5^i—Mn1—O11^i	93.04 (15)	C58—C57—C56	112.9 (8)
O5—Mn1—O11^i	86.96 (15)	N5—C59—C60	117.0 (5)
O10^i—Mn1—O11^i	87.42 (14)	C61—C60—C59	110.0 (6)
O10—Mn1—O11^i	92.58 (14)	C62—C61—C60	113.4 (8)
O11—Mn1—O11^i	180.0	C64—C63—N5	115.1 (5)
O17^ii—Mn2—O17	180.0	C63—C64—C65	111.9 (6)
O17^ii—Mn2—O24	92.49 (15)	C64—C65—C66	106.2 (9)
O17—Mn2—O24	87.51 (15)	C68—C67—N5	116.1 (5)
O17^ii—Mn2—O24^ii	87.51 (15)	C67—C68—C69	110.9 (6)
O17—Mn2—O24^ii	92.49 (15)	C70—C69—C68	114.3 (7)
O24—Mn2—O24^ii	180.0	C72—C71—N4	116.8 (6)
O17^ii—Mn2—O18	92.15 (15)	C73—C72—C71	111.0 (7)
O17—Mn2—O18	87.85 (15)	C74—C73—C72	116.8 (11)
O24—Mn2—O18	92.41 (15)	C76—C75—N4	118.7 (7)
O24^ii—Mn2—O18	87.58 (15)	C75—C76—C77	109.0 (8)
O17^ii—Mn2—O18^ii	87.85 (15)	C78—C77—C76	120.1 (13)
O17—Mn2—O18^ii	92.15 (15)	N4—C79—C80	115.0 (7)
O24—Mn2—O18^ii	87.59 (15)	C79—C80—C81	116.2 (9)
O24^ii—Mn2—O18^ii	92.42 (15)	C82—C81—C80	103.6 (11)
O18—Mn2—O18^ii	180.0	C84—C83—N4	115.5 (6)
Mo1—O3—Mo3	120.9 (2)	C85—C84—C83	112.2 (7)
Mo2—O4—Mo1	122.6 (2)	C84—C85—C86	113.6 (8)
C3—O5—Mn1	116.9 (3)	N6—C89—C88	173 (2)
C3—O5—Mo1	120.5 (3)	C5—N1—C4	119.9 (5)
Mn1—O5—Mo1	101.99 (15)	C24—N2—C23	119.2 (5)
C3—O5—Mo3	121.4 (3)	C51—N3—C39	111.2 (5)
Mn1—O5—Mo3	101.67 (15)	C51—N3—C43	106.7 (5)
Mo1—O5—Mo3	89.40 (12)	C39—N3—C43	110.8 (5)
Mo3^i—O7—Mo2	120.76 (19)	C51—N3—C47	110.0 (5)
C2—O10—Mn1	116.9 (3)	C39—N3—C47	107.8 (4)
C2—O10—Mo1	119.4 (3)	C43—N3—C47	110.4 (5)
Mn1—O10—Mo1	102.15 (15)	C79—N4—C75	107.1 (5)
C2—O10—Mo2	122.9 (3)	C79—N4—C83	112.3 (6)
Mn1—O10—Mo2	100.53 (15)	C75—N4—C83	111.7 (6)
Mo1—O10—Mo2	89.91 (12)	C79—N4—C71	109.3 (7)
C1^i—O11—Mn1	113.0 (3)	C75—N4—C71	109.7 (6)
C1^i—O11—Mo3^i	122.3 (3)	C83—N4—C71	106.7 (5)
Mn1—O11—Mo3^i	99.62 (14)	C59—N5—C63	110.9 (5)
C1^i—O11—Mo2	123.9 (3)	C59—N5—C55	111.3 (5)
Mn1—O11—Mo2	99.92 (14)	C63—N5—C55	106.8 (5)
Mo3^i—O11—Mo2	93.29 (12)	C59—N5—C67	106.5 (5)
Mo5—O14—Mo4	123.37 (19)	C63—N5—C67	110.6 (5)
C20—O17—Mn2	117.2 (3)	C55—N5—C67	110.8 (5)
C20—O17—Mo5	122.2 (3)

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+2, −z+1.

(2)

Crystal data

(C16H36N)3[MnMo6O24(C18H18N)2]·C4H10O	F(000) = 4776
Mr = 2312.73	Dx = 1.445 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 37.884 (6) Å	Cell parameters from 2633 reflections
b = 13.9437 (9) Å	θ = 2.9–29.0°
c = 25.336 (3) Å	µ = 0.88 mm^−1
β = 128.39 (2)°	T = 150 K
V = 10490 (2) Å^3	Block, yellow
Z = 4	0.2 × 0.1 × 0.1 mm

Data collection

Agilent Xcalibur Eos Gemini diffractometer	9215 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3720 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.089
Detector resolution: 16.2141 pixels mm^-1	θmax = 25.0°, θmin = 2.9°
ω scans	h = −44→34
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −10→16
Tmin = 0.876, Tmax = 1.000	l = −19→30
18273 measured reflections

Refinement

Refinement on F^2	148 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.093	H-atom parameters constrained
wR(F^2) = 0.308	w = 1/[σ^2(Fo^2) + (0.1262P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.99	(Δ/σ)max = 0.001
9215 reflections	Δρmax = 1.60 e Å^−3
681 parameters	Δρmin = −0.82 e Å^−3

Special details

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 > 2σ(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.

