# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2019

####################################################################### 
# 
# 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_LCU-105
_database_code_depnum_ccdc_archive 'CCDC 1918594'
loop_
_audit_author_name
_audit_author_address
'Li YunWu'
;Liaocheng University
China
;
_audit_update_record             
;
2019-05-25 deposited with the CCDC.	2019-08-23 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C36 H68 Co N6 O17'
_chemical_formula_weight         915.89

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'
Co Co 0.3494 0.9721 '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'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           13
_space_group_name_H-M_alt        'P 2/c'
_space_group_name_Hall           '-P 2yc'

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

_cell_length_a                   19.601(4)
_cell_length_b                   9.3797(19)
_cell_length_c                   18.630(4)
_cell_angle_alpha                90
_cell_angle_beta                 95.69(3)
_cell_angle_gamma                90
_cell_volume                     3408.3(12)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    26897
_cell_measurement_theta_min      3.090
_cell_measurement_theta_max      24.996

_exptl_crystal_description       block
_exptl_crystal_colour            purple
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_density_diffrn    1.113
_exptl_crystal_F_000             1144
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.180
_exptl_crystal_size_mid          0.160
_exptl_crystal_size_min          0.140
_exptl_absorpt_coefficient_mu    0.552
_shelx_estimated_absorpt_T_min   0.907
_shelx_estimated_absorpt_T_max   0.927
_exptl_absorpt_correction_type   'multi-scan(SADABS; Sheldrick,1996)'
_exptl_absorpt_correction_T_min  0.905
_exptl_absorpt_correction_T_max  0.926
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       ω
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            26897
_diffrn_reflns_av_unetI/netI     0.2056
_diffrn_reflns_av_R_equivalents  0.2573
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_theta_min         3.090
_diffrn_reflns_theta_max         24.996
_diffrn_reflns_theta_full        24.996
_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 0.998
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             5995
_reflns_number_gt                2730
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_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.
;

