# Supplementary Material (ESI) for Chemical Communications
# This journal is (c) The Royal Society of Chemistry 2009


data_global
_journal_name_full               Chem.Commun.

_journal_coden_Cambridge         0182
_journal_volume                  ?
_journal_page_first              ?
_journal_year                    ?

_publ_contact_author_name        'Ho-Chol Chang'
_publ_contact_author_email       CHANG@SCI.HOKUDAI.AC.JP

_publ_section_title              
;
Bimodal Three-Membered Valence Tautomerism
of an Alkyl Chain-Functionalized Manganese Complex
;
loop_
_publ_author_name
'Ho-Chol Chang.'
'Daisuke Kiriya'
'Susumu Kitagaw'
'Kohei Nakamura'

# Attachment 'MnC12Opy.cif'

data_crystalclear
_database_code_depnum_ccdc_archive 'CCDC 713275'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C86 H146 Mn N2 O8'
_chemical_formula_weight         1390.99

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Mn Mn 0.3368 0.7283 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           triclinic
_symmetry_space_group_name_H-M   P-1

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   10.4097(16)
_cell_length_b                   10.9988(18)
_cell_length_c                   20.504(3)
_cell_angle_alpha                72.214(7)
_cell_angle_beta                 76.395(9)
_cell_angle_gamma                84.972(10)
_cell_volume                     2172.4(6)
_cell_formula_units_Z            1
_cell_measurement_temperature    213(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       needle
_exptl_crystal_colour            purple
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.063
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             765
_exptl_absorpt_coefficient_mu    0.203
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_correction_T_min  0.9606
_exptl_absorpt_correction_T_max  0.9606
_exptl_absorpt_process_details   ?

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      213(2)
_diffrn_radiation_wavelength     0.71070
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  CCD
_diffrn_measurement_method       \w
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            36356
_diffrn_reflns_av_R_equivalents  0.0736
_diffrn_reflns_av_sigmaI/netI    0.0725
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_theta_min         3.06
_diffrn_reflns_theta_max         27.15
_reflns_number_total             9575
_reflns_number_gt                6257
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    SIR97
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_refine_special_details          
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ are statistically about twice as large as those based on F, and R-
factors based on ALL data will be even larger.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[\s^2^(Fo^2^)+(0.1655P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         9575
_refine_ls_number_parameters     439
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1113
_refine_ls_R_factor_gt           0.0881
_refine_ls_wR_factor_ref         0.2861
_refine_ls_wR_factor_gt          0.2482
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_restrained_S_all      1.057
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

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_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Mn1 Mn 0.5000 0.5000 0.0000 0.0359(2) Uani 1 2 d S . .
O1 O 0.46211(17) 0.55629(17) -0.08822(9) 0.0383(4) Uani 1 1 d . . .
O2 O 0.33564(17) 0.56737(17) 0.03150(9) 0.0386(4) Uani 1 1 d . . .
C1 C 0.3401(2) 0.6113(2) -0.08756(15) 0.0379(6) Uani 1 1 d . . .
C2 C 0.2695(3) 0.6151(2) -0.02064(15) 0.0373(6) Uani 1 1 d . . .
C3 C 0.1390(3) 0.6656(3) -0.00859(16) 0.0438(7) Uani 1 1 d . . .
C4 C 0.0897(3) 0.7135(3) -0.07007(19) 0.0549(8) Uani 1 1 d . . .
H1 H 0.0032 0.7479 -0.0661 0.066 Uiso 1 1 calc R . .
C5 C 0.1608(3) 0.7129(3) -0.13587(19) 0.0564(8) Uani 1 1 d . . .
H2 H 0.1220 0.7496 -0.1746 0.068 Uiso 1 1 calc R . .
C6 C 0.2879(3) 0.6600(3) -0.14724(16) 0.0443(7) Uani 1 1 d . . .
C7 C 0.0619(3) 0.6687(3) 0.06326(18) 0.0511(7) Uani 1 1 d . . .
C8 C -0.0846(3) 0.6992(5) 0.0640(2) 0.0844(13) Uani 1 1 d . . .
H3 H -0.1312 0.6999 0.1108 0.127 Uiso 1 1 calc R . .
H4 H -0.1217 0.6348 0.0508 0.127 Uiso 1 1 calc R . .
H5 H -0.0938 0.7823 0.0310 0.127 Uiso 1 1 calc R . .
C9 C 0.1198(4) 0.7719(4) 0.0835(2) 0.0710(10) Uani 1 1 d . . .
H6 H 0.0713 0.7751 0.1296 0.107 Uiso 1 1 calc R . .
H7 H 0.1128 0.8541 0.0493 0.107 Uiso 1 1 calc R . .
H8 H 0.2121 0.7517 0.0845 0.107 Uiso 1 1 calc R . .
C10 C 0.0692(4) 0.5415(3) 0.1193(2) 0.0717(10) Uani 1 1 d . . .
H9 H 0.0179 0.5477 0.1643 0.107 Uiso 1 1 calc R . .
H10 H 0.1605 0.5210 0.1223 0.107 Uiso 1 1 calc R . .
H11 H 0.0337 0.4749 0.1070 0.107 Uiso 1 1 calc R . .
C11 C 0.3651(3) 0.6545(3) -0.21959(16) 0.0540(8) Uani 1 1 d . . .
C12 C 0.3895(4) 0.5144(3) -0.2194(2) 0.0665(9) Uani 1 1 d . . .
H12 H 0.4380 0.5112 -0.2654 0.100 Uiso 1 1 calc R . .
