A new polymorph of tetra­ethyl­ammonium tris­(μ acetato O,O′)­tri μ chloro tri­chloro μ3 oxo triangulo trimolybdenum

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(1)metal-organic papers A new polymorph of tetraethylammonium tris(l-acetato-O,O0 )tri-l-chloro-trichlorol3-oxo-triangulo-trimolybdenum. Acta Crystallographica Section E. Structure Reports Online ISSN 1600-5368. Yu-Biao Chen, Zhao-Ji Li, Ye-Yan Qin, Yao Kang, Jian-Kai Cheng, Rui-Feng Hu, Yi-Hang Wen and Yuan-Gen Yao* The State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, People's Republic of China. The title compound, [(C2H5)4N][Mo3Cl6O(C2H3O2)3], has been synthesized by the reaction of MoCl33H2O with CH3COOH. The structure is a polymorph of the structure reported by Chen, Lu, Huang, Huang & Huang [Chin. J. Struct. Chem. (1993). 12, 117±123]. The crystal contains discrete cations and anions. The mono-oxo-capped trinuclear Mo cluster anion consists of three Cl atoms and three acetate groups that bridge the three edges of the Mo triangle; each Mo atom is also coordinated by one terminal Cl atom. The coordination around Mo is a distorted octahedron.. Received 30 July 2002 Accepted 2 August 2002 Online 23 August 2002. Correspondence e-mail: yyg@ms.fjirsm.ac.cn. Comment Key indicators Single-crystal X-ray study T = 293 K Ê Mean (C±C) = 0.020 A R factor = 0.071 wR factor = 0.157 Data-to-parameter ratio = 17.5 For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.. # 2002 International Union of Crystallography Printed in Great Britain ± all rights reserved. m490. Yu-Biao Chen et al.. . A series of trinuclear Mo3 cluster compounds with the cluster anions {[Mo3(3±O)(-X)3(-O2R)3X3]ÿ (R = H, ÐCH3, ÐC2H5, X = Cl, Br)} have been synthesized and structurally characterized (Cotton et al., 1991a,b; Zhuang et al., 1985, 1996; Chen et al., 1993; Wu et al., 1984; Lin & Chen, 1988). As an extension of these studies, we here report the synthesis and crystal structure of the title compound, (I), which was synthesized in a similar way to that described by Chen et al. (1993). However, the two crystal structures are polymorphs.. A view of the structure of (I) is shown in Fig. 1. The three Mo atoms of the cluster anion form an approximately equilateral triangle. On one side of the Mo3 plane, one 3-O atom binds the three Mo atoms together to form an Mo3O monocapped cluster skeleton. The three acetate (Ac) ligands and the 3-O atom are situated on the same side of the plane. In addition, three terminal Cl atoms and three bridging Cl atoms are situated on the other side of the Mo3 plane. Each unit cell consists of four formula units of [Et4N][Mo3OCl6(Ac)3], existing as discrete ions. The synthetic route and chemical composition of the title complex is identical to that of the complex reported by Chen et al. (1993). However, both structures are polymorphs. This re¯ects the diversity of crystal. (C8H20N)[Mo3Cl6O(C2H3O2)3]. DOI: 10.1107/S1600536802013892. Acta Cryst. (2002). E58, m490±m491.

(2) metal-organic papers Table 1. Ê ). Selected interatomic distances (A. Figure 1. A view of the asymmetric unit of the title compound, showing 30% probability displacement ellipsoids. H atoms have been omitted for clarity.. packing of this series of trinuclear Mo cluster compounds. The formal oxidation state of the Mo atoms is 3.33, so that the Mo3 core possesses eight electrons to form three metal±metal Ê ] is bonds. The average MoÐMo distance [2.5778 (14) A consistent with an eight-electron system and the angles are normal.. Experimental A mixture of 5.2 g (20 mmol) of MoCl33H2O in 40 ml of acetic acid was re¯uxed at 353 K for 2 h. After cooling, 40 ml of ethanol saturated with HCl and 2.0 g (7.8 mmol) of (Et)4NI was added and the mixture was stirred for 1 h. Several days later, crude crystals precipitated. On recrystallization from CH2Cl2, black single crystals were obtained. Crystal data (C8H20N)[Mo3Cl6O(C2H3O2)3] Mr = 823.90 Triclinic, P1 Ê a = 7.9356 (1) A Ê b = 14.4258 (1) A Ê c = 24.4415 (4) A = 96.613 (1)

(3) = 92.518 (1) = 91.815 (1) Ê3 V = 2774.80 (6) A. Z=4 Dx = 1.972 Mg mÿ3 Mo K radiation Cell parameters from 6220 re¯ections  = 0.8±25.1  = 1.95 mmÿ1 T = 293 (2) K Prism, black 0.84  0.20  0.02 mm. Data collection Siemens SMART CCD diffractometer ' and ! scans Absorption correction: multi-scan (SADABS; Sheldrick, 1996) Tmin = 0.680, Tmax = 1.000 14579 measured re¯ections. 9771 independent re¯ections 7292 re¯ections with I > 2(I) Rint = 0.041 max = 25.1 h = ÿ9 ! 9 k = ÿ15 ! 17 l = ÿ29 ! 26. Re®nement Re®nement on F 2 R[F 2 > 2(F 2)] = 0.071 wR(F 2) = 0.157 S = 1.07 9771 re¯ections 559 parameters Acta Cryst. (2002). E58, m490±m491. H atom not re®ned w = 1/[ 2(Fo2) + 55.1956P] where P = (Fo2 + 2Fc2)/3 (/)max = 0.005 Ê ÿ3 max = 0.80 e A Ê ÿ3 min = ÿ0.81 e A. Mo6ÐO14 Mo6ÐO10 Mo6ÐO11 Mo6ÐCl9 Mo6ÐCl12 Mo6ÐCl8 Mo6ÐMo4 Mo6ÐMo5 Mo2ÐO13 Mo2ÐO2 Mo2ÐO3 Mo2ÐCl2 Mo2ÐCl5 Mo2ÐCl1 Mo2ÐMo3 Mo2ÐMo1 Mo3ÐO13 Mo3ÐO5 Mo3ÐO4 Mo3ÐCl3 Mo3ÐCl6. 