Functional Versatility of a Series of Zr Metal-Organic Frameworks Probed by Solid-State Photoluminescence Spectroscopy.
Marshall, Ross J.; Kalinovskyy, Yaroslav; Griffin, Sarah L.; Wilson, Claire; Blight, Barry A.; Forgan, Ross S.; Journal of the American Chemical Society 139 (2017) 6253–6260; doi:10.1021/jacs.7b02184

data_4125937
_publ_section_title
;
 Functional Versatility of a Series of Zr Metal-Organic Frameworks Probed
 by Solid-State Photoluminescence Spectroscopy.
;
_journal_issue                   17
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              6253
_journal_page_last               6260
_journal_paper_doi               10.1021/jacs.7b02184
_journal_volume                  139
_journal_year                    2017
_chemical_formula_moiety         'C156 H96 O32 Zr6'
_chemical_formula_sum            'C156 H96 O32 Zr6'
_chemical_formula_weight         3029.64
_space_group_crystal_system      orthorhombic
_space_group_IT_number           74
_space_group_name_Hall           '-I 2b 2'
_space_group_name_H-M_alt        'I m m a'
_symmetry_space_group_name_Hall  '-I 2b 2'
_symmetry_space_group_name_H-M   'I m m a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-10-31
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   28.1510(2)
_cell_length_b                   28.1718(3)
_cell_length_c                   39.9493(4)
_cell_measurement_reflns_used    36359
_cell_measurement_temperature    99.9(4)
_cell_measurement_theta_max      73.8680
_cell_measurement_theta_min      1.9210
_cell_volume                     31682.4(5)
_computing_cell_refinement       'CrysAlisPro 1.171.38.42t (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.42t (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.42t (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.9(4)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            'Pilatus 200/300K'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w    -59.00  33.00   1.00   10.00    --  -38.50  57.00  30.00   92
  2  \w    -94.00  -5.00   1.00   10.00    --  -38.50 125.00 120.00   89
  3  \w    -55.00  37.00   1.00   10.00    --  -38.50  38.00 -60.00   92
  4  \w    -59.00  38.00   1.00   10.00    --  -38.50  38.00-180.00   97
  5  \w     19.00 117.00   1.00   10.00    --   38.89  57.00  30.00   98
  6  \w     26.00  96.00   1.00   10.00    --   38.89-125.00 -30.00   70
  7  \w     93.00 121.00   1.00   10.00    --   38.89  77.00  90.00   28
  8  \w     10.00  86.00   1.00   10.00    --   38.89  77.00  90.00   76
  9  \w    141.00 178.00   1.00   40.00    --  109.04  25.00 -30.00   37
 10  \w     30.00 128.00   1.00   40.00    --  109.04 -38.00  30.00   98
 11  \w     37.00 140.00   1.00   40.00    --  109.04 -25.00  30.00  103
 12  \w     84.00 125.00   1.00   40.00    --  109.04  25.00 -30.00   41
 13  \w     31.00 126.00   1.00   40.00    --  109.04 -50.00-120.00   95
 14  \w     41.00 116.00   1.00   40.00    --  109.04-111.00  60.00   75
 15  \w     31.00  96.00   1.00   40.00    --  109.04 -50.00 150.00   65
 16  \w     37.00 116.00   1.00   40.00    --  109.04-111.00 -90.00   79
 17  \w     27.00  53.00   1.00   40.00    --  109.04 -77.00  60.00   26
 18  \w     80.00 166.00   1.00   40.00    --  109.04  25.00  60.00   86
 19  \w     69.00 141.00   1.00   40.00    --  109.04 -77.00  60.00   72
 20  \w     30.00 117.00   1.00   40.00    --  109.04 -63.00-120.00   87
 21  \w     35.00 140.00   1.00   40.00    --  109.04 -25.00 -90.00  105
 22  \w     32.00 178.00   1.00   40.00    --  109.04  12.00 -60.00  146
 23  \w     32.00 149.00   1.00   40.00    --  109.04 -91.00  60.00  117
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Dual, Cu at zero, Pilatus 200/300K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0541273000
_diffrn_orient_matrix_UB_12      0.0069307000
_diffrn_orient_matrix_UB_13      0.0028618000
_diffrn_orient_matrix_UB_21      -0.0079511500
_diffrn_orient_matrix_UB_22      -0.0501662500
_diffrn_orient_matrix_UB_23      -0.0143178500
_diffrn_orient_matrix_UB_31      0.0011661000
_diffrn_orient_matrix_UB_32      -0.0206465000
_diffrn_orient_matrix_UB_33      0.0356863000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0654
_diffrn_reflns_av_unetI/netI     0.0359
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       47
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            122767
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        66.601
_diffrn_reflns_theta_max         66.601
_diffrn_reflns_theta_min         1.919
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.838
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.92023
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.42t (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    0.635
_exptl_crystal_description       lozenge
_exptl_crystal_F_000             6112
_exptl_crystal_size_max          0.07
_exptl_crystal_size_mid          0.042
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.788
_refine_diff_density_min         -4.047
_refine_diff_density_rms         0.141
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     475
_refine_ls_number_reflns         14629
_refine_ls_number_restraints     508
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0938
_refine_ls_R_factor_gt           0.0886
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1665P)^2^+205.8700P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2499
_refine_ls_wR_factor_ref         0.2547
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12990
_reflns_number_total             14629
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b02184_si_012.cif
_cod_data_source_block           Zr-L2
_cod_depositor_comments
'Adding full bibliography for 4125932--4125938.cif.'
