# Electronic Supplementary Material (ESI) for Dalton Transactions.
# 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_1-298K
_database_code_depnum_ccdc_archive 'CCDC 1545589'
_audit_update_record             
;
2017-04-24 deposited with the CCDC.
2017-11-14 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         
'6(C Ca0.17 Co0.17 N), 0.167(H6 N6), C H4 N2, H'
_chemical_formula_sum            'C7 H6 Ca Co N9'
_chemical_formula_weight         315.22

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'
Ca Ca 0.2262 0.3064 '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'

_space_group_crystal_system      hexagonal
_space_group_IT_number           194
_space_group_name_H-M_alt        'P 63/m m c'
_space_group_name_Hall           '-P 6c 2c'

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

_cell_length_a                   7.5725(11)
_cell_length_b                   7.5725(11)
_cell_length_c                   13.338(3)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     662.3(2)
_cell_formula_units_Z            2
_cell_measurement_temperature    298(2)
_cell_measurement_reflns_used    510
_cell_measurement_theta_min      1.9545
_cell_measurement_theta_max      27.4888

_exptl_crystal_description       block
_exptl_crystal_colour            pale-yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.580
_exptl_crystal_F_000             414
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          ?
_exptl_crystal_size_mid          ?
_exptl_crystal_size_min          ?
_exptl_absorpt_coefficient_mu    1.679
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   ?
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      298(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Saturn724+ (4x4 bin mode)'
_diffrn_measurement_method       CCD_Profile_fitting
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            4347
_diffrn_reflns_av_unetI/netI     0.0160
_diffrn_reflns_av_R_equivalents  0.0362
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_theta_min         3.055
_diffrn_reflns_theta_max         27.472
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measured_fraction_theta_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_point_group_measured_fraction_full 0.996
_reflns_number_total             324
_reflns_number_gt                318
_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    ?
_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)+(0.1110P)²+1.6837P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   .
_refine_ls_hydrogen_treatment    undef
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         324
_refine_ls_number_parameters     29
_refine_ls_number_restraints     34
_refine_ls_R_factor_all          0.0534
_refine_ls_R_factor_gt           0.0531
_refine_ls_wR_factor_ref         0.1891
_refine_ls_wR_factor_gt          0.1888
_refine_ls_goodness_of_fit_ref   1.326
_refine_ls_restrained_S_all      1.298
_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
Co1 Co 0.0000 1.0000 0.0000 0.0116(6) Uani 1 12 d S T P . .
Ca1 Ca 0.3333 0.6667 0.2500 0.0136(7) Uani 1 12 d S T P . .
C1 C 0.1180(4) 0.8820(4) 0.0820(3) 0.0191(11) Uani 1 2 d S T P . .
N1 N 0.1893(4) 0.8107(4) 0.1315(3) 0.0302(12) Uani 1 2 d S T P . .
N2 N 0.685(5) 0.474(3) 0.2500 0.036(5) Uani 0.1667 2 d DS TU P . .
N3 N 0.6667 0.3333 0.0796(9) 0.060(3) Uani 1 6 d DS TU P . .
C2 C 0.6667 0.3333 0.1814(10) 0.046(4) Uani 0.5 6 d DS TU P . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Co1 0.0134(7) 0.0134(7) 0.0079(9) 0.000 0.000 0.0067(4)
Ca1 0.0163(9) 0.0163(9) 0.0082(11) 0.000 0.000 0.0081(4)
C1 0.0223(18) 0.0223(18) 0.014(2) 0.0001(9) -0.0001(9) 0.012(2)
N1 0.038(2) 0.038(2) 0.025(2) 0.0035(10) -0.0035(10) 0.027(2)
N2 0.042(8) 0.038(7) 0.040(8) 0.000 0.000 0.029(6)
N3 0.066(5) 0.066(5) 0.047(6) 0.000 0.000 0.033(2)
C2 0.047(5) 0.047(5) 0.043(7) 0.000 0.000 0.024(3)

_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 C1 1.895(5) 13_575 ?
Co1 C1 1.895(5) 14_455 ?
Co1 C1 1.895(5) 2_675 ?
Co1 C1 1.895(5) 15_665 ?
Co1 C1 1.895(5) 3_465 ?
Co1 C1 1.895(5) . ?
Ca1 N1 2.463(5) . ?
Ca1 N1 2.463(5) 16_556 ?
Ca1 N1 2.463(5) 18_566 ?
Ca1 N1 2.463(5) 2_665 ?
Ca1 N1 2.463(5) 3_565 ?
Ca1 N1 2.463(5) 17_666 ?
C1 N1 1.145(7) . ?
N2 N2 0.79(6) 20_655 ?
N2 N2 1.20(6) 19_665 ?
N2 C2 1.357(10) 16_556 ?
N2 C2 1.357(10) . ?
N2 N2 1.74(3) 2_655 ?
N2 N2 1.74(3) 3_665 ?
N3 C2 1.357(10) . ?
C2 N2 1.357(10) 3_665 ?
C2 N2 1.357(10) 21 ?
C2 N2 1.357(10) 20_655 ?
C2 N2 1.357(10) 2_655 ?
C2 N2 1.357(10) 19_665 ?
C2 C2 1.83(3) 16_556 ?

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 Co1 C1 90.0(2) 13_575 14_455 ?
C1 Co1 C1 90.0(2) 13_575 2_675 ?
C1 Co1 C1 180.0(2) 14_455 2_675 ?
C1 Co1 C1 90.0(2) 13_575 15_665 ?
C1 Co1 C1 90.0(2) 14_455 15_665 ?
C1 Co1 C1 90.0(2) 2_675 15_665 ?
C1 Co1 C1 90.0(2) 13_575 3_465 ?
C1 Co1 C1 90.0(2) 14_455 3_465 ?
C1 Co1 C1 90.0(2) 2_675 3_465 ?
C1 Co1 C1 180.00(18) 15_665 3_465 ?
C1 Co1 C1 180.0(2) 13_575 . ?
C1 Co1 C1 90.0(2) 14_455 . ?
C1 Co1 C1 90.0(2) 2_675 . ?
C1 Co1 C1 90.0(2) 15_665 . ?
C1 Co1 C1 90.0(2) 3_465 . ?
N1 Ca1 N1 79.8(2) . 16_556 ?
N1 Ca1 N1 134.89(8) . 18_566 ?
N1 Ca1 N1 83.27(17) 16_556 18_566 ?
N1 Ca1 N1 83.27(17) . 2_665 ?
N1 Ca1 N1 134.89(8) 16_556 2_665 ?
N1 Ca1 N1 134.89(8) 18_566 2_665 ?
N1 Ca1 N1 83.27(17) . 3_565 ?
N1 Ca1 N1 134.89(8) 16_556 3_565 ?
N1 Ca1 N1 79.8(2) 18_566 3_565 ?
N1 Ca1 N1 83.27(17) 2_665 3_565 ?
N1 Ca1 N1 134.89(8) . 17_666 ?
N1 Ca1 N1 83.27(17) 16_556 17_666 ?
N1 Ca1 N1 83.27(17) 18_566 17_666 ?
N1 Ca1 N1 79.8(2) 2_665 17_666 ?
N1 Ca1 N1 134.89(8) 3_565 17_666 ?
N1 C1 Co1 180.0(5) . . ?
C1 N1 Ca1 175.4(4) . . ?
N2 N2 N2 119.999(12) 20_655 19_665 ?
N2 N2 C2 73.1(12) 20_655 16_556 ?
N2 N2 C2 63.7(12) 19_665 16_556 ?
N2 N2 C2 73.1(12) 20_655 . ?
N2 N2 C2 63.7(12) 19_665 . ?
C2 N2 C2 84.8(16) 16_556 . ?
N2 N2 N2 96.8(17) 20_655 2_655 ?
N2 N2 N2 23.2(17) 19_665 2_655 ?
C2 N2 N2 50.3(6) 16_556 2_655 ?
C2 N2 N2 50.3(6) . 2_655 ?
N2 N2 N2 36.8(18) 20_655 3_665 ?
N2 N2 N2 83.2(17) 19_665 3_665 ?
C2 N2 N2 50.3(6) 16_556 3_665 ?
C2 N2 N2 50.3(6) . 3_665 ?
N2 N2 N2 60.000(2) 2_655 3_665 ?
N3 C2 N2 132.4(8) . 3_665 ?
N3 C2 N2 132.4(8) . 21 ?
N2 C2 N2 34(2) 3_665 21 ?
N3 C2 N2 132.4(8) . 20_655 ?
N2 C2 N2 53(2) 3_665 20_655 ?
N2 C2 N2 79.5(12) 21 20_655 ?
N3 C2 N2 132.4(8) . 2_655 ?
N2 C2 N2 79.5(12) 3_665 2_655 ?
N2 C2 N2 53(2) 21 2_655 ?
N2 C2 N2 94.3(16) 20_655 2_655 ?
N3 C2 N2 132.4(8) . 19_665 ?
N2 C2 N2 94.3(16) 3_665 19_665 ?
N2 C2 N2 79.5(12) 21 19_665 ?
N2 C2 N2 79.5(12) 20_655 19_665 ?
N2 C2 N2 34(2) 2_655 19_665 ?
N3 C2 N2 132.4(8) . . ?
N2 C2 N2 79.5(12) 3_665 . ?
N2 C2 N2 94.3(16) 21 . ?
N2 C2 N2 34(2) 20_655 . ?
N2 C2 N2 79.5(12) 2_655 . ?
N2 C2 N2 53(2) 19_665 . ?
N3 C2 C2 180.0 . 16_556 ?
N2 C2 C2 47.6(8) 3_665 16_556 ?
N2 C2 C2 47.6(8) 21 16_556 ?
N2 C2 C2 47.6(8) 20_655 16_556 ?
N2 C2 C2 47.6(8) 2_655 16_556 ?
N2 C2 C2 47.6(8) 19_665 16_556 ?
N2 C2 C2 47.6(8) . 16_556 ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
N2 N2 C2 N3 -106.1(13) 20_655 . . . ?
N2 N2 C2 N3 116.8(15) 19_665 . . . ?
C2 N2 C2 N3 179.999(4) 16_556 . . . ?
N2 N2 C2 N3 139.4(4) 2_655 . . . ?
N2 N2 C2 N3 -139.4(4) 3_665 . . . ?
N2 N2 C2 N2 33.3(13) 20_655 . . 3_665 ?
N2 N2 C2 N2 -103.8(16) 19_665 . . 3_665 ?
C2 N2 C2 N2 -40.6(4) 16_556 . . 3_665 ?
N2 N2 C2 N2 -81.1(9) 2_655 . . 3_665 ?
N2 N2 C2 N2 63.8(13) 20_655 . . 21 ?
N2 N2 C2 N2 -73.3(12) 19_665 . . 21 ?
C2 N2 C2 N2 -10(3) 16_556 . . 21 ?
N2 N2 C2 N2 -51(3) 2_655 . . 21 ?
N2 N2 C2 N2 31(3) 3_665 . . 21 ?
N2 N2 C2 N2 -137.1(6) 19_665 . . 20_655 ?
C2 N2 C2 N2 -73.9(13) 16_556 . . 20_655 ?
N2 N2 C2 N2 -114.5(15) 2_655 . . 20_655 ?
N2 N2 C2 N2 -33.3(13) 3_665 . . 20_655 ?
N2 N2 C2 N2 114.5(15) 20_655 . . 2_655 ?
N2 N2 C2 N2 -22.6(15) 19_665 . . 2_655 ?
C2 N2 C2 N2 40.6(4) 16_556 . . 2_655 ?
N2 N2 C2 N2 81.1(9) 3_665 . . 2_655 ?
N2 N2 C2 N2 137.1(6) 20_655 . . 19_665 ?
C2 N2 C2 N2 63.2(15) 16_556 . . 19_665 ?
N2 N2 C2 N2 22.6(15) 2_655 . . 19_665 ?
N2 N2 C2 N2 103.8(16) 3_665 . . 19_665 ?
N2 N2 C2 C2 73.9(13) 20_655 . . 16_556 ?
N2 N2 C2 C2 -63.2(15) 19_665 . . 16_556 ?
N2 N2 C2 C2 -40.6(4) 2_655 . . 16_556 ?
N2 N2 C2 C2 40.6(4) 3_665 . . 16_556 ?

