# 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_PNPFetbpCN2
_database_code_depnum_ccdc_archive 'CCDC 1479238'
_audit_update_record             
;
2016-05-11 deposited with the CCDC.
2016-07-21 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C38 H20 Fe N6, C36 H30 N P2'
_chemical_formula_sum            'C74 H50 Fe N7 P2'
_chemical_formula_weight         1155.00

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'
P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Fe Fe 0.3463 0.8444 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           triclinic
_symmetry_space_group_name_H-M   'P -1'
_space_group_name_Hall           '-P 1'

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   10.5787(8)
_cell_length_b                   12.4102(10)
_cell_length_c                   12.9849(9)
_cell_angle_alpha                85.847(6)
_cell_angle_beta                 68.108(5)
_cell_angle_gamma                65.248(5)
_cell_volume                     1429.35(19)
_cell_formula_units_Z            1
_cell_measurement_temperature    296
_cell_measurement_reflns_used    11798
_cell_measurement_theta_min      3.20
_cell_measurement_theta_max      27.52

_exptl_crystal_description       Block
_exptl_crystal_colour            black
_exptl_crystal_size_max          0.10
_exptl_crystal_size_mid          0.10
_exptl_crystal_size_min          0.10
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.342
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             599
_exptl_absorpt_coefficient_mu    0.373
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_correction_T_min  0.8219
_exptl_absorpt_correction_T_max  0.9958
_exptl_absorpt_process_details   'ABSCOR (Higashi, 2001)'

_exptl_special_details           ?

_diffrn_ambient_temperature      296
_diffrn_radiation_wavelength     0.71075
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Rigaku R-AXIS RAPID'
_diffrn_measurement_method       ω
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            14237
_diffrn_reflns_av_R_equivalents  0.0195
_diffrn_reflns_av_sigmaI/netI    0.0249
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_theta_min         3.20
_diffrn_reflns_theta_max         27.48
_reflns_number_total             6543
_reflns_number_gt                5643
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'RAPID AUTO (Rigaku, 1999)'
_computing_cell_refinement       'RAPID AUTO'
_computing_data_reduction        'RAPID AUTO'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'