The inorganic part of the the aninon is disorederd around the site Mn centre with the occupancies ratio of around 0.71/0.29 for all the Mo centres, O ligands and the C atoms which linked O atoms. The organic part of the cluster is well located. The C4, N5, C6 and C7 of the anoin were restrained by DFIX command at 1.3 and 0.05. The C6, C7, C8, C9,C13,C14,C15,C16,C1,O8, C17 and C19 were restrained by SIMU and DELU command at 0.02. The C22 were restrained by simu command at 0.01. The atoms in the TBA cations were also restrained SIMU and DELU command at 0.02, and C33 C34 C22 C23 C29 C30 were restrained by DFIX command at 1.3 and 0.05. The solvent ether were disordered and only some fragment were identified.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Mn1	0.2500	0.7500	0.5000	0.0359 (6)
N1	0.1934 (4)	0.5478 (9)	0.1897 (6)	0.079 (4)
N2	0.0000	0.5783 (15)	0.2500	0.090 (6)
C4	0.3073 (6)	0.5879 (11)	0.5209 (8)	0.074 (4)
N5	0.3335 (6)	0.5060 (13)	0.5295 (9)	0.154 (8)
H5	0.3169	0.4558	0.5109	0.185*
C6	0.3703 (8)	0.4894 (17)	0.5544 (14)	0.194 (11)
H6A	0.3871	0.5093	0.6010	0.233*
H6B	0.3787	0.5337	0.5343	0.233*
C7	0.3905 (9)	0.3931 (18)	0.5571 (13)	0.153 (7)
C8	0.3614 (8)	0.3158 (17)	0.5416 (11)	0.134 (6)
H8	0.3347	0.3255	0.5351	0.160*
C9	0.3747 (6)	0.2190 (16)	0.5361 (10)	0.111 (5)
H9	0.3564	0.1650	0.5219	0.134*
C10	0.4175 (6)	0.2181 (11)	0.5544 (7)	0.071 (4)
C11	0.4433 (5)	0.1382 (12)	0.5576 (7)	0.068 (4)
C12	0.4341 (6)	0.0431 (14)	0.5454 (8)	0.090 (5)
H12	0.4067	0.0235	0.5338	0.108*
C13	0.4593 (7)	−0.0248 (14)	0.5480 (9)	0.100 (5)
H13	0.4497	−0.0882	0.5371	0.120*
C14	0.4991 (7)	0.0030 (14)	0.5671 (9)	0.108 (5)
H14	0.5173	−0.0440	0.5690	0.129*
C15	0.5162 (8)	0.0951 (16)	0.5845 (10)	0.134 (7)
H15	0.5451	0.1104	0.5998	0.161*
C16	0.4845 (7)	0.1677 (15)	0.5766 (10)	0.113 (6)
C17	0.4872 (6)	0.2744 (14)	0.5836 (10)	0.127 (7)
H17A	0.5134	0.2940	0.6282	0.152*
H17B	0.4882	0.3046	0.5501	0.152*
C18	0.4448 (6)	0.2973 (13)	0.5724 (8)	0.088 (5)
C19	0.4282 (7)	0.3866 (15)	0.5706 (11)	0.142 (7)
H19	0.4451	0.4415	0.5793	0.170*
C20	0.2342 (6)	0.5340 (11)	0.2649 (8)	0.092 (5)
H20A	0.2481	0.5961	0.2833	0.110*
H20B	0.2230	0.5122	0.2884	0.110*
C21	0.2697 (6)	0.4658 (11)	0.2800 (9)	0.094 (5)
H21A	0.2813	0.4869	0.2569	0.113*
H21B	0.2563	0.4029	0.2627	0.113*
C22	0.3087 (8)	0.4578 (15)	0.3554 (11)	0.145 (7)
H22A	0.2974	0.4595	0.3808	0.174*
H22B	0.3247	0.3979	0.3651	0.174*
C23	0.3392 (8)	0.5402 (15)	0.3742 (11)	0.166 (8)
H23A	0.3559	0.5295	0.3580	0.249*
H23B	0.3596	0.5466	0.4224	0.249*
H23C	0.3217	0.5978	0.3546	0.249*
C24	0.2096 (6)	0.5867 (11)	0.1527 (10)	0.098 (5)
H24A	0.2283	0.5385	0.1533	0.118*
H24B	0.1837	0.5972	0.1060	0.118*
C25	0.2360 (8)	0.6787 (14)	0.1804 (12)	0.140 (7)
H25A	0.2175	0.7275	0.1800	0.167*
H25B	0.2623	0.6687	0.2268	0.167*
C26	0.2504 (9)	0.7132 (17)	0.1414 (14)	0.160 (8)
H26A	0.2234	0.7205	0.0951	0.192*
H26B	0.2628	0.7769	0.1578	0.192*
C27	0.1724 (5)	0.4530 (11)	0.1592 (8)	0.087 (5)
H27A	0.1490	0.4629	0.1114	0.105*
H27B	0.1952	0.4128	0.1642	0.105*
C28	0.1524 (7)	0.3984 (13)	0.1850 (10)	0.120 (6)
H28A	0.1254	0.4325	0.1707	0.144*
H28B	0.1734	0.4026	0.2338	0.144*
C29	0.1398 (8)	0.2944 (16)	0.1675 (11)	0.161 (7)
H29A	0.1666	0.2549	0.1899	0.194*
H29B	0.1222	0.2734	0.1813	0.194*
C30	0.1129 (8)	0.2875 (17)	0.0934 (11)	0.185 (9)
H30A	0.0865	0.2495	0.0753	0.277*
H30B	0.1307	0.2578	0.0828	0.277*
H30C	0.1041	0.3505	0.0741	0.277*
C31	0.1618 (6)	0.6179 (11)	0.1874 (8)	0.098 (6)
H31A	0.1528	0.5912	0.2127	0.117*
H31B	0.1782	0.6768	0.2095	0.117*
C32	0.1203 (7)	0.6417 (15)	0.1177 (9)	0.128 (7)
H32A	0.1037	0.5843	0.0929	0.153*
H32B	0.1277	0.6768	0.0926	0.153*
C33	0.0921 (7)	0.7082 (17)	0.1329 (9)	0.148 (7)
H33A	0.0784	0.6685	0.1472	0.178*
H33B	0.1120	0.7538	0.1684	0.178*
C34	0.0571 (7)	0.7592 (18)	0.0702 (10)	0.186 (8)
H34A	0.0399	0.7990	0.0777	0.280*
H34B	0.0710	0.7984	0.0566	0.280*
H34C	0.0375	0.7135	0.0354	0.280*
C35	0.0258 (6)	0.5205 (14)	0.2350 (9)	0.111 (6)
H35A	0.0427	0.5636	0.2281	0.133*
H35B	0.0047	0.4856	0.1934	0.133*
C36	0.0587 (6)	0.4483 (14)	0.2913 (9)	0.112 (6)
H36A	0.0824	0.4818	0.3321	0.134*
H36B	0.0430	0.4067	0.3012	0.134*
C37	0.0783 (9)	0.3903 (18)	0.2635 (13)	0.145 (8)
H37A	0.0542	0.3564	0.2232	0.173*
H37B	0.0921	0.4336	0.2511	0.173*
C38	0.1105 (9)	0.3241 (18)	0.3109 (12)	0.170 (11)
H38A	0.1345	0.3576	0.3507	0.255*
H38B	0.1225	0.2896	0.2923	0.255*
H38C	0.0967	0.2799	0.3222	0.255*
C39	0.0326 (7)	0.6439 (13)	0.3117 (8)	0.117 (7)
H39A	0.0524	0.6029	0.3506	0.141*
H39B	0.0512	0.6780	0.3038	0.141*
C40	0.0134 (7)	0.7133 (14)	0.3293 (9)	0.121 (7)
H40A	−0.0057	0.6811	0.3370	0.145*
H40B	−0.0051	0.7578	0.2922	0.145*
C41	0.0501 (8)	0.7683 (13)	0.3922 (12)	0.156 (10)
H41A	0.0708	0.7212	0.4258	0.187*
H41B	0.0667	0.8043	0.3811	0.187*
C42	0.0395 (9)	0.8337 (14)	0.4240 (14)	0.180 (12)
H42A	0.0204	0.8838	0.3930	0.269*
H42B	0.0667	0.8612	0.4630	0.269*
H42C	0.0241	0.8000	0.4374	0.269*
C43	0.2818 (12)	0.661 (2)	0.140 (2)	0.26 (2)
H43A	0.2717	0.5961	0.1264	0.393*
H43B	0.3106	0.6619	0.1834	0.393*
H43C	0.2842	0.6902	0.1076	0.393*
C1	0.2580 (8)	0.5491 (13)	0.4817 (11)	0.073 (6)	0.709 (7)
H1A	0.2484	0.5191	0.4401	0.088*	0.709 (7)
H1B	0.2575	0.5007	0.5087	0.088*	0.709 (7)
C2	0.3251 (6)	0.6211 (15)	0.5925 (10)	0.067 (6)	0.709 (7)
H2A	0.3218	0.5683	0.6141	0.080*	0.709 (7)
H2B	0.3570	0.6350	0.6191	0.080*	0.709 (7)
C3	0.3138 (8)	0.6649 (15)	0.4874 (10)	0.074 (6)	0.709 (7)
H3A	0.3450	0.6853	0.5172	0.088*	0.709 (7)
H3B	0.3078	0.6391	0.4470	0.088*	0.709 (7)
O1	0.1721 (7)	0.4841 (11)	0.4764 (9)	0.114 (7)	0.709 (7)
O2	0.1468 (5)	0.6239 (10)	0.5180 (7)	0.082 (4)	0.709 (7)
O3	0.2856 (3)	0.7471 (7)	0.4694 (5)	0.039 (3)	0.709 (7)
O4	0.2686 (4)	0.7764 (9)	0.3394 (7)	0.055 (3)	0.709 (7)
O5	0.2385 (4)	0.5891 (8)	0.5855 (6)	0.061 (4)	0.709 (7)
O6	0.1971 (3)	0.7958 (8)	0.4062 (6)	0.049 (3)	0.709 (7)
O7	0.1871 (4)	0.8613 (10)	0.2874 (6)	0.072 (4)	0.709 (7)
O8	0.2281 (5)	0.6220 (8)	0.4669 (7)	0.059 (3)	0.709 (7)
O9	0.1568 (6)	0.5406 (12)	0.3362 (7)	0.114 (7)	0.709 (7)
O10	0.2101 (5)	0.6791 (8)	0.3471 (6)	0.064 (4)	0.709 (7)
O11	0.1170 (5)	0.7132 (14)	0.2877 (7)	0.114 (6)	0.709 (7)
O12	0.1460 (4)	0.6612 (11)	0.4128 (6)	0.074 (4)	0.709 (7)
Mo1	0.2336 (5)	0.8030 (11)	0.3573 (6)	0.049 (2)	0.709 (7)
