Hybrid amino/iminopyridines with auxiliary phosphines enabling active zinc catalysts for the ring-opening polymerization of lactide.
Xue, Xiaopan; Zhu, Dongzhi; Zhang, Wenjuan; Zheng, Tongxin; Wang, Rui; Ma, Yanping; Sun, Wen-Hua; Dalton transactions (Cambridge, England : 2003) 55 (2026) 3388–3399; doi:10.1039/d5dt02857d

data_7720091
_publ_section_title
;
 Hybrid amino/iminopyridines with auxiliary phosphines enabling active
 zinc catalysts for the ring-opening polymerization of lactide.
;
_journal_issue                   8
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              3388
_journal_page_last               3399
_journal_paper_doi               10.1039/d5dt02857d
_journal_volume                  55
_journal_year                    2026
_chemical_formula_moiety         'C35 H41 Cl2 N3 P Zn'
_chemical_formula_sum            'C35 H41 Cl2 N3 P Zn'
_chemical_formula_weight         670.95
_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
_atom_sites_solution_primary     iterative
_audit_creation_date             2023-05-31
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2025-11-28 deposited with the CCDC.	2026-01-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.0520(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.03300(10)
_cell_length_b                   28.6313(4)
_cell_length_c                   13.76800(10)
_cell_measurement_reflns_used    16197
_cell_measurement_temperature    169.99(10)
_cell_measurement_theta_max      75.1920
_cell_measurement_theta_min      3.0600
_cell_volume                     3555.72(7)
_computing_cell_refinement       'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.90a (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      169.99(10)
_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 0.968
_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   -116.00 -91.00   0.50    0.07    --  -48.81-141.00 134.00   50
  2  \w   -142.00-117.00   0.50    0.29    -- -103.25-141.00 134.00   50
  3  \w   -116.00 -77.00   0.50    0.07    --  -48.81-129.00 -53.00   78
  4  \w   -174.00-101.00   0.50    0.29    -- -103.25 -38.00-150.00  146
  5  \w    -22.00  23.00   0.50    0.07    --  -48.81  19.00-180.00   90
  6  \w    -58.00 -33.00   0.50    0.29    -- -103.25  57.00-150.00   50
  7  \w    -22.00  16.00   0.50    0.07    --  -48.81  19.00 -30.00   76
  8  \w    -22.00  25.00   0.50    0.07    --  -48.81  19.00  30.00   94
  9  \w    -62.00 -36.00   0.50    0.29    -- -103.25  57.00  30.00   52
 10  \w   -112.00 -47.00   0.50    0.29    -- -103.25 125.00   0.00  130
 11  \w   -126.00 -90.00   0.50    0.29    -- -103.25 144.00 -75.86   72
 12  \w    -73.00 -35.00   0.50    0.29    -- -103.25 144.00 -75.86   76
 13  \w    -55.00 -30.00   0.50    0.07    --  -48.81 129.00  20.00   50
 14  \w    -77.00 -50.00   0.50    0.29    -- -103.25 129.00  20.00   54
 15  \w   -111.00 -61.00   0.50    0.29    -- -103.25 141.00-167.00  100
 16  \w    -56.00 -31.00   0.50    0.29    -- -103.25 141.00-167.00   50
 17  \w    -63.00 -24.00   0.50    0.07    --  -48.81 141.00-167.00   78
 18  \w    150.00 175.00   0.50    0.29    --  101.25  19.00 150.00   50
 19  \w     97.00 125.00   0.50    0.29    --  101.25  19.00 150.00   56
 20  \w     41.00 115.00   0.50    0.07    --   48.81  38.00 120.00  148
 21  \w    100.00 125.00   0.50    0.29    --  101.25 129.00  20.00   50
 22  \w     94.00 168.00   0.50    0.29    --  101.25  38.00  30.00  148
 23  \w     32.00 108.00   0.50    0.29    --  101.25 -77.00 -60.00  152
 24  \w     31.00  93.00   0.50    0.29    --  101.25 -99.00 -60.00  124
 25  \w     48.00  73.00   0.50    0.29    --  101.25-129.00 -53.00   50
 26  \w     54.00  96.00   0.50    0.07    --   48.81-129.00 -53.00   84
 27  \w     42.00  67.00   0.50    0.07    --   48.81-141.00 134.00   50
 28  \w     37.00 117.00   0.50    0.29    --  101.25-141.00 134.00  160
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0460267000
_diffrn_orient_matrix_UB_12      -0.0514589000
_diffrn_orient_matrix_UB_13      0.0138929000
_diffrn_orient_matrix_UB_21      0.1596940000
_diffrn_orient_matrix_UB_22      0.0154531000
_diffrn_orient_matrix_UB_23      0.0290788000
_diffrn_orient_matrix_UB_31      -0.0397206000
_diffrn_orient_matrix_UB_32      0.0024114000
_diffrn_orient_matrix_UB_33      0.1073148000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0315
_diffrn_reflns_av_unetI/netI     0.0273
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.968
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -35
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            29627
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.700
_diffrn_reflns_theta_min         3.087
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.963
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70605
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.90a (Rigaku Oxford Diffraction, 2023)
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    1.253
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1404
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.805
_refine_diff_density_min         -0.884
_refine_diff_density_rms         0.102
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     666
_refine_ls_number_reflns         7156
_refine_ls_number_restraints     900
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0917
_refine_ls_R_factor_gt           0.0851
_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^)+(0.1702P)^2^+4.0542P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2573
_refine_ls_wR_factor_ref         0.2652
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6207
_reflns_number_total             7156
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02857d2.cif
_cod_data_source_block           Zn1
_cod_depositor_comments
'Adding full bibliography for 7720091--7720092.cif.'