_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)+(0.1000P)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    constr
_refine_ls_extinction_method     ShELXL
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         6543
_refine_ls_number_parameters     382
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0582
_refine_ls_R_factor_gt           0.0506
_refine_ls_wR_factor_ref         0.1519
_refine_ls_wR_factor_gt          0.1468
_refine_ls_goodness_of_fit_ref   1.226
_refine_ls_restrained_S_all      1.226
_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_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Fe1 Fe 0.5000 0.0000 1.0000 0.03079(12) Uani 1 2 d S . .
N16 N 0.5000 0.5000 0.5000 0.0564(6) Uani 1 2 d S . .
P1 P 0.49855(5) 0.38957(4) 0.56347(3) 0.03562(14) Uani 1 1 d . . .
N12 N 0.39022(16) 0.17170(13) 1.06638(12) 0.0345(3) Uani 1 1 d . . .
N13 N 0.69750(16) 0.01390(13) 0.94682(11) 0.0344(3) Uani 1 1 d . . .
C3 C 0.2379(2) 0.23239(15) 1.12487(14) 0.0361(4) Uani 1 1 d . . .
C15 C 0.3141(2) 0.36118(19) 0.77191(16) 0.0459(4) Uani 1 1 d . . .
H10 H 0.3344 0.2879 0.7405 0.055 Uiso 1 1 calc R . .
C1 C 0.48371(19) 0.04780(15) 0.85544(14) 0.0358(4) Uani 1 1 d . . .
N14 N 0.4780(2) 0.07268(17) 0.77015(15) 0.0536(4) Uani 1 1 d . . .
C16 C 0.3744(2) 0.43506(16) 0.70672(14) 0.0375(4) Uani 1 1 d . . .
C17 C 0.2477(3) 0.5810(2) 0.86478(18) 0.0591(6) Uani 1 1 d . . .
H11 H 0.2231 0.6558 0.8959 0.071 Uiso 1 1 calc R . .
C18 C 0.3408(2) 0.54527(19) 0.75432(16) 0.0481(5) Uani 1 1 d . . .
H12 H 0.3811 0.5950 0.7116 0.058 Uiso 1 1 calc R . .
C19 C 0.6824(2) 0.29138(17) 0.55969(15) 0.0403(4) Uani 1 1 d . . .
C20 C 0.4338(2) 0.30760(19) 0.50331(14) 0.0436(4) Uani 1 1 d . . .
C21 C 0.2241(3) 0.3970(2) 0.88312(18) 0.0583(6) Uani 1 1 d . . .
H13 H 0.1857 0.3469 0.9272 0.070 Uiso 1 1 calc R . .
C22 C 0.7036(3) 0.2185(2) 0.64341(18) 0.0561(5) Uani 1 1 d . . .
H14 H 0.6211 0.2199 0.7046 0.067 Uiso 1 1 calc R . .
C23 C 0.1910(3) 0.5068(2) 0.92912(17) 0.0602(6) Uani 1 1 d . . .
H15 H 0.1300 0.5307 1.0041 0.072 Uiso 1 1 calc R . .
C24 C 0.5056(3) 0.1855(2) 0.4798(2) 0.0653(6) Uani 1 1 d . . .
H16 H 0.5872 0.1411 0.4999 0.078 Uiso 1 1 calc R . .
C25 C 0.8075(3) 0.2872(3) 0.4695(2) 0.0650(6) Uani 1 1 d . . .
H17 H 0.7951 0.3356 0.4127 0.078 Uiso 1 1 calc R . .
C26 C 0.9692(3) 0.1417(3) 0.5475(3) 0.0792(8) Uani 1 1 d . . .
H18 H 1.0657 0.0926 0.5441 0.095 Uiso 1 1 calc R . .
C27 C 0.3352(4) 0.1936(3) 0.3961(2) 0.0783(8) Uani 1 1 d . . .
H19 H 0.3029 0.1553 0.3591 0.094 Uiso 1 1 calc R . .
C28 C 0.8476(3) 0.1436(2) 0.6359(2) 0.0724(7) Uani 1 1 d . . .
H20 H 0.8614 0.0941 0.6918 0.087 Uiso 1 1 calc R . .
C29 C 0.4544(3) 0.1291(3) 0.4253(2) 0.0766(8) Uani 1 1 d . . .
H21 H 0.5025 0.0467 0.4090 0.092 Uiso 1 1 calc R . .
C30 C 0.9497(3) 0.2118(3) 0.4635(3) 0.0856(9) Uani 1 1 d . . .
H22 H 1.0330 0.2085 0.4021 0.103 Uiso 1 1 calc R . .
C31 C 0.3123(3) 0.3717(3) 0.4738(2) 0.0747(8) Uani 1 1 d . . .
