Framework induced deformation modulates the photophysical properties of ZnTetra(4-pyridyl)porphyrin incorporated within a new metal organic framework, RWLAA-1.
Alanazi, Abdulaziz A.; Wojtas, Lukasz; Mayers, Jacob M.; Miksovska, Jaroslava; Larsen, Randy W.; Dalton transactions (Cambridge, England : 2003) 49 (2020) 11668–11674; doi:10.1039/d0dt02050h

data_7705000
_publ_section_title
;
 Framework induced deformation modulates the photophysical properties of
 ZnTetra(4-pyridyl)porphyrin incorporated within a new metal organic
 framework, RWLAA-1.
;
_journal_issue                   33
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              11668
_journal_page_last               11674
_journal_paper_doi               10.1039/d0dt02050h
_journal_volume                  49
_journal_year                    2020
_chemical_formula_moiety
'C307.5 H172.5 N49.5 O48 Zn18, 6(C3 H7 N O), 1.5(O)'
_chemical_formula_sum            'C325.5 H217.5 N55.5 O55.5 Zn18'
_chemical_formula_weight         6970.70
_space_group_crystal_system      hexagonal
_space_group_IT_number           175
_space_group_name_Hall           '-P 6'
_space_group_name_H-M_alt        'P 6/m'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2018-11-19
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-06-08 deposited with the CCDC.	2020-08-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            1
_cell_length_a                   26.8343(9)
_cell_length_b                   26.8343(9)
_cell_length_c                   14.8769(5)
_cell_measurement_reflns_used    9930
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      66.641
_cell_measurement_theta_min      2.971
_cell_volume                     9277.3(5)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker D8 Venture PHOTON II CPAD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0941
_diffrn_reflns_av_unetI/netI     0.0382
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            71805
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        66.722
_diffrn_reflns_theta_max         66.722
_diffrn_reflns_theta_min         3.527
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.823
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.8050
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1382 before and 0.0924 after correction.
The Ratio of minimum to maximum transmission is 0.8050.
The \l/2 correction factor is Not present.
;
_exptl_crystal_density_diffrn    1.248
_exptl_crystal_description       rods
_exptl_crystal_F_000             3543
_refine_diff_density_max         1.104
_refine_diff_density_min         -0.933
_refine_diff_density_rms         0.109
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.162
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     588
_refine_ls_number_reflns         5721
_refine_ls_number_restraints     1362
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.1112
_refine_ls_R_factor_gt           0.1024
_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^)+(0.1430P)^2^+27.4051P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2904
_refine_ls_wR_factor_ref         0.2974
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4962
_reflns_number_total             5721
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0dt02050h2.cif
_cod_data_source_block           RWLAA-1
_cod_depositor_comments          'Adding full bibliography for 7705000.cif.'
_cod_original_cell_volume        9277.3(7)
_cod_original_formula_sum        'C325.50 H217.50 N55.50 O55.50 Zn18'
_cod_database_code               7705000
_shelx_shelxl_version_number     2017/1
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O91-C92 = O56-C57
 1.26 with sigma of 0.02
 N58-C57 = N93-C92
 1.29 with sigma of 0.02
 N93-C95 = N93-C94 = N58-C60 = N58-C59
 1.48 with sigma of 0.02
 H95C-H80
 -2.2 with sigma of 0.02
