Atomically Precise, Thiolated Copper-Hydride Nanoclusters as Single-Site Hydrogenation Catalysts for Ketones in Mild Conditions.
Sun, Cunfa; Mammen, Nisha; Kaappa, Sami; Yuan, Peng; Deng, Guocheng; Zhao, Chaowei; Yan, Juanzhu; Malola, Sami; Honkala, Karoliina; Häkkinen, Hannu; Teo, Boon K.; Zheng, Nanfeng; ACS nano  (2019) –; doi:10.1021/acsnano.9b02052

data_4514411
_publ_section_title
;
 Atomically Precise, Thiolated Copper-Hydride Nanoclusters as Single-Site
 Hydrogenation Catalysts for Ketones in Mild Conditions.
;
_journal_name_full               'ACS nano'
_journal_paper_doi               10.1021/acsnano.9b02052
_journal_year                    2019
_chemical_formula_moiety
'C108 H64 Cl36 Cu25 S18, 3(C24 H20 P), C6 H13, C H2 Cl2, C6 H14'
_chemical_formula_sum            'C193 H143 Cl38 Cu25 P3 S18'
_chemical_formula_weight         6067.66
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2018-01-30
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                101.4694(16)
_cell_angle_beta                 90.9331(15)
_cell_angle_gamma                110.275(2)
_cell_formula_units_Z            2
_cell_length_a                   19.4870(4)
_cell_length_b                   19.7839(5)
_cell_length_c                   32.2015(5)
_cell_measurement_reflns_used    21469
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      64.7200
_cell_measurement_theta_min      3.5170
_cell_volume                     11363.7(4)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4741
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.984
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_details
;
  1 omega  -47.00   36.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.5672   37.0000  -60.0000 83

  2 omega  -95.00  -11.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.5672  125.0000   30.0000 84

  3 omega -120.00    0.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.5672  -19.0000  120.0000 120

  4 omega   24.00   71.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       91.1609  -30.0000  -90.0000 47

  5 omega   29.00  124.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       91.1609  -77.0000 -120.0000 95

  6 omega   61.00  167.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       91.1609   30.0000 -180.0000 106

  7 omega  100.00  155.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       91.1609  125.0000 -180.0000 55

  8 omega   87.00  148.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       91.1609   45.0000 -120.0000 61

  9 omega  101.00  149.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       91.1609  125.0000  -30.0000 48

 10 omega  141.00  166.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       91.1609  125.0000    0.0000 25

 11 omega   94.00  140.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       91.1609  125.0000   60.0000 46

 12 omega   32.00   74.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       91.1609  -30.0000   30.0000 42

 13 omega   68.00  121.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       91.1609  -77.0000   30.0000 53

 14 omega   35.00  106.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       91.1609 -125.0000   60.0000 71

 15 omega   29.00   56.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       91.1609  -77.0000   30.0000 27

 16 omega   14.00   40.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       91.1609  -30.0000 -120.0000 26

