# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2018

####################################################################### 
# 
# 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_P212121
_database_code_depnum_ccdc_archive 'CCDC 1860957'
_audit_update_record             
;
2018-08-08 deposited with the CCDC.
2018-11-02 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        '5-azonia-spiro[4,4]nonane tetrabromomanganese'
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         '2(C8 H16 N), Br4 Mn'
_chemical_formula_sum            'C16 H32 Br4 Mn N2'
_chemical_formula_weight         626.98

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'
Mn Mn 0.3368 0.7283 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_H-M_alt        'P 21 21 21'
_space_group_name_Hall           'P 2ac 2ab'

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

_cell_length_a                   9.2541(4)
_cell_length_b                   13.9651(6)
_cell_length_c                   17.9090(9)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     2314.46(18)
_cell_formula_units_Z            4
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    5324
_cell_measurement_theta_min      2.477
_cell_measurement_theta_max      31.408

_exptl_crystal_description       block
_exptl_crystal_colour            green
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.799
_exptl_crystal_F_000             1228
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.18
_exptl_absorpt_coefficient_mu    7.477
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   Multi-scan
_exptl_absorpt_correction_T_min  0.21
_exptl_absorpt_correction_T_max  0.26
_exptl_absorpt_process_details   'CrystalClear (Rigaku Inc., 2008)'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Rigaku, SCXmini'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            11475
_diffrn_reflns_av_unetI/netI     0.0535
_diffrn_reflns_av_R_equivalents  0.0448
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_theta_min         2.477
_diffrn_reflns_theta_max         24.995
_diffrn_reflns_theta_full        24.995
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_point_group_measured_fraction_full 0.977
_reflns_number_total             4053
_reflns_number_gt                2843
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.713
_reflns_Friedel_fraction_max     0.947
_reflns_Friedel_fraction_full    0.947