_cod_database_code               7720091
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C H N P Zn Cl'
_diffrn_oxdiff_digest_frames
;
018938413aa382d661160a7bd692db659702368316d
;
_diffrn_oxdiff_digest_hkl
;
01bb4c6342a967d946ba465bbf9d93a3f9c615
;
_reflns_odcompleteness_completeness 99.98
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 P3-C53 = P1-C1AA = P0AA-C23 = P1-C30 = P3-C5AA = P0AA-C0BA = P0AA-C8AA
 1.84 with sigma of 0.01
 C40-C36 = C40-C3AA = C39-C3AA = C39-C38 = C38-C37 = C37-C36 = C34-C5AA = C33-
 C34 = C33-C6AA = C48-C6AA = C48-C7AA = C7AA-C5AA
 1.39 with sigma of 0.01
 C25-C24 = C26-C25 = C27-C26 = C28-C27 = C29-C28 = C29-C24 = C35-C30 = C35-C46
 = C46-C45 = C45-C32 = C32-C31 = C31-C30
 1.39 with sigma of 0.01
 C52-C8AA = C56-C52 = C56-C55 = C55-C50 = C50-C49 = C49-C8AA = C64-C0BA = C64-
 C9AA = C9AA-C4AA = C65-C4AA = C65-C2AA = C0BA-C2AA
 1.39 with sigma of 0.01
 C54-C53 = C61-C1AA = C23-C22
 1.54 with sigma of 0.01
 C64-P0AA
 2.9 with sigma of 0.02
 C2AA-P0AA
 2.9 with sigma of 0.02
 C64-C2AA
 2.4 with sigma of 0.02
 C0BA-C9AA
 2.4 with sigma of 0.02
 C0BA-C65
 2.4 with sigma of 0.02
3. Restrained planarity
 C5AA, C34, C7AA, C6AA, C33, C48
 with sigma of 0.01
 C9AA, C2AA, C0BA, C65, C64, C4AA
 with sigma of 0.01
 C26, C25, C24, C27, C29, C28
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
C22 \\sim C1AA \\sim P0AA \\sim P1 \\sim C5AA \\sim C34 \\sim C7AA \\sim C30
\\sim C35 \\sim P3 \\sim C50 \\sim C52 \\sim C49 \\sim C8AA \\sim C54 \\sim C53
\\sim C55 \\sim C56 \\sim C61 \\sim C3AA \\sim C26 \\sim C25 \\sim C24 \\sim
C27 \\sim C37 \\sim C40 \\sim C36 \\sim C39 \\sim C38 \\sim C29 \\sim C28 \\sim
C2AA \\sim C0BA \\sim C23 \\sim C6AA \\sim C33 \\sim C48 \\sim C45 \\sim C46
\\sim C31 \\sim C32 \\sim C9AA \\sim C65 \\sim C64 \\sim C4AA: within 1.7A with
sigma of 0.01 and sigma for terminal atoms of 0.02
C9 \\sim C8 \\sim C0AA: within 1.7A with sigma of 0.02 and sigma for terminal
atoms of 0.04
Uanis(C22) \\sim Ueq, Uanis(C1AA) \\sim Ueq, Uanis(P0AA) \\sim Ueq, Uanis(P1)
\\sim Ueq, Uanis(C5AA) \\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C7AA) \\sim Ueq,
Uanis(C30) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(P3) \\sim Ueq, Uanis(C50)
\\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C8AA) \\sim Ueq,
Uanis(C54) \\sim Ueq, Uanis(C53) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C56)
\\sim Ueq, Uanis(C61) \\sim Ueq, Uanis(C3AA) \\sim Ueq, Uanis(C26) \\sim Ueq,
Uanis(C25) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C37)
