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_7720729
_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, F6 P, 0.5(C H2 Cl2), C H3 O, 2.5(C H4 O)'
_chemical_formula_sum            'C109 H107 Cl Cu4 F6 N6 O6.5 P5'
_chemical_formula_weight         2163.46
_chemical_name_systematic        Cu4-PF6
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2026-03-13
_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                 96.158(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   25.6195(6)
_cell_length_b                   14.7688(3)
_cell_length_c                   27.4973(6)
_cell_measurement_reflns_used    26102
_cell_measurement_temperature    200.00(10)
_cell_measurement_theta_max      28.4140
_cell_measurement_theta_min      2.2470
_cell_volume                     10344.1(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_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_environment      N~2~
_diffrn_ambient_temperature      200.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.895
_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    -93.00 -16.00   0.50   17.09    --  -10.60 -82.00  30.00  154
  2  \w   -100.00   9.00   0.50   17.09    --  -10.60 -77.00-120.00  218
  3  \w    -37.00  41.00   0.50   17.09    --   10.70 -57.00  90.00  156
  4  \w    -64.00   7.00   0.50   17.09    --   10.70 -57.00 -30.00  142
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0211509000
_diffrn_orient_matrix_UB_12      -0.0032162000
_diffrn_orient_matrix_UB_13      -0.0145735000
_diffrn_orient_matrix_UB_21      0.0180176000
_diffrn_orient_matrix_UB_22      -0.0009891000
_diffrn_orient_matrix_UB_23      0.0214744000
_diffrn_orient_matrix_UB_31      -0.0018113000
_diffrn_orient_matrix_UB_32      -0.0478909000
_diffrn_orient_matrix_UB_33      0.0005312000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0361
_diffrn_reflns_av_unetI/netI     0.0481
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.895
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            83076
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.895
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.794
_diffrn_reflns_theta_min         2.122
_diffrn_source                   'Rotating-anode X-ray tube (dual wavelength)'
_diffrn_source_type              'Rigaku (Mo) X-ray DW Source'
_exptl_absorpt_coefficient_mu    0.982
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.56524
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
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    1.389
_exptl_crystal_description       needle
_exptl_crystal_F_000             4468
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.529
_refine_diff_density_min         -0.463
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.010
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1467
_refine_ls_number_reflns         24134
_refine_ls_number_restraints     399
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0727
_refine_ls_R_factor_gt           0.0462
_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^)+(0.0501P)^2^+8.1471P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1045
_refine_ls_wR_factor_ref         0.1134
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17669
_reflns_number_total             24134
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6dt00475j2.cif
_cod_data_source_block           Cu4-PF6
_cod_depositor_comments
'Adding full bibliography for 7720727--7720731.cif.'
_cod_original_formula_sum        'C109 H107 Cl Cu4 F6 N6 O6.50 P5'
_cod_database_code               7720729
_shelxl_version_number           2013-2
_shelx_estimated_absorpt_t_max   0.971
_shelx_estimated_absorpt_t_min   0.900
_reflns_odcompleteness_completeness 99.91
_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, All N(H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 C99-C102
 1.5 with sigma of 0.01
 O5-C113
 1.25 with sigma of 0.01
 O13-C122
 1.4 with sigma of 0.01
 O8-C120
 1.45 with sigma of 0.01
 C104-C103 \\sim C107-C108
 with sigma of 0.01
 N7-C110 \\sim N5-C99 \\sim N5-C43 \\sim N7-C43
 with sigma of 0.01
 C101-C100 \\sim C112-C111
 with sigma of 0.01
 N4-C100 \\sim N9-C111
 with sigma of 0.01
 C109-C110 \\sim C102-C99
 with sigma of 0.01
 N9-C113 \\sim C113-N2
 with sigma of 0.01
 N4-C98 \\sim N2-C98 \\sim N9-C113
 with sigma of 0.01
 Cl1-C114 \\sim C114-Cl2
 with sigma of 0.01
 C116-O7 \\sim C117_$1-O11_$1
 with sigma of 0.01
 O9-C121 \\sim C120-O8
 with sigma of 0.01
 O11-C117 \\sim O10-C119
 with sigma of 0.01
 C115-O6 \\sim C118-O12
 with sigma of 0.01
3. Rigid bond restraints
 O6, C115
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O9, C121
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C99 \\sim C102 \\sim C109 \\sim C110: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02
C98 \\sim C100 \\sim C101 \\sim C111 \\sim C112: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02
N4 \\sim N9: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C98 \\sim C113: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