_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       'CrystalClear (Rigaku Inc., 2008)'
_computing_cell_refinement       'CrystalClear (Rigaku Inc., 2008)'
_computing_data_reduction        'CrystalClear (Rigaku Inc., 2008)'
_computing_structure_solution    'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'DIAMOND (Brandenburg & Putz, 2005)'
_computing_publication_material  'SHELXL-2014/7 (Sheldrick, 2014)'
_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)+(0.0724P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
;
 Flack x determined using 938 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.017(9)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         3960
_refine_ls_number_parameters     208
_refine_ls_number_restraints     61
_refine_ls_R_factor_all          0.0815
_refine_ls_R_factor_gt           0.0509
_refine_ls_wR_factor_ref         0.1243
_refine_ls_wR_factor_gt          0.1167
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_restrained_S_all      1.053
_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
Br1 Br 0.28768(9) 0.59993(5) 0.82956(5) 0.0873(2) Uani 1 1 d . . . . .
Br2 Br 0.72685(8) 0.55576(5) 0.85653(5) 0.0808(2) Uani 1 1 d . . . . .
Br3 Br 0.45522(7) 0.33174(4) 0.83636(4) 0.05935(17) Uani 1 1 d . . . . .
Br4 Br 0.44996(11) 0.50143(6) 1.02797(4) 0.0935(3) Uani 1 1 d . . . . .
C1 C 1.0723(9) 0.2396(6) 0.8943(5) 0.095(3) Uani 1 1 d . . . . .
H1A H 1.1715 0.2612 0.8990 0.114 Uiso 1 1 calc R U . . .
H1B H 1.0708 0.1702 0.8927 0.114 Uiso 1 1 calc R U . . .
C2 C 0.9813(10) 0.2767(7) 0.9570(5) 0.099(3) Uani 1 1 d . . . . .
H2A H 0.9896 0.2359 1.0006 0.118 Uiso 1 1 calc R U . . .
H2B H 1.0096 0.3413 0.9705 0.118 Uiso 1 1 calc R U . . .
C3 C 0.8314(10) 0.2751(7) 0.9270(5) 0.116(3) Uani 1 1 d . . . . .
H3A H 0.7799 0.3327 0.9414 0.139 Uiso 1 1 calc R U . . .
H3B H 0.7792 0.2200 0.9461 0.139 Uiso 1 1 calc R U . . .
C4 C 0.8445(7) 0.2692(6) 0.8405(5) 0.089(3) Uani 1 1 d . . . . .
H4A H 0.8107 0.2079 0.8220 0.107 Uiso 1 1 calc R U . . .
H4B H 0.7899 0.3200 0.8166 0.107 Uiso 1 1 calc R U . . .
C5 C 1.0568(9) 0.2359(5) 0.7571(5) 0.093(3) Uani 1 1 d . . . . .
H5A H 1.0069 0.1763 0.7465 0.111 Uiso 1 1 calc R U . . .
H5B H 1.1600 0.2242 0.7592 0.111 Uiso 1 1 calc R U . . .
C6 C 1.0200(13) 0.3122(7) 0.7004(5) 0.125(4) Uani 1 1 d . . . . .
H6A H 1.0882 0.3102 0.6593 0.150 Uiso 1 1 calc R U . . .
H6B H 0.9238 0.3015 0.6806 0.150 Uiso 1 1 calc R U . . .
C7 C 1.0268(12) 0.4048(6) 0.7372(5) 0.106(3) Uani 1 1 d . . . . .
H7A H 1.1085 0.4414 0.7189 0.128 Uiso 1 1 calc R U . . .
H7B H 0.9392 0.4410 0.7279 0.128 Uiso 1 1 calc R U . . .
C8 C 1.0428(8) 0.3859(5) 0.8162(4) 0.080(2) Uani 1 1 d . . . . .
H8A H 0.9791 0.4268 0.8451 0.096 Uiso 1 1 calc R U . . .
H8B H 1.1416 0.3974 0.8320 0.096 Uiso 1 1 calc R U . . .
C9 C 1.0790(10) 0.5234(6) 0.1427(5) 0.109(2) Uani 1 1 d . U . . .
H9A H 1.0986 0.5483 0.1923 0.130 Uiso 1 1 calc R U . . .
H9B H 1.1697 0.5074 0.1186 0.130 Uiso 1 1 calc R U . . .
C10 C 0.9789(14) 0.4373(7) 0.1460(6) 0.152(5) Uani 1 1 d . U . . .
H10A H 0.9985 0.3937 0.1050 0.183 Uiso 1 1 calc R U . . .
H10B H 0.9905 0.4031 0.1927 0.183 Uiso 1 1 calc R U . . .
C11 C 0.8371(15) 0.4763(9) 0.1400(8) 0.180(5) Uani 1 1 d . U . . .
H11A H 0.7808 0.4612 0.1841 0.216 Uiso 1 1 calc R U . . .
H11B H 0.7879 0.4506 0.0966 0.216 Uiso 1 1 calc R U . . .
C12 C 0.8557(10) 0.5813(8) 0.1327(6) 0.131(3) Uani 1 1 d D U . . .
H12A H 0.7793 0.6086 0.1023 0.157 Uiso 1 1 calc R U . . .
H12B H 0.8545 0.6118 0.1813 0.157 Uiso 1 1 calc R U . . .
C13 C 1.0052(13) 0.5701(6) 0.0157(5) 0.111(3) Uani 1 1 d . U . . .
H13A H 0.9215 0.5345 -0.0014 0.133 Uiso 1 1 calc R U . . .
H13B H 1.0919 0.5335 0.0051 0.133 Uiso 1 1 calc R U . . .
C14 C 1.0117(15) 0.6691(7) -0.0206(5) 0.149(4) Uani 1 1 d D U . . .
H14A H 1.0719 0.6676 -0.0649 0.179 Uiso 1 1 calc R U . . .
H14B H 0.9157 0.6905 -0.0346 0.179 Uiso 1 1 calc R U . . .
C15 C 1.0725(15) 0.7312(7) 0.0344(5) 0.165(5) Uani 1 1 d D U . . .
H15A H 1.0159 0.7895 0.0377 0.198 Uiso 1 1 calc R U . . .
H15B H 1.1704 0.7484 0.0204 0.198 Uiso 1 1 calc R U . . .
C16 C 1.0733(12) 0.6838(6) 0.1052(5) 0.127(3) Uani 1 1 d D U . . .
H16A H 1.0276 0.7238 0.1427 0.153 Uiso 1 1 calc R U . . .
H16B H 1.1719 0.6712 0.1208 0.153 Uiso 1 1 calc R U . . .
Mn1 Mn 0.47817(9) 0.49826(6) 0.88862(5) 0.0474(2) Uani 1 1 d . . . . .
N1 N 1.0029(5) 0.2811(3) 0.8274(3) 0.0549(15) Uani 1 1 d . . . . .
N2 N 0.9938(8) 0.5933(4) 0.0972(4) 0.0905(15) Uani 1 1 d D U . . .