1.995 (7) 2.071 (7) 2.079 (7) 2.406 (3) 2.415 (3) 2.430 (3) 2.5746 (14) 2.5894 (14) 1.981 (7) 2.078 (8) 2.089 (8) 2.405 (3) 2.406 (3) 2.418 (3) 2.5722 (14) 2.5798 (14) 1.992 (7) 2.068 (8) 2.068 (8) 2.413 (3) 2.414 (3). Mo3ÐCl2 Mo3ÐMo1 Mo5ÐO14 Mo5ÐO9 Mo5ÐO8 Mo5ÐCl11 Mo5ÐCl7 Mo5ÐCl8 Mo5ÐMo4 Mo1ÐO13 Mo1ÐO6 Mo1ÐO1 Mo1ÐCl4 Mo1ÐCl3 Mo1ÐCl1 Mo4ÐO14 Mo4ÐO12 Mo4ÐO7 Mo4ÐCl9 Mo4ÐCl10 Mo4ÐCl7. 2.417 (3) 2.5756 (13) 1.986 (7) 2.070 (7) 2.092 (7) 2.404 (3) 2.411 (3) 2.423 (3) 2.5751 (14) 1.985 (7) 2.070 (8) 2.080 (8) 2.406 (3) 2.409 (3) 2.425 (3) 1.997 (7) 2.063 (8) 2.070 (8) 2.417 (3) 2.419 (3) 2.422 (3). H atoms were placed in calculated positions and not re®ned. Data collection: SMART (Siemens, 1995); cell re®nement: SAINT (Siemens, 1995); data reduction: XPREP in SHELXTL-Plus (Sheldrick, 1991); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus; software used to prepare material for publication: SHELXL97.. This work was ®nancially supported by the NSF of China (Nos. 29733090 and 20173063), the State Key Basic Research and Development Plan of China (001CB108906), Key Project in KIP of CAS (KJCX2-H3) and the NNSF of Fujian Province (E0020001).. References Chen, Q. H., Lu, S. F., Huang, J. Q., Huang, Z. X. & Huang, X. Y. (1993). Chin. J. Struct. Chem. 12, 117±123. Cotton, F. A., Shang, M. Y. & Zhong, S. S. (1991a). J. Am. Chem. Soc. 113, 3007±3011. Cotton, F. A., Shang, M. Y. & Zhong, S. S. (1991b). J. Am. Chem. Soc. 113, 6917±6922. Lin, X. C. & Chen, G. (1988). Acta Chim. Sin. (Chin.), 46, 439±444. Sheldrick, G. M. (1990). Acta Cryst. A46, 467±473. Sheldrick, G. M. (1991). SHELXTL-Plus. Release 4.1. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Sheldrick, G. M. (1996). SADABS. University of GoÈttingen, Germany. Sheldrick, G. M. (1997). SHELXL97. University of GoÈttingen, Germany. Siemens (1995). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Wu, D. M., Zhuang, H. H., Zheng, J. J., Huang, J. L. & Lu, J. X. (1984). Chin. J. Struct. Chem. 3, 51±55. Zhuang, H. H., Wu, D. M., Huang, J. Q. & Huang, J. L. (1996). Chin. J. Struct. Chem. 15, 257±260. Zhuang, H. H., Wu, D. M., Zheng, J. J. Huang, J. Q. & Huang, J. L. (1985). Chin. Sci. Bull. (Chin.), 1220±1223.. Yu-Biao Chen et al.. . (C8H20N)[Mo3Cl6O(C2H3O2)3]. m491.

(4) supporting information. supporting information Acta Cryst. (2002). E58, m490–m491. [doi:10.1107/S1600536802013892]. A new polymorph of tetraethylammonium tris(µ-acetato-O,O′)tri-µ-chloro-trichloro-µ3-oxo-triangulo-trimolybdenum Yu-Biao Chen, Zhao-Ji Li, Ye-Yan Qin, Yao Kang, Jian-Kai Cheng, Rui-Feng Hu, Yi-Hang Wen and Yuan-Gen Yao S1. Comment A series of trinuclear Mo3 cluster compounds with the cluster anions {[Mo3(µ3-O)(µ-X)3(µ-O2R)3X3]− (R = H, –CH3, – C2H5, X = Cl, Br)} have been synthesized and structurally characterized (Cotton et al., 1991a,b; Zhuang et al., 1985, 1996; Chen et al., 1993; Wu et al., 1984; Lin & Chen, 1988). As an extension of these works, we here report the synthesis and crystal structure of the title compound, (I), which was synthesized in a similar way to that described by Chen et al. (1993). However, the two crystal structures are polymorphs. A view of the structure of (I) is shown in Fig. 1. The three Mo atoms of the cluster anion form an approximately equilateral triangle. On the side of the Mo3 plane, one µ3-O atom binds the three Mo atoms together to form an Mo3O mono-capped cluster skeleton. The three acetate (Ac) ligands and the µ3-O atom are situated on the same side of the plane. In addition, three terminal Cl atoms and three bridging Cl atoms are situated on the other side of the Mo3 plane. Each unit cell consists of four formula units of [Et4N][Mo3OCl6(Ac)3], which are discrete ions. The synthetic route and chemical composition of the title complex is identical to that of the complex reported by Chen et al. (1993). However, both structures are polymorphs. This reflects the diversity of crystal packing of this series of trinuclear Mo cluster compounds. The formal oxidation state of the Mo atoms is 3.33, so that the Mo3 core possesses eight electrons to form three metal–metal bonds. The average Mo—Mo distance [2.5778 (14) Å] is consistent with an eight-electron system. S2. Experimental A mixture of 5.2 g (20 mmol) of MoCl3·3H2O in 40 ml of acetic acid was refluxed at 353 K for 2 h. After cooling, 40 ml of ethanol saturated by HCl and 2.0 g (7.8 mmol) of (Et)4NI was added and the mixture was stirred for 1 h. Several days later, crude crystals precipitated. On recrystallization from CH2Cl2, black single crystals were obtained. S3. Refinement H atoms were all set to calculated positions and not refined.. Acta Cryst. (2002). E58, m490–m491. sup-1.

