# Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A.
# This journal is © The Royal Society of Chemistry 2017

####################################################################### 
# 
# 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_4_sq
_database_code_depnum_ccdc_archive 'CCDC 1533801'
_audit_update_record             
;
2017-02-23 deposited with the CCDC.
2017-05-14 downloaded from the CCDC.
;
_audit_creation_date             2017-02-12
# end Validation Reply Form
_audit_creation_method           
;
Olex2 1.2
(compiled 2017.01.04 svn.r3372 for OlexSys, GUI svn.r5292)
;
_shelx_SHELXL_version_number     2016/6
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         '0.25(C144 H108 Co12 N16 O36)'
_chemical_formula_sum            'C41 H38 Co3 N5 O10'
_chemical_formula_weight         937.55
_chemical_melting_point          ?
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'
Co Co 0.3494 0.9721 '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'
H H 0.0000 0.0000 '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      hexagonal
_space_group_IT_number           193
_space_group_name_H-M_alt        'P 63/m c m'
_space_group_name_Hall           '-P 6c 2'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-y, x-y, z'
'-x+y, -x, z'
'-x, -y, z+1/2'
'y, -x+y, z+1/2'
'x-y, x, z+1/2'
'y, x, -z+1/2'
'x-y, -y, -z+1/2'
'-x, -x+y, -z+1/2'
'-y, -x, -z'
'-x+y, y, -z'
'x, x-y, -z'
'-x, -y, -z'
'y, -x+y, -z'
'x-y, x, -z'
'x, y, -z-1/2'
'-y, x-y, -z-1/2'
'-x+y, -x, -z-1/2'
'-y, -x, z-1/2'
'-x+y, y, z-1/2'
'x, x-y, z-1/2'
'y, x, z'
'x-y, -y, z'
'-x, -x+y, z'

