Altering the solubility of metal-organic polyhedra <i>via</i> pendant functionalization of Cp<sub>3</sub>Zr<sub>3</sub>O(OH)<sub>3</sub> nodes.
Sullivan, Meghan G.; Sokolow, Gregory E.; Jensen, Eric T.; Crawley, Matthew R.; MacMillan, Samantha N.; Cook, Timothy R.; Dalton transactions (Cambridge, England : 2003) 52 (2023) 338–346; doi:10.1039/d2dt03401h

data_7711920
_publ_section_title
;
 Altering the solubility of metal-organic polyhedra <i>via</i> pendant
 functionalization of Cp<sub>3</sub>Zr<sub>3</sub>O(OH)<sub>3</sub> nodes.
;
_journal_issue                   2
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              338
_journal_page_last               346
_journal_paper_doi               10.1039/d2dt03401h
_journal_volume                  52
_journal_year                    2023
_chemical_formula_moiety         'C96 H84 O20 Zr6, 2(Cl), 0.5(O), 2(C3 H7 N O)'
_chemical_formula_sum            'C102 H98 Cl2 N2 O22.5 Zr6'
_chemical_formula_weight         2330.04
_chemical_name_common            ZrMOP-ben-lantern
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-11-29
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-12-02 deposited with the CCDC.	2022-12-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.6610(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   23.8868(3)
_cell_length_b                   14.9932(2)
_cell_length_c                   33.5014(3)
_cell_measurement_reflns_used    29676
_cell_measurement_temperature    101(1)
_cell_measurement_theta_max      76.7590
_cell_measurement_theta_min      2.6960
_cell_volume                     11658.7(2)
_computing_cell_refinement       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.58a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.15
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.985
_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   -119.00 -32.00   0.50    2.93    --  -48.30 -65.00   4.00  174
  2  \w    -65.00  24.00   0.50    2.93    --  -48.30  65.00 140.00  178
  3  \w    -23.00  65.00   0.50    2.93    --   48.30 -65.00   4.00  176
  4  \w    -70.00 -45.00   0.50   11.72    --  -86.25  65.00 140.00   50
  5  \w   -138.00-113.00   0.50   11.72    --  -86.25 -65.00   4.00   50
  6  \w    101.00 127.00   0.50   11.72    --  107.75  65.00 140.00   52
  7  \w     39.00  74.00   0.50   11.72    --  107.75 -65.00   4.00   70
  8  \w    142.00 168.00   0.50   11.72    --  107.75  65.00 140.00   52
  9  \w   -113.00 -88.00   0.50    2.93    --  -48.30-125.00-180.00   50
 10  \w     52.00  77.00   0.50    2.93    --   48.30  65.00 140.00   50
 11  \w     -8.00  20.00   0.50    2.93    --   48.30 -19.00-180.00   56
 12  \w    -45.00 -16.00   0.50   11.72    --  -86.25  45.00 -60.00   58
 13  \w     96.00 124.00   0.50   11.72    --  107.75  61.00-120.00   56
 14  \w    136.00 169.00   0.50   11.72    --  107.75  61.00-120.00   66
 15  \w     40.00  65.00   0.50   11.72    --  107.75 -61.00  60.00   50
 16  \w     36.00  66.00   0.50   11.72    --  107.75 -61.00  30.00   60
 17  \w     38.00  63.00   0.50   11.72    --  107.75 -61.00 -60.00   50
 18  \w     63.00  89.00   0.50   11.72    --  107.75 -94.00  60.00   52
 19  \w     42.00  71.00   0.50   11.72    --  107.75 -61.00 -90.00   58
 20  \w    102.00 134.00   0.50   11.72    --  107.75  15.00-120.00   64
 21  \w     36.00  65.00   0.50   11.72    --  107.75 -61.00  90.00   58