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_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)+(0.2000P)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         5995
_refine_ls_number_parameters     352
_refine_ls_number_restraints     116
_refine_ls_R_factor_all          0.2352
_refine_ls_R_factor_gt           0.1492
_refine_ls_wR_factor_ref         0.4167
_refine_ls_wR_factor_gt          0.3669
_refine_ls_goodness_of_fit_ref   1.130
_refine_ls_restrained_S_all      1.197
_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_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
C23 C 0.0310(11) -0.0792(16) 0.3710(7) 0.189(11) Uani 1 1 d D U . . .
C20 C 0.6421(13) 0.683(4) 0.572(2) 0.257(16) Uani 1 1 d D U . . .
N2 N 0.5777(17) 0.754(4) 0.5378(18) 0.326(18) Uani 1 1 d D U . . .
O7 O 0.1815(4) 0.7980(8) 0.5013(4) 0.050(2) Uani 1 1 d . . . . .
C16 C 0.2042(6) 0.6688(12) 0.5014(7) 0.052(3) Uani 1 1 d . . . . .
Co2 Co 0.24933(7) -0.05386(15) 0.50094(9) 0.0428(6) Uani 1 1 d . . . . .
O1 O 0.2883(4) -0.0468(9) 0.4102(5) 0.062(2) Uani 1 1 d . . . . .
O4 O 0.3202(4) 0.0672(8) 0.0822(4) 0.051(2) Uani 1 1 d . . . . .
O3 O 0.2365(4) 0.0427(10) 0.1500(5) 0.065(3) Uani 1 1 d . . . . .
O6 O 0.1112(4) 0.0773(9) 0.5402(6) 0.080(3) Uani 1 1 d . . . . .
O5 O 0.2098(4) 0.1345(8) 0.4983(5) 0.061(3) Uani 1 1 d . . . . .
C11 C 0.1545(5) 0.5535(12) 0.4982(7) 0.049(3) Uani 1 1 d . . . . .
C10 C 0.1763(6) 0.4155(12) 0.5046(7) 0.050(3) Uani 1 1 d . . . . .
H10 H 0.2236 0.3924 0.5059 0.060 Uiso 1 1 calc R U . . .
C12 C 0.0863(5) 0.5876(12) 0.4976(6) 0.043(3) Uani 1 1 d . . . . .
H12 H 0.0731 0.6850 0.4946 0.052 Uiso 1 1 calc R U . . .
C6 C 0.3233(6) -0.0162(12) 0.2697(6) 0.044(3) Uani 1 1 d . . . . .
H6 H 0.2756 -0.0137 0.2747 0.053 Uiso 1 1 calc R U . . .
C3 C 0.4616(5) -0.0258(14) 0.2519(7) 0.054(3) Uani 1 1 d . . . . .
C9 C 0.1284(6) 0.3121(11) 0.5091(7) 0.053(3) Uani 1 1 d . . . . .
C1 C 0.3695(5) -0.0477(13) 0.3270(7) 0.051(3) Uani 1 1 d . . . . .
C2 C 0.4410(6) -0.0577(15) 0.3214(8) 0.070(4) Uani 1 1 d . . . . .
H2 H 0.4727 -0.0839 0.3610 0.085 Uiso 1 1 calc R U . . .
C13 C 0.0359(5) 0.4837(12) 0.5011(7) 0.050(3) Uani 1 1 d . . . . .
C14 C 0.0599(5) 0.3428(10) 0.5088(7) 0.045(3) Uani 1 1 d . . . . .
H14 H 0.0283 0.2676 0.5139 0.054 Uiso 1 1 calc R U . . .
C5 C 0.3470(7) 0.0110(14) 0.2061(8) 0.061(4) Uani 1 1 d . . . . .
C4 C 0.4162(6) 0.0073(11) 0.1974(7) 0.044(3) Uani 1 1 d . . . . .
H4 H 0.4312 0.0289 0.1517 0.053 Uiso 1 1 calc R U . . .
C15 C 0.1501(6) 0.1609(13) 0.5164(8) 0.061(4) Uani 1 1 d . . . . .
C7 C 0.3471(6) -0.0811(14) 0.4004(8) 0.059(4) Uani 1 1 d . . . . .
O2 O 0.3858(4) -0.1466(10) 0.4430(5) 0.072(3) Uani 1 1 d . . . . .
C8 C 0.2959(5) 0.0447(12) 0.1422(7) 0.047(3) Uani 1 1 d . . . . .
O8 O 0.2655(4) 0.6449(10) 0.4988(6) 0.083(3) Uani 1 1 d . . . . .
O9 O -0.0284(6) 0.1434(15) 0.3613(5) 0.148(6) Uani 1 1 d D U . . .
C17 C 0.1606(10) 0.6487(19) 0.6727(9) 0.114(6) Uani 1 1 d D U . . .
C21 C 0.0746(9) 0.3087(13) 0.3175(4) 0.162(9) Uani 1 1 d D U . . .
C22 C 0.1482(8) 0.106(2) 0.3214(4) 0.232(13) Uani 1 1 d D U . . .
C24 C 0.0291(5) 0.0702(15) 0.3551(3) 0.218(8) Uani 1 1 d D U . . .
N1 N 0.2028(13) 0.518(3) 0.693(2) 0.322(18) Uani 1 1 d D U . . .
N3 N 0.0815(6) 0.1597(12) 0.33215(17) 0.219(8) Uani 1 1 d D U . . .
C19 C 0.5233(14) 0.696(5) 0.582(2) 0.33(2) Uani 1 1 d D U . . .
C18 C 0.148(2) 0.410(2) 0.706(2) 0.296(19) Uani 1 1 d D U . . .
O1W O 0.3733(3) 0.7197(6) 0.5430(3) 0.0183(14) Uani 1 1 d . . . . .
O2W O 0.8693(3) 0.1282(6) 0.3917(3) 0.0134(13) Uani 1 1 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
C23 C24 1.432(6) . ?
C20 N2 1.510(10) . ?
N2 C19 1.512(10) . ?
O7 C16 1.290(13) . ?
O7 Co2 1.924(7) 1_565 ?
C16 O8 1.228(12) . ?
C16 C11 1.452(15) . ?
Co2 O1 1.923(8) . ?
Co2 O7 1.923(7) 1_545 ?
Co2 O5 1.928(8) . ?
Co2 O4 1.955(8) 4_556 ?
O1 C7 1.229(13) . ?
O4 C8 1.274(14) . ?
O4 Co2 1.955(8) 4 ?
O3 C8 1.188(12) . ?
O6 C15 1.208(13) . ?
O5 C15 1.273(14) . ?
C11 C10 1.364(16) . ?
C11 C12 1.374(14) . ?
C10 C9 1.358(14) . ?
C10 H10 0.9500 . ?
C12 C13 1.394(14) . ?
C12 H12 0.9500 . ?
C6 C5 1.339(16) . ?
C6 C1 1.361(15) . ?
C6 H6 0.9500 . ?
C3 C4 1.320(15) . ?
C3 C2 1.425(18) . ?
C3 C3 1.51(2) 2_655 ?
C9 C14 1.372(14) . ?
C9 C15 1.483(15) . ?
C1 C2 1.418(15) . ?
C1 C7 1.510(18) . ?
C2 H2 0.9500 . ?
C13 C14 1.406(15) . ?
C13 C13 1.44(2) 3_566 ?
C14 H14 0.9500 . ?
C5 C4 1.382(16) . ?
C5 C8 1.512(17) . ?
C4 H4 0.9500 . ?
C7 O2 1.210(14) . ?
O9 C24 1.336(6) . ?
C17 N1 1.502(10) . ?
C21 N3 1.428(6) . ?
C22 N3 1.433(6) . ?
C24 N3 1.424(6) . ?
N1 C18 1.518(10) . ?

