# Supplementary Information (SI) for Inorganic Chemistry Frontiers.
# This journal is © the Partner Organisations 2026

####################################################################### 
# 
# 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_V-MOF_Bare
_audit_block_doi                 10.5517/ccdc.csd.cc2788kc
_database_code_depnum_ccdc_archive 'CCDC 2063532'
loop_
_citation_id
_citation_doi
_citation_year
1 10.1021/jacs.1c01883 2021
loop_
_audit_author_name
_audit_author_address
'Hayden A. Evans'
;NIST
United States of America
;
_audit_update_record             
;
2021-03-02 deposited with the CCDC.	2025-11-28 downloaded from the CCDC.
;
_chemical_name_mineral           V-MOF
_chemical_formula_sum            'C6 H2 Cl1.40 N3 O V'
_chemical_formula_weight         232.68
_cell_formula_units_Z            18
_cell_length_a                   38.8820(9)
_cell_length_b                   38.8820(9)
_cell_length_c                   8.310(1)
_cell_angle_alpha                90.0
_cell_angle_beta                 90.0
_cell_angle_gamma                120.0
_cell_volume                     10880(3)
_exptl_crystal_density_diffrn    0.643
_symmetry_cell_setting           trigonal
_symmetry_space_group_name_H-M   'R -3 m'
_symmetry_space_group_name_Hall  '-R 3 2'
_refine_ls_number_parameters     36
_refine_ls_goodness_of_fit_all   1.04
_refine_ls_number_restraints     0
_refine_ls_matrix_type           full
_diffrn_radiation_type           neutron
_diffrn_radiation_wavelength     2.079
_diffrn_measurement_device_type  'BT1 NCNR - Powder diffractometer'

_diffrn_ambient_temperature      100
_cell_measurement_temperature    100
_diffrn_ambient_pressure         ?
_cell_measurement_theta_max      120
_cell_measurement_theta_min      3
_cell_measurement_reflns_used    1166
_diffrn_reflns_number            1166
_diffrn_reflns_av_R_equivalents  0.0
_diffrn_measured_fraction_theta_full 1.0
_exptl_crystal_description       N/A

loop_
_symmetry_equiv_pos_site_id
_symmetry_equiv_pos_as_xyz
1 +x,+y,+z
2 -y,x-y,+z
3 y-x,-x,+z
4 y-x,+y,+z
5 -y,-x,+z
6 +x,x-y,+z
-1 -x,-y,-z
-2 +y,y-x,-z
-3 x-y,+x,-z
-4 x-y,-y,-z
-5 +y,+x,-z
-6 -x,y-x,-z
101 +x+1/3,+y+2/3,+z+2/3
102 -y+1/3,x-y+2/3,+z+2/3
103 y-x+1/3,-x+2/3,+z+2/3
104 y-x+1/3,+y+2/3,+z+2/3
105 -y+1/3,-x+2/3,+z+2/3
106 +x+1/3,x-y+2/3,+z+2/3
-101 -x+2/3,-y+1/3,-z+1/3
-102 +y+2/3,y-x+1/3,-z+1/3
-103 x-y+2/3,+x+1/3,-z+1/3
-104 x-y+2/3,-y+1/3,-z+1/3
-105 +y+2/3,+x+1/3,-z+1/3
-106 -x+2/3,y-x+1/3,-z+1/3
201 +x+2/3,+y+1/3,+z+1/3
202 -y+2/3,x-y+1/3,+z+1/3
203 y-x+2/3,-x+1/3,+z+1/3
204 y-x+2/3,+y+1/3,+z+1/3
205 -y+2/3,-x+1/3,+z+1/3
206 +x+2/3,x-y+1/3,+z+1/3
-201 -x+1/3,-y+2/3,-z+2/3
-202 +y+1/3,y-x+2/3,-z+2/3
-203 x-y+1/3,+x+2/3,-z+2/3
-204 x-y+1/3,-y+2/3,-z+2/3
-205 +y+1/3,+x+2/3,-z+2/3
-206 -x+1/3,y-x+2/3,-z+2/3

# ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS


loop_
_atom_site_type_symbol
_atom_site_label
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_occupancy
_atom_site_thermal_displace_type
_atom_site_U_iso_or_equiv
_atom_site_symmetry_multiplicity
V V_a 0.36496(25) 0.0316(3) 0.83333 1.0 Uiso 0.07599 18
Cl Cl_a 0.3920(4) 0.0 1.0 1.0 Uiso 0.07599 18
Cl Cl_b 0.243(1) 0.0 0.5 0.4 Uiso 0.07599 18
N N_a 0.3581(14) 0.0 0.5 1.0 Uiso 0.119(7) 18
N N_b 0.3847(9) 0.0143(10) 0.626(4) 1.0 Uiso 0.119(7) 36
C C_a 0.4184(13) 0.010(2) 0.573(6) 1.0 Uiso 0.119(7) 36
C C_b 0.4493(12) 0.0171(17) 0.658(6) 1.0 Uiso 0.119(7) 36
C C_c 0.4774(12) 0.0131(18) 0.570(5) 1.0 Uiso 0.119(7) 36
O O_a 0.5070(12) 0.014(2) 0.645(9) 1.0 Uiso 0.119(7) 18
H H_a 0.452(2) 0.028(3) 0.791(7) 1.0 Uiso 0.119(7) 36

# MOLECULAR GEOMETRY

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_1
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
V_a Cl_a 2.41331(30) . 1_555 N
V_a Cl_a 2.41478(30) . 102_544 N
V_a Cl_b 2.28304(31) . 203_555 N
V_a N_a 2.19206(30) . 203_555 N
V_a N_b 2.1273(4) . 1_555 N
V_a N_b 2.1283(4) . -105_435 N
Cl_a V_a 2.41331(30) . 1_555 N
Cl_a V_a 2.41331(30) . -4_557 N
Cl_a Cl_b 3.3830(4) . 102_545 N
Cl_a Cl_b 3.3830(4) . 203_555 N
Cl_a H_a 2.6652(4) . 1_555 N
Cl_a H_a 2.6652(4) . -4_557 N
Cl_b V_a 2.28303(31) . 102_544 N
Cl_b Cl_a 3.3830(4) . 102_544 N
Cl_b Cl_a 3.3830(4) . 203_554 N
N_a V_a 2.19206(30) . 102_544 N
N_a N_b 1.37830(22) . 1_555 N
N_a N_b 1.37830(22) . -4_556 N
N_b V_a 2.1273(4) . 1_555 N
N_b N_a 1.37830(22) . 1_555 N
N_b C_a 1.46891(18) . 1_555 N
C_a N_b 1.46891(18) . 1_555 N
C_a C_a 1.38747(28) . -4_556 N
C_a C_b 1.29873(16) . 1_555 N
C_a C_c 2.23623(30) . 1_555 N
C_b C_a 1.29873(16) . 1_555 N
C_b C_c 1.38648(17) . 1_555 N
C_b H_a 1.16932(28) . 1_555 N
C_c C_a 2.23623(30) . 1_555 N
C_c C_b 1.38648(17) . 1_555 N
C_c C_c 1.45991(26) . -4_556 N
C_c O_a 1.29373(16) . 1_545 N
O_a C_c 1.29373(16) . 1_565 N
O_a C_c 1.29373(16) . 4_665 N
H_a Cl_a 2.6652(4) . 1_555 N
H_a C_b 1.16932(28) . 1_555 N