H13 H 0.3054 0.4726 -0.2079 0.100 Uiso 1 1 calc R . .
H14 H 0.4404 0.4711 -0.1846 0.100 Uiso 1 1 calc R . .
C13 C 0.4990(4) 0.7189(4) -0.23872(18) 0.0669(10) Uani 1 1 d . . .
H15 H 0.5465 0.7142 -0.2847 0.100 Uiso 1 1 calc R . .
H16 H 0.5501 0.6756 -0.2041 0.100 Uiso 1 1 calc R . .
H17 H 0.4852 0.8077 -0.2395 0.100 Uiso 1 1 calc R . .
C14 C 0.2915(4) 0.7219(4) -0.2772(2) 0.0835(12) Uani 1 1 d . . .
H18 H 0.3434 0.7154 -0.3220 0.125 Uiso 1 1 calc R . .
H19 H 0.2775 0.8111 -0.2791 0.125 Uiso 1 1 calc R . .
H20 H 0.2068 0.6819 -0.2672 0.125 Uiso 1 1 calc R . .
N1 N 0.4156(2) 0.3298(2) 0.01686(11) 0.0371(5) Uani 1 1 d . . .
C15 C 0.4425(3) 0.2717(3) -0.03222(14) 0.0439(6) Uani 1 1 d . . .
H21 H 0.5010 0.3097 -0.0750 0.053 Uiso 1 1 calc R . .
C16 C 0.3861(3) 0.1544(3) -0.02242(15) 0.0464(7) Uani 1 1 d . . .
C17 C 0.3021(3) 0.0998(3) 0.04059(16) 0.0492(7) Uani 1 1 d . . .
H22 H 0.2637 0.0207 0.0489 0.059 Uiso 1 1 calc R . .
C18 C 0.2742(3) 0.1621(3) 0.09193(14) 0.0447(7) Uani 1 1 d . . .
C19 C 0.3323(3) 0.2779(3) 0.07889(15) 0.0421(6) Uani 1 1 d . . .
H23 H 0.3137 0.3207 0.1134 0.051 Uiso 1 1 calc R . .
O3 O 0.4222(3) 0.1079(2) -0.07749(12) 0.0702(7) Uani 1 1 d . . .
C20 C 0.3559(5) -0.0050(3) -0.0742(2) 0.0783(12) Uani 1 1 d . . .
H24 H 0.3963 -0.0808 -0.0463 0.094 Uiso 1 1 calc R . .
H25 H 0.2628 -0.0007 -0.0506 0.094 Uiso 1 1 calc R . .
C21 C 0.3626(10) -0.0167(5) -0.1378(4) 0.197(5) Uani 1 1 d . . .
H26 H 0.3089 -0.0906 -0.1303 0.236 Uiso 1 1 calc R . .
H27 H 0.4543 -0.0414 -0.1544 0.236 Uiso 1 1 calc R . .
C22 C 0.3275(8) 0.0808(6) -0.1960(3) 0.152(3) Uani 1 1 d . . .
H28 H 0.3227 0.1597 -0.1827 0.183 Uiso 1 1 calc R . .
H29 H 0.4058 0.0885 -0.2343 0.183 Uiso 1 1 calc R . .
C23 C 0.2321(11) 0.0896(6) -0.2246(6) 0.232(6) Uani 1 1 d . . .
H30 H 0.1555 0.1114 -0.1917 0.279 Uiso 1 1 calc R . .
H31 H 0.2179 0.0023 -0.2240 0.279 Uiso 1 1 calc R . .
C24 C 0.2175(7) 0.1708(5) -0.2948(4) 0.125(2) Uani 1 1 d . . .
H32 H 0.2670 0.1301 -0.3297 0.150 Uiso 1 1 calc R . .
H33 H 0.1240 0.1726 -0.2965 0.150 Uiso 1 1 calc R . .
C25 C 0.2618(8) 0.3041(5) -0.3158(3) 0.135(3) Uani 1 1 d . . .
H34 H 0.3524 0.3020 -0.3094 0.163 Uiso 1 1 calc R . .
H35 H 0.2063 0.3467 -0.2833 0.163 Uiso 1 1 calc R . .
C26 C 0.2599(6) 0.3842(6) -0.3884(3) 0.122(2) Uani 1 1 d . . .
H36 H 0.3141 0.3407 -0.4209 0.146 Uiso 1 1 calc R . .
H37 H 0.1689 0.3873 -0.3945 0.146 Uiso 1 1 calc R . .
C27 C 0.3053(7) 0.5148(6) -0.4098(3) 0.124(2) Uani 1 1 d . . .
H38 H 0.3937 0.5114 -0.4003 0.149 Uiso 1 1 calc R . .
H39 H 0.2471 0.5592 -0.3790 0.149 Uiso 1 1 calc R . .
C28 C 0.3128(7) 0.5953(8) -0.4829(3) 0.149(3) Uani 1 1 d . . .
H40 H 0.2238 0.6032 -0.4922 0.178 Uiso 1 1 calc R . .
H41 H 0.3684 0.5504 -0.5143 0.178 Uiso 1 1 calc R . .
C29 C 0.3654(8) 0.7260(7) -0.5018(4) 0.158(3) Uani 1 1 d . . .
H42 H 0.3101 0.7715 -0.4707 0.189 Uiso 1 1 calc R . .
H43 H 0.4547 0.7187 -0.4931 0.189 Uiso 1 1 calc R . .
C30 C 0.3708(10) 0.8038(11) -0.5758(5) 0.215(5) Uani 1 1 d . . .
H44 H 0.2830 0.8071 -0.5860 0.258 Uiso 1 1 calc R . .
