# Electronic Supplementary Material (ESI) for ChemComm.
# This journal is © The Royal Society of Chemistry 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_mc143
_database_code_depnum_ccdc_archive 'CCDC 1500468'
_audit_update_record             
;
2016-08-22 deposited with the CCDC.
2016-09-29 downloaded from the CCDC.
;
_audit_creation_date             2016-06-08
_audit_creation_method           
;
Olex2 1.2-ac21
(compiled 2015.09.16 svn.r134, GUI svn.r4998)
;
_shelxl_version_number           2014/6
_chemical_name_common            MnBrCO3dppz
_chemical_name_systematic        MnBrCO3dppz
_chemical_formula_moiety         'C10.5 H5 Br0.5 Mn0.5 N2 O1.5'
_chemical_formula_sum            'C10.50 H6 Br0.50 Mn0.50 N2 O2'
_chemical_formula_weight         259.60
_chemical_melting_point          ?
_chemical_oxdiff_formula         'C21 H10 N4O3 Br1 Mn1'
_chemical_oxdiff_usercomment     'Mn dppz br 100K'
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 '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'
Br Br -0.6763 1.2805 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Mn Mn -0.5299 2.8052 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_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.
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           12
_space_group_name_H-M_alt        'C 1 2/m 1'
_space_group_name_Hall           '-C 2y'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y, -z'
'x+1/2, y+1/2, z'
'-x+1/2, y+1/2, -z'
'-x, -y, -z'
'x, -y, z'
'-x+1/2, -y+1/2, -z'
'x+1/2, -y+1/2, z'