_refine_diff_density_max         1.238
_refine_diff_density_min         -1.352
_refine_diff_density_rms         0.163

_shelx_res_file                  
;

    1.res created by SHELXL-2014/7

TITL 1 in P6(3)/mmc
CELL 0.71073   7.5725   7.5725  13.3376  90.000  90.000 120.000
ZERR    6.00   0.0011   0.0011   0.0027   0.000   0.000   0.000
LATT 1
SYMM -Y, X-Y, Z
SYMM -X+Y, -X, Z
SYMM -X, -Y, 0.5+Z
SYMM Y, -X+Y, 0.5+Z
SYMM X-Y, X, 0.5+Z
SYMM Y, X, -Z
SYMM X-Y, -Y, -Z
SYMM -X, -X+Y, -Z
SYMM -Y, -X, 0.5-Z
SYMM -X+Y, Y, 0.5-Z
SYMM X, X-Y, 0.5-Z
SFAC C  H  N  O  Ca Co
UNIT 6 6 6 6 6 6
L.S. 200
ACTA
BOND
FMAP 2
PLAN 5
dfix 1.33 0.01 n2 c2 c2 n3
isor 0.01 n2 n3 c2
simu 0.01 n2 n3 c2
delu 0.01 n3 c2
delu 0.01 c2 n2
conf
WGHT    0.111000    1.683700
FVAR       0.64746
CO1   6    0.000000    1.000000    0.000000    10.08333    0.01345    0.01345 =
         0.00792    0.00000    0.00000    0.00672
CA1   5    0.333333    0.666667    0.250000    10.08333    0.01627    0.01627 =
         0.00821    0.00000    0.00000    0.00814
C1    1    0.117984    0.882016    0.082003    10.50000    0.02233    0.02233 =
         0.01360    0.00014   -0.00014    0.01181
N1    3    0.189272    0.810728    0.131549    10.50000    0.03778    0.03778 =
         0.02530    0.00347   -0.00347    0.02659
N2    3    0.684812    0.473813    0.250000    10.08333    0.04232    0.03785 =
         0.03955    0.00000    0.00000    0.02864
N3    3    0.666667    0.333333    0.079579    10.16667    0.06647    0.06647 =
         0.04687    0.00000    0.00000    0.03323
C2    1    0.666667    0.333333    0.181352    10.08333    0.04743    0.04743 =
         0.04286    0.00000    0.00000    0.02372
HKLF 4

REM  1 in P6(3)/mmc
REM R1 =  0.0531 for     318 Fo > 4sig(Fo)  and  0.0534 for all     324 data
REM     29 parameters refined using     34 restraints

END

WGHT      0.1110      1.6831

REM Highest difference peak  1.238,  deepest hole -1.352,  1-sigma level  0.163
Q1    1   0.1634  0.8366  0.2500  10.25000  0.05    0.26
Q2    1   0.2807  0.9043  0.2213  11.00000  0.05    0.24
Q3    1   0.1811  0.6615  0.0575  11.00000  0.05    0.21
Q4    1   0.8315  0.3343  0.0930  11.00000  0.05    0.20
Q5    1  -0.0900  0.6430  0.0636  11.00000  0.05    0.16
;
_shelx_res_checksum              37571

# start Validation Reply Form
_vrf_PLAT043_1-298K              
;
PROBLEM: Calculated and Reported Mol. Weight Differ by ..       6.05 Check 
RESPONSE: The hydrogen atoms were not added because of the highly disordered 
of the guest cation.
;
####################################################################### 
# 
# 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_2-298K
_database_code_depnum_ccdc_archive 'CCDC 1545591'
_audit_update_record             
;
2017-04-24 deposited with the CCDC.
2017-11-14 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         'C6 Ca Co N6, H2 N2, 2(C0.50 O0.50), 3(H)'
_chemical_formula_sum            'C7 H5 Ca Co N8 O'
_chemical_formula_weight         316.21

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'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ca Ca 0.2262 0.3064 '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'

_space_group_crystal_system      hexagonal
_space_group_IT_number           194
_space_group_name_H-M_alt        'P 63/m m c'
_space_group_name_Hall           '-P 6c 2c'

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

_cell_length_a                   7.5487(11)
_cell_length_b                   7.5487(11)
_cell_length_c                   13.313(3)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     657.0(2)
_cell_formula_units_Z            2
_cell_measurement_temperature    298(2)
_cell_measurement_reflns_used    450
_cell_measurement_theta_min      1.8945
_cell_measurement_theta_max      27.4754

_exptl_crystal_description       block
_exptl_crystal_colour            pale-yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.598
_exptl_crystal_F_000             430
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          ?
_exptl_crystal_size_mid          ?
_exptl_crystal_size_min          ?
_exptl_absorpt_coefficient_mu    1.696
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   ?
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      298(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Saturn724+ (4x4 bin mode)'
_diffrn_measurement_method       CCD_Profile_fitting
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            4303
_diffrn_reflns_av_unetI/netI     0.0189
_diffrn_reflns_av_R_equivalents  0.0419
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_theta_min         3.060
_diffrn_reflns_theta_max         27.416
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             322
_reflns_number_gt                319
_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    ?
_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)+(0.1287P)²+7.8612P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   .
_refine_ls_hydrogen_treatment    undef
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         322
_refine_ls_number_parameters     27
_refine_ls_number_restraints     26
_refine_ls_R_factor_all          0.0831
_refine_ls_R_factor_gt           0.0828
_refine_ls_wR_factor_ref         0.2429
_refine_ls_wR_factor_gt          0.2428
_refine_ls_goodness_of_fit_ref   1.244
_refine_ls_restrained_S_all      1.213
_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
C1 C 0.1185(6) 0.8815(6) 0.0811(5) 0.0168(16) Uani 1 2 d S T P . .
C2 C 0.6667 0.3333 0.182(2) 0.083(7) Uani 0.5 6 d DS TU P . .
Ca1 Ca 0.3333 0.6667 0.2500 0.0087(9) Uani 1 12 d S T P . .
Co1 Co 0.0000 1.0000 0.0000 0.0065(8) Uani 1 12 d S T P . .
N1 N 0.1906(6) 0.8094(6) 0.1298(6) 0.032(2) Uani 1 2 d S T P . .
N2 N 0.5899(19) 0.4101(19) 0.2500 0.089(7) Uani 0.6668 4 d DS TU P . .
O1 O 0.6667 0.3333 0.087(2) 0.060(8) Uani 0.5 6 d DS TU P . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
C1 0.020(3) 0.020(3) 0.013(3) 0.0008(15) -0.0008(15) 0.012(3)
C2 0.086(7) 0.086(7) 0.078(10) 0.000 0.000 0.043(4)
Ca1 0.0101(12) 0.0101(12) 0.0059(15) 0.000 0.000 0.0051(6)
Co1 0.0071(10) 0.0071(10) 0.0052(12) 0.000 0.000 0.0036(5)
N1 0.040(4) 0.040(4) 0.032(4) 0.0061(16) -0.0061(16) 0.032(4)
N2 0.092(7) 0.092(7) 0.085(10) 0.000 0.000 0.049(7)
O1 0.069(11) 0.069(11) 0.043(13) 0.000 0.000 0.035(5)

_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 N1 1.144(11) . ?
C1 Co1 1.889(8) . ?
C2 O1 1.263(5) . ?
C2 N2 1.349(10) 3_665 ?
C2 N2 1.349(10) 2_655 ?
C2 N2 1.349(10) . ?
C2 C2 1.80(5) 16_556 ?
Ca1 N1 2.458(7) 16_556 ?
Ca1 N1 2.458(7) . ?
Ca1 N1 2.458(7) 2_665 ?
Ca1 N1 2.458(7) 18_566 ?
Ca1 N1 2.458(7) 17_666 ?
Ca1 N1 2.458(7) 3_565 ?
Co1 C1 1.889(8) 14_455 ?
Co1 C1 1.889(8) 2_675 ?
Co1 C1 1.889(8) 13_575 ?
Co1 C1 1.889(8) 15_665 ?
Co1 C1 1.889(8) 3_465 ?
N2 C2 1.349(10) 16_556 ?
N2 N2 1.74(4) 3_665 ?
N2 N2 1.74(4) 2_655 ?