H45 H 0.4321 0.7631 -0.6073 0.258 Uiso 1 1 calc R . .
C31 C 0.4161(11) 0.9411(10) -0.5897(6) 0.280(8) Uani 1 1 d . . .
H46 H 0.4182 0.9891 -0.6382 0.420 Uiso 1 1 calc R . .
H47 H 0.5038 0.9383 -0.5806 0.420 Uiso 1 1 calc R . .
H48 H 0.3548 0.9822 -0.5590 0.420 Uiso 1 1 calc R . .
O4 O 0.1898(2) 0.10360(19) 0.15247(11) 0.0561(6) Uani 1 1 d . . .
C32 C 0.1646(3) 0.1613(3) 0.20814(16) 0.0528(8) Uani 1 1 d . . .
H49 H 0.1255 0.2468 0.1930 0.063 Uiso 1 1 calc R . .
H50 H 0.2472 0.1691 0.2215 0.063 Uiso 1 1 calc R . .
C33 C 0.0698(3) 0.0767(3) 0.26971(16) 0.0559(8) Uani 1 1 d . . .
H51 H 0.1099 -0.0086 0.2838 0.067 Uiso 1 1 calc R . .
H52 H -0.0113 0.0683 0.2551 0.067 Uiso 1 1 calc R . .
C34 C 0.0350(4) 0.1294(3) 0.33242(18) 0.0625(9) Uani 1 1 d . . .
H53 H 0.1151 0.1300 0.3497 0.075 Uiso 1 1 calc R . .
H54 H 0.0034 0.2180 0.3170 0.075 Uiso 1 1 calc R . .
C35 C -0.0697(4) 0.0532(3) 0.39209(17) 0.0647(9) Uani 1 1 d . . .
H55 H -0.1476 0.0485 0.3739 0.078 Uiso 1 1 calc R . .
H56 H -0.0962 0.0990 0.4275 0.078 Uiso 1 1 calc R . .
C36 C -0.0262(4) -0.0817(3) 0.42748(17) 0.0629(9) Uani 1 1 d . . .
H57 H -0.0024 -0.1286 0.3925 0.075 Uiso 1 1 calc R . .
H58 H 0.0532 -0.0774 0.4445 0.075 Uiso 1 1 calc R . .
C37 C -0.1307(4) -0.1553(3) 0.48837(18) 0.0659(9) Uani 1 1 d . . .
H59 H -0.2088 -0.1626 0.4709 0.079 Uiso 1 1 calc R . .
H60 H -0.1571 -0.1067 0.5224 0.079 Uiso 1 1 calc R . .
C38 C -0.0858(4) -0.2879(4) 0.52550(19) 0.0713(10) Uani 1 1 d . . .
H61 H -0.0579 -0.3360 0.4913 0.086 Uiso 1 1 calc R . .
H62 H -0.0086 -0.2804 0.5436 0.086 Uiso 1 1 calc R . .
C39 C -0.1905(4) -0.3624(4) 0.5856(2) 0.0783(11) Uani 1 1 d . . .
H63 H -0.2664 -0.3729 0.5673 0.094 Uiso 1 1 calc R . .
H64 H -0.2207 -0.3130 0.6190 0.094 Uiso 1 1 calc R . .
C40 C -0.1426(5) -0.4931(4) 0.6240(2) 0.0849(13) Uani 1 1 d . . .
H65 H -0.1098 -0.5412 0.5901 0.102 Uiso 1 1 calc R . .
H66 H -0.0683 -0.4822 0.6433 0.102 Uiso 1 1 calc R . .
C41 C -0.2470(5) -0.5707(4) 0.6829(2) 0.0890(14) Uani 1 1 d . . .
H67 H -0.2789 -0.5227 0.7170 0.107 Uiso 1 1 calc R . .
H68 H -0.3218 -0.5802 0.6636 0.107 Uiso 1 1 calc R . .
C42 C -0.2023(5) -0.7012(4) 0.7211(3) 0.1017(16) Uani 1 1 d . . .
H69 H -0.1656 -0.7478 0.6869 0.122 Uiso 1 1 calc R . .
H70 H -0.1314 -0.6920 0.7433 0.122 Uiso 1 1 calc R . .
C43 C -0.3097(6) -0.7783(5) 0.7760(3) 0.121(2) Uani 1 1 d . . .
H71 H -0.2745 -0.8614 0.7980 0.181 Uiso 1 1 calc R . .
H72 H -0.3800 -0.7888 0.7546 0.181 Uiso 1 1 calc R . .
H73 H -0.3443 -0.7346 0.8113 0.181 Uiso 1 1 calc R . .

