Optical detection of alcohols with a Cu(I)HETPHEN complex by reversible aldehyde to hemiacetal conversion.
Wang, Lei; Xie, Zhu-Lin; Li, Xin; Lynch, Vincent M.; Mulfort, Karen L.; The Analyst 148 (2023) 4274–4278; doi:10.1039/d3an01005h

data_1569695
_publ_section_title
;
 Optical detection of alcohols with a Cu(I)HETPHEN complex by reversible
 aldehyde to hemiacetal conversion.
;
_journal_issue                   18
_journal_name_full               'The Analyst'
_journal_page_first              4274
_journal_page_last               4278
_journal_paper_doi               10.1039/d3an01005h
_journal_volume                  148
_journal_year                    2023
_chemical_formula_moiety         'C46 H43.778 Cu N4 O4, F6 P'
_chemical_formula_sum            'C46 H43.78 Cu F6 N4 O4 P'
_chemical_formula_weight         925.14
_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   geom
_audit_block_doi                 10.5517/ccdc.csd.cc2dqcj1
_audit_creation_date             2021-09-15
_audit_creation_method
;
Olex2 1.3
(compiled 2020.07.31 svn.rc2a77460 for OlexSys, GUI svn.r6145)
;
_audit_update_record
;
2023-05-31 deposited with the CCDC.	2023-08-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 104.9231(17)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.7098(2)
_cell_length_b                   20.7473(3)
_cell_length_c                   14.7414(3)
_cell_measurement_reflns_used    13547
_cell_measurement_temperature    100.00(18)
_cell_measurement_theta_max      76.2750
_cell_measurement_theta_min      3.7430
_cell_volume                     4347.17(13)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Shelxtl-Plus/XP, Bruker AXS, Inc. 2009'
_computing_publication_material  'Shelxtl-Plus, Bruker AXS, Inc. 2009'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(18)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.944
_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   -119.00 -35.00   0.50    4.00    --  -48.32 -72.00-168.00  168
  2  \w    -32.00  13.00   0.50    4.00    --  -48.32  72.00 -38.00   90
  3  \w     27.00  60.00   0.50    4.00    --   48.32 -72.00-168.00   66
  4  \w   -152.00 -89.00   0.50   16.00    -- -105.12 -72.00-168.00  126
  5  \w     49.00  75.00   0.50   16.00    --  105.12 -72.00-168.00   52
  6  \w    113.00 177.00   0.50   16.00    --  105.12  72.00 -38.00  128
  7  \w    -23.00  26.00   0.50    4.00    --   48.32 -19.00  30.00   98
  8  \w    -17.00  19.00   0.50    4.00    --   48.32 -19.00-180.00   72
  9  \w   -128.00 -84.00   0.50   16.00    -- -105.12 -95.00 -60.00   88
 10  \w   -124.00 -77.00   0.50   16.00    -- -105.12-125.00   0.00   94
 11  \w   -175.00-132.00   0.50   16.00    -- -105.12 -95.00 -60.00   86
 12  \w   -100.50 -34.00   0.50   16.00    -- -105.12 125.00-150.00  133
 13  \w   -174.00-136.00   0.50   16.00    -- -105.12-125.00   0.00   76
 14  \w     42.00  87.00   0.50   16.00    --  105.12 -95.00   0.00   90
 15  \w     39.00 103.00   0.50   16.00    --  105.12 -95.00 120.00  128
 16  \w     38.00  70.00   0.50   16.00    --  105.12 -61.00 120.00   64
 17  \w    147.00 173.00   0.50   16.00    --  105.12  61.00-120.00   52
 18  \w     97.00 143.00   0.50   16.00    --  105.12  61.00-120.00   92
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0275904000