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
N1 C1 Co1 179.7(7) . . ?
O1 C2 N2 131.9(15) . 3_665 ?
O1 C2 N2 131.9(15) . 2_655 ?
N2 C2 N2 80(2) 3_665 2_655 ?
O1 C2 N2 131.9(15) . . ?
N2 C2 N2 80(2) 3_665 . ?
N2 C2 N2 80(2) 2_655 . ?
O1 C2 C2 180.0 . 16_556 ?
N2 C2 C2 48.1(15) 3_665 16_556 ?
N2 C2 C2 48.1(15) 2_655 16_556 ?
N2 C2 C2 48.1(15) . 16_556 ?
N1 Ca1 N1 81.2(4) 16_556 . ?
N1 Ca1 N1 135.38(13) 16_556 2_665 ?
N1 Ca1 N1 82.2(3) . 2_665 ?
N1 Ca1 N1 82.2(3) 16_556 18_566 ?
N1 Ca1 N1 135.38(13) . 18_566 ?
N1 Ca1 N1 135.38(13) 2_665 18_566 ?
N1 Ca1 N1 82.2(3) 16_556 17_666 ?
N1 Ca1 N1 135.38(13) . 17_666 ?
N1 Ca1 N1 81.2(4) 2_665 17_666 ?
N1 Ca1 N1 82.2(3) 18_566 17_666 ?
N1 Ca1 N1 135.38(13) 16_556 3_565 ?
N1 Ca1 N1 82.2(3) . 3_565 ?
N1 Ca1 N1 82.2(3) 2_665 3_565 ?
N1 Ca1 N1 81.2(4) 18_566 3_565 ?
N1 Ca1 N1 135.38(13) 17_666 3_565 ?
C1 Co1 C1 180.0(3) 14_455 2_675 ?
C1 Co1 C1 90.6(3) 14_455 13_575 ?
C1 Co1 C1 89.4(3) 2_675 13_575 ?
C1 Co1 C1 90.6(3) 14_455 15_665 ?
C1 Co1 C1 89.4(3) 2_675 15_665 ?
C1 Co1 C1 90.6(3) 13_575 15_665 ?
C1 Co1 C1 89.4(3) 14_455 3_465 ?
C1 Co1 C1 90.6(3) 2_675 3_465 ?
C1 Co1 C1 89.4(3) 13_575 3_465 ?
C1 Co1 C1 180.0(3) 15_665 3_465 ?
C1 Co1 C1 89.5(3) 14_455 . ?
C1 Co1 C1 90.5(3) 2_675 . ?
C1 Co1 C1 180.0 13_575 . ?
C1 Co1 C1 89.4(3) 15_665 . ?
C1 Co1 C1 90.6(3) 3_465 . ?
C1 N1 Ca1 173.9(7) . . ?
C2 N2 C2 84(3) 16_556 . ?
C2 N2 N2 49.9(11) 16_556 3_665 ?
C2 N2 N2 49.9(11) . 3_665 ?
C2 N2 N2 49.9(11) 16_556 2_655 ?
C2 N2 N2 49.9(11) . 2_655 ?
N2 N2 N2 59.999(4) 3_665 2_655 ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
O1 C2 N2 C2 180.000(5) . . . 16_556 ?
N2 C2 N2 C2 -40.8(8) 3_665 . . 16_556 ?
N2 C2 N2 C2 40.8(8) 2_655 . . 16_556 ?
O1 C2 N2 N2 -139.2(8) . . . 3_665 ?
N2 C2 N2 N2 81.7(16) 2_655 . . 3_665 ?
C2 C2 N2 N2 40.8(8) 16_556 . . 3_665 ?
O1 C2 N2 N2 139.2(8) . . . 2_655 ?
N2 C2 N2 N2 -81.7(16) 3_665 . . 2_655 ?
C2 C2 N2 N2 -40.8(8) 16_556 . . 2_655 ?

_refine_diff_density_max         1.778
_refine_diff_density_min         -2.700
_refine_diff_density_rms         0.284

_shelx_res_file                  
;

    1.res created by SHELXL-2014/7

TITL 1 in P6(3)/mmc
CELL 0.71073   7.5487   7.5487  13.3131  90.000  90.000 120.000
ZERR    5.00   0.0011   0.0011   0.0027   0.000   0.000   0.000
LATT 1
SYMM -Y, X-Y, Z
SYMM -X+Y, -X, Z
SYMM -X, -Y, 0.5+Z
SYMM Y, -X+Y, 0.5+Z
SYMM X-Y, X, 0.5+Z
SYMM Y, X, -Z
SYMM X-Y, -Y, -Z
SYMM -X, -X+Y, -Z
SYMM -Y, -X, 0.5-Z
SYMM -X+Y, Y, 0.5-Z
SYMM X, X-Y, 0.5-Z
SFAC C  H  N  O  Cl Ca Co
UNIT 5 5 5 5 5 5 5
L.S. 200
ACTA
BOND
FMAP 2
PLAN 10
isor 0.01 c2 n2
simu 0.01 o1 n2 c2
dfix 0.9 0.01 n2 h1
dfix 1.26 0.005 c2 o1
dfix 1.33 0.01 c2 n2
conf
FREE Ca1  N2
WGHT    0.128700    7.861200
FVAR       0.66901
C1    1    0.118531    0.881469    0.081133    10.50000    0.01978    0.01978 =
         0.01321    0.00076   -0.00076    0.01169
C2    1    0.666667    0.333333    0.182338    10.08333    0.08554    0.08554 =
         0.07763    0.00000    0.00000    0.04277
CA1   6    0.333333    0.666667    0.250000    10.08333    0.01013    0.01013 =
         0.00586    0.00000    0.00000    0.00506
CO1   7    0.000000    1.000000    0.000000    10.08333    0.00713    0.00713 =
         0.00517    0.00000    0.00000    0.00356
N1    3    0.190604    0.809396    0.129828    10.50000    0.03994    0.03994 =
         0.03229    0.00610   -0.00610    0.03195
N2    3    0.589893    0.410107    0.250000    10.16670    0.09199    0.09199 =
         0.08516    0.00000    0.00000    0.04856
O1    4    0.666667    0.333333    0.087448    10.08333    0.06901    0.06901 =
         0.04273    0.00000    0.00000    0.03451
HKLF 4

REM  1 in P6(3)/mmc
REM R1 =  0.0828 for     319 Fo > 4sig(Fo)  and  0.0831 for all     322 data
REM     27 parameters refined using     26 restraints

END

WGHT      0.1287      7.8728

REM Highest difference peak  1.861,  deepest hole -3.448,  1-sigma level  0.284
Q1    1   0.7586  0.5172  0.2500  10.25000  0.05    1.30
Q2    1   0.0234  0.7708  0.2500  10.50000  0.05    0.66
Q3    1   0.1758  0.6340  0.0559  11.00000  0.05    0.54
Q4    1   0.1833  0.8167  0.2244  10.50000  0.05    0.53
Q5    1   0.4818  0.3977  0.2500  10.50000  0.05    0.49
Q6    1   0.1210  0.8790  0.2500  10.25000  0.05    0.42
Q7    1  -0.0756  0.6393  0.0653  11.00000  0.05    0.41
Q8    1   0.0347  0.6411  0.0873  11.00000  0.05    0.33
Q9    1   0.7150  0.5591  0.0750  11.00000  0.05    0.29
Q10   1   0.3857  0.3465  0.1987  11.00000  0.05    0.23
;
_shelx_res_checksum              26589

# start Validation Reply Form
_vrf_PLAT043_2-298K              
;
PROBLEM: Calculated and Reported Mol. Weight Differ by ..       5.04 Check 
RESPONSE: The hydrogen atoms were not added because of the highly disordered 
of the guest cation.
;
####################################################################### 
# 
# 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_3-298K
_database_code_depnum_ccdc_archive 'CCDC 1545593'
_audit_update_record             
;
2017-04-24 deposited with the CCDC.
2017-11-14 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         
'6(C Ca0.17 Co0.17 N), 2(C0.50 S0.50), 2(H N), 3(H)'
_chemical_formula_sum            'C7 H5 Ca Co N8 S'
_chemical_formula_weight         332.27

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'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ca Ca 0.2262 0.3064 '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'

_space_group_crystal_system      hexagonal
_space_group_IT_number           194
_space_group_name_H-M_alt        'P 63/m m c'
_space_group_name_Hall           '-P 6c 2c'

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

_cell_length_a                   7.5237(11)
_cell_length_b                   7.5237(11)
_cell_length_c                   13.576(3)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     665.5(2)
_cell_formula_units_Z            2
_cell_measurement_temperature    298(2)
_cell_measurement_reflns_used    480
_cell_measurement_theta_min      2.1000
_cell_measurement_theta_max      27.5101