Mo2	0.16110 (17)	0.6620 (3)	0.3518 (3)	0.0483 (9)	0.709 (7)
Mo3	0.17936 (14)	0.6044 (3)	0.4954 (2)	0.0450 (8)	0.709 (7)
Mo1'	0.2280 (11)	0.819 (3)	0.3567 (12)	0.047 (5)	0.291 (7)
Mo2'	0.1718 (5)	0.6284 (9)	0.3586 (7)	0.058 (3)	0.291 (7)
Mo3'	0.1891 (4)	0.5713 (7)	0.4992 (6)	0.050 (2)	0.291 (7)
O1'	0.2426 (9)	0.6796 (17)	0.4223 (14)	0.044 (7)	0.291 (7)
O2'	0.1778 (12)	0.780 (2)	0.3338 (16)	0.084 (11)	0.291 (7)
O3'	0.3139 (12)	0.775 (2)	0.5501 (16)	0.069 (10)	0.291 (7)
O4'	0.2572 (11)	0.632 (2)	0.5415 (15)	0.073 (10)	0.291 (7)
O5'	0.1799 (11)	0.567 (2)	0.4165 (14)	0.069 (10)	0.291 (7)
O6'	0.2233 (17)	0.924 (3)	0.332 (3)	0.128 (16)*	0.291 (7)
O7'	0.2034 (13)	0.669 (2)	0.5676 (19)	0.084 (11)*	0.291 (7)
O8'	0.1237 (15)	0.599 (3)	0.450 (2)	0.103 (13)*	0.291 (7)
O9'	0.1686 (11)	0.578 (2)	0.3034 (17)	0.069 (9)*	0.291 (7)
O10'	0.1981 (15)	0.475 (3)	0.528 (2)	0.097 (13)*	0.291 (7)
O11'	0.2404 (12)	0.766 (2)	0.3122 (17)	0.061 (10)*	0.291 (7)
O12'	0.1114 (17)	0.659 (3)	0.318 (3)	0.118 (15)*	0.291 (7)
C1'	0.2773 (18)	0.622 (3)	0.443 (2)	0.057 (12)*	0.291 (7)
C2'	0.337 (3)	0.678 (5)	0.553 (4)	0.13 (3)*	0.291 (7)
C3'	0.2872 (19)	0.555 (4)	0.545 (3)	0.069 (14)*	0.291 (7)
C103	−0.0837 (13)	0.988 (2)	0.259 (2)	0.102 (11)*	0.5
O30	−0.0940 (15)	1.014 (3)	0.290 (2)	0.228 (18)*	0.5
C104	−0.0188 (12)	1.012 (3)	0.4775 (19)	0.106 (12)*	0.5
C100	−0.0425 (14)	1.009 (2)	0.385 (2)	0.117 (13)*	0.5
C102	−0.0539 (19)	1.065 (4)	0.263 (3)	0.174 (19)*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0314 (14)	0.0468 (14)	0.0270 (12)	−0.0105 (11)	0.0169 (11)	−0.0097 (11)
N1	0.060 (8)	0.098 (9)	0.063 (8)	0.011 (7)	0.031 (7)	−0.016 (7)
N2	0.052 (12)	0.146 (17)	0.057 (12)	0.000	0.027 (10)	0.000
C4	0.088 (12)	0.081 (10)	0.067 (10)	0.017 (10)	0.056 (10)	0.009 (9)
N5	0.109 (14)	0.184 (17)	0.145 (16)	0.107 (13)	0.067 (13)	0.017 (13)
C6	0.125 (16)	0.155 (13)	0.190 (18)	0.055 (13)	0.043 (15)	−0.031 (15)
C7	0.093 (12)	0.140 (11)	0.165 (13)	0.048 (10)	0.050 (11)	−0.014 (11)
C8	0.090 (11)	0.160 (12)	0.135 (12)	0.042 (10)	0.062 (10)	0.015 (12)
C9	0.074 (11)	0.163 (12)	0.110 (13)	0.004 (11)	0.063 (10)	0.010 (12)
C10	0.079 (11)	0.069 (10)	0.048 (9)	−0.001 (10)	0.032 (8)	0.003 (8)
C11	0.070 (11)	0.076 (10)	0.040 (8)	0.007 (9)	0.025 (8)	0.000 (8)
C12	0.103 (15)	0.113 (14)	0.069 (11)	0.015 (12)	0.059 (11)	0.018 (11)
C13	0.118 (13)	0.107 (12)	0.077 (11)	0.007 (10)	0.061 (11)	−0.006 (9)
C14	0.113 (12)	0.118 (10)	0.100 (11)	−0.005 (10)	0.070 (10)	0.006 (9)
C15	0.100 (12)	0.138 (12)	0.101 (11)	−0.007 (9)	0.032 (10)	0.006 (11)
C16	0.093 (11)	0.111 (10)	0.088 (11)	−0.017 (9)	0.032 (9)	−0.012 (10)
C17	0.074 (12)	0.136 (13)	0.122 (14)	−0.038 (11)	0.037 (10)	−0.035 (12)
C18	0.069 (12)	0.093 (12)	0.080 (12)	0.014 (11)	0.035 (10)	−0.010 (10)
C19	0.087 (12)	0.100 (12)	0.155 (15)	0.017 (10)	0.034 (13)	−0.002 (11)
C20	0.085 (13)	0.094 (12)	0.069 (11)	0.020 (10)	0.035 (10)	−0.010 (9)
C21	0.082 (12)	0.093 (11)	0.087 (13)	0.028 (10)	0.041 (10)	−0.004 (10)
C22	0.157 (11)	0.155 (10)	0.125 (10)	−0.015 (7)	0.089 (8)	0.000 (8)
C23	0.170 (13)	0.171 (13)	0.132 (12)	−0.008 (10)	0.082 (11)	0.002 (10)
C24	0.090 (12)	0.086 (10)	0.116 (13)	0.013 (9)	0.062 (11)	−0.004 (10)
C25	0.121 (14)	0.114 (12)	0.148 (15)	0.002 (10)	0.066 (11)	0.026 (11)
C26	0.125 (16)	0.147 (16)	0.161 (18)	−0.024 (12)	0.065 (13)	0.031 (14)
C27	0.075 (11)	0.078 (9)	0.077 (10)	0.009 (8)	0.031 (8)	−0.032 (8)
C28	0.094 (12)	0.122 (11)	0.109 (11)	−0.021 (10)	0.046 (9)	0.007 (10)
C29	0.120 (13)	0.161 (12)	0.148 (14)	−0.020 (11)	0.055 (11)	−0.014 (13)
C30	0.128 (15)	0.179 (13)	0.156 (15)	−0.016 (12)	0.043 (13)	−0.029 (13)
C31	0.108 (15)	0.102 (12)	0.073 (11)	0.029 (11)	0.051 (11)	−0.026 (10)
C32	0.101 (13)	0.189 (16)	0.066 (11)	0.050 (11)	0.038 (10)	0.006 (11)
C33	0.100 (12)	0.237 (16)	0.094 (11)	0.085 (11)	0.054 (9)	0.009 (11)
C34	0.124 (13)	0.254 (18)	0.115 (13)	0.081 (11)	0.041 (11)	0.004 (12)
C35	0.057 (10)	0.175 (16)	0.097 (12)	−0.005 (10)	0.047 (9)	0.008 (10)
C36	0.072 (11)	0.159 (16)	0.084 (12)	−0.003 (11)	0.038 (9)	0.015 (10)
C37	0.14 (2)	0.18 (2)	0.12 (2)	0.003 (18)	0.088 (19)	0.008 (17)
C38	0.14 (2)	0.20 (3)	0.095 (18)	−0.015 (19)	0.036 (17)	0.015 (17)
C39	0.137 (19)	0.133 (15)	0.044 (10)	−0.030 (14)	0.037 (12)	−0.012 (11)
C40	0.17 (2)	0.123 (16)	0.074 (14)	0.015 (15)	0.078 (15)	0.004 (12)
C41	0.19 (3)	0.093 (14)	0.15 (2)	−0.010 (14)	0.09 (2)	−0.069 (14)
C42	0.22 (3)	0.102 (15)	0.25 (3)	−0.021 (16)	0.16 (3)	−0.068 (18)
C43	0.22 (4)	0.25 (4)	0.40 (6)	−0.08 (3)	0.24 (4)	−0.08 (4)
C1	0.101 (14)	0.046 (10)	0.068 (12)	−0.012 (10)	0.049 (11)	−0.011 (10)
C2	0.045 (12)	0.107 (15)	0.071 (14)	0.022 (12)	0.047 (11)	0.018 (12)
C3	0.091 (18)	0.089 (15)	0.044 (12)	0.029 (14)	0.043 (13)	0.018 (11)
O1	0.19 (2)	0.092 (11)	0.079 (12)	−0.092 (12)	0.095 (14)	−0.046 (9)
O2	0.060 (9)	0.116 (11)	0.065 (10)	−0.029 (8)	0.036 (8)	−0.015 (8)
O3	0.024 (6)	0.057 (7)	0.028 (6)	−0.007 (5)	0.011 (5)	−0.016 (5)
O4	0.039 (8)	0.083 (9)	0.064 (8)	−0.013 (7)	0.043 (7)	−0.016 (7)
O5	0.061 (9)	0.076 (8)	0.044 (7)	−0.003 (7)	0.032 (7)	0.005 (6)
O6	0.026 (6)	0.077 (8)	0.040 (7)	−0.001 (6)	0.018 (5)	0.003 (6)
O7	0.042 (8)	0.113 (11)	0.039 (7)	−0.001 (8)	0.014 (6)	0.006 (7)
O8	0.080 (9)	0.055 (7)	0.079 (9)	0.001 (7)	0.068 (8)	−0.004 (7)
O9	0.174 (18)	0.126 (13)	0.060 (10)	−0.079 (13)	0.082 (12)	−0.045 (10)
O10	0.082 (10)	0.072 (8)	0.043 (8)	−0.027 (7)	0.042 (8)	−0.023 (6)
O11	0.076 (12)	0.203 (18)	0.046 (9)	−0.021 (12)	0.030 (9)	0.000 (11)
O12	0.038 (8)	0.135 (12)	0.038 (7)	−0.026 (8)	0.019 (6)	−0.010 (8)
Mo1	0.050 (4)	0.060 (3)	0.040 (2)	−0.006 (3)	0.029 (2)	−0.0071 (17)
Mo2	0.0428 (19)	0.061 (3)	0.0292 (11)	−0.0130 (15)	0.0163 (12)	−0.0115 (17)
Mo3	0.0461 (17)	0.044 (2)	0.0411 (12)	−0.0083 (14)	0.0251 (12)	−0.0062 (16)
Mo1'	0.034 (5)	0.083 (15)	0.024 (4)	0.000 (6)	0.018 (3)	0.004 (6)
Mo2'	0.066 (7)	0.066 (7)	0.040 (5)	−0.024 (4)	0.033 (5)	−0.027 (5)
Mo3'	0.070 (6)	0.036 (5)	0.057 (4)	−0.008 (4)	0.046 (4)	−0.005 (4)
O1'	0.032 (16)	0.046 (15)	0.07 (2)	−0.009 (13)	0.037 (15)	0.002 (14)
O2'	0.09 (3)	0.10 (3)	0.04 (2)	0.02 (2)	0.030 (19)	0.028 (19)
O3'	0.09 (3)	0.054 (18)	0.06 (2)	−0.018 (18)	0.05 (2)	−0.031 (16)
O4'	0.08 (2)	0.09 (2)	0.06 (2)	−0.06 (2)	0.05 (2)	−0.044 (18)
O5'	0.07 (2)	0.08 (2)	0.028 (16)	−0.033 (19)	0.018 (16)	−0.010 (15)

