# Supplementary Material (ESI) for Chemical Communications
# This journal is (c) The Royal Society of Chemistry 2006


data_global
_journal_name_full               Chem.Commun.

_journal_coden_Cambridge         0182

_publ_contact_author_name        'Jean-Marc Latour'
_publ_contact_author_address     
;
Dr J.-M. LATOUR
Laboratoire DRDC/PMB
UMR 5155 CEA - CNRS - UJF
CEA - Grenoble
38054 Grenoble Cedex 9
France
;
_Publ_contact_letter             

;
_publ_contact_author_phone       '(33) 438 78 44 07'
_publ_contact_author_email       Jean-Marc.Latour@cea.fr

loop_
_publ_author_name
_publ_author_address

'Lionel Dubois'
; Laboratoire DRDC/PMB
UMR 5155 CEA - CNRS - UJF
CEA - Grenoble
38054 Grenoble Cedex 9
France
;
'Lilian Jacquamet'
; Laboratoire LCCP, IBS
UMR 5075CEA-CNRS-UJF
38027 Grenoble Cedex 1
France
;
'Jacques Pecaut'
; Laboratoire LCIB,
UMR E CEA - UJF
CEA - Grenoble
38054 Grenoble Cedex 9
France
;
'Jean-Marc Latour'
; Laboratoire DRDC/PMB
UMR 5155 CEA - CNRS - UJF
CEA - Grenoble
38054 Grenoble Cedex 9
France
;

_publ_section_title              
;
X-ray photoreduction of a di(\m-oxo)MnIIIMnIV complex
occurs at temperatures as low as 20 K
;

# Attachment 'NaMn2PDA2.cif'

data_NaMn2PDA2
_database_code_depnum_ccdc_archive 'CCDC 611555'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C20 H38 Mn2 N4 Na O19'
_chemical_formula_weight         771.41
_exptl_crystal_colour            green
_exptl_crystal_preparation       'acetone - water'

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'
Na Na 0.0362 0.0249 '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           Monoclinic
_symmetry_space_group_name_H-M   C2/c

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'x, -y, z+1/2'
'x+1/2, y+1/2, z'
'x+1/2, -y+1/2, z+1/2'
'-x, -y, -z'
'-x, y, -z-1/2'
'-x+1/2, -y+1/2, -z'
'-x+1/2, y+1/2, -z-1/2'

_cell_length_a                   18.9552(19)
_cell_length_b                   6.7285(7)
_cell_length_c                   24.535(3)
_cell_angle_alpha                90.00
_cell_angle_beta                 94.816(2)
_cell_angle_gamma                90.00
_cell_volume                     3118.2(6)
_cell_formula_units_Z            4
_cell_measurement_temperature    298(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       needles
#_exptl_crystal_colour green
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.15
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.643
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1596
_exptl_absorpt_coefficient_mu    0.912
_exptl_absorpt_correction_type   SADABS
_exptl_absorpt_correction_T_min  0.49
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_process_details   ?

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      223(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            9671
_diffrn_reflns_av_R_equivalents  0.0629
_diffrn_reflns_av_sigmaI/netI    0.0577
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_theta_min         1.67
_diffrn_reflns_theta_max         28.96
_reflns_number_total             3730
_reflns_number_gt                2979
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SHELXTL'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_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^)+(0.1209P)^2^+13.5579P] 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     SHELXL
_refine_ls_extinction_coef       0.0110(12)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_number_reflns         3730
_refine_ls_number_parameters     237
_refine_ls_number_restraints     9
_refine_ls_R_factor_all          0.0966
_refine_ls_R_factor_gt           0.0803
_refine_ls_wR_factor_ref         0.2242
_refine_ls_wR_factor_gt          0.2136
_refine_ls_goodness_of_fit_ref   1.167
_refine_ls_restrained_S_all      1.165
_refine_ls_shift/su_max          0.029
_refine_ls_shift/su_mean         0.001

