# Electronic Supplementary Material (ESI) for Organic Chemistry Frontiers.
# This journal is © the Partner Organisations 2020

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_150336
_database_code_depnum_ccdc_archive 'CCDC 1922813'
loop_
_audit_author_name
_audit_author_address
'Ting-Shen Kuo '
;National Taiwan Normal University
Taiwan
;
_audit_update_record             
;
2019-06-13 deposited with the CCDC.	2020-07-23 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/6
_chemical_name_systematic        
'Vanadyl 3-t-butyl-5-bromo-N-salicylidene-t-leucinate'
_chemical_name_common            'catalyst 1f'
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C19 H31 Br N O6 V'
_chemical_formula_weight         500.30

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
V V 0.3005 0.5294 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_H-M_alt        'C 2'
_space_group_name_Hall           'C 2y'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y, -z'
'x+1/2, y+1/2, z'
'-x+1/2, y+1/2, -z'

_cell_length_a                   27.3247(8)
_cell_length_b                   7.3295(2)
_cell_length_c                   11.7690(3)
_cell_angle_alpha                90
_cell_angle_beta                 102.472(2)
_cell_angle_gamma                90
_cell_volume                     2301.43(11)
_cell_formula_units_Z            4
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    5659
_cell_measurement_theta_min      2.5772
_cell_measurement_theta_max      26.3007

_exptl_crystal_description       lump
_exptl_crystal_colour            brown
_exptl_crystal_density_meas      'not measured'
_exptl_crystal_density_method    'not measured'
_exptl_crystal_density_diffrn    1.444
_exptl_crystal_F_000             1032
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.12
_exptl_absorpt_coefficient_mu    2.199
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.742
_exptl_absorpt_correction_T_max  0.9485
_exptl_absorpt_process_details   'SADABS V2014/3 (Bruker AXS Inc.)'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean 8.3333
_diffrn_reflns_number            10084
_diffrn_reflns_av_unetI/netI     0.0470
_diffrn_reflns_av_R_equivalents  0.0237
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_theta_min         1.526
_diffrn_reflns_theta_max         26.394
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             4260
_reflns_number_gt                3926
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.850
_reflns_Friedel_fraction_max     0.997
_reflns_Friedel_fraction_full    1.000

