Optimizing Electron Transfer from CdSe QDs to Hydrogenase for Photocatalytic H2 Production
Sanchez, Monica Kiewit; Wu, Chang-hao; Adams, Michael W.; Dyer, Richard Brian; Chemical Communications  (2019) –; doi:10.1039/C9CC01150A

data_7123297
_publ_section_title
;
 Optimizing Electron Transfer from CdSe QDs to Hydrogenase for
 Photocatalytic H2 Production
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C9CC01150A
_journal_year                    2019
_chemical_formula_moiety         '2(Br), 0.5(O), C13 H14 N2'
_chemical_formula_sum            'C13 H15 Br2 N2 O0.5'
_chemical_formula_weight         367.07
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2019-02-07
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2018.07.26 svn.r3523 for OlexSys, GUI svn.r5532)
;
_audit_update_record
;
2019-02-08 deposited with the CCDC.    2019-04-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.743(2)
_cell_angle_gamma                90
_cell_formula_units_Z            32
_cell_length_a                   44.5365(10)
_cell_length_b                   14.2236(5)
_cell_length_c                   17.4936(4)
_cell_measurement_reflns_used    3600
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30.456
_cell_measurement_theta_min      2.344
_cell_volume                     11043.7(5)
_computing_cell_refinement       'CrysAlisPro 1.171.40.15a (Rigaku OD, 2018)'
_computing_data_collection       'APEX2 v2014.11 (Bruker, 2014)'
_computing_data_reduction        'CrysAlisPro 1.171.40.15a (Rigaku OD, 2018)'
_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 (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 7.495
_diffrn_measured_fraction_theta_full 0.999
_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     -6.76 199.24   0.50   20.00    --   31.63  73.80  64.24  412
  2  \w     -6.76 199.24   0.50   20.00    --   31.63  73.80  19.24  412
  3  \w     -6.76 199.24   0.50   20.00    --   31.63  73.80-115.76  412
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0094378000
_diffrn_orient_matrix_UB_12      -0.0304062000
_diffrn_orient_matrix_UB_13      -0.0233194000
_diffrn_orient_matrix_UB_21      -0.0097700000
_diffrn_orient_matrix_UB_22      0.0381732000
_diffrn_orient_matrix_UB_23      -0.0102769000
_diffrn_orient_matrix_UB_31      0.0084332000
_diffrn_orient_matrix_UB_32      0.0099820000
_diffrn_orient_matrix_UB_33      -0.0317381000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0648
_diffrn_reflns_av_unetI/netI     0.0576
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       64
_diffrn_reflns_limit_h_min       -63
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            73108
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         30.999
_diffrn_reflns_theta_min         2.246
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    5.857
_exptl_absorpt_correction_T_max  0.12413
_exptl_absorpt_correction_T_min  0.09399
_exptl_absorpt_correction_type   sphere
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.15a (Rigaku Oxford Diffraction, 2018)
Spherical absorption correction
 using equivalent radius and absorption coefficient.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.766
_exptl_crystal_description       prism
_exptl_crystal_F_000             5791
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by as supplied'
_exptl_crystal_size_max          0.687
_exptl_crystal_size_mid          0.467
_exptl_crystal_size_min          0.292
_exptl_crystal_size_rad          0.4
_refine_diff_density_max         1.331
_refine_diff_density_min         -0.607
_refine_diff_density_rms         0.161
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     658
_refine_ls_number_reflns         17503
_refine_ls_number_restraints     726
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.1074
_refine_ls_R_factor_gt           0.0524
_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^)+(0.0491P)^2^+20.9503P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1004
_refine_ls_wR_factor_ref         0.1179
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10735
_reflns_number_total             17503
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc01150a2.cif
_cod_data_source_block           dq03
_cod_original_formula_sum        'C13 H15 Br2 N2 O0.50'
_cod_database_code               7123297
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C416  H448  Br64  N64  O16  '
_reflns_odcompleteness_completeness 99.33
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.93
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(Br2) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(Br9B) = Uanis(Br9)
Uanis(Br3) = Uanis(Br3B)
Uanis(Br4) = Uanis(Br4B)
Uanis(O2W) = Uanis(Br2)
Uanis(O1W) = Uanis(Br1)
Uanis(O3W) = Uanis(Br10)
Uanis(O4W) = Uanis(Br5)
3. Rigid body (RIGU) restrains
 N1_1, N2_1, C1_1, C2_1, C3_1, C4_1, C5_1, C6_1, C7_1, C8_1, C9_1, C10_1,
 C11_1, C12_1, C13_1
 N1_2, N2_2, C1_2, C2_2, C3_2, C4_2, C5_2, C6_2, C7_2, C8_2, C9_2, C10_2,
 C11_2, C12_2, C13_2
 N1_3, N2_3, C1_3, C2_3, C3_3, C4_3, C5_3, C6_3, C7_3, C8_3, C9_3, C10_3,
 C11_3, C12_3, C13_3
 N1_4, N2_4, C1_4, C2_4, C3_4, C4_4, C5_4, C6_4, C7_4, C8_4, C9_4, C10_4,
 C11_4, C12_4, C13_4
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Same fragment restrains
{N1_2, N2_2, C1_2, C2_2, C3_2, C4_2, C5_2, C6_2, C7_2, C8_2, C9_2, C10_2,
C11_2, C12_2, C13_2}
{N1_3, N2_3, C1_3, C2_3, C3_3, C4_3, C5_3, C6_3, C7_3, C8_3, C9_3, C10_3,
C11_3, C12_3, C13_3}
{N1_4, N2_4, C1_4, C2_4, C3_4, C4_4, C5_4, C6_4, C7_4, C8_4, C9_4, C10_4,
C11_4, C12_4, C13_4}
as
{N1_1, N2_1, C1_1, C2_1, C3_1, C4_1, C5_1, C6_1, C7_1, C8_1, C9_1, C10_1,
C11_1, C12_1, C13_1} sigma for 1-2: 0.001 1-3: 0.001
5. Others
 Sof(Br11)=Sof(Br5)=Sof(O1W)=Sof(O2W)=1-FVAR(1)
 Sof(Br2)=Sof(Br1)=Sof(O3W)=Sof(O4W)=FVAR(1)
 Sof(Br9B)=1-FVAR(3)
 Sof(Br9)=FVAR(3)
 Sof(Br3)=1-FVAR(4)
 Sof(Br3B)=FVAR(4)
 Sof(Br4B)=1-FVAR(5)
 Sof(Br4)=FVAR(5)
6.a Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B),
 C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B)
6.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C8(H8), C9(H9), C10(H10), C11(H11), C12(H12), C13(H13),
 C6(H6), C7(H7), C8(H8), C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C6(H6),
  C7(H7), C8(H8), C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C6(H6),
 C7(H7), C8(H8), C9(H9), C10(H10), C11(H11), C12(H12), C13(H13)
;
_shelx_res_checksum              83769
_shelx_hkl_checksum              29740
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a loop with paratone oil'
_olex2_submission_original_sample_id DQ03
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.783
_oxdiff_exptl_absorpt_empirical_full_min 0.668