_diffrn_orient_matrix_UB_12      -0.0637018000
_diffrn_orient_matrix_UB_13      -0.0535010000
_diffrn_orient_matrix_UB_21      0.0126624000
_diffrn_orient_matrix_UB_22      0.0318277000
_diffrn_orient_matrix_UB_23      -0.0904911000
_diffrn_orient_matrix_UB_31      0.1040048000
_diffrn_orient_matrix_UB_32      -0.0207678000
_diffrn_orient_matrix_UB_33      0.0256690000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0320
_diffrn_reflns_av_unetI/netI     0.0295
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.944
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            24795
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.944
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.637
_diffrn_reflns_theta_min         3.764
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.694
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.632
_exptl_absorpt_correction_type   'gaussian and multi-scan'
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.414
_exptl_crystal_description       plate
_exptl_crystal_F_000             1911
_exptl_crystal_size_max          0.292
_exptl_crystal_size_mid          0.132
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.936
_refine_diff_density_min         -0.498
_refine_diff_density_rms         0.067
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.179
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     695
_refine_ls_number_reflns         8654
_refine_ls_number_restraints     357
_refine_ls_restrained_S_all      1.180
_refine_ls_R_factor_all          0.0668
_refine_ls_R_factor_gt           0.0605
_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^)+(0.0763P)^2^+2.9839P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1633
_refine_ls_wR_factor_ref         0.1675
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7507
_reflns_number_total             8654
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3an01005h2.cif
_cod_data_source_block           cu-chovl
_cod_depositor_comments
'Adding full bibliography for 1569695--1569696.cif.'
_cod_original_cell_volume        4347.18(12)
_cod_database_code               1569695
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C48 H48 N4 O2 F6 P Cu'
_shelx_estimated_absorpt_t_max   0.891
_shelx_estimated_absorpt_t_min   0.638
_reflns_odcompleteness_completeness 98.70
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 C43-O2
 1.5 with sigma of 0.02
 C38-C45 \\sim C38-C45A
 with sigma of 0.02
 O1-O2 \\sim O1A-O2A
 with sigma of 0.04
 O2-C43 \\sim O2A-C43A
 with sigma of 0.02
 O1-C33 \\sim O1A-C33
 with sigma of 0.04
 C45-O4 \\sim C45A-O4A
 with sigma of 0.02
 O1-C43 \\sim O1A-C43A
 with sigma of 0.02
 O2-C33 \\sim O2A-C33
 with sigma of 0.04
 C38-O4 \\sim C38-O4A
 with sigma of 0.04
 O3-C45 \\sim O3A-C45A
 with sigma of 0.02
 O3-C46 \\sim O3A-C46A
 with sigma of 0.02
 O3-O4 \\sim O3A-O4A
 with sigma of 0.04
 C45-C46 \\sim C45A-C46A
 with sigma of 0.04
 C38-O3 \\sim C38-O3A
 with sigma of 0.04
 C26-C29 \\sim C26A-C29A
 with sigma of 0.04
 C10-C22 \\sim C10-C22A
 with sigma of 0.02
 C22-C23 \\sim C22A-C23A
 with sigma of 0.02
 C22-C27 \\sim C22A-C27A
 with sigma of 0.02
 C23-C28 \\sim C23A-C28A
 with sigma of 0.02
 C23-C24 \\sim C23A-C24A
 with sigma of 0.02
 C27-C26 \\sim C27A-C26A
