# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2017

####################################################################### 
# 
# 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_mn_100
_database_code_depnum_ccdc_archive 'CCDC 1530423'
_audit_update_record             
;
2017-01-31 deposited with the CCDC.
2017-06-02 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C3 H3 Mn O6, C2 H7 N2'
_chemical_formula_sum            'C5 H10 Mn N2 O6'
_chemical_formula_weight         249.09

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'

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/n'
_space_group_name_Hall           '-P 2yn'

_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+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, -y-1/2, z-1/2'

_cell_length_a                   8.6727(11)
_cell_length_b                   11.9317(13)
_cell_length_c                   9.0332(12)
_cell_angle_alpha                90
_cell_angle_beta                 92.233(14)
_cell_angle_gamma                90
_cell_volume                     934.0(2)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    1272
_cell_measurement_theta_min      2.83
_cell_measurement_theta_max      26.20

_exptl_crystal_description       parallelepiped
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.771
_exptl_crystal_F_000             508
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.210
_exptl_crystal_size_mid          0.200
_exptl_crystal_size_min          0.190
_exptl_absorpt_coefficient_mu    1.421
_shelx_estimated_absorpt_T_min   0.755
_shelx_estimated_absorpt_T_max   0.774
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.80827
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_measurement_device_type  'KUMA KM-4 with CCD detector'
_diffrn_measurement_method       ω-scan
_diffrn_detector_area_resol_mean 10.6249
_diffrn_reflns_number            6100
_diffrn_reflns_av_unetI/netI     0.0690
_diffrn_reflns_av_R_equivalents  0.0303
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_theta_min         2.830
_diffrn_reflns_theta_max         29.396
_diffrn_reflns_theta_full        26.200
_diffrn_measured_fraction_theta_max 0.862
_diffrn_measured_fraction_theta_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.862
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.862
_diffrn_reflns_point_group_measured_fraction_full 0.990
_reflns_number_total             2220
_reflns_number_gt                1438
_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       
;
CrysAlis CCD 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
;
_computing_cell_refinement       
;
CrysAlis Red 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
;
_computing_data_reduction        
;
CrysAlis Red 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
;
_computing_structure_solution    'SHELXT (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    
;
Brandenburg & Putz (2006). Diamond 3.0. Crystal and Molecular
Structure Visualisation, University of Bonn, Germany
;
_computing_publication_material  'SHELXL-2014/7 (Sheldrick, 2014)'
_refine_special_details          
; 
 Refinement of F² against ALL reflections.  The weighted R-factor wR and 
 goodness of fit S are based on F², conventional R-factors R are based 
 on F, with F set to zero for negative F². The threshold expression of 
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is 
 not relevant to the choice of reflections for refinement.  R-factors based 
 on F² are statistically about twice as large as those based on F, and R- 
 factors based on ALL data will be even larger. 
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0321P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         2220
_refine_ls_number_parameters     140
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0840
_refine_ls_R_factor_gt           0.0487
_refine_ls_wR_factor_ref         0.1013
_refine_ls_wR_factor_gt          0.0852
_refine_ls_goodness_of_fit_ref   1.000
_refine_ls_restrained_S_all      1.000
_refine_ls_shift/su_max          0.001
_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
Mn Mn 0.25494(4) 0.25299(3) 0.75184(5) 0.01374(15) Uani 1 1 d . . . . .
O1 O 0.4156(2) 0.18900(18) 0.5876(2) 0.0223(5) Uani 1 1 d . . . . .
O2 O 0.5652(2) 0.19629(18) 0.3946(2) 0.0204(5) Uani 1 1 d . . . . .
C1 C 0.5252(3) 0.2265(3) 0.5187(4) 0.0218(7) Uani 1 1 d . . . . .
H4 H 0.5846 0.2842 0.5658 0.026 Uiso 1 1 calc R U . . .
O3 O 0.4116(2) 0.33290(18) 0.9123(2) 0.0225(5) Uani 1 1 d . . . . .
O4 O 0.5772(2) 0.31741(17) 1.1033(2) 0.0207(5) Uani 1 1 d . . . . .
C2 C 0.5223(3) 0.2863(3) 0.9828(3) 0.0180(7) Uani 1 1 d . . . . .
H2 H 0.5668 0.2221 0.9393 0.022 Uiso 1 1 calc R U . . .
O5 O 0.2194(2) 0.40974(17) 0.6369(2) 0.0233(5) Uani 1 1 d . . . . .
O6 O 0.2162(2) 0.59705(17) 0.6256(2) 0.0214(5) Uani 1 1 d . . . . .
C3 C 0.2331(4) 0.5043(3) 0.6911(4) 0.0228(7) Uani 1 1 d . . . . .
H3 H 0.2595 0.5076 0.7941 0.027 Uiso 1 1 calc R U . . .
N1 N 0.2410(3) 0.5073(2) 0.0897(3) 0.0231(6) Uani 1 1 d . . . . .
H11 H 0.186(4) 0.554(3) 0.034(3) 0.028 Uiso 1 1 d . U . . .
H12 H 0.299(4) 0.468(3) 0.054(4) 0.028 Uiso 1 1 d . U . . .
N2 N 0.1557(3) 0.5822(2) 0.3038(3) 0.0280(7) Uani 1 1 d . . . . .
H21 H 0.093(4) 0.624(3) 0.256(4) 0.034 Uiso 1 1 d . U . . .
H22 H 0.169(4) 0.584(3) 0.402(4) 0.034 Uiso 1 1 d . U . . .
C4 C 0.2448(3) 0.5125(2) 0.2332(4) 0.0205(7) Uani 1 1 d . . . . .
C5 C 0.3555(4) 0.4404(3) 0.3194(4) 0.0396(10) Uani 1 1 d . . . . .
H51 H 0.3993 0.3845 0.2536 0.059 Uiso 1 1 calc R U . . .
H52 H 0.3017 0.4024 0.3985 0.059 Uiso 1 1 calc R U . . .
H53 H 0.4387 0.4869 0.3630 0.059 Uiso 1 1 calc R U . . .