Geometric parameters (Å, º)

Mn1—O4'^i	1.88 (3)	C37—C38	1.40 (3)
Mn1—O4'	1.88 (3)	C39—C40	1.43 (2)
Mn1—O3^i	1.928 (10)	C40—C41	1.52 (2)
Mn1—O3	1.928 (10)	C41—C42	1.43 (2)
Mn1—O8	1.927 (12)	C1—O8	1.39 (2)
Mn1—O8^i	1.927 (12)	C2—O6^i	1.444 (19)
Mn1—O3'^i	1.94 (3)	C3—O3	1.43 (2)
Mn1—O3'	1.94 (3)	O1—Mo3	1.721 (14)
Mn1—O6	2.038 (11)	O2—Mo3	1.673 (15)
Mn1—O6^i	2.039 (11)	O3—Mo3^i	2.319 (11)
Mn1—O1'^i	2.06 (3)	O3—Mo1	2.368 (15)
Mn1—O1'	2.06 (3)	O4—Mo1	1.686 (18)
N1—C27	1.487 (17)	O5—Mo1^i	1.893 (19)
N1—C24	1.508 (19)	O5—Mo3	1.980 (13)
N1—C31	1.516 (17)	O6—C2^i	1.444 (19)
N1—C20	1.547 (18)	O6—Mo2	2.215 (12)
N2—C35	1.485 (19)	O6—Mo1	2.363 (18)
N2—C35^ii	1.485 (19)	O7—Mo1	1.739 (17)
N2—C39^ii	1.552 (18)	O8—Mo3	2.379 (12)
N2—C39	1.552 (18)	O8—Mo2	2.462 (15)
C4—C3'	1.32 (5)	O9—Mo2	1.723 (16)
C4—N5	1.436 (17)	O10—Mo1	1.89 (2)
C4—C3	1.48 (2)	O10—Mo2	1.946 (14)
C4—C2'	1.54 (8)	O11—Mo2	1.603 (17)
C4—C2	1.56 (2)	O12—Mo3	1.822 (13)
C4—C1	1.57 (2)	O12—Mo2	1.953 (13)
C4—C1'	1.62 (5)	Mo1—O5^i	1.893 (19)
N5—C6	1.14 (2)	Mo3—O3^i	2.319 (11)
C6—C7	1.52 (2)	Mo1'—O6'	1.56 (6)
C7—C19	1.25 (3)	Mo1'—O11'	1.64 (5)
C7—C8	1.41 (3)	Mo1'—O2'	1.70 (5)
C8—C9	1.48 (2)	Mo1'—O7'^i	2.07 (5)
C9—C10	1.38 (2)	Mo1'—O4'^i	2.38 (4)
C10—C18	1.38 (2)	Mo1'—O1'	2.39 (4)
C10—C11	1.45 (2)	Mo2'—O9'	1.50 (3)
C11—C12	1.36 (2)	Mo2'—O5'	1.55 (3)
C11—C16	1.38 (2)	Mo2'—O12'	1.89 (5)
C12—C13	1.32 (2)	Mo2'—O1'	2.22 (3)
C13—C14	1.32 (2)	Mo2'—O2'	2.25 (3)
C14—C15	1.38 (2)	Mo2'—O3'^i	2.43 (3)
C15—C16	1.49 (3)	Mo3'—O10'	1.47 (4)
C16—C17	1.49 (2)	Mo3'—O5'	1.90 (3)
C17—C18	1.48 (2)	Mo3'—O7'	2.00 (4)
C18—C19	1.38 (2)	Mo3'—O8'	2.00 (4)
C20—C21	1.490 (19)	Mo3'—O4'	2.25 (3)
C21—C22	1.53 (2)	Mo3'—O3'^i	2.45 (3)
C22—C23	1.482 (10)	O1'—C1'	1.34 (5)
C24—C25	1.50 (2)	O3'—C2'	1.59 (8)
C25—C26	1.48 (3)	O3'—Mo2'^i	2.43 (3)
C26—C43	1.42 (3)	O3'—Mo3'^i	2.45 (3)
C27—C28	1.48 (2)	O4'—C3'	1.52 (6)
C28—C29	1.51 (2)	O4'—Mo1'^i	2.38 (4)
C29—C30	1.483 (10)	O7'—Mo1'^i	2.07 (5)
C31—C32	1.50 (2)	C103—O30	1.13 (5)
C32—C33	1.63 (2)	C103—C102	1.51 (5)
C33—C34	1.474 (10)	C104—C104^iii	1.20 (7)
C35—C36	1.55 (2)	C104—C100	1.93 (5)
C36—C37	1.53 (3)
O4'^i—Mn1—O4'	180.0	Mo1—O10—Mo2	119.5 (8)
O3^i—Mn1—O3	180.0	Mo3—O12—Mo2	125.2 (8)
O3^i—Mn1—O8	88.6 (4)	O4—Mo1—O7	107.3 (9)
O3—Mn1—O8	91.4 (4)	O4—Mo1—O10	98.4 (9)
O3^i—Mn1—O8^i	91.4 (4)	O7—Mo1—O10	101.2 (9)
O3—Mn1—O8^i	88.6 (4)	O4—Mo1—O5^i	102.9 (9)
O8—Mn1—O8^i	180.0	O7—Mo1—O5^i	98.0 (9)
O4'^i—Mn1—O3'^i	96.0 (14)	O10—Mo1—O5^i	145.5 (9)
O4'—Mn1—O3'^i	84.0 (14)	O4—Mo1—O6	160.8 (9)
O4'^i—Mn1—O3'	84.0 (14)	O7—Mo1—O6	90.1 (8)
O4'—Mn1—O3'	96.0 (14)	O10—Mo1—O6	69.6 (7)
O3'^i—Mn1—O3'	180.0	O5^i—Mo1—O6	82.0 (7)
O3^i—Mn1—O6	92.1 (4)	O4—Mo1—O3	92.5 (8)
O3—Mn1—O6	87.9 (4)	O7—Mo1—O3	159.6 (10)
O8—Mn1—O6	86.4 (5)	O10—Mo1—O3	80.4 (7)
O8^i—Mn1—O6	93.6 (5)	O5^i—Mo1—O3	72.0 (6)
O3^i—Mn1—O6^i	87.9 (4)	O6—Mo1—O3	71.2 (5)
O3—Mn1—O6^i	92.1 (4)	O11—Mo2—O9	108.4 (9)
O8—Mn1—O6^i	93.6 (5)	O11—Mo2—O10	108.4 (8)
O8^i—Mn1—O6^i	86.4 (5)	O9—Mo2—O10	93.6 (7)
O6—Mn1—O6^i	180.0 (6)	O11—Mo2—O12	99.9 (7)
O4'^i—Mn1—O1'^i	90.1 (11)	O9—Mo2—O12	98.3 (7)
O4'—Mn1—O1'^i	89.9 (11)	O10—Mo2—O12	143.9 (6)
O3'^i—Mn1—O1'^i	94.8 (11)	O11—Mo2—O6	96.1 (8)
O3'—Mn1—O1'^i	85.2 (11)	O9—Mo2—O6	154.7 (7)
O4'^i—Mn1—O1'	89.9 (11)	O10—Mo2—O6	72.1 (5)
O4'—Mn1—O1'	90.1 (11)	O12—Mo2—O6	83.3 (5)
O3'^i—Mn1—O1'	85.2 (11)	O11—Mo2—O8	163.8 (7)
O3'—Mn1—O1'	94.8 (11)	O9—Mo2—O8	86.0 (7)
O1'^i—Mn1—O1'	180.0	O10—Mo2—O8	77.2 (5)
C27—N1—C24	106.8 (12)	O12—Mo2—O8	69.9 (5)
C27—N1—C31	113.6 (13)	O6—Mo2—O8	70.8 (4)
C24—N1—C31	111.0 (13)	O2—Mo3—O1	103.4 (8)
C27—N1—C20	109.4 (12)	O2—Mo3—O12	100.9 (7)
C24—N1—C20	109.2 (13)	O1—Mo3—O12	103.1 (8)
C31—N1—C20	106.8 (11)	O2—Mo3—O5	99.9 (6)
C35—N2—C35^ii	114 (2)	O1—Mo3—O5	94.9 (8)
C35—N2—C39^ii	107.4 (10)	O12—Mo3—O5	148.4 (6)
C35^ii—N2—C39^ii	109.9 (11)	O2—Mo3—O3^i	95.3 (5)
C35—N2—C39	109.9 (11)	O1—Mo3—O3^i	158.8 (8)
C35^ii—N2—C39	107.4 (10)	O12—Mo3—O3^i	82.9 (5)
C39^ii—N2—C39	107.8 (18)	O5—Mo3—O3^i	71.7 (4)
C3'—C4—N5	101 (3)	O2—Mo3—O8	164.6 (6)
N5—C4—C3	108.8 (15)	O1—Mo3—O8	91.9 (7)
C3'—C4—C2'	119 (4)	O12—Mo3—O8	73.8 (5)
N5—C4—C2'	111 (3)	O5—Mo3—O8	79.9 (5)
N5—C4—C2	107.4 (14)	O3^i—Mo3—O8	69.9 (4)
C3—C4—C2	110.2 (15)	O6'—Mo1'—O11'	99 (3)
N5—C4—C1	105.0 (15)	O6'—Mo1'—O2'	110 (3)
C3—C4—C1	116.3 (16)	O11'—Mo1'—O2'	111 (3)
C2—C4—C1	108.7 (14)	O6'—Mo1'—O7'^i	93 (3)
C3'—C4—C1'	120 (3)	O11'—Mo1'—O7'^i	87 (2)
N5—C4—C1'	108 (2)	O2'—Mo1'—O7'^i	147 (2)
C2'—C4—C1'	98 (4)	O6'—Mo1'—O4'^i	93 (2)
C6—N5—C4	137 (2)	O11'—Mo1'—O4'^i	154 (2)
N5—C6—C7	128 (3)	O2'—Mo1'—O4'^i	85.7 (19)
C19—C7—C8	126 (2)	O7'^i—Mo1'—O4'^i	69.9 (15)
C19—C7—C6	122 (3)	O6'—Mo1'—O1'	164 (3)
C8—C7—C6	112 (2)	O11'—Mo1'—O1'	94 (2)
C7—C8—C9	118 (2)	O2'—Mo1'—O1'	72.8 (17)
C10—C9—C8	111.9 (19)	O7'^i—Mo1'—O1'	78.8 (15)
C9—C10—C18	125.9 (17)	O4'^i—Mo1'—O1'	71.6 (13)
C9—C10—C11	129.5 (16)	O9'—Mo2'—O5'	118.5 (18)
C18—C10—C11	104.6 (15)	O9'—Mo2'—O12'	103 (2)
C12—C11—C16	116.5 (17)	O5'—Mo2'—O12'	96 (2)
C12—C11—C10	131.9 (17)	O9'—Mo2'—O1'	100.8 (16)
C16—C11—C10	111.6 (16)	O5'—Mo2'—O1'	92.9 (14)
C13—C12—C11	128.0 (19)	O12'—Mo2'—O1'	146.3 (16)
C12—C13—C14	116 (2)	O9'—Mo2'—O2'	98.1 (17)
C13—C14—C15	126 (2)	O5'—Mo2'—O2'	141.6 (15)
C14—C15—C16	114 (2)	O12'—Mo2'—O2'	86.1 (17)
C11—C16—C15	119.2 (19)	O1'—Mo2'—O2'	67.4 (12)
C11—C16—C17	108.5 (19)	O9'—Mo2'—O3'^i	170.9 (17)
C15—C16—C17	132 (2)	O5'—Mo2'—O3'^i	67.0 (14)
C18—C17—C16	101.9 (17)	O12'—Mo2'—O3'^i	82.5 (17)
C10—C18—C19	118.5 (17)	O1'—Mo2'—O3'^i	71.1 (11)
C10—C18—C17	113.1 (15)	O2'—Mo2'—O3'^i	75.2 (12)
C19—C18—C17	128.0 (19)	O10'—Mo3'—O5'	110 (2)
C7—C19—C18	120 (2)	O10'—Mo3'—O7'	110 (2)
C21—C20—N1	116.6 (13)	O5'—Mo3'—O7'	138.1 (15)
C20—C21—C22	112.6 (16)	O10'—Mo3'—O8'	108 (2)
C23—C22—C21	107.5 (18)	O5'—Mo3'—O8'	90.9 (17)
C25—C24—N1	115.2 (16)	O7'—Mo3'—O8'	88.3 (16)
C26—C25—C24	112 (2)	O10'—Mo3'—O4'	105 (2)
C43—C26—C25	121 (3)	O5'—Mo3'—O4'	84.6 (13)
C28—C27—N1	118.7 (14)	O7'—Mo3'—O4'	73.7 (14)
C27—C28—C29	121.4 (19)	O8'—Mo3'—O4'	146.4 (15)
C30—C29—C28	106.2 (19)	O10'—Mo3'—O3'^i	168.6 (19)
C32—C31—N1	114.4 (13)	O5'—Mo3'—O3'^i	63.0 (11)
C31—C32—C33	102.1 (14)	O7'—Mo3'—O3'^i	75.4 (12)
C34—C33—C32	107.7 (16)	O8'—Mo3'—O3'^i	82.4 (14)
N2—C35—C36	113.6 (15)	O4'—Mo3'—O3'^i	65.9 (13)
C37—C36—C35	105.4 (18)	C1'—O1'—Mn1	113 (3)
C38—C37—C36	111 (2)	C1'—O1'—Mo2'	123 (3)
C40—C39—N2	118.1 (17)	Mn1—O1'—Mo2'	103.5 (10)
C39—C40—C41	110.9 (18)	C1'—O1'—Mo1'	121 (3)
C42—C41—C40	121 (2)	Mn1—O1'—Mo1'	96.4 (12)
O8—C1—C4	111.6 (14)	Mo2'—O1'—Mo1'	95.8 (13)
O6^i—C2—C4	115.2 (14)	Mo1'—O2'—Mo2'	119 (2)
O3—C3—C4	114.0 (16)	C2'—O3'—Mn1	108 (3)
C3—O3—Mn1	117.2 (10)	C2'—O3'—Mo2'^i	129 (4)
C3—O3—Mo3^i	117.1 (12)	Mn1—O3'—Mo2'^i	99.9 (13)
Mn1—O3—Mo3^i	101.7 (4)	C2'—O3'—Mo3'^i	129 (3)
C3—O3—Mo1	123.0 (10)	Mn1—O3'—Mo3'^i	100.4 (14)
Mn1—O3—Mo1	102.0 (6)	Mo2'^i—O3'—Mo3'^i	85.1 (9)
Mo3^i—O3—Mo1	91.0 (5)	C3'—O4'—Mn1	120 (3)
Mo1^i—O5—Mo3	119.3 (7)	C3'—O4'—Mo3'	111 (2)
C2^i—O6—Mn1	113.0 (10)	Mn1—O4'—Mo3'	109.6 (17)
C2^i—O6—Mo2	123.2 (11)	C3'—O4'—Mo1'^i	118 (3)
Mn1—O6—Mo2	103.9 (5)	Mn1—O4'—Mo1'^i	101.9 (15)
C2^i—O6—Mo1	121.1 (10)	Mo3'—O4'—Mo1'^i	93.0 (14)
Mn1—O6—Mo1	98.8 (5)	Mo2'—O5'—Mo3'	145 (2)
Mo2—O6—Mo1	92.6 (6)	Mo3'—O7'—Mo1'^i	112 (2)
C1—O8—Mn1	120.2 (12)	O1'—C1'—C4	115 (3)
C1—O8—Mo3	119.9 (11)	C4—C2'—O3'	118 (5)
Mn1—O8—Mo3	99.7 (5)	C4—C3'—O4'	110 (4)
C1—O8—Mo2	123.6 (11)	O30—C103—C102	107 (4)
Mn1—O8—Mo2	98.9 (5)	C104^iii—C104—C100	122 (5)
Mo3—O8—Mo2	87.6 (5)

