A stable superatomic Cu<sub>6</sub>(SMPP)<sub>6</sub> nanocluster with dual emission.
Wu, Haiming; Anumula, Rajini; Andrew, Gaya N.; Luo, Zhixun; Nanoscale 15 (2023) 4137–4142; doi:10.1039/d2nr07223h

data_1568532
_publ_section_title
;
 A stable superatomic Cu<sub>6</sub>(SMPP)<sub>6</sub> nanocluster with
 dual emission.
;
_journal_issue                   8
_journal_name_full               Nanoscale
_journal_page_first              4137
_journal_page_last               4142
_journal_paper_doi               10.1039/d2nr07223h
_journal_volume                  15
_journal_year                    2023
_chemical_formula_moiety
'2(C21 H27 Cu3 N6 S3), C H2.03 Cl2.03, C H2 Cl2'
_chemical_formula_sum            'C44 H58.03 Cl4.03 Cu6 N12 S6'
_chemical_formula_weight         1471.33
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-05-10
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-12-18 deposited with the CCDC.	2023-02-03 downloaded from the CCDC.
;
_cell_angle_alpha                78.740(3)
_cell_angle_beta                 88.981(3)
_cell_angle_gamma                86.659(3)
_cell_formula_units_Z            2
_cell_length_a                   9.2167(4)
_cell_length_b                   13.7793(6)
_cell_length_c                   23.2892(7)
_cell_measurement_reflns_used    11074
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      29.2970
_cell_measurement_theta_min      3.5380
_cell_volume                     2895.8(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.45i (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.45i (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.45i (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      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.879
_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   -104.00  -1.00   0.50   15.00    --  -15.10  45.00 154.28  206
  2  \w   -103.00  74.00   0.50   15.00    --  -15.10  45.00  60.00  354
  3  \w    -63.00 -36.00   0.50   15.00    --  -15.10  45.00  12.99   54
  4  \w    -17.00  54.00   0.50   15.00    --  -15.10  45.00  12.99  142
  5  \w    -87.00  32.00   0.50   15.00    --  -15.10  45.00 120.00  238
  6  \w    -25.00   3.00   0.50   15.00    --  -15.10  45.00 -19.79   56
  7  \w     10.00  51.00   0.50   15.00    --  -15.10  45.00 -19.79   82
  8  \w     16.00  43.00   0.50   15.00    --  -15.10  45.00  -9.59   54
  9  \w    -24.00  73.00   0.50   15.00    --  -15.10  45.00 179.35  194
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC10 (RCD3): fixed-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0082390000
_diffrn_orient_matrix_UB_12      0.0514588000
_diffrn_orient_matrix_UB_13      0.0001302000
_diffrn_orient_matrix_UB_21      0.0099245000
_diffrn_orient_matrix_UB_22      0.0106747000
_diffrn_orient_matrix_UB_23      -0.0308169000
_diffrn_orient_matrix_UB_31      -0.0760037000
_diffrn_orient_matrix_UB_32      -0.0012044000
_diffrn_orient_matrix_UB_33      -0.0038323000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0459
_diffrn_reflns_av_unetI/netI     0.0576
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.879
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            50454
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.879
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.834
_diffrn_reflns_theta_min         3.426
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.609
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.67845
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.45i (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.687
_exptl_crystal_description       block
_exptl_crystal_F_000             1489
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.15
_refine_diff_density_max         3.783
_refine_diff_density_min         -1.464
_refine_diff_density_rms         0.288
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.150
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     733
_refine_ls_number_reflns         16012
_refine_ls_number_restraints     327
_refine_ls_restrained_S_all      1.147
_refine_ls_R_factor_all          0.1457
_refine_ls_R_factor_gt           0.1189
