# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2015

####################################################################### 
# 
# 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_[Re(CO)3(phen)(nHo)(CO)3]CF3SO3
_database_code_depnum_ccdc_archive 'CCDC 1038266'
_audit_update_record             
;
2015-08-31 deposited with the CCDC.
2015-09-07 downloaded from the CCDC.
;
_audit_creation_method           SHELXL-2014
_chemical_name_systematic        
'fac-tricarbonyl(1,10 phenanthroline)(9H-pyrido[3,4-b]indole)rhenium(I) trifluoromethanesulfonate hemihydrate'
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C27 H16 F3 N4 O6 Re S'
_chemical_formula_weight         767.70

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'
F F 0.0171 0.0103 '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'
Re Re -1.0185 7.2310 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.1246 0.1234 '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'

_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                   11.7831(2)
_cell_length_b                   13.8328(3)
_cell_length_c                   17.5603(3)
_cell_angle_alpha                90
_cell_angle_beta                 94.139(2)
_cell_angle_gamma                90
_cell_volume                     2854.75(9)
_cell_formula_units_Z            4
_cell_measurement_temperature    295(2)
_cell_measurement_reflns_used    5158
_cell_measurement_theta_min      3.7830
_cell_measurement_theta_max      28.9030
_exptl_crystal_description       fragment
_exptl_crystal_colour            yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.786
_exptl_crystal_F_000             1488
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.331
_exptl_crystal_size_mid          0.194
_exptl_crystal_size_min          0.183
_exptl_absorpt_coefficient_mu    4.397
_shelx_estimated_absorpt_T_min   0.324
_shelx_estimated_absorpt_T_max   0.500
_exptl_absorpt_correction_T_min  0.78617
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_special_details           
;
 ?
;
_diffrn_ambient_temperature      295(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'Enhance (Mo) X-ray Source'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            Eos
_diffrn_detector_area_resol_mean 16.0604
_diffrn_reflns_number            16412
_diffrn_reflns_av_unetI/netI     0.0383
_diffrn_reflns_av_R_equivalents  0.0317
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_theta_min         2.945
_diffrn_reflns_theta_max         27.000
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measured_fraction_theta_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_point_group_measured_fraction_full 0.997
_reflns_number_total             6163
_reflns_number_gt                4988
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Data were apparently pre-merged, so _diffrn_reflns_number
 etc. will have to be added later.
 