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       'APEX2 (Bruker AXS, 2010)'
_computing_cell_refinement       'SAINT V8.34A (Bruker AXS Inc., 2013)'
_computing_data_reduction        'SAINT V8.34A (Bruker AXS Inc., 2013)'
_computing_structure_solution    ?
_computing_structure_refinement  'SHELXL-2014 (Sheldrick, 2014)'
_computing_molecular_graphics    'SHELXTL (Sheldrick, 2008)'
_computing_publication_material  SHELXTL
_refine_special_details          
;
 Refined as a 2-component inversion twin.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0944P)²+2.5084P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.013(10)
_chemical_absolute_configuration rm
_refine_ls_number_reflns         4260
_refine_ls_number_parameters     262
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0275
_refine_ls_R_factor_gt           0.0249
_refine_ls_wR_factor_ref         0.0762
_refine_ls_wR_factor_gt          0.0711
_refine_ls_goodness_of_fit_ref   0.558
_refine_ls_restrained_S_all      0.558
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Br1 Br 0.22415(2) 0.39283(6) -0.21051(3) 0.05409(14) Uani 1 1 d . . . . .
C1 C 0.28024(14) 0.4071(10) 0.4012(4) 0.0700(14) Uani 1 1 d . . . . .
H1A H 0.2738 0.3131 0.3431 0.105 Uiso 1 1 calc R U . . .
H1B H 0.2793 0.5240 0.3640 0.105 Uiso 1 1 calc R U . . .
H1C H 0.2551 0.4028 0.4470 0.105 Uiso 1 1 calc R U . . .
C2 C 0.33210(13) 0.3772(8) 0.4804(3) 0.0500(10) Uani 1 1 d . . . . .
C3 C 0.37351(11) 0.4159(5) 0.4122(3) 0.0360(7) Uani 1 1 d . . . . .
H3 H 0.3733 0.5469 0.3955 0.043 Uiso 1 1 calc R U . . .
C5 C 0.36446(11) 0.1912(5) 0.0596(3) 0.0324(7) Uani 1 1 d . . . . .
C6 C 0.35023(11) 0.0968(5) -0.0469(3) 0.0311(6) Uani 1 1 d . . . . .
C7 C 0.37945(12) -0.0692(5) -0.0757(3) 0.0402(8) Uani 1 1 d . . . . .
C8 C 0.43302(19) -0.0102(10) -0.0820(6) 0.0821(18) Uani 1 1 d . . . . .
H8A H 0.4315 0.0744 -0.1450 0.123 Uiso 1 1 calc R U . . .
H8B H 0.4520 -0.1155 -0.0948 0.123 Uiso 1 1 calc R U . . .
H8C H 0.4489 0.0472 -0.0102 0.123 Uiso 1 1 calc R U . . .
C9 C 0.33601(19) 0.1798(9) 0.5243(5) 0.0727(15) Uani 1 1 d . . . . .
H9A H 0.3676 0.1626 0.5779 0.109 Uiso 1 1 calc R U . . .
H9B H 0.3337 0.0981 0.4597 0.109 Uiso 1 1 calc R U . . .
H9C H 0.3092 0.1552 0.5630 0.109 Uiso 1 1 calc R U . . .
C10 C 0.42553(12) 0.3660(6) 0.4843(3) 0.0395(8) Uani 1 1 d . . . . .
C11 C 0.30818(12) 0.1636(5) -0.1260(3) 0.0370(7) Uani 1 1 d . . . . .
H11 H 0.2980 0.1075 -0.1981 0.044 Uiso 1 1 calc R U . . .
C12 C 0.28169(12) 0.3108(5) -0.0987(3) 0.0374(7) Uani 1 1 d . . . . .
C13 C 0.29440(12) 0.3988(6) 0.0060(3) 0.0375(7) Uani 1 1 d . . . . .
H13 H 0.2751 0.4950 0.0236 0.045 Uiso 1 1 calc R U . . .
C14 C 0.33703(12) 0.3405(5) 0.0857(3) 0.0350(7) Uani 1 1 d . . . . .
C15 C 0.35467(13) 0.4417(5) 0.1982(3) 0.0389(8) Uani 1 1 d . . . . .
H15A H 0.3844 0.5113 0.1941 0.047 Uiso 1 1 calc R U . . .
H15B H 0.3289 0.5269 0.2089 0.047 Uiso 1 1 calc R U . . .
C16 C 0.3556(2) -0.1556(8) -0.1915(4) 0.0734(15) Uani 1 1 d . . . . .
H16A H 0.3220 -0.1924 -0.1905 0.110 Uiso 1 1 calc R U . . .
H16B H 0.3748 -0.2603 -0.2045 0.110 Uiso 1 1 calc R U . . .
