Construction of Bowl-Shaped Copper Clusters and Nitrate-Selective Sensing
Huo, Nannan; Zhang, De-Ke; Wei, Yu-Zhen; Luo, Peng; Li, Si; Dalton Transactions  (2026) –; doi:10.1039/D6DT00475J

data_7720730
_publ_section_title
;
 Construction of bowl-shaped copper clusters and nitrate-selective
 sensing.
;
_journal_issue                   15
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              6015
_journal_page_last               6023
_journal_paper_doi               10.1039/d6dt00475j
_journal_volume                  55
_journal_year                    2026
_chemical_formula_moiety         'C105 H93 Cu4 N6 O3 P4, B F4, C H4 O'
_chemical_formula_sum            'C106 H97 B Cu4 F4 N6 O4 P4'
_chemical_formula_weight         1983.74
_chemical_name_systematic        Cu4-BF4
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2025-11-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2026-03-13 deposited with the CCDC.	2026-03-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.3480(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.81400(10)
_cell_length_b                   14.46030(10)
_cell_length_c                   50.8898(4)
_cell_measurement_reflns_used    54261
_cell_measurement_temperature    200
_cell_measurement_theta_max      75.1270
_cell_measurement_theta_min      3.1520
_cell_volume                     9388.54(12)
_computing_cell_refinement       'CrysAlisPro 1.171.42.92a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.92a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.92a (Rigaku OD, 2023)'
_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    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      200
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.985
_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    -54.00 -18.28   0.38    0.09    --  -97.00  45.00-150.00   94
  2  \w    -53.00 -24.88   0.38    0.09    --  -97.00  45.00 -90.00   74
  3  \w    -53.00 -26.78   0.38    0.09    --  -97.00  45.00 -60.00   69
  4  \w    -47.00 -17.74   0.38    0.09    --  -97.00  45.00  90.00   77
  5  \w    -50.00 -21.88   0.38    0.09    --  -97.00  45.00 150.00   74
  6  \w    -43.00  30.72   0.38    0.04    --  -37.15  38.00  60.00  194
  7  \w    -47.00  16.08   0.38    0.04    --   37.15 -19.00 -60.00  166
  8  \w    -44.00  22.12   0.38    0.04    --   37.15 -19.00  60.00  174
  9  \w     76.00 168.72   0.38    0.09    --  108.41 125.00  90.00  244
 10  \w    128.00 166.76   0.38    0.09    --  108.41 106.00  70.00  102
 11  \w    -47.00  18.36   0.38    0.04    --   37.15 -19.00-180.00  172
 12  \w     38.00 101.08   0.38    0.09    --  108.41 -77.00-180.00  166
 13  \w     37.00  63.22   0.38    0.09    --  108.41 -61.00-120.00   69
 14  \w     71.00  97.22   0.38    0.09    --  108.41 -77.00   0.00   69
 15  \w     37.00  64.36   0.38    0.09    --  108.41 -77.00   0.00   72
 16  \w     54.00  80.22   0.38    0.09    --  108.41 -77.00 150.00   69
 17  \w     38.00  67.64   0.38    0.09    --  108.41 -61.00 120.00   78
 18  \w     34.00  67.06   0.38    0.09    --  108.41 -61.00  30.00   87
 19  \w     39.00  65.22   0.38    0.09    --  108.41 -61.00   0.00   69
 20  \w     38.00  66.50   0.38    0.09    --  108.41 -61.00-180.00   75
 21  \w     22.00 130.30   0.38    0.09    --  108.41   0.00-150.00  285
 22  \w    142.00 166.70   0.38    0.09    --  108.41   0.00-150.00   65
 23  \w     82.00 143.94   0.38    0.09    --  108.41  45.00-150.00  163
 24  \w    149.00 173.70   0.38    0.09    --  108.41   0.00   0.00   65
 25  \w     29.00 174.16   0.38    0.09    --  108.41  15.00  60.00  382
 26  \w     31.00 100.16   0.38    0.09    --  108.41   0.00   0.00  182
 27  \w     68.00  94.22   0.38    0.09    --  108.41 -95.00-150.00   69
 28  \w     33.00 111.28   0.38    0.09    --  108.41-125.00-180.00  206