 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       
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_cell_refinement       
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_reduction        
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_structure_solution    'SHELXS-2014 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2014 (Sheldrick, 2014)'
_computing_molecular_graphics    'ORTEP-3 (Farrugia, 1997)'
_computing_publication_material  'SHELXL-2014 (Sheldrick, 2014)'
_refine_special_details          SQUEEZE
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0436P)²] 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     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         6163
_refine_ls_number_parameters     379
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0441
_refine_ls_R_factor_gt           0.0305
_refine_ls_wR_factor_ref         0.0834
_refine_ls_wR_factor_gt          0.0773
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_restrained_S_all      1.053
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
# SQUEEZE RESULTS (APPEND TO CIF)
# Note: Data are Listed for all Voids in the P1 Unit Cell
# i.e. Centre of Gravity, Solvent Accessible Volume,
# Recovered number of Electrons in the Void and
# Details about the Squeezed Material
loop_
_platon_squeeze_void_nr
_platon_squeeze_void_average_x
_platon_squeeze_void_average_y
_platon_squeeze_void_average_z
_platon_squeeze_void_volume
_platon_squeeze_void_count_electrons
_platon_squeeze_void_content
1 0.000 0.000 0.500 151 27 ' '
2 0.500 0.500 0.000 151 27 ' '
_platon_squeeze_details          
;
;
# start Validation Reply Form
_vrf_PLAT231_ReCO3phennHoCO3CF3SO3 
;
PROBLEM: Hirshfeld Test (Solvent)   S1     --  C4      ..       17.5 su    
RESPONSE: The CF3SO3 counter-ion show some positional disorder 
;
# end Validation Reply Form 
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
C1 C 0.4102(5) 0.4526(4) 0.2252(3) 0.0609(13) Uani 1 1 d . . . . .
C2 C 0.4653(4) 0.4006(3) 0.3696(3) 0.0401(9) Uani 1 1 d . . . . .
C3 C 0.5688(4) 0.3148(3) 0.2599(3) 0.0441(10) Uani 1 1 d . . . . .
C4 C 0.7246(3) 0.0319(3) 0.1397(3) 0.0465(11) Uani 1 1 d . . . . .
C10 C 0.0577(4) 0.3872(4) 0.3445(3) 0.0561(12) Uani 1 1 d . . . . .
H10 H 0.0237 0.4217 0.3822 0.067 Uiso 1 1 calc R U . . .
C11 C 0.2229(3) 0.2349(3) 0.1812(2) 0.0345(8) Uani 1 1 d . . . . .
C12 C 0.1607(4) 0.1777(3) 0.1262(2) 0.0372(9) Uani 1 1 d . . . . .
C13 C 0.2219(4) 0.1279(3) 0.0733(2) 0.0438(10) Uani 1 1 d . . . . .
H13 H 0.1845 0.0882 0.0368 0.053 Uiso 1 1 calc R U . . .
C14 C 0.3374(4) 0.1383(3) 0.0760(2) 0.0502(11) Uani 1 1 d . . . . .
H14 H 0.3789 0.1064 0.0406 0.060 Uiso 1 1 calc R U . . .
C15 C 0.3933(4) 0.1968(3) 0.1320(3) 0.0474(11) Uani 1 1 d . . . . .
H15 H 0.4720 0.2029 0.1329 0.057 Uiso 1 1 calc R U . . .
C16 C 0.1642(3) 0.2859(3) 0.2368(2) 0.0346(8) Uani 1 1 d . . . . .
C17 C 0.0451(4) 0.2818(3) 0.2355(2) 0.0425(10) Uani 1 1 d . . . . .
C18 C -0.0082(4) 0.3345(3) 0.2914(3) 0.0543(12) Uani 1 1 d . . . . .
H18 H -0.0870 0.3339 0.2925 0.065 Uiso 1 1 calc R U . . .
C21 C 0.4241(4) 0.1104(3) 0.3244(3) 0.0457(11) Uani 1 1 d . . . . .
H21 H 0.4541 0.1042 0.2771 0.055 Uiso 1 1 calc R U . . .
C22 C 0.4129(4) 0.0281(3) 0.3675(3) 0.0476(11) Uani 1 1 d . . . . .
H22 H 0.4353 -0.0316 0.3494 0.057 Uiso 1 1 calc R U . . .
