# Electronic Supplementary Material (ESI) for RSC Advances.
# This journal is © The Royal Society of Chemistry 2019

####################################################################### 
# 
# 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_1
_database_code_depnum_ccdc_archive 'CCDC 1879191'
_audit_update_record             
;
2018-11-15 deposited with the CCDC.
2019-01-21 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2016/6
_shelx_SHELXL_version_number     2016/6
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C15 H14 Br N2 O3 V'
_chemical_formula_weight         401.12

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'
V V 0.3005 0.5294 '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'

_space_group_crystal_system      monoclinic
_space_group_IT_number           7
_space_group_name_H-M_alt        'P c'
_space_group_name_Hall           'P -2yc'

_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+1/2'

_cell_length_a                   12.7168(14)
_cell_length_b                   6.1962(5)
_cell_length_c                   9.6410(11)
_cell_angle_alpha                90
_cell_angle_beta                 91.740(10)
_cell_angle_gamma                90
_cell_volume                     759.32(13)
_cell_formula_units_Z            2
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    4316
_cell_measurement_theta_min      3.205
_cell_measurement_theta_max      27.50

_exptl_crystal_description       block
_exptl_crystal_colour            green
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.754
_exptl_crystal_F_000             400
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.16
_exptl_absorpt_coefficient_mu    3.297
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details   'ABSPACK, Oxford Diffraction Ltd'
_exptl_absorpt_correction_T_min  0.558
_exptl_absorpt_correction_T_max  0.590
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      150(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_measurement_device_type  'Oxford Diffaction X-Calibor System'
_diffrn_measurement_method       '321 frames, counting time 10 s.'
_diffrn_standards_interval_count n/a
_diffrn_standards_interval_time  n/a
_diffrn_standards_decay_%        n/a

_diffrn_reflns_number            4316
_diffrn_reflns_av_unetI/netI     0.0961
_diffrn_reflns_av_R_equivalents  0.0534
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_k_min       -5
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_theta_min         3.205
_diffrn_reflns_theta_max         27.495
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.859
_diffrn_reflns_point_group_measured_fraction_full 0.872
_reflns_number_total             3000
_reflns_number_gt                2678
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.717
_reflns_Friedel_fraction_max     0.719
_reflns_Friedel_fraction_full    0.744

_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       'Crysalis, Oxford Diffraction'
_computing_cell_refinement       'Crysalis, Oxford Diffraction'
_computing_data_reduction        'Crysalis, Oxford Diffraction'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-2016/6 (Sheldrick, 2016)'
_computing_molecular_graphics    PLATON(Spek,2004)
_computing_publication_material  'SHELXL-2016/6, PLATON, WINGX (Ferrugia, 2012)'