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 0.0137(3) 0.0053(2) 0.0223(3) 0.00030(17) 0.00169(18) 0.00025(16)
O1 0.0218(11) 0.0145(12) 0.0310(13) -0.0018(10) 0.0056(10) -0.0026(9)
O2 0.0171(10) 0.0164(12) 0.0279(13) -0.0004(10) 0.0042(9) -0.0022(9)
C1 0.0188(16) 0.0170(16) 0.030(2) -0.0005(14) 0.0014(14) -0.0021(13)
O3 0.0205(11) 0.0157(12) 0.0311(13) -0.0007(9) -0.0006(9) 0.0026(9)
O4 0.0193(11) 0.0130(11) 0.0293(13) 0.0009(9) -0.0041(9) 0.0040(9)
C2 0.0126(14) 0.0083(14) 0.033(2) -0.0003(13) -0.0013(14) 0.0012(11)
O5 0.0341(12) 0.0091(11) 0.0266(13) 0.0019(9) 0.0007(10) -0.0026(9)
O6 0.0330(12) 0.0068(10) 0.0246(13) 0.0010(9) 0.0026(9) -0.0014(9)
C3 0.0309(18) 0.0135(16) 0.0241(17) 0.0023(14) 0.0038(14) 0.0044(14)
N1 0.0283(16) 0.0124(14) 0.0287(17) 0.0002(12) 0.0039(12) 0.0064(12)
N2 0.0286(16) 0.0228(16) 0.0326(17) -0.0036(14) 0.0012(14) 0.0137(13)
C4 0.0178(17) 0.0140(16) 0.030(2) 0.0037(14) 0.0035(14) 0.0016(12)
C5 0.033(2) 0.052(3) 0.034(2) 0.0103(19) 0.0061(16) 0.0234(19)