C23 C 0.3684(4) 0.0350(3) 0.4372(2) 0.0404(10) Uani 1 1 d . . . . .
C24 C 0.3435(4) -0.0295(3) 0.4975(3) 0.0457(10) Uani 1 1 d . . . . .
C25 C 0.3528(5) -0.1289(3) 0.5080(3) 0.0573(13) Uani 1 1 d . . . . .
H25 H 0.3825 -0.1678 0.4711 0.069 Uiso 1 1 calc R U . . .
C26 C 0.3171(6) -0.1686(3) 0.5742(4) 0.0685(16) Uani 1 1 d . . . . .
H26 H 0.3217 -0.2352 0.5814 0.082 Uiso 1 1 calc R U . . .
C27 C 0.2744(5) -0.1113(4) 0.6302(3) 0.0686(15) Uani 1 1 d . . . . .
H27 H 0.2528 -0.1406 0.6746 0.082 Uiso 1 1 calc R U . . .
C28 C 0.2628(5) -0.0128(4) 0.6225(3) 0.0589(13) Uani 1 1 d . . . . .
H28 H 0.2327 0.0249 0.6601 0.071 Uiso 1 1 calc R U . . .
C29 C 0.2986(4) 0.0277(3) 0.5553(3) 0.0466(11) Uani 1 1 d . . . . .
C110 C 0.1751(4) 0.3883(3) 0.3413(2) 0.0489(11) Uani 1 1 d . . . . .
H110 H 0.2184 0.4248 0.3772 0.059 Uiso 1 1 calc R U . . .
C111 C -0.0153(4) 0.2260(3) 0.1778(3) 0.0471(11) Uani 1 1 d . . . . .
H111 H -0.0943 0.2241 0.1758 0.057 Uiso 1 1 calc R U . . .
C112 C 0.0396(4) 0.1757(3) 0.1260(3) 0.0468(11) Uani 1 1 d . . . . .
H112 H -0.0021 0.1391 0.0894 0.056 Uiso 1 1 calc R U . . .
C210 C 0.3385(4) 0.1289(3) 0.4614(2) 0.0391(9) Uani 1 1 d . . . . .
C211 C 0.3523(3) 0.2080(3) 0.4162(2) 0.0398(9) Uani 1 1 d . . . . .
H211 H 0.3325 0.2689 0.4334 0.048 Uiso 1 1 calc R U . . .
F1 F 0.8233(3) 0.0436(2) 0.18246(17) 0.0716(8) Uani 1 1 d . . . . .
F2 F 0.7251(3) -0.06337(19) 0.11934(18) 0.0752(9) Uani 1 1 d . . . . .
F3 F 0.6439(3) 0.0366(2) 0.19208(17) 0.0746(9) Uani 1 1 d . . . . .
N11 N 0.3379(3) 0.2438(2) 0.18382(18) 0.0368(7) Uani 1 1 d . . . . .
N12 N 0.2285(3) 0.3393(2) 0.2889(2) 0.0373(8) Uani 1 1 d . . . . .
N21 N 0.3942(3) 0.1989(2) 0.34677(19) 0.0378(8) Uani 1 1 d . . . . .
N22 N 0.2985(3) 0.1236(2) 0.5327(2) 0.0466(9) Uani 1 1 d . . . . .
H22A H 0.2770 0.1719 0.5590 0.056 Uiso 1 1 calc R U . . .
O1 O 0.4064(5) 0.5267(3) 0.1965(3) 0.1020(16) Uani 1 1 d . . . . .
O2 O 0.4994(3) 0.4390(2) 0.42345(18) 0.0567(8) Uani 1 1 d . . . . .
O3 O 0.6636(3) 0.3081(3) 0.2490(2) 0.0652(10) Uani 1 1 d . . . . .
O4 O 0.7933(3) 0.0942(2) 0.01890(18) 0.0558(8) Uani 1 1 d . . . . .
O5 O 0.7000(3) 0.2036(2) 0.0998(2) 0.0638(9) Uani 1 1 d . . . . .
O6 O 0.5912(3) 0.0781(3) 0.0316(2) 0.0699(10) Uani 1 1 d . . . . .
Re Re 0.41115(2) 0.33151(2) 0.27864(2) 0.03757(7) Uani 1 1 d . . . . .
S1 S 0.69951(9) 0.10994(7) 0.06466(6) 0.0390(2) Uani 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
C1 O1 1.142(6) . ?
C1 Re 1.919(6) . ?
C2 O2 1.132(5) . ?
C2 Re 1.930(4) . ?
C3 O3 1.151(6) . ?
C3 Re 1.923(5) . ?
C4 F1 1.348(5) . ?
C4 F2 1.365(5) . ?
C4 F3 1.371(5) . ?
C4 S1 1.713(5) . ?
C10 C18 1.377(7) . ?
C10 C110 1.389(6) . ?
C11 N11 1.358(5) . ?
C11 C16 1.423(5) . ?
C11 C12 1.413(5) . ?
C12 C13 1.397(6) . ?
C12 C112 1.427(6) . ?
C13 C14 1.365(6) . ?
C14 C15 1.401(6) . ?
C15 N11 1.328(5) . ?
C16 N12 1.364(5) . ?
C16 C17 1.403(6) . ?
C17 C18 1.407(6) . ?
C17 C111 1.423(6) . ?
C21 N21 1.340(5) . ?
C21 C22 1.379(6) . ?
C22 C23 1.368(6) . ?
C23 C24 1.432(6) . ?
C23 C210 1.419(6) . ?
C24 C25 1.390(6) . ?
C24 C29 1.419(6) . ?
C25 C26 1.379(8) . ?
C26 C27 1.385(8) . ?
C27 C28 1.375(7) . ?
C28 C29 1.399(7) . ?
C29 N22 1.385(5) . ?
C110 N12 1.336(5) . ?
C111 C112 1.347(6) . ?
C210 N22 1.371(5) . ?
C210 C211 1.370(6) . ?
C211 N21 1.354(5) . ?
N11 Re 2.187(3) . ?
N12 Re 2.176(4) . ?
N21 Re 2.207(3) . ?
O4 S1 1.429(3) . ?
O5 S1 1.435(4) . ?
O6 S1 1.433(3) . ?