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
Mn Mn 0.29415(3) 0.69927(10) 0.54291(3) 0.0164(3) Uani 1 1 d . . .
O1 O 0.28228(16) 0.9076(5) 0.49541(13) 0.0213(7) Uani 1 1 d . . .
O2 O 0.23447(19) 0.7828(5) 0.60710(16) 0.0315(8) Uani 1 1 d . . .
O3 O 0.1556(2) 0.6465(7) 0.65757(19) 0.0472(12) Uani 1 1 d . . .
O4 O 0.37744(17) 0.8122(5) 0.58531(13) 0.0202(7) Uani 1 1 d . . .
O5 O 0.45134(19) 0.7708(5) 0.65970(14) 0.0278(8) Uani 1 1 d . . .
O6 O 0.5000 0.3836(11) 0.7500 0.072(3) Uani 1 2 d SD . .
H1O6 H 0.499(6) 0.327(13) 0.7190(19) 0.086 Uiso 1 1 d D . .
O7 O 0.3901(2) 0.8387(8) 0.7746(2) 0.0467(11) Uani 1 1 d D . .
H1O7 H 0.363(4) 0.745(9) 0.783(3) 0.056 Uiso 1 1 d D . .
H2O7 H 0.382(4) 0.848(13) 0.8080(10) 0.056 Uiso 1 1 d D . .
N1 N 0.30901(18) 0.4585(5) 0.59720(15) 0.0157(7) Uani 1 1 d . . .
N2 N 0.36571(19) 0.5194(6) 0.50210(16) 0.0198(8) Uani 1 1 d . . .
C1 C 0.3267(2) 0.2780(6) 0.56595(19) 0.0217(9) Uani 1 1 d . . .
H1A H 0.2834 0.2163 0.5502 0.026 Uiso 1 1 calc R . .
H1B H 0.3512 0.1830 0.5905 0.026 Uiso 1 1 calc R . .
C2 C 0.3728(2) 0.3313(6) 0.52114(19) 0.0198(9) Uani 1 1 d . . .
C3 C 0.4152(3) 0.1949(7) 0.4979(2) 0.0270(10) Uani 1 1 d . . .
H3 H 0.4200 0.0666 0.5118 0.032 Uiso 1 1 calc R . .
C4 C 0.4510(3) 0.2524(8) 0.4533(2) 0.0329(12) Uani 1 1 d . . .
H4 H 0.4790 0.1616 0.4364 0.040 Uiso 1 1 calc R . .
C5 C 0.4446(3) 0.4459(9) 0.4342(2) 0.0350(12) Uani 1 1 d . . .
H5 H 0.4684 0.4871 0.4046 0.042 Uiso 1 1 calc R . .
C6 C 0.4023(3) 0.5755(8) 0.4599(2) 0.0277(10) Uani 1 1 d . . .
H6 H 0.3988 0.7064 0.4478 0.033 Uiso 1 1 calc R . .
C7 C 0.2402(2) 0.4348(7) 0.6218(2) 0.0239(10) Uani 1 1 d . . .
H7A H 0.2478 0.3672 0.6567 0.029 Uiso 1 1 calc R . .
H7B H 0.2083 0.3546 0.5978 0.029 Uiso 1 1 calc R . .
C8 C 0.2073(2) 0.6371(8) 0.6299(2) 0.0251(10) Uani 1 1 d . . .
C9 C 0.3675(2) 0.5138(7) 0.63917(19) 0.0229(9) Uani 1 1 d . . .
H9A H 0.4036 0.4113 0.6404 0.028 Uiso 1 1 calc R . .
H9B H 0.3489 0.5187 0.6748 0.028 Uiso 1 1 calc R . .
C10 C 0.4013(2) 0.7120(7) 0.62802(19) 0.0203(9) Uani 1 1 d . . .
Na Na 0.5000 0.7239(4) 0.7500 0.0275(6) Uani 1 2 d S . .
O8 O 0.3187(5) 0.0806(15) 0.6945(4) 0.123(4) Uani 1 1 d D . .
H1O8 H 0.349(5) 0.009(18) 0.713(5) 0.148 Uiso 1 1 d D . .
H2O8 H 0.307(8) 0.160(19) 0.719(5) 0.148 Uiso 1 1 d D . .
O9 O 0.3114(3) 0.5011(10) 0.7734(3) 0.0785(18) Uani 1 1 d D . .
H1O9 H 0.270(2) 0.517(16) 0.784(4) 0.094 Uiso 1 1 d D . .
H2O9 H 0.3559(10) 0.484(17) 0.778(4) 0.094 Uiso 1 1 d D . .
O10 O 0.0018(2) 0.6656(6) 0.6499(2) 0.0408(10) Uani 1 1 d D . .
H1O1 H 0.0463(7) 0.648(12) 0.653(3) 0.049 Uiso 1 1 d D . .
H2O1 H -0.010(4) 0.665(12) 0.6157(6) 0.049 Uiso 1 1 d D . .