_cell_length_a                   17.7662(12)
_cell_length_b                   17.7662(12)
_cell_length_c                   26.797(2)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     7324.9(11)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    39887
_cell_measurement_temperature    296
_cell_measurement_theta_max      24.996
_cell_measurement_theta_min      2.016
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    0.707
_exptl_absorpt_correction_T_max  0.856
_exptl_absorpt_correction_T_min  0.844
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            violet
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    0.850
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             1920
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.22
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.1187
_diffrn_reflns_av_unetI/netI     0.0393
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            39887
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        24.996
_diffrn_reflns_theta_max         24.996
_diffrn_reflns_theta_min         2.016
_diffrn_ambient_temperature      296.15
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       ?
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   ?
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                1684
_reflns_number_total             2326
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _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       ?
_computing_data_collection       ?
_computing_data_reduction        ?
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_refine_diff_density_max         0.982
_refine_diff_density_min         -0.869
_refine_diff_density_rms         0.102
_refine_ls_extinction_coef       0.0008(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.078
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     88
_refine_ls_number_reflns         2326
_refine_ls_number_restraints     120
_refine_ls_R_factor_all          0.0920
_refine_ls_R_factor_gt           0.0669
_refine_ls_restrained_S_all      1.162
_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)+(0.1163P)²+17.0953P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1847
_refine_ls_wR_factor_ref         0.2094
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All O(H) groups
2. Uiso/Uaniso restraints and constraints
C5 \\sim C4 \\sim C3 \\sim C2 \\sim C1 \\sim C8 \\sim C6 \\sim C7 \\sim N2
\\sim N1: within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.03
Uanis(C6) \\sim Ueq, Uanis(C7) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.001
3.a Ternary CH refined with riding coordinates:
 O2(H2)
3.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C2(H2A), C6(H6), C7(H7)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_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
Co1 Co 0.12895(4) 1.000000 0.53892(3) 0.0222(3) Uani 1 2 d S T P . .
O2 O 0.000000 0.9019(2) 0.53888(12) 0.0143(8) Uani 1 2 d S T P . .
H2 H 0.000000 0.853779 0.556761 0.017 Uiso 1 2 calc RS T P . .
O1 O 0.1670(2) 0.9084(2) 0.53329(12) 0.0362(8) Uani 1 1 d . . . . .
N2 N 0.1438(3) 1.000000 0.6180(2) 0.0397(14) Uani 1 2 d S TU P . .
N1 N 0.333333 0.666667 0.500000 0.051(2) Uani 1 6 d S TU P . .
C5 C 0.1477(2) 0.8523(2) 0.500000 0.0343(14) Uani 1 2 d S TU P . .
C4 C 0.1966(2) 0.8034(2) 0.500000 0.0400(15) Uani 1 2 d S TU P . .
C3 C 0.1700(3) 0.7304(4) 0.4706(2) 0.0472(12) Uani 1 1 d . U . . .
H3 H 0.121237 0.711601 0.450437 0.057 Uiso 1 1 calc R . . . .
C2 C 0.2135(4) 0.6851(4) 0.4706(2) 0.0519(13) Uani 1 1 d . U . . .
H2A H 0.193587 0.635808 0.450789 0.062 Uiso 1 1 calc R . . . .
C1 C 0.2878(2) 0.7122(2) 0.500000 0.0474(16) Uani 1 2 d S TU P . .
C8 C 0.1522(5) 1.000000 0.7228(3) 0.0493(18) Uani 1 2 d S TU P . .
C6 C 0.1125(6) 0.9309(5) 0.6437(3) 0.093(2) Uani 1 1 d . U . . .
H6 H 0.085711 0.878438 0.626495 0.112 Uiso 1 1 calc R . . . .
C7 C 0.1149(6) 0.9270(6) 0.6954(3) 0.096(2) Uani 1 1 d . U . . .
H7 H 0.090310 0.873228 0.711207 0.115 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
Co1 O2 2.0720(12) . ?
Co1 O2 2.0720(12) 2_675 ?
Co1 O2 2.156(3) 15_666 ?
Co1 O1 2.056(3) 23_675 ?
Co1 O1 2.056(3) . ?
Co1 N2 2.136(6) . ?
O2 H2 0.9800 . ?
O1 C5 1.251(4) . ?
N2 C6 1.268(8) . ?
N2 C6 1.268(8) 23_675 ?
N1 C1 1.401(7) . ?
N1 C1 1.402(7) 3_565 ?
N1 C1 1.402(7) 2_665 ?
C5 C4 1.505(9) . ?
C4 C3 1.383(6) . ?
C4 C3 1.383(6) 10_666 ?
C3 H3 0.9300 . ?
C3 C2 1.366(7) . ?
C2 H2A 0.9300 . ?
C2 C1 1.400(6) . ?
C8 C8 1.456(14) 16_557 ?
C8 C7 1.342(9) 23_675 ?
C8 C7 1.342(9) . ?
C6 H6 0.9300 . ?
C6 C7 1.389(10) . ?
C7 H7 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
O2 Co1 O2 93.5(2) . 2_675 ?
O2 Co1 O2 79.94(14) 2_675 15_666 ?
O2 Co1 O2 79.94(14) . 15_666 ?
O2 Co1 N2 94.91(15) 2_675 . ?
O2 Co1 N2 94.91(15) . . ?
O1 Co1 O2 174.60(14) 23_675 . ?
O1 Co1 O2 174.60(14) . 2_675 ?
O1 Co1 O2 96.50(12) . 15_666 ?
O1 Co1 O2 96.49(12) 23_675 15_666 ?
O1 Co1 O2 89.81(15) 23_675 2_675 ?
O1 Co1 O2 89.81(15) . . ?
O1 Co1 O1 86.6(2) . 23_675 ?
O1 Co1 N2 89.03(15) 23_675 . ?
O1 Co1 N2 89.03(15) . . ?
N2 Co1 O2 172.4(2) . 15_666 ?
Co1 O2 Co1 94.24(10) 3_465 14_456 ?
Co1 O2 Co1 146.5(2) . 3_465 ?
Co1 O2 Co1 94.24(10) . 14_456 ?
Co1 O2 H2 104.6 . . ?
Co1 O2 H2 104.6 3_465 . ?
Co1 O2 H2 104.6 14_456 . ?
C5 O1 Co1 128.0(3) . . ?
C6 N2 Co1 123.0(4) . . ?
C6 N2 Co1 123.0(4) 23_675 . ?
C6 N2 C6 113.9(8) 23_675 . ?
C1 N1 C1 120.000(2) . 3_565 ?
C1 N1 C1 120.000(1) . 2_665 ?
C1 N1 C1 120.000(1) 3_565 2_665 ?
O1 C5 O1 126.1(6) 10_666 . ?
O1 C5 C4 116.9(3) . . ?
O1 C5 C4 116.9(3) 10_666 . ?
C3 C4 C5 121.1(3) . . ?
C3 C4 C5 121.1(3) 10_666 . ?
C3 C4 C3 117.9(6) . 10_666 ?
C4 C3 H3 119.2 . . ?
C2 C3 C4 121.6(5) . . ?
C2 C3 H3 119.2 . . ?
C3 C2 H2A 119.6 . . ?
C3 C2 C1 120.8(5) . . ?
C1 C2 H2A 119.6 . . ?
C2 C1 N1 121.3(3) 10_666 . ?
C2 C1 N1 121.3(3) . . ?
C2 C1 C2 117.5(7) . 10_666 ?
C7 C8 C8 123.2(4) . 16_557 ?
C7 C8 C8 123.2(4) 23_675 16_557 ?
C7 C8 C7 113.6(9) . 23_675 ?
N2 C6 H6 117.2 . . ?
N2 C6 C7 125.5(8) . . ?
C7 C6 H6 117.2 . . ?
C8 C7 C6 120.7(8) . . ?
C8 C7 H7 119.7 . . ?
C6 C7 H7 119.7 . . ?

_olex2_submission_special_instructions 'No special instructions were received'
# start Validation Reply Form
_vrf_CHEMW03_4_sq                
;
PROBLEM: ALERT: The ratio of given/expected molecular weight as
RESPONSE: Disordered solvent was accounted for using SQUEEZE procedure
from Platon software (Spek, 1990) but added to the total content in
order to obtain more accurate value for density, absorption coefficient
and F000.
;