_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 O5 2.156(2) . ?
Mn O3 2.168(2) . ?
Mn O4 2.173(2) 4_565 ?
Mn O6 2.175(2) 2_546 ?
Mn O1 2.211(2) . ?
Mn O2 2.214(2) 4_566 ?
O1 C1 1.240(3) . ?
O2 C1 1.240(3) . ?
O2 Mn 2.214(2) 4_665 ?
C1 H4 0.9500 . ?
O3 C2 1.260(3) . ?
O4 C2 1.229(3) . ?
O4 Mn 2.173(2) 4_666 ?
C2 H2 0.9500 . ?
O5 C3 1.234(3) . ?
O6 C3 1.261(3) . ?
O6 Mn 2.175(2) 2_556 ?
C3 H3 0.9500 . ?
N1 C4 1.297(4) . ?
N1 H11 0.87(3) . ?
N1 H12 0.77(3) . ?
N2 C4 1.317(4) . ?
N2 H21 0.85(3) . ?
N2 H22 0.89(3) . ?
C4 C5 1.487(4) . ?
C5 H51 0.9800 . ?
C5 H52 0.9800 . ?
C5 H53 0.9800 . ?

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
O5 Mn O3 90.83(8) . . ?
O5 Mn O4 87.32(8) . 4_565 ?
O3 Mn O4 173.56(7) . 4_565 ?
O5 Mn O6 177.62(7) . 2_546 ?
O3 Mn O6 88.81(8) . 2_546 ?
O4 Mn O6 92.78(8) 4_565 2_546 ?
O5 Mn O1 93.34(8) . . ?
O3 Mn O1 101.88(7) . . ?
O4 Mn O1 84.39(7) 4_565 . ?
O6 Mn O1 89.03(8) 2_546 . ?
O5 Mn O2 87.02(8) . 4_566 ?
O3 Mn O2 87.18(7) . 4_566 ?
O4 Mn O2 86.57(8) 4_565 4_566 ?
O6 Mn O2 90.62(8) 2_546 4_566 ?
O1 Mn O2 170.93(7) . 4_566 ?
C1 O1 Mn 136.7(2) . . ?
C1 O2 Mn 133.46(19) . 4_665 ?
O2 C1 O1 126.6(3) . . ?
O2 C1 H4 116.7 . . ?
O1 C1 H4 116.7 . . ?
C2 O3 Mn 126.1(2) . . ?
C2 O4 Mn 132.22(19) . 4_666 ?
O4 C2 O3 125.2(3) . . ?
O4 C2 H2 117.4 . . ?
O3 C2 H2 117.4 . . ?
C3 O5 Mn 126.3(2) . . ?
C3 O6 Mn 120.2(2) . 2_556 ?
O5 C3 O6 127.5(3) . . ?
O5 C3 H3 116.3 . . ?
O6 C3 H3 116.3 . . ?
C4 N1 H11 122(2) . . ?
C4 N1 H12 117(3) . . ?
H11 N1 H12 120(3) . . ?
C4 N2 H21 120(2) . . ?
C4 N2 H22 116(2) . . ?
H21 N2 H22 123(3) . . ?
N1 C4 N2 121.4(3) . . ?
N1 C4 C5 119.1(3) . . ?
N2 C4 C5 119.4(3) . . ?
C4 C5 H51 109.5 . . ?
C4 C5 H52 109.5 . . ?
H51 C5 H52 109.5 . . ?
C4 C5 H53 109.5 . . ?
H51 C5 H53 109.5 . . ?
H52 C5 H53 109.5 . . ?

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
N1 H11 O1 0.87(3) 2.13(3) 2.989(4) 169(3) 2
N1 H12 O3 0.77(3) 2.30(3) 3.045(3) 164(3) 1_554
N2 H21 O2 0.85(3) 2.08(3) 2.910(4) 167(3) 2
N2 H22 O6 0.89(3) 2.05(3) 2.939(4) 175(3) .
C5 H52 O5 0.98 2.30 3.165(4) 147.1 .