_cell_length_a                   23.4756(5)
_cell_length_b                   12.4761(3)
_cell_length_c                   7.29758(16)
_cell_angle_alpha                90
_cell_angle_beta                 97.067(2)
_cell_angle_gamma                90
_cell_volume                     2121.11(8)
_cell_formula_units_Z            8
_cell_measurement_reflns_used    5605
_cell_measurement_temperature    292.78(10)
_cell_measurement_theta_max      77.0350
_cell_measurement_theta_min      3.7780
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    7.582
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65337
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.38.43d (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            Orange
_exptl_crystal_density_diffrn    1.626
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             1032
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0372
_diffrn_reflns_av_unetI/netI     0.0263
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            11582
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.309
_diffrn_reflns_theta_min         3.795
_diffrn_reflns_v_R_equivalents   ?
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      292.78(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2303
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω   -110.00 -18.00   1.00    1.00    --  -38.50 -38.00-150.00   92
  2  ω    -64.00  30.00   1.00    1.00    --  -38.50  57.00   0.00   94
  3  ω     17.00 111.00   1.00    1.00    --   42.14  57.00-150.00   94
  4  ω     23.00  96.00   1.00    1.00    --   42.14-125.00 -90.00   73
  5  ω    100.00 178.00   1.00    1.64    --  111.00 111.00 -30.00   78
  6  ω     71.00 178.00   1.00    1.64    --  111.00  15.00 -60.00  107
  7  ω    100.00 178.00   1.00    1.64    --  111.00 111.00  60.00   78
  8  ω    100.00 178.00   1.00    1.64    --  111.00 111.00 150.00   78
  9  ω     99.00 178.00   1.00    1.64    --  111.00  88.00 -74.00   79
 10  ω     40.00 141.00   1.00    1.64    --  111.00 -77.00-180.00  101
 11  ω     31.00 109.00   1.00    1.64    --  111.00 -94.00  60.00   78
 12  ω     41.00 133.00   1.00    1.64    --  111.00 -45.00 150.00   92
 13  ω     85.00 178.00   1.00    1.64    --  111.00  61.00 150.00   93
 14  ω    -29.00  63.00   1.00    1.00    --   42.14 -38.00  60.00   92
 15  ω     17.00 111.00   1.00    1.00    --   42.14  57.00  30.00   94
 16  ω     17.00 111.00   1.00    1.00    --   42.14  57.00 120.00   94
 17  ω     81.00 176.00   1.00    1.64    --  111.00  77.00  90.00   95
 18  ω     85.00 178.00   1.00    1.64    --  111.00  61.00-150.00   93
 19  ω     71.00 178.00   1.00    1.64    --  111.00  15.00  60.00  107
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0099969000
_diffrn_orient_matrix_UB_12      0.0753962000
_diffrn_orient_matrix_UB_13      0.1601252000
_diffrn_orient_matrix_UB_21      0.0421614000
_diffrn_orient_matrix_UB_22      0.0813919000
_diffrn_orient_matrix_UB_23      -0.0667219000
_diffrn_orient_matrix_UB_31      -0.0499666000
_diffrn_orient_matrix_UB_32      0.0541268000
_diffrn_orient_matrix_UB_33      -0.1231991000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                2142
_reflns_number_total             2340
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.38.43d (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43d (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43d (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_refine_diff_density_max         0.533
_refine_diff_density_min         -0.383
_refine_diff_density_rms         0.065
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     142
_refine_ls_number_reflns         2340
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0304
_refine_ls_R_factor_gt           0.0268
_refine_ls_restrained_S_all      1.061
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0352P)²+2.2005P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0690
_refine_ls_wR_factor_ref         0.0717
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C12(H12), C11(H11), C10(H10), C16(H16), C17(H17)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   ?
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
Br1 Br 0.73841(2) 0.5000 1.10981(4) 0.02280(10) Uani 1 2 d S T P . .
Mn2 Mn 0.79583(2) 0.5000 0.83710(6) 0.01902(12) Uani 1 2 d S T P . .
O3 O 0.86318(9) 0.5000 0.5233(3) 0.0270(4) Uani 1 2 d S T P . .
O5 O 0.87488(7) 0.66597(14) 1.0096(2) 0.0367(4) Uani 1 1 d . . . . .
N7 N 0.73578(7) 0.39514(13) 0.7123(2) 0.0187(3) Uani 1 1 d . . . . .
N14 N 0.55203(7) 0.38620(15) 0.3391(2) 0.0243(4) Uani 1 1 d . . . . .
C12 C 0.73562(9) 0.28814(16) 0.7271(3) 0.0211(4) Uani 1 1 d . . . . .
H12 H 0.7660 0.2547 0.7990 0.025 Uiso 1 1 calc R . . . .
C8 C 0.69074(8) 0.44200(15) 0.6087(3) 0.0187(4) Uani 1 1 d . . . . .
C4 C 0.83714(12) 0.5000 0.6412(4) 0.0211(6) Uani 1 2 d S T P . .
C9 C 0.64506(8) 0.38435(16) 0.5159(3) 0.0202(4) Uani 1 1 d . . . . .
C13 C 0.59645(8) 0.44279(16) 0.4182(3) 0.0209(4) Uani 1 1 d . . . . .
C11 C 0.69149(9) 0.22496(17) 0.6382(3) 0.0235(4) Uani 1 1 d . . . . .
H11 H 0.6928 0.1508 0.6513 0.028 Uiso 1 1 calc R . . . .
C15 C 0.50637(9) 0.44278(18) 0.2584(3) 0.0254(4) Uani 1 1 d . . . . .
C10 C 0.64614(9) 0.27234(17) 0.5312(3) 0.0226(4) Uani 1 1 d . . . . .
H10 H 0.6168 0.2310 0.4702 0.027 Uiso 1 1 calc R . . . .
C6 C 0.84368(9) 0.60235(18) 0.9455(3) 0.0259(4) Uani 1 1 d . . . . .
C16 C 0.45745(9) 0.3870(2) 0.1734(3) 0.0305(5) Uani 1 1 d . . . . .
H16 H 0.4570 0.3125 0.1725 0.037 Uiso 1 1 calc R . . . .
C17 C 0.41100(9) 0.4433(2) 0.0929(3) 0.0335(5) Uani 1 1 d . . . . .
H17 H 0.3790 0.4065 0.0374 0.040 Uiso 1 1 calc R . . . .


_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
Br1 Mn2 2.5373(5) . ?
Mn2 N7 2.0524(17) . ?
Mn2 N7 2.0524(16) 6_565 ?
Mn2 C4 1.824(3) . ?
Mn2 C6 1.816(2) 6_565 ?
Mn2 C6 1.816(2) . ?
O3 C4 1.115(4) . ?
O5 C6 1.141(3) . ?
N7 C12 1.339(3) . ?
N7 C8 1.354(3) . ?
N14 C13 1.331(3) . ?
N14 C15 1.356(3) . ?
C12 H12 0.9300 . ?
C12 C11 1.396(3) . ?
C8 C8 1.447(4) 6_565 ?
C8 C9 1.395(3) . ?
C9 C13 1.464(3) . ?
C9 C10 1.402(3) . ?
C13 C13 1.428(4) 6_565 ?
C11 H11 0.9300 . ?
C11 C10 1.374(3) . ?
C15 C15 1.428(5) 6_565 ?
C15 C16 1.419(3) . ?
C10 H10 0.9300 . ?
C16 H16 0.9300 . ?
C16 C17 1.367(3) . ?
C17 C17 1.416(5) 6_565 ?
C17 H17 0.9300 . ?

