A Diaminopropane-Appended Metal‒Organic Framework Enabling Efficient CO2 Capture from Coal Flue Gas via a Mixed Adsorption Mechanism
Milner, Phillip J.; Siegelman, Rebecca L.; Forse, Alexander C.; Gonzalez, Miguel I.; Runčevski, Tomče; Martell, Jeffrey D.; Reimer, Jeffrey A.; Long, Jeffrey R.; Journal of the American Chemical Society  (2017) –; doi:10.1021/jacs.7b07612

data_4126400
_publ_section_title
;
 A Diaminopropane-Appended Metal--Organic Framework Enabling Efficient CO2
 Capture from Coal Flue Gas via a Mixed Adsorption Mechanism
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.7b07612
_journal_year                    2017
_chemical_formula_moiety         'C20.5 H24.2 N2.6 O6 Zn2'
_chemical_formula_sum            'C20.5 H24.2 N2.6 O6 Zn2'
_chemical_formula_weight         533.79
_chemical_name_common            Zn2(dobpdc)(dmpn)1.3
_space_group_crystal_system      trigonal
_space_group_IT_number           152
_space_group_name_Hall           'P 31 2"'
_space_group_name_H-M_alt        'P 31 2 1'
_symmetry_space_group_name_Hall  'P 31 2"'
_symmetry_space_group_name_H-M   'P 31 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     'intrinsic phasing'
_atom_sites_solution_secondary   difmap
_audit_creation_date             2017-05-22
_audit_creation_method
;
Olex2 1.2
(compiled Mar 28 2017 19:26:29 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            3
_cell_length_a                   21.4559(7)
_cell_length_b                   21.4559(7)
_cell_length_c                   6.7954(3)
_cell_measurement_reflns_used    9801
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30.605
_cell_measurement_theta_min      2.390
_cell_volume                     2709.19(17)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'Bruker APEX3 Bruker-AXS, Madison WI'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 10.42
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker D8 with PHOTON 100 detector'
_diffrn_measurement_method       '\f and \w shutterless scans'
_diffrn_radiation_monochromator  'silicon 111'
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.7749
_diffrn_reflns_av_R_equivalents  0.0662
_diffrn_reflns_av_unetI/netI     0.0397
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            40073
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        27.706
_diffrn_reflns_theta_max         30.629
_diffrn_reflns_theta_min         2.390
_diffrn_source
;
Advanced Light Source, station 11.3.1
;
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.709
_exptl_absorpt_correction_T_max  0.935
_exptl_absorpt_correction_T_min  0.6987
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/2 (Bruker,2014) was used for absorption correction. 
wR2(int) was 0.1673 before and 0.0705 after correction. 
The Ratio of minimum to maximum transmission is 0.7473. 
The \l/2 correction factor is Not present.'
;
_exptl_crystal_colour            'pale yellow'
_exptl_crystal_colour_primary    'pale yellow'
_exptl_crystal_density_diffrn    1.002
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             839
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.191
_refine_diff_density_min         -3.317
_refine_diff_density_rms         0.182
_refine_ls_abs_structure_details
;
 Refined as a 2-component inversion twin.
Thermal parameters were refined anisotropically for all non-hydrogen atoms. 
All hydrogen atoms were placed in ideal positions and refined using a 
riding model. The structure shows 2,2-dimethyl-1,3-propanediaminemine 
coordinated to Zn centers of a metal-organic framework. Due to the mobility 
of the diamine within the framework pore, the diamine required distance 
(SADI for C-C bonds) and displacement parameter (SIMU and RIGU) restraints. 
The chemical occupancy of the diamine refined to 65(2)% and was fixed in the 
final refinement. However, the occupancy of the nitrogen bound to Zn (N1) was 
kept at full occupancy to account for solvent or water that is bound on sites 
where the diamine is absent. The reported formula, however, reflects the 
nitrogen content for the diamine alone.
;
_refine_ls_abs_structure_Flack   0.47(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.303
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     167
_refine_ls_number_reflns         4317
_refine_ls_number_restraints     114
_refine_ls_restrained_S_all      1.291
_refine_ls_R_factor_all          0.1000
_refine_ls_R_factor_gt           0.0955
_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^)+(0.0475P)^2^+28.2157P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2221
_refine_ls_wR_factor_ref         0.2240
_reflns_Friedel_coverage         0.857
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                4073
_reflns_number_total             4317
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b07612_si_002.cif
_cod_data_source_block           rls075s
_cod_original_cell_volume        2709.2(2)
_cod_database_code               4126400
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.935
_shelx_estimated_absorpt_t_min   0.808
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.53(5)
 0.47(5)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H) groups, All N(H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C10-C9 \\sim C11-C9
 with sigma of 0.02
 C9-C8 \\sim C12-C9
 with sigma of 0.02
 C10-C11 \\sim C8-C12
 with sigma of 0.02
4. Rigid body (RIGU) restrains
 N1, N2, C8, C9, C10, C11, C12
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O1, O2, O3, C1, C2, C3, C4, C5, C6, C7
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: N2(0.65) H2A(0.43) H2B(0.43) H2C(0.43) C8(0.65) H8A(0.65)
 H8B(0.65) C9(0.65) C10(0.65) H10A(0.65) H10B(0.65) H10C(0.65) C11(0.65)
 H11A(0.65) H11B(0.65) H11C(0.65) C12(0.65) H12A(0.65) H12B(0.65)
6.a Secondary CH2 refined with riding coordinates:
 N1(H1A,H1B), C8(H8A,H8B), C12(H12A,H12B)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C6(H6)
6.c Idealised Me refined as rotating group:
 N2(H2A,H2B,H2C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C)
;
_shelx_res_checksum              13990
_shelx_hkl_checksum              34476
_olex2_submission_special_instructions 'No special instructions were received'