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 C1 Re 176.2(5) . . ?
O2 C2 Re 178.0(4) . . ?
O3 C3 Re 177.7(4) . . ?
F1 C4 F2 104.0(4) . . ?
F1 C4 F3 103.5(3) . . ?
F2 C4 F3 103.8(4) . . ?
F1 C4 S1 116.5(3) . . ?
F2 C4 S1 114.2(3) . . ?
F3 C4 S1 113.4(3) . . ?
C18 C10 C110 119.5(4) . . ?
N11 C11 C16 117.7(3) . . ?
N11 C11 C12 122.8(4) . . ?
C16 C11 C12 119.5(4) . . ?
C13 C12 C11 117.6(4) . . ?
C13 C12 C112 123.6(4) . . ?
C11 C12 C112 118.8(4) . . ?
C14 C13 C12 119.1(4) . . ?
C13 C14 C15 120.2(4) . . ?
N11 C15 C14 122.3(4) . . ?
N12 C16 C17 122.6(4) . . ?
N12 C16 C11 117.1(4) . . ?
C17 C16 C11 120.3(3) . . ?
C16 C17 C18 117.6(4) . . ?
C16 C17 C111 118.8(4) . . ?
C18 C17 C111 123.6(4) . . ?
C10 C18 C17 119.3(4) . . ?
N21 C21 C22 123.8(4) . . ?
C23 C22 C21 119.4(4) . . ?
C22 C23 C24 136.9(4) . . ?
C22 C23 C210 116.9(4) . . ?
C24 C23 C210 106.2(4) . . ?
C25 C24 C29 119.1(4) . . ?
C25 C24 C23 134.1(4) . . ?
C29 C24 C23 106.8(4) . . ?
C26 C25 C24 118.7(5) . . ?
C25 C26 C27 121.2(5) . . ?
C26 C27 C28 122.4(5) . . ?
C29 C28 C27 116.4(5) . . ?
N22 C29 C28 129.2(4) . . ?
N22 C29 C24 108.8(4) . . ?
C28 C29 C24 122.1(4) . . ?
N12 C110 C10 122.8(4) . . ?
C112 C111 C17 121.4(4) . . ?
C111 C112 C12 121.2(4) . . ?
N22 C210 C211 129.4(4) . . ?
N22 C210 C23 109.6(4) . . ?
C211 C210 C23 121.0(4) . . ?
N21 C211 C210 120.9(4) . . ?
C15 N11 C11 118.1(3) . . ?
C15 N11 Re 127.4(3) . . ?
C11 N11 Re 114.5(2) . . ?
C110 N12 C16 118.1(4) . . ?
C110 N12 Re 126.9(3) . . ?
C16 N12 Re 114.9(3) . . ?
C21 N21 C211 118.0(4) . . ?
C21 N21 Re 124.4(3) . . ?
C211 N21 Re 117.6(3) . . ?
C210 N22 C29 108.6(4) . . ?
C1 Re C3 89.6(2) . . ?
C1 Re C2 87.86(19) . . ?
C3 Re C2 86.30(17) . . ?
C1 Re N12 91.5(2) . . ?
C3 Re N12 173.48(14) . . ?
C2 Re N12 100.17(15) . . ?
C1 Re N11 97.09(17) . . ?
C3 Re N11 97.82(15) . . ?
C2 Re N11 173.55(15) . . ?
N12 Re N11 75.66(12) . . ?
C1 Re N21 173.11(19) . . ?
C3 Re N21 96.83(16) . . ?
C2 Re N21 90.01(15) . . ?
N12 Re N21 82.39(12) . . ?
N11 Re N21 84.59(12) . . ?
O4 S1 O5 113.6(2) . . ?
O4 S1 O6 115.3(2) . . ?
O5 S1 O6 115.3(2) . . ?
O4 S1 C4 103.8(2) . . ?
O5 S1 C4 104.1(2) . . ?
O6 S1 C4 102.6(2) . . ?

