Spin-crossover iron(II) complexes featuring boronic acid and boronic ester groups: synthesis and magnetic properties
Zhang, Minghui; Heinemann, Frank; Khusniyarov, Marat M.; CrystEngComm  (2026) –; doi:10.1039/D6CE00062B

data_7251767
_publ_section_title
;
 Spin-crossover iron(ii) complexes featuring boronic acid and boronic
 ester groups: synthesis and magnetic properties
;
_journal_issue                   15
_journal_name_full               CrystEngComm
_journal_page_first              2355
_journal_page_last               2363
_journal_paper_doi               10.1039/D6CE00062B
_journal_volume                  28
_journal_year                    2026
_chemical_formula_moiety         'C40 H56 B2 Fe N10 O4, 2(Cl O4), 2(C4 H10 O)'
_chemical_formula_sum            'C48 H76 B2 Cl2 Fe N10 O14'
_chemical_formula_weight         1165.55
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_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
_atom_sites_solution_primary     direct
_audit_creation_date             2022-06-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2025-10-13 deposited with the CCDC.	2026-03-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.181(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.4968(12)
_cell_length_b                   18.4483(13)
_cell_length_c                   20.7114(16)
_cell_measurement_reflns_used    9502
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30.43
_cell_measurement_theta_min      2.26
_cell_volume                     6301.9(8)
_computing_cell_refinement       'SAINT V8.38A (Bruker AXS, 2016)'
_computing_data_collection       'Bruker APEX3 (Bruker AXS, 2015)'
_computing_data_reduction        'SAINT V8.38A (Bruker AXS, 2016)'
_computing_molecular_graphics    'SHELXTL 6.12 (Bruker AXS, 2002)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELX XT 2014/5 (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker Kappa ImuS Duo Photon II CPAD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'Quazar focussing montel optics'
_diffrn_radiation_source         'ImuS high brilliance micro-focus tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0652
_diffrn_reflns_av_unetI/netI     0.0211
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            281194
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.103
_diffrn_reflns_theta_min         2.208
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.388
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.6971
_exptl_absorpt_correction_type   multi-scan'
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0930 before and 0.0637 after correction.
The Ratio of minimum to maximum transmission is 0.9343.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.228
_exptl_crystal_description       block
_exptl_crystal_F_000             2464
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: methanol, diethyl ether'
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.859
_refine_diff_density_min         -0.641
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.074
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     927
_refine_ls_number_reflns         13889
_refine_ls_number_restraints     695
_refine_ls_restrained_S_all      1.120
_refine_ls_R_factor_all          0.0704
_refine_ls_R_factor_gt           0.0573
_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^)+(0.0781P)^2^+9.2738P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1537
_refine_ls_wR_factor_ref         0.1648
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11553
_reflns_number_total             13889
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6ce00062b2.cif
_cod_data_source_block           mmk2203
_cod_depositor_comments
'Adding full bibliography for 7251766--7251769.cif.'
_cod_database_code               7251767
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.933
_shelx_estimated_absorpt_t_min   0.913
_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, All O(H) groups
2. Uiso/Uaniso restraints and constraints
C12 \\sim C13 \\sim C14 \\sim C15 \\sim C12A \\sim C13A \\sim C14A \\sim C15A:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C17 \\sim C18 \\sim C19 \\sim C20 \\sim C17A \\sim C18A \\sim C19A \\sim C20A:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C101 \\sim C102 \\sim O103 \\sim C104 \\sim C105 \\sim C111 \\sim C112 \\sim
O113 \\sim C114 \\sim C115: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
C201 \\sim C202 \\sim O203 \\sim C204 \\sim C205 \\sim C211 \\sim C212 \\sim