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
C20 N2 C19 102.5(9) . . ?
C16 O7 Co2 116.1(7) . 1_565 ?
O8 C16 O7 120.6(10) . . ?
O8 C16 C11 121.1(10) . . ?
O7 C16 C11 118.0(10) . . ?
O1 Co2 O7 111.3(4) . 1_545 ?
O1 Co2 O5 98.0(3) . . ?
O7 Co2 O5 112.7(3) 1_545 . ?
O1 Co2 O4 111.7(3) . 4_556 ?
O7 Co2 O4 112.9(3) 1_545 4_556 ?
O5 Co2 O4 109.3(4) . 4_556 ?
C7 O1 Co2 125.6(9) . . ?
C8 O4 Co2 111.7(7) . 4 ?
C15 O5 Co2 123.3(8) . . ?
C10 C11 C12 121.2(10) . . ?
C10 C11 C16 120.0(10) . . ?
C12 C11 C16 118.3(10) . . ?
C9 C10 C11 118.1(10) . . ?
C9 C10 H10 121.0 . . ?
C11 C10 H10 121.0 . . ?
C11 C12 C13 122.0(10) . . ?
C11 C12 H12 119.0 . . ?
C13 C12 H12 119.0 . . ?
C5 C6 C1 118.2(11) . . ?
C5 C6 H6 120.9 . . ?
C1 C6 H6 120.9 . . ?
C4 C3 C2 121.2(11) . . ?
C4 C3 C3 124.2(14) . 2_655 ?
C2 C3 C3 114.6(13) . 2_655 ?
C10 C9 C14 122.1(10) . . ?
C10 C9 C15 119.7(10) . . ?
C14 C9 C15 118.1(10) . . ?
C6 C1 C2 122.8(12) . . ?
C6 C1 C7 121.7(10) . . ?
C2 C1 C7 115.5(12) . . ?
C1 C2 C3 115.1(12) . . ?
C1 C2 H2 122.5 . . ?
C3 C2 H2 122.5 . . ?
C12 C13 C14 115.5(10) . . ?
C12 C13 C13 123.2(13) . 3_566 ?
C14 C13 C13 121.4(13) . 3_566 ?
C9 C14 C13 121.0(10) . . ?
C9 C14 H14 119.5 . . ?
C13 C14 H14 119.5 . . ?
C6 C5 C4 121.9(13) . . ?
C6 C5 C8 118.5(11) . . ?
C4 C5 C8 119.6(12) . . ?
C3 C4 C5 120.7(12) . . ?
C3 C4 H4 119.6 . . ?
C5 C4 H4 119.6 . . ?
O6 C15 O5 126.9(12) . . ?
O6 C15 C9 118.0(12) . . ?
O5 C15 C9 115.1(11) . . ?
O2 C7 O1 124.9(13) . . ?
O2 C7 C1 118.7(11) . . ?
O1 C7 C1 116.2(12) . . ?
O3 C8 O4 124.4(12) . . ?
O3 C8 C5 118.8(12) . . ?
O4 C8 C5 116.7(10) . . ?
O9 C24 N3 111.3(11) . . ?
O9 C24 C23 119.3(9) . . ?
N3 C24 C23 129.4(13) . . ?
C17 N1 C18 101.7(9) . . ?
C24 N3 C21 125.2(12) . . ?
C24 N3 C22 122.1(12) . . ?
C21 N3 C22 112.7(8) . . ?