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
Mn 0.0135(4) 0.0147(4) 0.0211(4) -0.0017(2) 0.0011(2) -0.0016(2)
O1 0.0170(14) 0.0230(17) 0.0243(16) -0.0036(13) 0.0042(12) -0.0087(13)
O2 0.0248(18) 0.0185(17) 0.051(2) 0.0030(16) 0.0010(16) 0.0032(14)
O3 0.040(2) 0.047(3) 0.059(3) 0.011(2) 0.029(2) 0.017(2)
O4 0.0199(15) 0.0161(15) 0.0240(16) -0.0009(12) -0.0005(12) -0.0023(12)
O5 0.0269(18) 0.0251(18) 0.0299(18) 0.0001(14) -0.0062(14) -0.0090(14)
O6 0.140(8) 0.026(3) 0.048(4) 0.000 -0.004(5) 0.000
O7 0.038(2) 0.054(3) 0.050(3) -0.013(2) 0.016(2) 0.001(2)
N1 0.0127(16) 0.0103(16) 0.0244(18) -0.0009(13) 0.0035(13) -0.0022(13)
N2 0.0193(18) 0.0123(17) 0.027(2) 0.0033(14) -0.0002(15) 0.0000(14)
C1 0.027(2) 0.0100(19) 0.029(2) 0.0016(17) 0.0067(18) 0.0004(17)
C2 0.022(2) 0.0104(19) 0.027(2) 0.0016(16) 0.0026(17) -0.0030(16)
C3 0.024(2) 0.019(2) 0.038(3) -0.003(2) 0.004(2) 0.0007(19)
C4 0.025(2) 0.029(3) 0.047(3) -0.006(2) 0.013(2) 0.004(2)
C5 0.027(3) 0.046(3) 0.033(3) 0.007(2) 0.011(2) -0.006(2)
C6 0.025(2) 0.027(2) 0.032(3) 0.008(2) 0.0026(19) -0.005(2)
C7 0.018(2) 0.021(2) 0.034(3) 0.0068(19) 0.0076(18) -0.0005(17)
C8 0.020(2) 0.023(2) 0.033(2) 0.0016(19) 0.0057(18) 0.0071(18)
C9 0.025(2) 0.020(2) 0.022(2) 0.0018(17) -0.0038(17) 0.0005(18)
C10 0.017(2) 0.020(2) 0.025(2) -0.0018(17) 0.0034(16) 0.0032(17)
Na 0.0284(14) 0.0246(14) 0.0289(14) 0.000 -0.0007(11) 0.000
O8 0.105(6) 0.121(7) 0.154(8) 0.095(6) 0.070(6) 0.068(5)
O9 0.066(4) 0.054(4) 0.119(5) -0.017(4) 0.024(4) -0.008(3)
O10 0.034(2) 0.027(2) 0.061(3) 0.0019(19) 0.004(2) 0.0007(17)

_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
Mn O1 1.809(3) 7_566 ?
Mn O1 1.825(3) . ?
Mn O4 1.969(3) . ?
Mn O2 2.092(4) . ?
Mn N1 2.102(4) . ?
Mn N2 2.129(4) . ?
Mn Mn 2.6662(13) 7_566 ?
O1 Mn 1.809(3) 7_566 ?
O2 C8 1.259(6) . ?
O3 C8 1.240(6) . ?
O4 C10 1.295(6) . ?
O5 C10 1.240(6) . ?
O5 Na 2.348(3) . ?
O6 Na 2.290(8) . ?
O7 Na 2.347(4) . ?
N1 C1 1.490(5) . ?
N1 C7 1.490(5) . ?
N1 C9 1.495(6) . ?
N2 C6 1.347(6) . ?
N2 C2 1.352(6) . ?
C1 C2 1.503(6) . ?
C2 C3 1.376(7) . ?
C3 C4 1.389(8) . ?
C4 C5 1.385(8) . ?
C5 C6 1.373(8) . ?
C7 C8 1.517(7) . ?
C9 C10 1.514(6) . ?
Na O7 2.347(4) 6_657 ?
Na O5 2.348(3) 6_657 ?