(5) supporting information. Figure 1 A view of the structure of the title compound, showing 30% probability displacement ellipsoids. H atoms have been omitted for clarity. (I) Crystal data (C2H5N)[Mo3Cl6O(C2H3O2)3] Mr = 823.90 Triclinic, P1 a = 7.9356 (1) Å b = 14.4258 (1) Å c = 24.4415 (4) Å α = 96.613 (1)° β = 92.518 (1)° γ = 91.815 (1)° V = 2774.80 (6) Å3. Z=4 F(000) = 1616 Dx = 1.972 Mg m−3 Mo Kα radiation, λ = 0.71073 Å Cell parameters from 6220 reflections θ = 0.8–25.1° µ = 1.95 mm−1 T = 293 K Prism, black 0.84 × 0.20 × 0.02 mm. Data collection Siemens SMART CCD diffractometer Radiation source: fine-focus sealed tube Graphite monochromator φ and ω scans Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) Tmin = 0.680, Tmax = 1.000. Acta Cryst. (2002). E58, m490–m491. 14579 measured reflections 9771 independent reflections 7292 reflections with I > 2σ(I) Rint = 0.041 θmax = 25.1°, θmin = 0.8° h = −9→9 k = −15→17 l = −29→26. sup-2.

(6) supporting information Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.071 wR(F2) = 0.157 S = 1.07 9771 reflections 559 parameters 0 restraints Primary atom site location: structure-invariant direct methods. Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ2(Fo2) + 55.1956P] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max = 0.005 Δρmax = 0.80 e Å−3 Δρmin = −0.81 e Å−3. Special details Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. 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 > σ(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). Mo6 Mo2 Mo3 Mo5 Mo1 Mo4 Cl8 Cl7 Cl9 Cl1 Cl3 Cl11 Cl4 Cl2 Cl6 Cl10 Cl12 Cl5 O14 O13 O10 O5 O12 O11 O9. x. y. z. Uiso*/Ueq. 0.69390 (12) 0.22701 (13) 0.36214 (13) 0.73040 (12) 0.23874 (12) 0.82278 (13) 0.4600 (4) 0.6312 (4) 0.5832 (4) −0.0231 (4) 0.1564 (4) 0.6126 (4) 0.0944 (4) 0.1377 (4) 0.3975 (5) 0.8318 (5) 0.5202 (4) 0.0636 (4) 0.9010 (8) 0.4228 (9) 0.7550 (10) 0.5505 (9) 0.9833 (10) 0.8755 (10) 0.7905 (10). 0.11122 (7) −0.12059 (7) −0.26659 (7) 0.25706 (7) −0.27048 (7) 0.26484 (7) 0.1752 (2) 0.3743 (2) 0.1835 (2) −0.1937 (2) −0.3845 (2) 0.3444 (2) −0.3673 (2) −0.1886 (2) −0.3570 (2) 0.3646 (2) −0.0258 (2) 0.0122 (2) 0.1849 (5) −0.1900 (5) 0.0364 (5) −0.3465 (6) 0.1812 (5) 0.0473 (5) 0.1633 (5). 0.39186 (4) 0.10533 (4) 0.13669 (4) 0.46432 (4) 0.03718 (4) 0.36521 (4) 0.44300 (13) 0.40919 (12) 0.31459 (13) 0.05651 (13) 0.09652 (13) 0.54238 (13) −0.03834 (13) 0.18511 (12) 0.21331 (14) 0.29225 (13) 0.35826 (14) 0.13473 (15) 0.4221 (3) 0.0772 (3) 0.4569 (3) 0.1020 (3) 0.3191 (3) 0.3432 (3) 0.5195 (3). 0.0368 (2) 0.0397 (2) 0.0398 (2) 0.0362 (2) 0.0382 (2) 0.0391 (2) 0.0500 (7) 0.0476 (7) 0.0510 (8) 0.0489 (7) 0.0482 (7) 0.0521 (8) 0.0558 (8) 0.0510 (7) 0.0622 (9) 0.0602 (9) 0.0530 (8) 0.0616 (9) 0.0342 (16) 0.0388 (17) 0.0405 (18) 0.046 (2) 0.0439 (19) 0.0396 (18) 0.0410 (18). Acta Cryst. (2002). E58, m490–m491. sup-3.

