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_7123295
_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         'C15 H18 N2, 2(Br), 4(H2 O)'
_chemical_formula_sum            'C15 H26 Br2 N2 O4'
_chemical_formula_weight         458.20
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2yc'
_space_group_name_H-M_alt        'I 1 2/c 1'
_symmetry_space_group_name_Hall  '-I 2yc'
_symmetry_space_group_name_H-M   'I 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-02-08
_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                 94.682(12)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   21.061(2)
_cell_length_b                   6.7995(7)
_cell_length_c                   26.557(3)
_cell_measurement_reflns_used    20087
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30.53
_cell_measurement_theta_min      3.079
_cell_volume                     3790.4(7)
_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-2014 (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 0.991
_diffrn_measured_fraction_theta_max 0.992
_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     -5.76 200.24   0.50   20.00    --   31.63  73.80 -70.76  412
  2  \w     -5.76 200.24   0.50   20.00    --   31.63  73.80-160.76  412
  3  \w     -5.76 200.24   0.50   20.00    --   31.63  73.80  64.24  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      0.0109470000
_diffrn_orient_matrix_UB_12      0.0141704000
_diffrn_orient_matrix_UB_13      0.0256692000
_diffrn_orient_matrix_UB_21      0.0312738000
_diffrn_orient_matrix_UB_22      0.0151263000
_diffrn_orient_matrix_UB_23      -0.0071347000
_diffrn_orient_matrix_UB_31      -0.0061539000
_diffrn_orient_matrix_UB_32      0.1020593000
_diffrn_orient_matrix_UB_33      -0.0025187000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0305
_diffrn_reflns_av_unetI/netI     0.0254
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            24618
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         30.541
_diffrn_reflns_theta_min         1.539
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_current           1.4
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_diffrn_source_voltage           50
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.297
_exptl_absorpt_correction_T_max  0.13186
_exptl_absorpt_correction_T_min  0.10037
_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    1.606
_exptl_crystal_description       prism
_exptl_crystal_F_000             1856
_exptl_crystal_recrystallization_method 'Evaporation from water'
_exptl_crystal_size_max          0.534
_exptl_crystal_size_mid          0.391
_exptl_crystal_size_min          0.144
_exptl_crystal_size_rad          0.4
_refine_diff_density_max         0.717
_refine_diff_density_min         -0.953
_refine_diff_density_rms         0.097
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.087
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     229
_refine_ls_number_reflns         5768
_refine_ls_number_restraints     60
_refine_ls_restrained_S_all      1.091
_refine_ls_R_factor_all          0.0374
_refine_ls_R_factor_gt           0.0310
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0334P)^2^+9.4144P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0735
_refine_ls_wR_factor_ref         0.0772
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5118
_reflns_number_total             5768
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc01150a2.cif
_cod_data_source_block           mk-5-10-2016
_cod_database_code               7123295
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C120  H192  Br16  N16  O24  '
_reflns_odcompleteness_completeness 99.39
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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, All O(H) groups, All O(H,H) groups, All O(H,H,H,H,H,H)
  groups
2. Restrained distances
 H1C-O1w = O1w-H1D
 0.995 with sigma of 0.002
 H1D-Br1_$1
 2.3 with sigma of 0.01
 H3C-O3w = O3w-H3D
 0.995 with sigma of 0.02
 H2C-Br1
 2.31 with sigma of 0.01
 H2D-O2w = O2w-H2C
 0.995 with sigma of 0.005
 H3BA-O3w
 1.973 with sigma of 0.02
 H3BB-Br2b_$3
 2.25 with sigma of 0.02
 H2BA-Br2a_$4
 2.25 with sigma of 0.02
 H1C-H1D
 1.579 with sigma of 0.01
 H3C-H3D
 1.6 with sigma of 0.04
 H2D-H2C
 1.55 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(Br2b) = Uanis(O3B)
Uanis(O2B) = Uanis(Br2a)
4. Rigid body (RIGU) restrains
 C3, C4
 with sigma for 1-2 distances of 0.0005 and sigma for 1-3 distances of 0.0005
 C3, N1
 with sigma for 1-2 distances of 0.0005 and sigma for 1-3 distances of 0.0005
 C4, C5
 with sigma for 1-2 distances of 0.0005 and sigma for 1-3 distances of 0.0005
 C5, N2
 with sigma for 1-2 distances of 0.0005 and sigma for 1-3 distances of 0.0005
 C1, C2
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 C2, N1
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 N1, C3
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 N1, C6
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 C6, C7
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 C7, C8
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 C7, C14
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 C9, C2
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 C1, C10
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 C10, C11
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 C11, C12
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 C12, C13
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 C12, C15
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
5. Others
 Fixed Sof: Br2a(0.5) Br2b(0.5) O3B(0.5) H3BA(0.5) H3BB(0.5) O2B(0.5)
 H2BA(0.5) H2BB(0.5)
6.a Free rotating group:
 O3B(H3BA,H3BB), O2B(H3C,H3D,H2C,H2D,H2BA,H2BB)
6.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C5(H5A,H5B), C4(H4A,H4B)
6.c Aromatic/amide H refined with riding coordinates:
 C13(H13), C6(H6), C9(H9), C11(H11), C8(H8), C10(H10)
6.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C)
;
_shelx_res_checksum              33060
_shelx_hkl_checksum              88143
_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
'5,5'-dimethyl-2,2'-bipyridine-Propyl bridged'
_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 2.316
_oxdiff_exptl_absorpt_empirical_full_min 0.677