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
Mn1 0.0313(3) 0.0359(3) 0.0374(3) -0.0067(2) -0.0064(2) -0.0028(2)
O1 0.0340(9) 0.0388(10) 0.0390(10) -0.0067(8) -0.0079(7) -0.0016(7)
O2 0.0329(9) 0.0411(10) 0.0405(10) -0.0094(8) -0.0090(7) 0.0000(7)
C1 0.0327(13) 0.0333(13) 0.0486(15) -0.0085(11) -0.0138(11) -0.0053(10)
C2 0.0355(13) 0.0289(12) 0.0486(15) -0.0078(11) -0.0145(11) -0.0054(10)
C3 0.0338(13) 0.0411(15) 0.0586(18) -0.0156(13) -0.0123(12) -0.0022(11)
C4 0.0378(15) 0.0597(19) 0.074(2) -0.0248(17) -0.0239(15) 0.0114(13)
C5 0.0535(18) 0.0550(18) 0.067(2) -0.0113(16) -0.0342(16) 0.0004(14)
C6 0.0454(15) 0.0403(15) 0.0488(16) -0.0092(12) -0.0168(13) -0.0059(11)
C7 0.0335(14) 0.0485(16) 0.071(2) -0.0229(15) -0.0041(13) 0.0033(12)
C8 0.0369(18) 0.117(3) 0.099(3) -0.043(3) -0.0054(19) 0.0144(19)
C9 0.064(2) 0.076(2) 0.075(3) -0.036(2) 0.0049(18) -0.0144(18)
C10 0.060(2) 0.064(2) 0.071(2) -0.0132(18) 0.0173(18) -0.0064(16)
C11 0.0565(18) 0.0621(19) 0.0427(16) -0.0076(14) -0.0190(14) -0.0028(14)
C12 0.076(2) 0.073(2) 0.061(2) -0.0343(18) -0.0170(18) 0.0022(18)
C13 0.066(2) 0.082(2) 0.0440(18) -0.0058(17) -0.0049(15) -0.0214(18)
C14 0.092(3) 0.107(3) 0.056(2) -0.019(2) -0.038(2) 0.014(2)
N1 0.0336(11) 0.0376(11) 0.0362(12) -0.0062(9) -0.0054(9) -0.0033(8)
C15 0.0440(15) 0.0465(15) 0.0385(15) -0.0072(12) -0.0088(12) -0.0075(12)
C16 0.0545(17) 0.0463(16) 0.0393(15) -0.0101(12) -0.0117(13) -0.0107(13)
C17 0.0560(18) 0.0387(15) 0.0502(17) -0.0032(13) -0.0151(14) -0.0134(13)
C18 0.0438(15) 0.0444(15) 0.0383(15) 0.0004(12) -0.0080(12) -0.0097(12)
C19 0.0394(14) 0.0424(14) 0.0402(15) -0.0064(12) -0.0067(11) -0.0049(11)
O3 0.102(2) 0.0579(14) 0.0519(14) -0.0215(11) -0.0001(13) -0.0326(13)
C20 0.125(4) 0.056(2) 0.060(2) -0.0197(18) -0.017(2) -0.032(2)
C21 0.400(13) 0.086(4) 0.141(6) 0.021(4) -0.163(7) -0.112(6)
C22 0.278(9) 0.105(4) 0.098(4) 0.004(3) -0.104(5) -0.078(5)
C23 0.361(14) 0.089(4) 0.315(13) -0.009(6) -0.255(12) -0.050(6)
C24 0.155(6) 0.110(4) 0.155(6) -0.055(4) -0.104(5) 0.015(4)
C25 0.219(8) 0.092(4) 0.140(5) -0.047(4) -0.114(5) 0.016(4)
C26 0.129(5) 0.152(6) 0.102(4) -0.052(4) -0.059(4) 0.050(4)
C27 0.180(6) 0.117(4) 0.096(4) -0.047(4) -0.064(4) 0.045(4)
C28 0.127(5) 0.205(8) 0.092(4) -0.025(5) -0.031(4) 0.063(5)
C29 0.174(7) 0.143(6) 0.115(5) -0.018(5) -0.004(5) 0.071(6)
C30 0.164(8) 0.230(10) 0.160(8) 0.035(8) -0.011(6) 0.073(7)
C31 0.241(12) 0.189(9) 0.246(12) 0.046(9) 0.078(10) 0.105(9)
O4 0.0644(14) 0.0504(12) 0.0442(12) -0.0034(10) -0.0004(10) -0.0229(10)
C32 0.0542(18) 0.0543(17) 0.0424(16) -0.0031(13) -0.0057(13) -0.0157(14)
C33 0.0527(18) 0.0564(18) 0.0462(17) 0.0003(14) -0.0031(14) -0.0119(14)
C34 0.067(2) 0.063(2) 0.0484(18) -0.0079(16) -0.0058(16) -0.0053(16)
C35 0.068(2) 0.064(2) 0.0466(19) -0.0051(16) 0.0014(16) -0.0041(16)
C36 0.062(2) 0.070(2) 0.0450(18) -0.0084(16) 0.0005(15) -0.0021(16)
C37 0.068(2) 0.068(2) 0.0488(19) -0.0086(16) 0.0036(16) -0.0076(17)
C38 0.079(3) 0.068(2) 0.051(2) -0.0083(17) 0.0050(18) -0.0060(18)
C39 0.088(3) 0.070(2) 0.058(2) -0.0082(19) 0.010(2) -0.009(2)
C40 0.094(3) 0.067(2) 0.068(3) -0.003(2) 0.009(2) 0.004(2)
C41 0.095(3) 0.061(2) 0.081(3) -0.001(2) 0.010(2) 0.003(2)
C42 0.115(4) 0.076(3) 0.082(3) 0.002(2) 0.001(3) 0.015(3)
C43 0.125(4) 0.089(3) 0.100(4) 0.017(3) 0.007(3) 0.001(3)

_geom_special_details            
;
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.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Mn1 O1 1.8492(18) . ?
Mn1 O1 1.8493(18) 2_665 ?
Mn1 O2 1.8557(18) . ?
Mn1 O2 1.8558(18) 2_665 ?
Mn1 N1 2.036(2) . ?
Mn1 N1 2.036(2) 2_665 ?
O1 C1 1.357(3) . ?
O2 C2 1.354(3) . ?
C1 C6 1.393(4) . ?
C1 C2 1.407(4) . ?
C2 C3 1.417(4) . ?
C3 C4 1.408(4) . ?
C3 C7 1.512(4) . ?
C4 C5 1.380(5) . ?