 with sigma of 0.02
 C27-C30 \\sim C27A-C30A
 with sigma of 0.02
 C24-C26 \\sim C24A-C26A
 with sigma of 0.04
 C24-C25 \\sim C24A-C25A
 with sigma of 0.02
 C25-C26 \\sim C25A-C26A
 with sigma of 0.02
 C25-C29 \\sim C25A-C29A
 with sigma of 0.02
 C28-C24 \\sim C28A-C24A
 with sigma of 0.04
 C27-C25 \\sim C27A-C25A
 with sigma of 0.04
 C24-C29 \\sim C24A-C29A
 with sigma of 0.04
 C26-C30 \\sim C26A-C30A
 with sigma of 0.04
 C10-C23 \\sim C10-C23A
 with sigma of 0.04
 C10-C27 \\sim C10-C27A
 with sigma of 0.04
 C22-C28 \\sim C22A-C28A
 with sigma of 0.04
 C22-C24 \\sim C22A-C24A
 with sigma of 0.04
 C22-C26 \\sim C22A-C26A
 with sigma of 0.04
 C22-C30 \\sim C22A-C30A
 with sigma of 0.04
 C23-C27 \\sim C23A-C27A
 with sigma of 0.04
 C23-C25 \\sim C23A-C25A
 with sigma of 0.04
 C33-C43 \\sim C33-C43A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O1 \\sim O2 \\sim C43 \\sim C44 \\sim O1A \\sim O2A \\sim C43A: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
O3 \\sim C45 \\sim C46 \\sim O3A \\sim O4A \\sim C45A \\sim C46A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C28 \\sim C29 \\sim C30 \\sim C28A \\sim C29A \\sim C30A: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
C23 \\sim C24 \\sim C25 \\sim C26 \\sim C27 \\sim C23A \\sim C24A \\sim C25A
\\sim C26A \\sim C27A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
Uanis(C22A) \\sim Ueq, Uanis(C22) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O1) = Uanis(O1A)
Uanis(C22) = Uanis(C22A)
Uanis(C28) = Uanis(C28A)
Uanis(C45) = Uanis(C45A)
Uanis(C43A) = Uanis(C43)
4. Others
 Sof(O3A)=Sof(O4A)=Sof(H4A)=Sof(C45A)=Sof(H45A)=Sof(C46A)=Sof(H46D)=Sof(H46E)=
 Sof(H46F)=1-FVAR(1)
 Sof(O3)=Sof(O4)=Sof(H4)=Sof(C45)=Sof(H45)=Sof(C46)=Sof(H46A)=Sof(H46B)=
 Sof(H46C)=FVAR(1)
 Sof(C22A)=Sof(C23A)=Sof(C24A)=Sof(H24A)=Sof(C25A)=Sof(C26A)=Sof(H26A)=
 Sof(C27A)=Sof(C28A)=Sof(H28D)=Sof(H28E)=Sof(H28F)=Sof(C29A)=Sof(H29D)=
 Sof(H29E)=Sof(H29F)=Sof(C30A)=Sof(H30D)=Sof(H30E)=Sof(H30F)=1-FVAR(2)
 Sof(C22)=Sof(C23)=Sof(C24)=Sof(H24)=Sof(C25)=Sof(C26)=Sof(H26)=Sof(C27)=
 Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=
 Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=FVAR(2)
 Sof(O1A)=Sof(O2A)=Sof(C43A)=Sof(H43A)=Sof(C44A)=Sof(H44D)=Sof(H44E)=Sof(H44F)=
 1-FVAR(3)
 Sof(O1)=Sof(O2)=Sof(H2A)=Sof(C43)=Sof(H43)=Sof(C44)=Sof(H44A)=Sof(H44B)=
 Sof(H44C)=FVAR(3)
5.a Ternary CH refined with riding coordinates:
 C43(H43), C45(H45), C43A(H43A), C45A(H45A)
5.b Me refined with riding coordinates:
 C21(H21A,H21B,H21C)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C8(H8), C9(H9), C15(H15), C17(H17), C31(H31),
 C32(H32), C35(H35), C36(H36), C39(H39), C40(H40), C24(H24), C26(H26),
 C24A(H24A), C26A(H26A)
5.d Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C28(H28A,H28B,H28C), C29(H29A,H29B,
 H29C), C30(H30A,H30B,H30C), C44(H44A,H44B,H44C), C46(H46A,H46B,H46C),
 C28A(H28D,H28E,H28F), C29A(H29D,H29E,H29F), C30A(H30D,H30E,H30F), C44A(H44D,
 H44E,H44F), C46A(H46D,H46E,H46F)
5.e Idealised tetrahedral OH refined as rotating group:
 O2(H2A), O4(H4), O4A(H4A)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              68248
_shelx_fab_checksum              93036
_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 2.133
_oxdiff_exptl_absorpt_empirical_full_min 0.629