Design of cost-efficient and photocatalytically active Zn-based MOFs decorated with Cu2O nanoparticles for CO2 methanation
Cabrero-Antonino, Maria; Remiro-Buenamañana, Sonia; Souto, Manuel; García-Valdivia, Antonio Andres; Choquesillo-Lazarte, Duane; Navalon, Sergio; Rodríguez Diéguez, Antonio; Minguez Espallargas, Guillermo; Garcia, Hermenegildo; Chemical Communications  (2019) –; doi:10.1039/C9CC04446A

data_7124000
_publ_section_title
;
 Design of cost-efficient and photocatalytically active Zn-based MOFs
 decorated with Cu2O nanoparticles for CO2 methanation
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C9CC04446A
_journal_year                    2019
_chemical_formula_moiety         'C15 H7 N6 O7 Zn4'
_chemical_formula_sum            'C15 H7 N6 O7 Zn4'
_chemical_formula_weight         644.75
_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_date             2019-08-12
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2019.07.31 svn.r3643 for OlexSys, GUI svn.r5859)
;
_audit_update_record
;
2019-08-12 deposited with the CCDC.    2019-08-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.296(16)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.643(2)
_cell_length_b                   14.593(2)
_cell_length_c                   10.9639(16)
_cell_measurement_reflns_used    755
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      13.7730
_cell_measurement_theta_min      4.1330
_cell_volume                     2662.8(6)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      120(2)
_diffrn_detector_area_resol_mean 16.0267
_diffrn_detector_type            Sapphire3
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_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    -83.00   9.00   1.00   30.00    --  -15.12 -67.00 -57.24   92
  2  \w    -63.00   7.00   1.00   30.00    --  -15.12 -62.00-173.43   70
  3  \w    -27.00   6.00   1.00   30.00    --  -15.12 -57.00  30.00   33
  4  \w    -29.00   9.00   1.00   30.00    --  -15.12 -67.00  89.15   38
  5  \w    -53.00  42.00   1.00   30.00    --   16.14 -70.00 177.63   95
  6  \w    -31.00  44.00   1.00   30.00    --   18.00 -70.00 119.38   75
  7  \w    -35.00  43.00   1.00   30.00    --   18.00 -69.00 -96.49   78
  8  \w    -51.00  44.00   1.00   30.00    --   18.00 -70.00 -19.16   95
  9  \w    -19.00  44.00   1.00   30.00    --   18.00 -70.00  51.74   63
 10  \w     -5.00  32.00   1.00   30.00    --   16.14  57.00 -30.00   37
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Single source at offset, Sapphire3'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1211
_diffrn_reflns_av_unetI/netI     0.0796
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            6607
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        17.216
_diffrn_reflns_theta_max         17.216
_diffrn_reflns_theta_min         3.354
_exptl_absorpt_coefficient_mu    3.600
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77243
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.'
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.608
_exptl_crystal_description       block
_exptl_crystal_F_000             1260
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.683
_refine_diff_density_min         -0.591
_refine_diff_density_rms         0.149
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.165
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     156
_refine_ls_number_reflns         805
_refine_ls_number_restraints     263
_refine_ls_restrained_S_all      1.001
_refine_ls_R_factor_all          0.1239
_refine_ls_R_factor_gt           0.1035
_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^)+(0.1337P)^2^+94.3016P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2575
_refine_ls_wR_factor_ref         0.2778
_reflns_Friedel_coverage         0.000
_reflns_number_gt                646
_reflns_number_total             805
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc04446a2.cif
_cod_data_source_block           1916084
_cod_original_cell_volume        2662.8(7)
_cod_database_code               7124000
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.672
_shelx_estimated_absorpt_t_min   0.633
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 O8A-C7A = O9A-C7A
 1.25 with sigma of 0.01
 O9B-C7B = O8B-C7B
 1.25 with sigma of 0.02
 C7B-C6B
 1.5 with sigma of 0.02
 O8B-O9B
 2.25 with sigma of 0.02
 O8B-C7B = O9B-C7B
 1.25 with sigma of 0.02
 C7A-C6A
 1.5 with sigma of 0.02
 C1-O2
 1.22 with sigma of 0.001
3. Restrained planarity
 C6B, O9B, C7B, O8B
 with sigma of 0.1
 C6A, C7A, O9A, O8A
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(C11A) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(O2) \\sim Ueq, Uanis(C1) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.001
Uanis(C7A) = Uanis(C7B)
Uanis(O9B) = Uanis(O9A)
Uanis(O8B) = Uanis(O8A)
Uanis(C3B) = Uanis(C4B) = Uanis(C5B) = Uanis(C6B) = Uanis(C10B) = Uanis(C11B) =
Uanis(C3A) = Uanis(C4A) = Uanis(C5A) = Uanis(C6A) = Uanis(C10A)
5. Rigid body (RIGU) restrains
 Zn1, Zn3, O1, N1, N2B, C3B, C11B, N12B, O8A, O9A, N2A, N12A, C7A, C11A, C10A,
 C6A, C5A, C4A, C3A, O8B, O9B, C4B, C5B, C6B, C7B, C10B, Zn2
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O2, C1
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
6. Others
 Sof(N2B)=Sof(C3B)=Sof(C11B)=Sof(N12B)=Sof(O8B)=Sof(O9B)=Sof(C4B)=Sof(H4B)=
 Sof(C5B)=Sof(H5B)=Sof(C6B)=Sof(C7B)=Sof(C10B)=Sof(H10B)=1-FVAR(1)
 Sof(O8A)=Sof(O9A)=Sof(N2A)=Sof(N12A)=Sof(C7A)=Sof(C11A)=Sof(C10A)=Sof(H10A)=
 Sof(C6A)=Sof(C5A)=Sof(H5A)=Sof(C4A)=Sof(H4A)=Sof(C3A)=FVAR(1)
 Fixed Sof: Zn2(0.5) O2(0.5)
7.a Aromatic/amide H refined with riding coordinates:
 C10A(H10A), C5A(H5A), C4A(H4A), C4B(H4B), C5B(H5B), C10B(H10B), C1(H1)
7.b Fitted pentagon refined as free rotating group:
 N1(N2B,C3B,C11B,N12B)
7.c Fitted hexagon refined as free rotating group:
 C11A(C10A,C6A,C5A,C4A,C3A)
;
_shelx_res_checksum              91079
_olex2_submission_special_instructions 'No special instructions were received'