 22  \w     36.00  69.00   0.50   11.72    --  107.75 -94.00  86.56   66
 23  \w     72.00  98.00   0.50   11.72    --  107.75 -77.00-180.00   52
 24  \w     55.00 110.00   0.50   11.72    --  107.75-125.00  30.00  110
 25  \w     40.00  65.00   0.50   11.72    --  107.75 -77.00-180.00   50
 26  \w     67.00 104.00   0.50   11.72    --  107.75 -94.00 150.00   74
 27  \w     98.00 124.00   0.50   11.72    --  107.75  15.00 120.00   52
 28  \w    151.00 178.00   0.50   11.72    --  107.75  15.00 120.00   54
 29  \w    132.00 164.00   0.50   11.72    --  107.75  15.00 150.00   64
 30  \w     98.00 129.00   0.50   11.72    --  107.75  30.00-120.00   62
 31  \w    132.00 157.00   0.50   11.72    --  107.75  30.00-120.00   50
 32  \w     94.00 120.00   0.50   11.72    --  107.75  61.00  30.00   52
 33  \w    128.00 178.00   0.50   11.72    --  107.75  61.00  30.00  100
 34  \w     42.00  67.00   0.50   11.72    --  107.75 -61.00 -30.00   50
 35  \w     96.00 121.00   0.50   11.72    --  107.75 125.00-120.00   50
 36  \w    134.00 172.00   0.50   11.72    --  107.75 125.00-120.00   76
 37  \w     98.00 142.00   0.50   11.72    --  107.75 125.00  30.00   88
 38  \w    112.00 145.00   0.50   11.72    --  107.75 125.00 150.00   66
 39  \w     97.00 127.00   0.50   11.72    --  107.75  15.00 150.00   60
 40  \w     75.00 106.00   0.50   11.72    --  107.75 -94.00  86.56   62
 41  \w     97.00 178.00   0.50   11.72    --  107.75  61.00 150.00  162
 42  \w     43.00  68.00   0.50   11.72    --  107.75 -77.00 120.00   50
 43  \w     72.00 105.00   0.50   11.72    --  107.75 -77.00 150.00   66
 44  \w    132.00 158.00   0.50   11.72    --  107.75  99.00-164.34   52
 45  \w     41.00  84.00   0.50   11.72    --  107.75 -77.00 -90.00   86
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0376
_diffrn_reflns_av_unetI/netI     0.0280
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            65182
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.138
_diffrn_reflns_theta_min         2.715
_exptl_absorpt_coefficient_mu    5.170
_exptl_absorpt_correction_T_max  0.973
_exptl_absorpt_correction_T_min  0.672
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.58a (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_density_diffrn    1.327
_exptl_crystal_description       block
_exptl_crystal_F_000             4712
_exptl_crystal_recrystallization_method 'Grown from reaction mixture'
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.097
_exptl_crystal_size_min          0.048
_refine_diff_density_max         1.935
_refine_diff_density_min         -0.880
_refine_diff_density_rms         0.128
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     703
_refine_ls_number_reflns         12303
_refine_ls_number_restraints     712
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0766
_refine_ls_R_factor_gt           0.0678
_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^)+(0.1124P)^2^+70.4729P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1992
_refine_ls_wR_factor_ref         0.2098
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10424
_reflns_number_total             12303
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt03401h2.cif
_cod_data_source_block           rmc25_abs
_cod_depositor_comments
'Adding full bibliography for 7711919--7711923.cif.'
