Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2005 data_global _journal_coden_Cambridge 222 loop_ _publ_author_name _publ_author_address _publ_author_footnote 'Euan Brechin' ; ? # Address for author 1 ; ; ? # Footnote for author 1 ; 'George Christou' ; ? # Address 2 ; ; ? # Footnote 2 ; 'Constantinos J. Milios' '' '' 'Muralee Murugesu' '' '' 'S. Parsons' '' '' _publ_contact_author_name 'Euan Brechin' _publ_contact_author_address ; Department of Chemistry University of Edinburgh West Mains Raod Edinburgh EH9 3JJ UNITED KINGDOM ; _publ_contact_author_email EBRECHIN@STAFFMAIL.ED.AC.UK _publ_requested_journal 'Dalton Transactions' _publ_section_title ; 1,1,1-tris(hydroxymethyl)propane in manganese carboxylate chemistry: synthesis, structure and magnetic properties of a mixed-valence [MnIII4MnII4] cluster featuring the novel [Mn8(?3-OR)6(?2-OR)8]6+ core. ; _journal_coden_ASTM ? _journal_coeditor_code ? _journal_coeditor_name ? _journal_coeditor_notes ? _journal_date_accepted ? _journal_date_from_coeditor ? _journal_date_printers_final ? _journal_date_printers_first ? _journal_date_proofs_in ? _journal_date_proofs_out ? # PROCESSING SUMMARY (IUCr Office Use Only): _journal_date_recd_electronic ? _journal_date_to_coeditor ? _journal_issue ? _journal_name_full ? _journal_page_first ? _journal_page_last ? _journal_suppl_publ_number ? _journal_suppl_publ_pages ? _journal_techeditor_code ? _journal_techeditor_notes ? _journal_volume ? _journal_year ? _publ_contact_author_fax '+44 1865 000000' _publ_contact_author_phone '+44 1865 000000' # Check this file using the IUCr facility at: # http://checkcif.iucr.org/ # The content below is held in the file 'script/refcif.dat'. This is a text # file which you may edit to reflect local conditions. # Items which need looking at are represented by a '?'. # Items for which there are choices are prefixed with 'choose from'. _publ_contact_letter ; Please consider this CIF submission for publication as a Short Format Paper in Acta Crystallographica E. The figures have been sent by mail. ; _publ_requested_category CO # choose from: FI FM FO CI CM CO AD _publ_requested_coeditor_name 'Prof William Clegg' data_eb0525 _database_code_depnum_ccdc_archive 'CCDC 280380' _audit_creation_date 05-05-10 _audit_creation_method CRYSTALS_ver_12.80 _chemical_compound_source 'C. Milios/E. Brechin, Reaction CM122' _exptl_crystal_recrystallization_method 'Slow evaporation fo MeCN' _oxford_structure_analysis_title 'eb0525 in P-1' _chemical_name_systematic ? _chemical_melting_point ? _cell_length_a 11.4048(2) _cell_length_b 12.8147(3) _cell_length_c 14.1353(3) _cell_angle_alpha 108.2590(10) _cell_angle_beta 97.2100(10) _cell_angle_gamma 110.7390(10) _cell_volume 1768.50(7) _symmetry_cell_setting Triclinic _symmetry_space_group_name_H-M 'P -1 ' _symmetry_space_group_name_Hall '-P 1' loop_ _symmetry_equiv_pos_as_xyz x,y,z -x,-y,-z loop_ _atom_type_symbol _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_Cromer_Mann_a1 _atom_type_scat_Cromer_Mann_b1 _atom_type_scat_Cromer_Mann_a2 _atom_type_scat_Cromer_Mann_b2 _atom_type_scat_Cromer_Mann_a3 _atom_type_scat_Cromer_Mann_b3 _atom_type_scat_Cromer_Mann_a4 _atom_type_scat_Cromer_Mann_b4 _atom_type_scat_Cromer_Mann_c _atom_type_scat_source C 0.0033 0.0016 2.3100 20.8439 1.0200 10.2075 1.5886 0.5687 0.8650 51.6512 0.2156 'International Tables Vol C 4.2.6.8 and 6.1.1.4' H 0.0000 0.0000 0.4930 10.5109 0.3229 26.1257 0.1402 3.1424 0.0408 57.7998 0.0030 'International Tables Vol C 4.2.6.8 and 6.1.1.4' O 0.0106 0.0060 3.0485 13.2771 2.2868 5.7011 1.5463 0.3239 0.8670 32.9089 0.2508 'International Tables Vol C 4.2.6.8 and 6.1.1.4' Mn 0.3368 0.7283 11.2819 5.3409 7.3573 0.3432 3.0193 17.8674 2.2441 83.7543 1.0896 'International Tables Vol C 4.2.6.8 and 6.1.1.4' Br -0.2901 2.4595 17.1789 2.1723 5.2358 16.5796 5.6377 0.2609 3.9851 41.4328 2.9557 'International Tables Vol C 4.2.6.8 and 6.1.1.4' N 0.0061 0.0033 12.2126 0.0057 3.1322 9.8933 2.0125 28.9975 1.1663 0.5826 -11.5290 'International Tables Vol C 4.2.6.8 and 6.1.1.4' _cell_formula_units_Z 1 # Given Formula = C50 H94 Br4 Mn8 N2 O24 # Dc = 1.75 Fooo = 940.00 Mu = 37.10 M = 933.17 # Found Formula = C50 H94 Br4 Mn8 N2 O24 # Dc = 1.75 FOOO = 940.00 Mu = 37.10 M = 933.17 _chemical_formula_sum 'C50 H94 Br4 Mn8 N2 O24' _chemical_formula_moiety 'C46 H88 Br4 Mn8 O24, 2(C2 H3 N)' _chemical_formula_weight 1866.34 _cell_measurement_reflns_used 5370 _cell_measurement_theta_min 2 _cell_measurement_theta_max 24 _cell_measurement_temperature 150 _exptl_crystal_description blcok _exptl_crystal_colour brown _exptl_crystal_size_min 0.09 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_max 0.26 _exptl_crystal_density_diffrn 1.752 _exptl_crystal_density_meas ? # Non-dispersive F(000): _exptl_crystal_F_000 940 _exptl_absorpt_coefficient_mu 3.710 # Sheldrick geometric approximatio 0.57 0.72 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details 'SADABS v 2001/1' _exptl_absorpt_correction_T_min 0.57 _exptl_absorpt_correction_T_max 0.72 _diffrn_measurement_device_type 'Bruker SMART' _diffrn_radiation_monochromator graphite _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71073 _diffrn_measurement_method '\f & \w scans' _exptl_special_details ; Oxford Cryosystems LT device. Data collection strategy optimised with COSMO ; _computing_data_collection 'SMART (Siemens, 1993)' _computing_data_reduction 'SAINT (Siemens ,1995)' _computing_cell_refinement 'SAINT (Siemens ,1995)' _computing_structure_solution 'SHELXS 86 (Sheldrick, 1986)' _computing_structure_refinement 'CRYSTALS (Betteridge et al., 2003)' _computing_publication_material 'CRYSTALS, PLATON, ENCIFER, XCIF' _computing_molecular_graphics 'CAMERON (Watkin et al., 1996)' _diffrn_standards_interval_time ? _diffrn_standards_interval_count ? _diffrn_standards_number 0 _diffrn_standards_decay_% ? _diffrn_ambient_temperature 150 _diffrn_reflns_number 36443 _reflns_number_total 9899 _diffrn_reflns_av_R_equivalents 0.032 # Number of reflections with Friedels Law is 9899 # Number of reflections without Friedels Law is 0 # Theoretical number of reflections is about 10816 _diffrn_reflns_theta_min 1.574 _diffrn_reflns_theta_max 30.526 _diffrn_measured_fraction_theta_max 0.914 _diffrn_reflns_theta_full 27.779 _diffrn_measured_fraction_theta_full 0.996 _diffrn_reflns_limit_h_min -16 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -17 _diffrn_reflns_limit_k_max 17 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 20 _reflns_limit_h_min -16 _reflns_limit_h_max 16 _reflns_limit_k_min -17 _reflns_limit_k_max 16 _reflns_limit_l_min 0 _reflns_limit_l_max 20 _oxford_diffrn_Wilson_B_factor 2.32 _oxford_diffrn_Wilson_scale 8.00 _atom_sites_solution_primary direct #heavy,direct,difmap,geom # _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_diff_density_min -1.01 _refine_diff_density_max 2.51 _refine_ls_number_reflns 9894 _refine_ls_number_restraints 6 _refine_ls_number_parameters 402 #_refine_ls_R_factor_ref 0.0881 _refine_ls_wR_factor_ref 0.1667 _refine_ls_goodness_of_fit_ref 1.0035 #_reflns_number_all 9894 _refine_ls_R_factor_all 0.0881 _refine_ls_wR_factor_all 0.1667 # No actual I/u(I) cutoff was used for refinement. The # threshold below is used for "_gt" information ONLY: _reflns_threshold_expression I>2.00u(I) _reflns_number_gt 5761 _refine_ls_R_factor_gt 0.0483 _refine_ls_wR_factor_gt 0.1236 _refine_ls_shift/su_max 0.000415 # choose from: rm (reference molecule of known chirality), # ad (anomolous dispersion - Flack), rmad (rm and ad), # syn (from synthesis), unk (unknown) or . (not applicable). _chemical_absolute_configuration . _refine_special_details ; Disorder: Disorder was found for two methyl C-atoms in the t-bu ligand, which is not an uncommon situation. The disorder was modelled for C- and H- atoms using distance restraints and PART instructions and the total occupancy at each atom site was kept as 1 during the refinement by means of a SUMFIX constraint. Disorder was also found for the Me group of the MeCN solvent and it was treated in a similar manner. All carbon atoms involved in disorder were modelled with isotropic thermal parameters. H-atom Placement: H-atoms were added geometrically and fixed during refinement for all concerning atoms, with the exception of water H1 and H2, which were found on a difference map and were freely refined subject to distance restraints. The metal oxidation state, hydrogen bonding pattern andthe presence of water in the reaction scheme, strongly suggest water and not an hydroxyl group as the ligand. 912_ALERT_3_B # Missing FCF Reflections Above STH/L=0.6 ...... 933 911_ALERT_3_C # Missing FCF Refl. Between TH(Min) & STH/L=0.6 2 Completeness and resolution used for refinement are shown below: #=============================================================================== Resolution & Completeness Statistics (Cumulative) #=============================================================================== Theta sin(th)/Lambda Complete Expected Measured Missing #------------------------------------------------------------------------------- 20.82 0.500 1.000 3695 3695 0 23.01 0.550 1.000 4923 4923 0 25.24 0.600 1.000 6400 6398 2 #----------------------------------------------------------- ACTA Min. Res. ---- 27.51 0.650 0.999 8136 8125 11 29.84 0.700 0.946 10164 9613 551 30.53 0.715 0.914 10834 9899 935 #=============================================================================== 201_ALERT_2_B Isotropic non-H Atoms in Main Residue(s) ....... 2 202_ALERT_3_C Isotropic non-H Atoms in Anion/Solvent ......... 