Hydrophobic Polyoxometalate-Based Metal-Organic Framework for Efficient CO<sub>2</sub> Photoconversion.
Li, Xiao-Xin; Liu, Jiang; Zhang, Lei; Dong, Long-Zhang; Xin, Zhi-Feng; Li, Shun-Li; Huang-Fu, Xue-Qing; Huang, Kai; Lan, Ya-Qian; ACS applied materials & interfaces 11 (2019) 25790–25795; doi:10.1021/acsami.9b03861

data_4514453
_publ_section_title
;
 Hydrophobic Polyoxometalate-Based Metal-Organic Framework for Efficient
 CO<sub>2</sub> Photoconversion.
;
_journal_issue                   29
_journal_name_full               'ACS applied materials &amp; interfaces'
_journal_page_first              25790
_journal_page_last               25795
_journal_paper_doi               10.1021/acsami.9b03861
_journal_volume                  11
_journal_year                    2019
_chemical_formula_moiety         'C124 H80 F24 Mo24 O104 P2 Zn8, 5(C16 H36 N)'
_chemical_formula_sum            'C204 H260 F24 Mo24 N5 O104 P2 Zn8'
_chemical_formula_weight         7789.61
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-01-25
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 101.090(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   16.6538(15)
_cell_length_b                   26.557(2)
_cell_length_c                   33.040(3)
_cell_measurement_reflns_used    9051
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      27.494
_cell_measurement_theta_min      2.49
_cell_volume                     14340(2)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 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    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0299
_diffrn_reflns_av_unetI/netI     0.0179
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       34
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            134621
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.534
_diffrn_reflns_theta_min         1.495
_diffrn_source                   'SSRF, Beamline B17B'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.770
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5292
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0852 before and 0.0443 after correction. The Ratio of minimum to maximum transmission is 0.7098. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'dull dark brown'
_exptl_crystal_colour_lustre     dull
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.804
_exptl_crystal_description       block
_exptl_crystal_F_000             7690
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.29
_exptl_crystal_size_min          0.26
_refine_diff_density_max         0.811
_refine_diff_density_min         -1.219
_refine_diff_density_rms         0.117
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.170
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1181
_refine_ls_number_reflns         16441
_refine_ls_number_restraints     777
_refine_ls_restrained_S_all      1.160
_refine_ls_R_factor_all          0.0514
_refine_ls_R_factor_gt           0.0402
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0241P)^2^+146.3831P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0954
_refine_ls_wR_factor_ref         0.1035
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14210
_reflns_number_total             16441
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            am9b03861_si_001.cif
_cod_data_source_block           NNU29
_cod_database_code               4514453
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.656
_shelx_estimated_absorpt_t_min   0.610
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C34-C35 = C34-C33 = C32-C33 = N1-C32 = N1-C36 = C37-C36 = C37-C38 = C39-C38 =
 N1-C40 = C41-C40 = C42-C41 = C42-C43 = N1-C44 = C44-C45 = C46-C45 = C46-C47
 1.5 with sigma of 0.02
 N2-C48A = N2-C48B = C49A-C48A = C49B-C48B = C50A-C49A = C50B-C49B = C51B-C50B
 = C50A-C51A
 1.52 with sigma of 0.02
 C62A-C61A
 1.5 with sigma of 0.02
 C63A-C62A
 1.5 with sigma of 0.02
 C63A-C61A
 2.7 with sigma of 0.02
 C63B-C61B
 2.7 with sigma of 0.02
 C61B-C62B = C62B-C63B
 1.5 with sigma of 0.02
 C53B-C54A
 1.5 with sigma of 0.02
 C55A-C53A
 2.6 with sigma of 0.02
 C55A-C54A
 1.5 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
F1A \\sim F2A \\sim F3A \\sim C16A \\sim F1B \\sim F2B \\sim F3B \\sim C16B:
within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02