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_2
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
Cl_a V_a Cl_a 175.7909(4) 1_555 . 102_544 N
Cl_a V_a Cl_b 92.12350(20) 1_555 . 203_555 N
Cl_a V_a N_a 87.91410(20) 1_555 . 203_555 N
Cl_a V_a N_b 89.188(16) 1_555 . 1_555 N
Cl_a V_a N_b 90.945(16) 1_555 . -105_435 N
Cl_a V_a Cl_b 92.08540(20) 102_544 . 203_555 N
Cl_a V_a N_a 87.87700(20) 102_544 . 203_555 N
Cl_a V_a N_b 90.930(16) 102_544 . 1_555 N
Cl_a V_a N_b 89.124(16) 102_544 . -105_435 N
Cl_b V_a N_a 180.0 203_555 . 203_555 N
Cl_b V_a N_b 88.73560(20) 203_555 . 1_555 N
Cl_b V_a N_b 88.70970(30) 203_555 . -105_435 N
N_a V_a N_b 91.29150(30) 203_555 . 1_555 N
N_a V_a N_b 91.26320(20) 203_555 . -105_435 N
N_b V_a N_b 177.4450(5) 1_555 . -105_435 N
V_a Cl_a V_a 92.711(11) 1_555 . -4_557 N
V_a N_a N_b 123.265(7) 102_544 . 1_555 N
V_a N_a N_b 123.285(7) 102_544 . -4_556 N
N_b N_a N_b 113.450(13) 1_555 . -4_556 N
V_a N_b N_a 115.218(13) 1_555 . 1_555 N
V_a N_b C_a 139.6520(22) 1_555 . 1_555 N
N_a N_b C_a 104.980(11) 1_555 . 1_555 N
N_b C_a C_a 108.056(5) 1_555 . -4_556 N
N_b C_a C_b 126.567(12) 1_555 . 1_555 N
C_a C_a C_b 124.388(7) -4_556 . 1_555 N
C_a C_b C_c 112.734(15) 1_555 . 1_555 N
C_a C_b H_a 119.790(9) 1_555 . 1_555 N
C_c C_b H_a 127.304(6) 1_555 . 1_555 N
C_b C_c C_c 118.613(8) 1_555 . -4_556 N
C_b C_c O_a 118.891(15) 1_555 . 1_545 N
C_c C_c O_a 113.450(8) -4_556 . 1_545 N
C_c O_a C_c 122.336(14) 1_565 . 4_665 N

# start Validation Reply Form
_vrf_ATOM007_V-MOF_Bare          
;
PROBLEM: atom_site_aniso_label is missing 
RESPONSE: This is a refinement of powder data and therefore only isotropic values were obtained.
;
_vrf_PLAT602_V-MOF_Bare          
;
PROBLEM: Solvent Accessible VOID(S) in Structure
RESPONSE: This is expected as it is a porous structure.
;
_vrf_PLAT701_V-MOF_Bare          
;
PROBLEM: Bond calc check
RESPONSE: This is a result of the distorted organic ligand modeling. 
;
_vrf_PLAT341_V-MOF_Bare          
;
PROBLEM: Precision on C-C Bonds
RESPONSE: This is consistent with expected values. 
;
_vrf_PLAT702_V-MOF_Bare          
;
PROBLEM: Angle calc check
RESPONSE: This N-V bonding angle is consistent with previously reported metal-ligand bonding. 
;
_vrf_PLAT049_V-MOF_Bare          
;
PROBLEM: Calculated density less than 1.0 gcm3
RESPONSE: This is expected as it is a porous structure.
;
_vrf_PLAT201_V-MOF_Bare          
;
PROBLEM: Isotropic non-H Atoms in Main Residue(s) .......          7 Report
RESPONSE: All atoms were refined isotropically.
;
# end Validation Reply Form
_chemical_name_systematic        V2Cl2.8(btdd)
_chemical_properties_physical    
Air-sensitive,Moisture-sensitive,Hygroscopic,Oxygen-sensitive
####################################################################### 
# 
# 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_Co2Cl2bbta_2mbarNO_298K
_audit_block_doi                 10.5517/ccdc.csd.cc28f4nj
_database_code_depnum_ccdc_archive 'CCDC 2098007'
loop_
_citation_id
_citation_doi
_citation_year
1 10.1039/D1SC03994F 2021
loop_
_audit_author_name
_audit_author_address
'Julia Oktawiec'
;UC Berkeley
United States of America
;
_audit_update_record             
;
2021-07-20 deposited with the CCDC.	2025-11-28 downloaded from the CCDC.
;

_vrf_PLAT601_Co2Cl2bbta_2mbarNO_298K 
;
PROBLEM: Unit Cell Contains Solvent Accessible VOIDS of .        611 Ang**3
RESPONSE: This amount of solvent accessible voids is common for desolvated
and highly porous materials, of this framework is one.
;

_chemical_name_common            Co2Cl2bbta_2mbarNO_298K
_chemical_name_systematic        ?
_chemical_formula_moiety         'C3 H Cl Co N3.80, 0.398(O2)'
_chemical_formula_sum            'C3 H Cl Co N3.80 O0.80'
_chemical_melting_point          ?
_chemical_formula_weight         197.31


loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_source

C C 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Co Co 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