1 094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.49 301_ALERT_3_C Main Residue Disorder ......................... 5.00 Perc. 302_ALERT_4_C Anion/Solvent Disorder ......................... 25.00 Perc. 412_ALERT_2_C Short Intra XH3 .. XHn H3242 .. H4125 .. 1.83 Ang. 341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 9 See above under disorder treatment. 220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.88 Ratio This refers to C(61), terminal methyl; no disorder was modelled for this atom. 745_ALERT_1_C D-H Calc 0.83(7), Rep 0.83200 ...... Missing su O1 -H1 1.555 1.555 746_ALERT_1_C H...A Calc 1.96(7), Rep 1.95700 ...... Missing su H1 -O14 1.555 2.555 747_ALERT_1_C D...A Calc 2.773(6), Rep 2.77300 ...... Missing su O1 -O14 1.555 2.555 No su output by CRYSTALS. 720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 25 764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.14 Ratio 795_ALERT_4_C C-Atom in CIF Coordinate List out of Sequence .. C11 796_ALERT_4_C O-Atom in CIF Coordinate List out of Sequence .. O23 Noted, no action taken. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_hydrogen_treatment mixed # none, undef, noref, refall, # refxyz, refU, constr or mixed _refine_ls_weighting_scheme calc _refine_ls_weighting_details ; Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A~0~*T~0~(x)+A~1~*T~1~(x) ... +A~n-1~]*T~n-1~(x)] where A~i~ are the Chebychev coefficients listed below and x= Fcalc/Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)^2^]^2^ A~i~ are: 92.9 154. 95.7 41.9 9.71 ; _publ_section_abstract # Text of the abstract ; ? ; _publ_section_comment # Text of the paper ; ? ; _publ_section_acknowledgements # Acknowledgments ; ? ; _publ_section_figure_captions # Captions to figures ; ? ; _publ_section_exptl_refinement # Some potentially useful phrases are: ; Because the data were collected with molybdenum radiation, there were no measurable anomalous differences, as a consequence of which it was admissible to merge Friedel pairs of reflections. All hydrogen atoms were found in difference density syntheses. Hydrogen atoms were placed geometrically after each cycle. Hydrogen atoms were placed geometrically after each cycle, the preferred orientations of those groups whose conformations could not be assigned unambiguously having been previously identified by examination of a difference Fourier map. Hydrogen atoms were seen in a difference density synthesis. Those attached to carbon atoms were repositioned geometrically. Hydrogen were initially refined with soft restraints on the bonds to regularise their geometry (bond lengths to accepted values, angles either set by symmetry or to accepted values, and U[iso] dependent upon the adjacent bonded atom), after which they were refined with riding constraints only. donated by Bill Clegg: The H atoms were all located in a difference map, but those attached to carbon atoms were repositioned geometrically. The H atoms were initially refined with soft restraints on the bond lengths and angles to regularise their geometry (C---H in the range 0.93-98, O---N in the range 0.86-0.89 and O---H = 0.82 \%A) and isotropic adps (U(H) in the range 1.2-1.5 times U~equiv~ of the adjacent atom), after which they were refined with riding constraints. . ; _publ_section_exptl_prep ; ? ; # End of 'script/refcif.dat' # Insert your own references if required - in alphabetical order _publ_section_references ; Betteridge, P.W., Carruthers, J.R., Cooper, R.I., Prout, K., Watkin, D.J. (2003). J. Appl. Cryst. 36, 1487. Prince, E. Mathematical Techniques in Crystallography and Materials Science Springer-Verlag, New York, 1982. Siemens Industrial Automation, Inc (1993) SMART: Area-Detector Software Package; Madison, WI. Siemens Industrial Automation, Inc (1995). SAINT: Area-Detector Integration Software.; Madison, WI. Siemens Industrial Automation, Inc (1996). SADABS: Area-Detector Absorption Correction;: Madison, WI. Sheldrick, G.M. (1986). SHELXS86. Program for the solution of crystal structures. Univ. of G\"ottingen, Federal Republic of Germany. Watkin D.J. (1994), Acta Cryst, A50, 411-437 Watkin, D.J., Prout, C.K. & Pearce, L.J. (1996) CAMERON, Chemical Crystallography Laboratory, OXFORD, UK. ; # Uequiv = arithmetic mean of Ui i.e. Ueqiv = (U1+U2+U3)/3 # Replace last . with number of unfound hydrogen atomsattached to an atom. # ..._refinement_flags_... # . no refinement constraints S special position constraint on site # G rigid group refinement of site R riding atom # D distance or angle restraint on site T thermal displacement constraints # U Uiso or Uij restraint (rigid bond) P partial occupancy constraint loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_occupancy _atom_site_adp_type _atom_site_refinement_flags_posn _atom_site_refinement_flags_adp _atom_site_refinement_flags_occupancy _atom_site_disorder_assembly _atom_site_disorder_group _atom_site_attached_hydrogens C124 C 0.2693(5) 0.2514(4) -0.0133(3) 0.0288 1.0000 Uani . . . . . . C224 C 0.2382(5) 0.2697(5) -0.1142(4) 0.0413 1.0000 Uani D . . . . . C324 C 0.3509(7) 0.3606(7) -0.1276(5) 0.0530 1.0000 Uani . . . . . . C4124 C 0.172(2) 0.3574(18) -0.0850(17) 0.065(6) 0.387(16) Uiso D . P 1 1 . C4224 C 0.1120(9) 0.2850(11) -0.1256(9) 0.052(3) 0.613(16) Uiso D . P 1 2 . C5124 C 0.1198(18) 0.1609(17) -0.1988(16) 0.082(8) 0.387(16) Uiso D . P 1 1 . C5224 C 0.2138(9) 0.1498(7) -0.2060(6) 0.039(2) 0.613(16) Uiso D . P 1 2 . Br4 Br 0.16169(6) -0.13201(5) 0.01701(5) 0.0431 1.0000 Uani . . . . . . O21 O 0.4771(3) 0.5007(3) 0.2617(2) 0.0287 1.0000 Uani . . . . . . O31 O 0.2663(3) 0.2796(3) 0.2277(2) 0.0263 1.0000 Uani . . . . . . O41 O 0.3722(3) 0.4492(3) 0.4286(2) 0.0292 1.0000 Uani . . . . . . C11 C 0.2555(5) 0.4783(5) 0.2826(4) 0.0320 1.0000 Uani . . . . . . C21 C 0.3751(5) 0.5387(5) 0.2468(4) 0.0335 1.0000 Uani . . . . . . C31 C 0.1860(5) 0.3428(4) 0.2196(3) 0.0284 1.0000 Uani . . . . . . C41 C 0.2913(5) 0.5037(5) 0.3988(3) 0.0318 1.0000 Uani . . . . . . C51 C 0.1592(6) 0.5367(6) 0.2697(4) 0.0413 1.0000 Uani . . . . . . C61 C 0.1004(8) 0.5225(8) 0.1618(6) 0.0645 1.0000 Uani . . . . . . O23 O 0.1363(4) 0.1972(4) 0.3922(3) 0.0379 1.0000 Uani . . . . . . O33 O 0.4004(3) 0.2849(3) 0.4906(2) 0.0292 1.0000 Uani . . . . . . O43 O 0.2945(4) 0.1164(3) 0.2821(2) 0.0300 1.0000 Uani . . . . . . C13 C 0.2429(6) 0.0680(5) 0.4318(4) 0.0375 1.0000 Uani . . . . . . C23 C 0.1195(6) 0.0889(6) 0.4117(5) 0.0455 1.0000 Uani . . . . . . C33 C 0.3533(6) 0.1809(5) 0.5171(4) 0.0356 1.0000 Uani . . . . . . C43 C 0.2840(6) 0.0324(5) 0.3317(4) 0.0382 1.0000 Uani . . . . . . O22 O 0.5285(3) 0.3484(3) 0.3233(2) 0.0273 1.0000 Uani . . . . . . O32 O 0.4236(3) 0.1778(3) 0.1245(2) 0.0286 1.0000 Uani . . . . . . O42 O 0.6555(4) 0.3888(3) 0.1699(3) 0.0359 1.0000 Uani . . . . . . C53 C 0.2059(7) -0.0380(6) 0.4690(5) 0.0491 1.0000 Uani . . . . . . C63 C 0.3047(10) -0.0905(7) 0.4795(6) 0.0687 1.0000 Uani . . . . . . C12 C 0.6404(5) 0.2261(5) 0.2341(4) 0.0335 1.0000 Uani . . . . . . C22 C 0.6107(5) 0.2876(5) 0.3352(4) 0.0340 1.0000 Uani . . . . . . C32 C 0.5118(5) 0.1312(5) 0.1543(4) 0.0320 1.0000 Uani . . . . . . C42 C 0.7196(5) 0.3161(5) 0.1933(4) 0.0372 1.0000 Uani . . . . . . C52 C 0.7181(6) 0.1549(6) 0.2565(4) 0.0412 1.0000 Uani . . . . . . C62 C 0.8515(6) 0.2275(7) 0.3331(6) 0.0531 1.0000 Uani . . . . . . Mn1 Mn 0.58158(8) 0.54072(7) 0.41211(5) 0.0289 1.0000 Uani . . . . . . Mn2 Mn 0.45404(7) 0.33996(6) 0.18692(5) 0.0252 1.0000 Uani . . . . . . Mn3 Mn 0.32985(7) 0.27796(6) 0.35904(5) 0.0259 1.0000 Uani . . . . . . Mn4 Mn 0.22024(7) 0.08993(7) 0.12237(5) 0.0276 1.0000 Uani . . . . . . Br1 Br 0.82231(6) 0.61279(5) 0.38678(4) 0.0408 1.0000 Uani . . . . . . O12 O 0.3694(3) 0.3362(3) 0.0564(2) 0.0296 1.0000 Uani . . . . . . O1 O 0.0188(4) 0.0544(4) 0.1247(3) 0.0368 1.0000 Uani D . . . . . O14 O 0.1960(3) 0.1590(3) -0.0031(2) 0.0301 1.0000 Uani . . . . . . C1 C 0.4458(8) 0.8203(7) 0.1846(5) 0.0582 1.0000 Uani D . . . . . N1 N 0.4612(9) 0.8506(7) 0.2712(5) 0.0717 1.0000 Uani . . . . . . C211 C 0.398(2) 0.7561(17) 0.0730(6) 0.061(5) 0.54(3) Uiso D . P 2 1 . C212 C 0.4523(17) 0.8057(16) 0.0791(8) 0.042(4) 0.46(3) Uiso D . P 2 2 . H3241 H 0.3252 0.3687 -0.1943 0.0641 1.0000 Uiso . . . . . . H3242 H 0.3802 0.4403 -0.0690 0.0641 1.0000 Uiso . . . . . . H3243 H 0.4236 0.3341 -0.1286 0.0641 1.0000 Uiso . . . . . . H211 H 0.4112 0.6280 0.2861 0.0415 1.0000 Uiso . . . . . . H212 H 0.3452 0.5197 0.1714 0.0415 1.0000 Uiso . . . . . . H311 H 0.1083 0.3089 0.2445 0.0346 1.0000 Uiso . . . . . . H312 H 0.1570 0.3294 0.1453 0.0346 1.0000 Uiso . . . . . . H411 H 0.3381 0.5932 0.4374 0.0377 1.0000 Uiso . . . . . . H412 H 0.2087 0.4728 0.4190 0.0377 1.0000 Uiso . . . . . . H511 H 0.2065 0.6253 0.3122 0.0517 1.0000 Uiso . . . . . . H512 H 0.0855 0.5004 0.2977 0.0517 1.0000 Uiso . . . . . . H611 H 0.0407 0.5642 0.1651 0.0867 1.0000 Uiso . . . . . . H612 H 0.1714 0.5596 0.1319 0.0867 1.0000 Uiso . . . . . . H613 H 0.0504 0.4347 0.1174 0.0867 1.0000 Uiso . . . . . . H231 H 0.0846 0.0939 0.4736 0.0498 1.0000 Uiso . . . . . . H232 H 0.0547 0.0177 0.3500 0.0498 1.0000 Uiso . . . . . . H331 H 0.3205 0.2030 0.5796 0.0412 1.0000 Uiso . . . . . . H332 H 0.4277 0.1599 0.5339 0.0412 1.0000 Uiso . . . . . . H431 H 0.3705 0.0297 0.3483 0.0455 1.0000 Uiso . . . . . . H432 H 0.2180 -0.0495 0.2831 0.0455 1.0000 Uiso . . . . . . H531 H 0.1896 -0.0087 0.5382 0.0582 1.0000 Uiso . . . . . . H532 H 0.1239 -0.1049 0.4185 0.0582 1.0000 Uiso . . . . . . H631 H 0.2698 -0.1580 0.5038 0.0870 1.0000 Uiso . . . . . . H632 H 0.3876 -0.0261 0.5306 0.0870 1.0000 Uiso . . . . . . H633 H 0.3218 -0.1223 