\\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C39) \\sim Ueq,
Uanis(C38) \\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C2AA) \\sim Ueq, Uanis(C0BA)
\\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C64) \\sim Ueq, Uanis(C6AA) \\sim Ueq,
Uanis(C33) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C46)
\\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C9AA) \\sim Ueq,
Uanis(C65) \\sim Ueq, Uanis(C4AA) \\sim Ueq, Uanis(C28) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
5. Others
 Sof(H8B)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=1-FVAR(1)
 Sof(H8A)=Sof(C0AA)=Sof(H0AA)=Sof(H0AB)=Sof(H0AC)=FVAR(1)
 Fixed Sof: C22(0.3) H22A(0.3) H22B(0.3) C1AA(0.35) H1AA(0.35) H1AB(0.35)
 P0AA(0.3) P1(0.35) C5AA(0.35) C34(0.35) H34(0.35) C7AA(0.35) H7AA(0.35)
 C6AA(0.35) H6AA(0.35) C33(0.35) H33(0.35) C48(0.35) H48(0.35) C45(0.35)
 H45(0.35) C30(0.35) C46(0.35) H46(0.35) C31(0.35) H31(0.35) C35(0.35)
 H35(0.35) C32(0.35) H32(0.35) P3(0.35) C50(0.3) H50(0.3) C52(0.3) H52(0.3)
 C49(0.3) H49(0.3) C8AA(0.3) C54(0.35) H54A(0.35) H54B(0.35) C53(0.35)
 H53A(0.35) H53B(0.35) C55(0.3) H55(0.3) C56(0.3) H56(0.3) C61(0.35) H61A(0.35)
 H61B(0.35) C3AA(0.35) H3AA(0.35) C26(0.35) H26(0.35) C25(0.35) H25(0.35)
 C24(0.35) C27(0.35) H27(0.35) C37(0.35) H37(0.35) C40(0.35) H40(0.35)
 C36(0.35) C39(0.35) H39(0.35) C38(0.35) H38(0.35) C29(0.35) H29(0.35)
 C28(0.35) H28(0.35) C9AA(0.3) H9AA(0.3) C2AA(0.3) H2AA(0.3) C0BA(0.3) C23(0.3)
 H23A(0.3) H23B(0.3) C65(0.3) H65(0.3) C64(0.3) H64(0.3) C4AA(0.3) H4AA(0.3)
6.a Ternary CH refined with riding coordinates:
 C19(H19), C16(H16), C8(H8A), C8(H8B)
6.b Secondary CH2 refined with riding coordinates:
 C22(H22A,H22B), C1AA(H1AA,H1AB), C54(H54A,H54B), C53(H53A,H53B), C61(H61A,
 H61B), C23(H23A,H23B)
6.c Aromatic/amide H refined with riding coordinates:
 C14(H14), C4(H4), C13(H13), C12(H12), C5(H5), C6(H6), C34(H34), C7AA(H7AA),
 C6AA(H6AA), C33(H33), C48(H48), C45(H45), C46(H46), C31(H31), C35(H35),
 C32(H32), C50(H50), C52(H52), C49(H49), C55(H55), C56(H56), C3AA(H3AA),
 C26(H26), C25(H25), C27(H27), C37(H37), C40(H40), C39(H39), C38(H38), C29(H29),
  C28(H28), C9AA(H9AA), C2AA(H2AA), C65(H65), C64(H64), C4AA(H4AA)
6.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C20(H20A,H20B,H20C), C17(H17A,H17B,H17C), C21(H21A,H21B,
 H21C), C18(H18A,H18B,H18C), C0AA(H0AA,H0AB,H0AC), C9(H9A,H9B,H9C)
;
_shelx_res_checksum              36303
_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 1.754
_oxdiff_exptl_absorpt_empirical_full_min 0.716