Symmetry codes: (i) −x+1/2, −y+3/2, −z+1; (ii) −x, y, −z+1/2; (iii) −x, −y+2, −z+1.

(3)

Crystal data

(C16H36N)3[MnMo6O24(C15H16N)2]·C4H10O	F(000) = 4616
Mr = 2236.64	Dx = 1.510 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 37.431 (4) Å	Cell parameters from 5947 reflections
b = 13.1303 (4) Å	θ = 3.0–29.1°
c = 25.288 (2) Å	µ = 0.93 mm^−1
β = 127.639 (15)°	T = 151 K
V = 9842 (2) Å^3	BLOCK, yellow
Z = 4	0.2 × 0.1 × 0.1 mm

Data collection

Agilent Xcalibur Eos Gemini diffractometer	9143 independent reflections
Radiation source: fine-focus sealed tube	5391 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.108
ω scans	θmax = 25.5°, θmin = 3.1°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	h = −45→43
Tmin = 0.76, Tmax = 1.0	k = −15→15
31540 measured reflections	l = −30→29

Refinement

Refinement on F^2	22 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.067	H-atom parameters constrained
wR(F^2) = 0.204	w = 1/[σ^2(Fo^2) + (0.0841P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.99	(Δ/σ)max = 0.020
9143 reflections	Δρmax = 1.58 e Å^−3
543 parameters	Δρmin = −0.87 e Å^−3

Special details

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. The solvent ether molecule was disordered and this disorder results in site occupancies of 0.5 being assigned to all the atoms which also were restrained by DFIX command at 1.40 and 0.01. The C27, C28, C43, C44 of TBA cations were restrained by SIMU and DELU command at 0.02.