0.4108 0.0870 1.0000 Uiso . . . . . . H221 H 0.6948 0.3483 0.3868 0.0425 1.0000 Uiso . . . . . . H222 H 0.5663 0.2242 0.3616 0.0425 1.0000 Uiso . . . . . . H321 H 0.5330 0.0889 0.0909 0.0387 1.0000 Uiso . . . . . . H322 H 0.4673 0.0719 0.1843 0.0387 1.0000 Uiso . . . . . . H421 H 0.8043 0.3717 0.2463 0.0457 1.0000 Uiso . . . . . . H422 H 0.7362 0.2707 0.1285 0.0457 1.0000 Uiso . . . . . . H521 H 0.7299 0.1094 0.1894 0.0531 1.0000 Uiso . . . . . . H522 H 0.6643 0.0964 0.2837 0.0531 1.0000 Uiso . . . . . . H621 H 0.8912 0.1713 0.3407 0.0669 1.0000 Uiso . . . . . . H622 H 0.9084 0.2858 0.3073 0.0669 1.0000 Uiso . . . . . . H623 H 0.8428 0.2729 0.4016 0.0669 1.0000 Uiso . . . . . . H1 H -0.044(6) -0.013(5) 0.096(6) 0.0540 1.0000 Uiso D . . . . . H2 H -0.005(7) 0.100(6) 0.104(6) 0.0540 1.0000 Uiso D . . . . . H4124 H 0.1469 0.3768 -0.1457 0.0781 0.387(16) Uiso . . P 1 1 . H4125 H 0.2338 0.4342 -0.0261 0.0781 0.387(16) Uiso . . P 1 1 . H4126 H 0.0923 0.3193 -0.0636 0.0781 0.387(16) Uiso . . P 1 1 . H4224 H 0.0912 0.2971 -0.1911 0.0624 0.613(16) Uiso . . P 1 2 . H4225 H 0.1212 0.3572 -0.0655 0.0624 0.613(16) Uiso . . P 1 2 . H4226 H 0.0399 0.2112 -0.1273 0.0624 0.613(16) Uiso . . P 1 2 . H5124 H 0.1059 0.1795 -0.2621 0.0977 0.387(16) Uiso . . P 1 1 . H5125 H 0.1379 0.0872 -0.2167 0.0977 0.387(16) Uiso . . P 1 1 . H5126 H 0.0407 0.1467 -0.1729 0.0977 0.387(16) Uiso . . P 1 1 . H5224 H 0.1935 0.1586 -0.2731 0.0467 0.613(16) Uiso . . P 1 2 . H5225 H 0.2940 0.1341 -0.1990 0.0467 0.613(16) Uiso . . P 1 2 . H5226 H 0.1394 0.0807 -0.2038 0.0467 0.613(16) Uiso . . P 1 2 . H2111 H 0.4562 0.8032 0.0389 0.0744 0.54(3) Uiso . . P 2 1 . H2112 H 0.3077 0.7471 0.0489 0.0744 0.54(3) Uiso . . P 2 1 . H2113 H 0.3992 0.6744 0.0532 0.0744 0.54(3) Uiso . . P 2 1 . H2121 H 0.3784 0.7303 0.0291 0.0500 0.46(3) Uiso . . P 2 2 . H2122 H 0.4468 0.8772 0.0659 0.0500 0.46(3) Uiso . . P 2 2 . H2123 H 0.5366 0.8030 0.0699 0.0500 0.46(3) Uiso . . P 2 2 . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 C124 0.036(2) 0.032(2) 0.0176(18) 0.0065(17) 0.0019(17) 0.017(2) C224 0.045(3) 0.051(3) 0.023(2) 0.017(2) 0.002(2) 0.014(3) C324 0.059(4) 0.066(4) 0.036(3) 0.032(3) 0.006(3) 0.020(3) Br4 0.0473(3) 0.0329(3) 0.0407(3) 0.0015(2) 0.0027(2) 0.0217(2) O21 0.0351(17) 0.0263(16) 0.0184(14) 0.0037(12) 0.0002(12) 0.0127(14) O31 0.0327(17) 0.0290(16) 0.0137(12) 0.0023(12) -0.0019(11) 0.0168(14) O41 0.0377(18) 0.0308(17) 0.0172(13) 0.0035(12) 0.0004(12) 0.0194(15) C11 0.043(3) 0.036(2) 0.0212(19) 0.0082(18) 0.0003(18) 0.025(2) C21 0.045(3) 0.032(2) 0.026(2) 0.0086(19) 0.0027(19) 0.024(2) C31 0.032(2) 0.034(2) 0.0205(18) 0.0076(18) 0.0023(16) 0.019(2) C41 0.040(3) 0.036(2) 0.0187(18) 0.0032(18) -0.0005(17) 0.024(2) C51 0.049(3) 0.046(3) 0.035(3) 0.011(2) 0.003(2) 0.032(3) C61 0.078(5) 0.085(5) 0.055(4) 0.032(4) 0.011(4) 0.060(5) O23 0.038(2) 0.042(2) 0.0314(18) 0.0126(16) 0.0038(15) 0.0172(17) O33 0.0383(18) 0.0293(16) 0.0170(13) 0.0051(12) -0.0004(12) 0.0168(15) O43 0.0417(19) 0.0270(16) 0.0171(13) 0.0055(12) 0.0013(13) 0.0147(15) C13 0.051(3) 0.031(2) 0.024(2) 0.0074(19) 0.005(2) 0.014(2) C23 0.041(3) 0.043(3) 0.041(3) 0.012(3) 0.009(2) 0.009(3) C33 0.046(3) 0.038(3) 0.020(2) 0.0114(19) 0.0003(19) 0.017(2) C43 0.058(3) 0.033(3) 0.023(2) 0.011(2) 0.007(2) 0.020(2) O22 0.0345(17) 0.0305(16) 0.0181(13) 0.0061(12) 0.0028(12) 0.0193(14) O32 0.0372(18) 0.0288(16) 0.0175(13) 0.0050(12) 0.0019(12) 0.0163(14) O42 0.040(2) 0.040(2) 0.0307(17) 0.0137(15) 0.0078(15) 0.0211(17) C53 0.067(4) 0.043(3) 0.037(3) 0.019(3) 0.015(3) 0.018(3) C63 0.111(7) 0.056(4) 0.052(4) 0.030(4) 0.022(4) 0.040(5) C12 0.043(3) 0.040(3) 0.021(2) 0.0065(19) 0.0038(19) 0.028(2) C22 0.037(3) 0.044(3) 0.025(2) 0.009(2) 0.0055(19) 0.027(2) C32 0.039(3) 0.032(2) 0.026(2) 0.0080(19) 0.0074(19) 0.019(2) C42 0.034(3) 0.047(3) 0.033(2) 0.012(2) 0.008(2) 0.023(2) C52 0.051(3) 0.048(3) 0.034(3) 0.013(2) 0.009(2) 0.035(3) C62 0.041(3) 0.068(4) 0.059(4) 0.031(3) 0.007(3) 0.028(3) Mn1 0.0365(4) 0.0296(4) 0.0155(3) 0.0025(3) -0.0002(3) 0.0158(3) Mn2 0.0317(4) 0.0262(3) 0.0148(3) 0.0043(2) 0.0012(2) 0.0139(3) Mn3 0.0328(4) 0.0286(3) 0.0143(3) 0.0044(2) 0.0013(2) 0.0156(3) Mn4 0.0342(4) 0.0278(3) 0.0159(3) 0.0044(3) 0.0016(3) 0.0127(3) Br1 0.0384(3) 0.0467(3) 0.0280(2) 0.0057(2) 0.0067(2) 0.0159(2) O12 0.0356(18) 0.0294(16) 0.0190(14) 0.0079(13) 0.0007(13) 0.0119(14) O1 0.038(2) 0.0335(19) 0.0261(16) 0.0048(15) 0.0023(14) 0.0092(16) O14 0.0351(18) 0.0311(17) 0.0196(14) 0.0085(13) -0.0005(12) 0.0127(15) C1 0.092(5) 0.060(4) 0.044(3) 0.019(3) 0.016(3) 0.056(4) N1 0.111(6) 0.078(5) 0.047(3) 0.026(3) 0.025(4) 0.060(4) _refine_ls_extinction_method None _oxford_refine_ls_scale 0.3428(4) loop_ _geom_bond_atom_site_label_1 _geom_bond_site_symmetry_1 _geom_bond_atom_site_label_2 _geom_bond_site_symmetry_2 _geom_bond_distance _geom_bond_publ_flag C124 . C224 . 