_exptl_crystal_description       block
_exptl_crystal_colour            pale-yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.658
_exptl_crystal_F_000             425
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          ?
_exptl_crystal_size_mid          ?
_exptl_crystal_size_min          ?
_exptl_absorpt_coefficient_mu    1.825
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   ?
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      298(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Saturn724+ (4x4 bin mode)'
_diffrn_measurement_method       CCD_Profile_fitting
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            3869
_diffrn_reflns_av_unetI/netI     0.0181
_diffrn_reflns_av_R_equivalents  0.0325
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_theta_min         3.001
_diffrn_reflns_theta_max         27.420
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             328
_reflns_number_gt                326
_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    ?
_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)+(0.1585P)²+3.3798P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   .
_refine_ls_hydrogen_treatment    undef
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         328
_refine_ls_number_parameters     27
_refine_ls_number_restraints     26
_refine_ls_R_factor_all          0.0753
_refine_ls_R_factor_gt           0.0751
_refine_ls_wR_factor_ref         0.2425
_refine_ls_wR_factor_gt          0.2424
_refine_ls_goodness_of_fit_ref   1.229
_refine_ls_restrained_S_all      1.233
_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
C2 C 0.6667 0.3333 0.1989(8) 0.047(3) Uani 0.5 6 d DS TU P . .
Co1 Co 0.0000 1.0000 0.0000 0.0095(8) Uani 1 12 d S T P . .
Ca1 Ca 0.3333 0.6667 0.2500 0.0124(9) Uani 1 12 d S T P . .
C1 C 0.1179(5) 0.8821(5) 0.0819(4) 0.0156(14) Uani 1 2 d S T P . .
N1 N 0.1878(5) 0.8122(5) 0.1341(4) 0.0257(15) Uani 1 2 d S T P . .
S1 S 0.6667 0.3333 0.0731(5) 0.0345(17) Uani 0.5 6 d DS TU P . .
N2 N 0.7535(9) 0.5069(18) 0.2500 0.052(3) Uani 0.6668 4 d DS TU P . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
C2 0.056(4) 0.056(4) 0.029(5) 0.000 0.000 0.0278(19)
Co1 0.0106(9) 0.0106(9) 0.0074(12) 0.000 0.000 0.0053(5)
Ca1 0.0143(11) 0.0143(11) 0.0084(14) 0.000 0.000 0.0072(6)
C1 0.017(2) 0.017(2) 0.014(3) -0.0006(11) 0.0006(11) 0.009(2)
N1 0.031(3) 0.031(3) 0.023(3) 0.0022(11) -0.0022(11) 0.022(3)
S1 0.045(2) 0.045(2) 0.013(2) 0.000 0.000 0.0225(12)
N2 0.064(4) 0.054(4) 0.033(5) 0.000 0.000 0.027(2)

_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
C2 N2 1.327(9) 2_655 ?
C2 N2 1.327(9) . ?
C2 N2 1.327(9) 3_665 ?
C2 C2 1.39(2) 16_556 ?
C2 S1 1.708(10) . ?
Co1 C1 1.897(6) 14_455 ?
Co1 C1 1.897(6) 2_675 ?
Co1 C1 1.897(6) 13_575 ?
Co1 C1 1.897(6) 15_665 ?
Co1 C1 1.897(6) 3_465 ?
Co1 C1 1.897(6) . ?
Ca1 N1 2.464(6) 16_556 ?
Ca1 N1 2.464(6) . ?
Ca1 N1 2.464(6) 18_566 ?
Ca1 N1 2.464(6) 2_665 ?
Ca1 N1 2.464(6) 3_565 ?
Ca1 N1 2.464(6) 17_666 ?
C1 N1 1.154(8) . ?
N2 C2 1.327(9) 16_556 ?

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
N2 C2 N2 95.1(8) 2_655 . ?
N2 C2 N2 95.1(8) 2_655 3_665 ?
N2 C2 N2 95.1(8) . 3_665 ?
N2 C2 C2 58.5(6) 2_655 16_556 ?
N2 C2 C2 58.5(6) . 16_556 ?
N2 C2 C2 58.5(6) 3_665 16_556 ?
N2 C2 S1 121.5(6) 2_655 . ?
N2 C2 S1 121.5(6) . . ?
N2 C2 S1 121.5(6) 3_665 . ?
C2 C2 S1 180.0 16_556 . ?
C1 Co1 C1 180.0(3) 14_455 2_675 ?
C1 Co1 C1 89.1(3) 14_455 13_575 ?
C1 Co1 C1 90.9(3) 2_675 13_575 ?
C1 Co1 C1 89.1(3) 14_455 15_665 ?
C1 Co1 C1 90.9(3) 2_675 15_665 ?
C1 Co1 C1 89.1(3) 13_575 15_665 ?
C1 Co1 C1 90.9(3) 14_455 3_465 ?
C1 Co1 C1 89.1(3) 2_675 3_465 ?
C1 Co1 C1 90.9(3) 13_575 3_465 ?
C1 Co1 C1 180.0(2) 15_665 3_465 ?
C1 Co1 C1 90.9(3) 14_455 . ?
C1 Co1 C1 89.1(3) 2_675 . ?
C1 Co1 C1 180.0(3) 13_575 . ?
C1 Co1 C1 90.9(3) 15_665 . ?
C1 Co1 C1 89.1(3) 3_465 . ?
N1 Ca1 N1 79.4(3) 16_556 . ?
N1 Ca1 N1 83.6(2) 16_556 18_566 ?
N1 Ca1 N1 134.75(9) . 18_566 ?
N1 Ca1 N1 134.75(9) 16_556 2_665 ?
N1 Ca1 N1 83.6(2) . 2_665 ?
N1 Ca1 N1 134.74(9) 18_566 2_665 ?
N1 Ca1 N1 134.75(9) 16_556 3_565 ?
N1 Ca1 N1 83.6(2) . 3_565 ?
N1 Ca1 N1 79.4(3) 18_566 3_565 ?
N1 Ca1 N1 83.6(2) 2_665 3_565 ?
N1 Ca1 N1 83.6(2) 16_556 17_666 ?
N1 Ca1 N1 134.75(9) . 17_666 ?
N1 Ca1 N1 83.6(2) 18_566 17_666 ?
N1 Ca1 N1 79.4(3) 2_665 17_666 ?
N1 Ca1 N1 134.74(9) 3_565 17_666 ?
N1 C1 Co1 178.1(6) . . ?
C1 N1 Ca1 178.1(5) . . ?
C2 N2 C2 63.1(12) 16_556 . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
N2 C2 N2 C2 47.8(5) 2_655 . . 16_556 ?
N2 C2 N2 C2 -47.8(5) 3_665 . . 16_556 ?
S1 C2 N2 C2 179.998(1) . . . 16_556 ?

_refine_diff_density_max         1.912
_refine_diff_density_min         -1.794
_refine_diff_density_rms         0.221

_shelx_res_file                  
;

    1.res created by SHELXL-2014/7

TITL 1 in P6(3)/mmc
CELL 0.71073   7.5237   7.5237  13.5762  90.000  90.000 120.000
ZERR    5.00   0.0011   0.0011   0.0027   0.000   0.000   0.000
LATT 1
SYMM -Y, X-Y, Z
SYMM -X+Y, -X, Z
SYMM -X, -Y, 0.5+Z
SYMM Y, -X+Y, 0.5+Z
SYMM X-Y, X, 0.5+Z
SYMM Y, X, -Z
SYMM X-Y, -Y, -Z
SYMM -X, -X+Y, -Z
SYMM -Y, -X, 0.5-Z
SYMM -X+Y, Y, 0.5-Z
SYMM X, X-Y, 0.5-Z
SFAC C  H  N  O  S  Ca Co
UNIT 5 5 5 5 5 5 5
L.S. 200
ACTA
BOND
FMAP 2
PLAN 10
simu 0.003 s1 c2 n2
isor 0.01 n2 s1
dfix 1.7 0.01 s1 c2
dfix 1.33 0.01 c2 n2
dfix 1.1 0.01 s1 h1
conf
WGHT    0.158500    3.379800
FVAR       0.34437
C2    1    0.666667    0.333333    0.198882    10.08333    0.05550    0.05550 =
         0.02897    0.00000    0.00000    0.02775
CO1   7    0.000000    1.000000    0.000000    10.08333    0.01063    0.01063 =
         0.00738    0.00000    0.00000    0.00532
CA1   6    0.333333    0.666667    0.250000    10.08333    0.01432    0.01432 =
         0.00844    0.00000    0.00000    0.00716
C1    1    0.117892    0.882108    0.081922    10.50000    0.01673    0.01673 =
         0.01385   -0.00057    0.00057    0.00871
N1    3    0.187818    0.812182    0.134062    10.50000    0.03123    0.03123 =
         0.02279    0.00225   -0.00225    0.02182
S1    5    0.666667    0.333333    0.073089    10.08333    0.04510    0.04510 =
         0.01341    0.00000    0.00000    0.02255
N2    3    0.753460    0.506920    0.250000    10.16670    0.06367    0.05439 =
         0.03339    0.00000    0.00000    0.02719
HKLF 4

REM  1 in P6(3)/mmc
REM R1 =  0.0751 for     326 Fo > 4sig(Fo)  and  0.0753 for all     328 data
REM     27 parameters refined using     26 restraints

END

WGHT      0.1593      3.3152

REM Highest difference peak  1.912,  deepest hole -1.794,  1-sigma level  0.221
Q1    1   0.8190  0.4095  0.2500  10.25000  0.05    1.19
Q2    1   0.8381  0.4929  0.2500  10.50000  0.05    1.15
Q3    1   0.7672  0.5344  0.0594  10.50000  0.05    0.39
Q4    1   0.1339  0.8661  0.2281  10.50000  0.05    0.31
Q5    1   0.0380  0.7767  0.2073  11.00000  0.05    0.29
Q6    1   0.0828  0.7203  0.2500  10.50000  0.05    0.29
Q7    1  -0.0648  0.6345  0.0592  11.00000  0.05    0.26
Q8    1   0.0124  0.7825  0.1883  11.00000  0.05    0.22
Q9    1   0.3395  0.4573  0.2500  10.50000  0.05    0.20
Q10   1   0.2682  0.7318  0.0855  10.50000  0.05    0.20
;
_shelx_res_checksum              89441