_refine_diff_density_max         1.322
_refine_diff_density_min         -0.436
_refine_diff_density_rms         0.097

_shelx_res_file                  
;

    mn_100.res created by SHELXL-2014/7


TITL mn_100_a.res in P2(1)/n
CELL 0.71073 8.6727 11.9317 9.0332 90 92.233 90
ZERR 4 0.0011 0.0013 0.0012 0 0.014 0
LATT 1
SYMM 0.5-X,0.5+Y,0.5-Z
SFAC C H N O Mn
UNIT 20 40 8 24 4
TEMP -173
L.S. 5
PLAN  6
BOND $H
eqiv $1 -X+0.5, Y+0.5, -Z+0.5
HTAB N1 O1_$1
EQIV $2 X, Y, Z-1
HTAB N1 O3_$2
EQIV $3 -X+0.5, Y+0.5, -Z+0.5
HTAB N2 O2_$3
HTAB N2 O6
htab C5 O5
htab 2
FMAP 2
ACTA 52.4
size 0.21 0.20 0.19
WGHT    0.032100
FVAR       0.54837
MN    5    0.254940    0.252988    0.751835    11.00000    0.01366    0.00531 =
         0.02233    0.00030    0.00169    0.00025
O1    4    0.415568    0.188997    0.587554    11.00000    0.02180    0.01450 =
         0.03105   -0.00180    0.00562   -0.00256
O2    4    0.565222    0.196293    0.394642    11.00000    0.01715    0.01641 =
         0.02791   -0.00039    0.00419   -0.00222
C1    1    0.525209    0.226477    0.518710    11.00000    0.01883    0.01695 =
         0.02970   -0.00047    0.00141   -0.00209
AFIX  43
H4    2    0.584555    0.284160    0.565802    11.00000   -1.20000
AFIX   0
O3    4    0.411571    0.332900    0.912276    11.00000    0.02048    0.01568 =
         0.03109   -0.00071   -0.00057    0.00263
O4    4    0.577231    0.317414    1.103299    11.00000    0.01931    0.01299 =
         0.02929    0.00089   -0.00408    0.00397
C2    1    0.522288    0.286349    0.982779    11.00000    0.01258    0.00830 =
         0.03298   -0.00027   -0.00126    0.00120
AFIX  43
H2    2    0.566797    0.222130    0.939261    11.00000   -1.20000
AFIX   0
O5    4    0.219403    0.409745    0.636883    11.00000    0.03410    0.00912 =
         0.02657    0.00186    0.00070   -0.00259
O6    4    0.216163    0.597050    0.625616    11.00000    0.03303    0.00675 =
         0.02461    0.00102    0.00264   -0.00139
C3    1    0.233121    0.504270    0.691104    11.00000    0.03087    0.01349 =
         0.02414    0.00228    0.00376    0.00437
AFIX  43
H3    2    0.259505    0.507555    0.794075    11.00000   -1.20000
AFIX   0
N1    3    0.241029    0.507345    0.089701    11.00000    0.02828    0.01237 =
         0.02873    0.00025    0.00391    0.00644
H11   2    0.185917    0.553535    0.034480    11.00000   -1.20000
H12   2    0.299098    0.467700    0.054081    11.00000   -1.20000
N2    3    0.155705    0.582219    0.303819    11.00000    0.02859    0.02281 =
         0.03261   -0.00355    0.00120    0.01369
H21   2    0.092674    0.624190    0.255947    11.00000   -1.20000
H22   2    0.168832    0.584237    0.402332    11.00000   -1.20000
C4    1    0.244790    0.512503    0.233219    11.00000    0.01777    0.01405 =
         0.02979    0.00374    0.00352    0.00159
C5    1    0.355546    0.440421    0.319448    11.00000    0.03343    0.05156 =
         0.03405    0.01031    0.00613    0.02336
AFIX 137
H51   2    0.399257    0.384483    0.253614    11.00000   -1.50000
H52   2    0.301698    0.402368    0.398518    11.00000   -1.50000
H53   2    0.438682    0.486902    0.363045    11.00000   -1.50000
AFIX   0
HKLF 4

REM  mn_100_a.res in P2(1)/n
REM R1 =  0.0487 for    1438 Fo > 4sig(Fo)  and  0.0840 for all    2220 data
REM    140 parameters refined using      0 restraints