1.535(7) yes C124 . O12 . 1.275(6) yes C124 . O14 . 1.248(6) yes C224 . C324 . 1.478(9) yes C224 . C4124 . 1.549(7) yes C224 . C5124 . 1.553(7) yes C224 . C324 . 1.478(9) yes C224 . C4224 . 1.515(6) yes C224 . C5224 . 1.574(6) yes C324 . H3241 . 1.000 no C324 . H3242 . 1.000 no C324 . H3243 . 1.000 no C4124 . H4124 . 1.000 no C4124 . H4125 . 1.004 no C4124 . H4126 . 0.999 no C4224 . H4224 . 1.000 no C4224 . H4225 . 1.002 no C4224 . H4226 . 1.000 no C5124 . H5124 . 1.004 no C5124 . H5125 . 1.000 no C5124 . H5126 . 0.994 no C5224 . H5224 . 0.998 no C5224 . H5225 . 1.003 no C5224 . H5226 . 0.999 no Br4 . Mn4 . 2.5504(9) yes O21 . C21 . 1.428(6) yes O21 . Mn1 . 2.110(3) yes O21 . Mn2 . 1.900(3) yes O31 . C31 . 1.436(5) yes O31 . Mn2 . 2.221(4) yes O31 . Mn3 . 1.916(3) yes O31 . Mn4 . 2.244(3) yes O41 . Mn1 2_666 2.199(3) yes O41 . C41 . 1.436(6) yes O41 . Mn1 . 2.336(4) yes O41 . Mn3 . 1.948(3) yes C11 . C21 . 1.545(8) yes C11 . C31 . 1.521(7) yes C11 . C41 . 1.540(6) yes C11 . C51 . 1.555(7) yes C21 . H211 . 1.000 no C21 . H212 . 1.000 no C31 . H311 . 1.000 no C31 . H312 . 1.000 no C41 . H411 . 1.000 no C41 . H412 . 1.000 no C51 . C61 . 1.514(9) yes C51 . H511 . 0.999 no C51 . H512 . 1.001 no C61 . H611 . 1.001 no C61 . H612 . 1.000 no C61 . H613 . 0.999 no O23 . C23 . 1.450(8) yes O23 . Mn3 . 2.260(4) yes O33 . Mn1 2_666 2.147(3) yes O33 . C33 . 1.436(6) yes O33 . Mn3 . 1.893(3) yes O43 . C43 . 1.438(6) yes O43 . Mn3 . 1.876(3) yes O43 . Mn4 . 2.184(3) yes C13 . C23 . 1.532(9) yes C13 . C33 . 1.539(7) yes C13 . C43 . 1.532(8) yes C13 . C53 . 1.548(8) yes C23 . H231 . 0.999 no C23 . H232 . 1.000 no C33 . H331 . 1.000 no C33 . H332 . 1.000 no C43 . H431 . 1.001 no C43 . H432 . 1.000 no O22 . C22 . 1.440(6) yes O22 . Mn1 . 2.198(3) yes O22 . Mn2 . 1.960(3) yes O22 . Mn3 . 2.309(4) yes O32 . C32 . 1.422(6) yes O32 . Mn2 . 1.866(3) yes O32 . Mn4 . 2.181(4) yes O42 . C42 . 1.458(6) yes O42 . Mn2 . 2.224(4) yes C53 . C63 . 1.516(12) yes C53 . H531 . 0.999 no C53 . H532 . 1.000 no C63 . H631 . 1.000 no C63 . H632 . 0.999 no C63 . H633 . 1.001 no C12 . C22 . 1.543(7) yes C12 . C32 . 1.538(7) yes C12 . C42 . 1.514(8) yes C12 . C52 . 1.548(7) yes C22 . H221 . 0.999 no C22 . H222 . 1.001 no C32 . H321 . 1.000 no C32 . H322 . 1.000 no C42 . H421 . 1.000 no C42 . H422 . 1.001 no C52 . C62 . 1.519(9) yes C52 . H521 . 1.000 no C52 . H522 . 1.001 no C62 . H621 . 1.000 no C62 . H622 . 1.000 no C62 . H623 . 0.999 no Mn1 . Mn3 2_666 3.1130(9) yes Mn1 . Mn1 2_666 3.4835(16) yes Mn1 . Mn2 . 3.1501(9) yes Mn1 . Mn3 . 3.3426(11) yes Mn1 . Br1 . 2.6790(10) yes Mn2 . Mn3 . 3.1362(10) yes Mn2 . Mn4 . 3.1169(11) yes Mn2 . O12 . 1.950(3) yes Mn4 . O1 . 2.185(4) yes Mn4 . O14 . 2.245(3) yes O1 . H1 . 0.83(4) no O1 . H2 . 0.83(4) no C1 . N1 . 1.132(8) yes C1 . C211 . 1.454(6) yes C1 . N1 . 1.132(8) yes C1 . C212 . 1.458(6) yes C211 . H2111 . 1.008 no C211 . H2112 . 0.994 no C211 . H2113 . 1.002 no C212 . H2121 . 0.994 no C212 . H2122 . 1.011 no C212 . H2123 . 0.997 no loop_ _geom_angle_atom_site_label_1 _geom_angle_site_symmetry_1 _geom_angle_atom_site_label_2 _geom_angle_site_symmetry_2 _geom_angle_atom_site_label_3 _geom_angle_site_symmetry_3 _geom_angle _geom_angle_publ_flag C224 . C124 . O12 . 115.8(4) yes C224 . C124 . O14 . 119.7(4) yes O12 . C124 . O14 . 124.4(4) yes C124 . C224 . C324 . 112.9(4) yes C124 . C224 . C4124 . 102.2(9) yes C324 . C224 . C4124 . 92.8(10) yes C124 . C224 . C5124 . 113.8(11) yes C324 . C224 . C5124 . 128.4(11) yes C4124 . C224 . C5124 . 97.6(14) yes C124 . C224 . C324 . 112.9(4) yes C124 . C224 . C4224 . 109.2(6) yes C324 . C224 . C4224 . 117.3(6) yes C124 . C224 . C5224 . 107.3(5) yes C324 . C224 . C5224 . 102.5(6) yes C4224 . C224 . C5224 . 106.9(7) yes C224 . C324 . H3241 . 109.4 no C224 . C324 . H3242 . 109.5 no H3241 . C324 . H3242 . 109.5 no C224 . C324 . H3243 . 109.5 no H3241 . C324 . H3243 . 109.5 no H3242 . C324 . H3243 . 109.5 no C224 . C4124 . H4124 . 109.7 no C224 . C4124 . H4125 . 109.5 no H4124 . C4124 . H4125 . 109.1 no C224 . C4124 . H4126 . 109.8 no H4124 . C4124 . H4126 . 109.5 no H4125 . C4124 . H4126 . 109.2 no C224 . C4224 . H4224 . 109.6 no C224 . C4224 . H4225 . 109.5 no H4224 . C4224 . H4225 . 109.3 no C224 . C4224 . H4226 . 109.6 no H4224 . C4224 . H4226 . 109.5 no H4225 . C4224 . H4226 . 109.3 no C224 . C5124 . H5124 . 109.1 no C224 . C5124 . H5125 . 109.4 no H5124 . C5124 . H5125 . 109.1 no C224 . C5124 . H5126 . 109.7 no H5124 . C5124 . H5126 . 109.6 no H5125 . C5124 . H5126 . 109.9 no C224 . C5224 . H5224 . 109.5 no C224 . C5224 . H5225 . 109.3 no H5224 . C5224 . H5225 . 109.4 no C224 . C5224 . H5226 . 109.5 no H5224 . C5224 . H5226 . 109.7 no H5225 . C5224 . H5226 . 109.4 no C21 . O21 . Mn1 . 120.5(3) yes C21 . O21 . Mn2 . 