_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 Mn1 2.4985(11) . ?
Br2 Mn1 2.5043(11) . ?
Br3 Mn1 2.5158(10) . ?
Br4 Mn1 2.5095(11) . ?
C1 N1 1.478(10) . ?
C1 C2 1.496(12) . ?
C2 C3 1.488(13) . ?
C3 C4 1.555(12) . ?
C4 N1 1.494(8) . ?
C5 N1 1.494(10) . ?
C5 C6 1.511(13) . ?
C6 C7 1.453(13) . ?
C7 C8 1.447(12) . ?
C8 N1 1.523(8) . ?
C9 N2 1.496(11) . ?
C9 C10 1.519(14) . ?
C10 C11 1.425(19) . ?
C11 C12 1.482(16) . ?
C12 N2 1.437(11) . ?
C13 N2 1.500(11) . ?
C13 C14 1.529(13) . ?
C14 C15 1.429(13) . ?
C15 C16 1.430(12) . ?
C16 N2 1.469(11) . ?

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
N1 C1 C2 103.2(7) . . ?
C3 C2 C1 104.4(7) . . ?
C2 C3 C4 106.8(7) . . ?
N1 C4 C3 103.1(6) . . ?
N1 C5 C6 101.1(6) . . ?
C7 C6 C5 108.2(8) . . ?
C8 C7 C6 106.6(7) . . ?
C7 C8 N1 106.2(6) . . ?
N2 C9 C10 102.5(8) . . ?
C11 C10 C9 104.8(9) . . ?
C10 C11 C12 106.2(10) . . ?
N2 C12 C11 104.9(9) . . ?
N2 C13 C14 102.8(7) . . ?
C15 C14 C13 105.8(8) . . ?
C14 C15 C16 109.4(8) . . ?
C15 C16 N2 108.0(8) . . ?
Br1 Mn1 Br2 111.65(4) . . ?
Br1 Mn1 Br4 109.73(4) . . ?
Br2 Mn1 Br4 108.55(4) . . ?
Br1 Mn1 Br3 107.95(4) . . ?
Br2 Mn1 Br3 106.77(4) . . ?
Br4 Mn1 Br3 112.18(4) . . ?
C1 N1 C5 111.9(6) . . ?
C1 N1 C4 104.8(6) . . ?
C5 N1 C4 114.4(6) . . ?
C1 N1 C8 112.1(6) . . ?
C5 N1 C8 102.4(5) . . ?
C4 N1 C8 111.4(5) . . ?
C12 N2 C16 120.2(8) . . ?
C12 N2 C9 98.8(7) . . ?
C16 N2 C9 104.2(7) . . ?
C12 N2 C13 117.8(8) . . ?
C16 N2 C13 104.2(7) . . ?
C9 N2 C13 110.6(7) . . ?

_refine_diff_density_max         0.735
_refine_diff_density_min         -0.491
_refine_diff_density_rms         0.097


_exptl_crystal_preparation       Luminescent