O213 \\sim C214 \\sim C215 \\sim C221 \\sim C222 \\sim O223 \\sim C224 \\sim
C225: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C13) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C17) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C20)
\\sim Ueq, Uanis(C17A) \\sim Ueq, Uanis(C18A) \\sim Ueq, Uanis(C19A) \\sim Ueq,
Uanis(C20A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C201) \\sim Ueq, Uanis(C202) \\sim Ueq, Uanis(O203) \\sim Ueq,
Uanis(C204) \\sim Ueq, Uanis(C205) \\sim Ueq, Uanis(C211) \\sim Ueq,
Uanis(C212) \\sim Ueq, Uanis(O213) \\sim Ueq, Uanis(C214) \\sim Ueq,
Uanis(C215) \\sim Ueq, Uanis(C221) \\sim Ueq, Uanis(C222) \\sim Ueq,
Uanis(O223) \\sim Ueq, Uanis(C224) \\sim Ueq, Uanis(C225) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
3. Same fragment restrains
{C32, C33, C34, C35} sigma for 1-2: 0.02, 1-3: 0.04
as
{C17A, C18A, C19A, C20A}
{C101, C102, O103, C104, C105} sigma for 1-2: 0.02, 1-3: 0.04
as
{C111, C112, O113, C114, C115}
{C101, C102, O103, C104, C105} sigma for 1-2: 0.02, 1-3: 0.04
as
{C201, C202, O203, C204, C205}
{C101, C102, O103, C104, C105} sigma for 1-2: 0.02, 1-3: 0.04
as
{C211, C212, O213, C214, C215}
{C101, C102, O103, C104, C105} sigma for 1-2: 0.02, 1-3: 0.04
as
{C221, C222, O223, C224, C225}
4. Others
 1*[Sof(C201)+Sof(H20G)+Sof(H20H)+Sof(H20I)+Sof(C202)+Sof(H20J)+Sof(H20K)+
 Sof(O203)+Sof(C204)+Sof(H20L)+Sof(H20M)+Sof(C205)+Sof(H20N)+Sof(H20O)+
 Sof(H20P)]+1*[Sof(C211)+Sof(H21A)+Sof(H21B)+Sof(H21C)+Sof(C212)+Sof(H21D)+
 Sof(H21E)+Sof(O213)+Sof(C214)+Sof(H21F)+Sof(H21G)+Sof(C215)+Sof(H21H)+
 Sof(H21I)+Sof(H21J)]+1*[Sof(C221)+Sof(H22A)+Sof(H22B)+Sof(H22C)+Sof(C222)+
 Sof(H22D)+Sof(H22E)+Sof(O223)+Sof(C224)+Sof(H22F)+Sof(H22G)+Sof(C225)+
 Sof(H22H)+Sof(H22I)+Sof(H22J)]=1 with esd of 0.001
 Sof(C12A)=Sof(C13A)=Sof(H13D)=Sof(H13E)=Sof(H13F)=Sof(C14A)=Sof(H14D)=
 Sof(H14E)=Sof(H14F)=Sof(C15A)=Sof(H15D)=Sof(H15E)=Sof(H15F)=1-FVAR(1)
 Sof(C12)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C14)=Sof(H14A)=Sof(H14B)=
 Sof(H14C)=Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=FVAR(1)
 Sof(C17A)=Sof(C18A)=Sof(H18D)=Sof(H18E)=Sof(H18F)=Sof(C19A)=Sof(H19D)=
 Sof(H19E)=Sof(H19F)=Sof(C20A)=Sof(H20D)=Sof(H20E)=Sof(H20F)=1-FVAR(2)
 Sof(C17)=Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=Sof(C19)=Sof(H19A)=Sof(H19B)=
 Sof(H19C)=Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=FVAR(2)
 Sof(C111)=Sof(H11A)=Sof(H11B)=Sof(H11C)=Sof(C112)=Sof(H11D)=Sof(H11E)=
 Sof(O113)=Sof(C114)=Sof(H11F)=Sof(H11G)=Sof(C115)=Sof(H11H)=Sof(H11I)=
 Sof(H11J)=1-FVAR(3)
 Sof(C101)=Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C102)=Sof(H10D)=Sof(H10E)=
 Sof(O103)=Sof(C104)=Sof(H10F)=Sof(H10G)=Sof(C105)=Sof(H10H)=Sof(H10I)=
 Sof(H10J)=FVAR(3)
 Sof(C201)=Sof(H20G)=Sof(H20H)=Sof(H20I)=Sof(C202)=Sof(H20J)=Sof(H20K)=
 Sof(O203)=Sof(C204)=Sof(H20L)=Sof(H20M)=Sof(C205)=Sof(H20N)=Sof(H20O)=
 Sof(H20P)=FVAR(4)
 Sof(C211)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C212)=Sof(H21D)=Sof(H21E)=
 Sof(O213)=Sof(C214)=Sof(H21F)=Sof(H21G)=Sof(C215)=Sof(H21H)=Sof(H21I)=
 Sof(H21J)=FVAR(5)
 Sof(C221)=Sof(H22A)=Sof(H22B)=Sof(H22C)=Sof(C222)=Sof(H22D)=Sof(H22E)=
 Sof(O223)=Sof(C224)=Sof(H22F)=Sof(H22G)=Sof(C225)=Sof(H22H)=Sof(H22I)=
 Sof(H22J)=FVAR(6)
5.a Riding coordinates:
 O1(H1), O3(H3)
5.b Secondary CH2 refined with riding coordinates:
 C102(H10D,H10E), C104(H10F,H10G), C112(H11D,H11E), C114(H11F,H11G), C202(H20J,
 H20K), C204(H20L,H20M), C212(H21D,H21E), C214(H21F,H21G), C222(H22D,H22E),
 C224(H22F,H22G)
5.c Me refined with riding coordinates:
 C101(H10A,H10B,H10C), C105(H10H,H10I,H10J), C111(H11A,H11B,H11C), C115(H11H,
 H11I,H11J), C201(H20G,H20H,H20I), C205(H20N,H20O,H20P), C211(H21A,H21B,H21C),
 C215(H21H,H21I,H21J), C221(H22A,H22B,H22C), C225(H22H,H22I,H22J)
5.d Aromatic/amide H refined with riding coordinates:
 C1(H1A), C3(H3A), C5(H5), C7(H7), C9(H9), C11(H11), C21(H21), C23(H23),
 C25(H25), C27(H27), C29(H29), C31(H31)
5.e Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C13A(H13D,H13E,
 H13F), C14A(H14D,H14E,H14F), C15A(H15D,H15E,H15F), C16(H16A,H16B,H16C),
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C18A(H18D,H18E,
 H18F), C19A(H19D,H19E,H19F), C20A(H20D,H20E,H20F), C33(H33A,H33B,H33C),
 C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C38(H38A,H38B,
 H38C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C)
;
_shelx_res_checksum              96648
_olex2_submission_special_instructions 'No special instructions were received'