 29  \w     44.00  69.08   0.38    0.09    --  108.41-125.00 -90.00   66
 30  \w     76.00 101.08   0.38    0.09    --  108.41-125.00 -90.00   66
 31  \w     33.00 111.28   0.38    0.09    --  108.41-125.00 -30.00  206
 32  \w     59.00 111.06   0.38    0.09    --  108.41-125.00 -60.00  137
 33  \w     72.00  98.22   0.38    0.09    --  108.41-125.00 120.00   69
 34  \w     75.00 111.10   0.38    0.09    --  108.41-125.00 150.00   95
 35  \w     42.00  67.08   0.38    0.09    --  108.41-125.00 150.00   66
 36  \w     37.00  63.22   0.38    0.09    --  108.41-125.00 120.00   69
 37  \w     44.00  69.08   0.38    0.09    --  108.41 -95.00  90.00   66
 38  \w     28.00  99.06   0.38    0.09    --  108.41 -95.00   0.00  187
 39  \w     81.00 106.08   0.38    0.09    --  108.41-106.00 -29.00   66
 40  \w     34.00  67.06   0.38    0.04    --   37.15-106.00 -29.00   87
 41  \w      2.00  27.08   0.38    0.04    --   37.15-106.00 -29.00   66
 42  \w    -84.00 -18.26   0.38    0.04    --  -37.15 106.00  70.00  173
 43  \w    -54.00 -24.74   0.38    0.09    --  -97.00 125.00 120.00   77
 44  \w   -100.00 -72.64   0.38    0.09    --  -97.00 125.00 120.00   72
 45  \w    -88.00 -61.78   0.38    0.09    --  -97.00 106.00  70.00   69
 46  \w    -93.00 -66.78   0.38    0.04    --  -37.15 125.00  30.00   69
 47  \w    -78.00 -28.98   0.38    0.04    --  -37.15 125.00 -30.00  129
 48  \w   -127.00 -58.98   0.38    0.09    --  -97.00 146.00-120.43  179
 49  \w   -142.08 -60.00   0.38    0.09    --  -97.00 -30.00-150.00  216
 50  \w   -173.00 -90.92   0.38    0.09    --  -97.00-106.00 -29.00  216
 51  \w   -110.00  -9.68   0.38    0.04    --  -37.15 -57.00 -90.00  264
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0035068000
_diffrn_orient_matrix_UB_12      0.0425458000
_diffrn_orient_matrix_UB_13      0.0276597000
_diffrn_orient_matrix_UB_21      0.0985179000
_diffrn_orient_matrix_UB_22      -0.0554241000
_diffrn_orient_matrix_UB_23      0.0099677000
_diffrn_orient_matrix_UB_31      0.0697148000
_diffrn_orient_matrix_UB_32      0.0804213000
_diffrn_orient_matrix_UB_33      -0.0077657000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0623
_diffrn_reflns_av_unetI/netI     0.0341
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       63
_diffrn_reflns_limit_l_min       -63
_diffrn_reflns_number            111641
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.457
_diffrn_reflns_theta_min         3.178
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.185
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.67135
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.92a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear whiteish blue'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   whiteish
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.403
_exptl_crystal_description       needle
_exptl_crystal_F_000             4096
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.492
_refine_diff_density_min         -0.636
_refine_diff_density_rms         0.066
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1253
_refine_ls_number_reflns         19160
_refine_ls_number_restraints     366
_refine_ls_restrained_S_all      1.016
_refine_ls_R_factor_all          0.0429
_refine_ls_R_factor_gt           0.0393
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
;
 w=1/[\s^2^(Fo^2^)+(0.0673P)^2^+4.6844P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1068
_refine_ls_wR_factor_ref         0.1097
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17306
_reflns_number_total             19160
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6dt00475j2.cif
_cod_data_source_block           Cu4-BF4
_cod_depositor_comments
'Adding full bibliography for 7720727--7720731.cif.'