(7) supporting information O8 O2 O3 O7 O4 O1 O6 C11 C1 C3 C5 C10 H10A H10B H10C C9 C6 H6A H6B H6C C12 H12A H12B H12C C7 C4 H4A H4B H4C C8 H8A H8B H8C C2 H2A H2B H2C C13 H13A H13B C18 H18A H18B H18C C20 H20A H20B H20C. 0.9480 (9) 0.2718 (10) 0.4213 (11) 1.0235 (10) 0.5359 (10) 0.2837 (10) 0.4457 (10) 0.9857 (15) 0.2924 (15) 0.5353 (16) 0.5578 (15) 0.8372 (16) 0.8603 0.9359 0.7456 0.7898 (14) 0.7068 (16) 0.6983 0.7104 0.8079 1.1214 (17) 1.1079 1.2298 1.1136 1.0493 (16) 0.6768 (18) 0.6616 0.7819 0.6781 1.2075 (16) 1.2736 1.2718 1.1783 0.3262 (17) 0.3395 0.4276 0.2332 0.1502 (18) 0.0957 0.2696 0.2127 (19) 0.2680 0.2722 0.0988 0.3920 (19) 0.4322 0.4552 0.4061. Acta Cryst. (2002). E58, m490–m491. 0.3402 (5) −0.0505 (6) −0.0456 (6) 0.3480 (6) −0.1736 (6) −0.1805 (6) −0.3482 (6) 0.0940 (9) −0.0934 (10) −0.0858 (9) −0.3674 (8) 0.0139 (9) 0.0517 −0.0194 −0.0298 0.0757 (9) −0.4188 (10) −0.4304 −0.4771 −0.3821 0.0416 (10) −0.0236 0.0648 0.0502 0.3649 (8) −0.0276 (11) 0.0369 −0.0468 −0.0354 0.4187 (9) 0.4332 0.3817 0.4755 −0.0345 (11) −0.0743 0.0032 0.0053 0.3095 (10) 0.2535 0.3076 0.2066 (10) 0.1500 0.2585 0.2026 0.4114 (10) 0.4670 0.3593 0.4194. 0.4881 (3) 0.0375 (3) 0.1533 (3) 0.4019 (3) 0.1807 (3) −0.0217 (3) 0.0159 (3) 0.3200 (4) −0.0102 (5) 0.1790 (5) 0.0504 (5) 0.5491 (5) 0.5838 0.5388 0.5525 0.5056 (5) 0.0306 (6) −0.0089 0.0459 0.0420 0.2906 (6) 0.2946 0.3063 0.2523 0.4531 (5) 0.2088 (6) 0.2042 0.1940 0.2473 0.4754 (6) 0.4453 0.4984 0.4967 −0.0559 (6) −0.0895 −0.0466 −0.0606 0.7284 (5) 0.7389 0.7383 0.5789 (6) 0.5673 0.5663 0.5636 0.6635 (6) 0.6493 0.6489 0.7030. 0.0414 (18) 0.047 (2) 0.052 (2) 0.048 (2) 0.050 (2) 0.050 (2) 0.048 (2) 0.046 (3) 0.051 (3) 0.049 (3) 0.045 (3) 0.052 (3) 0.077* 0.077* 0.077* 0.044 (3) 0.061 (4) 0.091* 0.091* 0.091* 0.061 (4) 0.092* 0.092* 0.092* 0.045 (3) 0.069 (4) 0.104* 0.104* 0.104* 0.062 (4) 0.093* 0.093* 0.093* 0.066 (4) 0.099* 0.099* 0.099* 0.061 (4) 0.073* 0.073* 0.066 (4) 0.099* 0.099* 0.099* 0.068 (4) 0.102* 0.102* 0.102*. sup-4.

(8) supporting information C17 H17A H17B C19 H19A H19B C16 H16A H16B H16C C21 H21A H21B C15 H15A H15B C23 H23A H23B C24 H24A H24B H24C C28 H28A H28B H28C C25 H25A H25B C14 H14A H14B H14C C27 H27A H27B C22 H22A H22B H22C C26 H26A H26B H26C N1 N2. 0.211 (2) 0.1530 0.3266 0.2077 (19) 0.1461 0.1951 −0.1645 (18) −0.2791 −0.1599 −0.1234 1.105 (2) 1.0794 1.0768 −0.0565 (17) −0.1036 −0.0640 1.342 (2) 1.2884 1.4628 1.293 (2) 1.3304 1.3449 1.1725 1.314 (2) 1.3522 1.1942 1.3709 1.379 (3) 1.3443 1.3367 0.079 (2) 0.0988 −0.0397 0.1340 1.351 (2) 1.4714 1.2959 0.993 (2) 0.8772 1.0172 1.0141 1.569 (3) 1.6086 1.6053 1.6129 0.1278 (13) 1.2964 (15). Acta Cryst. (2002). E58, m490–m491. 0.2206 (9) 0.1670 0.2223 0.3934 (9) 0.4471 0.3882 0.2270 (12) 0.2331 0.2287 0.1687 0.3311 (11) 0.3837 0.3479 0.3063 (11) 0.3646 0.3040 0.2272 (10) 0.1750 0.2209 0.2195 (12) 0.1615 0.2705 0.2214 0.3886 (13) 0.3758 0.3975 0.4441 0.3995 (11) 0.4548 0.4035 0.3933 (12) 0.3895 0.3947 0.4492 0.3071 (12) 0.2981 0.2513 0.2490 (13) 0.2651 0.2326 0.1969 0.4016 (16) 0.4572 0.3477 0.4014 0.3082 (7) 0.3163 (7). 0.6416 (6) 0.6538 0.6565 0.6468 (6) 0.6613 0.6069 0.6631 (6) 0.6501 0.7025 0.6469 0.1646 (6) 0.1910 0.1281 0.6471 (6) 0.6620 0.6072 0.1351 (6) 0.1503 0.1392 0.0744 (6) 0.0565 0.0586 0.0694 0.2696 (7) 0.3057 0.2692 0.2607 0.1495 (8) 0.1721 0.1121 0.7609 (6) 0.7996 0.7524 0.7514 0.2277 (6) 0.2294 0.2383 0.1741 (8) 0.1704 0.2106 0.1475 0.1502 (10) 0.1360 0.1277 0.1874 0.6656 (4) 0.1693 (4). 0.065 (4) 0.078* 0.078* 0.062 (4) 0.075* 0.075* 0.078 (5) 0.117* 0.117* 0.117* 0.072 (4) 0.086* 0.086* 0.069 (4) 0.082* 0.082* 0.072 (4) 0.086* 0.086* 0.088 (5) 0.131* 0.131* 0.131* 0.095 (6) 0.142* 0.142* 0.142* 0.092 (6) 0.111* 0.111* 0.087 (5) 0.130* 0.130* 0.130* 0.088 (5) 0.105* 0.105* 0.099 (6) 0.148* 0.148* 0.148* 0.126 (8) 0.189* 0.189* 0.189* 0.049 (3) 0.058 (3). sup-5.