N1 \\sim C32 \\sim C33 \\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim C38 \\sim
C39 \\sim C40 \\sim C41 \\sim C42 \\sim C43 \\sim C44 \\sim C45 \\sim C46 \\sim
C47: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
N3 \\sim C56A \\sim C57A \\sim C58A \\sim C59A \\sim C60A \\sim C61A \\sim C62A
\\sim C63A \\sim C56B \\sim C57B \\sim C58B \\sim C59B \\sim C60B \\sim C61B
\\sim C62B \\sim C63B: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
F4A \\sim F5A \\sim F6A \\sim C17B \\sim F4B \\sim F5B \\sim F6B \\sim C17A:
within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02
N2 \\sim C48B \\sim C49B \\sim C50B \\sim C51B \\sim C52B \\sim C53B \\sim C54B
\\sim C55B \\sim C48A \\sim C49A \\sim C50A \\sim C51A \\sim C52A \\sim C53A
\\sim C54A \\sim C55A: within 1.7A with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(N1) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C32) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C36) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C17B) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(F5B) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
4. Others
 Sof(C56B)=Sof(H56c)=Sof(H56d)=Sof(C57B)=Sof(H57c)=Sof(H57d)=Sof(C58B)=
 Sof(H58c)=Sof(H58d)=Sof(C59B)=Sof(H59d)=Sof(H59e)=Sof(H59f)=Sof(C60B)=
 Sof(H60c)=Sof(H60d)=Sof(C61B)=Sof(H61c)=Sof(H61d)=Sof(C62B)=Sof(H62c)=
 Sof(H62d)=Sof(C63B)=Sof(H63d)=Sof(H63e)=Sof(H63f)=1-FVAR(1)
 Sof(C56A)=Sof(H56a)=Sof(H56b)=Sof(C57A)=Sof(H57a)=Sof(H57b)=Sof(C58A)=
 Sof(H58a)=Sof(H58b)=Sof(C59A)=Sof(H59a)=Sof(H59b)=Sof(H59c)=Sof(C60A)=
 Sof(H60a)=Sof(H60b)=Sof(C61A)=Sof(H61a)=Sof(H61b)=Sof(C62A)=Sof(H62a)=
 Sof(H62b)=Sof(C63A)=Sof(H63a)=Sof(H63b)=Sof(H63c)=FVAR(1)
 Sof(C48A)=Sof(H48c)=Sof(H48d)=Sof(C49A)=Sof(H49c)=Sof(H49d)=Sof(C50A)=
 Sof(H50c)=Sof(H50d)=Sof(C51A)=Sof(H51d)=Sof(H51e)=Sof(H51f)=Sof(C52A)=
 Sof(H52c)=Sof(H52d)=Sof(C53A)=Sof(H53c)=Sof(H53d)=Sof(C54A)=Sof(H54c)=
 Sof(H54d)=Sof(C55A)=Sof(H55d)=Sof(H55e)=Sof(H55f)=1-FVAR(2)
 Sof(C48B)=Sof(H48a)=Sof(H48b)=Sof(C49B)=Sof(H49a)=Sof(H49b)=Sof(C50B)=
 Sof(H50a)=Sof(H50b)=Sof(C51B)=Sof(H51a)=Sof(H51b)=Sof(H51c)=Sof(C52B)=
 Sof(H52a)=Sof(H52b)=Sof(C53B)=Sof(H53a)=Sof(H53b)=Sof(C54B)=Sof(H54a)=
 Sof(H54b)=Sof(C55B)=Sof(H55a)=Sof(H55b)=Sof(H55c)=FVAR(2)
 Fixed Sof: F1A(0.5) F2A(0.5) F3A(0.5) F4A(0.5) F5A(0.5) F6A(0.5) C16A(0.5)
 C17B(0.5) F1B(0.5) F2B(0.5) F3B(0.5) F4B(0.5) F5B(0.5) F6B(0.5) C16B(0.5)
 C17A(0.5) N1(0.25) C32(0.25) H32a(0.25) H32b(0.25) C33(0.25) H33a(0.25)
 H33b(0.25) C34(0.25) H34a(0.25) H34b(0.25) C35(0.25) H35a(0.25) H35b(0.25)
 H35c(0.25) C36(0.25) H36a(0.25) H36b(0.25) C37(0.25) H37a(0.25) H37b(0.25)
 C38(0.25) H38a(0.25) H38b(0.25) C39(0.25) H39a(0.25) H39b(0.25) H39c(0.25)
 C40(0.25) H40a(0.25) H40b(0.25) C41(0.25) H41a(0.25) H41b(0.25) C42(0.25)
 H42a(0.25) H42b(0.25) C43(0.25) H43a(0.25) H43b(0.25) H43c(0.25) C44(0.25)
 H44a(0.25) H44b(0.25) C45(0.25) H45a(0.25) H45b(0.25) C46(0.25) H46a(0.25)
 H46b(0.25) C47(0.25) H47a(0.25) H47b(0.25) H47c(0.25)
5.a Riding coordinates:
 C55A(H55d,H55e,H55f)
5.b Secondary CH2 refined with riding coordinates:
 C8(H8a,H8b), C24(H24a,H24b), C48B(H48a,H48b), C49B(H49a,H49b), C50B(H50a,
 H50b), C52B(H52a,H52b), C53B(H53a,H53b), C54B(H54a,H54b), C48A(H48c,H48d),
 C49A(H49c,H49d), C50A(H50c,H50d), C52A(H52c,H52d), C53A(H53c,H53d), C54A(H54c,
 H54d), C56A(H56a,H56b), C57A(H57a,H57b), C58A(H58a,H58b), C60A(H60a,H60b),
 C61A(H61a,H61b), C62A(H62a,H62b), C56B(H56c,H56d), C57B(H57c,H57d), C58B(H58c,
 H58d), C60B(H60c,H60d), C61B(H61c,H61d), C62B(H62c,H62d), C32(H32a,H32b),
 C33(H33a,H33b), C34(H34a,H34b), C36(H36a,H36b), C37(H37a,H37b), C38(H38a,H38b),
  C40(H40a,H40b), C41(H41a,H41b), C42(H42a,H42b), C44(H44a,H44b), C45(H45a,
 H45b), C46(H46a,H46b)
5.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C10(H10), C11(H11), C13(H13), C14(H14),
 C19(H19), C20(H20), C22(H22), C23(H23), C26(H26), C27(H27), C29(H29), C30(H30)
5.d Idealised Me refined as rotating group:
 C51B(H51a,H51b,H51c), C55B(H55a,H55b,H55c), C51A(H51d,H51e,H51f), C59A(H59a,
 H59b,H59c), C63A(H63a,H63b,H63c), C59B(H59d,H59e,H59f), C63B(H63d,H63e,H63f),
 C35(H35a,H35b,H35c), C39(H39a,H39b,H39c), C43(H43a,H43b,H43c), C47(H47a,H47b,
 H47c)
;
_olex2_submission_special_instructions 'No special instructions were received'