_refine_diff_density_max         0.950
_refine_diff_density_min         -0.608
_refine_diff_density_rms         0.145

# 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 0.115 0.104 0.698 7 1 ' '
2 0.885 0.104 0.802 6 1 ' '
3 0.500 0.435 0.750 425 86 ' '
4 0.500 0.565 0.250 426 8 ' '
5 0.000 0.383 0.750 34 7 ' '
6 0.000 0.616 0.250 34 7 ' '
7 0.115 0.896 0.198 7 1 ' '
8 0.885 0.896 0.302 7 1 ' '
_platon_squeeze_details          
;

In order to subtract the contribution from the disordered solvent molecules,
the SQUEEZE command was applied, which gave a new HKL file.
The number of located electrons, 174 in two voids per unit cell,
is included in the formula, formula weight, calculated density, and F(000).
These residual electron density were assigned to three DMAC and three water.
So SQUEEZE removed three DMAC and three water per unit cell.
So the tentative formula for this compound is presented as in the text.
See refs. (a) O. V. Dolomanov, D. B. Cordes, N. R. Champness, A. J. Blake,
L. R. Hanton, G. B. Jameson, M. Schroder and C. Wilson. Chem. Commun.,
2004, 642; (b) Y. Du, A. L. Thompson and D. O. Hare.Chem. Commun. 2008, 5987;
(c) Y. F. Bi, X. T. Wang, W. P. Liao, X. F. Wang, X. W. Wang, H. J. Zhang,
and S. Gao, J. Am. Chem. Soc. 2009, 131, 11650.

PLAT430_ALERT_2_A Short Inter D...A Contact  O1W .. O2 .. 2.28 Ang  
PLAT430_ALERT_2_A Short Inter D...A Contact  O1W .. O8 .. 2.30 Ang  
PLAT430_ALERT_2_A Short Inter D...A Contact  O1W .. O4 .. 2.40 Ang  
PLAT430_ALERT_2_A Short Inter D...A Contact  O2W .. O9 .. 2.14 Ang  
PLAT430_ALERT_2_A Short Inter D...A Contact  O2W .. O3 .. 2.29 Ang  
PLAT430_ALERT_2_A Short Inter D...A Contact  O2W .. O6 .. 2.32 Ang  
PLAT430_ALERT_2_A Short Inter D...A Contact  O2W .. O7 .. 2.42 Ang  
These alerts arise because of missing water molecules in the model resulting
in apparent large structural voids and missing H-bonds.