_cod_database_code               7720730
_shelxl_version_number           2013-2
_shelx_estimated_absorpt_t_max   0.899
_shelx_estimated_absorpt_t_min   0.735
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Uiso/Uaniso restraints and constraints
H55 \\sim C18 \\sim C42 \\sim C59 \\sim C93 \\sim C96 \\sim C105 \\sim C107
\\sim C108 \\sim C109 \\sim C110 \\sim C111 \\sim C112: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02
C16 \\sim C57 \\sim C87 \\sim C99 \\sim C100 \\sim C101 \\sim C113 \\sim C114
\\sim C115 \\sim C116 \\sim C117 \\sim C118: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02
3. Others
 Sof(C107)=Sof(H107)=Sof(C108)=Sof(H108)=Sof(C109)=Sof(C110)=Sof(H110)=
 Sof(C111)=Sof(H111)=Sof(C112)=Sof(H112)=1-FVAR(1)
 Sof(C18)=Sof(C42)=Sof(H42)=Sof(C59)=Sof(H59)=Sof(C93)=Sof(H93)=Sof(C96)=
 Sof(H96)=Sof(C105)=Sof(H105)=FVAR(1)
 Sof(C113)=Sof(H113)=Sof(C114)=Sof(H114)=Sof(C115)=Sof(H115)=Sof(C116)=
 Sof(H116)=Sof(C117)=Sof(H117)=Sof(C118)=1-FVAR(2)
 Sof(C16)=Sof(C57)=Sof(H57)=Sof(C87)=Sof(H87)=Sof(C99)=Sof(H99)=Sof(C100)=
 Sof(H100)=Sof(C101)=Sof(H101)=FVAR(2)
4.a Secondary CH2 refined with riding coordinates:
 C88(H88A,H88B), C97(H97A,H97B), C98(H98A,H98B)
4.b Aromatic/amide H refined with riding coordinates:
 N1(H1), N2(H2), N3(H3), N4(H4), N5(H5), N6(H6), C15(H15), C19(H19), C23(H23),
 C24(H24), C25(H25), C26(H26), C27(H27), C29(H29), C30(H30), C32(H32), C36(H36),
  C37(H37), C38(H38), C39(H39), C41(H41), C43(H43), C44(H44), C45(H45),
 C46(H46), C47(H47), C48(H48), C49(H49), C51(H51), C52(H52), C53(H53), C54(H54),
  C55(H55), C56(H56), C58(H58), C60(H60), C61(H61), C62(H62), C63(H63),
 C64(H64), C65(H65), C66(H66), C67(H67), C68(H68), C69(H69), C70(H70), C71(H71),
  C72(H72), C73(H73), C74(H74), C75(H75), C76(H76), C77(H77), C78(H78),
 C79(H79), C80(H80), C81(H81), C82(H82), C83(H83), C84(H84), C85(H85), C86(H86),
  C89(H89), C90(H90), C91(H91), C92(H92), C94(H94), C95(H95), C42(H42),
 C57(H57), C59(H59), C87(H87), C93(H93), C96(H96), C99(H99), C100(H100),
 C101(H101), C105(H105), C107(H107), C108(H108), C110(H110), C111(H111),
 C112(H112), C113(H113), C114(H114), C115(H115), C116(H116), C117(H117)
4.c Fitted hexagon refined as free rotating group:
 C107(C108,C109,C110,C111,C112), C113(C114,C115,C116,C117,C118)
4.d Idealised Me refined as rotating group:
 C102(H10A,H10B,H10C), C103(H10D,H10E,H10F), C104(H10G,H10H,H10I), C106(H10J,
 H10K,H10L)
4.e Idealised tetrahedral OH refined as rotating group:
 O4(H4A)
;
_shelx_res_checksum              99817
_olex2_submission_original_sample_id Cu4-BF4
_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 3.887
_oxdiff_exptl_absorpt_empirical_full_min 0.444