#==============================================================================
# 1. POWDER SPECIMEN AND CRYSTAL DATA

_exptl_crystal_colour            brown
_exptl_crystal_description       powder
_diffrn_ambient_temperature      298
_diffrn_ambient_pressure         ?
_symmetry_cell_setting           hexagonal
_symmetry_space_group_name_h-m   'R -3 m'
_symmetry_Int_Tables_number      166
_space_group_name_Hall           '-R 3 2"'
_chemical_absolute_configuration ?
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.45411
_diffrn_source_type              ?
_cell_measurement_temperature    298
_cell_length_a                   24.48533(39)
_cell_length_b                   24.48533(39)
_cell_length_c                   8.30560(15)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     4312.35(16)
_cell_formula_units_Z            18

loop_
_symmetry_equiv_pos_as_xyz
'-x, -x+y, -z'
'-x, -y, -z'
'-x+y, -x, z'
'-x+y, y, z'
'-y, -x, z'
'-y, x-y, z'
'y, -x+y, -z'
'y, x, -z'
'x-y, -y, -z'
'x-y, x, -z'
'x, y, z'
'x, x-y, z'
'-x-1/3, -x+y+1/3, -z+1/3'
'-x-1/3, -y+1/3, -z+1/3'
'-x+y-1/3, -x+1/3, z+1/3'
'-x+y-1/3, y+1/3, z+1/3'
'-y-1/3, -x+1/3, z+1/3'
'-y-1/3, x-y+1/3, z+1/3'
'y-1/3, -x+y+1/3, -z+1/3'
'y-1/3, x+1/3, -z+1/3'
'x-y-1/3, -y+1/3, -z+1/3'
'x-y-1/3, x+1/3, -z+1/3'
'x-1/3, y+1/3, z+1/3'
'x-1/3, x-y+1/3, z+1/3'
'-x+1/3, -x+y-1/3, -z-1/3'
'-x+1/3, -y-1/3, -z-1/3'
'-x+y+1/3, -x-1/3, z-1/3'
'-x+y+1/3, y-1/3, z-1/3'
'-y+1/3, -x-1/3, z-1/3'
'-y+1/3, x-y-1/3, z-1/3'
'y+1/3, -x+y-1/3, -z-1/3'
'y+1/3, x-1/3, -z-1/3'
'x-y+1/3, -y-1/3, -z-1/3'
'x-y+1/3, x-1/3, -z-1/3'
'x+1/3, y-1/3, z-1/3'
'x+1/3, x-y-1/3, z-1/3'

# The next three fields give the specimen dimensions in mm.  The equatorial 
# plane contains the incident and diffracted beam.

_pd_spec_size_axial              10 # perpendicular to 
# equatorial plane

_pd_spec_size_equat              0.5 # parallel to 
# scattering vector 
# in transmission

_pd_spec_size_thick              ? # parallel to 
# scattering vector 
# in reflection

# The next five fields are character fields that describe the specimen.

_pd_spec_mounting                
;
packed powder in flame-sealed borosilicate glass capillary
;
_pd_spec_mount_mode              transmission # options are 'reflection' 
# or 'transmission'

_pd_spec_shape                   cylinder # options are 'cylinder',
# 'flat_sheet' or 'irregular'

_pd_char_particle_morphology     ?
_pd_char_colour                  brown # use ICDD colour descriptions


# The next four fields are normally only needed for transmission experiments.
_exptl_absorpt_coefficient_mu    ?
_exptl_absorpt_correction_type   ?
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?

#==============================================================================
# 2. EXPERIMENTAL DATA


_exptl_special_details           
; ?
;

# This following item is used to identify the equipment used to record the
# powder pattern when the diffractogram was measured at a laboratory
# other than the authors' home institution, e.g. when neutron or synchrotron
# radiation is used.



_pd_instr_location               
; Advanced Photon Source, Argonne National Laboratory
;

_diffrn_source_target            ?
_diffrn_measurement_device_type  custom
_diffrn_detector_type            'Perkin Elmer a-Si Flat Panel'
_pd_meas_scan_method             fixed
# options are 'step', 'cont',
# 'tof', 'fixed' or
# 'disp' (= dispersive)
_pd_meas_special_details         
;  ?
;

# The following six items are used for angular dispersive measurements only.

_diffrn_radiation_monochromator  'DCM Si(111)'

# The following four items give details of the measured (not processed)
# powder pattern.  Angles are in degrees.

_pd_meas_number_of_points        2999
_pd_meas_2theta_range_min        1.0
_pd_meas_2theta_range_max        19.493833
_pd_meas_2theta_range_inc        0.006167


# The following three items are used for time-of-flight measurements only.

_pd_instr_dist_src/spec          ?
_pd_instr_dist_spec/detc         ?
_pd_meas_2theta_fixed            ?