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 > 2σ(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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Mo1	0.22977 (3)	0.32515 (5)	0.35755 (3)	0.0265 (2)
Mo2	0.31512 (3)	0.42818 (5)	0.50430 (3)	0.0262 (2)
Mo3	0.16436 (3)	0.14502 (5)	0.35278 (3)	0.0291 (2)
Mn1	0.2500	0.2500	0.5000	0.0173 (4)
O1	0.1838 (2)	0.3827 (4)	0.2898 (3)	0.0390 (15)
O2	0.25663 (18)	0.4372 (3)	0.4179 (2)	0.0288 (13)
O3	0.21013 (18)	0.1850 (3)	0.3455 (2)	0.0260 (13)
O4	0.19603 (18)	0.3017 (3)	0.4088 (2)	0.0267 (13)
O5	0.1615 (2)	0.0196 (4)	0.3329 (3)	0.0482 (17)
O6	0.1167 (2)	0.2000 (4)	0.2861 (3)	0.0463 (17)
O7	0.2659 (2)	0.3085 (4)	0.3385 (3)	0.0326 (14)
O8	0.28509 (17)	0.2620 (3)	0.4686 (2)	0.0229 (12)
O9	0.27003 (19)	0.3910 (3)	0.5355 (2)	0.0275 (13)
O10	0.34910 (19)	0.4098 (4)	0.4812 (3)	0.0327 (14)
O11	0.3213 (2)	0.5526 (4)	0.5257 (3)	0.0358 (14)
O12	0.3524 (2)	0.3599 (4)	0.5894 (3)	0.0337 (14)
C53	0.0774 (7)	0.4822 (14)	0.2310 (10)	0.055 (5)*	0.5
C1	0.3144 (3)	0.1768 (5)	0.4822 (4)	0.031 (2)
H1A	0.3453	0.2010	0.5090	0.037*
H1B	0.3068	0.1524	0.4402	0.037*
C2	0.1707 (3)	0.3835 (6)	0.4104 (4)	0.032 (2)
H2A	0.1393	0.3631	0.3850	0.038*
H2B	0.1719	0.4431	0.3889	0.038*
C3	0.2649 (3)	0.0400 (5)	0.4783 (4)	0.0295 (19)
H3A	0.2571	0.0153	0.4362	0.035*
H3B	0.2657	−0.0183	0.5026	0.035*
C4	0.3117 (3)	0.0875 (5)	0.5185 (4)	0.0269 (18)
C5	0.3545 (3)	−0.0808 (6)	0.5603 (4)	0.037 (2)
H5A	0.3272	−0.1214	0.5381	0.045*
H5B	0.3652	−0.0681	0.6057	0.045*
C6	0.3895 (3)	−0.1384 (6)	0.5619 (4)	0.036 (2)
C7	0.3857 (3)	−0.2407 (6)	0.5505 (4)	0.032 (2)
H7	0.3602	−0.2750	0.5394	0.038*
C8	0.4200 (3)	−0.2950 (6)	0.5552 (4)	0.031 (2)
C9	0.4179 (3)	−0.4011 (6)	0.5452 (4)	0.040 (2)
H9	0.3937	−0.4369	0.5376	0.048*
C10	0.4504 (3)	−0.4547 (6)	0.5464 (4)	0.039 (2)
H10	0.4473	−0.5243	0.5376	0.046*
C11	0.4882 (3)	−0.4010 (7)	0.5612 (5)	0.049 (3)
H11	0.5111	−0.4359	0.5643	0.059*
C12	0.4914 (3)	−0.2999 (7)	0.5709 (5)	0.052 (3)
H12	0.5159	−0.2648	0.5792	0.063*
C13	0.4576 (3)	−0.2459 (6)	0.5687 (4)	0.042 (2)
C14	0.4607 (4)	−0.1369 (6)	0.5793 (6)	0.061 (3)
H14	0.4856	−0.1008	0.5895	0.073*
C15	0.4263 (3)	−0.0876 (7)	0.5741 (5)	0.052 (3)
H15	0.4278	−0.0172	0.5788	0.063*
C21	0.0257 (3)	0.0123 (7)	0.2339 (4)	0.050 (3)
H21A	0.0429	0.0577	0.2270	0.059*
H21B	0.0040	−0.0225	0.1920	0.059*
C22	0.0576 (3)	−0.0664 (7)	0.2854 (5)	0.046 (2)
H22A	0.0418	−0.1093	0.2963	0.056*
H22B	0.0824	−0.0331	0.3259	0.056*
C23	0.0757 (4)	−0.1318 (7)	0.2552 (5)	0.055 (3)
H23A	0.0509	−0.1689	0.2169	0.066*
H23B	0.0883	−0.0871	0.2397	0.066*
C24	0.1115 (4)	−0.2065 (8)	0.3049 (5)	0.071 (4)
H24A	0.1362	−0.1702	0.3430	0.107*
H24B	0.1222	−0.2438	0.2844	0.107*
H24C	0.0989	−0.2530	0.3188	0.107*
C25	0.0340 (4)	0.1350 (8)	0.3106 (5)	0.067 (3)
H25A	0.0526	0.1725	0.3026	0.080*
H25B	0.0534	0.0878	0.3469	0.080*
C26	0.0136 (5)	0.2107 (11)	0.3324 (8)	0.138 (7)
H26A	−0.0065	0.1753	0.3383	0.165*
H26B	−0.0035	0.2628	0.2986	0.165*
C27	0.0562 (4)	0.2631 (10)	0.4041 (8)	0.118 (5)
H27A	0.0769	0.2095	0.4333	0.142*
H27B	0.0723	0.3084	0.3951	0.142*
C28	0.0436 (5)	0.3178 (12)	0.4379 (8)	0.134 (6)
H28A	0.0701	0.3453	0.4784	0.201*
H28B	0.0238	0.3724	0.4101	0.201*
H28C	0.0284	0.2733	0.4483	0.201*
C29	0.2873 (4)	0.6331 (7)	0.3577 (5)	0.054 (3)
H29A	0.3138	0.6471	0.4030	0.064*
H29B	0.2716	0.5762	0.3596	0.064*
C30	0.2564 (4)	0.7264 (8)	0.3315 (5)	0.065 (3)
H30A	0.2687	0.7787	0.3198	0.077*
H30B	0.2270	0.7076	0.2911	0.077*
C31	0.2502 (5)	0.7710 (10)	0.3817 (6)	0.089 (4)
H31A	0.2794	0.7935	0.4209	0.107*
H31B	0.2310	0.8306	0.3618	0.107*
C32	0.2314 (6)	0.7032 (12)	0.4021 (8)	0.130 (7)
H32A	0.2287	0.7370	0.4332	0.196*
H32B	0.2021	0.6819	0.3639	0.196*
H32C	0.2506	0.6448	0.4231	0.196*
C33	0.3297 (3)	0.5046 (6)	0.3468 (4)	0.047 (3)
H33A	0.3101	0.4533	0.3445	0.056*
H33B	0.3538	0.5174	0.3937	0.056*
C34	0.3504 (5)	0.4606 (8)	0.3159 (6)	0.080 (4)
H34A	0.3289	0.4662	0.2677	0.095*
H34B	0.3769	0.5000	0.3304	0.095*
C35	0.3635 (5)	0.3519 (8)	0.3343 (7)	0.082 (4)
H35A	0.3366	0.3124	0.3172	0.099*
H35B	0.3759	0.3276	0.3123	0.099*
C36	0.3961 (5)	0.3330 (8)	0.4053 (6)	0.081 (4)
H36A	0.4027	0.2615	0.4128	0.122*
H36B	0.4233	0.3702	0.4226	0.122*
H36C	0.3838	0.3549	0.4275	0.122*
C37	0.2631 (3)	0.5877 (6)	0.2433 (4)	0.046 (3)
H37A	0.2747	0.5710	0.2189	0.055*
H37B	0.2472	0.6520	0.2261	0.055*
C38	0.2290 (4)	0.5040 (7)	0.2294 (4)	0.052 (3)
H38A	0.2443	0.4387	0.2449	0.063*
H38B	0.2173	0.5195	0.2536	0.063*
C39	0.1913 (4)	0.4982 (6)	0.1569 (4)	0.056 (3)
H39A	0.1753	0.4347	0.1481	0.067*
H39B	0.2039	0.4961	0.1329	0.067*
C40	0.1585 (4)	0.5825 (7)	0.1297 (5)	0.062 (3)
H40A	0.1355	0.5722	0.0828	0.094*
H40B	0.1450	0.5843	0.1520	0.094*
H40C	0.1736	0.6458	0.1368	0.094*
C41	0.3315 (4)	0.6838 (6)	0.3166 (4)	0.049 (3)
H41A	0.3429	0.6580	0.2937	0.059*