H23 H 0.2632 0.4542 0.4896 0.090 Uiso 1 1 calc R . .
C32 C 0.2629(4) 0.3139(4) 0.4207(3) 0.0912(10) Uani 1 1 d . . .
H24 H 0.1800 0.3575 0.4019 0.109 Uiso 1 1 calc R . .
C46 C 0.83690(19) -0.07374(16) 0.88926(14) 0.0365(4) Uani 1 1 d . . .
C49 C 0.8675(2) -0.18805(17) 0.85594(15) 0.0405(4) Uani 1 1 d . . .
H25 H 0.9677 -0.2394 0.8173 0.049 Uiso 1 1 calc R . .
C40 C 0.7165(2) 0.11384(17) 0.95961(15) 0.0382(4) Uani 1 1 d . . .
C41 C 1.1071(2) -0.0818(2) 0.81024(19) 0.0532(5) Uani 1 1 d . . .
H26 H 1.1578 -0.1607 0.7794 0.064 Uiso 1 1 calc R . .
C48 C 0.6040(2) 0.22231(18) 1.01389(17) 0.0457(4) Uani 1 1 d . . .
H27 H 0.6323 0.2835 1.0160 0.055 Uiso 1 1 calc R . .
C38 C 0.4538(2) 0.24809(16) 1.06519(15) 0.0394(4) Uani 1 1 d . . .
C42 C 0.8746(2) 0.08921(17) 0.90912(15) 0.0397(4) Uani 1 1 d . . .
C47 C 0.9505(2) -0.02886(17) 0.86548(15) 0.0395(4) Uani 1 1 d . . .
C33 C 0.2028(2) 0.35185(16) 1.16389(15) 0.0403(4) Uani 1 1 d . . .
C43 C 0.9530(2) 0.1592(2) 0.89861(17) 0.0508(5) Uani 1 1 d . . .
H28 H 0.9023 0.2393 0.9262 0.061 Uiso 1 1 calc R . .
C39 C 0.3386(2) 0.36185(17) 1.12617(16) 0.0428(4) Uani 1 1 d . . .
C34 C 0.0753(3) 0.5498(2) 1.2519(2) 0.0601(6) Uani 1 1 d . . .
H29 H -0.0127 0.6143 1.2938 0.072 Uiso 1 1 calc R . .
C35 C 0.2117(3) 0.5595(2) 1.2153(2) 0.0645(6) Uani 1 1 d . . .
H30 H 0.2130 0.6297 1.2344 0.077 Uiso 1 1 calc R . .
C36 C 0.3449(3) 0.4665(2) 1.1512(2) 0.0568(5) Uani 1 1 d . . .
H31 H 0.4355 0.4735 1.1256 0.068 Uiso 1 1 calc R . .
C37 C 0.0681(2) 0.44639(18) 1.22731(18) 0.0501(5) Uani 1 1 d . . .
H32 H -0.0229 0.4401 1.2520 0.060 Uiso 1 1 calc R . .
C44 C 1.1069(3) 0.1062(2) 0.8464(2) 0.0594(6) Uani 1 1 d . . .
H33 H 1.1611 0.1508 0.8398 0.071 Uiso 1 1 calc R . .
C45 C 1.1833(2) -0.0134(2) 0.8030(2) 0.0606(6) Uani 1 1 d . . .
H34 H 1.2877 -0.0473 0.7687 0.073 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
Fe1 C1 1.9746(18) 2_657 ?
Fe1 C1 1.9747(18) . ?
Fe1 N12 2.0197(14) . ?
Fe1 N12 2.0197(14) 2_657 ?
Fe1 N13 2.0199(14) 2_657 ?
Fe1 N13 2.0199(14) . ?
N16 P1 1.5499(4) . ?
N16 P1 1.5499(4) 2_666 ?
P1 C20 1.792(2) . ?
P1 C16 1.7925(17) . ?
P1 C19 1.795(2) . ?
N12 C38 1.369(2) . ?
N12 C3 1.376(2) . ?
N13 C46 1.367(2) . ?
N13 C40 1.367(2) . ?
C3 C49 1.377(3) 2_657 ?
C3 C33 1.449(2) . ?
C15 C21 1.379(3) . ?
C15 C16 1.393(3) . ?
C1 N14 1.145(2) . ?
C16 C18 1.389(3) . ?
C17 C23 1.372(4) . ?
C17 C18 1.377(3) . ?
C19 C25 1.386(3) . ?
C19 C22 1.386(3) . ?
C20 C24 1.377(3) . ?
C20 C31 1.378(3) . ?
C21 C23 1.379(4) . ?
C22 C28 1.382(4) . ?
C24 C29 1.401(3) . ?
C25 C30 1.374(4) . ?
C26 C28 1.361(4) . ?
C26 C30 1.367(4) . ?
C27 C29 1.357(5) . ?
C27 C32 1.359(5) . ?
C31 C32 1.384(4) . ?
C46 C49 1.380(3) . ?
C46 C47 1.452(2) . ?
C49 C3 1.377(3) 2_657 ?
C40 C48 1.376(3) . ?
C40 C42 1.451(2) . ?
C41 C45 1.373(3) . ?
C41 C47 1.400(3) . ?
C48 C38 1.374(3) . ?
C38 C39 1.451(3) . ?
C42 C47 1.381(3) . ?
C42 C43 1.401(3) . ?
C33 C39 1.391(3) . ?
