Trapping of soluble, KCl-stabilized Cu(I) hydrides with CO<sub>2</sub> gives crystalline formates.
Grasruck, Alexander; Parla, Giorgio; Lou, Lisha; Langer, Jens; Neiß, Christian; Herrera, Alberto; Frieß, Sybille; Görling, Andreas; Schmid, Günter; Dorta, Romano; Chemical communications (Cambridge, England)  (2023) –; doi:10.1039/d3cc03033d

data_7132308
_publ_section_title
;
 Trapping of soluble, KCl-stabilized Cu(I) hydrides with CO<sub>2</sub>
 gives crystalline formates.
;
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_paper_doi               10.1039/d3cc03033d
_journal_year                    2023
_chemical_formula_moiety         'C59 H56 B Cu N2 O2 P2, 1.429(C6 H6)'
_chemical_formula_sum            'C67.57 H64.57 B Cu N2 O2 P2'
_chemical_formula_weight         1072.97
_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             2022-04-11
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2023-05-24 deposited with the CCDC.	2023-10-30 downloaded from the CCDC.
;
_cell_angle_alpha                76.2750(10)
_cell_angle_beta                 78.6300(10)
_cell_angle_gamma                78.9470(10)
_cell_formula_units_Z            6
_cell_length_a                   14.3056(2)
_cell_length_b                   22.4286(3)
_cell_length_c                   28.0190(3)
_cell_measurement_reflns_used    54013
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      73.6200
_cell_measurement_theta_min      3.2470
_cell_volume                     8462.19(19)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2903
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.964
_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  -2.00   1.00    4.00    --  -40.61 125.00  30.00   91
  2  \w   -117.00  -8.00   1.00    4.00    --  -40.61 -77.00 -30.00  109
  3  \w    -65.00  34.00   1.00    4.00    --  -40.61  38.00-150.00   99
  4  \w   -115.00 -16.00   1.00    4.00    --  -40.61 -38.00-150.00   99
  5  \w     35.00 136.00   1.00   16.00    --  107.07 -61.00-120.00  101
  6  \w     81.00 178.00   1.00   16.00    --  107.07  45.00  90.00   97
  7  \w     31.00 135.00   1.00   16.00    --  107.07 -30.00  60.00  104
  8  \w     34.00 118.00   1.00   16.00    --  107.07-125.00-150.00   84
  9  \w     34.00 118.00   1.00   16.00    --  107.07-125.00 -90.00   84
 10  \w     81.00 178.00   1.00   16.00    --  107.07  45.00  30.00   97
 11  \w     34.00 118.00   1.00   16.00    --  107.07-125.00  30.00   84
 12  \w     25.00 160.00   1.00   16.00    --  107.07 -15.00 -90.00  135
 13  \w     31.00 140.00   1.00   16.00    --  107.07 -77.00  30.00  109
 14  \w   -113.00 -12.00   1.00    4.00    --  -40.61 -57.00  30.00  101
 15  \w   -117.00  -8.00   1.00    4.00    --  -40.61 -77.00 120.00  109
 16  \w      1.00  82.00   1.00    4.00    --   40.61 -99.00 -30.00   81
 17  \w     74.00 178.00   1.00   16.00    --  107.07  77.00-150.00  104
 18  \w     78.00 178.00   1.00   16.00    --  107.07  61.00 150.00  100
 19  \w     78.00 178.00   1.00   16.00    --  107.07  61.00 -30.00  100
 20  \w     78.00 178.00   1.00   16.00    --  107.07  61.00 120.00  100
 21  \w     78.00 178.00   1.00   16.00    --  107.07  61.00-180.00  100
 22  \w     79.00 178.00   1.00   16.00    --  107.07  30.00 -60.00   99
 23  \w   -117.00  -8.00   1.00    4.00    --  -40.61 -77.00-150.00  109
 24  \w      8.00 117.00   1.00    4.00    --   40.61  77.00  90.00  109
 25  \w      1.00  82.00   1.00    4.00    --   40.61 -99.00-120.00   81