(9) supporting information Atomic displacement parameters (Å2). Mo6 Mo2 Mo3 Mo5 Mo1 Mo4 Cl8 Cl7 Cl9 Cl1 Cl3 Cl11 Cl4 Cl2 Cl6 Cl10 Cl12 Cl5 O14 O13 O10 O5 O12 O11 O9 O8 O2 O3 O7 O4 O1 O6 C11 C1 C3 C5 C10 C9 C6 C12 C7 C4 C8 C2 C13. U11. U22. U33. U12. U13. U23. 0.0367 (5) 0.0402 (6) 0.0399 (6) 0.0364 (5) 0.0360 (5) 0.0445 (6) 0.0404 (16) 0.0526 (18) 0.0553 (18) 0.0385 (15) 0.0484 (17) 0.0545 (18) 0.0507 (18) 0.0588 (19) 0.075 (2) 0.087 (3) 0.0469 (17) 0.061 (2) 0.031 (4) 0.038 (4) 0.047 (5) 0.036 (4) 0.053 (5) 0.046 (5) 0.052 (5) 0.040 (4) 0.046 (5) 0.058 (5) 0.055 (5) 0.043 (5) 0.050 (5) 0.041 (5) 0.046 (7) 0.037 (7) 0.050 (8) 0.048 (7) 0.060 (8) 0.031 (6) 0.046 (8) 0.055 (8) 0.051 (7) 0.063 (9) 0.047 (8) 0.057 (9) 0.062 (9). 0.0361 (5) 0.0425 (6) 0.0457 (6) 0.0356 (5) 0.0463 (6) 0.0372 (5) 0.0472 (17) 0.0428 (16) 0.0499 (18) 0.0565 (18) 0.0458 (17) 0.0524 (18) 0.067 (2) 0.0577 (19) 0.065 (2) 0.0516 (19) 0.0489 (18) 0.054 (2) 0.038 (4) 0.049 (5) 0.034 (4) 0.058 (5) 0.041 (5) 0.035 (4) 0.039 (5) 0.044 (5) 0.052 (5) 0.043 (5) 0.049 (5) 0.061 (6) 0.061 (6) 0.055 (5) 0.062 (9) 0.072 (10) 0.055 (8) 0.034 (6) 0.053 (8) 0.057 (8) 0.067 (9) 0.063 (9) 0.034 (6) 0.085 (11) 0.057 (8) 0.087 (11) 0.072 (10). 0.0373 (5) 0.0369 (5) 0.0341 (5) 0.0363 (5) 0.0323 (5) 0.0361 (5) 0.0606 (19) 0.0499 (17) 0.0472 (17) 0.0510 (18) 0.0506 (17) 0.0483 (17) 0.0465 (18) 0.0377 (16) 0.0494 (19) 0.0456 (18) 0.060 (2) 0.069 (2) 0.033 (4) 0.030 (4) 0.040 (5) 0.047 (5) 0.040 (4) 0.037 (4) 0.031 (4) 0.038 (4) 0.044 (5) 0.053 (5) 0.042 (5) 0.041 (5) 0.041 (5) 0.047 (5) 0.027 (6) 0.045 (8) 0.040 (7) 0.057 (8) 0.045 (7) 0.044 (7) 0.067 (9) 0.067 (9) 0.053 (8) 0.054 (8) 0.079 (10) 0.060 (9) 0.047 (8). 0.0032 (4) 0.0026 (4) 0.0017 (4) 0.0019 (4) 0.0059 (4) 0.0056 (4) 0.0016 (13) 0.0153 (14) 0.0063 (14) 0.0069 (13) −0.0053 (14) 0.0036 (15) 0.0119 (16) 0.0017 (15) 0.0062 (18) 0.0096 (17) −0.0040 (14) 0.0130 (16) 0.003 (3) 0.001 (4) −0.001 (3) 0.011 (4) 0.007 (4) 0.012 (4) 0.000 (4) −0.005 (4) 0.001 (4) 0.001 (4) −0.003 (4) −0.003 (4) 0.008 (4) 0.008 (4) 0.005 (6) −0.003 (6) −0.003 (6) 0.009 (5) 0.007 (6) −0.002 (5) 0.018 (7) 0.020 (7) 0.009 (5) −0.029 (8) −0.015 (6) −0.006 (8) −0.010 (7). −0.0019 (4) 0.0015 (4) −0.0034 (4) 0.0016 (4) −0.0017 (4) 0.0020 (4) 0.0040 (14) 0.0055 (14) −0.0110 (14) −0.0043 (13) −0.0023 (14) 0.0094 (14) −0.0122 (14) 0.0114 (14) −0.0091 (17) 0.0106 (17) −0.0059 (15) 0.0065 (17) −0.007 (3) 0.003 (3) 0.004 (4) 0.000 (4) 0.009 (4) 0.000 (4) −0.002 (3) 0.007 (4) 0.002 (4) −0.003 (4) 0.008 (4) −0.016 (4) 0.000 (4) 0.002 (4) −0.003 (5) −0.005 (6) 0.011 (6) 0.004 (6) 0.008 (6) 0.009 (5) −0.003 (7) 0.011 (7) 0.005 (6) −0.013 (7) −0.007 (7) −0.002 (7) −0.001 (7). 0.0037 (4) 0.0066 (4) 0.0081 (4) 0.0035 (4) 0.0050 (4) 0.0059 (4) −0.0021 (14) 0.0112 (13) 0.0078 (14) 0.0041 (14) 0.0101 (14) −0.0019 (14) −0.0051 (15) 0.0077 (14) 0.0228 (16) 0.0163 (15) −0.0016 (15) 0.0003 (16) 0.004 (3) 0.009 (3) 0.003 (3) 0.014 (4) 0.008 (4) −0.002 (3) 0.001 (3) −0.001 (4) 0.015 (4) 0.003 (4) 0.014 (4) −0.001 (4) 0.014 (4) 0.002 (4) 0.004 (6) 0.018 (7) −0.002 (6) 0.015 (6) 0.019 (6) 0.009 (6) −0.005 (7) 0.008 (7) 0.010 (6) −0.007 (8) 0.000 (7) 0.038 (8) 0.003 (7). Acta Cryst. (2002). E58, m490–m491. sup-6.