H16C H 0.3549 -0.0687 -0.2529 0.110 Uiso 1 1 calc R U . . .
C17 C 0.3828(2) -0.2143(6) 0.0186(5) 0.0706(14) Uani 1 1 d . . . . .
H17A H 0.4049 -0.1731 0.0887 0.106 Uiso 1 1 calc R U . . .
H17B H 0.3955 -0.3256 -0.0069 0.106 Uiso 1 1 calc R U . . .
H17C H 0.3501 -0.2357 0.0333 0.106 Uiso 1 1 calc R U . . .
C18 C 0.5083(2) -0.1459(7) 0.3479(4) 0.0657(13) Uani 1 1 d . . . . .
H18A H 0.5237 -0.1298 0.4286 0.099 Uiso 1 1 calc R U . . .
H18B H 0.5330 -0.1848 0.3063 0.099 Uiso 1 1 calc R U . . .
H18C H 0.4824 -0.2365 0.3404 0.099 Uiso 1 1 calc R U . . .
C19 C 0.49097(19) 0.4171(8) 0.1694(4) 0.0647(12) Uani 1 1 d . . . . .
H19A H 0.5015 0.3026 0.1430 0.097 Uiso 1 1 calc R U . . .
H19B H 0.5192 0.4983 0.1877 0.097 Uiso 1 1 calc R U . . .
H19C H 0.4655 0.4699 0.1092 0.097 Uiso 1 1 calc R U . . .
C20 C 0.3378(2) 0.5110(12) 0.5828(5) 0.091(2) Uani 1 1 d . . . . .
H20A H 0.3097 0.4986 0.6190 0.137 Uiso 1 1 calc R U . . .
H20B H 0.3391 0.6336 0.5548 0.137 Uiso 1 1 calc R U . . .
H20C H 0.3681 0.4845 0.6385 0.137 Uiso 1 1 calc R U . . .
N1 N 0.36633(10) 0.3163(4) 0.2999(2) 0.0327(6) Uani 1 1 d . . . . .
O1 O 0.40646(8) 0.1439(4) 0.13639(19) 0.0389(5) Uani 1 1 d . . . . .
O2 O 0.44485(11) 0.4567(5) 0.5680(2) 0.0590(8) Uani 1 1 d . . . . .
O3 O 0.44501(9) 0.2216(4) 0.4508(2) 0.0403(6) Uani 1 1 d . . . . .
O4 O 0.39630(10) -0.0502(4) 0.3232(2) 0.0486(6) Uani 1 1 d . . . . .
O5 O 0.48725(9) 0.0204(4) 0.3014(2) 0.0418(6) Uani 1 1 d . . . . .
O6 O 0.47136(8) 0.3883(4) 0.2704(2) 0.0423(5) Uani 1 1 d . . . . .
V1 V 0.42787(2) 0.11942(7) 0.29531(4) 0.03285(14) Uani 1 1 d . . . . .
H2 H 0.4966 0.3762 0.3388 0.050 Uiso 1 1 d . . . . .
H1 H 0.3404 0.2499 0.3053 0.050 Uiso 1 1 d . . . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Br1 C12 1.916(3) . ?
C1 C2 1.534(5) . ?
C1 H1A 0.9600 . ?
C1 H1B 0.9600 . ?
C1 H1C 0.9600 . ?
C2 C9 1.533(8) . ?
C2 C20 1.535(7) . ?
C2 C3 1.548(5) . ?
C3 N1 1.485(4) . ?
C3 C10 1.534(4) . ?
C3 H3 0.9800 . ?
C5 O1 1.344(4) . ?
C5 C14 1.398(5) . ?
C5 C6 1.411(5) . ?
C6 C11 1.402(4) . ?
C6 C7 1.533(5) . ?
C7 C16 1.516(5) . ?
C7 C17 1.526(6) . ?
C7 C8 1.543(6) . ?
C8 H8A 0.9600 . ?
C8 H8B 0.9600 . ?
C8 H8C 0.9600 . ?
C9 H9A 0.9600 . ?
C9 H9B 0.9600 . ?
C9 H9C 0.9600 . ?
C10 O2 1.212(4) . ?
C10 O3 1.284(5) . ?
C11 C12 1.376(5) . ?
C11 H11 0.9300 . ?
C12 C13 1.367(5) . ?
C13 C14 1.396(4) . ?
C13 H13 0.9300 . ?
C14 C15 1.503(5) . ?
C15 N1 1.488(4) . ?
C15 H15A 0.9700 . ?
C15 H15B 0.9700 . ?
C16 H16A 0.9600 . ?
C16 H16B 0.9600 . ?
C16 H16C 0.9600 . ?
C17 H17A 0.9600 . ?
C17 H17B 0.9600 . ?
C17 H17C 0.9600 . ?
C18 O5 1.407(5) . ?
C18 H18A 0.9600 . ?
C18 H18B 0.9600 . ?
C18 H18C 0.9600 . ?
C19 O6 1.421(5) . ?
C19 H19A 0.9600 . ?
C19 H19B 0.9600 . ?
C19 H19C 0.9600 . ?
C20 H20A 0.9600 . ?
C20 H20B 0.9600 . ?
C20 H20C 0.9600 . ?
N1 V1 2.225(3) . ?
N1 H1 0.8733 . ?
O1 V1 1.844(2) . ?
O3 V1 1.939(2) . ?
O4 V1 1.587(3) . ?
O5 V1 1.764(2) . ?
O6 V1 2.352(3) . ?
O6 H2 0.9443 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C2 C1 H1A 109.5 . . ?
C2 C1 H1B 109.5 . . ?
H1A C1 H1B 109.5 . . ?
C2 C1 H1C 109.5 . . ?