_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^)+(0.1367P)^2^+39.3159P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3059
_refine_ls_wR_factor_ref         0.3213
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11924
_reflns_number_total             16012
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2nr07223h2.cif
_cod_data_source_block           mx7941
_cod_original_cell_volume        2895.81(19)
_cod_database_code               1568532
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CHAuCuNS
_reflns_odcompleteness_completeness 99.71
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.82
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H44B,H44A,H44D,H44C,H44E,H44F} of C44, All C(H,H) groups,
  All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, {H28A,H28B,H28C,H28D,H28E,H28F} of C28
2. Restrained distances
 C41A-C40 = C41-C40 = C42A-C41A = C42-C41
 1.54 with sigma of 0.01
 C26A-C24 = C26-C24 = C27A-C26A = C27-C26 = C28-C27 = C28-C27A
 1.54 with sigma of 0.01
 C13-C12 = C14-C13
 1.54 with sigma of 0.01
 C34-C33 = C35-C34
 1.54 with sigma of 0.01
 Cl15-C44 = Cl4-C44 = Cl3A-C44 = Cl26-C44 = Cl3-C44 = Cl0A-C44
 1.76 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C40 \\sim C41 \\sim C41A \\sim C42 \\sim C42A: within 1.7A with sigma of 0.02
and sigma for terminal atoms of 0.04
C26 \\sim C26A \\sim C27 \\sim C27A: within 1.7A with sigma of 0.02 and sigma
for terminal atoms of 0.04
C12 \\sim C13 \\sim C14: within 1.7A with sigma of 0.02 and sigma for terminal
atoms of 0.04
C33 \\sim C34 \\sim C35: within 1.7A with sigma of 0.02 and sigma for terminal
atoms of 0.04
Cl0A \\sim Cl3 \\sim Cl3A \\sim Cl4 \\sim Cl15 \\sim Cl26 \\sim C44: within
1.9A with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C40) \\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C42) \\sim Ueq, Uanis(C41A)
\\sim Ueq, Uanis(C42A) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C26) \\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C26A) \\sim Ueq, Uanis(C27A)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C12) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C14) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C33) \\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C35) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(Cl0A) \\sim Ueq, Uanis(Cl3) \\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(Cl3A)
\\sim Ueq, Uanis(Cl4) \\sim Ueq, Uanis(Cl15) \\sim Ueq, Uanis(Cl26) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 1*[Sof(Cl3)+Sof(Cl4)+Sof(H44B)+Sof(H44A)]+1*[Sof(Cl0A)+Sof(Cl3A)+Sof(H44D)+
 Sof(H44C)]+1*[Sof(Cl15)+Sof(Cl26)+Sof(H44E)+Sof(H44F)]=1 with esd of 0.01
 Sof(Cl3)=Sof(Cl4)=Sof(H44B)=Sof(H44A)=FVAR(1)
 Sof(Cl0A)=Sof(Cl3A)=Sof(H44D)=Sof(H44C)=FVAR(2)
 Sof(Cl15)=Sof(Cl26)=Sof(H44E)=Sof(H44F)=FVAR(3)
 Sof(H40C)=Sof(H40D)=Sof(C41A)=Sof(H41C)=Sof(H41D)=Sof(C42A)=Sof(H42D)=
 Sof(H42E)=Sof(H42F)=1-FVAR(4)
 Sof(H40A)=Sof(H40B)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(C42)=Sof(H42A)=Sof(H42B)=
 Sof(H42C)=FVAR(4)
 Sof(C26A)=Sof(H26C)=Sof(H26D)=Sof(C27A)=Sof(H27C)=Sof(H27D)=Sof(H28D)=
 Sof(H28E)=Sof(H28F)=1-FVAR(5)
 Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H28A)=Sof(H28B)=
 Sof(H28C)=FVAR(5)
5.a Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C6(H6A,H6B), C12(H12A,H12B), C13(H13A,H13B), C19(H19A,H19B),
 C20(H20A,H20B), C26(H26A,H26B), C26A(H26C,H26D), C27(H27A,H27B), C27A(H27C,
 H27D), C33(H33A,H33B), C34(H34A,H34B), C40(H40A,H40B), C40(H40C,H40D),
 C41(H41A,H41B), C41A(H41C,H41D), C44(H44B,H44A), C44(H44D,H44C), C44(H44E,
 H44F), C43(H43A,H43B)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C9(H9), C11(H11), C16(H16), C18(H18), C23(H23), C25(H25),
 C30(H30), C32(H32), C37(H37), C39(H39)
5.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C14(H14A,H14B,H14C), C21(H21A,H21B,H21C), C28(H28A,H28B,
 H28C), C28(H28D,H28E,H28F), C35(H35A,H35B,H35C), C42(H42A,H42B,H42C),
 C42A(H42D,H42E,H42F)
;
_shelx_res_checksum              35153
_shelx_hkl_checksum              78129
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.374
_oxdiff_exptl_absorpt_empirical_full_min 0.755