(10) supporting information C18 C20 C17 C19 C16 C21 C15 C23 C24 C28 C25 C14 C27 C22 C26 N1 N2. 0.077 (10) 0.088 (11) 0.088 (11) 0.086 (11) 0.058 (9) 0.086 (11) 0.053 (8) 0.076 (10) 0.104 (14) 0.113 (15) 0.135 (18) 0.102 (14) 0.101 (13) 0.088 (13) 0.113 (18) 0.061 (7) 0.078 (8). 0.056 (9) 0.068 (10) 0.043 (8) 0.051 (8) 0.101 (13) 0.073 (10) 0.082 (11) 0.060 (9) 0.096 (13) 0.108 (15) 0.055 (10) 0.094 (13) 0.097 (13) 0.099 (14) 0.126 (19) 0.039 (6) 0.049 (6). 0.064 (9) 0.049 (8) 0.065 (9) 0.051 (8) 0.068 (10) 0.054 (9) 0.069 (10) 0.081 (11) 0.063 (10) 0.058 (10) 0.091 (13) 0.062 (10) 0.068 (11) 0.104 (15) 0.15 (2) 0.047 (6) 0.046 (6). 0.009 (7) −0.008 (8) 0.014 (7) 0.001 (7) −0.021 (9) 0.031 (9) 0.007 (8) 0.012 (8) 0.028 (11) −0.002 (12) 0.000 (10) −0.014 (11) 0.006 (10) 0.018 (11) −0.018 (15) 0.011 (5) 0.007 (6). 0.015 (8) 0.000 (8) 0.004 (8) −0.003 (7) −0.006 (8) −0.014 (8) −0.005 (7) 0.001 (8) 0.012 (9) −0.004 (10) 0.006 (12) 0.020 (9) −0.030 (10) 0.022 (11) 0.030 (15) 0.000 (5) −0.009 (6). −0.007 (7) 0.015 (7) 0.004 (7) 0.012 (6) −0.009 (9) −0.004 (8) −0.001 (8) 0.009 (8) −0.003 (9) −0.002 (10) 0.026 (9) 0.002 (9) 0.034 (10) −0.021 (11) 0.040 (16) −0.001 (5) 0.011 (5). Geometric parameters (Å, º) Mo6—O14 Mo6—O10 Mo6—O11 Mo6—Cl9 Mo6—Cl12 Mo6—Cl8 Mo6—Mo4 Mo6—Mo5 Mo2—O13 Mo2—O2 Mo2—O3 Mo2—Cl2 Mo2—Cl5 Mo2—Cl1 Mo2—Mo3 Mo2—Mo1 Mo3—O13 Mo3—O5 Mo3—O4 Mo3—Cl3 Mo3—Cl6 Mo3—Cl2 Mo3—Mo1 Mo5—O14 Mo5—O9 Mo5—O8 Mo5—Cl11 Mo5—Cl7. Acta Cryst. (2002). E58, m490–m491. 1.995 (7) 2.071 (7) 2.079 (7) 2.406 (3) 2.415 (3) 2.430 (3) 2.5746 (14) 2.5894 (14) 1.981 (7) 2.078 (8) 2.089 (8) 2.405 (3) 2.406 (3) 2.418 (3) 2.5722 (14) 2.5798 (14) 1.992 (7) 2.068 (8) 2.068 (8) 2.413 (3) 2.414 (3) 2.417 (3) 2.5756 (13) 1.986 (7) 2.070 (7) 2.092 (7) 2.404 (3) 2.411 (3). Mo4—O7 Mo4—Cl9 Mo4—Cl10 Mo4—Cl7 O10—C9 O5—C5 O12—C11 O11—C11 O9—C9 O8—C7 O2—C1 O3—C3 O7—C7 O4—C3 O1—C1 O6—C5 C11—C12 C1—C2 C3—C4 C5—C6 C10—C9 C7—C8 C13—C14 C13—N1 C18—C17 C20—C19 C17—N1 C19—N1. 2.070 (8) 2.417 (3) 2.419 (3) 2.422 (3) 1.272 (13) 1.265 (14) 1.262 (14) 1.279 (14) 1.269 (14) 1.270 (14) 1.274 (15) 1.272 (15) 1.255 (14) 1.272 (15) 1.256 (15) 1.259 (14) 1.496 (16) 1.507 (17) 1.491 (16) 1.485 (16) 1.508 (16) 1.502 (16) 1.51 (2) 1.536 (16) 1.524 (18) 1.508 (19) 1.513 (15) 1.493 (16). sup-7.