 26  \w     74.00 178.00   1.00   16.00    --  107.07  77.00  30.00  104
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0725423000
_diffrn_orient_matrix_UB_12      -0.0346091000
_diffrn_orient_matrix_UB_13      -0.0364746000
_diffrn_orient_matrix_UB_21      -0.0835583000
_diffrn_orient_matrix_UB_22      -0.0228048000
_diffrn_orient_matrix_UB_23      -0.0143421000
_diffrn_orient_matrix_UB_31      -0.0103753000
_diffrn_orient_matrix_UB_32      0.0583104000
_diffrn_orient_matrix_UB_33      -0.0418391000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0289
_diffrn_reflns_av_unetI/netI     0.0245
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.964
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            126024
_diffrn_reflns_point_group_measured_fraction_full 0.986
_diffrn_reflns_point_group_measured_fraction_max 0.964
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.776
_diffrn_reflns_theta_min         3.188
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.442
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70769
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.263
_exptl_crystal_description       plank
_exptl_crystal_F_000             3384
_exptl_crystal_size_max          0.385
_exptl_crystal_size_mid          0.338
_exptl_crystal_size_min          0.121
_refine_diff_density_max         0.698
_refine_diff_density_min         -0.643
_refine_diff_density_rms         0.052
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2488
_refine_ls_number_reflns         32991
_refine_ls_number_restraints     1592
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0604
_refine_ls_R_factor_gt           0.0495
_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^)+(0.0587P)^2^+7.1117P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1258
_refine_ls_wR_factor_ref         0.1358
_reflns_Friedel_coverage         0.000
_reflns_number_gt                27678
_reflns_number_total             32991
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc03033d2.cif
_cod_data_source_block           rodo181018c
_cod_database_code               7132308
_shelx_shelxl_version_number     2019/2
_chemical_oxdiff_formula         'C59 H56 B1 Cu1 N2 O2 P2'
_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
 C218-B1 \\sim C2-B1 \\sim C216-B1 \\sim C4-B1 \\sim C214-B1 \\sim C6-B1 \\sim
C122-B3 \\sim C228-B3A ~
 C124-B3 \\sim C120-B3 \\sim C230-B3A \\sim C226-B3A
 with sigma of 0.02
 Cu3-O5 \\sim Cu3A-O5A
 with sigma of 0.02
 Cu3-P6 \\sim Cu3A-P6A
 with sigma of 0.02
 Cu3A-P5A \\sim Cu3-P5
 with sigma of 0.02
 C220-B2 \\sim C61-B2 \\sim C222-B2 \\sim C63-B2 \\sim C65-B2 \\sim C224-B2
 with sigma of 0.02
 C216-C217 \\sim C5-C4 \\sim C7-C6 \\sim C214-C215 \\sim C3-C2 \\sim C219-C218
\\sim C227-C226 \\sim C125-
 C124 \\sim C229-C228 \\sim C123-C122 \\sim C121-C120 \\sim C231-C230 \\sim
C61-C62 \\sim C221-C220
 with sigma of 0.02
 C66-C65 \\sim C224-C225 \\sim C64-C63 \\sim C222-C223 \\sim C61-C62 \\sim
C221-C220
 with sigma of 0.02
 H61a-H60 \\sim H60-H22l
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C5 \\sim C217: within 2A with sigma of 0.02 and sigma for terminal atoms of
0.04 within 2A
C120 \\sim C121 \\sim C122 \\sim C123 \\sim C124 \\sim C125 \\sim B3 \\sim C226
\\sim C227 \\sim C228 \\sim C229 \\sim C230 \\sim C231 \\sim B3A: within 4A
with sigma of 0.02 and sigma for terminal atoms of 0.04 within 4A
C192 \\sim C193 \\sim C190 \\sim C191 \\sim C194 \\sim C195 \\sim C246 \\sim