_refine_diff_density_max         1.686
_refine_diff_density_min         -0.573
_refine_diff_density_rms         0.103

_shelxl_version_number           2014-3


_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: Dichloromethane'
####################################################################### 
# 
# 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_[Re(CO)3(bipy)(nHo)(CO)3]CF3SO3
_database_code_depnum_ccdc_archive 'CCDC 1038267'
_audit_update_record             
;
2015-08-14 deposited with the CCDC.
2015-09-07 downloaded from the CCDC.
;
_audit_creation_method           SHELXL-2014
_chemical_name_systematic        
"fac-tricarbonyl(2,2' bipyridine)(9H-pyrido[3,4-b]indole)rhenium(I) trifluoromethanesulfonate"
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C25 H16 F3 N4 O6 Re S'
_chemical_formula_weight         743.68

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'
F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Re Re -1.0185 7.2310 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      trigonal
_space_group_IT_number           144
_space_group_name_H-M_alt        'P 31'
_space_group_name_Hall           'P 31'

_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'
'-y, x-y, z+1/3'
'-x+y, -x, z+2/3'

_cell_length_a                   15.1660(9)
_cell_length_b                   15.1660(9)
_cell_length_c                   9.9800(7)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     1987.9(3)
_cell_formula_units_Z            3
_cell_measurement_temperature    295(2)
_cell_measurement_reflns_used    15861

_cell_measurement_theta_min      2.546

_cell_measurement_theta_max      27.103
_exptl_crystal_description       fragment
_exptl_crystal_colour            yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.864
_exptl_crystal_F_000             1080
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.211
_exptl_crystal_size_mid          0.066
_exptl_crystal_size_min          0.059
_shelx_estimated_absorpt_T_min   0.435
_shelx_estimated_absorpt_T_max   0.768
loop_
_exptl_crystal_face_index_h
_exptl_crystal_face_index_k
_exptl_crystal_face_index_l
_exptl_crystal_face_perp_dist
3 1 0 0.0280
-3 -1 0 0.0310
4 -1 0 0.0340
-5 1 0 0.0340
8 -2 -3 0.0520
0 0 1 0.0980
0 0 -1 0.1130
1 -3 0 0.0310
-1 3 0 0.0350
_exptl_absorpt_coefficient_mu    4.6900
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details   
;
a grid of  8 x 8 x 8 = 512 sampling points was used
;
_exptl_absorpt_correction_T_min  0.5149
_exptl_absorpt_correction_T_max  0.7808
_exptl_absorpt_correction_T_ave  0.7068
_exptl_special_details           
;
 ?
;
_diffrn_ambient_temperature      295(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_measurement_device_type  KappaCCD

_diffrn_measurement_device       '95mm CCD camera on κ-goniostat'

_diffrn_detector_area_resol_mean 9

_diffrn_radiation_monochromator  'horizonally mounted graphite crystal'
_diffrn_reflns_number            10339
_diffrn_reflns_av_unetI/netI     0.0694
_diffrn_reflns_av_R_equivalents  0.0624
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_theta_min         2.686
_diffrn_reflns_theta_max         25.995
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_point_group_measured_fraction_full 0.985
_reflns_number_total             5145
_reflns_number_gt                4106
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.972
_reflns_Friedel_fraction_max     0.970
_reflns_Friedel_fraction_full    0.972

