Ligand Excess "Inverse-Defected" Zr<sub>6</sub> Tetrahedral Tetracarboxylate Framework and Its Thermal Transformation.
Nateghi, Bahareh; Domasevitch, Kostiantyn V.; Bulánek, Roman; Janiak, Christoph; Boldog, Ishtvan; Inorganic chemistry 58 (2019) 12786–12797; doi:10.1021/acs.inorgchem.9b01721

data_4345990
_publ_section_title
;
 Ligand Excess &quot;Inverse-Defected&quot; Zr<sub>6</sub> Tetrahedral
 Tetracarboxylate Framework and Its Thermal Transformation.
;
_journal_issue                   19
_journal_name_full               'Inorganic chemistry'
_journal_page_first              12786
_journal_page_last               12797
_journal_paper_doi               10.1021/acs.inorgchem.9b01721
_journal_volume                  58
_journal_year                    2019
_chemical_formula_moiety
;
(Zr 4+)6, C28H29O8 4-, (C28H29O8 3-)2, (O 2-)4, (O H -)6, 2(H2 O), 
;
_chemical_formula_sum            'C114 H96 O36 Zr6'
_chemical_formula_weight         2589.34
_chemical_name_common
;
coordination-polymeric hexazirconium heptahydroxo pentaaqua complex 
with two anions of tetra-1,3,5,7-(carboxyphenyl)adamantane, 
solvate with N,N-dimethylformamide, formic acid and water
;
_chemical_name_systematic
;
poly{[\m~8~-((adamantane-1,3,5,7-tetrayl)tetra(phen-4-yl))tetra(carboxylate-\
\k<i>O:</i>\k<i>O'</i>)][bis(\m~6~-((adamantane-1,3,5,7-\
tetrayl)tetra(phen-4-yl))(tri(carboxylate-\
\k<i>O:</i>\k<i>O')</i>)(carboxylic acid))]
tetra(\m~3~-oxo)tetra(\m~3~-hydroxo)di(hydroxo)tetraaquahexazirconium(IV)},
solvate with N,N-dimethylformamide, formic acid and water
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_method           SHELXL-2014
_cell_angle_alpha                90
_cell_angle_beta                 101.91(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   24.261(5)
_cell_length_b                   30.967(6)
_cell_length_c                   25.454(5)
_cell_measurement_reflns_used    4467
_cell_measurement_temperature    180(2)
_cell_measurement_theta_max      45
_cell_measurement_theta_min      4
_cell_volume                     18712(7)
_computing_molecular_graphics    'Diamond 3.2i (Putz, 2012)'
_computing_publication_material  'publCIF (Westrip, 2010)'
_computing_structure_refinement  'SHELXL-2014 (Sheldrick, 2014)'
_computing_structure_solution    'SHELXS-2008 (Sheldrick, 2008)'
_diffrn_ambient_temperature      180(2)
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.981
_diffrn_measurement_device_type  IPDS
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54186
_diffrn_reflns_av_R_equivalents  0.0268
_diffrn_reflns_av_unetI/netI     0.0196
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       37
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            96167
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        67.686
_diffrn_reflns_theta_max         68.929
_diffrn_reflns_theta_min         3.165
_diffrn_source                   'fine-focus sealed tube'
_exptl_absorpt_coefficient_mu    3.058
_exptl_absorpt_correction_T_max  0.876
_exptl_absorpt_correction_T_min  0.855
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   '(SADABS, 2008)'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    0.919
_exptl_crystal_description       prism
_exptl_crystal_F_000             5232
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.02
_platon_squeeze_details
;
The compound contains primarily DMF in the voids of the structure,
 with possible presence of formic acid and water. According to the 
total potential solvent accessible void there could be up to 
10328/(4*128) = 20.17 molecules of DMF (128 is the molecular volume 
calculated for liquid state, Z = 4). The electron count in the voids 
suggest the presence of 2682/(4*40) = 16.76 molecules of DMF
or molecules of comparable size, i.e. formic acid. 
The isolated compound has lost a significant part of the guest 
molecules upon drying. The presence of approx. 4 molecules of DMF, 
2 molecules of formic acid and 4 molecules of water could be 
ascribed according to the TGA.
;
_refine_diff_density_max         0.696
_refine_diff_density_min         -0.565
_refine_diff_density_rms         0.061
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.985
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     822
_refine_ls_number_reflns         17063
_refine_ls_number_restraints     201
_refine_ls_restrained_S_all      1.013
_refine_ls_R_factor_all          0.0392
_refine_ls_R_factor_gt           0.0341
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0769P)^2^+11.1598P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1072
_refine_ls_wR_factor_ref         0.1100
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14264
_reflns_number_total             17063
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic9b01721_si_002.cif
_cod_data_source_block           1_I-HCOOH-squeeze
_cod_database_code               4345990
_shelxl_version_number           2014-3
_platon_squeeze_void_probe_radius 1.20