C247 \\sim C244 \\sim C248 \\sim C249: within 4A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 4A
P5 \\sim P5A: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
C223 \\sim C64 \\sim C222 \\sim C63 \\sim C61 \\sim C62 \\sim C221 \\sim C220
\\sim C224 \\sim C65 \\sim C66 \\sim C225 \\sim B2: within 4A with sigma of
0.02 and sigma for terminal atoms of 0.04 within 4A
4. Rigid body (RIGU) restrains
 C120, C121, C123, C124, C125, B3, C226, C227, C228, C229, C230, C231, B3A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C190, C191, C192, C193, C194, C195, C244, C245, C246, C247, C248, C249
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 B2, C63, C64, C65, C66, C222, C223, C224, C225
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 1*[Sof(C202)+Sof(H202)+Sof(C203)+Sof(H203)+Sof(C204)+Sof(H204)+Sof(C199)+
 Sof(H199)+Sof(C200)+Sof(H200)+Sof(C201)+Sof(H201)]+1*[Sof(C211)+Sof(H211)+
 Sof(C212)+Sof(H212)+Sof(C213)+Sof(H213)]+1*[Sof(C209)+Sof(H209)+Sof(C208)+
 Sof(H208)+Sof(C207)+Sof(H207)+Sof(C206)+Sof(H206)+Sof(C205)+Sof(H205)+
 Sof(C210)+Sof(H210)]=1 with esd of 0.0001
 Sof(H11a)=Sof(Cu3A)=Sof(P5A)=Sof(P6A)=Sof(O5A)=Sof(O6A)=Sof(C226)=Sof(H22a)=
 Sof(H22b)=Sof(C227)=Sof(H22c)=Sof(H22d)=Sof(H22e)=Sof(C228)=Sof(H22f)=
 Sof(H22g)=Sof(C229)=Sof(H22h)=Sof(H22i)=Sof(H22j)=Sof(C230)=Sof(H23a)=
 Sof(H23b)=Sof(C231)=Sof(H23c)=Sof(H23d)=Sof(H23e)=Sof(C232)=Sof(C233)=
 Sof(H233)=Sof(C234)=Sof(H234)=Sof(C235)=Sof(H235)=Sof(C236)=Sof(H236)=
 Sof(C237)=Sof(H237)=Sof(C238)=Sof(C239)=Sof(H239)=Sof(C240)=Sof(H240)=
 Sof(C241)=Sof(H241)=Sof(C242)=Sof(H242)=Sof(C243)=Sof(H243)=Sof(B3A)=1-FVAR(1)
 Sof(H119)=Sof(Cu3)=Sof(P5)=Sof(P6)=Sof(O5)=Sof(O6)=Sof(C120)=Sof(H12a)=
 Sof(H12b)=Sof(C121)=Sof(H12c)=Sof(H12d)=Sof(H12e)=Sof(C122)=Sof(H12f)=
 Sof(H12g)=Sof(C123)=Sof(H12h)=Sof(H12i)=Sof(H12j)=Sof(C124)=Sof(H12k)=
 Sof(H12l)=Sof(C125)=Sof(H12m)=Sof(H12n)=Sof(H12o)=Sof(C126)=Sof(C127)=
 Sof(H127)=Sof(C128)=Sof(H128)=Sof(C129)=Sof(H129)=Sof(C130)=Sof(H130)=
 Sof(C131)=Sof(H131)=Sof(C152)=Sof(C153)=Sof(H153)=Sof(C154)=Sof(H154)=
 Sof(C155)=Sof(H155)=Sof(C156)=Sof(H156)=Sof(C157)=Sof(H157)=Sof(B3)=FVAR(1)
 Sof(C2)=Sof(H2a)=Sof(H2b)=Sof(C3)=Sof(H3a)=Sof(H3b)=Sof(H3c)=Sof(C4)=Sof(H4a)=
 Sof(H4b)=Sof(C5)=Sof(H5a)=Sof(H5b)=Sof(H5c)=Sof(C6)=Sof(H6a)=Sof(H6b)=Sof(C7)=
 Sof(H7a)=Sof(H7b)=Sof(H7c)=1-FVAR(2)
 Sof(C214)=Sof(H21a)=Sof(H21b)=Sof(C215)=Sof(H21c)=Sof(H21d)=Sof(H21e)=
 Sof(C216)=Sof(H21f)=Sof(H21g)=Sof(C217)=Sof(H21h)=Sof(H21i)=Sof(H21j)=
 Sof(C218)=Sof(H21k)=Sof(H21l)=Sof(C219)=Sof(H21m)=Sof(H21n)=Sof(H21o)=FVAR(2)
 Sof(C61)=Sof(H61a)=Sof(H61b)=Sof(C62)=Sof(H62a)=Sof(H62b)=Sof(H62c)=Sof(C63)=
 Sof(H63a)=Sof(H63b)=Sof(C64)=Sof(H64a)=Sof(H64b)=Sof(H64c)=Sof(C65)=Sof(H65a)=
 Sof(H65b)=Sof(C66)=Sof(H66a)=Sof(H66b)=Sof(H66c)=1-FVAR(3)
 Sof(C220)=Sof(H22k)=Sof(H22l)=Sof(C221)=Sof(H22m)=Sof(H22n)=Sof(H22o)=
 Sof(C222)=Sof(H22p)=Sof(H22q)=Sof(C223)=Sof(H22r)=Sof(H22s)=Sof(H22t)=
 Sof(C224)=Sof(H22u)=Sof(H22v)=Sof(C225)=Sof(H22w)=Sof(H22x)=Sof(H22y)=FVAR(3)
 Sof(C248)=Sof(H248)=Sof(C247)=Sof(H247)=Sof(C246)=Sof(H246)=Sof(C245)=
 Sof(H245)=Sof(C244)=Sof(H244)=Sof(C249)=Sof(H249)=1-FVAR(4)
 Sof(C190)=Sof(H190)=Sof(C195)=Sof(H195)=Sof(C194)=Sof(H194)=Sof(C193)=
 Sof(H193)=Sof(C192)=Sof(H192)=Sof(C191)=Sof(H191)=FVAR(4)
 Sof(C202)=Sof(H202)=Sof(C203)=Sof(H203)=Sof(C204)=Sof(H204)=Sof(C199)=
 Sof(H199)=Sof(C200)=Sof(H200)=Sof(C201)=Sof(H201)=FVAR(5)