 O56-N58 = O91-N93
 2.22 with sigma of 0.04
 C57-C60 = C57-C59 = C92-C95 = C92-C94
 2.42 with sigma of 0.04
 C95-C94 = C60-C59
 2.54 with sigma of 0.04
 C79-C76 \\sim C79-C46
 with sigma of 0.02
 C63-C62 \\sim C64-C63 \\sim C65-C64 \\sim C66-C65 \\sim C33-C32 \\sim C34-C33
\\sim C35-C34 \\sim C36-C35
 \\sim C84-C83 \\sim C84-C79 \\sim C80-C79 \\sim C81-C80
 with sigma of 0.02
 N61-C66 \\sim N61-C62 \\sim N31-C36 \\sim N31-C32 \\sim N82-C83 \\sim N82-C81
 with sigma of 0.02
 Zn30-N37 \\sim Zn60-N67 \\sim Zn60-N75 \\sim Zn30-N45 \\sim Zn60-N347 \\sim
Zn30-N55
 with sigma of 0.02
 N55-C47 \\sim N347-C77 \\sim N45-C44 \\sim N75-C74 \\sim N75-C71 \\sim N45-C41
\\sim N67-C68 \\sim N37-C38
 with sigma of 0.02
 C39-C38 \\sim C69-C68 \\sim C42-C41 \\sim C72-C71 \\sim C74-C73 \\sim C44-C43
\\sim C78-C77 \\sim C48-C47
 with sigma of 0.02
 C43-C42 \\sim C73-C72 \\sim C78-C78_$1 \\sim C48-C48_$1 \\sim C69-C69_$1 \\sim
C39-C39_$1
 with sigma of 0.02
 C70-C64 \\sim C40-C34 \\sim C79-C76 \\sim C79-C46
 with sigma of 0.02
3. Restrained planarity
 O56, C57, N58, C60, C59
 with sigma of 0.1
 O91, C92, N93, C95, C94
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Zn30 \\sim N31 \\sim C32 \\sim C33 \\sim C34 \\sim C35 \\sim C36 \\sim N37
\\sim C38 \\sim C39 \\sim C40 \\sim N45 \\sim C41 \\sim C42 \\sim C43 \\sim C44
\\sim C46 \\sim C47 \\sim C48 \\sim N55 \\sim Zn60 \\sim N61 \\sim C62 \\sim
C63 \\sim C64 \\sim C65 \\sim C66 \\sim N67 \\sim C68 \\sim C69 \\sim C70 \\sim
N75 \\sim C74 \\sim C73 \\sim C72 \\sim C71 \\sim C76 \\sim C77 \\sim C78 \\sim
C79 \\sim C80 \\sim C81 \\sim N82 \\sim C83 \\sim C84 \\sim O85 \\sim N347
\\sim O56 \\sim C57 \\sim N58 \\sim C60 \\sim C59 \\sim O92: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
O91 \\sim C92 \\sim N93 \\sim C94 \\sim C95: within 2A with sigma of 0.02 and
sigma for terminal atoms of 0.04
5. Rigid body (RIGU) restrains
 Zn30, N31, C32, C33, C34, C35, C36, N37, C38, C39, C40, N45, C41, C42, C43,
 C44, C46, C47, C48, N55, Zn60, N61, C62, C63, C64, C65, C66, N67, C68, C69,
 C70, N75, C74, C73, C72, C71, C76, C77, C78, C79, C80, C81, N82, C83, C84, O85,
  N347, O56, C57, N58, C60, C59, O92
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O91, C92, N93, C94, C95
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
6. Others
 Fixed Sof: Zn1(0.25) Zn3(0.25) O21(0.25) C22(0.25) O23(0.25) Zn30(0.25)
 N31(0.5) C32(0.5) H32(0.5) C33(0.5) H33(0.5) C34(0.5) C35(0.5) H35(0.5)
 C36(0.5) H36(0.5) N37(0.25) C38(0.5) C39(0.5) H39(0.5) C40(0.5) N45(0.5)
 C41(0.5) C42(0.5) H42(0.5) C43(0.5) H43(0.5) C44(0.5) C46(0.5) C47(0.5)
 C48(0.5) H48(0.5) N55(0.25) O56(0.25) Zn60(0.25) N61(0.5) C62(0.5) H62(0.5)
 C63(0.5) H63(0.5) C64(0.5) C65(0.5) H65(0.5) C66(0.5) H66(0.5) N67(0.25)
 C68(0.5) C69(0.5) H69(0.5) C70(0.5) N75(0.5) C74(0.5) C73(0.5) H73(0.5)
 C72(0.5) H72(0.5) C71(0.5) C76(0.5) C77(0.5) C78(0.5) H78(0.5) O85(0.25)
 C57(0.125) H57(0.125) N58(0.125) C60(0.125) H60A(0.125) H60B(0.125)
 H60C(0.125) C59(0.125) H59C(0.125) H59B(0.125) H59A(0.125) N347(0.25) O91(0.5)
 C92(0.5) H92(0.5) N93(0.5) C94(0.5) H94A(0.5) H94B(0.5) H94C(0.5) C95(0.5)
 H95A(0.5) H95B(0.5) H95C(0.5) O92(0.125)
7.a Me refined with riding coordinates:
 C60(H60A,H60B,H60C), C59(H59C,H59B,H59A), C94(H94A,H94B,H94C), C95(H95A,H95B,
 H95C)
7.b Aromatic/amide H refined with riding coordinates:
 C13(H13), C15(H15), C17(H17), C32(H32), C33(H33), C35(H35), C36(H36),
 C39(H39), C42(H42), C43(H43), C48(H48), C62(H62), C63(H63), C65(H65), C66(H66),
  C69(H69), C73(H73), C72(H72), C78(H78), C80(H80), C81(H81), C83(H83),
 C84(H84), C57(H57), C92(H92)
7.c Fitted pentagon refined as free rotating group:
 N45(C41,C42,C43,C44), N75(C74,C73,C72,C71)
;
_shelx_res_checksum              82361
_shelx_fab_checksum              88591
_olex2_submission_special_instructions 'No special instructions were received'