C4 H1 0.9400 . ?
C5 C6 1.395(4) . ?
C5 H2 0.9400 . ?
C6 C11 1.528(4) . ?
C7 C10 1.524(5) . ?
C7 C8 1.530(4) . ?
C7 C9 1.534(5) . ?
C8 H3 0.9700 . ?
C8 H4 0.9700 . ?
C8 H5 0.9700 . ?
C9 H6 0.9700 . ?
C9 H7 0.9700 . ?
C9 H8 0.9700 . ?
C10 H9 0.9700 . ?
C10 H10 0.9700 . ?
C10 H11 0.9700 . ?
C11 C14 1.525(4) . ?
C11 C13 1.531(5) . ?
C11 C12 1.538(5) . ?
C12 H12 0.9700 . ?
C12 H13 0.9700 . ?
C12 H14 0.9700 . ?
C13 H15 0.9700 . ?
C13 H16 0.9700 . ?
C13 H17 0.9700 . ?
C14 H18 0.9700 . ?
C14 H19 0.9700 . ?
C14 H20 0.9700 . ?
N1 C15 1.315(4) . ?
N1 C19 1.349(3) . ?
C15 C16 1.403(4) . ?
C15 H21 0.9400 . ?
C16 O3 1.341(4) . ?
C16 C17 1.371(4) . ?
C17 C18 1.387(4) . ?
C17 H22 0.9400 . ?
C18 O4 1.351(3) . ?
C18 C19 1.383(4) . ?
C19 H23 0.9400 . ?
O3 C20 1.449(4) . ?
C20 C21 1.332(7) . ?
C20 H24 0.9800 . ?
C20 H25 0.9800 . ?
C21 C22 1.437(7) . ?
C21 H26 0.9800 . ?
C21 H27 0.9800 . ?
C22 C23 1.250(9) . ?
C22 H28 0.9800 . ?
C22 H29 0.9800 . ?
C23 C24 1.478(9) . ?
C23 H30 0.9800 . ?
C23 H31 0.9800 . ?
C24 C25 1.479(7) . ?
C24 H32 0.9800 . ?
C24 H33 0.9800 . ?
C25 C26 1.483(7) . ?
C25 H34 0.9800 . ?
C25 H35 0.9800 . ?
C26 C27 1.455(8) . ?
C26 H36 0.9800 . ?
C26 H37 0.9800 . ?
C27 C28 1.478(7) . ?
C27 H38 0.9800 . ?
C27 H39 0.9800 . ?
C28 C29 1.488(10) . ?
C28 H40 0.9800 . ?
C28 H41 0.9800 . ?
C29 C30 1.486(10) . ?
C29 H42 0.9800 . ?
C29 H43 0.9800 . ?
C30 C31 1.543(14) . ?
C30 H44 0.9800 . ?
C30 H45 0.9800 . ?
C31 H46 0.9700 . ?
C31 H47 0.9700 . ?
C31 H48 0.9700 . ?
O4 C32 1.431(4) . ?
C32 C33 1.513(4) . ?
C32 H49 0.9800 . ?
C32 H50 0.9800 . ?
C33 C34 1.524(5) . ?
C33 H51 0.9800 . ?
C33 H52 0.9800 . ?
C34 C35 1.515(4) . ?
C34 H53 0.9800 . ?
C34 H54 0.9800 . ?
C35 C36 1.521(5) . ?
C35 H55 0.9800 . ?
C35 H56 0.9800 . ?
C36 C37 1.515(4) . ?
C36 H57 0.9800 . ?
C36 H58 0.9800 . ?
C37 C38 1.515(5) . ?
C37 H59 0.9800 . ?
C37 H60 0.9800 . ?
C38 C39 1.511(5) . ?
C38 H61 0.9800 . ?
C38 H62 0.9800 . ?
C39 C40 1.518(5) . ?
C39 H63 0.9800 . ?
C39 H64 0.9800 . ?
C40 C41 1.511(5) . ?
C40 H65 0.9800 . ?
C40 H66 0.9800 . ?
C41 C42 1.503(6) . ?
C41 H67 0.9800 . ?
C41 H68 0.9800 . ?
C42 C43 1.492(6) . ?
C42 H69 0.9800 . ?
C42 H70 0.9800 . ?
C43 H71 0.9700 . ?
C43 H72 0.9700 . ?
C43 H73 0.9700 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O1 Mn1 O1 180.0 . 2_665 ?
O1 Mn1 O2 86.20(8) . . ?
O1 Mn1 O2 93.80(8) 2_665 . ?
O1 Mn1 O2 93.80(8) . 2_665 ?
O1 Mn1 O2 86.20(8) 2_665 2_665 ?
O2 Mn1 O2 180.0 . 2_665 ?
O1 Mn1 N1 89.68(8) . . ?
O1 Mn1 N1 90.32(8) 2_665 . ?
O2 Mn1 N1 90.00(8) . . ?
O2 Mn1 N1 90.00(8) 2_665 . ?
O1 Mn1 N1 90.32(8) . 2_665 ?
O1 Mn1 N1 89.68(8) 2_665 2_665 ?
O2 Mn1 N1 90.00(8) . 2_665 ?
O2 Mn1 N1 90.00(8) 2_665 2_665 ?
N1 Mn1 N1 180.0 . 2_665 ?
C1 O1 Mn1 112.70(17) . . ?
C2 O2 Mn1 111.99(17) . . ?
O1 C1 C6 123.7(3) . . ?
O1 C1 C2 114.0(2) . . ?
C6 C1 C2 122.3(2) . . ?
O2 C2 C1 115.0(2) . . ?