END

WGHT      0.0308      0.0000

REM Instructions for potential hydrogen bonds
EQIV $4 x, y, z+1
HTAB C3 N1_$4
HTAB N1 O1_$1
HTAB N1 O3_$2
HTAB N2 O2_$1
HTAB N2 O6
HTAB C5 O4_$2
HTAB C5 O5

REM Highest difference peak  1.322,  deepest hole -0.436,  1-sigma level  0.097
Q1    1   0.2504  0.2543  0.6417  11.00000  0.05    1.32
Q2    1   0.2585  0.2526  0.8629  11.00000  0.05    1.13
Q3    1   0.1564  0.2486  0.8337  11.00000  0.05    0.40
Q4    1   0.1498  0.3610  0.1894  11.00000  0.05    0.39
Q5    1   0.2489  0.3372  0.9027  11.00000  0.05    0.39
Q6    1   0.3471  0.2560  0.6578  11.00000  0.05    0.38
;
_shelx_res_checksum              55855
####################################################################### 
# 
# 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_mn330
_database_code_depnum_ccdc_archive 'CCDC 1530424'
_audit_update_record             
;
2017-01-31 deposited with the CCDC.
2017-06-02 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C3 H3 Mn O6, C2 H7 N2'
_chemical_formula_sum            'C5 H10 Mn N2 O6'
_chemical_formula_weight         249.09

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'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           74
_space_group_name_H-M_alt        'I m m a'
_space_group_name_Hall           '-I 2b 2'

_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+1/2, z'
'-x, y+1/2, -z'
'x, -y, -z'
'x+1/2, y+1/2, z+1/2'
'-x+1/2, -y+1, z+1/2'
'-x+1/2, y+1, -z+1/2'
'x+1/2, -y+1/2, -z+1/2'
'-x, -y, -z'
'x, y-1/2, -z'
'x, -y-1/2, z'
'-x, y, z'
'-x+1/2, -y+1/2, -z+1/2'
'x+1/2, y, -z+1/2'
'x+1/2, -y, z+1/2'
'-x+1/2, y+1/2, z+1/2'

_cell_length_a                   8.7482(17)
_cell_length_b                   12.089(2)
_cell_length_c                   9.0317(18)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     955.1(3)
_cell_formula_units_Z            4
_cell_measurement_temperature    320(2)
_cell_measurement_reflns_used    468
_cell_measurement_theta_min      2.82
_cell_measurement_theta_max      28.0