_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       'Collect (Bruker AXS BV, 1997-2004)'
_computing_cell_refinement       'HKL Scalepack (Otwinowski & Minor 1997)'
_computing_data_reduction        
'HKL Denzo and Scalepack (Otwinowski & Minor 1997)'
_computing_structure_solution    'SHELXS-2014 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2014 (Sheldrick, 2014)'
_computing_molecular_graphics    'ORTEP-3 (Farrugia, 1997)'
_computing_publication_material  'SHELXL-2014 (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)+(0.0917P)²] 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       0.029(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_abs_structure_details 
;
 Flack x determined using 1693 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.021(15)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         5145
_refine_ls_number_parameters     357
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0648
_refine_ls_R_factor_gt           0.0537
_refine_ls_wR_factor_ref         0.1457
_refine_ls_wR_factor_gt          0.1390
_refine_ls_goodness_of_fit_ref   0.984
_refine_ls_restrained_S_all      0.984
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
# start Validation Reply Form
_vrf_PLAT342_ReCO3bipynHoCO3CF3SO3 
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............     0.0375 Ang.  
RESPONSE: The crystal includes a disordered counter-ion
;
# end Validation Reply Form 
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
C1 C 0.584(2) 0.322(2) 0.7354(17) 0.086(6) Uani 1 1 d . . . . .
C2 C 0.4372(14) 0.1574(17) 0.8463(19) 0.079(5) Uani 1 1 d . . . . .
C3 C 0.4434(16) 0.3245(19) 0.897(2) 0.093(6) Uani 1 1 d . . . . .
C4 C 0.220(3) -0.294(3) 0.622(4) 0.140(10) Uiso 1 1 d . . . . .
C11 C 0.4264(16) 0.3316(17) 0.4535(18) 0.081(5) Uani 1 1 d . . . . .
C12 C 0.4171(19) 0.389(2) 0.359(3) 0.107(8) Uani 1 1 d . . . . .
H12 H 0.4107 0.3698 0.2691 0.128 Uiso 1 1 calc R U . . .
C13 C 0.417(2) 0.477(3) 0.393(3) 0.114(8) Uani 1 1 d . . . . .
H13 H 0.4136 0.5182 0.3270 0.137 Uiso 1 1 calc R U . . .
C14 C 0.4214(19) 0.5026(19) 0.519(4) 0.112(9) Uani 1 1 d . . . . .
H14 H 0.4195 0.5611 0.5419 0.134 Uiso 1 1 calc R U . . .
C15 C 0.4289(15) 0.4430(14) 0.619(2) 0.088(5) Uani 1 1 d . . . . .
H15 H 0.4336 0.4622 0.7087 0.105 Uiso 1 1 calc R U . . .
C16 C 0.4263(15) 0.2383(17) 0.427(2) 0.081(5) Uani 1 1 d . . . . .
C17 C 0.4234(19) 0.198(2) 0.303(2) 0.108(8) Uani 1 1 d . . . . .
H17 H 0.4260 0.2344 0.2265 0.130 Uiso 1 1 calc R U . . .
C18 C 0.416(2) 0.102(3) 0.289(2) 0.112(8) Uani 1 1 d . . . . .
H18 H 0.4126 0.0751 0.2037 0.135 Uiso 1 1 calc R U . . .
C19 C 0.415(2) 0.047(2) 0.403(3) 0.108(8) Uani 1 1 d . . . . .
H19 H 0.4105 -0.0160 0.3955 0.130 Uiso 1 1 calc R U . . .
C21 C 0.2140(14) 0.2227(16) 0.7300(18) 0.072(4) Uani 1 1 d . . . . .
H21 H 0.2504 0.2934 0.7340 0.087 Uiso 1 1 calc R U . . .
C22 C 0.1106(16) 0.1755(15) 0.7296(18) 0.073(4) Uani 1 1 d . . . . .
H22 H 0.0779 0.2135 0.7333 0.088 Uiso 1 1 calc R U . . .