RINTA01_ALERT_3_A  The value of Rint is greater than 0.25  Rint given   0.257
PLAT020_ALERT_3_A The Value of Rint is Greater Than 0.12 ....... 0.257 Report
Due to the limited crystal quality, the more solvents, and the relatively 
high ?°restraints?+- in the both compounds, which all result the higher R value.
;



####################################################################### 
# 
# 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_LCU-106
_database_code_depnum_ccdc_archive 'CCDC 1918595'
loop_
_audit_author_name
_audit_author_address
'Li YunWu'
;Liaocheng University
China
;
_audit_update_record             
;
2019-05-25 deposited with the CCDC.	2019-08-23 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C48 H62 Co N8 Na2 O18'
_chemical_formula_weight         1057.65

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 '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 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Co Co -2.3653 3.6143 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Na Na 0.1353 0.1239 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_H-M_alt        'C 2/c'
_space_group_name_Hall           '-C 2yc'

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

_cell_length_a                   17.6254(16)
_cell_length_b                   19.9755(15)
_cell_length_c                   15.3066(11)
_cell_angle_alpha                90
_cell_angle_beta                 104.504(8)
_cell_angle_gamma                90
_cell_volume                     5217.3(7)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    16997
_cell_measurement_theta_min      3.406
_cell_measurement_theta_max      71.217