_exptl_crystal_description       parallelepiped
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      1.73
_exptl_crystal_density_method    floatation
_exptl_crystal_density_diffrn    1.732
_exptl_crystal_F_000             508
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.210
_exptl_crystal_size_mid          0.200
_exptl_crystal_size_min          0.190
_exptl_absorpt_coefficient_mu    1.390
_shelx_estimated_absorpt_T_min   0.368
_shelx_estimated_absorpt_T_max   0.769
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.89821
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_diffrn_ambient_temperature      320(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_measurement_device_type  'KUMA KM-4 with CCD detector'
_diffrn_measurement_method       ω-scan
_diffrn_detector_area_resol_mean 10.6249
_diffrn_reflns_number            20981
_diffrn_reflns_av_unetI/netI     0.0130
_diffrn_reflns_av_R_equivalents  0.0419
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_theta_min         2.815
_diffrn_reflns_theta_max         29.543
_diffrn_reflns_theta_full        28.000
_diffrn_measured_fraction_theta_max 0.973
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             721
_reflns_number_gt                621
_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       
;
CrysAlis CCD 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
;
_computing_cell_refinement       
;
CrysAlis Red 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
;
_computing_data_reduction        
;
CrysAlis Red 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
;
_computing_structure_solution    'SHELXT (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    
;
Brandenburg & Putz (2006). Diamond 3.0. Crystal and Molecular
Structure Visualisation, University of Bonn, Germany
;
_computing_publication_material  'SHELXL-2014/7 (Sheldrick, 2014)'
_refine_special_details          
; 
 Refinement of F² against ALL reflections.  The weighted R-factor wR and 
 goodness of fit S are based on F², conventional R-factors R are based 
 on F, with F set to zero for negative F². The threshold expression of 
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is 
 not relevant to the choice of reflections for refinement.  R-factors based 
 on F² are statistically about twice as large as those based on F, and R- 
 factors based on ALL data will be even larger. 
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0608P)²+0.7230P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         721
_refine_ls_number_parameters     58
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0371
_refine_ls_R_factor_gt           0.0315
_refine_ls_wR_factor_ref         0.0898
_refine_ls_wR_factor_gt          0.0855
_refine_ls_goodness_of_fit_ref   1.004
_refine_ls_restrained_S_all      1.004
_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
Mn Mn 0.0000 0.5000 0.5000 0.02407(19) Uani 1 4 d S T P . .
O1 O 0.0000 0.65833(14) 0.38771(19) 0.0501(5) Uani 1 2 d S T P . .
O2 O 0.17145(19) 0.43787(12) 0.34529(15) 0.0563(4) Uani 1 1 d . . . . .
C1 C 0.0000 0.7500 0.4448(4) 0.0454(9) Uani 1 4 d S T P . .
H1 H 0.0000 0.7500 0.5478 0.055 Uiso 1 4 calc R U P . .
C2 C 0.2500 0.4730(2) 0.2500 0.0570(8) Uani 1 2 d S T P . .
H2 H 0.2500 0.5500 0.2500 0.068 Uiso 1 2 calc R U P . .
N1 N 0.0000 0.2500 0.1594(4) 0.0574(10) Uani 1 4 d S T P A .
H1N H 0.0000 0.316(4) 0.190(4) 0.069 Uiso 1 2 d S U P . .
C3 C 0.0000 0.2500 0.0144(4) 0.0486(10) Uani 1 4 d S T P . .
C4 C -0.101(3) 0.312(3) -0.075(3) 0.069(8) Uani 0.25 1 d . . P A -1
H4A H -0.1724 0.2628 -0.1225 0.103 Uiso 0.25 1 calc R U P A -1
H4B H -0.0441 0.3512 -0.1492 0.103 Uiso 0.25 1 calc R U P A -1
H4C H -0.1561 0.3638 -0.0148 0.103 Uiso 0.25 1 calc R U P A -1
N2 N -0.082(2) 0.3325(19) -0.053(2) 0.050(4) Uani 0.25 1 d . . P A -2
H2A H -0.1291 0.3806 0.0002 0.060 Uiso 0.25 1 calc R U P A -2
H2B H -0.0852 0.3362 -0.1477 0.060 Uiso 0.25 1 calc R U P A -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
Mn 0.0251(3) 0.0220(3) 0.0250(3) 0.00008(14) 0.000 0.000
O1 0.0878(15) 0.0249(8) 0.0377(9) 0.0016(7) 0.000 0.000
O2 0.0627(9) 0.0518(8) 0.0543(8) 0.0042(7) 0.0286(7) 0.0116(7)
C1 0.079(3) 0.0299(16) 0.0272(16) 0.000 0.000 0.000
C2 0.0634(19) 0.0354(11) 0.072(2) 0.000 0.0349(17) 0.000
N1 0.090(3) 0.0459(19) 0.0365(17) 0.000 0.000 0.000
C3 0.040(2) 0.063(3) 0.042(2) 0.000 0.000 0.000
C4 0.069(9) 0.092(15) 0.046(9) -0.012(7) -0.019(6) 0.052(10)
N2 0.060(7) 0.063(6) 0.027(5) 0.001(6) 0.011(6) 0.021(5)

_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 2.1661(17) . ?
Mn O1 2.1661(17) 9_566 ?
Mn O2 2.1831(13) 12 ?
Mn O2 2.1831(13) . ?
Mn O2 2.1831(13) 4_566 ?
Mn O2 2.1831(13) 9_566 ?
O1 C1 1.222(2) . ?
O2 C2 1.1806(17) . ?
C1 O1 1.222(2) 2_565 ?
C1 H1 0.9300 . ?
C2 O2 1.1806(17) 7_545 ?
C2 H2 0.9300 . ?
N1 C3 1.310(5) . ?
N1 H1N 0.85(4) . ?
C3 N2 1.37(2) . ?
C3 C4 1.41(2) . ?
C4 H4A 0.9600 . ?
C4 H4B 0.9600 . ?
C4 H4C 0.9600 . ?
N2 H2A 0.8600 . ?
N2 H2B 0.8600 . ?