_cod_original_formula_sum        'C102 H98 Cl2 N2 O22.50 Zr6'
_cod_database_code               7711920
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.789
_shelx_estimated_absorpt_t_min   0.576
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All O(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C36-C35 = C33-C32 = C32-C31
 1.37 with sigma of 0.02
 C36-C31
 1.38 with sigma of 0.02
 C35-C34 = C34-C33
 1.36 with sigma of 0.02
 C24-C19 = C21-C22 = C22-C23
 1.37 with sigma of 0.02
 C24-C23
 1.38 with sigma of 0.02
 C19-C20 = C20-C21
 1.36 with sigma of 0.02
 C59-C60 = C56-C57 = C57-C58
 1.37 with sigma of 0.02
 C59-C58
 1.38 with sigma of 0.02
 C60-C55 = C55-C56
 1.36 with sigma of 0.02
 C47-C46
 1.38 with sigma of 0.02
 C41-C37 = C41-C40 = C37-C38 = C38-C39 = C39-C40
 1.42 with sigma of 0.02
 C48-C43 = C43-C44
 1.36 with sigma of 0.02
 C47-C48 = C44-C45 = C45-C46
 1.37 with sigma of 0.02
 Zr3-C29 = Zr3-C28 = Zr3-C27 = Zr3-C25 = Zr3-C26
 2.5 with sigma of 0.1
 Zr2-C52 = Zr2-C51 = Zr2-C50 = Zr2-C53 = Zr2-C49
 2.5 with sigma of 0.1
 C19-C21
 2.36 with sigma of 0.04
 C24-C20 = C20-C22 = C21-C23
 2.37 with sigma of 0.04
 C59-C57
 2.38 with sigma of 0.04
 C35-C33
 2.36 with sigma of 0.04
 C24-C22
 2.38 with sigma of 0.04
 C59-C55 = C55-C57 = C56-C58
 2.37 with sigma of 0.04
 C60-C56
 2.36 with sigma of 0.04
 C36-C34 = C34-C32 = C33-C31
 2.37 with sigma of 0.04
 C36-C32
 2.38 with sigma of 0.04
 C41-C38 = C41-C39 = C37-C39 = C38-C40
 2.29 with sigma of 0.04
 C47-C43 = C43-C45 = C44-C46
 2.37 with sigma of 0.04
 C47-C45
 2.38 with sigma of 0.04
 C48-C44
 2.36 with sigma of 0.04
 C36-C35 \\sim C35-C34 \\sim C34-C33 \\sim C33-C32 \\sim C32-C31 \\sim C31-C36
 with sigma of 0.02
 C36-C32 \\sim C36-C34 \\sim C32-C34 \\sim C33-C35 \\sim C33-C31 \\sim C31-C35
 with sigma of 0.04
 C24-C19 \\sim C19-C20 \\sim C20-C21 \\sim C21-C22 \\sim C22-C23 \\sim C23-C24
 with sigma of 0.02
 C24-C22 \\sim C24-C20 \\sim C22-C20 \\sim C21-C19 \\sim C21-C23 \\sim C23-C19
 with sigma of 0.04
 C59-C60 \\sim C60-C55 \\sim C55-C56 \\sim C56-C57 \\sim C57-C58 \\sim C58-C59
 with sigma of 0.02
 C59-C57 \\sim C59-C55 \\sim C57-C55 \\sim C56-C60 \\sim C56-C58 \\sim C58-C60
 with sigma of 0.04
 C37-C38 \\sim C41-C37 \\sim C38-C39 \\sim C41-C40 \\sim C39-C40
 with sigma of 0.02
 C38-C40 \\sim C37-C39 \\sim C41-C39 \\sim C41-C38 \\sim C37-C40
 with sigma of 0.04
 C47-C48 \\sim C48-C43 \\sim C43-C44 \\sim C44-C45 \\sim C45-C46 \\sim C46-C47
 with sigma of 0.02
 C47-C45 \\sim C47-C43 \\sim C45-C43 \\sim C44-C48 \\sim C44-C46 \\sim C46-C48
 with sigma of 0.04
 C63-C61 \\sim C65-C64
 with sigma of 0.04
 C62-C61 \\sim C66-C64
 with sigma of 0.04
 O12-N1 \\sim O13-N2
 with sigma of 0.04
 O12-C62 \\sim O13-C66
 with sigma of 0.02
 C63-C62 \\sim C65-C66
 with sigma of 0.04
 N1-C63 \\sim N2-C65
 with sigma of 0.02
 N1-C62 \\sim N2-C66
 with sigma of 0.02
 N1-C61 \\sim N2-C64
 with sigma of 0.02
3. Restrained planarity
 C31, C32, C33, C34, C35, C36
 with sigma of 0.1
 C55, C56, C57, C58, C59, C60
 with sigma of 0.1
 C19, C20, C21, C22, C23, C24
 with sigma of 0.1
 C37, C38, C39, C40, C41
 with sigma of 0.1
 C43, C44, C45, C46, C47, C48
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C31 \\sim C32 \\sim C33 \\sim C34 \\sim C35 \\sim C36: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
C55 \\sim C56 \\sim C57 \\sim C58 \\sim C59 \\sim C60: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