_exptl_crystal_description       block
_exptl_crystal_colour            purple
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_density_diffrn    1.346
_exptl_crystal_F_000             2156
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.180
_exptl_crystal_size_mid          0.160
_exptl_crystal_size_min          0.140
_exptl_absorpt_coefficient_mu    3.400
_shelx_estimated_absorpt_T_min   0.580
_shelx_estimated_absorpt_T_max   0.648
_exptl_absorpt_correction_type   'multi-scan(SADABS; Sheldrick,1996)'
_exptl_absorpt_correction_T_min  0.560
_exptl_absorpt_correction_T_max  0.614
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_type           CuK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       ω
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            16997
_diffrn_reflns_av_unetI/netI     0.0579
_diffrn_reflns_av_R_equivalents  0.0540
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_theta_min         3.406
_diffrn_reflns_theta_max         71.217
_diffrn_reflns_theta_full        67.684
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             5028
_reflns_number_gt                4091
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_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       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_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)+(0.2800P)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         5028
_refine_ls_number_parameters     332
_refine_ls_number_restraints     93
_refine_ls_R_factor_all          0.1261
_refine_ls_R_factor_gt           0.1128
_refine_ls_wR_factor_ref         0.3526
_refine_ls_wR_factor_gt          0.3335
_refine_ls_goodness_of_fit_ref   1.105
_refine_ls_restrained_S_all      1.386
_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_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
C19 C 0.7712(9) 0.8421(10) 0.1560(12) 0.37(2) Uani 1 1 d D U . . .
C20 C 0.8350(13) 0.9277(5) 0.0955(7) 0.289(18) Uani 1 1 d D U . . .
C17 C 0.9600(6) 0.8957(5) 0.5730(6) 0.070(3) Uani 1 1 d . . . . .
H17A H 0.9189 0.9212 0.5910 0.106 Uiso 1 1 calc R U . . .
H17B H 1.0031 0.9258 0.5696 0.106 Uiso 1 1 calc R U . . .
H17C H 0.9796 0.8605 0.6176 0.106 Uiso 1 1 calc R U . . .
Co1 Co 0.5000 0.23684(5) -0.2500 0.0152(4) Uani 1 2 d S T P . .
O1 O 0.5369(2) 0.18692(18) -0.1356(2) 0.0223(8) Uani 1 1 d . . . . .
O7 O 0.9188(2) 0.19674(18) 0.2561(3) 0.0243(8) Uani 1 1 d . . . . .
O8 O 0.8126(2) 0.2541(2) 0.1800(3) 0.0284(9) Uani 1 1 d . . . . .
O2 O 0.4162(2) 0.1454(2) -0.1715(3) 0.0259(9) Uani 1 1 d . . . . .
O4 O 0.4140(2) -0.0386(2) 0.1629(3) 0.0283(9) Uani 1 1 d . . . . .
O3 O 0.3254(2) 0.0088(2) 0.0510(3) 0.0345(10) Uani 1 1 d . . . . .
O6 O 0.8826(3) -0.0287(3) 0.3735(5) 0.0651(19) Uani 1 1 d . . . . .
O5 O 0.7617(3) -0.0627(2) 0.3694(3) 0.0385(11) Uani 1 1 d . . . . .
C1 C 0.4977(3) 0.1173(3) -0.0282(3) 0.0209(11) Uani 1 1 d . . . . .
C13 C 0.4809(3) 0.1517(2) -0.1188(3) 0.0204(10) Uani 1 1 d . . . . .
C16 C 0.8452(3) 0.2030(3) 0.2181(3) 0.0205(10) Uani 1 1 d . . . . .
C7 C 0.6722(3) 0.0847(3) 0.1690(4) 0.0221(11) Uani 1 1 d . . . . .