(11) supporting information Mo5—Cl8 Mo5—Mo4 Mo1—O13 Mo1—O6 Mo1—O1 Mo1—Cl4 Mo1—Cl3 Mo1—Cl1 Mo4—O14 Mo4—O12. 2.423 (3) 2.5751 (14) 1.985 (7) 2.070 (8) 2.080 (8) 2.406 (3) 2.409 (3) 2.425 (3) 1.997 (7) 2.063 (8). C16—C15 C21—C22 C21—N2 C15—N1 C23—N2 C23—C24 C28—C27 C25—N2 C25—C26 C27—N2. 1.51 (2) 1.50 (2) 1.542 (18) 1.510 (16) 1.511 (17) 1.51 (2) 1.51 (2) 1.488 (18) 1.50 (3) 1.495 (17). O14—Mo6—O10 O14—Mo6—O11 O10—Mo6—O11 O14—Mo6—Cl9 O10—Mo6—Cl9 O11—Mo6—Cl9 O14—Mo6—Cl12 O10—Mo6—Cl12 O11—Mo6—Cl12 Cl9—Mo6—Cl12 O14—Mo6—Cl8 O10—Mo6—Cl8 O11—Mo6—Cl8 Cl9—Mo6—Cl8 Cl12—Mo6—Cl8 O14—Mo6—Mo4 O10—Mo6—Mo4 O11—Mo6—Mo4 Cl9—Mo6—Mo4 Cl12—Mo6—Mo4 Cl8—Mo6—Mo4 O14—Mo6—Mo5 O10—Mo6—Mo5 O11—Mo6—Mo5 Cl9—Mo6—Mo5 Cl12—Mo6—Mo5 Cl8—Mo6—Mo5 Mo4—Mo6—Mo5 O13—Mo2—O2 O13—Mo2—O3 O2—Mo2—O3 O13—Mo2—Cl2 O2—Mo2—Cl2 O3—Mo2—Cl2 O13—Mo2—Cl5 O2—Mo2—Cl5 O3—Mo2—Cl5. 81.2 (3) 79.2 (3) 92.5 (3) 107.6 (2) 171.1 (2) 90.5 (2) 157.5 (2) 84.1 (2) 84.5 (2) 87.87 (11) 106.7 (2) 88.8 (2) 174.0 (2) 87.41 (11) 89.86 (11) 49.9 (2) 130.7 (2) 85.0 (2) 57.94 (8) 144.06 (9) 98.51 (8) 49.3 (2) 85.3 (2) 128.3 (2) 99.42 (8) 145.94 (9) 57.62 (8) 59.82 (4) 80.8 (3) 80.4 (3) 92.6 (3) 107.6 (2) 171.5 (2) 90.0 (3) 157.9 (2) 84.5 (2) 83.9 (2). O13—Mo1—Cl4 O6—Mo1—Cl4 O1—Mo1—Cl4 O13—Mo1—Cl3 O6—Mo1—Cl3 O1—Mo1—Cl3 Cl4—Mo1—Cl3 O13—Mo1—Cl1 O6—Mo1—Cl1 O1—Mo1—Cl1 Cl4—Mo1—Cl1 Cl3—Mo1—Cl1 O13—Mo1—Mo3 O6—Mo1—Mo3 O1—Mo1—Mo3 Cl4—Mo1—Mo3 Cl3—Mo1—Mo3 Cl1—Mo1—Mo3 O13—Mo1—Mo2 O6—Mo1—Mo2 O1—Mo1—Mo2 Cl4—Mo1—Mo2 Cl3—Mo1—Mo2 Cl1—Mo1—Mo2 Mo3—Mo1—Mo2 O14—Mo4—O12 O14—Mo4—O7 O12—Mo4—O7 O14—Mo4—Cl9 O12—Mo4—Cl9 O7—Mo4—Cl9 O14—Mo4—Cl10 O12—Mo4—Cl10 O7—Mo4—Cl10 Cl9—Mo4—Cl10 O14—Mo4—Cl7 O12—Mo4—Cl7. 157.7 (2) 84.7 (2) 84.3 (3) 107.3 (2) 89.5 (2) 172.1 (2) 88.18 (12) 106.8 (2) 173.5 (2) 89.3 (2) 89.26 (11) 88.16 (11) 49.8 (2) 84.9 (2) 130.1 (2) 144.41 (10) 57.80 (8) 98.90 (8) 49.3 (2) 128.7 (2) 85.4 (2) 145.42 (9) 99.56 (8) 57.68 (8) 59.86 (4) 80.5 (3) 80.4 (3) 91.4 (3) 107.1 (2) 89.8 (2) 172.5 (2) 160.1 (2) 85.9 (2) 85.6 (2) 87.16 (12) 106.9 (2) 172.6 (2). Acta Cryst. (2002). E58, m490–m491. sup-8.

(12) supporting information Cl2—Mo2—Cl5 O13—Mo2—Cl1 O2—Mo2—Cl1 O3—Mo2—Cl1 Cl2—Mo2—Cl1 Cl5—Mo2—Cl1 O13—Mo2—Mo3 O2—Mo2—Mo3 O3—Mo2—Mo3 Cl2—Mo2—Mo3 Cl5—Mo2—Mo3 Cl1—Mo2—Mo3 O13—Mo2—Mo1 O2—Mo2—Mo1 O3—Mo2—Mo1 Cl2—Mo2—Mo1 Cl5—Mo2—Mo1 Cl1—Mo2—Mo1 Mo3—Mo2—Mo1 O13—Mo3—O5 O13—Mo3—O4 O5—Mo3—O4 O13—Mo3—Cl3 O5—Mo3—Cl3 O4—Mo3—Cl3 O13—Mo3—Cl6 O5—Mo3—Cl6 O4—Mo3—Cl6 Cl3—Mo3—Cl6 O13—Mo3—Cl2 O5—Mo3—Cl2 O4—Mo3—Cl2 Cl3—Mo3—Cl2 Cl6—Mo3—Cl2 O13—Mo3—Mo2 O5—Mo3—Mo2 O4—Mo3—Mo2 Cl3—Mo3—Mo2 Cl6—Mo3—Mo2 Cl2—Mo3—Mo2 O13—Mo3—Mo1 O5—Mo3—Mo1 O4—Mo3—Mo1 Cl3—Mo3—Mo1 Cl6—Mo3—Mo1 Cl2—Mo3—Mo1 Mo2—Mo3—Mo1 O14—Mo5—O9. Acta Cryst. (2002). E58, m490–m491. 