# Electronic Supplementary Material (ESI) for Dalton Transactions.
# 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_TPP_MnPc_CN2_2
_database_code_depnum_ccdc_archive 'CCDC 1517719'
_audit_update_record             
;
2016-12-27 deposited with the CCDC.
2016-12-27 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            'C92 H52 N20 Mn2 P'
_chemical_melting_point          ?
_chemical_formula_moiety         '2(C34 H16 Mn N10), C24 H20 P'
_chemical_formula_sum            'C92 H52 Mn2 N20 P'
_chemical_formula_weight         1578.39

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Mn Mn 0.3368 0.7283 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
C C 0.0033 0.0016 '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'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           tetragonal
_symmetry_space_group_name_H-M   P_42/n:2
_symmetry_space_group_name_Hall  -p_4bc
_symmetry_Int_Tables_number      86

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

_cell_length_a                   21.7113(11)
_cell_length_b                   21.7113(11)
_cell_length_c                   7.4439(5)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     3508.9(3)
_cell_formula_units_Z            2
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    24833
_cell_measurement_theta_min      1.33
_cell_measurement_theta_max      28.5

_exptl_crystal_description       needle
_exptl_crystal_colour            black
_exptl_crystal_size_max          0.387
_exptl_crystal_size_mid          0.082
_exptl_crystal_size_min          0.072
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.494
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1618
_exptl_absorpt_coefficient_mu    0.452
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS (Bruker, 2004)'
_exptl_absorpt_correction_T_min  0.898
_exptl_absorpt_correction_T_max  0.971

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71069
_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       ω
_diffrn_reflns_number            4372
_diffrn_reflns_av_R_equivalents  0.0000
_diffrn_reflns_av_unetI/netI     0.1087
_diffrn_reflns_limit_h_min       0
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_theta_min         1.33
_diffrn_reflns_theta_max         28.50
_reflns_number_total             4372
_reflns_number_gt                2390
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'APEX (Bruker, 2000)'
_computing_cell_refinement       'SAINT (Bruker, 2000)'
_computing_data_reduction        'SAINT (Bruker, 2000)'
_computing_structure_solution    SIR97
_computing_structure_refinement  'SHELXL97 (Sheldrick, 1997)'
_computing_publication_material  'SHELXL97 (Sheldrick, 1997)'
_computing_molecular_graphics    VESTA