O2 C2 C3 122.4(3) . . ?
C1 C2 C3 122.6(2) . . ?
C4 C3 C2 113.3(3) . . ?
C4 C3 C7 123.7(3) . . ?
C2 C3 C7 123.0(3) . . ?
C5 C4 C3 123.8(3) . . ?
C5 C4 H1 118.1 . . ?
C3 C4 H1 118.1 . . ?
C4 C5 C6 122.7(3) . . ?
C4 C5 H2 118.7 . . ?
C6 C5 H2 118.7 . . ?
C1 C6 C5 115.2(3) . . ?
C1 C6 C11 121.9(3) . . ?
C5 C6 C11 122.9(3) . . ?
C3 C7 C10 112.3(2) . . ?
C3 C7 C8 111.6(3) . . ?
C10 C7 C8 106.9(3) . . ?
C3 C7 C9 108.4(3) . . ?
C10 C7 C9 108.4(3) . . ?
C8 C7 C9 109.0(3) . . ?
C7 C8 H3 109.5 . . ?
C7 C8 H4 109.5 . . ?
H3 C8 H4 109.5 . . ?
C7 C8 H5 109.5 . . ?
H3 C8 H5 109.5 . . ?
H4 C8 H5 109.5 . . ?
C7 C9 H6 109.5 . . ?
C7 C9 H7 109.5 . . ?
H6 C9 H7 109.5 . . ?
C7 C9 H8 109.5 . . ?
H6 C9 H8 109.5 . . ?
H7 C9 H8 109.5 . . ?
C7 C10 H9 109.5 . . ?
C7 C10 H10 109.5 . . ?
H9 C10 H10 109.5 . . ?
C7 C10 H11 109.5 . . ?
H9 C10 H11 109.5 . . ?
H10 C10 H11 109.5 . . ?
C14 C11 C6 112.2(3) . . ?
C14 C11 C13 107.4(3) . . ?
C6 C11 C13 110.7(3) . . ?
C14 C11 C12 108.2(3) . . ?
C6 C11 C12 109.7(3) . . ?
C13 C11 C12 108.5(3) . . ?
C11 C12 H12 109.5 . . ?
C11 C12 H13 109.5 . . ?
H12 C12 H13 109.5 . . ?
C11 C12 H14 109.5 . . ?
H12 C12 H14 109.5 . . ?
H13 C12 H14 109.5 . . ?
C11 C13 H15 109.5 . . ?
C11 C13 H16 109.5 . . ?
H15 C13 H16 109.5 . . ?
C11 C13 H17 109.5 . . ?
H15 C13 H17 109.5 . . ?
H16 C13 H17 109.5 . . ?
C11 C14 H18 109.5 . . ?
C11 C14 H19 109.5 . . ?
H18 C14 H19 109.5 . . ?
C11 C14 H20 109.5 . . ?
H18 C14 H20 109.5 . . ?
H19 C14 H20 109.5 . . ?
C15 N1 C19 120.8(2) . . ?
C15 N1 Mn1 120.14(18) . . ?
C19 N1 Mn1 119.08(18) . . ?
N1 C15 C16 121.7(3) . . ?
N1 C15 H21 119.2 . . ?
C16 C15 H21 119.2 . . ?
O3 C16 C17 127.1(3) . . ?
O3 C16 C15 114.6(3) . . ?
C17 C16 C15 118.3(3) . . ?
C16 C17 C18 119.5(3) . . ?
C16 C17 H22 120.2 . . ?
C18 C17 H22 120.2 . . ?
O4 C18 C19 124.1(3) . . ?
O4 C18 C17 116.5(2) . . ?
C19 C18 C17 119.4(3) . . ?
N1 C19 C18 120.3(3) . . ?
N1 C19 H23 119.8 . . ?
C18 C19 H23 119.8 . . ?
C16 O3 C20 117.5(3) . . ?
C21 C20 O3 112.2(4) . . ?
C21 C20 H24 109.2 . . ?
O3 C20 H24 109.2 . . ?
C21 C20 H25 109.2 . . ?
O3 C20 H25 109.2 . . ?
H24 C20 H25 107.9 . . ?
C20 C21 C22 125.6(7) . . ?
C20 C21 H26 105.9 . . ?
C22 C21 H26 105.9 . . ?
C20 C21 H27 105.9 . . ?
C22 C21 H27 105.9 . . ?
H26 C21 H27 106.2 . . ?
C23 C22 C21 130.8(7) . . ?
C23 C22 H28 104.6 . . ?
C21 C22 H28 104.6 . . ?
C23 C22 H29 104.6 . . ?
C21 C22 H29 104.6 . . ?
H28 C22 H29 105.7 . . ?
C22 C23 C24 128.8(9) . . ?
C22 C23 H30 105.1 . . ?
C24 C23 H30 105.1 . . ?
C22 C23 H31 105.1 . . ?
C24 C23 H31 105.1 . . ?
H30 C23 H31 105.9 . . ?
C25 C24 C23 116.5(5) . . ?
C25 C24 H32 108.2 . . ?
C23 C24 H32 108.2 . . ?
C25 C24 H33 108.2 . . ?
C23 C24 H33 108.2 . . ?
H32 C24 H33 107.3 . . ?
C24 C25 C26 117.6(5) . . ?
C24 C25 H34 107.9 . . ?
C26 C25 H34 107.9 . . ?
C24 C25 H35 107.9 . . ?
C26 C25 H35 107.9 . . ?
H34 C25 H35 107.2 . . ?
C27 C26 C25 117.8(5) . . ?
C27 C26 H36 107.8 . . ?