# start Validation Reply Form
_vrf_PLAT043_3-298K              
;
PROBLEM: Calculated and Reported Mol. Weight Differ by ..       5.04 Check 
RESPONSE: The hydrogen atoms were not added because of the highly disordered 
of the guest cation.
;
####################################################################### 
# 
# 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_3-93K
_database_code_depnum_ccdc_archive 'CCDC 1545594'
_audit_update_record             
;
2017-04-24 deposited with the CCDC.
2017-11-14 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         
'6(C Ca0.17 Co0.17 N), 2(C0.50 S0.50), 2(H N), 3(H)'
_chemical_formula_sum            'C7 H5 Ca Co N8 S'
_chemical_formula_weight         332.27

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'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ca Ca 0.2262 0.3064 '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'

_space_group_crystal_system      hexagonal
_space_group_IT_number           194
_space_group_name_H-M_alt        'P 63/m m c'
_space_group_name_Hall           '-P 6c 2c'

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

_cell_length_a                   7.505(7)
_cell_length_b                   7.505(7)
_cell_length_c                   13.575(18)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     662.1(16)
_cell_formula_units_Z            2
_cell_measurement_temperature    93(2)
_cell_measurement_reflns_used    307
_cell_measurement_theta_min      1.5006
_cell_measurement_theta_max      27.4855

_exptl_crystal_description       block
_exptl_crystal_colour            pale-yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.666
_exptl_crystal_F_000             425
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          ?
_exptl_crystal_size_mid          ?
_exptl_crystal_size_min          ?
_exptl_absorpt_coefficient_mu    1.834
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   ?
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      93(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Saturn724+ (4x4 bin mode)'
_diffrn_measurement_method       CCD_Profile_fitting
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            4404
_diffrn_reflns_av_unetI/netI     0.0145
_diffrn_reflns_av_R_equivalents  0.0302
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_theta_min         3.001
_diffrn_reflns_theta_max         27.418
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.982
_diffrn_measured_fraction_theta_full 0.977
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_Laue_measured_fraction_full 0.977
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_point_group_measured_fraction_full 0.977
_reflns_number_total             321
_reflns_number_gt                314
_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    ?
_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)+(0.1104P)²+5.8061P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   .
_refine_ls_hydrogen_treatment    undef
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         321
_refine_ls_number_parameters     27
_refine_ls_number_restraints     14
_refine_ls_R_factor_all          0.0703
_refine_ls_R_factor_gt           0.0697
_refine_ls_wR_factor_ref         0.2140
_refine_ls_wR_factor_gt          0.2136
_refine_ls_goodness_of_fit_ref   1.259
_refine_ls_restrained_S_all      1.275
_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
Co1 Co 1.0000 0.0000 0.0000 0.0079(8) Uani 1 12 d S T P . .
Ca1 Ca 0.6667 0.3333 0.2500 0.0091(8) Uani 1 12 d S T P . .
N1 N 0.8117(5) 0.1883(5) 0.1338(4) 0.0161(13) Uani 1 2 d S T P . .
C1 C 0.8819(5) 0.1181(5) 0.0823(4) 0.0111(13) Uani 1 2 d S T P . .
S1 S 0.3333 0.6667 0.0732(4) 0.0133(12) Uani 0.5 6 d DS TU P . .
C2 C 0.3333 0.6667 0.1991(8) 0.027(6) Uani 0.5 6 d DS T P . .
N2 N 0.5067(19) 0.7533(9) 0.2500 0.069(6) Uani 0.6668 4 d DS TU P . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Co1 0.0092(9) 0.0092(9) 0.0052(11) 0.000 0.000 0.0046(5)
Ca1 0.0110(11) 0.0110(11) 0.0053(14) 0.000 0.000 0.0055(5)
N1 0.018(2) 0.018(2) 0.015(3) 0.0000(11) 0.0000(11) 0.010(2)
C1 0.011(2) 0.011(2) 0.009(3) 0.0007(11) -0.0007(11) 0.005(2)
S1 0.0173(18) 0.0173(18) 0.005(2) 0.000 0.000 0.0087(9)
C2 0.027(9) 0.027(9) 0.028(15) 0.000 0.000 0.013(4)
N2 0.046(8) 0.099(10) 0.044(8) 0.000 0.000 0.023(4)

_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 C1 1.899(7) 15_545 ?
Co1 C1 1.899(7) 3_765 ?
Co1 C1 1.899(7) 13_755 ?
Co1 C1 1.899(7) 2_645 ?
Co1 C1 1.899(7) 14_665 ?
Co1 C1 1.899(7) . ?
Ca1 N1 2.458(6) 16_556 ?
Ca1 N1 2.458(6) 17_656 ?
Ca1 N1 2.458(6) 3_665 ?
Ca1 N1 2.458(6) 18_666 ?
Ca1 N1 2.458(6) . ?
Ca1 N1 2.458(6) 2_655 ?
N1 C1 1.150(9) . ?
S1 C2 1.709(10) . ?
C2 N2 1.321(9) 2_665 ?
C2 N2 1.321(10) 3_565 ?
C2 N2 1.321(9) . ?
C2 C2 1.38(2) 16_556 ?
N2 C2 1.321(9) 16_556 ?

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 Co1 C1 180.0(3) 15_545 3_765 ?
C1 Co1 C1 88.9(3) 15_545 13_755 ?
C1 Co1 C1 91.1(3) 3_765 13_755 ?
C1 Co1 C1 91.1(3) 15_545 2_645 ?
C1 Co1 C1 88.9(3) 3_765 2_645 ?
C1 Co1 C1 91.1(3) 13_755 2_645 ?
C1 Co1 C1 88.9(3) 15_545 14_665 ?
C1 Co1 C1 91.1(3) 3_765 14_665 ?
C1 Co1 C1 88.9(3) 13_755 14_665 ?
C1 Co1 C1 180.0(3) 2_645 14_665 ?
C1 Co1 C1 91.1(3) 15_545 . ?
C1 Co1 C1 88.9(3) 3_765 . ?
C1 Co1 C1 180.0 13_755 . ?
C1 Co1 C1 88.9(3) 2_645 . ?
C1 Co1 C1 91.1(3) 14_665 . ?
N1 Ca1 N1 83.2(2) 16_556 17_656 ?
N1 Ca1 N1 134.90(9) 16_556 3_665 ?
N1 Ca1 N1 134.90(9) 17_656 3_665 ?
N1 Ca1 N1 83.2(2) 16_556 18_666 ?
N1 Ca1 N1 83.2(2) 17_656 18_666 ?
N1 Ca1 N1 79.8(3) 3_665 18_666 ?
N1 Ca1 N1 79.8(3) 16_556 . ?
N1 Ca1 N1 134.90(9) 17_656 . ?
N1 Ca1 N1 83.2(2) 3_665 . ?
N1 Ca1 N1 134.90(9) 18_666 . ?
N1 Ca1 N1 134.90(9) 16_556 2_655 ?
N1 Ca1 N1 79.8(3) 17_656 2_655 ?
N1 Ca1 N1 83.2(2) 3_665 2_655 ?
N1 Ca1 N1 134.90(9) 18_666 2_655 ?
N1 Ca1 N1 83.2(2) . 2_655 ?
C1 N1 Ca1 177.6(5) . . ?
N1 C1 Co1 178.5(6) . . ?
N2 C2 N2 95.2(8) 2_665 3_565 ?
N2 C2 N2 95.2(8) 2_665 . ?
N2 C2 N2 95.2(8) 3_565 . ?
N2 C2 C2 58.5(6) 2_665 16_556 ?
N2 C2 C2 58.5(6) 3_565 16_556 ?
N2 C2 C2 58.5(6) . 16_556 ?
N2 C2 S1 121.5(6) 2_665 . ?
N2 C2 S1 121.5(6) 3_565 . ?
N2 C2 S1 121.5(6) . . ?
C2 C2 S1 180.0 16_556 . ?
C2 N2 C2 63.0(11) 16_556 . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
N2 C2 N2 C2 47.8(5) 2_665 . . 16_556 ?
N2 C2 N2 C2 -47.8(5) 3_565 . . 16_556 ?
S1 C2 N2 C2 180.002(2) . . . 16_556 ?