 17 omega   45.00   70.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       91.1609 -125.0000 -150.0000 25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0045099000
_diffrn_orient_matrix_UB_12      0.0698977000
_diffrn_orient_matrix_UB_13      -0.0121963000
_diffrn_orient_matrix_UB_21      0.0843273000
_diffrn_orient_matrix_UB_22      0.0363889000
_diffrn_orient_matrix_UB_23      0.0070989000
_diffrn_orient_matrix_UB_31      0.0057310000
_diffrn_orient_matrix_UB_32      -0.0320194000
_diffrn_orient_matrix_UB_33      -0.0469522000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0555
_diffrn_reflns_av_unetI/netI     0.0650
_diffrn_reflns_Laue_measured_fraction_full 0.984
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            68335
_diffrn_reflns_point_group_measured_fraction_full 0.984
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        61.169
_diffrn_reflns_theta_max         61.169
_diffrn_reflns_theta_min         3.542
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.666
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65590
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear reddish red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.773
_exptl_crystal_description       block
_exptl_crystal_F_000             6010
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.275
_refine_diff_density_min         -0.958
_refine_diff_density_rms         0.123
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2538
_refine_ls_number_reflns         34378
_refine_ls_number_restraints     137
_refine_ls_restrained_S_all      5.928
_refine_ls_R_factor_all          0.0774
_refine_ls_R_factor_gt           0.0556
_refine_ls_shift/su_max          3.165
_refine_ls_shift/su_mean         0.013
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0800P)^2^+13.1454P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1432
_refine_ls_wR_factor_ref         0.1629
_reflns_Friedel_coverage         0.000
_reflns_number_gt                25776
_reflns_number_total             34378
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            nn9b02052_si_002.cif
_cod_data_source_block           scf-(3)-2017-10-19-4redblock-2
_cod_database_code               4514411
_shelx_shelxl_version_number     2016/4
_shelx_estimated_absorpt_t_max   0.478
_shelx_estimated_absorpt_t_min   0.098
_reflns_odcompleteness_completeness 98.42
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     61.08
_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
2. Restrained distances
 C0AA-Cl0A = Cl6-C0AA
 1.3 with sigma of 0.02
 Cl0A-Cl6
 2.5 with sigma of 0.02
 C10-C8
 1.75 with sigma of 0.02
 Cl6-C0AA
 1.7 with sigma of 0.02
 Cl0A-C0AA
 1.7 with sigma of 0.02
 C7-C11
 1.45 with sigma of 0.02
 C1AA-C10
 2.57 with sigma of 0.02
 C8-C5
 2.57 with sigma of 0.02
 C1AA-C11
 1.6 with sigma of 0.02
 C5-C8
 2.4 with sigma of 0.02
 C8-C10
 1.46 with sigma of 0.02
 C5-C10
 1.38 with sigma of 0.02
 C7-C1AA
 2.381 with sigma of 0.02
 C8-C1AA
 1.599 with sigma of 0.02
 C11-C8
 2.619 with sigma of 0.02
 HH-Cu04
 1.85 with sigma of 0.02
 HG-Cu08
 1.85 with sigma of 0.02
 HE-Cu0D
 1.85 with sigma of 0.02
 HE-Cu0C
 1.85 with sigma of 0.02
 HI-Cu0A
 1.85 with sigma of 0.02
 HI-Cu05
 1.95 with sigma of 0.02
 Cu01-HI
 2.3 with sigma of 0.02
3. Restrained planarity
 C10, C8, C1AA, C5, C11, C7
 with sigma of 0.1
 C5, C8, C10, C1AA, C11, C7
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(C1AA) \\sim Ueq, Uanis(C0AA) \\sim Ueq, Uanis(Cl0A) \\sim Ueq, Uanis(Cl6)
\\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C8) \\sim Ueq,
Uanis(C11) \\sim Ueq, Uanis(C7) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(Cl6) \\sim Ueq, Uanis(C0AA) \\sim Ueq, Uanis(Cl0A) \\sim Ueq, Uanis(C8)
\\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C1AA) \\sim Ueq, Uanis(C11) \\sim Ueq,
Uanis(C7) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C0AA) \\sim Ueq, Uanis(Cl0A) \\sim Ueq, Uanis(Cl6) \\sim Ueq, Uanis(C8)
\\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C1AA) \\sim Ueq, Uanis(C11) \\sim Ueq,
Uanis(C7) \\sim Ueq, Uanis(C5) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C0AA) \\sim Ueq, Uanis(Cl0A) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C1AA)