H1A C1 H1C 109.5 . . ?
H1B C1 H1C 109.5 . . ?
C9 C2 C1 109.1(5) . . ?
C9 C2 C20 110.5(5) . . ?
C1 C2 C20 108.0(4) . . ?
C9 C2 C3 110.0(4) . . ?
C1 C2 C3 110.0(3) . . ?
C20 C2 C3 109.2(4) . . ?
N1 C3 C10 107.6(3) . . ?
N1 C3 C2 113.6(3) . . ?
C10 C3 C2 111.3(3) . . ?
N1 C3 H3 108.0 . . ?
C10 C3 H3 108.0 . . ?
C2 C3 H3 108.0 . . ?
O1 C5 C14 118.3(3) . . ?
O1 C5 C6 120.2(3) . . ?
C14 C5 C6 121.4(3) . . ?
C11 C6 C5 116.6(3) . . ?
C11 C6 C7 121.5(3) . . ?
C5 C6 C7 121.9(3) . . ?
C16 C7 C17 108.0(4) . . ?
C16 C7 C6 112.8(3) . . ?
C17 C7 C6 110.1(3) . . ?
C16 C7 C8 107.6(4) . . ?
C17 C7 C8 108.8(4) . . ?
C6 C7 C8 109.5(4) . . ?
C7 C8 H8A 109.5 . . ?
C7 C8 H8B 109.5 . . ?
H8A C8 H8B 109.5 . . ?
C7 C8 H8C 109.5 . . ?
H8A C8 H8C 109.5 . . ?
H8B C8 H8C 109.5 . . ?
C2 C9 H9A 109.5 . . ?
C2 C9 H9B 109.5 . . ?
H9A C9 H9B 109.5 . . ?
C2 C9 H9C 109.5 . . ?
H9A C9 H9C 109.5 . . ?
H9B C9 H9C 109.5 . . ?
O2 C10 O3 124.4(3) . . ?
O2 C10 C3 120.5(3) . . ?
O3 C10 C3 115.0(3) . . ?
C12 C11 C6 121.1(3) . . ?
C12 C11 H11 119.5 . . ?
C6 C11 H11 119.5 . . ?
C13 C12 C11 122.4(3) . . ?
C13 C12 Br1 118.8(3) . . ?
C11 C12 Br1 118.7(3) . . ?
C12 C13 C14 118.3(3) . . ?
C12 C13 H13 120.9 . . ?
C14 C13 H13 120.9 . . ?
C13 C14 C5 120.1(3) . . ?
C13 C14 C15 120.2(3) . . ?
C5 C14 C15 119.7(3) . . ?
N1 C15 C14 112.1(3) . . ?
N1 C15 H15A 109.2 . . ?
C14 C15 H15A 109.2 . . ?
N1 C15 H15B 109.2 . . ?
C14 C15 H15B 109.2 . . ?
H15A C15 H15B 107.9 . . ?
C7 C16 H16A 109.5 . . ?
C7 C16 H16B 109.5 . . ?
H16A C16 H16B 109.5 . . ?
C7 C16 H16C 109.5 . . ?
H16A C16 H16C 109.5 . . ?
H16B C16 H16C 109.5 . . ?
C7 C17 H17A 109.5 . . ?
C7 C17 H17B 109.5 . . ?
H17A C17 H17B 109.5 . . ?
C7 C17 H17C 109.5 . . ?
H17A C17 H17C 109.5 . . ?
H17B C17 H17C 109.5 . . ?
O5 C18 H18A 109.5 . . ?
O5 C18 H18B 109.5 . . ?
H18A C18 H18B 109.5 . . ?
O5 C18 H18C 109.5 . . ?
H18A C18 H18C 109.5 . . ?
H18B C18 H18C 109.5 . . ?
O6 C19 H19A 109.5 . . ?
O6 C19 H19B 109.5 . . ?
H19A C19 H19B 109.5 . . ?
O6 C19 H19C 109.5 . . ?
H19A C19 H19C 109.5 . . ?
H19B C19 H19C 109.5 . . ?
C2 C20 H20A 109.5 . . ?
C2 C20 H20B 109.5 . . ?
H20A C20 H20B 109.5 . . ?
C2 C20 H20C 109.5 . . ?
H20A C20 H20C 109.5 . . ?
H20B C20 H20C 109.5 . . ?
C3 N1 C15 112.1(3) . . ?
C3 N1 V1 112.65(18) . . ?
C15 N1 V1 114.4(2) . . ?
C3 N1 H1 99.4 . . ?
C15 N1 H1 111.5 . . ?
V1 N1 H1 105.6 . . ?
C5 O1 V1 138.2(2) . . ?
C10 O3 V1 125.2(2) . . ?
C18 O5 V1 131.8(3) . . ?
C19 O6 V1 121.4(3) . . ?
C19 O6 H2 112.9 . . ?
V1 O6 H2 96.4 . . ?
O4 V1 O5 101.85(14) . . ?
O4 V1 O1 102.60(13) . . ?
O5 V1 O1 99.73(11) . . ?
O4 V1 O3 97.99(13) . . ?
O5 V1 O3 95.02(11) . . ?
O1 V1 O3 151.50(12) . . ?
O4 V1 N1 93.20(13) . . ?
O5 V1 N1 163.45(12) . . ?
O1 V1 N1 83.44(10) . . ?
O3 V1 N1 75.89(10) . . ?
O4 V1 O6 173.59(13) . . ?
O5 V1 O6 82.22(12) . . ?
O1 V1 O6 81.39(10) . . ?
O3 V1 O6 76.60(10) . . ?
N1 V1 O6 82.21(10) . . ?

_refine_diff_density_max         0.561
_refine_diff_density_min         -0.339
_refine_diff_density_rms         0.044

_shelxl_version_number           2014/6



_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: methanol and CH2Cl2'
