# Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics.
# This journal is © the Owner Societies 2016

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_MnMOF
_database_code_depnum_ccdc_archive 'CCDC 1484654'
_audit_update_record             
;
2016-06-10 deposited with the CCDC.
2016-11-29 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014

_chemical_name_systematic        MnACDC
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C4 H4 Mn O6'
_chemical_formula_sum            'C4 H4 Mn O6'
_chemical_formula_weight         203.01

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0040 0.0020 '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'
O O 0.0133 0.0073 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Mn Mn 0.3550 0.8563 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_H-M_alt        'C 2/c'
_space_group_name_Hall           '-C 2yc'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

loop_
_space_group_symop_operation_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                   13.4976(8)
_cell_length_b                   7.1793(4)
_cell_length_c                   7.8799(5)
_cell_angle_alpha                90
_cell_angle_beta                 123.405(2)
_cell_angle_gamma                90
_cell_volume                     637.44(7)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    5662
_cell_measurement_theta_min      3.67
_cell_measurement_theta_max      43.81

_exptl_crystal_description       block
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    2.115
_exptl_crystal_F_000             404
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.020
_exptl_crystal_size_mid          0.020
_exptl_crystal_size_min          0.010
_exptl_absorpt_coefficient_mu    2.573
_shelx_estimated_absorpt_T_min   0.952
_shelx_estimated_absorpt_T_max   0.976
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.9391
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_process_details   
;
SADABS-2014/2 (Bruker,2014/2) was used for absorption correction.
;

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.7749
_diffrn_radiation_type           synchrotron
_diffrn_source                   synchrotron
_diffrn_measurement_device_type  'Bruker PHOTON100'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            4229
_diffrn_reflns_av_unetI/netI     0.0231
_diffrn_reflns_av_R_equivalents  0.0370
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_theta_min         3.669
_diffrn_reflns_theta_max         28.967
_diffrn_reflns_theta_full        27.706
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             649
_reflns_number_gt                629
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       'APEX II (Bruker 2013)'
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_structure_solution    'SHELXT-2014 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2014 (Sheldrick, 2014)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_refine_special_details          
;
 ?
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0189P)²+0.7414P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   difmap
_refine_ls_hydrogen_treatment    refall
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         649
_refine_ls_number_parameters     60
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0182
_refine_ls_R_factor_gt           0.0174
_refine_ls_wR_factor_ref         0.0462
_refine_ls_wR_factor_gt          0.0458
_refine_ls_goodness_of_fit_ref   1.114
_refine_ls_restrained_S_all      1.114
_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_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
C1 C 0.36004(11) 0.62308(17) 0.94915(19) 0.0071(3) Uani 1 1 d . . . . .
C2 C 0.45867(12) 0.62926(18) 1.1635(2) 0.0082(3) Uani 1 1 d . . . . .
O1 O 0.39780(9) 0.86706(15) 0.50086(16) 0.0111(2) Uani 1 1 d . . . . .
O2 O 0.37367(9) 0.71568(14) 0.82721(14) 0.0082(2) Uani 1 1 d . . . . .
O3 O 0.27133(8) 0.52668(13) 0.90351(14) 0.0104(2) Uani 1 1 d . . . . .
Mn1 Mn 0.2500 0.7500 0.5000 0.00570(12) Uani 1 2 d S . P . .
H1A H 0.464(2) 0.818(3) 0.550(4) 0.038(6) Uiso 1 1 d . . . . .
H1B H 0.376(2) 0.914(3) 0.398(4) 0.032(6) Uiso 1 1 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
C1 0.0076(6) 0.0061(6) 0.0061(6) -0.0006(5) 0.0028(5) 0.0017(5)
C2 0.0093(6) 0.0082(6) 0.0086(6) 0.0002(5) 0.0059(5) -0.0012(5)
O1 0.0080(5) 0.0155(5) 0.0098(5) 0.0045(4) 0.0050(4) 0.0022(4)
O2 0.0081(5) 0.0097(4) 0.0056(5) 0.0003(4) 0.0030(4) -0.0007(4)
O3 0.0083(4) 0.0109(5) 0.0084(5) 0.0020(4) 0.0023(4) -0.0023(4)
Mn1 0.00498(17) 0.00698(18) 0.00403(17) -0.00029(9) 0.00178(13) 0.00037(9)

_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
C1 O3 1.2521(16) . ?
C1 O2 1.2624(16) . ?
C1 C2 1.4668(17) . ?
C2 C2 1.195(3) 2_657 ?
O1 Mn1 2.1612(10) . ?
O1 H1A 0.84(2) . ?
O1 H1B 0.77(2) . ?
O2 Mn1 2.1808(10) . ?
O3 Mn1 2.2018(9) 4_546 ?
Mn1 O1 2.1613(10) 7_566 ?
Mn1 O2 2.1808(10) 7_566 ?
Mn1 O3 2.2018(9) 6_565 ?
Mn1 O3 2.2018(9) 4_556 ?