C23 C 0.0544(14) 0.0695(15) 0.7235(16) 0.066(4) Uani 1 1 d . . . . .
C24 C -0.0549(17) -0.0099(16) 0.7209(16) 0.073(5) Uani 1 1 d . . . . .
C25 C -0.1431(17) -0.0036(18) 0.718(2) 0.087(6) Uani 1 1 d . . . . .
H25 H -0.1424 0.0581 0.7150 0.104 Uiso 1 1 calc R U . . .
C26 C -0.2272(17) -0.092(2) 0.719(3) 0.090(7) Uani 1 1 d . . . . .
H26 H -0.2878 -0.0903 0.7220 0.108 Uiso 1 1 calc R U . . .
C27 C -0.236(2) -0.193(2) 0.716(2) 0.095(7) Uani 1 1 d . . . . .
H27 H -0.2986 -0.2524 0.7129 0.114 Uiso 1 1 calc R U . . .
C28 C -0.1457(17) -0.195(2) 0.719(2) 0.090(6) Uani 1 1 d . . . . .
H28 H -0.1448 -0.2563 0.7209 0.108 Uiso 1 1 calc R U . . .
C29 C -0.0551(13) -0.0995(16) 0.7191(15) 0.071(4) Uani 1 1 d . . . . .
C110 C 0.4219(15) 0.0911(17) 0.525(2) 0.090(5) Uani 1 1 d . . . . .
H110 H 0.4240 0.0570 0.6011 0.108 Uiso 1 1 calc R U . . .
C210 C 0.1111(13) 0.0189(14) 0.7203(15) 0.065(4) Uani 1 1 d . . . . .
C211 C 0.2161(14) 0.0708(16) 0.7178(17) 0.072(4) Uani 1 1 d . . . . .
H211 H 0.2511 0.0352 0.7110 0.086 Uiso 1 1 calc R U . . .
N11 N 0.4295(13) 0.3564(13) 0.5853(16) 0.084(4) Uani 1 1 d . . . . .
N12 N 0.4253(11) 0.1805(13) 0.5401(13) 0.077(4) Uani 1 1 d . . . . .
N21 N 0.2674(12) 0.1725(12) 0.7251(14) 0.073(4) Uani 1 1 d . . . . .
N22 N 0.0443(12) -0.0844(12) 0.7171(15) 0.072(4) Uani 1 1 d . . . . .
H22A H 0.0605 -0.1313 0.7143 0.087 Uiso 1 1 calc R U . . .
O1 O 0.6711(11) 0.3625(14) 0.7410(16) 0.103(5) Uani 1 1 d . . . . .
O2 O 0.4363(13) 0.0933(13) 0.9280(15) 0.097(4) Uani 1 1 d . . . . .
O3 O 0.4469(14) 0.3641(15) 0.9976(16) 0.111(5) Uani 1 1 d . . . . .
O4 O 0.2806(18) -0.1142(17) 0.686(3) 0.155(9) Uani 1 1 d . . . . .
O5 O 0.1033(16) -0.2373(16) 0.720(3) 0.139(8) Uani 1 1 d . . . . .
O6 O 0.235(2) -0.240(2) 0.865(2) 0.169(10) Uani 1 1 d . . . . .
F1 F 0.3087(12) -0.2898(17) 0.635(3) 0.177(9) Uani 1 1 d . . . . .
F2 F 0.199(3) -0.278(4) 0.502(4) 0.29(2) Uani 1 1 d . . . . .
F3 F 0.1494(19) -0.3937(17) 0.664(5) 0.25(2) Uani 1 1 d . . . . .
S1 S 0.2060(5) -0.2113(5) 0.7329(8) 0.1072(19) Uani 1 1 d . . . . .
Re Re 0.43721(5) 0.25338(5) 0.73396(7) 0.0690(3) Uani 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
C1 O1 1.15(3) . ?
C1 Re 1.93(3) . ?
C2 O2 1.26(3) . ?
C2 Re 1.84(2) . ?
C3 O3 1.16(3) . ?
C3 Re 1.93(3) . ?
C4 F2 1.29(5) . ?
C4 F1 1.32(4) . ?
C4 F3 1.41(5) . ?
C4 S1 1.76(4) . ?
C11 N11 1.36(2) . ?
C11 C12 1.34(3) . ?
C11 C16 1.44(3) . ?
C12 C13 1.38(4) . ?
C13 C14 1.31(5) . ?
C14 C15 1.39(4) . ?
C15 N11 1.36(3) . ?
C16 C17 1.38(3) . ?
C16 N12 1.42(3) . ?
C17 C18 1.41(4) . ?
C18 C19 1.40(4) . ?
C19 C110 1.37(3) . ?
C21 N21 1.36(2) . ?
C21 C22 1.36(3) . ?
C22 C23 1.39(3) . ?
C23 C210 1.41(3) . ?
C23 C24 1.48(3) . ?
C24 C29 1.36(3) . ?
C24 C25 1.39(3) . ?
C25 C26 1.31(3) . ?
C26 C27 1.48(3) . ?
C27 C28 1.38(4) . ?
C28 C29 1.42(3) . ?
C29 N22 1.41(2) . ?
C110 N12 1.34(3) . ?
C210 N22 1.38(2) . ?
C210 C211 1.38(2) . ?
C211 N21 1.34(3) . ?
N11 Re 2.200(16) . ?
N12 Re 2.190(15) . ?
N21 Re 2.233(16) . ?
O4 S1 1.41(2) . ?
O5 S1 1.41(2) . ?
O6 S1 1.52(2) . ?