C37 \\sim C38 \\sim C39 \\sim C40 \\sim C41: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim C48: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
O12 \\sim N1 \\sim C61 \\sim C62 \\sim C63: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(C42) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C18) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C30) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C43) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C46)
\\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C42) \\sim Ueq,
Uanis(C56) \\sim Ueq, Uanis(C57) \\sim Ueq, Uanis(C58) \\sim Ueq, Uanis(C59)
\\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C55) \\sim Ueq: with sigma of 0.1 and
sigma for terminal atoms of 0.2
5. Rigid body (RIGU) restrains
 C55, C56, C57, C58, C59, C60
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C19, C20, C21, C22, C23, C24
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C43, C44, C45, C46, C47, C48
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C37, C38, C39, C40, C41
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C42
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C31, C32, C33, C34, C35, C36
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C13, C14, C15, C16, C17
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C13, C14, C15, C16, C17, C18, C19
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C49)=Sof(H49)=Sof(C50)=Sof(H50)=Sof(C51)=Sof(H51)=Sof(C52)=Sof(H52)=
 Sof(C53)=Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(C55)=Sof(C56)=Sof(H56)=Sof(C57)=
 Sof(H57)=Sof(C58)=Sof(H58)=Sof(C59)=Sof(H59)=Sof(C60)=Sof(H60)=1-FVAR(1)
 Sof(C37)=Sof(C38)=Sof(H38)=Sof(C39)=Sof(H39)=Sof(C40)=Sof(H40)=Sof(C41)=
 Sof(H41)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(C43)=Sof(C44)=Sof(H44)=Sof(C45)=
 Sof(H45)=Sof(C46)=Sof(H46)=Sof(C47)=Sof(H47)=Sof(C48)=Sof(H48)=FVAR(1)
 Fixed Sof: O11(0.25) O12(0.75) N1(0.75) C61(0.75) H61A(0.75) H61B(0.75)
 H61C(0.75) C62(0.75) H62(0.75) C63(0.75) H63A(0.75) H63B(0.75) H63C(0.75)
 O13(0.25) N2(0.25) C64(0.25) H64A(0.25) H64B(0.25) H64C(0.25) C65(0.25)
 H65A(0.25) H65B(0.25) H65C(0.25) C66(0.25) H66(0.25)
7.a Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C30(H30A,H30B), C54(H54A,H54B), C42(H42A,H42B)
7.b Me refined with riding coordinates:
 C63(H63A,H63B,H63C), C64(H64A,H64B,H64C)
7.c Aromatic/amide H refined with riding coordinates:
 O2(H2), O3(H3), O4(H4), C3(H3A), C4(H4A), C7(H7), C8(H8), C11(H11), C12(H12),
 C13(H13), C14(H14), C15(H15), C16(H16), C24(H24), C20(H20), C21(H21), C22(H22),
  C23(H23), C25(H25), C26(H26), C27(H27), C28(H28), C32(H32), C33(H33),
 C34(H34), C35(H35), C36(H36), C49(H49), C50(H50), C51(H51), C52(H52), C56(H56),
  C57(H57), C58(H58), C59(H59), C60(H60), C38(H38), C39(H39), C40(H40),
 C41(H41), C44(H44), C45(H45), C46(H46), C47(H47), C48(H48), C62(H62), C66(H66)
7.d Fitted hexagon refined as free rotating group:
 C24(C19,C20,C21,C22,C23)
7.e Idealised Me refined as rotating group:
 C61(H61A,H61B,H61C), C65(H65A,H65B,H65C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 645 electrons were 
found in a volume of 2281\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
4[C3H7NO] per Asymmetric Unit 
which account for 640 electrons 
per unit cell.
;
_shelx_res_checksum              20755
_shelx_hkl_checksum              43525
_shelx_fab_checksum              44643
_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
;