H41B	0.3124	0.7420	0.2916	0.059*
C42	0.3709 (4)	0.7194 (8)	0.3855 (4)	0.057 (3)
H42A	0.3877	0.6610	0.4135	0.069*
H42B	0.3599	0.7570	0.4060	0.069*
C43	0.4016 (5)	0.7875 (13)	0.3801 (7)	0.113 (5)
H43A	0.3838	0.8297	0.3405	0.135*
H43B	0.4193	0.8316	0.4189	0.135*
C44	0.4304 (5)	0.7230 (13)	0.3765 (7)	0.133 (6)
H44A	0.4502	0.7637	0.3731	0.200*
H44B	0.4479	0.6818	0.4160	0.200*
H44C	0.4125	0.6799	0.3380	0.200*
C51	0.0413 (8)	0.4779 (16)	0.1154 (11)	0.075 (7)*	0.5
C52	0.0769 (9)	0.5206 (19)	0.1791 (10)	0.101 (9)*	0.5
C54	0.0460 (17)	0.516 (5)	0.241 (3)	0.28 (3)*	0.5
C55	0.0153 (13)	0.5539 (18)	0.250 (2)	0.147 (14)*	0.5
N1	0.3444 (2)	0.0140 (5)	0.5260 (3)	0.0340 (17)
H1	0.3579	0.0287	0.5091	0.041*
N2	0.3027 (3)	0.6015 (5)	0.3165 (3)	0.042 (2)
N3	0.0000	0.0762 (7)	0.2500	0.044 (3)
C56	0.0000	0.6537 (17)	0.2500	0.048 (7)*	0.5
C50	0.0270 (16)	0.506 (3)	0.0504 (14)	0.169 (16)*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mo1	0.0401 (5)	0.0280 (4)	0.0187 (4)	0.0037 (3)	0.0217 (4)	0.0034 (3)
Mo2	0.0360 (5)	0.0252 (4)	0.0251 (4)	−0.0007 (3)	0.0227 (4)	−0.0008 (3)
Mo3	0.0339 (5)	0.0380 (4)	0.0173 (4)	−0.0046 (3)	0.0166 (3)	−0.0055 (3)
Mn1	0.0227 (9)	0.0200 (8)	0.0117 (7)	0.0029 (6)	0.0118 (7)	0.0008 (6)
O1	0.043 (4)	0.045 (3)	0.025 (3)	0.002 (3)	0.019 (3)	0.003 (3)
O2	0.032 (3)	0.033 (3)	0.027 (3)	0.000 (2)	0.020 (3)	−0.001 (2)
O3	0.036 (3)	0.026 (3)	0.022 (3)	0.005 (2)	0.020 (3)	0.000 (2)
O4	0.037 (4)	0.028 (3)	0.026 (3)	0.012 (2)	0.025 (3)	0.002 (2)
O5	0.063 (5)	0.047 (4)	0.044 (4)	−0.018 (3)	0.038 (4)	−0.017 (3)
O6	0.039 (4)	0.066 (4)	0.025 (3)	−0.001 (3)	0.015 (3)	0.002 (3)
O7	0.046 (4)	0.034 (3)	0.034 (3)	−0.003 (3)	0.033 (3)	−0.001 (2)
O8	0.024 (3)	0.027 (3)	0.020 (3)	0.001 (2)	0.015 (2)	−0.004 (2)
O9	0.040 (4)	0.020 (2)	0.032 (3)	0.005 (2)	0.027 (3)	0.001 (2)
O10	0.035 (4)	0.042 (3)	0.031 (3)	0.000 (3)	0.025 (3)	0.001 (2)
O11	0.043 (4)	0.027 (3)	0.044 (3)	0.001 (3)	0.030 (3)	0.001 (2)
O12	0.036 (4)	0.044 (3)	0.021 (3)	0.000 (3)	0.018 (3)	0.003 (2)
C1	0.042 (5)	0.029 (4)	0.033 (5)	0.011 (4)	0.028 (4)	0.004 (3)
C2	0.033 (5)	0.036 (4)	0.020 (4)	0.007 (4)	0.014 (4)	0.002 (3)
C3	0.048 (6)	0.020 (4)	0.035 (5)	0.005 (4)	0.033 (4)	−0.005 (3)
C4	0.037 (5)	0.028 (4)	0.025 (4)	0.007 (4)	0.024 (4)	−0.002 (3)
C5	0.048 (6)	0.032 (4)	0.039 (5)	0.010 (4)	0.030 (5)	0.009 (4)
C6	0.047 (6)	0.030 (4)	0.036 (5)	0.002 (4)	0.028 (5)	0.002 (4)
C7	0.037 (5)	0.035 (5)	0.029 (4)	0.003 (4)	0.024 (4)	0.002 (4)
C8	0.035 (5)	0.030 (4)	0.022 (4)	0.001 (4)	0.014 (4)	0.007 (3)
C9	0.041 (6)	0.044 (5)	0.029 (5)	−0.003 (4)	0.017 (4)	−0.003 (4)
C10	0.051 (6)	0.036 (5)	0.035 (5)	0.016 (4)	0.030 (5)	0.009 (4)
C11	0.048 (7)	0.052 (6)	0.056 (6)	0.022 (5)	0.036 (5)	0.001 (5)
C12	0.041 (6)	0.053 (6)	0.063 (7)	0.006 (5)	0.032 (6)	0.001 (5)
C13	0.047 (6)	0.036 (5)	0.045 (5)	0.010 (4)	0.030 (5)	0.002 (4)
C14	0.051 (7)	0.031 (5)	0.099 (9)	−0.005 (4)	0.045 (7)	0.001 (5)
C15	0.042 (6)	0.034 (5)	0.086 (8)	0.004 (4)	0.041 (6)	−0.010 (5)
C21	0.044 (6)	0.065 (6)	0.043 (6)	0.002 (5)	0.028 (5)	0.002 (5)
C22	0.040 (6)	0.061 (6)	0.044 (5)	0.004 (5)	0.029 (5)	0.005 (5)
C23	0.048 (7)	0.071 (7)	0.048 (6)	0.013 (5)	0.031 (6)	0.005 (5)
C24	0.094 (10)	0.074 (7)	0.064 (7)	0.030 (7)	0.057 (7)	0.014 (6)
C25	0.040 (7)	0.088 (8)	0.076 (8)	−0.010 (6)	0.038 (6)	−0.038 (6)
C26	0.081 (12)	0.141 (12)	0.210 (19)	−0.058 (10)	0.098 (13)	−0.110 (13)
C27	0.060 (8)	0.088 (8)	0.164 (12)	−0.020 (6)	0.047 (8)	−0.078 (7)
C28	0.084 (9)	0.122 (10)	0.159 (12)	−0.032 (8)	0.055 (8)	−0.042 (8)
C29	0.071 (8)	0.052 (6)	0.039 (5)	0.000 (5)	0.035 (6)	0.010 (5)
C30	0.076 (9)	0.062 (6)	0.053 (7)	0.013 (6)	0.038 (6)	0.010 (5)
C31	0.082 (11)	0.094 (9)	0.071 (9)	0.010 (8)	0.036 (8)	−0.001 (8)
C32	0.144 (17)	0.134 (13)	0.146 (15)	0.075 (12)	0.105 (14)	0.085 (11)
C33	0.053 (7)	0.047 (5)	0.034 (5)	−0.001 (5)	0.024 (5)	0.010 (4)
C34	0.121 (12)	0.066 (7)	0.078 (8)	0.019 (7)	0.075 (9)	0.004 (6)
C35	0.121 (13)	0.063 (7)	0.092 (10)	−0.015 (7)	0.080 (10)	−0.001 (7)
C36	0.089 (11)	0.081 (8)	0.094 (10)	−0.004 (7)	0.067 (9)	−0.015 (7)
C37	0.064 (7)	0.051 (5)	0.024 (5)	−0.009 (5)	0.027 (5)	0.014 (4)
C38	0.067 (8)	0.053 (6)	0.034 (5)	−0.019 (5)	0.030 (5)	0.007 (4)
C39	0.079 (8)	0.040 (5)	0.044 (6)	−0.016 (5)	0.035 (6)	0.002 (4)
C40	0.069 (8)	0.064 (7)	0.068 (7)	0.005 (6)	0.049 (7)	0.014 (6)
C41	0.079 (8)	0.035 (5)	0.031 (5)	−0.001 (5)	0.033 (5)	0.012 (4)
C42	0.065 (8)	0.068 (6)	0.033 (5)	−0.008 (6)	0.027 (5)	−0.005 (5)
C43	0.063 (10)	0.198 (15)	0.065 (7)	−0.043 (9)	0.033 (7)	−0.032 (8)
C44	0.083 (11)	0.223 (16)	0.068 (7)	−0.042 (10)	0.034 (8)	−0.019 (9)
N1	0.043 (5)	0.042 (4)	0.031 (4)	0.013 (3)	0.030 (4)	0.010 (3)
N2	0.058 (6)	0.044 (4)	0.024 (4)	−0.008 (4)	0.025 (4)	0.003 (3)
N3	0.040 (7)	0.047 (6)	0.045 (7)	0.000	0.026 (6)	0.000