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
N7 Mn2 Br1 86.89(5) . . ?
N7 Mn2 Br1 86.89(5) 6_565 . ?
N7 Mn2 N7 79.20(9) . 6_565 ?
C4 Mn2 Br1 179.97(9) . . ?
C4 Mn2 N7 93.13(8) . . ?
C4 Mn2 N7 93.13(8) . 6_565 ?
C6 Mn2 Br1 91.04(7) . . ?
C6 Mn2 Br1 91.04(7) 6_565 . ?
C6 Mn2 N7 174.58(8) . . ?
C6 Mn2 N7 95.70(8) . 6_565 ?
C6 Mn2 N7 95.70(8) 6_565 . ?
C6 Mn2 N7 174.58(8) 6_565 6_565 ?
C6 Mn2 C4 88.94(9) . . ?
C6 Mn2 C4 88.94(9) 6_565 . ?
C6 Mn2 C6 89.34(14) 6_565 . ?
C12 N7 Mn2 127.47(14) . . ?
C12 N7 C8 117.72(17) . . ?
C8 N7 Mn2 114.77(13) . . ?
C13 N14 C15 116.59(19) . . ?
N7 C12 H12 118.8 . . ?
N7 C12 C11 122.32(19) . . ?
C11 C12 H12 118.8 . . ?
N7 C8 C8 115.57(11) . 6_565 ?
N7 C8 C9 123.30(18) . . ?
C9 C8 C8 121.03(12) . 6_565 ?
O3 C4 Mn2 178.9(3) . . ?
C8 C9 C13 119.10(18) . . ?
C8 C9 C10 118.03(18) . . ?
C10 C9 C13 122.73(18) . . ?
N14 C13 C9 118.00(19) . . ?
N14 C13 C13 122.04(12) . 6_565 ?
C13 C13 C9 119.87(11) 6_565 . ?
C12 C11 H11 120.0 . . ?
C10 C11 C12 119.98(19) . . ?
C10 C11 H11 120.0 . . ?
N14 C15 C15 121.37(12) . 6_565 ?
N14 C15 C16 119.3(2) . . ?
C16 C15 C15 119.37(14) . 6_565 ?
C9 C10 H10 120.7 . . ?
C11 C10 C9 118.64(19) . . ?
C11 C10 H10 120.7 . . ?
O5 C6 Mn2 177.9(2) . . ?
C15 C16 H16 120.1 . . ?
C17 C16 C15 119.7(2) . . ?
C17 C16 H16 120.1 . . ?
C16 C17 C17 120.89(15) . 6_565 ?
C16 C17 H17 119.6 . . ?
C17 C17 H17 119.6 6_565 . ?

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
Mn2 N7 C12 C11 178.57(14) . . . . ?
Mn2 N7 C8 C8 -2.58(13) . . . 6_565 ?
Mn2 N7 C8 C9 -178.79(14) . . . . ?
N7 C12 C11 C10 -0.1(3) . . . . ?
N7 C8 C9 C13 175.73(16) . . . . ?
N7 C8 C9 C10 0.0(3) . . . . ?
N14 C15 C16 C17 179.51(18) . . . . ?
C12 N7 C8 C8 175.42(13) . . . 6_565 ?
C12 N7 C8 C9 -0.8(3) . . . . ?
C12 C11 C10 C9 -0.8(3) . . . . ?
C8 N7 C12 C11 0.9(3) . . . . ?
C8 C8 C9 C13 -0.3(2) 6_565 . . . ?
C8 C8 C9 C10 -176.06(12) 6_565 . . . ?
C8 C9 C13 N14 -176.46(17) . . . . ?
C8 C9 C13 C13 0.3(2) . . . 6_565 ?
C8 C9 C10 C11 0.8(3) . . . . ?
C13 N14 C15 C15 0.2(2) . . . 6_565 ?
C13 N14 C15 C16 -179.36(17) . . . . ?
C13 C9 C10 C11 -174.79(17) . . . . ?
C15 N14 C13 C9 176.48(16) . . . . ?
C15 N14 C13 C13 -0.2(2) . . . 6_565 ?
C15 C15 C16 C17 -0.1(2) 6_565 . . . ?
C15 C16 C17 C17 0.1(2) . . . 6_565 ?
C10 C9 C13 N14 -0.9(3) . . . . ?
C10 C9 C13 C13 175.85(14) . . . 6_565 ?

_smtbx_masks_special_details     ?
loop_
_smtbx_masks_void_nr
_smtbx_masks_void_average_x
_smtbx_masks_void_average_y
_smtbx_masks_void_average_z
_smtbx_masks_void_volume
_smtbx_masks_void_count_electrons
_smtbx_masks_void_content
1 0.000 0.500 -0.618 192.6 46.8 ?
2 0.500 0.000 -0.194 192.6 46.8 ?

_olex2_date_sample_data_collection 2016-06-08
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.520
_oxdiff_exptl_absorpt_empirical_full_min 0.788