_refine_diff_density_max         1.937
_refine_diff_density_min         -0.948
_refine_diff_density_rms         0.183

_shelx_res_file                  
;

    1.res created by SHELXL-2014/7

TITL 1 in P6(3)/mmc
CELL 0.71073   7.5046   7.5046  13.5748  90.000  90.000 120.000
ZERR    5.00   0.0073   0.0073   0.0180   0.000   0.000   0.000
LATT 1
SYMM -Y, X-Y, Z
SYMM -X+Y, -X, Z
SYMM -X, -Y, 0.5+Z
SYMM Y, -X+Y, 0.5+Z
SYMM X-Y, X, 0.5+Z
SYMM Y, X, -Z
SYMM X-Y, -Y, -Z
SYMM -X, -X+Y, -Z
SYMM -Y, -X, 0.5-Z
SYMM -X+Y, Y, 0.5-Z
SYMM X, X-Y, 0.5-Z
SFAC C  H  N  O  S  Ca Co
UNIT 5 5 5 5 5 5 5
L.S. 200
ACTA
BOND
FMAP 2
PLAN 20
dfix 1.7 0.01 s1 c2
dfix 1.1 0.01 s1 h1
dfix 1.33 0.01 c2 n2
isor 0.01 s1 n2
simu 0.01 co1 ca1
conf
WGHT    0.110400    5.806100
FVAR       1.16627
CO1   7    1.000000    0.000000    0.000000    10.08333    0.00918    0.00918 =
         0.00519    0.00000    0.00000    0.00459
CA1   6    0.666667    0.333333    0.250000    10.08333    0.01095    0.01095 =
         0.00535    0.00000    0.00000    0.00548
N1    3    0.811677    0.188323    0.133806    10.50000    0.01786    0.01786 =
         0.01462    0.00004   -0.00004    0.01037
C1    1    0.881860    0.118140    0.082257    10.50000    0.01134    0.01134 =
         0.00944    0.00074   -0.00074    0.00477
S1    5    0.333333    0.666667    0.073238    10.08333    0.01732    0.01732 =
         0.00535    0.00000    0.00000    0.00866
C2    1    0.333333    0.666667    0.199124    10.08333    0.02687    0.02687 =
         0.02809    0.00000    0.00000    0.01344
N2    3    0.506674    0.753337    0.250000    10.16670    0.04632    0.09938 =
         0.04409    0.00000    0.00000    0.02316
HKLF 4

REM  1 in P6(3)/mmc
REM R1 =  0.0697 for     314 Fo > 4sig(Fo)  and  0.0703 for all     321 data
REM     27 parameters refined using     14 restraints

END

WGHT      0.1104      5.8072

REM Highest difference peak  1.937,  deepest hole -0.948,  1-sigma level  0.183
Q1    1   0.4916  0.8234  0.2500  10.50000  0.05    1.31
Q2    1   0.4104  0.8209  0.2500  10.25000  0.05    1.12
Q3    1   0.4790  0.9579  0.2500  10.25000  0.05    0.28
Q4    1   0.2186  0.4371  0.0525  10.50000  0.05    0.23
Q5    1   0.8474  0.1526  0.2188  10.50000  0.05    0.22
Q6    1   0.5159  0.8263  0.1758  11.00000  0.05    0.21
Q7    1   0.6355 -0.0512  0.1023  11.00000  0.05    0.21
Q8    1   0.5580  0.7790  0.1831  10.50000  0.05    0.21
Q9    1   0.7683  0.2317  0.1827  10.50000  0.05    0.19
Q10   1   0.4522  0.9044  0.1866  10.50000  0.05    0.19
Q11   1   1.0695  0.1391  0.0430  10.50000  0.05    0.18
Q12   1   0.6760 -0.1620  0.0819  10.50000  0.05    0.18
Q13   1   1.0880  0.3612  0.0542  11.00000  0.05    0.18
Q14   1   0.6016  0.9505  0.2075  11.00000  0.05    0.18
Q15   1   0.9279  0.3196  0.2500  10.50000  0.05    0.17
Q16   1   0.7561  0.0815  0.2168  11.00000  0.05    0.17
Q17   1   0.8070 -0.0278  0.0360  11.00000  0.05    0.17
Q18   1   0.7525  0.2475  0.1432  10.50000  0.05    0.16
Q19   1   0.3148  0.8569  0.0549  11.00000  0.05    0.15
Q20   1   0.2366  0.4733  0.1090  10.50000  0.05    0.15
;
_shelx_res_checksum              50990

# start Validation Reply Form
_vrf_PLAT043_3-93K               
;
PROBLEM: Calculated and Reported Mol. Weight Differ by ..       5.04 Check 
RESPONSE:The hydrogen atoms were not added because of the highly disordered 
of the guest cation.
;
# end Validation Reply Form
# end of cif
####################################################################### 
# 
# 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_2-93K
_database_code_depnum_ccdc_archive 'CCDC 1545592'
_audit_update_record             
;
2017-04-24 deposited with the CCDC.
2017-11-14 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         'C6 Ca Co N6, 0.667(N3), 2(C0.50 O0.50), 5(H)'
_chemical_formula_sum            'C7 H5 Ca Co N8 O'
_chemical_formula_weight         316.20

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'
Ca Ca 0.2262 0.3064 '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'

_space_group_crystal_system      hexagonal
_space_group_IT_number           194
_space_group_name_H-M_alt        'P 63/m m c'
_space_group_name_Hall           '-P 6c 2c'

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

_cell_length_a                   7.529(6)
_cell_length_b                   7.529(6)
_cell_length_c                   13.243(14)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     650.1(13)
_cell_formula_units_Z            2
_cell_measurement_temperature    93(2)
_cell_measurement_reflns_used    291
_cell_measurement_theta_min      3.0772
_cell_measurement_theta_max      27.4855

_exptl_crystal_description       block
_exptl_crystal_colour            pale-yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.615
_exptl_crystal_F_000             414
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          ?
_exptl_crystal_size_mid          ?
_exptl_crystal_size_min          ?
_exptl_absorpt_coefficient_mu    1.714
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   ?
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      93(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Saturn724+ (4x4 bin mode)'
_diffrn_measurement_method       CCD_Profile_fitting
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            4233
_diffrn_reflns_av_unetI/netI     0.0159
_diffrn_reflns_av_R_equivalents  0.0281
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_theta_min         3.124
_diffrn_reflns_theta_max         27.471
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.975
_diffrn_measured_fraction_theta_full 0.969
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_Laue_measured_fraction_full 0.969
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_point_group_measured_fraction_full 0.969
_reflns_number_total             311
_reflns_number_gt                306
_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    ?
_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)+(0.1106P)²+12.3126P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   .
_refine_ls_hydrogen_treatment    undef
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         311
_refine_ls_number_parameters     27
_refine_ls_number_restraints     20
_refine_ls_R_factor_all          0.0874
_refine_ls_R_factor_gt           0.0870
_refine_ls_wR_factor_ref         0.2302
_refine_ls_wR_factor_gt          0.2299
_refine_ls_goodness_of_fit_ref   1.135
_refine_ls_restrained_S_all      1.114
_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
Co1 Co 1.0000 0.0000 0.0000 0.0053(9) Uani 1 12 d S T P . .
Ca1 Ca 0.6667 0.3333 0.2500 0.0065(9) Uani 1 12 d S T P . .
C1 C 0.8812(6) 0.1188(6) 0.0815(5) 0.0133(16) Uani 1 2 d S T P . .
N1 N 0.8089(6) 0.1911(6) 0.1302(5) 0.0239(17) Uani 1 2 d S T P . .
O1 O 0.3333 0.6667 0.0872(17) 0.048(7) Uani 0.5 6 d DS TU P . .
N2 N 0.4090(16) 0.5910(16) 0.2500 0.077(7) Uani 0.6667 4 d DS TU P . .
C2 C 0.3333 0.6667 0.1820(17) 0.067(7) Uani 0.5 6 d DS TU P . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Co1 0.0058(10) 0.0058(10) 0.0043(12) 0.000 0.000 0.0029(5)
Ca1 0.0077(12) 0.0077(12) 0.0040(15) 0.000 0.000 0.0039(6)
C1 0.016(3) 0.016(3) 0.010(3) -0.0001(14) 0.0001(14) 0.009(3)
N1 0.029(3) 0.029(3) 0.024(4) -0.0043(15) 0.0043(15) 0.022(3)
O1 0.056(10) 0.056(10) 0.031(12) 0.000 0.000 0.028(5)
N2 0.081(8) 0.081(8) 0.061(9) 0.000 0.000 0.035(7)
C2 0.074(9) 0.074(9) 0.055(12) 0.000 0.000 0.037(4)

_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 C1 1.888(8) 13_755 ?
Co1 C1 1.888(8) 15_545 ?
Co1 C1 1.888(8) 3_765 ?
Co1 C1 1.888(8) . ?
Co1 C1 1.888(8) 14_665 ?
Co1 C1 1.888(8) 2_645 ?
Ca1 N1 2.441(7) . ?
Ca1 N1 2.441(7) 16_556 ?
Ca1 N1 2.441(7) 3_665 ?
Ca1 N1 2.441(7) 17_656 ?
Ca1 N1 2.441(7) 18_666 ?
Ca1 N1 2.441(7) 2_655 ?
C1 N1 1.143(10) . ?
O1 C2 1.255(5) . ?
N2 C2 1.336(5) 16_556 ?
N2 C2 1.336(5) . ?
N2 N2 1.71(4) 2_665 ?
N2 N2 1.71(4) 3_565 ?
C2 N2 1.336(5) 2_665 ?
C2 N2 1.336(5) 3_565 ?
C2 C2 1.80(5) 16_556 ?