C25 C26 H36 107.8 . . ?
C27 C26 H37 107.8 . . ?
C25 C26 H37 107.8 . . ?
H36 C26 H37 107.2 . . ?
C26 C27 C28 119.6(6) . . ?
C26 C27 H38 107.4 . . ?
C28 C27 H38 107.4 . . ?
C26 C27 H39 107.4 . . ?
C28 C27 H39 107.4 . . ?
H38 C27 H39 107.0 . . ?
C27 C28 C29 116.6(7) . . ?
C27 C28 H40 108.1 . . ?
C29 C28 H40 108.1 . . ?
C27 C28 H41 108.1 . . ?
C29 C28 H41 108.1 . . ?
H40 C28 H41 107.3 . . ?
C30 C29 C28 114.9(8) . . ?
C30 C29 H42 108.5 . . ?
C28 C29 H42 108.5 . . ?
C30 C29 H43 108.5 . . ?
C28 C29 H43 108.5 . . ?
H42 C29 H43 107.5 . . ?
C29 C30 C31 111.7(10) . . ?
C29 C30 H44 109.3 . . ?
C31 C30 H44 109.3 . . ?
C29 C30 H45 109.3 . . ?
C31 C30 H45 109.3 . . ?
H44 C30 H45 107.9 . . ?
C30 C31 H46 109.5 . . ?
C30 C31 H47 109.5 . . ?
H46 C31 H47 109.5 . . ?
C30 C31 H48 109.5 . . ?
H46 C31 H48 109.5 . . ?
H47 C31 H48 109.5 . . ?
C18 O4 C32 118.1(2) . . ?
O4 C32 C33 107.6(2) . . ?
O4 C32 H49 110.2 . . ?
C33 C32 H49 110.2 . . ?
O4 C32 H50 110.2 . . ?
C33 C32 H50 110.2 . . ?
H49 C32 H50 108.5 . . ?
C32 C33 C34 112.2(3) . . ?
C32 C33 H51 109.2 . . ?
C34 C33 H51 109.2 . . ?
C32 C33 H52 109.2 . . ?
C34 C33 H52 109.2 . . ?
H51 C33 H52 107.9 . . ?
C35 C34 C33 113.1(3) . . ?
C35 C34 H53 109.0 . . ?
C33 C34 H53 109.0 . . ?
C35 C34 H54 108.9 . . ?
C33 C34 H54 108.9 . . ?
H53 C34 H54 107.8 . . ?
C34 C35 C36 114.4(3) . . ?
C34 C35 H55 108.7 . . ?
C36 C35 H55 108.7 . . ?
C34 C35 H56 108.7 . . ?
C36 C35 H56 108.7 . . ?
H55 C35 H56 107.6 . . ?
C37 C36 C35 113.7(3) . . ?
C37 C36 H57 108.8 . . ?
C35 C36 H57 108.8 . . ?
C37 C36 H58 108.8 . . ?
C35 C36 H58 108.8 . . ?
H57 C36 H58 107.7 . . ?
C36 C37 C38 113.8(3) . . ?
C36 C37 H59 108.8 . . ?
C38 C37 H59 108.8 . . ?
C36 C37 H60 108.8 . . ?
C38 C37 H60 108.8 . . ?
H59 C37 H60 107.7 . . ?
C39 C38 C37 113.9(3) . . ?
C39 C38 H61 108.8 . . ?
C37 C38 H61 108.8 . . ?
C39 C38 H62 108.8 . . ?
C37 C38 H62 108.8 . . ?
H61 C38 H62 107.7 . . ?
C38 C39 C40 113.4(3) . . ?
C38 C39 H63 108.9 . . ?
C40 C39 H63 108.9 . . ?
C38 C39 H64 108.9 . . ?
C40 C39 H64 108.9 . . ?
H63 C39 H64 107.7 . . ?
C41 C40 C39 114.2(4) . . ?
C41 C40 H65 108.7 . . ?
C39 C40 H65 108.7 . . ?
C41 C40 H66 108.7 . . ?
C39 C40 H66 108.7 . . ?
H65 C40 H66 107.6 . . ?
C42 C41 C40 115.2(4) . . ?
C42 C41 H67 108.5 . . ?
C40 C41 H67 108.5 . . ?
C42 C41 H68 108.5 . . ?
C40 C41 H68 108.5 . . ?
H67 C41 H68 107.5 . . ?
C43 C42 C41 113.8(4) . . ?
C43 C42 H69 108.8 . . ?
C41 C42 H69 108.8 . . ?
C43 C42 H70 108.8 . . ?
C41 C42 H70 108.8 . . ?
H69 C42 H70 107.7 . . ?
C42 C43 H71 109.5 . . ?
C42 C43 H72 109.5 . . ?
H71 C43 H72 109.5 . . ?
C42 C43 H73 109.5 . . ?
H71 C43 H73 109.5 . . ?
H72 C43 H73 109.5 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
O1 Mn1 O1 C1 19(5) 2_665 . . . ?
O2 Mn1 O1 C1 -2.16(16) . . . . ?
O2 Mn1 O1 C1 177.84(16) 2_665 . . . ?
N1 Mn1 O1 C1 87.87(16) . . . . ?
N1 Mn1 O1 C1 -92.13(16) 2_665 . . . ?
O1 Mn1 O2 C2 3.20(16) . . . . ?
O1 Mn1 O2 C2 -176.80(16) 2_665 . . . ?
O2 Mn1 O2 C2 -163(6) 2_665 . . . ?
N1 Mn1 O2 C2 -86.48(16) . . . . ?
N1 Mn1 O2 C2 93.52(16) 2_665 . . . ?