C33 C37 1.396(3) . ?
C43 C44 1.374(3) . ?
C39 C36 1.394(3) . ?
C34 C37 1.383(3) . ?
C34 C35 1.395(4) . ?
C35 C36 1.384(3) . ?
C44 C45 1.397(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
C1 Fe1 C1 180.00(11) 2_657 . ?
C1 Fe1 N12 88.69(6) 2_657 . ?
C1 Fe1 N12 91.31(6) . . ?
C1 Fe1 N12 91.31(6) 2_657 2_657 ?
C1 Fe1 N12 88.69(6) . 2_657 ?
N12 Fe1 N12 180.0 . 2_657 ?
C1 Fe1 N13 88.94(6) 2_657 2_657 ?
C1 Fe1 N13 91.06(6) . 2_657 ?
N12 Fe1 N13 90.01(6) . 2_657 ?
N12 Fe1 N13 89.99(6) 2_657 2_657 ?
C1 Fe1 N13 91.06(6) 2_657 . ?
C1 Fe1 N13 88.94(6) . . ?
N12 Fe1 N13 89.99(6) . . ?
N12 Fe1 N13 90.01(6) 2_657 . ?
N13 Fe1 N13 180.0 2_657 . ?
P1 N16 P1 179.999(2) . 2_666 ?
N16 P1 C20 110.47(7) . . ?
N16 P1 C16 110.31(6) . . ?
C20 P1 C16 107.99(9) . . ?
N16 P1 C19 111.54(6) . . ?
C20 P1 C19 108.38(9) . . ?
C16 P1 C19 108.04(8) . . ?
C38 N12 C3 107.20(14) . . ?
C38 N12 Fe1 126.48(12) . . ?
C3 N12 Fe1 126.28(12) . . ?
C46 N13 C40 107.04(14) . . ?
C46 N13 Fe1 126.63(12) . . ?
C40 N13 Fe1 126.32(12) . . ?
N12 C3 C49 125.82(16) . 2_657 ?
N12 C3 C33 110.02(16) . . ?
C49 C3 C33 124.17(17) 2_657 . ?
C21 C15 C16 119.9(2) . . ?
N14 C1 Fe1 178.05(18) . . ?
C18 C16 C15 119.38(17) . . ?
C18 C16 P1 119.16(14) . . ?
C15 C16 P1 121.45(15) . . ?
C23 C17 C18 120.3(2) . . ?
C17 C18 C16 120.1(2) . . ?
C25 C19 C22 118.8(2) . . ?
C25 C19 P1 119.03(16) . . ?
C22 C19 P1 122.20(15) . . ?
C24 C20 C31 119.5(2) . . ?
C24 C20 P1 122.74(17) . . ?
C31 C20 P1 117.64(18) . . ?
C23 C21 C15 120.1(2) . . ?
C28 C22 C19 119.9(2) . . ?
C17 C23 C21 120.3(2) . . ?
C20 C24 C29 119.2(3) . . ?
C30 C25 C19 120.4(2) . . ?
C28 C26 C30 120.0(2) . . ?
C29 C27 C32 120.3(2) . . ?
C26 C28 C22 120.6(2) . . ?
C27 C29 C24 120.6(3) . . ?
C26 C30 C25 120.3(3) . . ?
C20 C31 C32 120.3(3) . . ?
C27 C32 C31 120.2(3) . . ?
N13 C46 C49 125.78(16) . . ?
N13 C46 C47 110.13(16) . . ?
C49 C46 C47 124.08(17) . . ?
C3 C49 C46 125.42(17) 2_657 . ?
N13 C40 C48 125.85(16) . . ?
N13 C40 C42 110.13(16) . . ?
C48 C40 C42 124.01(17) . . ?
C45 C41 C47 117.9(2) . . ?
C38 C48 C40 125.69(18) . . ?
N12 C38 C48 125.59(17) . . ?
N12 C38 C39 109.99(16) . . ?
C48 C38 C39 124.42(18) . . ?
C47 C42 C43 120.59(18) . . ?
C47 C42 C40 106.37(16) . . ?
C43 C42 C40 133.04(18) . . ?
C42 C47 C41 121.10(17) . . ?
C42 C47 C46 106.32(16) . . ?
C41 C47 C46 132.58(18) . . ?
C39 C33 C37 121.19(18) . . ?
C39 C33 C3 106.30(16) . . ?
C37 C33 C3 132.51(19) . . ?
C44 C43 C42 118.1(2) . . ?
C33 C39 C36 121.04(18) . . ?
C33 C39 C38 106.49(17) . . ?
C36 C39 C38 132.45(19) . . ?
C37 C34 C35 121.5(2) . . ?
C36 C35 C34 121.2(2) . . ?
C35 C36 C39 117.7(2) . . ?
C34 C37 C33 117.4(2) . . ?
C43 C44 C45 121.17(19) . . ?
C41 C45 C44 121.1(2) . . ?

_diffrn_measured_fraction_theta_max 0.997
_diffrn_reflns_theta_full        27.48
_diffrn_measured_fraction_theta_full 0.997
_refine_diff_density_max         0.569
_refine_diff_density_min         -0.237
_refine_diff_density_rms         0.084