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 180.00(4) . 9_566 ?
O1 Mn O2 90.25(5) . 12 ?
O1 Mn O2 89.75(5) 9_566 12 ?
O1 Mn O2 90.25(5) . . ?
O1 Mn O2 89.75(5) 9_566 . ?
O2 Mn O2 86.79(9) 12 . ?
O1 Mn O2 89.75(5) . 4_566 ?
O1 Mn O2 90.25(5) 9_566 4_566 ?
O2 Mn O2 180.00(5) 12 4_566 ?
O2 Mn O2 93.21(9) . 4_566 ?
O1 Mn O2 89.75(5) . 9_566 ?
O1 Mn O2 90.25(5) 9_566 9_566 ?
O2 Mn O2 93.21(9) 12 9_566 ?
O2 Mn O2 180.00(6) . 9_566 ?
O2 Mn O2 86.79(9) 4_566 9_566 ?
C1 O1 Mn 127.1(2) . . ?
C2 O2 Mn 137.95(16) . . ?
O1 C1 O1 130.1(4) 2_565 . ?
O1 C1 H1 115.0 2_565 . ?
O1 C1 H1 115.0 . . ?
O2 C2 O2 137.8(3) 7_545 . ?
O2 C2 H2 111.1 7_545 . ?
O2 C2 H2 111.1 . . ?
C3 N1 H1N 109(3) . . ?
N1 C3 N2 116.3(8) . . ?
N1 C3 C4 124.9(11) . . ?
C3 C4 H4A 109.5 . . ?
C3 C4 H4B 109.5 . . ?
H4A C4 H4B 109.5 . . ?
C3 C4 H4C 109.5 . . ?
H4A C4 H4C 109.5 . . ?
H4B C4 H4C 109.5 . . ?
C3 N2 H2A 120.0 . . ?
C3 N2 H2B 120.0 . . ?
H2A N2 H2B 120.0 . . ?

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
N1 H1N O2 0.85(4) 2.52(3) 3.198(2) 137.1(17) .
N1 H1N O2 0.85(4) 2.52(3) 3.198(2) 137.1(17) 12
N2 H2A O2 0.86 2.34 3.131(19) 153.1 14_455
N2 H2B O1 0.86 2.29 3.111(18) 158.8 9_565

_refine_diff_density_max         0.478
_refine_diff_density_min         -0.647
_refine_diff_density_rms         0.071

_shelx_res_file                  
;

    mn330.res created by SHELXL-2014/7

TITL aa in Imma
CELL 0.71073   8.7482  12.0885   9.0317  90.000  90.000  90.000
ZERR    4.00   0.0017   0.0024   0.0018   0.000   0.000   0.000
LATT  2
SYMM -X, 0.5-Y, Z
SYMM -X, 0.5+Y, -Z
SYMM X, -Y, -Z
SFAC C H N O MN
UNIT 20 40 8 24 4