_cod_original_cell_volume        31682.3(5)
_cod_database_code               4125937
_chemical_oxdiff_formula         'C H N O Zr'
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.8433(17) 0.1567(17)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C3-C2 = C7-C2 = C7-C6 = C5-C4 = C4-C3 = C6-C5 = C11-C10 = C15-C10 = C12-C11 =
 C15-C14 = C14-C13 = C13-C12 = C25-C20 = C25-C24 = C24-C23 = C23-C22 = C22-C21 =
  C21-C20 = C3A-C2A = C4A-C3A = C5A-C4A = C11A-C10A = C3B-C2B = C4B-C3B = C5B-
 C4B = C11B-C10B
 1.39 with sigma of 0.02
 C9B-C8B = C19-C18 = C9-C8 = C9A-C8A
 1.18 with sigma of 0.02
 C8-C5 = C9-C10 = C18-C13 = C20-C19 = C8B-C5B = C9B-C10B = C8A-C5A = C9A-C10A
 1.434 with sigma of 0.02
 C12B-C11B = C16-C12 = C17-C15 = C12A-C11A
 1.51 with sigma of 0.02
 C2A-C1A \\sim C2-C1 \\sim C2B-C1B
 with sigma of 0.02
 O10-C1B \\sim O5-C1 \\sim O6-C1 \\sim O9-C1A
 with sigma of 0.02
 C2-C6 \\sim C2-C4 \\sim C7-C5 \\sim C3-C5 \\sim C3-C7 \\sim C4-C6 \\sim
C10-C14 \\sim C10-C12 \\sim C11-C13 ~
 C13-C15 \\sim C11-C15 \\sim C12-C14 \\sim C20-C22 \\sim C21-C23 \\sim C22-C24
\\sim C23-C25 \\sim C24-C20
 \\sim C21-C25
 with sigma of 0.02
 C2A-C4A \\sim C3A-C5A \\sim C3A-C3A_$1 \\sim C4A-C4A_$1
 with sigma of 0.02
 C10A-C11A_$2 \\sim C11A_$1-C10A_$2
 with sigma of 0.02
 C11A-C11A_$1 \\sim C11A_$2-C11A_$3
 with sigma of 0.02
 C2B-C4B \\sim C3B-C5B \\sim C3B-C3B_$4 \\sim C4B-C4B_$4
 with sigma of 0.02
 C10B-C11B_$5 \\sim C11B-C10B_$6 \\sim C11B_$5-C11B_$6 \\sim C11B_$4-C11B
 with sigma of 0.02
4. Restrained planarity
 C10A, C11A, C12A, C11A_$1, C11A_$2, C10A_$2, C11A_$3
 with sigma of 0.1
 C12B_$4, C10B, C11B_$4, C11B_$6, C10B_$5, C11B_$5, C11B
 with sigma of 0.1
5. Uiso/Uaniso restraints and constraints
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9
\\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17
\\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25
\\sim C26 \\sim C1A \\sim C2A \\sim C3A \\sim C4A \\sim C5A \\sim C8A \\sim C9A
\\sim C10A \\sim C11A \\sim C12A \\sim C1B \\sim C2B \\sim C3B \\sim C4B \\sim
C5B \\sim C8B \\sim C9B \\sim C10B \\sim C11B \\sim C12B: within 2A with sigma
of 0.04 and sigma for terminal atoms of 0.08
6. Others
 Fixed Sof: C12A(0.5) H12A(0.5) H12B(0.5) H12C(0.5) C12B(0.5) H12D(0.5)
 H12E(0.5) H12F(0.5)
7.a Me refined with riding coordinates:
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C12A(H12A,H12B,H12C), C12B(H12D,
 H12E,H12F)
7.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C11(H11), C14(H14), C21(H21), C22(H22),
 C24(H24), C25(H25), C3A(H3A), C4A(H4A), C3B(H3B), C4B(H4B)
;
_shelx_res_checksum              34412
_shelx_hkl_checksum              98845
_shelx_fab_checksum              48703
_shelx_shelxl_version_number     2016/6
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.710
_oxdiff_exptl_absorpt_empirical_full_min 0.746