O2 \\sim O5: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
O6 \\sim O11 \\sim O7 \\sim O10 \\sim O8 \\sim O9: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02
C115: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
O11 \\sim O10 \\sim O9 \\sim O8 \\sim O13 \\sim O12 \\sim O6: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.01
C114 \\sim C115 \\sim C117 \\sim C116 \\sim C119 \\sim C118 \\sim C120 \\sim
C121 \\sim C122: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01
Uanis(C108) \\sim Ueq, Uanis(C107) \\sim Ueq, Uanis(C103) \\sim Ueq,
Uanis(C104) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(N6) \\sim Ueq, Uanis(N8) \\sim Ueq, Uanis(C106) \\sim Ueq, Uanis(C105)
\\sim Ueq, Uanis(O4) \\sim Ueq, Uanis(O3) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(N5) \\sim Ueq, Uanis(N7) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C110) \\sim Ueq, Uanis(C99) \\sim Ueq, Uanis(C109) \\sim Ueq, Uanis(C102)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(N4) \\sim Ueq, Uanis(N9) \\sim Ueq, Uanis(C111) \\sim Ueq, Uanis(C100)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C114) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C117) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(O5) \\sim Ueq, Uanis(O2) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C98) \\sim Ueq, Uanis(C113) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(Cl2) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C116) \\sim Ueq, Uanis(O7) \\sim Ueq, Uanis(C117) \\sim Ueq, Uanis(O11)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O8) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(O9) \\sim Ueq, Uanis(O12) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(O11) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(O13) \\sim Ueq, Uanis(C122) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O13) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C120) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O12) \\sim Ueq, Uanis(O6) \\sim Ueq, Uanis(C118) \\sim Ueq, Uanis(C115)
\\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C120) \\sim Ueq, Uanis(C122) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(C121) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
5. Others
 Sof(H3B)=Sof(O4)=Sof(N6)=Sof(H6)=Sof(C106)=1-FVAR(1)
 Sof(H3A)=Sof(O3)=Sof(N8)=Sof(H8A)=Sof(C105)=FVAR(1)
 Sof(N9)=Sof(H9)=Sof(C111)=Sof(H11C)=Sof(H11D)=Sof(C112)=Sof(H11E)=Sof(H11F)=
 Sof(H11G)=1-FVAR(2)
 Sof(N4)=Sof(H4)=Sof(C100)=Sof(H10A)=Sof(H10B)=Sof(C101)=Sof(H10C)=Sof(H10D)=
 Sof(H10E)=FVAR(2)
 Sof(H2A)=Sof(O2)=Sof(C98)=1-FVAR(3)
 Sof(H2B)=Sof(O5)=Sof(C113)=FVAR(3)
 Fixed Sof: N5(0.5) H5(0.5) C99(0.5) H99A(0.5) H99B(0.5) C102(0.5) H10F(0.5)
 H10G(0.5) H10H(0.5) C103(0.6) H10I(0.6) H10J(0.6) C104(0.6) H10K(0.6)
 H10L(0.6) H10M(0.6) N7(0.5) H7(0.5) C107(0.4) H10N(0.4) H10O(0.4) C108(0.4)
 H10P(0.4) H10Q(0.4) H10R(0.4) C109(0.5) H10S(0.5) H10T(0.5) H10U(0.5)
 C110(0.5) H11A(0.5) H11B(0.5) Cl1(0.5) Cl2(0.5) C114(0.5) H11Q(0.5) H11R(0.5)
 O6(0.6) C115(0.6) H11S(0.6) H11T(0.6) H11U(0.6) O11(0.5) H11(0.5) C117(0.5)
 H11H(0.5) H11I(0.5) H11J(0.5) O7(0.5) H7A(0.5) C116(0.5) H11K(0.5) H11L(0.5)
 H11M(0.5) O10(0.33333) H10(0.33333) C119(0.33333) H11N(0.33333) H11O(0.33333)
 H11P(0.33333) O12(0.4) C118(0.4) H11W(0.4) H11V(0.4) H11X(0.4) O8(0.5)
 H8B(0.5) C120(0.5) H12A(0.5) H12B(0.5) H12C(0.5) O9(0.33333) H9A(0.33333)
 C121(0.33333) H12D(0.33333) H12E(0.33333) H12F(0.33333) O13(0.33333)
 H13(0.33333) C122(0.33333) H12G(0.33333) H12H(0.33333) H12I(0.33333)
6.a Everything fixed:
 H11, H10, H8B, H9A
6.b Riding coordinates:
 N3(H3A), C115(H11S,H11T,H11U), C118(H11W,H11V,H11X)
6.c Secondary CH2 refined with riding coordinates:
 C99(H99A,H99B), C100(H10A,H10B), C103(H10I,H10J), C107(H10N,H10O), C110(H11A,
 H11B), C111(H11C,H11D), C114(H11Q,H11R)
6.d Aromatic/amide H refined with riding coordinates:
 N1(H1), N2(H2A), N2(H2B), N3(H3B), C8(H8), C15(H15), C19(H19), C20(H20),
 C23(H23), C24(H24), C25(H25), C26(H26), C27(H27), C31(H31), C32(H32), C34(H34),
  C35(H35), C37(H37), C38(H38), C39(H39), C41(H41), C42(H42), C44(H44),
 C45(H45), C46(H46), C47(H47), C48(H48), C49(H49), C50(H50), C51(H51), C52(H52),
  C53(H53), C54(H54), C55(H55), C56(H56), C57(H57), C58(H58), C59(H59),
 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), C87(H87), C88(H88), C89(H89),
 C90(H90), C91(H91), C92(H92), C93(H93), C94(H94), C95(H95), C96(H96), C97(H97),
  N4(H4), N5(H5), N8(H8A), N6(H6), N7(H7), N9(H9)
6.e Idealised Me refined as rotating group:
 C101(H10C,H10D,H10E), C102(H10F,H10G,H10H), C104(H10K,H10L,H10M), C108(H10P,
 H10Q,H10R), C109(H10S,H10T,H10U), C112(H11E,H11F,H11G), C117(H11H,H11I,H11J),
 C116(H11K,H11L,H11M), C119(H11N,H11O,H11P), C120(H12A,H12B,H12C), C121(H12D,
 H12E,H12F), C122(H12G,H12H,H12I)
6.f Idealised tetrahedral OH refined as rotating group:
 O7(H7A), O13(H13)
;
_shelx_res_checksum              25810
_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 1.648
_oxdiff_exptl_absorpt_empirical_full_min 0.598