\\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C5) \\sim Ueq,
Uanis(C07D) \\sim Ueq, Uanis(C07H) \\sim Ueq, Uanis(C07I) \\sim Ueq,
Uanis(Cl2A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C8) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C0AA) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(Cl0A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Cl6) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Cl0A) \\sim Ueq, Uanis(C0AA) \\sim Ueq, Uanis(Cl6) \\sim Ueq, Uanis(C11)
\\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C1AA) \\sim Ueq,
Uanis(C5) \\sim Ueq, Uanis(C7) \\sim Ueq, : with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C0AA) \\sim Ueq, Uanis(Cl0A) \\sim Ueq, Uanis(Cl6) \\sim Ueq, Uanis(C8)
\\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C1AA) \\sim Ueq, Uanis(C5) \\sim Ueq,
Uanis(C11) \\sim Ueq, Uanis(C7) \\sim Ueq, : with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C0AA) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C1AA)
\\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C7) \\sim Ueq,
Uanis(Cl6) \\sim Ueq, Uanis(Cl0A) \\sim Ueq, : with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(Cl0A) \\sim Ueq, Uanis(C0AA) \\sim Ueq, Uanis(Cl6) \\sim Ueq, Uanis(C8)
\\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C1AA) \\sim Ueq, Uanis(C5) \\sim Ueq,
Uanis(C11) \\sim Ueq, Uanis(C7) \\sim Ueq, : with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C8) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C1AA) \\sim Ueq, Uanis(C5)
\\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C0AA) \\sim Ueq,
Uanis(Cl0A) \\sim Ueq, Uanis(Cl6) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(Cl27) \\sim Ueq, Uanis(Cl29) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(Cl29) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Cl6) \\sim Ueq, Uanis(Cl0A) \\sim Ueq, Uanis(C0AA) \\sim Ueq, Uanis(C8)
\\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C1AA) \\sim Ueq, Uanis(C5) \\sim Ueq,
Uanis(C11) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C07D) \\sim Ueq, Uanis(C07F)
\\sim Ueq, Uanis(C07H) \\sim Ueq, Uanis(C07E) \\sim Ueq, Uanis(C07I) \\sim Ueq,
Uanis(C07G) \\sim Ueq, : with sigma of 0.01 and sigma for terminal atoms of 0.02
5.a Secondary CH2 refined with riding coordinates:
 C07D(H07C,H07D), C07F(H07F,H07G), C07H(H07K,H07L), C8(H8A,H8B), C10(H10A,
 H10B), C0AA(H0AA,H0AB), C1AA(H1AA,H1AB), C11(H11A,H11B)
5.b Aromatic/amide H refined with riding coordinates:
 C02D(H02D), C02H(H02H), C02J(H02J), C02M(H02M), C02O(H02O), C02S(H02S),
 C02V(H02V), C02X(H02X), C02Z(H02Z), C030(H030), C031(H031), C032(H032),
 C038(H038), C039(H039), C03C(H03C), C03D(H03D), C03F(H03F), C03H(H03H),
 C03K(H03K), C03L(H03L), C03M(H03M), C03O(H03O), C03P(H03P), C03Q(H03Q),
 C03R(H03R), C03T(H03T), C03V(H03V), C040(H040), C042(H042), C043(H043),
 C045(H045), C046(H046), C048(H048), C049(H049), C04C(H04C), C04D(H04D),
 C04F(H04F), C04G(H04G), C04L(H04L), C04M(H04M), C04N(H04N), C04P(H04P),
 C04S(H04S), C04T(H04T), C04U(H04U), C04W(H04W), C04X(H04X), C050(H050),
 C051(H051), C052(H052), C053(H053), C054(H054), C055(H055), C057(H057),
 C058(H058), C059(H059), C05A(H05A), C05B(H05B), C05C(H05C), C05D(H05D),
 C05F(H05F), C05J(H05J), C05K(H05K), C05L(H05L), C05M(H05M), C05P(H05P),
 C05S(H05S), C05T(H05T), C05U(H05U), C05V(H05V), C05W(H05W), C05X(H05X),
 C05Y(H05Y), C05Z(H05Z), C062(H062), C063(H063), C065(H065), C066(H066),
 C067(H067), C06A(H06A), C06B(H06B), C06C(H06C), C06D(H06D), C06E(H06E),
 C06F(H06F), C06G(H06G), C06H(H06H), C06I(H06I), C06J(H06J), C06K(H06K),
 C06L(H06L), C06M(H06M), C06N(H06N), C06O(H06O), C06P(H06P), C06Q(H06Q),
 C06R(H06R), C06S(H06S), C06T(H06T), C06U(H06U), C06V(H06V), C06W(H06W),
 C06Y(H06Y), C06Z(H06Z), C070(H070), C072(H072), C073(H073), C074(H074),
 C075(H075), C076(H076), C078(H078), C079(H079), C07A(H07A), C07B(H07B),
 C07E(H07E)
5.c Idealised Me refined as rotating group:
 C07G(H07H,H07I,H07J), C07I(H07M,H07N,H07O), C5(H5A,H5B,H5C), C7(H7A,H7B,H7C)
;
_olex2_submission_special_instructions 'No special instructions were received'