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
O3 C1 O2 126.12(12) . . ?
O3 C1 C2 117.75(11) . . ?
O2 C1 C2 116.13(11) . . ?
C2 C2 C1 177.42(14) 2_657 . ?
Mn1 O1 H1A 126.3(17) . . ?
Mn1 O1 H1B 110.8(16) . . ?
H1A O1 H1B 111(2) . . ?
C1 O2 Mn1 128.46(8) . . ?
C1 O3 Mn1 133.28(8) . 4_546 ?
O1 Mn1 O1 180.0 . 7_566 ?
O1 Mn1 O2 93.68(4) . 7_566 ?
O1 Mn1 O2 86.32(4) 7_566 7_566 ?
O1 Mn1 O2 86.32(4) . . ?
O1 Mn1 O2 93.68(4) 7_566 . ?
O2 Mn1 O2 180.0 7_566 . ?
O1 Mn1 O3 93.21(4) . 6_565 ?
O1 Mn1 O3 86.79(4) 7_566 6_565 ?
O2 Mn1 O3 81.61(4) 7_566 6_565 ?
O2 Mn1 O3 98.39(4) . 6_565 ?
O1 Mn1 O3 86.79(4) . 4_556 ?
O1 Mn1 O3 93.21(4) 7_566 4_556 ?
O2 Mn1 O3 98.39(4) 7_566 4_556 ?
O2 Mn1 O3 81.61(4) . 4_556 ?
O3 Mn1 O3 180.0 6_565 4_556 ?

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
O3 C1 O2 Mn1 1.85(19) . . . . ?
C2 C1 O2 Mn1 -178.71(8) . . . . ?
O2 C1 O3 Mn1 137.76(11) . . . 4_546 ?
C2 C1 O3 Mn1 -41.67(17) . . . 4_546 ?

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
O1 H1A O2 0.84(2) 1.98(3) 2.8161(14) 176(2) 2_656
O1 H1B O3 0.77(2) 2.14(2) 2.8172(14) 146(2) 7_566

_refine_diff_density_max         0.361
_refine_diff_density_min         -0.258
_refine_diff_density_rms         0.065

_shelxl_version_number           2014-1

_shelx_res_file                  
;
TITL shelxt_a.res in C2/c
CELL  0.77490  13.4976   7.1793   7.8799   90.000  123.405   90.000
ZERR     4.00   0.0008   0.0004   0.0005    0.000    0.002    0.000
LATT   7
SYMM  - X,   Y, 1/2 - Z
SFAC  C    H    O    MN
DISP    C     0.00399    0.00196         8.55
DISP    H     0.00000    0.00000         0.67
DISP    O     0.01328    0.00733        32.03
DISP    MN    0.35495    0.85629      3739.57
UNIT  16 16 24 4
ACTA
BOND $H
CONF
EQIV $1 -x+1, y, -z+3/2
HTAB O1 O2_$1
EQIV $2 -x+1/2, -y+3/2, -z+1
HTAB O1 O3_$2
TEMP -173
SIZE 0.02 0.02 0.01
MERG   2
FMAP   2
PLAN   5
BOND   $H
LIST  4
L.S.  20
SHEL 999 0.8
WGHT    0.018900    0.741400
FVAR       0.21213
C1    1    0.360043    0.623076    0.949146    11.00000    0.00762    0.00611 =
         0.00605   -0.00061    0.00280    0.00166
C2    1    0.458675    0.629263    1.163517    11.00000    0.00928    0.00820 =
         0.00860    0.00022    0.00594   -0.00120
O1    3    0.397795    0.867055    0.500858    11.00000    0.00795    0.01555 =
         0.00979    0.00450    0.00497    0.00224
O2    3    0.373667    0.715683    0.827211    11.00000    0.00808    0.00975 =
         0.00560    0.00033    0.00296   -0.00073
O3    3    0.271330    0.526684    0.903508    11.00000    0.00834    0.01092 =
         0.00840    0.00203    0.00231   -0.00234
MN1   4    0.250000    0.750000    0.500000    10.50000    0.00498    0.00698 =
         0.00403   -0.00029    0.00178    0.00037
H1A   2    0.464382    0.817593    0.549604    11.00000    0.03828
H1B   2    0.376474    0.913805    0.398442    11.00000    0.03153
HKLF    4

REM  shelxt_a.res in C2/c
REM R1 =  0.0174 for     629 Fo > 4sig(Fo)  and  0.0182 for all     649 data
REM     60 parameters refined using      0 restraints

END

WGHT      0.0189      0.7414

REM Highest difference peak  0.361,  deepest hole -0.258,  1-sigma level  0.065
Q1    1   0.4108  0.6266  1.0629  11.00000  0.05    0.36
Q2    1   0.5305  0.6493  1.2206  11.00000  0.05    0.23
Q3    1   0.3278  0.7049  0.7410  11.00000  0.05    0.20
Q4    1   0.3189  0.5388  0.9172  11.00000  0.05    0.18
Q5    1   0.4908  0.5650  1.2000  11.00000  0.05    0.18
;
_shelx_res_checksum              35324

_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_solvent_exptl_crystal_recrystallization_method 'Water / Methanol'
_exptl_crystal_preparation       ', Magnetic properties'