_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     
'calc w=1/[σ²(Fo²)+(0.0206P)²+0.0000P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         4372
_refine_ls_number_parameters     293
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0848
_refine_ls_R_factor_gt           0.0448
_refine_ls_wR_factor_ref         0.0776
_refine_ls_wR_factor_gt          0.0705
_refine_ls_goodness_of_fit_ref   0.702
_refine_ls_restrained_S_all      0.702
_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_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Mn1 Mn 0.5000 0.0000 0.5000 0.02605(12) Uani 1 2 d S . .
P1 P 0.2500 0.2500 0.7500 0.0301(3) Uani 1 4 d S . .
N1 N 0.55196(8) 0.04257(8) 0.6745(3) 0.0259(4) Uani 1 1 d . . .
N2 N 0.57627(8) 0.13559(8) 0.5096(3) 0.0294(4) Uani 1 1 d . . .
N3 N 0.51173(8) 0.06793(8) 0.3315(3) 0.0262(4) Uani 1 1 d . . .
N4 N 0.44336(8) 0.03510(8) 0.0917(3) 0.0276(5) Uani 1 1 d . . .
N5 N 0.37887(11) 0.07011(10) 0.6174(3) 0.0568(7) Uani 1 1 d . . .
C1 C 0.57164(10) 0.01848(10) 0.8360(3) 0.0273(6) Uani 1 1 d . . .
C2 C 0.61484(10) 0.06113(10) 0.9186(3) 0.0263(5) Uani 1 1 d . . .
C3 C 0.64735(11) 0.05824(12) 1.0784(4) 0.0328(6) Uani 1 1 d . . .
C4 C 0.68436(12) 0.10815(13) 1.1200(4) 0.0396(7) Uani 1 1 d . . .
C5 C 0.68902(11) 0.15853(12) 1.0058(4) 0.0382(6) Uani 1 1 d . . .
C6 C 0.65732(11) 0.16055(11) 0.8457(4) 0.0331(6) Uani 1 1 d . . .
C7 C 0.61994(10) 0.11120(10) 0.8031(3) 0.0267(5) Uani 1 1 d . . .
C8 C 0.58079(10) 0.09806(10) 0.6493(3) 0.0274(5) Uani 1 1 d . . .
C9 C 0.54314(10) 0.12140(10) 0.3654(3) 0.0276(5) Uani 1 1 d . . .
C10 C 0.53351(10) 0.16434(10) 0.2179(3) 0.0273(5) Uani 1 1 d . . .
C11 C 0.55284(11) 0.22440(11) 0.1904(4) 0.0331(6) Uani 1 1 d . . .
C12 C 0.53234(11) 0.25382(11) 0.0383(4) 0.0364(7) Uani 1 1 d . . .
C13 C 0.49457(12) 0.22446(12) -0.0848(4) 0.0376(7) Uani 1 1 d . . .
C14 C 0.47551(11) 0.16417(12) -0.0597(4) 0.0336(6) Uani 1 1 d . . .
C15 C 0.49526(10) 0.13492(10) 0.0952(3) 0.0269(5) Uani 1 1 d . . .
C16 C 0.48163(10) 0.07415(10) 0.1696(3) 0.0274(6) Uani 1 1 d . . .
C17 C 0.42315(11) 0.04440(10) 0.5832(3) 0.0318(6) Uani 1 1 d . . .
C18 C 0.18628(10) 0.23403(10) 0.6040(3) 0.0320(6) Uani 1 1 d . . .
C19 C 0.19188(12) 0.18629(12) 0.4824(4) 0.0442(7) Uani 1 1 d . . .
C20 C 0.14558(14) 0.17484(13) 0.3602(4) 0.0522(8) Uani 1 1 d . . .
C21 C 0.09390(14) 0.21137(16) 0.3590(4) 0.0612(9) Uani 1 1 d . . .
C22 C 0.08845(12) 0.25920(15) 0.4776(4) 0.0590(9) Uani 1 1 d . . .
C23 C 0.13498(12) 0.27154(12) 0.5995(4) 0.0452(7) Uani 1 1 d . . .
H1 H 0.6437(9) 0.0245(9) 1.154(3) 0.022(6) Uiso 1 1 d . . .
H2 H 0.7083(10) 0.1073(10) 1.224(3) 0.038(7) Uiso 1 1 d . . .
H3 H 0.7119(9) 0.1929(9) 1.037(3) 0.036(7) Uiso 1 1 d . . .
H4 H 0.6622(10) 0.1927(9) 0.765(3) 0.034(7) Uiso 1 1 d . . .
H5 H 0.5793(9) 0.2438(10) 0.284(3) 0.040(7) Uiso 1 1 d . . .
H6 H 0.5439(9) 0.2954(9) 0.024(3) 0.033(7) Uiso 1 1 d . . .
H7 H 0.4817(9) 0.2465(9) -0.183(3) 0.032(7) Uiso 1 1 d . . .
H8 H 0.4507(10) 0.1449(10) -0.136(3) 0.036(7) Uiso 1 1 d . . .
H9 H 0.2275 0.1612 0.4830 0.053 Uiso 1 1 d . . .
H10 H 0.1492 0.1419 0.2767 0.061 Uiso 1 1 d . . .
H11 H 0.0618 0.2037 0.2752 0.072 Uiso 1 1 d . . .
H12 H 0.0523 0.2841 0.4758 0.069 Uiso 1 1 d . . .
H13 H 0.1316 0.3057 0.6790 0.053 Uiso 1 1 d . . .


_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
Mn1 N3 1.9529(18) . ?
Mn1 N3 1.9530(18) 5_656 ?
Mn1 N1 1.9529(18) 5_656 ?
Mn1 N1 1.9529(18) . ?
Mn1 C17 2.024(2) . ?
Mn1 C17 2.024(2) 5_656 ?
P1 C18 1.793(2) 8_657 ?
P1 C18 1.793(2) 7_567 ?
P1 C18 1.793(2) . ?
P1 C18 1.793(2) 2 ?
N1 C8 1.370(3) . ?
N1 C1 1.379(3) . ?
N2 C8 1.325(3) . ?
N2 C9 1.328(3) . ?
N3 C9 1.370(3) . ?
N3 C16 1.377(3) . ?
N4 C16 1.321(3) . ?
N4 C1 1.322(3) 5_656 ?
N5 C17 1.140(3) . ?
C1 N4 1.322(3) 5_656 ?
C1 C2 1.454(3) . ?
C2 C3 1.385(3) . ?
C2 C7 1.390(3) . ?
C3 C4 1.384(3) . ?
C4 C5 1.389(4) . ?
C5 C6 1.376(4) . ?
C6 C7 1.381(3) . ?
C7 C8 1.454(3) . ?
C9 C10 1.456(3) . ?
C10 C11 1.385(3) . ?
C10 C15 1.390(3) . ?
C11 C12 1.374(3) . ?
C12 C13 1.385(3) . ?
C13 C14 1.385(3) . ?
C14 C15 1.385(3) . ?
C15 C16 1.461(3) . ?
C18 C23 1.380(3) . ?
C18 C19 1.382(3) . ?
C19 C20 1.379(3) . ?
C20 C21 1.374(4) . ?
C21 C22 1.368(4) . ?
C22 C23 1.384(4) . ?