C6 C 0.4393(3) 0.0801(3) -0.0053(3) 0.0207(10) Uani 1 1 d . . . . .
H6 H 0.3881 0.0787 -0.0444 0.025 Uiso 1 1 calc R U . . .
C2 C 0.5728(3) 0.1189(2) 0.0289(4) 0.0207(10) Uani 1 1 d . . . . .
H2 H 0.6124 0.1446 0.0126 0.025 Uiso 1 1 calc R U . . .
C8 C 0.7198(3) 0.1406(2) 0.1702(3) 0.0209(11) Uani 1 1 d . . . . .
H8 H 0.6990 0.1786 0.1350 0.025 Uiso 1 1 calc R U . . .
C14 C 0.3971(3) 0.0011(3) 0.1011(4) 0.0226(11) Uani 1 1 d . . . . .
C3 C 0.5907(3) 0.0831(2) 0.1102(4) 0.0213(11) Uani 1 1 d . . . . .
C9 C 0.7961(3) 0.1421(3) 0.2212(4) 0.0222(11) Uani 1 1 d . . . . .
C5 C 0.4566(3) 0.0448(3) 0.0761(4) 0.0219(11) Uani 1 1 d . . . . .
C4 C 0.5322(3) 0.0455(3) 0.1329(3) 0.0210(10) Uani 1 1 d . . . . .
H4 H 0.5437 0.0202 0.1871 0.025 Uiso 1 1 calc R U . . .
C11 C 0.7790(4) 0.0329(3) 0.2798(5) 0.0338(14) Uani 1 1 d . . . . .
C10 C 0.8266(3) 0.0869(3) 0.2753(4) 0.0271(12) Uani 1 1 d . . . . .
H10 H 0.8799 0.0866 0.3086 0.032 Uiso 1 1 calc R U . . .
C12 C 0.7025(3) 0.0309(3) 0.2259(4) 0.0304(13) Uani 1 1 d . . . . .
H12 H 0.6707 -0.0072 0.2277 0.036 Uiso 1 1 calc R U . . .
C15 C 0.8105(4) -0.0237(3) 0.3468(5) 0.0368(14) Uani 1 1 d . . . . .
Na1 Na 0.84548(14) 0.36348(10) 0.18253(15) 0.0284(6) Uani 1 1 d . . . . .
N1 N 0.9276(5) 0.8652(4) 0.4844(6) 0.070(2) Uani 1 1 d . . . . .
H1A H 0.9664 0.8432 0.4665 0.084 Uiso 1 1 calc R U . . .
H1B H 0.9087 0.8978 0.4433 0.084 Uiso 1 1 calc R U . . .
C18 C 0.8579(7) 0.8129(5) 0.4877(7) 0.077(3) Uani 1 1 d . . . . .
H18A H 0.8762 0.7814 0.5375 0.115 Uiso 1 1 calc R U . . .
H18B H 0.8428 0.7883 0.4306 0.115 Uiso 1 1 calc R U . . .
H18C H 0.8125 0.8376 0.4971 0.115 Uiso 1 1 calc R U . . .
O9 O 0.9065(15) 0.7931(10) 0.2560(11) 0.64(3) Uani 1 1 d D U . . .
N2 N 0.8485(7) 0.8703(3) 0.1575(3) 0.51(2) Uani 1 1 d D U . . .
C21 C 0.9253(10) 0.8468(10) 0.2100(10) 0.52(2) Uani 1 1 d D U . . .
N3 N 0.9468(18) 0.7636(17) 0.086(3) 0.305(17) Uani 1 1 d D U . . .
C22 C 0.9006(17) 0.7151(12) 0.1238(19) 0.183(9) Uani 1 1 d D U . . .
C23 C 0.895(3) 0.8214(15) 0.057(3) 0.34(2) 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
C19 N2 1.468(6) . ?
C20 N2 1.468(6) . ?
C17 N1 1.466(13) . ?
Co1 O7 1.971(4) 7_655 ?
Co1 O7 1.971(4) 8_455 ?
Co1 O1 1.978(4) . ?
Co1 O1 1.978(4) 2_654 ?
Co1 Na1 3.330(2) 8_455 ?
Co1 Na1 3.330(2) 7_655 ?
O1 C13 1.289(6) . ?
O1 Na1 2.564(5) 7_655 ?
O7 C16 1.288(6) . ?
O7 Co1 1.971(4) 7_655 ?
O8 C16 1.243(7) . ?
O8 Na1 2.258(4) . ?
O2 C13 1.227(7) . ?
O2 Na1 2.276(4) 8_455 ?
O4 C14 1.212(7) . ?
O4 Na1 2.358(4) 3_445 ?
O3 C14 1.314(7) . ?
O6 C15 1.238(8) . ?
O5 C15 1.272(8) . ?
O5 Na1 2.370(5) 4_645 ?
C1 C6 1.385(7) . ?
C1 C2 1.391(7) . ?
C1 C13 1.508(7) . ?
C16 C9 1.500(7) . ?
C7 C8 1.395(7) . ?
C7 C12 1.401(7) . ?
C7 C3 1.493(7) . ?
C6 C5 1.399(7) . ?
C2 C3 1.401(7) . ?
C8 C9 1.376(8) . ?
C14 C5 1.485(7) . ?
C3 C4 1.387(7) . ?
C9 C10 1.403(8) . ?
C5 C4 1.397(8) . ?
C11 C10 1.378(8) . ?
C11 C12 1.394(8) . ?
C11 C15 1.534(8) . ?
Na1 O2 2.276(4) 8_556 ?
Na1 O4 2.358(4) 3 ?
Na1 O5 2.371(5) 4_655 ?
Na1 O1 2.564(5) 7_655 ?
Na1 Co1 3.330(2) 7_655 ?
N1 C18 1.623(14) . ?
O9 C21 1.369(7) . ?
N2 C21 1.468(7) . ?
N3 C23 1.469(7) . ?
N3 C22 1.472(7) . ?