Mn1 O1 C1 C6 -179.33(19) . . . . ?
Mn1 O1 C1 C2 0.7(3) . . . . ?
Mn1 O2 C2 C1 -3.6(3) . . . . ?
Mn1 O2 C2 C3 176.63(18) . . . . ?
O1 C1 C2 O2 2.0(3) . . . . ?
C6 C1 C2 O2 -178.0(2) . . . . ?
O1 C1 C2 C3 -178.3(2) . . . . ?
C6 C1 C2 C3 1.7(4) . . . . ?
O2 C2 C3 C4 178.3(2) . . . . ?
C1 C2 C3 C4 -1.4(4) . . . . ?
O2 C2 C3 C7 -1.0(4) . . . . ?
C1 C2 C3 C7 179.2(2) . . . . ?
C2 C3 C4 C5 -0.6(4) . . . . ?
C7 C3 C4 C5 178.8(3) . . . . ?
C3 C4 C5 C6 2.4(5) . . . . ?
O1 C1 C6 C5 -180.0(2) . . . . ?
C2 C1 C6 C5 0.0(4) . . . . ?
O1 C1 C6 C11 0.4(4) . . . . ?
C2 C1 C6 C11 -179.6(3) . . . . ?
C4 C5 C6 C1 -2.0(4) . . . . ?
C4 C5 C6 C11 177.6(3) . . . . ?
C4 C3 C7 C10 133.8(3) . . . . ?
C2 C3 C7 C10 -46.9(4) . . . . ?
C4 C3 C7 C8 13.8(4) . . . . ?
C2 C3 C7 C8 -167.0(3) . . . . ?
C4 C3 C7 C9 -106.4(3) . . . . ?
C2 C3 C7 C9 72.9(4) . . . . ?
C1 C6 C11 C14 -176.1(3) . . . . ?
C5 C6 C11 C14 4.3(4) . . . . ?
C1 C6 C11 C13 -56.1(4) . . . . ?
C5 C6 C11 C13 124.3(3) . . . . ?
C1 C6 C11 C12 63.6(4) . . . . ?
C5 C6 C11 C12 -116.0(3) . . . . ?
O1 Mn1 N1 C15 45.2(2) . . . . ?
O1 Mn1 N1 C15 -134.8(2) 2_665 . . . ?
O2 Mn1 N1 C15 131.4(2) . . . . ?
O2 Mn1 N1 C15 -48.6(2) 2_665 . . . ?
N1 Mn1 N1 C15 -46(8) 2_665 . . . ?
O1 Mn1 N1 C19 -134.9(2) . . . . ?
O1 Mn1 N1 C19 45.1(2) 2_665 . . . ?
O2 Mn1 N1 C19 -48.7(2) . . . . ?
O2 Mn1 N1 C19 131.3(2) 2_665 . . . ?
N1 Mn1 N1 C19 134(8) 2_665 . . . ?
C19 N1 C15 C16 0.1(4) . . . . ?
Mn1 N1 C15 C16 -180.0(2) . . . . ?
N1 C15 C16 O3 179.4(3) . . . . ?
N1 C15 C16 C17 -0.7(4) . . . . ?
O3 C16 C17 C18 -179.2(3) . . . . ?
C15 C16 C17 C18 0.8(4) . . . . ?
C16 C17 C18 O4 179.4(3) . . . . ?
C16 C17 C18 C19 -0.5(4) . . . . ?
C15 N1 C19 C18 0.2(4) . . . . ?
Mn1 N1 C19 C18 -179.6(2) . . . . ?
O4 C18 C19 N1 -180.0(3) . . . . ?
C17 C18 C19 N1 -0.1(4) . . . . ?
C17 C16 O3 C20 7.2(5) . . . . ?
C15 C16 O3 C20 -172.9(3) . . . . ?
C16 O3 C20 C21 157.8(5) . . . . ?
O3 C20 C21 C22 -51.4(10) . . . . ?
C20 C21 C22 C23 -109.4(12) . . . . ?
C21 C22 C23 C24 -161.5(9) . . . . ?
C22 C23 C24 C25 -43.1(15) . . . . ?
C23 C24 C25 C26 174.5(7) . . . . ?
C24 C25 C26 C27 -179.1(6) . . . . ?
C25 C26 C27 C28 176.2(6) . . . . ?
C26 C27 C28 C29 -177.5(6) . . . . ?
C27 C28 C29 C30 -179.8(6) . . . . ?
C28 C29 C30 C31 175.6(7) . . . . ?
C19 C18 O4 C32 -3.6(4) . . . . ?
C17 C18 O4 C32 176.5(3) . . . . ?
C18 O4 C32 C33 -179.0(3) . . . . ?
O4 C32 C33 C34 -179.7(3) . . . . ?
C32 C33 C34 C35 174.5(3) . . . . ?
C33 C34 C35 C36 66.4(4) . . . . ?
C34 C35 C36 C37 178.3(3) . . . . ?
C35 C36 C37 C38 -177.7(3) . . . . ?
C36 C37 C38 C39 -179.1(3) . . . . ?
C37 C38 C39 C40 -177.9(4) . . . . ?
C38 C39 C40 C41 -178.3(4) . . . . ?
C39 C40 C41 C42 179.2(4) . . . . ?
C40 C41 C42 C43 -176.5(5) . . . . ?

_diffrn_measured_fraction_theta_max 0.993
_diffrn_reflns_theta_full        27.15
_diffrn_measured_fraction_theta_full 0.993
_refine_diff_density_max         1.603
_refine_diff_density_min         -0.898
_refine_diff_density_rms         0.071