121.4(3) yes Mn1 . O21 . Mn2 . 103.43(15) yes C31 . O31 . Mn2 . 117.9(3) yes C31 . O31 . Mn3 . 119.5(3) yes Mn2 . O31 . Mn3 . 98.33(13) yes C31 . O31 . Mn4 . 124.9(3) yes Mn2 . O31 . Mn4 . 88.56(12) yes Mn3 . O31 . Mn4 . 100.86(14) yes Mn1 2_666 O41 . C41 . 120.9(3) yes Mn1 2_666 O41 . Mn1 . 100.32(13) yes C41 . O41 . Mn1 . 110.8(3) yes Mn1 2_666 O41 . Mn3 . 97.13(14) yes C41 . O41 . Mn3 . 122.0(3) yes Mn1 . O41 . Mn3 . 102.19(14) yes C21 . C11 . C31 . 111.9(4) yes C21 . C11 . C41 . 112.1(4) yes C31 . C11 . C41 . 110.4(4) yes C21 . C11 . C51 . 108.5(4) yes C31 . C11 . C51 . 108.8(4) yes C41 . C11 . C51 . 104.9(4) yes C11 . C21 . O21 . 114.9(4) yes C11 . C21 . H211 . 108.1 no O21 . C21 . H211 . 108.1 no C11 . C21 . H212 . 108.0 no O21 . C21 . H212 . 108.1 no H211 . C21 . H212 . 109.5 no C11 . C31 . O31 . 113.3(4) yes C11 . C31 . H311 . 108.5 no O31 . C31 . H311 . 108.5 no C11 . C31 . H312 . 108.5 no O31 . C31 . H312 . 108.5 no H311 . C31 . H312 . 109.4 no C11 . C41 . O41 . 115.1(4) yes C11 . C41 . H411 . 108.1 no O41 . C41 . H411 . 108.0 no C11 . C41 . H412 . 108.0 no O41 . C41 . H412 . 108.0 no H411 . C41 . H412 . 109.5 no C11 . C51 . C61 . 118.1(5) yes C11 . C51 . H511 . 107.4 no C61 . C51 . H511 . 107.3 no C11 . C51 . H512 . 107.2 no C61 . C51 . H512 . 107.2 no H511 . C51 . H512 . 109.4 no C51 . C61 . H611 . 109.4 no C51 . C61 . H612 . 109.4 no H611 . C61 . H612 . 109.4 no C51 . C61 . H613 . 109.5 no H611 . C61 . H613 . 109.5 no H612 . C61 . H613 . 109.5 no C23 . O23 . Mn3 . 111.7(3) yes Mn1 2_666 O33 . C33 . 122.5(3) yes Mn1 2_666 O33 . Mn3 . 100.64(15) yes C33 . O33 . Mn3 . 120.9(3) yes C43 . O43 . Mn3 . 120.8(3) yes C43 . O43 . Mn4 . 132.0(3) yes Mn3 . O43 . Mn4 . 104.41(15) yes C23 . C13 . C33 . 110.9(5) yes C23 . C13 . C43 . 110.1(4) yes C33 . C13 . C43 . 111.0(5) yes C23 . C13 . C53 . 105.8(5) yes C33 . C13 . C53 . 109.3(4) yes C43 . C13 . C53 . 109.6(5) yes C13 . C23 . O23 . 115.6(5) yes C13 . C23 . H231 . 107.9 no O23 . C23 . H231 . 108.0 no C13 . C23 . H232 . 107.8 no O23 . C23 . H232 . 108.0 no H231 . C23 . H232 . 109.5 no C13 . C33 . O33 . 114.8(4) yes C13 . C33 . H331 . 108.1 no O33 . C33 . H331 . 108.1 no C13 . C33 . H332 . 108.1 no O33 . C33 . H332 . 108.1 no H331 . C33 . H332 . 109.5 no C13 . C43 . O43 . 112.4(4) yes C13 . C43 . H431 . 108.7 no O43 . C43 . H431 . 108.8 no C13 . C43 . H432 . 108.8 no O43 . C43 . H432 . 108.8 no H431 . C43 . H432 . 109.4 no C22 . O22 . Mn1 . 124.2(3) yes C22 . O22 . Mn2 . 121.0(3) yes Mn1 . O22 . Mn2 . 98.35(14) yes C22 . O22 . Mn3 . 116.8(3) yes Mn1 . O22 . Mn3 . 95.73(12) yes Mn2 . O22 . Mn3 . 94.21(13) yes C32 . O32 . Mn2 . 122.5(3) yes C32 . O32 . Mn4 . 118.8(3) yes Mn2 . O32 . Mn4 . 100.44(15) yes C42 . O42 . Mn2 . 115.6(3) yes C13 . C53 . C63 . 117.0(6) yes C13 . C53 . H531 . 107.5 no C63 . C53 . H531 . 107.6 no C13 . C53 . H532 . 107.5 no C63 . C53 . H532 . 107.6 no H531 . C53 . H532 . 109.5 no C53 . C63 . H631 . 109.5 no C53 . C63 . H632 . 109.5 no H631 . C63 . H632 . 109.5 no C53 . C63 . H633 . 109.5 no H631 . C63 . H633 . 109.4 no H632 . C63 . H633 . 109.4 no C22 . C12 . C32 . 109.0(4) yes C22 . C12 . C42 . 112.5(4) yes C32 . C12 . C42 . 112.1(4) yes C22 . C12 . C52 . 108.1(4) yes C32 . C12 . C52 . 106.0(4) yes C42 . C12 . C52 . 108.8(5) yes C12 . C22 . O22 . 113.9(4) yes C12 . C22 . H221 . 108.4 no O22 . C22 . H221 . 108.4 no C12 . C22 . H222 . 108.3 no O22 . C22 . H222 . 108.3 no H221 . C22 . H222 . 109.4 no C12 . C32 . O32 . 115.2(4) yes C12 . C32 . H321 . 108.0 no O32 . C32 . H321 . 108.0 no C12 . C32 . H322 . 108.0 no O32 . C32 . H322 . 108.0 no H321 . C32 . H322 . 109.5 no C12 . C42 . O42 . 113.5(4) yes C12 . C42 . H421 . 108.5 no O42 . C42 . H421 . 108.5 no C12 . C42 . H422 . 108.5 no O42 . C42 . H422 . 108.4 no H421 . C42 . H422 . 109.4 no C12 . C52 . C62 . 117.3(5) yes C12 . C52 . H521 . 107.5 no C62 . C52 . H521 . 107.5 no C12 . C52 . H522 . 107.4 no C62 . C52 . H522 . 107.4 no H521 . C52 . H522 . 109.4 no C52 . C62 . H621 . 109.5 no C52 . C62 . H622 . 109.4 no H621 . C62 . H622 . 109.5 no C52 . C62 . H623 . 109.5 no H621 . C62 . H623 . 109.5 no H622 . C62 . H623 . 109.5 no O41 2_666 Mn1 . O22 . 101.14(12) yes O41 2_666 Mn1 . O33 2_666 74.18(12) yes O22 . Mn1 . O33 2_666 168.53(14) yes O41 2_666 Mn1 . O21 . 161.74(14) yes O22 . Mn1 . O21 . 73.55(12) yes O33 2_666 Mn1 . O21 . 107.55(12) yes O41 2_666 Mn1 . O41 . 79.68(13) yes O22 . Mn1 . O41 . 78.00(12) yes O33 2_666 Mn1 . O41 . 90.77(13) yes O21 . Mn1 . O41 . 82.12(13) yes O41 2_666 Mn1 . Mn3 2_666 38.37(9) yes O22 . Mn1 . Mn3 2_666 139.51(9) yes O33 2_666 Mn1 . Mn3 2_666 36.70(8) yes O21 . Mn1 . Mn3 2_666 143.63(10) yes O41 . Mn1 . Mn3 2_666 90.32(8) yes O41 2_666 Mn1 . Mn1 2_666 41.29(10) yes O22 . Mn1 . Mn1 2_666 89.00(9) yes O33 2_666 Mn1 . Mn1 2_666 80.61(10) yes O21 . Mn1 . Mn1 2_666 120.50(11) yes O41 . Mn1 . Mn1 2_666 38.39(8) yes O41 2_666 Mn1 . Mn2 . 