 Sof(C209)=Sof(H209)=Sof(C208)=Sof(H208)=Sof(C207)=Sof(H207)=Sof(C206)=
 Sof(H206)=Sof(C205)=Sof(H205)=Sof(C210)=Sof(H210)=FVAR(6)
 Sof(C211)=Sof(H211)=Sof(C212)=Sof(H212)=Sof(C213)=Sof(H213)=FVAR(7)
6.a Secondary CH2 refined with riding coordinates:
 C2(H2a,H2b), C4(H4a,H4b), C6(H6a,H6b), C214(H21a,H21b), C216(H21f,H21g),
 C218(H21k,H21l), C61(H61a,H61b), C63(H63a,H63b), C65(H65a,H65b), C220(H22k,
 H22l), C222(H22p,H22q), C224(H22u,H22v), C120(H12a,H12b), C122(H12f,H12g),
 C124(H12k,H12l), C226(H22a,H22b), C228(H22f,H22g), C230(H23a,H23b)
6.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C15(H15), C16(H16),
 C17(H17), C18(H18), C19(H19), C21(H21), C22(H22), C23(H23), C24(H24), C26(H26),
  C27(H27), C29(H29), C30(H30), C31(H31), C32(H32), C35(H35), C36(H36),
 C37(H37), C38(H38), C39(H39), C41(H41), C42(H42), C43(H43), C44(H44), C45(H45),
  C47(H47), C48(H48), C49(H49), C50(H50), C52(H52), C53(H53), C55(H55),
 C56(H56), C57(H57), C58(H58), C60(H60), C68(H68), C69(H69), C70(H70), C71(H71),
  C72(H72), C74(H74), C75(H75), C76(H76), C77(H77), C78(H78), C80(H80),
 C81(H81), C82(H82), C83(H83), C85(H85), C86(H86), C88(H88), C89(H89), C90(H90),
  C91(H91), C94(H94), C95(H95), C96(H96), C97(H97), C98(H98), C100(H100),
 C101(H101), C102(H102), C103(H103), C104(H104), C106(H106), C107(H107),
 C108(H108), C109(H109), C111(H111), C112(H112), C114(H114), C115(H115),
 C116(H116), C117(H117), C119(H119), C119(H11a), C133(H133), C134(H134),
 C135(H135), C136(H136), C137(H137), C139(H139), C140(H140), C141(H141),
 C142(H142), C144(H144), C145(H145), C147(H147), C148(H148), C149(H149),
 C150(H150), C159(H159), C160(H160), C161(H161), C162(H162), C163(H163),
 C165(H165), C166(H166), C167(H167), C168(H168), C170(H170), C171(H171),
 C173(H173), C174(H174), C175(H175), C176(H176), C127(H127), C128(H128),
 C129(H129), C130(H130), C131(H131), C153(H153), C154(H154), C155(H155),
 C156(H156), C157(H157), C233(H233), C234(H234), C235(H235), C236(H236),
 C237(H237), C239(H239), C240(H240), C241(H241), C242(H242), C243(H243),
 C178(H178), C179(H179), C180(H180), C181(H181), C182(H182), C183(H183),
 C184(H184), C185(H185), C186(H186), C187(H187), C188(H188), C189(H189),
 C196(H196), C197(H197), C198(H198), C190(H190), C195(H195), C194(H194),
 C193(H193), C192(H192), C191(H191), C211(H211), C212(H212), C213(H213),
 C248(H248), C247(H247), C246(H246), C245(H245), C244(H244), C249(H249),
 C202(H202), C203(H203), C204(H204), C199(H199), C200(H200), C201(H201),
 C209(H209), C208(H208), C207(H207), C206(H206), C205(H205), C210(H210)
6.c Fitted hexagon refined as free rotating group:
 C190(C195,C194,C193,C192,C191), C248(C247,C246,C245,C244,C249), C202(C203,
 C204,C199,C200,C201), C209(C208,C207,C206,C205,C210)
6.d Idealised Me refined with riding coordinates:
 C221(H22m,H22n,H22o)
6.e Idealised Me refined as rotating group:
 C3(H3a,H3b,H3c), C5(H5a,H5b,H5c), C7(H7a,H7b,H7c), C215(H21c,H21d,H21e),
 C217(H21h,H21i,H21j), C219(H21m,H21n,H21o), C62(H62a,H62b,H62c), C64(H64a,H64b,
 H64c), C66(H66a,H66b,H66c), C223(H22r,H22s,H22t), C225(H22w,H22x,H22y),
 C121(H12c,H12d,H12e), C123(H12h,H12i,H12j), C125(H12m,H12n,H12o), C227(H22c,
 H22d,H22e), C229(H22h,H22i,H22j), C231(H23c,H23d,H23e)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              82874
_shelx_hkl_checksum              35679
_olex2_date_sample_data_collection 2021-07-01
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.772
_oxdiff_exptl_absorpt_empirical_full_min 0.568