87.75 (12) 107.2 (2) 88.9 (2) 172.4 (2) 87.40 (11) 88.84 (12) 49.8 (2) 130.3 (2) 85.5 (2) 57.99 (8) 144.07 (10) 99.17 (8) 49.5 (2) 85.2 (2) 129.6 (2) 99.28 (9) 145.34 (10) 57.94 (8) 59.99 (4) 80.6 (3) 80.7 (3) 92.1 (3) 106.9 (2) 89.1 (2) 172.4 (3) 159.4 (2) 85.2 (2) 84.9 (3) 87.68 (12) 106.8 (2) 172.6 (2) 89.5 (3) 88.42 (11) 87.73 (12) 49.5 (2) 129.8 (2) 85.4 (2) 99.66 (8) 143.94 (10) 57.54 (8) 49.5 (2) 85.4 (2) 130.0 (2) 57.64 (8) 144.14 (10) 99.08 (8) 60.15 (4) 80.5 (3). O7—Mo4—Cl7 Cl9—Mo4—Cl7 Cl10—Mo4—Cl7 O14—Mo4—Mo6 O12—Mo4—Mo6 O7—Mo4—Mo6 Cl9—Mo4—Mo6 Cl10—Mo4—Mo6 Cl7—Mo4—Mo6 O14—Mo4—Mo5 O12—Mo4—Mo5 O7—Mo4—Mo5 Cl9—Mo4—Mo5 Cl10—Mo4—Mo5 Cl7—Mo4—Mo5 Mo6—Mo4—Mo5 Mo5—Cl8—Mo6 Mo5—Cl7—Mo4 Mo6—Cl9—Mo4 Mo2—Cl1—Mo1 Mo1—Cl3—Mo3 Mo2—Cl2—Mo3 Mo5—O14—Mo6 Mo5—O14—Mo4 Mo6—O14—Mo4 Mo2—O13—Mo1 Mo2—O13—Mo3 Mo1—O13—Mo3 C9—O10—Mo6 C5—O5—Mo3 C11—O12—Mo4 C11—O11—Mo6 C9—O9—Mo5 C7—O8—Mo5 C1—O2—Mo2 C3—O3—Mo2 C7—O7—Mo4 C3—O4—Mo3 C1—O1—Mo1 C5—O6—Mo1 O12—C11—O11 O12—C11—C12 O11—C11—C12 O1—C1—O2 O1—C1—C2 O2—C1—C2 O3—C3—O4 O3—C3—C4. 89.0 (2) 88.79 (11) 86.72 (11) 49.8 (2) 85.7 (2) 129.9 (2) 57.54 (8) 143.66 (10) 99.71 (8) 49.5 (2) 129.8 (2) 85.3 (2) 99.54 (9) 143.23 (9) 57.59 (8) 60.37 (4) 64.49 (8) 64.39 (8) 64.52 (8) 64.38 (8) 64.57 (8) 64.47 (8) 81.1 (3) 80.5 (3) 80.3 (2) 81.2 (3) 80.7 (3) 80.7 (3) 122.4 (7) 122.5 (7) 122.8 (8) 122.4 (7) 122.6 (7) 122.0 (8) 122.3 (8) 122.1 (8) 123.4 (8) 123.3 (8) 122.4 (8) 123.2 (8) 123.6 (11) 118.3 (12) 118.0 (12) 124.6 (12) 118.2 (12) 117.1 (13) 123.6 (11) 118.7 (12). sup-9.

(13) supporting information O14—Mo5—O8 O9—Mo5—O8 O14—Mo5—Cl11 O9—Mo5—Cl11 O8—Mo5—Cl11 O14—Mo5—Cl7 O9—Mo5—Cl7 O8—Mo5—Cl7 Cl11—Mo5—Cl7 O14—Mo5—Cl8 O9—Mo5—Cl8 O8—Mo5—Cl8 Cl11—Mo5—Cl8 Cl7—Mo5—Cl8 O14—Mo5—Mo4 O9—Mo5—Mo4 O8—Mo5—Mo4 Cl11—Mo5—Mo4 Cl7—Mo5—Mo4 Cl8—Mo5—Mo4 O14—Mo5—Mo6 O9—Mo5—Mo6 O8—Mo5—Mo6 Cl11—Mo5—Mo6 Cl7—Mo5—Mo6 Cl8—Mo5—Mo6 Mo4—Mo5—Mo6 O13—Mo1—O6 O13—Mo1—O1 O6—Mo1—O1. Acta Cryst. (2002). E58, m490–m491. 79.6 (3) 92.3 (3) 157.4 (2) 84.4 (2) 84.3 (2) 107.7 (2) 171.8 (2) 89.8 (2) 87.89 (11) 107.2 (2) 89.6 (2) 173.1 (2) 89.34 (11) 87.52 (11) 49.9 (2) 130.1 (2) 85.2 (2) 144.26 (9) 58.02 (8) 98.69 (9) 49.6 (2) 85.3 (2) 128.8 (2) 145.66 (9) 99.60 (8) 57.90 (8) 59.80 (4) 79.7 (3) 80.6 (3) 92.2 (3). O4—C3—C4 O6—C5—O5 O6—C5—C6 O5—C5—C6 O9—C9—O10 O9—C9—C10 O10—C9—C10 O7—C7—O8 O7—C7—C8 O8—C7—C8 C14—C13—N1 N1—C17—C18 N1—C19—C20 C22—C21—N2 C16—C15—N1 N2—C23—C24 N2—C25—C26 N2—C27—C28 C19—N1—C15 C19—N1—C17 C15—N1—C17 C19—N1—C13 C15—N1—C13 C17—N1—C13 C25—N2—C27 C25—N2—C23 C27—N2—C23 C25—N2—C21 C27—N2—C21 C23—N2—C21. 117.7 (12) 123.7 (11) 119.1 (12) 117.2 (11) 124.4 (11) 118.1 (11) 117.5 (11) 123.9 (11) 119.0 (12) 117.1 (11) 114.3 (12) 114.9 (11) 115.6 (11) 115.7 (12) 116.2 (12) 116.2 (12) 116.2 (15) 115.8 (13) 106.7 (10) 111.3 (11) 111.0 (11) 111.2 (10) 111.4 (10) 105.3 (10) 111.5 (13) 111.3 (12) 106.9 (11) 105.9 (12) 110.2 (12) 111.1 (11). sup-10.

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