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
N3 Mn1 N3 179.999(1) . 5_656 ?
N3 Mn1 N1 90.32(7) . 5_656 ?
N3 Mn1 N1 89.67(7) 5_656 5_656 ?
N3 Mn1 N1 89.68(7) . . ?
N3 Mn1 N1 90.32(7) 5_656 . ?
N1 Mn1 N1 180.0 5_656 . ?
N3 Mn1 C17 86.81(8) . . ?
N3 Mn1 C17 93.19(8) 5_656 . ?
N1 Mn1 C17 87.29(8) 5_656 . ?
N1 Mn1 C17 92.71(8) . . ?
N3 Mn1 C17 93.19(8) . 5_656 ?
N3 Mn1 C17 86.82(8) 5_656 5_656 ?
N1 Mn1 C17 92.71(8) 5_656 5_656 ?
N1 Mn1 C17 87.29(8) . 5_656 ?
C17 Mn1 C17 180.0 . 5_656 ?
C18 P1 C18 105.40(16) 8_657 7_567 ?
C18 P1 C18 111.54(8) 8_657 . ?
C18 P1 C18 111.54(8) 7_567 . ?
C18 P1 C18 111.54(8) 8_657 2 ?
C18 P1 C18 111.54(8) 7_567 2 ?
C18 P1 C18 105.41(16) . 2 ?
C8 N1 C1 108.12(19) . . ?
C8 N1 Mn1 126.10(16) . . ?
C1 N1 Mn1 125.39(15) . . ?
C8 N2 C9 122.14(19) . . ?
C9 N3 C16 108.34(19) . . ?
C9 N3 Mn1 125.90(16) . . ?
C16 N3 Mn1 125.03(15) . . ?
C16 N4 C1 122.7(2) . 5_656 ?
N4 C1 N1 127.7(2) 5_656 . ?
N4 C1 C2 123.2(2) 5_656 . ?
N1 C1 C2 109.07(19) . . ?
C3 C2 C7 121.7(2) . . ?
C3 C2 C1 131.5(2) . . ?
C7 C2 C1 106.7(2) . . ?
C4 C3 C2 116.9(2) . . ?
C3 C4 C5 121.5(3) . . ?
C6 C5 C4 121.2(2) . . ?
C5 C6 C7 117.9(2) . . ?
C6 C7 C2 120.7(2) . . ?
C6 C7 C8 132.6(2) . . ?
C2 C7 C8 106.7(2) . . ?
N2 C8 N1 127.9(2) . . ?
N2 C8 C7 122.7(2) . . ?
N1 C8 C7 109.4(2) . . ?
N2 C9 N3 128.0(2) . . ?
N2 C9 C10 122.6(2) . . ?
N3 C9 C10 109.4(2) . . ?
C11 C10 C15 121.1(2) . . ?
C11 C10 C9 132.1(2) . . ?
C15 C10 C9 106.69(19) . . ?
C12 C11 C10 117.5(2) . . ?
C11 C12 C13 121.5(2) . . ?
C12 C13 C14 121.5(3) . . ?
C15 C14 C13 116.9(2) . . ?
C14 C15 C10 121.4(2) . . ?
C14 C15 C16 131.8(2) . . ?
C10 C15 C16 106.7(2) . . ?
N4 C16 N3 128.3(2) . . ?
N4 C16 C15 122.7(2) . . ?
N3 C16 C15 108.9(2) . . ?
N5 C17 Mn1 175.1(2) . . ?
C23 C18 C19 119.8(2) . . ?
C23 C18 P1 121.6(2) . . ?
C19 C18 P1 118.30(18) . . ?
C20 C19 C18 120.2(2) . . ?
C21 C20 C19 119.7(3) . . ?
C22 C21 C20 120.3(3) . . ?
C21 C22 C23 120.5(3) . . ?
C18 C23 C22 119.4(3) . . ?

_diffrn_measured_fraction_theta_max 0.986
_diffrn_reflns_theta_full        28.50
_diffrn_measured_fraction_theta_full 0.986
_refine_diff_density_max         0.497
_refine_diff_density_min         -0.625
_refine_diff_density_rms         0.047