# The following fields are used to identify the programs used.

_computing_data_collection       ?
_computing_cell_refinement       'TOPAS, Bruker AXS 2005, Karlsruhe, Germany'
_computing_data_reduction        ?
_computing_structure_solution    'TOPAS, Bruker AXS 2005, Karlsruhe, Germany'
_computing_structure_refinement  'TOPAS, Bruker AXS 2005, Karlsruhe, Germany'
_computing_molecular_graphics    ?
_computing_publication_material  'TOPAS, Bruker AXS 2005, Karlsruhe, Germany'

#==============================================================================

# 3. REFINEMENT DATA

# Use the next field to give any special details about the fitting of the
# powder pattern.
_pd_proc_ls_special_details      
;
  
        
;
# The next three items are given as text
_pd_proc_ls_profile_function     'fundamental parameters approach'
_pd_proc_ls_background_function  'Chebychev polynomial'
_pd_proc_ls_pref_orient_corr     March-Dollase
_pd_proc_ls_prof_R_factor        0.027
_pd_proc_ls_prof_wR_factor       0.037
_pd_proc_ls_prof_wR_expected     0.022
_refine_ls_R_I_factor            0.010


_refine_special_details          
; ?
;

_refine_ls_structure_factor_coef Inet
_refine_ls_matrix_type           fullcycle
_refine_ls_weighting_scheme      sigma
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_parameters     43
_refine_ls_number_restraints     0
_refine_ls_number_constraints    7
# The following item is 'CHI squared'
_refine_ls_goodness_of_fit_all   1.68

_refine_ls_restrained_S_all      ?
_refine_ls_restrained_S_obs      ?
_refine_ls_shift/su_max          .01
_refine_ls_shift/su_mean         ?


# The following four items apply to angular dispersive measurements.
# 2theta minimum, maximum and increment (in degrees) are for the 
# intensities used in the refinement.
_pd_proc_2theta_range_min        1.500
_pd_proc_2theta_range_max        19.493833
_pd_proc_2theta_range_inc        0.01

loop_
_pd_proc_wavelength
0.45411

_pd_block_diffractogram_id       ? # The id used for the block
# containing the powder 
# pattern profile (section 11).

# Give appropriate details in the next two text fields.
_pd_proc_info_excluded_regions   ?
_pd_proc_info_data_reduction     ?

#==============================================================================

# 4. ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_symmetry_multiplicity
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_occupancy
_atom_site_U_iso_or_equiv
_atom_site_thermal_displace_type

Co1 Co 18 0.384160(72) 0.3333333 0.3333333 1 0.096(3) Uiso
Cl1 Cl 18 0.3333333 0.24151(10) 0.1666667 1 0.164(4) Uiso
N2 N 18 0.29698(33) 0.3333333 0.3333333 1 0.038(5) Uiso
N1 N 36 0.25825(15) 0.31331(17) 0.20911(57) 1 0.038(5) Uiso
C1 C 36 0.20879(16) 0.32043(21) 0.25537(53) 1 0.038(5) Uiso
C2 C 18 0.15471(20) 0.30942(39) 0.17466(98) 1 0.038(5) Uiso
H1 H 18 0.146264 0.292529 0.0508384 1 0.038(5) Uiso
N3 N 18 0.20654(33) 0.20654(33) 0 0.7950(83) 0.174(17) Uiso
O1 O 36 0.34258(46) 0.49819(24) 0.57727(76) 0.3975(41) 0.43(4) Uiso

#==============================================================================
#5. MOLECULAR GEOMETRY

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
N1 N2 1.319(6) 1.555 N
N1 C1 1.362(6) 1.555 N
C1 C2 1.385(9) 1.555 N
Co1 Cl1 2.3921(17) 1.555 N


loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_publ_flag
Co1 N2 C1 160.65(13) N
Co1 N3 O1 38.42(10) N
N2 N1 Co1 122.2(3) N