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 Mn O1 85.59(15) 7_566 . ?
O1 Mn O4 179.17(15) 7_566 . ?
O1 Mn O4 95.24(14) . . ?
O1 Mn O2 92.17(14) 7_566 . ?
O1 Mn O2 103.25(14) . . ?
O4 Mn O2 87.64(14) . . ?
O1 Mn N1 94.69(14) 7_566 . ?
O1 Mn N1 179.29(14) . . ?
O4 Mn N1 84.48(13) . . ?
O2 Mn N1 77.40(14) . . ?
O1 Mn N2 92.51(14) 7_566 . ?
O1 Mn N2 100.69(14) . . ?
O4 Mn N2 87.34(14) . . ?
O2 Mn N2 155.89(15) . . ?
N1 Mn N2 78.65(14) . . ?
O1 Mn Mn 43.03(11) 7_566 7_566 ?
O1 Mn Mn 42.56(10) . 7_566 ?
O4 Mn Mn 137.80(10) . 7_566 ?
O2 Mn Mn 100.51(11) . 7_566 ?
N1 Mn Mn 137.72(10) . 7_566 ?
N2 Mn Mn 99.01(11) . 7_566 ?
Mn O1 Mn 94.41(14) 7_566 . ?
C8 O2 Mn 113.1(3) . . ?
C10 O4 Mn 115.9(3) . . ?
C10 O5 Na 140.2(3) . . ?
C1 N1 C7 111.3(3) . . ?
C1 N1 C9 111.8(3) . . ?
C7 N1 C9 111.8(4) . . ?
C1 N1 Mn 109.0(3) . . ?
C7 N1 Mn 105.3(3) . . ?
C9 N1 Mn 107.3(3) . . ?
C6 N2 C2 119.1(4) . . ?
C6 N2 Mn 126.2(3) . . ?
C2 N2 Mn 114.7(3) . . ?
N1 C1 C2 110.6(3) . . ?
N2 C2 C3 121.7(4) . . ?
N2 C2 C1 115.5(4) . . ?
C3 C2 C1 122.6(4) . . ?
C2 C3 C4 118.8(5) . . ?
C5 C4 C3 119.6(5) . . ?
C6 C5 C4 118.6(5) . . ?
N2 C6 C5 122.2(5) . . ?
N1 C7 C8 109.9(4) . . ?
O3 C8 O2 125.1(5) . . ?
O3 C8 C7 118.0(5) . . ?
O2 C8 C7 116.9(4) . . ?
N1 C9 C10 113.3(4) . . ?
O5 C10 O4 122.5(4) . . ?
O5 C10 C9 118.7(4) . . ?
O4 C10 C9 118.7(4) . . ?
O6 Na O7 109.20(15) . . ?
O6 Na O7 109.20(15) . 6_657 ?
O7 Na O7 141.6(3) . 6_657 ?
O6 Na O5 97.71(11) . 6_657 ?
O7 Na O5 90.00(15) . 6_657 ?
O7 Na O5 84.94(16) 6_657 6_657 ?
O6 Na O5 97.71(12) . . ?
O7 Na O5 84.94(16) . . ?
O7 Na O5 90.00(15) 6_657 . ?
O5 Na O5 164.6(2) 6_657 . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
O6 H1O6 O10 0.851(5) 2.016(13) 2.863(6) 173(10) 3_545
O7 H1O7 O9 0.851(5) 1.91(4) 2.716(8) 157(8) .
O7 H2O7 O3 0.850(5) 2.31(8) 2.838(6) 120(7) 8_557
O8 H1O8 O7 0.850(5) 2.01(5) 2.810(9) 158(13) 1_545
O9 H1O9 O8 0.851(5) 1.858(17) 2.705(10) 174(11) 8_557
O10 H1O1 O3 0.850(5) 2.066(14) 2.910(6) 172(8) .

_diffrn_measured_fraction_theta_max 0.904
_diffrn_reflns_theta_full        28.96
_diffrn_measured_fraction_theta_full 0.904
_refine_diff_density_max         1.893
_refine_diff_density_min         -1.305
_refine_diff_density_rms         0.215

#---------------------------