TEMP 47
L.S. 5
BOND $H
HTAB 2
HTAB N1 O2
EQIV $1 -X, Y, Z
HTAB N1 O2_$1
EQIV $2 X-0.5, Y, -Z+0.5
HTAB N2 O2_$2
EQIV $3 -X, -Y+1, -Z
HTAB N2 O1_$3
FMAP 2
PLAN 20
ACTA 56
size 0.21 0.2 0.9
WGHT    0.060800    0.723000
FVAR       0.64452
MOLE   1
MN    5    0.000000    0.500000    0.500000    10.25000    0.02513    0.02203 =
         0.02504    0.00008    0.00000    0.00000
O1    4    0.000000    0.658331    0.387712    10.50000    0.08779    0.02493 =
         0.03771    0.00158    0.00000    0.00000
O2    4    0.171446    0.437866    0.345294    11.00000    0.06272    0.05175 =
         0.05430    0.00425    0.02857    0.01165
C1    1    0.000000    0.750000    0.444813    10.25000    0.07927    0.02988 =
         0.02716    0.00000    0.00000    0.00000
AFIX  43
H1    2    0.000000    0.750001    0.547783    10.25000   -1.20000
AFIX   0
C2    1    0.250000    0.473040    0.250000    10.50000    0.06338    0.03543 =
         0.07226    0.00000    0.03488    0.00000
AFIX  43
H2    2    0.250000    0.549973    0.250000    10.50000   -1.20000
AFIX   0
N1    3    0.000000    0.250000    0.159400    10.25000    0.08980    0.04593 =
         0.03649    0.00000    0.00000    0.00000
H1N   2    0.000000    0.316328    0.190438    10.50000   -1.20000
C3    1    0.000000    0.250000    0.014409    10.25000    0.04037    0.06291 =
         0.04239    0.00000    0.00000    0.00000
PART -1
C4    1   -0.101285    0.311935   -0.075222    10.25000    0.06920    0.09166 =
         0.04588   -0.01152   -0.01944    0.05221
AFIX 137
H4A   2   -0.172401    0.262845   -0.122507    10.25000   -1.50000
H4B   2   -0.044100    0.351155   -0.149211    10.25000   -1.50000
H4C   2   -0.156092    0.363839   -0.014776    10.25000   -1.50000
AFIX   0

PART 0
PART -2
N2    3   -0.081508    0.332501   -0.052656    10.25000    0.06018    0.06263 =
         0.02665    0.00072    0.01131    0.02069
AFIX  93
H2A   2   -0.129070    0.380644    0.000188    10.25000   -1.20000
H2B   2   -0.085206    0.336244   -0.147676    10.25000   -1.20000
part 0
AFIX   0
hklf 4

REM  aa in Imma
REM R1 =  0.0315 for     621 Fo > 4sig(Fo)  and  0.0371 for all     721 data
REM     58 parameters refined using      0 restraints

END

WGHT      0.0547      0.6317

REM Instructions for potential hydrogen bonds
EQIV $4 -x, -y+1, -z+1
HTAB C1 N1_$4
HTAB N1 O2
HTAB N1 O2_$1
HTAB C4 O1_$3
HTAB C4 O2_$2
HTAB N2 O2_$2
HTAB N2 O1_$3

REM Highest difference peak  0.478,  deepest hole -0.647,  1-sigma level  0.071
Q1    1   0.0000  0.5481  0.4173  10.50000  0.05    0.48
Q2    1   0.0000  0.4520  0.4165  10.50000  0.05    0.42
Q3    1   0.1009  0.4591  0.3185  11.00000  0.05    0.32
Q4    1   0.0000  0.5816  0.3484  10.50000  0.05    0.27
Q5    1   0.0000  0.4173  0.3502  10.50000  0.05    0.23
Q6    1   0.1645  0.5369  0.1736  11.00000  0.05    0.20
Q7    1   0.2183  0.4734  0.3578  11.00000  0.05    0.19
Q8    1  -0.1015  0.4354 -0.2086  11.00000  0.05    0.17
Q9    1   0.0000  0.3774  0.2646  10.50000  0.05    0.17
Q10   1   0.0930  0.3005  0.2089  11.00000  0.05    0.16
Q11   1  -0.0730  0.7500  0.5429  10.50000  0.05    0.16
Q12   1   0.0920  0.5381  0.3156  11.00000  0.05    0.16
Q13   1   0.0720  0.6577  0.4384  11.00000  0.05    0.16
Q14   1   0.0946  0.5007  0.3974  11.00000  0.05    0.15
Q15   1   0.0000  0.6235  0.2729  10.50000  0.05    0.15
Q16   1  -0.2743  0.3738 -0.0087  11.00000  0.05    0.14
Q17   1  -0.0986  0.3208  0.0030  11.00000  0.05    0.14
Q18   1   0.0541  0.2688  0.0749  11.00000  0.05    0.14
Q19   1   0.0000  0.2500 -0.1901  10.25000  0.05    0.13
Q20   1   0.0000  0.3417 -0.0473  10.50000  0.05    0.13
;
_shelx_res_checksum              72421