Geometric parameters (Å, º)

Mo1—O7	1.704 (6)	C7—C8	1.406 (12)
Mo1—O1	1.693 (5)	C8—C13	1.388 (13)
Mo1—O2	1.906 (5)	C8—C9	1.410 (11)
Mo1—O3	1.936 (5)	C9—C10	1.390 (12)
Mo1—O4	2.316 (5)	C10—C11	1.413 (13)
Mo1—O8	2.399 (5)	C11—C12	1.343 (12)
Mo2—O11	1.691 (5)	C12—C13	1.420 (13)
Mo2—O10	1.711 (6)	C13—C14	1.448 (11)
Mo2—O12	1.928 (5)	C14—C15	1.372 (14)
Mo2—O2	1.933 (5)	C21—N3	1.506 (10)
Mo2—O9	2.311 (6)	C21—C22	1.513 (12)
Mo2—O8	2.366 (5)	C22—C23	1.554 (13)
Mo3—O6	1.696 (6)	C23—C24	1.510 (13)
Mo3—O5	1.705 (5)	C25—N3	1.477 (10)
Mo3—O3	1.906 (6)	C25—C26	1.544 (16)
Mo3—O12^i	1.912 (6)	C26—C27	1.665 (17)
Mo3—O4	2.365 (5)	C27—C28	1.399 (9)
Mo3—O9^i	2.400 (5)	C29—N2	1.525 (12)
Mn1—O8^i	1.912 (5)	C29—C30	1.531 (13)
Mn1—O8	1.912 (5)	C30—C31	1.536 (16)
Mn1—O9^i	1.994 (5)	C31—C32	1.415 (19)
Mn1—O9	1.994 (5)	C33—N2	1.510 (11)
Mn1—O4	2.043 (5)	C33—C34	1.513 (15)
Mn1—O4^i	2.043 (5)	C34—C35	1.489 (13)
O4—C2	1.451 (9)	C35—C36	1.448 (15)
O8—C1	1.454 (8)	C37—N2	1.517 (10)
O9—C3^i	1.447 (9)	C37—C38	1.552 (12)
O9—Mo3^i	2.400 (5)	C38—C39	1.483 (12)
O12—Mo3^i	1.912 (6)	C39—C40	1.475 (13)
C53—C52	1.396 (10)	C41—C42	1.514 (12)
C53—C54	1.404 (10)	C41—N2	1.523 (11)
C1—C4	1.529 (10)	C42—C43	1.528 (18)
C2—C4^i	1.537 (10)	C43—C44	1.415 (9)
C3—O9^i	1.447 (9)	C51—C50	1.430 (10)
C3—C4	1.523 (12)	C51—C52	1.437 (10)
C4—N1	1.477 (10)	C54—C55	1.410 (10)
C4—C2^i	1.537 (10)	C55—C55^ii	1.13 (5)
C5—N1	1.429 (9)	C55—C56	1.427 (10)
C5—C6	1.492 (12)	N3—C25^ii	1.477 (10)
C6—C7	1.363 (10)	N3—C21^ii	1.506 (10)
C6—C15	1.387 (13)	C56—C55^ii	1.427 (10)
O7—Mo1—O1	105.3 (3)	Mo2—O8—Mo1	89.86 (15)
O7—Mo1—O2	101.8 (2)	C3^i—O9—Mn1	115.9 (5)
O1—Mo1—O2	100.3 (2)	C3^i—O9—Mo2	121.7 (4)
O7—Mo1—O3	97.1 (2)	Mn1—O9—Mo2	101.2 (2)
O1—Mo1—O3	102.2 (2)	C3^i—O9—Mo3^i	122.1 (4)
O2—Mo1—O3	145.5 (2)	Mn1—O9—Mo3^i	100.39 (19)
O7—Mo1—O4	159.8 (2)	Mo2—O9—Mo3^i	90.5 (2)
O1—Mo1—O4	93.4 (3)	Mo3^i—O12—Mo2	121.2 (3)
O2—Mo1—O4	81.7 (2)	C52—C53—C54	121 (3)
O3—Mo1—O4	71.19 (19)	O8—C1—C4	114.6 (7)
O7—Mo1—O8	91.1 (2)	O4—C2—C4^i	113.4 (6)
O1—Mo1—O8	162.9 (2)	O9^i—C3—C4	114.0 (6)
O2—Mo1—O8	70.92 (18)	N1—C4—C3	110.1 (6)
O3—Mo1—O8	80.18 (18)	N1—C4—C1	103.1 (6)
O4—Mo1—O8	71.06 (18)	C3—C4—C1	112.6 (7)
O11—Mo2—O10	105.1 (3)	N1—C4—C2^i	106.3 (6)
O11—Mo2—O12	103.2 (2)	C3—C4—C2^i	112.2 (7)
O10—Mo2—O12	97.7 (3)	C1—C4—C2^i	111.9 (6)
O11—Mo2—O2	98.1 (2)	N1—C5—C6	111.1 (7)
O10—Mo2—O2	100.8 (2)	C7—C6—C15	118.7 (9)
O12—Mo2—O2	146.9 (2)	C7—C6—C5	121.2 (8)
O11—Mo2—O9	94.6 (2)	C15—C6—C5	120.0 (7)
O10—Mo2—O9	159.7 (2)	C6—C7—C8	120.7 (9)
O12—Mo2—O9	72.6 (2)	C13—C8—C7	121.4 (7)
O2—Mo2—O9	80.8 (2)	C13—C8—C9	116.0 (8)
O11—Mo2—O8	162.3 (2)	C7—C8—C9	122.6 (8)
O10—Mo2—O8	91.1 (2)	C10—C9—C8	123.1 (9)
O12—Mo2—O8	81.28 (19)	C9—C10—C11	118.4 (8)
O2—Mo2—O8	71.27 (18)	C12—C11—C10	120.2 (9)
O9—Mo2—O8	70.11 (17)	C11—C12—C13	120.7 (10)
O6—Mo3—O5	106.2 (3)	C8—C13—C12	121.5 (8)
O6—Mo3—O3	104.5 (3)	C8—C13—C14	117.4 (9)
O5—Mo3—O3	97.8 (3)	C12—C13—C14	121.1 (10)
O6—Mo3—O12^i	97.9 (3)	C15—C14—C13	118.9 (10)
O5—Mo3—O12^i	101.6 (3)	C14—C15—C6	122.8 (8)
O3—Mo3—O12^i	144.8 (2)	N3—C21—C22	116.5 (7)
O6—Mo3—O4	93.6 (2)	C21—C22—C23	107.9 (8)
O5—Mo3—O4	159.1 (3)	C24—C23—C22	112.5 (8)
O3—Mo3—O4	70.53 (19)	N3—C25—C26	114.0 (9)
O12^i—Mo3—O4	81.4 (2)	C25—C26—C27	107.6 (11)
O6—Mo3—O9^i	162.5 (2)	C28—C27—C26	115.0 (12)
O5—Mo3—O9^i	89.5 (2)	N2—C29—C30	115.1 (8)
O3—Mo3—O9^i	80.4 (2)	C31—C30—C29	113.8 (9)
O12^i—Mo3—O9^i	70.8 (2)	C32—C31—C30	114.9 (12)
O4—Mo3—O9^i	71.84 (16)	N2—C33—C34	117.0 (8)
O8^i—Mn1—O8	180.0	C35—C34—C33	112.4 (10)
O8^i—Mn1—O9^i	86.9 (2)	C36—C35—C34	114.7 (10)
O8—Mn1—O9^i	93.1 (2)	N2—C37—C38	114.7 (6)
O8^i—Mn1—O9	93.1 (2)	C39—C38—C37	110.3 (7)
O8—Mn1—O9	86.9 (2)	C38—C39—C40	115.5 (9)
O9^i—Mn1—O9	180.0	C42—C41—N2	114.3 (7)
O8^i—Mn1—O4	92.3 (2)	C41—C42—C43	109.6 (9)
O8—Mn1—O4	87.7 (2)	C44—C43—C42	107.5 (15)
O9^i—Mn1—O4	87.7 (2)	C50—C51—C52	129 (3)
O9—Mn1—O4	92.3 (2)	C53—C52—C51	113 (2)
O8^i—Mn1—O4^i	87.7 (2)	C53—C54—C55	177 (6)
O8—Mn1—O4^i	92.3 (2)	C55^ii—C55—C54	157 (4)
O9^i—Mn1—O4^i	92.3 (2)	C55^ii—C55—C56	66.6 (12)
O9—Mn1—O4^i	87.7 (2)	C54—C55—C56	134 (4)
O4—Mn1—O4^i	180.0	C5—N1—C4	122.6 (7)
Mo1—O2—Mo2	122.5 (3)	C29—N2—C37	111.7 (8)
Mo3—O3—Mo1	121.6 (3)	C29—N2—C33	107.2 (6)
C2—O4—Mn1	115.2 (4)	C37—N2—C33	111.7 (7)
C2—O4—Mo1	120.5 (4)	C29—N2—C41	111.5 (7)
Mn1—O4—Mo1	100.1 (2)	C37—N2—C41	104.5 (6)
C2—O4—Mo3	124.3 (5)	C33—N2—C41	110.2 (8)
Mn1—O4—Mo3	100.12 (18)	C25^ii—N3—C25	116.9 (11)
Mo1—O4—Mo3	91.50 (17)	C25^ii—N3—C21	107.3 (6)
C1—O8—Mn1	116.6 (4)	C25—N3—C21	106.5 (6)
C1—O8—Mo2	120.4 (5)	C25^ii—N3—C21^ii	106.5 (6)
Mn1—O8—Mo2	101.79 (19)	C25—N3—C21^ii	107.3 (6)
C1—O8—Mo1	122.0 (4)	C21—N3—C21^ii	112.3 (10)
Mn1—O8—Mo1	101.2 (2)	C55^ii—C56—C55	47 (2)

Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) −x, y, −z+1/2.