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 C1 Re 177.5(17) . . ?
O2 C2 Re 177.4(16) . . ?
O3 C3 Re 177(2) . . ?
F2 C4 F1 115(4) . . ?
F2 C4 F3 111(4) . . ?
F1 C4 F3 103(3) . . ?
F2 C4 S1 109(3) . . ?
F1 C4 S1 113(3) . . ?
F3 C4 S1 106(3) . . ?
N11 C11 C12 120(2) . . ?
N11 C11 C16 115.5(16) . . ?
C12 C11 C16 124(2) . . ?
C13 C12 C11 120(3) . . ?
C14 C13 C12 120(3) . . ?
C13 C14 C15 120(3) . . ?
N11 C15 C14 119(2) . . ?
C17 C16 N12 117(2) . . ?
C17 C16 C11 126(2) . . ?
N12 C16 C11 117.1(17) . . ?
C16 C17 C18 121(2) . . ?
C17 C18 C19 120(2) . . ?
C110 C19 C18 117(3) . . ?
N21 C21 C22 123.9(19) . . ?
C21 C22 C23 119.1(17) . . ?
C22 C23 C210 116.1(16) . . ?
C22 C23 C24 136.7(17) . . ?
C210 C23 C24 107.2(16) . . ?
C29 C24 C23 104.8(16) . . ?
C29 C24 C25 123(2) . . ?
C23 C24 C25 131.9(19) . . ?
C26 C25 C24 114(2) . . ?
C25 C26 C27 127(2) . . ?
C26 C27 C28 117(2) . . ?
C29 C28 C27 116(2) . . ?
C24 C29 C28 123(2) . . ?
C24 C29 N22 111.8(18) . . ?
C28 C29 N22 125(2) . . ?
N12 C110 C19 123(2) . . ?
N22 C210 C211 129.2(17) . . ?
N22 C210 C23 108.5(15) . . ?
C211 C210 C23 122.3(18) . . ?
N21 C211 C210 119.8(18) . . ?
C15 N11 C11 119.4(18) . . ?
C15 N11 Re 123.1(14) . . ?
C11 N11 Re 117.5(14) . . ?
C110 N12 C16 121.0(17) . . ?
C110 N12 Re 124.3(14) . . ?
C16 N12 Re 114.6(13) . . ?
C211 N21 C21 118.7(16) . . ?
C211 N21 Re 118.8(13) . . ?
C21 N21 Re 122.4(13) . . ?
C210 N22 C29 107.7(16) . . ?
O4 S1 O5 117.2(15) . . ?
O4 S1 O6 113.0(17) . . ?
O5 S1 O6 115.8(17) . . ?
O4 S1 C4 102.6(18) . . ?
O5 S1 C4 104.5(17) . . ?
O6 S1 C4 100.7(18) . . ?
C2 Re C1 88.2(8) . . ?
C2 Re C3 84.7(9) . . ?
C1 Re C3 88.2(9) . . ?
C2 Re N12 99.9(7) . . ?
C1 Re N12 93.6(7) . . ?
C3 Re N12 175.0(8) . . ?
C2 Re N11 174.5(7) . . ?
C1 Re N11 94.3(7) . . ?
C3 Re N11 100.2(8) . . ?
N12 Re N11 75.1(6) . . ?
C2 Re N21 92.6(7) . . ?
C1 Re N21 178.1(7) . . ?
C3 Re N21 93.5(7) . . ?
N12 Re N21 84.6(6) . . ?
N11 Re N21 84.7(6) . . ?

_refine_diff_density_max         1.444
_refine_diff_density_min         -1.038
_refine_diff_density_rms         0.128

_shelxl_version_number           2014-3


_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: Dichlomethane, iso-octane'