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 Co1 C1 90.5(3) 13_755 15_545 ?
C1 Co1 C1 89.5(3) 13_755 3_765 ?
C1 Co1 C1 180.0(4) 15_545 3_765 ?
C1 Co1 C1 180.0 13_755 . ?
C1 Co1 C1 89.5(3) 15_545 . ?
C1 Co1 C1 90.5(3) 3_765 . ?
C1 Co1 C1 90.5(3) 13_755 14_665 ?
C1 Co1 C1 90.5(3) 15_545 14_665 ?
C1 Co1 C1 89.5(3) 3_765 14_665 ?
C1 Co1 C1 89.5(3) . 14_665 ?
C1 Co1 C1 89.5(3) 13_755 2_645 ?
C1 Co1 C1 89.5(3) 15_545 2_645 ?
C1 Co1 C1 90.5(3) 3_765 2_645 ?
C1 Co1 C1 90.5(3) . 2_645 ?
C1 Co1 C1 180.0(4) 14_665 2_645 ?
N1 Ca1 N1 81.1(4) . 16_556 ?
N1 Ca1 N1 82.3(3) . 3_665 ?
N1 Ca1 N1 135.34(13) 16_556 3_665 ?
N1 Ca1 N1 135.34(13) . 17_656 ?
N1 Ca1 N1 82.3(3) 16_556 17_656 ?
N1 Ca1 N1 135.34(13) 3_665 17_656 ?
N1 Ca1 N1 135.34(13) . 18_666 ?
N1 Ca1 N1 82.3(3) 16_556 18_666 ?
N1 Ca1 N1 81.1(4) 3_665 18_666 ?
N1 Ca1 N1 82.3(3) 17_656 18_666 ?
N1 Ca1 N1 82.3(3) . 2_655 ?
N1 Ca1 N1 135.34(13) 16_556 2_655 ?
N1 Ca1 N1 82.3(3) 3_665 2_655 ?
N1 Ca1 N1 81.1(4) 17_656 2_655 ?
N1 Ca1 N1 135.34(13) 18_666 2_655 ?
N1 C1 Co1 179.5(7) . . ?
C1 N1 Ca1 173.8(6) . . ?
C2 N2 C2 85(3) 16_556 . ?
C2 N2 N2 50.3(10) 16_556 2_665 ?
C2 N2 N2 50.3(10) . 2_665 ?
C2 N2 N2 50.3(10) 16_556 3_565 ?
C2 N2 N2 50.3(10) . 3_565 ?
N2 N2 N2 60.000(6) 2_665 3_565 ?
O1 C2 N2 132.4(13) . 2_665 ?
O1 C2 N2 132.4(13) . 3_565 ?
N2 C2 N2 79(2) 2_665 3_565 ?
O1 C2 N2 132.4(13) . . ?
N2 C2 N2 79(2) 2_665 . ?
N2 C2 N2 79(2) 3_565 . ?
O1 C2 C2 180.0 . 16_556 ?
N2 C2 C2 47.6(13) 2_665 16_556 ?
N2 C2 C2 47.6(13) 3_565 16_556 ?
N2 C2 C2 47.6(13) . 16_556 ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C2 N2 C2 O1 180.000(1) 16_556 . . . ?
N2 N2 C2 O1 139.4(7) 2_665 . . . ?
N2 N2 C2 O1 -139.4(7) 3_565 . . . ?
C2 N2 C2 N2 40.6(7) 16_556 . . 2_665 ?
N2 N2 C2 N2 81.1(14) 3_565 . . 2_665 ?
C2 N2 C2 N2 -40.6(7) 16_556 . . 3_565 ?
N2 N2 C2 N2 -81.1(14) 2_665 . . 3_565 ?
N2 N2 C2 C2 -40.6(7) 2_665 . . 16_556 ?
N2 N2 C2 C2 40.6(7) 3_565 . . 16_556 ?

_refine_diff_density_max         2.627
_refine_diff_density_min         -2.127
_refine_diff_density_rms         0.198

_shelx_res_file                  
;

    1.res created by SHELXL-2014/7

TITL 1 in P6(3)/mmc
CELL 0.71073   7.5288   7.5288  13.2434  90.000  90.000 120.000
ZERR    6.00   0.0063   0.0063   0.0139   0.000   0.000   0.000
LATT 1
SYMM -Y, X-Y, Z
SYMM -X+Y, -X, Z
SYMM -X, -Y, 0.5+Z
SYMM Y, -X+Y, 0.5+Z
SYMM X-Y, X, 0.5+Z
SYMM Y, X, -Z
SYMM X-Y, -Y, -Z
SYMM -X, -X+Y, -Z
SYMM -Y, -X, 0.5-Z
SYMM -X+Y, Y, 0.5-Z
SYMM X, X-Y, 0.5-Z
SFAC C  H  N  O  Ca Co
UNIT 6 6 6 6 6 6
L.S. 200
ACTA
BOND
FMAP 2
PLAN 15
dfix 1.33 0.005 c2 n2
dfix 1.25 0.005 o1 c2
isor 0.01 n2
simu 0.01 c2 n2 o1
dfix 0.9 0.01 n2 h2
dfix 1.1 0.01 o1 h1
conf
FREE N2   Ca1
WGHT    0.110600   12.312600
FVAR       1.25695
CO1   6    1.000000    0.000000    0.000000    10.08333    0.00577    0.00577 =
         0.00428    0.00000    0.00000    0.00288
CA1   5    0.666667    0.333333    0.250000    10.08333    0.00774    0.00774 =
         0.00404    0.00000    0.00000    0.00387
C1    1    0.881239    0.118761    0.081503    10.50000    0.01570    0.01570 =
         0.01008   -0.00014    0.00014    0.00914
N1    3    0.808909    0.191091    0.130209    10.50000    0.02857    0.02857 =
         0.02439   -0.00431    0.00431    0.02157
O1    4    0.333333    0.666667    0.087177    10.08333    0.05609    0.05609 =
         0.03104    0.00000    0.00000    0.02805
N2    3    0.408954    0.591046    0.250000    10.16667    0.08069    0.08069 =
         0.06133    0.00000    0.00000    0.03484
C2    1    0.333333    0.666667    0.181954    10.08333    0.07371    0.07371 =
         0.05473    0.00000    0.00000    0.03686
HKLF 4

REM  1 in P6(3)/mmc
REM R1 =  0.0870 for     306 Fo > 4sig(Fo)  and  0.0874 for all     311 data
REM     27 parameters refined using     20 restraints

END

WGHT      0.1104     12.0717

REM Highest difference peak  2.777,  deepest hole -2.117,  1-sigma level  0.211
Q1    1   0.5099  0.7550  0.2500  10.25000  0.05    1.62
Q2    1   0.7685  0.0207  0.2500  10.50000  0.05    0.61
Q3    1   0.8187  0.1813  0.2255  10.50000  0.05    0.50
Q4    1   0.8215  0.1785  0.0636  10.50000  0.05    0.33
Q5    1   0.3823  0.3958  0.2500  10.50000  0.05    0.30
Q6    1   1.0753  0.3599  0.0685  11.00000  0.05    0.29
Q7    1   0.6154  0.2309  0.0659  10.50000  0.05    0.29
Q8    1   0.5217  0.4783  0.2500  10.25000  0.05    0.29
Q9    1   0.2005  0.4010  0.1417  10.50000  0.05    0.26
Q10   1   1.1623  0.3246  0.0899  10.50000  0.05    0.25
Q11   1   0.4407  0.5593  0.1623  10.50000  0.05    0.24
Q12   1   0.7411  0.2589  0.0587  10.50000  0.05    0.23
Q13   1   0.3333  0.6667 -0.0254  10.16667  0.05    0.22
Q14   1   0.9404  0.0596  0.2500  10.25000  0.05    0.19
Q15   1   0.7582  0.2418  0.1099  10.50000  0.05    0.16
;
_shelx_res_checksum              52489

# start Validation Reply Form
_vrf_PLAT043_2-93K               
;
PROBLEM: Calculated and Reported Mol. Weight Differ by ..       5.04 Check 
RESPONSE: The hydrogen atoms were not added because of the highly disordered 
of the guest cation.
;
####################################################################### 
# 
# 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_1-93K
_database_code_depnum_ccdc_archive 'CCDC 1545590'
_audit_update_record             
;
2017-04-24 deposited with the CCDC.
2017-11-14 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         '6(C Ca0.17 Co0.17 N), C H4 N2, H N, H'
_chemical_formula_sum            'C7 H6 Ca Co N9'
_chemical_formula_weight         315.22

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'
Ca Ca 0.2262 0.3064 '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'

_space_group_crystal_system      hexagonal
_space_group_IT_number           194
_space_group_name_H-M_alt        'P 63/m m c'
_space_group_name_Hall           '-P 6c 2c'

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

_cell_length_a                   7.575(7)
_cell_length_b                   7.575(7)
_cell_length_c                   13.31(2)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     661.6(16)
_cell_formula_units_Z            2
_cell_measurement_temperature    93(2)
_cell_measurement_reflns_used    291
_cell_measurement_theta_min      1.5300
_cell_measurement_theta_max      27.4855

_exptl_crystal_description       block
_exptl_crystal_colour            pale-yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.583
_exptl_crystal_F_000             414
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          ?
_exptl_crystal_size_mid          ?
_exptl_crystal_size_min          ?
_exptl_absorpt_coefficient_mu    1.681
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   ?
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      93(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Saturn724+ (4x4 bin mode)'
_diffrn_measurement_method       CCD_Profile_fitting
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            4404
_diffrn_reflns_av_unetI/netI     0.0205
_diffrn_reflns_av_R_equivalents  0.0358
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_theta_min         3.060
_diffrn_reflns_theta_max         27.475
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measured_fraction_theta_full 0.981
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_Laue_measured_fraction_full 0.981
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_point_group_measured_fraction_full 0.981
_reflns_number_total             320
_reflns_number_gt                305
_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    ?
_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)+(0.1099P)²+5.9259P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   .
_refine_ls_hydrogen_treatment    undef
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         320
_refine_ls_number_parameters     27
_refine_ls_number_restraints     59
_refine_ls_R_factor_all          0.0718
_refine_ls_R_factor_gt           0.0702
_refine_ls_wR_factor_ref         0.2072
_refine_ls_wR_factor_gt          0.2052
_refine_ls_goodness_of_fit_ref   1.205
_refine_ls_restrained_S_all      1.119
_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
C1 C 0.8816(5) 0.1184(5) 0.0826(4) 0.0139(11) Uani 1 2 d S TU P . .
C2 C 0.3333 0.6667 0.1844(10) 0.035(3) Uani 0.5 6 d DS TU P . .
Ca1 Ca 0.6667 0.3333 0.2500 0.0085(8) Uani 1 12 d S TU P . .
Co1 Co 1.0000 0.0000 0.0000 0.0071(7) Uani 1 12 d S TU P . .
N1 N 0.8102(4) 0.1898(4) 0.1320(4) 0.0148(11) Uani 1 2 d S TU P . .
N2 N 0.2458(12) 0.492(2) 0.2500 0.038(3) Uani 0.3333 4 d DS TU P . .
N3 N 0.3333 0.6667 0.0753(8) 0.034(3) Uani 1 6 d DS TU P . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
C1 0.0156(14) 0.0156(14) 0.0114(17) -0.0001(7) 0.0001(7) 0.0085(15)
C2 0.039(4) 0.039(4) 0.028(5) 0.000 0.000 0.0193(19)
Ca1 0.0110(10) 0.0110(10) 0.0035(12) 0.000 0.000 0.0055(5)
Co1 0.0093(8) 0.0093(8) 0.0027(10) 0.000 0.000 0.0047(4)
N1 0.0163(14) 0.0163(14) 0.0120(17) -0.0004(7) 0.0004(7) 0.0085(15)
N2 0.045(5) 0.037(4) 0.029(5) 0.000 0.000 0.019(2)
N3 0.036(4) 0.036(4) 0.028(5) 0.000 0.000 0.0182(18)