138.08(9) yes O22 . Mn1 . Mn2 . 38.00(8) yes O33 2_666 Mn1 . Mn2 . 143.26(9) yes O21 . Mn1 . Mn2 . 35.93(9) yes O41 . Mn1 . Mn2 . 81.59(8) yes O41 2_666 Mn1 . Mn3 . 86.96(10) yes O22 . Mn1 . Mn3 . 43.41(9) yes O33 2_666 Mn1 . Mn3 . 125.22(10) yes O21 . Mn1 . Mn3 . 77.23(10) yes O41 . Mn1 . Mn3 . 34.72(8) yes O41 2_666 Mn1 . Br1 . 99.06(10) yes O22 . Mn1 . Br1 . 93.91(10) yes O33 2_666 Mn1 . Br1 . 97.17(10) yes O21 . Mn1 . Br1 . 98.73(10) yes O41 . Mn1 . Br1 . 171.32(9) yes Mn3 2_666 Mn1 . Mn1 2_666 60.58(2) yes Mn3 2_666 Mn1 . Mn2 . 171.89(4) yes Mn1 2_666 Mn1 . Mn2 . 111.82(4) yes Mn3 2_666 Mn1 . Mn3 . 114.80(3) yes Mn1 2_666 Mn1 . Mn3 . 54.22(2) yes Mn2 . Mn1 . Mn3 . 57.68(2) yes Mn3 2_666 Mn1 . Br1 . 93.94(3) yes Mn1 2_666 Mn1 . Br1 . 139.68(4) yes Mn2 . Mn1 . Br1 . 94.00(3) yes Mn3 . Mn1 . Br1 . 136.93(3) yes O31 . Mn2 . O42 . 168.68(12) yes O31 . Mn2 . O22 . 84.38(13) yes O42 . Mn2 . O22 . 85.01(14) yes O31 . Mn2 . Mn1 . 88.88(8) yes O42 . Mn2 . Mn1 . 86.18(10) yes O22 . Mn2 . Mn1 . 43.65(10) yes O31 . Mn2 . O21 . 86.79(14) yes O42 . Mn2 . O21 . 96.01(15) yes O22 . Mn2 . O21 . 83.85(14) yes Mn1 . Mn2 . O21 . 40.65(10) yes O31 . Mn2 . O32 . 88.33(14) yes O42 . Mn2 . O32 . 88.06(15) yes O22 . Mn2 . O32 . 91.87(14) yes Mn1 . Mn2 . O32 . 135.47(10) yes O21 . Mn2 . O32 . 173.80(15) yes O31 . Mn2 . Mn3 . 37.20(8) yes O42 . Mn2 . Mn3 . 131.92(10) yes O22 . Mn2 . Mn3 . 47.23(10) yes Mn1 . Mn2 . Mn3 . 64.24(2) yes O21 . Mn2 . Mn3 . 85.47(11) yes O31 . Mn2 . Mn4 . 46.02(8) yes O42 . Mn2 . Mn4 . 131.54(10) yes O22 . Mn2 . Mn4 . 95.61(11) yes Mn1 . Mn2 . Mn4 . 126.09(3) yes O21 . Mn2 . Mn4 . 132.33(11) yes O31 . Mn2 . O12 . 91.62(13) yes O42 . Mn2 . O12 . 99.16(14) yes O22 . Mn2 . O12 . 175.08(15) yes Mn1 . Mn2 . O12 . 133.62(10) yes O21 . Mn2 . O12 . 93.07(14) yes O32 . Mn2 . Mn3 . 88.33(11) yes O32 . Mn2 . Mn4 . 43.50(11) yes Mn3 . Mn2 . Mn4 . 61.85(2) yes O32 . Mn2 . O12 . 90.89(14) yes Mn3 . Mn2 . O12 . 128.82(11) yes Mn4 . Mn2 . O12 . 83.61(11) yes O23 . Mn3 . O22 . 176.21(13) yes O23 . Mn3 . Mn1 2_666 85.01(10) yes O22 . Mn3 . Mn1 2_666 96.70(8) yes O23 . Mn3 . Mn2 . 142.33(10) yes O22 . Mn3 . Mn2 . 38.56(8) yes Mn1 2_666 Mn3 . Mn2 . 123.18(3) yes O23 . Mn3 . O41 . 99.73(15) yes O22 . Mn3 . O41 . 83.81(14) yes Mn1 2_666 Mn3 . O41 . 44.50(10) yes Mn2 . Mn3 . O41 . 88.13(11) yes O23 . Mn3 . O31 . 98.20(14) yes O22 . Mn3 . O31 . 82.98(13) yes Mn1 2_666 Mn3 . O31 . 135.30(10) yes Mn2 . Mn3 . O31 . 44.48(10) yes O41 . Mn3 . O31 . 91.49(13) yes O23 . Mn3 . O33 . 84.31(15) yes O22 . Mn3 . O33 . 94.64(14) yes Mn1 2_666 Mn3 . O33 . 42.66(10) yes Mn2 . Mn3 . O33 . 133.20(12) yes O41 . Mn3 . O33 . 86.06(14) yes O23 . Mn3 . O43 . 84.18(16) yes O22 . Mn3 . O43 . 92.37(14) yes Mn1 2_666 Mn3 . O43 . 139.96(10) yes Mn2 . Mn3 . O43 . 86.64(11) yes O41 . Mn3 . O43 . 174.75(15) yes O23 . Mn3 . Mn1 . 142.56(10) yes O22 . Mn3 . Mn1 . 40.86(8) yes Mn1 2_666 Mn3 . Mn1 . 65.20(3) yes Mn2 . Mn3 . Mn1 . 58.08(2) yes O41 . Mn3 . Mn1 . 43.09(11) yes O31 . Mn3 . O33 . 176.77(16) yes O31 . Mn3 . O43 . 84.44(14) yes O33 . Mn3 . O43 . 97.87(14) yes O31 . Mn3 . Mn1 . 88.82(11) yes O33 . Mn3 . Mn1 . 87.95(11) yes O43 . Mn3 . Mn1 . 133.22(12) yes Br4 . Mn4 . O43 . 105.02(9) yes Br4 . Mn4 . O32 . 102.52(9) yes O43 . Mn4 . O32 . 85.92(13) yes Br4 . Mn4 . O31 . 174.38(9) yes O43 . Mn4 . O31 . 70.27(12) yes O32 . Mn4 . O31 . 80.47(12) yes Br4 . Mn4 . Mn2 . 138.20(4) yes O43 . Mn4 . Mn2 . 82.32(10) yes O32 . Mn4 . Mn2 . 36.06(9) yes O31 . Mn4 . Mn2 . 45.42(9) yes Br4 . Mn4 . O1 . 92.60(11) yes O43 . Mn4 . O1 . 97.81(14) yes O32 . Mn4 . O1 . 162.98(15) yes O31 . Mn4 . O1 . 85.16(14) yes Mn2 . Mn4 . O1 . 127.73(11) yes Br4 . Mn4 . O14 . 101.37(9) yes O43 . Mn4 . O14 . 152.33(13) yes O32 . Mn4 . O14 . 80.37(13) yes O31 . Mn4 . O14 . 83.76(12) yes Mn2 . Mn4 . O14 . 72.44(9) yes O1 . Mn4 . O14 . 89.09(14) yes Mn2 . O12 . C124 . 128.7(3) yes Mn4 . O1 . H1 . 125(5) no Mn4 . O1 . H2 . 111(5) no H1 . O1 . H2 . 105(7) no Mn4 . O14 . C124 . 130.2(3) yes N1 . C1 . C211 . 165.6(13) yes N1 . C1 . C212 . 167.2(12) yes C1 . C211 . H2111 . 109.2 no C1 . C211 . H2112 . 110.2 no H2111 . C211 . H2112 . 109.3 no C1 . C211 . H2113 . 109.7 no H2111 . C211 . H2113 . 108.7 no H2112 . C211 . H2113 . 109.8 no C1 . C212 . H2121 . 110.0 no C1 . C212 . H2122 . 109.0 no H2121 . C212 . H2122 . 109.0 no C1 . C212 . H2123 . 109.8 no H2121 . C212 . H2123 . 110.2 no H2122 . C212 . H2123 . 108.8 no loop_ _geom_hbond_atom_site_label_D _geom_hbond_site_symmetry_D _geom_hbond_atom_site_label_H _geom_hbond_site_symmetry_H _geom_hbond_atom_site_label_A _geom_hbond_site_symmetry_A _geom_hbond_angle_DHA _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_publ_flag O1 . H1 . O14 2_555 166.6 0.832 1.957 2.773 yes