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
O7 Co1 O7 95.4(2) 7_655 8_455 ?
O7 Co1 O1 107.44(15) 7_655 . ?
O7 Co1 O1 112.27(16) 8_455 . ?
O7 Co1 O1 112.27(16) 7_655 2_654 ?
O7 Co1 O1 107.44(15) 8_455 2_654 ?
O1 Co1 O1 119.4(2) . 2_654 ?
O7 Co1 Na1 159.65(12) 7_655 8_455 ?
O7 Co1 Na1 82.67(12) 8_455 8_455 ?
O1 Co1 Na1 91.89(11) . 8_455 ?
O1 Co1 Na1 50.23(12) 2_654 8_455 ?
O7 Co1 Na1 82.67(12) 7_655 7_655 ?
O7 Co1 Na1 159.65(12) 8_455 7_655 ?
O1 Co1 Na1 50.23(12) . 7_655 ?
O1 Co1 Na1 91.89(11) 2_654 7_655 ?
Na1 Co1 Na1 106.01(8) 8_455 7_655 ?
C13 O1 Co1 110.7(3) . . ?
C13 O1 Na1 123.7(3) . 7_655 ?
Co1 O1 Na1 93.42(15) . 7_655 ?
C16 O7 Co1 125.1(3) . 7_655 ?
C16 O8 Na1 134.4(4) . . ?
C13 O2 Na1 147.6(4) . 8_455 ?
C14 O4 Na1 127.4(4) . 3_445 ?
C15 O5 Na1 145.7(5) . 4_645 ?
C6 C1 C2 120.2(5) . . ?
C6 C1 C13 119.3(5) . . ?
C2 C1 C13 120.3(5) . . ?
O2 C13 O1 123.7(5) . . ?
O2 C13 C1 119.7(5) . . ?
O1 C13 C1 116.6(4) . . ?
O8 C16 O7 125.9(5) . . ?
O8 C16 C9 118.6(5) . . ?
O7 C16 C9 115.5(5) . . ?
C8 C7 C12 118.1(5) . . ?
C8 C7 C3 120.7(5) . . ?
C12 C7 C3 121.2(5) . . ?
C1 C6 C5 119.1(5) . . ?
C1 C2 C3 120.9(5) . . ?
C9 C8 C7 121.6(5) . . ?
O4 C14 O3 123.0(5) . . ?
O4 C14 C5 122.2(5) . . ?
O3 C14 C5 114.8(5) . . ?
C4 C3 C2 118.8(5) . . ?
C4 C3 C7 121.6(5) . . ?
C2 C3 C7 119.6(5) . . ?
C8 C9 C10 119.5(5) . . ?
C8 C9 C16 119.3(5) . . ?
C10 C9 C16 121.2(5) . . ?
C4 C5 C6 120.6(5) . . ?
C4 C5 C14 118.1(5) . . ?
C6 C5 C14 121.0(5) . . ?
C3 C4 C5 120.2(5) . . ?
C10 C11 C12 120.3(5) . . ?
C10 C11 C15 119.1(5) . . ?
C12 C11 C15 120.6(5) . . ?
C11 C10 C9 119.7(5) . . ?
C11 C12 C7 120.5(5) . . ?
O6 C15 O5 124.6(6) . . ?
O6 C15 C11 116.8(6) . . ?
O5 C15 C11 118.6(5) . . ?
O8 Na1 O2 90.96(17) . 8_556 ?
O8 Na1 O4 159.72(19) . 3 ?
O2 Na1 O4 91.02(17) 8_556 3 ?
O8 Na1 O5 114.59(18) . 4_655 ?
O2 Na1 O5 124.91(18) 8_556 4_655 ?
O4 Na1 O5 80.34(17) 3 4_655 ?
O8 Na1 O1 80.65(15) . 7_655 ?
O2 Na1 O1 87.79(15) 8_556 7_655 ?
O4 Na1 O1 79.26(15) 3 7_655 ?
O5 Na1 O1 141.49(17) 4_655 7_655 ?
O8 Na1 Co1 67.04(12) . 7_655 ?
O2 Na1 Co1 56.24(11) 8_556 7_655 ?
O4 Na1 Co1 97.66(13) 3 7_655 ?
O5 Na1 Co1 177.60(15) 4_655 7_655 ?
O1 Na1 Co1 36.36(8) 7_655 7_655 ?
C17 N1 C18 111.1(8) . . ?
C21 N2 C19 127.7(12) . . ?
C21 N2 C20 125.5(13) . . ?
C19 N2 C20 106.9(7) . . ?
O9 C21 N2 102.9(13) . . ?
C23 N3 C22 105.9(9) . . ?

_refine_diff_density_max         1.752
_refine_diff_density_min         -0.992
_refine_diff_density_rms         0.175