_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 N1 1.144(8) . ?
C1 Co1 1.904(6) . ?
C2 N2 1.443(10) 3_565 ?
C2 N2 1.443(10) 2_665 ?
C2 N2 1.443(10) . ?
C2 N3 1.453(10) . ?
C2 C2 1.75(3) 16_556 ?
Ca1 N1 2.452(6) 3_665 ?
Ca1 N1 2.452(6) 17_656 ?
Ca1 N1 2.452(6) 18_666 ?
Ca1 N1 2.452(6) 2_655 ?
Ca1 N1 2.452(6) . ?
Ca1 N1 2.452(6) 16_556 ?
Co1 C1 1.904(6) 15_545 ?
Co1 C1 1.904(6) 3_765 ?
Co1 C1 1.904(6) 14_665 ?
Co1 C1 1.904(6) 2_645 ?
Co1 C1 1.904(6) 13_755 ?
N2 C2 1.443(10) 16_556 ?

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
N1 C1 Co1 179.8(6) . . ?
N2 C2 N2 87.1(11) 3_565 2_665 ?
N2 C2 N2 87.1(10) 3_565 . ?
N2 C2 N2 87.1(11) 2_665 . ?
N2 C2 N3 127.3(7) 3_565 . ?
N2 C2 N3 127.3(7) 2_665 . ?
N2 C2 N3 127.3(7) . . ?
N2 C2 C2 52.7(7) 3_565 16_556 ?
N2 C2 C2 52.7(7) 2_665 16_556 ?
N2 C2 C2 52.7(7) . 16_556 ?
N3 C2 C2 180.0 . 16_556 ?
N1 Ca1 N1 134.85(9) 3_665 17_656 ?
N1 Ca1 N1 79.7(3) 3_665 18_666 ?
N1 Ca1 N1 83.35(19) 17_656 18_666 ?
N1 Ca1 N1 83.35(19) 3_665 2_655 ?
N1 Ca1 N1 79.7(3) 17_656 2_655 ?
N1 Ca1 N1 134.85(9) 18_666 2_655 ?
N1 Ca1 N1 83.34(19) 3_665 . ?
N1 Ca1 N1 134.85(9) 17_656 . ?
N1 Ca1 N1 134.85(9) 18_666 . ?
N1 Ca1 N1 83.34(19) 2_655 . ?
N1 Ca1 N1 134.85(9) 3_665 16_556 ?
N1 Ca1 N1 83.35(19) 17_656 16_556 ?
N1 Ca1 N1 83.35(19) 18_666 16_556 ?
N1 Ca1 N1 134.85(9) 2_655 16_556 ?
N1 Ca1 N1 79.7(3) . 16_556 ?
C1 Co1 C1 180.0(4) 15_545 3_765 ?
C1 Co1 C1 90.0(3) 15_545 14_665 ?
C1 Co1 C1 90.0(3) 3_765 14_665 ?
C1 Co1 C1 90.0(3) 15_545 2_645 ?
C1 Co1 C1 90.0(3) 3_765 2_645 ?
C1 Co1 C1 180.0(4) 14_665 2_645 ?
C1 Co1 C1 90.0(3) 15_545 . ?
C1 Co1 C1 90.0(3) 3_765 . ?
C1 Co1 C1 90.0(3) 14_665 . ?
C1 Co1 C1 90.0(3) 2_645 . ?
C1 Co1 C1 90.0(3) 15_545 13_755 ?
C1 Co1 C1 90.0(3) 3_765 13_755 ?
C1 Co1 C1 90.0(3) 14_665 13_755 ?
C1 Co1 C1 90.0(3) 2_645 13_755 ?
C1 Co1 C1 180.0 . 13_755 ?
C1 N1 Ca1 175.2(5) . . ?
C2 N2 C2 74.5(14) . 16_556 ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
N2 C2 N2 C2 -43.6(5) 3_565 . . 16_556 ?
N2 C2 N2 C2 43.6(5) 2_665 . . 16_556 ?
N3 C2 N2 C2 179.999(6) . . . 16_556 ?

_refine_diff_density_max         2.140
_refine_diff_density_min         -0.840
_refine_diff_density_rms         0.176

_shelx_res_file                  
;

    1.res created by SHELXL-2014/7

TITL 1 in P6(3)/mmc
CELL 0.71073   7.5750   7.5750  13.3135  90.000  90.000 120.000
ZERR    6.00   0.0069   0.0069   0.0198   0.000   0.000   0.000
LATT 1
SYMM -Y, X-Y, Z
SYMM -X+Y, -X, Z
SYMM -X, -Y, 0.5+Z
SYMM Y, -X+Y, 0.5+Z
SYMM X-Y, X, 0.5+Z
SYMM Y, X, -Z
SYMM X-Y, -Y, -Z
SYMM -X, -X+Y, -Z
SYMM -Y, -X, 0.5-Z
SYMM -X+Y, Y, 0.5-Z
SYMM X, X-Y, 0.5-Z
SFAC C  H  N  O  Ca Co
UNIT 6 6 6 6 6 6
L.S. 200
ACTA
BOND
FMAP 2
PLAN 20
conf
simu 0.003 n2 n3 c2
simu 0.001 n1 c1
delu 0.003 n2 n3 c2
isor 0.01 n2 c2 c1 n1
isor 0.01 ca1 co1
isor 0.003 c1
dfix 1.45 0.01 c2 n2 c2 n3
WGHT    0.109900    5.925900
FVAR       1.24148
C1    1    0.881558    0.118442    0.082595    10.50000    0.01557    0.01557 =
         0.01143   -0.00008    0.00008    0.00847
C2    1    0.333333    0.666667    0.184395    10.08333    0.03856    0.03856 =
         0.02815    0.00000    0.00000    0.01928
CA1   5    0.666667    0.333333    0.250000    10.08333    0.01100    0.01100 =
         0.00346    0.00000    0.00000    0.00550
CO1   6    1.000000    0.000000    0.000000    10.08333    0.00934    0.00934 =
         0.00268    0.00000    0.00000    0.00467
N1    3    0.810162    0.189838    0.131971    10.50000    0.01634    0.01634 =
         0.01201   -0.00037    0.00037    0.00850
N2    3    0.245825    0.491651    0.250000    10.08333    0.04452    0.03717 =
         0.02904    0.00000    0.00000    0.01859
N3    3    0.333333    0.666667    0.075259    10.16667    0.03649    0.03649 =
         0.02811    0.00000    0.00000    0.01824
HKLF 4

REM  1 in P6(3)/mmc
REM R1 =  0.0702 for     305 Fo > 4sig(Fo)  and  0.0718 for all     320 data
REM     27 parameters refined using     59 restraints

END

WGHT      0.1100      5.9148

REM Highest difference peak  2.140,  deepest hole -0.840,  1-sigma level  0.176
Q1    1   0.3350  0.5147  0.2500  10.50000  0.05    2.14
Q2    1   0.1851  0.5925  0.2500  10.25000  0.05    1.75
Q3    1   0.0527  0.5264  0.2500  10.25000  0.05    0.50
Q4    1   0.7430  0.1341  0.1181  11.00000  0.05    0.25
Q5    1   0.7436  0.0764  0.2289  11.00000  0.05    0.24
Q6    1   0.8507  0.1492  0.2227  10.50000  0.05    0.23
Q7    1   0.1920  0.8080  0.0830  10.50000  0.05    0.22
Q8    1   0.2294  0.4588  0.0849  10.50000  0.05    0.19
Q9    1   0.3972  0.7943  0.1511  10.50000  0.05    0.18
Q10   1   0.8498  0.1502  0.1554  10.50000  0.05    0.17
Q11   1   0.2667  0.5334  0.1420  10.50000  0.05    0.17
Q12   1   0.6222  0.4800  0.2500  10.50000  0.05    0.16
Q13   1   0.7306  0.2694  0.0642  10.50000  0.05    0.16
Q14   1   0.4984  0.9969  0.0549  10.50000  0.05    0.15
Q15   1   0.7781 -0.0114  0.1991  11.00000  0.05    0.14
Q16   1   0.1762  0.2106  0.2500  10.50000  0.05    0.13
Q17   1   1.0000  0.0000  0.1718  10.16667  0.05    0.13
Q18   1   0.8831  0.3530  0.0687  11.00000  0.05    0.11
Q19   1   0.9329  0.0671  0.1606  10.50000  0.05    0.11
Q20   1   1.1305  0.2611  0.1296  10.50000  0.05    0.11
;
_shelx_res_checksum              44886

# start Validation Reply Form
_vrf_PLAT043_1-93K               
;
PROBLEM: Calculated and Reported Mol. Weight Differ by ..       6.05 Check 
RESPONSE:The hydrogen atoms were not added because of the highly disordered 
of the guest cation.
;