_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0608P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
;
 Flack x determined using 818 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.006(17)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         3490
_refine_ls_number_parameters     199
_refine_ls_number_restraints     2
_refine_ls_R_factor_all          0.0693
_refine_ls_R_factor_gt           0.0609
_refine_ls_wR_factor_ref         0.1446
_refine_ls_wR_factor_gt          0.1345
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_restrained_S_all      1.069
_refine_ls_shift/su_max          0.000
_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
V1 V 0.36740(14) 0.5573(2) 0.09289(18) 0.0176(4) Uani 1 1 d . . . . .
O1 O 0.3959(6) 0.3067(11) 0.0600(8) 0.0272(18) Uani 1 1 d . . . . .
O2 O 0.4306(7) 0.6385(11) 0.2323(8) 0.0246(17) Uani 1 1 d . . . . .
O11 O 0.2299(6) 0.5029(11) 0.1573(8) 0.0266(17) Uani 1 1 d . . . . .
C12 C 0.1605(8) 0.6433(15) 0.2043(12) 0.018(2) Uani 1 1 d . . . . .
C13 C 0.0932(10) 0.5831(16) 0.3080(12) 0.027(3) Uani 1 1 d . . . . .
H13 H 0.098359 0.445706 0.346493 0.033 Uiso 1 1 calc R U . . .
C14 C 0.0187(8) 0.7258(15) 0.3546(10) 0.020(2) Uani 1 1 d . . . . .
H14 H -0.027256 0.681866 0.422365 0.024 Uiso 1 1 calc R U . . .
C15 C 0.0114(8) 0.9315(17) 0.3022(12) 0.023(2) Uani 1 1 d . . . . .
C16 C 0.0751(8) 0.9975(16) 0.1990(11) 0.020(2) Uani 1 1 d . . . . .
H16 H 0.067843 1.135490 0.162077 0.024 Uiso 1 1 calc R U . . .
C17 C 0.1521(9) 0.8561(16) 0.1485(11) 0.023(2) Uani 1 1 d . . . . .
C18 C 0.2160(8) 0.9290(15) 0.0353(11) 0.018(2) Uani 1 1 d . . . . .
H18 H 0.200461 1.061951 -0.005171 0.022 Uiso 1 1 calc R U . . .
N19 N 0.2932(7) 0.8190(12) -0.0121(8) 0.0159(17) Uani 1 1 d . . . . .
C20 C 0.3474(11) 0.9082(17) -0.1314(13) 0.025(3) Uani 1 1 d . . . . .
H20A H 0.328590 1.058670 -0.144690 0.030 Uiso 1 1 calc R U . . .
H20B H 0.327573 0.829340 -0.215094 0.030 Uiso 1 1 calc R U . . .
C21 C 0.4628(10) 0.8872(14) -0.1014(13) 0.021(3) Uani 1 1 d . . . . .
H21A H 0.485180 0.991147 -0.031333 0.025 Uiso 1 1 calc R U . . .
H21B H 0.501367 0.914640 -0.184859 0.025 Uiso 1 1 calc R U . . .
N22 N 0.4840(7) 0.6624(12) -0.0506(9) 0.0168(17) Uani 1 1 d . . . . .
H22 H 0.473830 0.569831 -0.132373 0.020 Uiso 1 1 calc R U . . .
C23 C 0.5896(8) 0.6194(16) 0.0001(10) 0.017(2) Uani 1 1 d . . . . .
C24 C 0.6356(10) 0.4256(18) -0.0284(15) 0.033(3) Uani 1 1 d . . . . .
H24 H 0.598699 0.325523 -0.082829 0.039 Uiso 1 1 calc R U . . .
C25 C 0.7340(11) 0.376(2) 0.0211(15) 0.039(3) Uani 1 1 d . . . . .
H25 H 0.764879 0.245095 -0.002444 0.047 Uiso 1 1 calc R U . . .
C26 C 0.7882(10) 0.521(2) 0.1071(14) 0.039(3) Uani 1 1 d . . . . .
H26 H 0.853779 0.485308 0.145902 0.046 Uiso 1 1 calc R U . . .
C27 C 0.7440(9) 0.717(2) 0.1337(13) 0.034(3) Uani 1 1 d . . . . .
H27 H 0.781294 0.817259 0.187446 0.041 Uiso 1 1 calc R U . . .
C28 C 0.6440(9) 0.768(2) 0.0816(13) 0.032(3) Uani 1 1 d . . . . .
H28 H 0.614023 0.900961 0.101373 0.038 Uiso 1 1 calc R U . . .
Br1 Br -0.08886(8) 1.12472(16) 0.37517(9) 0.0307(3) Uani 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
V1 O1 1.628(7) . ?
V1 O2 1.625(8) . ?
V1 O11 1.904(8) . ?
V1 N19 2.118(8) . ?
V1 N22 2.159(8) . ?
O11 C12 1.328(11) . ?
C12 C13 1.387(16) . ?
C12 C17 1.427(14) . ?
C13 C14 1.381(15) . ?
C13 H13 0.9300 . ?
C14 C15 1.373(14) . ?
C14 H14 0.9300 . ?
C15 C16 1.365(15) . ?
C15 Br1 1.899(11) . ?
C16 C17 1.412(14) . ?
C16 H16 0.9300 . ?
C17 C18 1.452(14) . ?
C18 N19 1.290(12) . ?
C18 H18 0.9300 . ?
N19 C20 1.466(15) . ?
C20 C21 1.493(14) . ?
C20 H20A 0.9700 . ?
C20 H20B 0.9700 . ?
C21 N22 1.499(11) . ?
C21 H21A 0.9700 . ?
C21 H21B 0.9700 . ?
N22 C23 1.441(13) . ?
N22 H22 0.9800 . ?
C23 C24 1.367(14) . ?
C23 C28 1.383(15) . ?
C24 C25 1.362(17) . ?
C24 H24 0.9300 . ?
C25 C26 1.394(19) . ?
C25 H25 0.9300 . ?
C26 C27 1.364(18) . ?
C26 H26 0.9300 . ?
C27 C28 1.390(16) . ?
C27 H27 0.9300 . ?
C28 H28 0.9300 . ?

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
O1 V1 O2 110.4(4) . . ?
O1 V1 O11 96.1(3) . . ?
O2 V1 O11 102.8(4) . . ?
O1 V1 N19 137.4(4) . . ?
O2 V1 N19 111.1(3) . . ?
O11 V1 N19 83.8(3) . . ?
O1 V1 N22 90.1(3) . . ?
O2 V1 N22 96.0(4) . . ?
O11 V1 N22 156.6(3) . . ?
N19 V1 N22 76.5(3) . . ?
C12 O11 V1 128.4(6) . . ?
O11 C12 C13 120.0(9) . . ?
O11 C12 C17 121.3(10) . . ?
C13 C12 C17 118.7(9) . . ?
C14 C13 C12 120.4(10) . . ?
C14 C13 H13 119.8 . . ?
C12 C13 H13 119.8 . . ?
C15 C14 C13 120.9(10) . . ?
C15 C14 H14 119.5 . . ?
C13 C14 H14 119.5 . . ?
C16 C15 C14 120.7(10) . . ?
C16 C15 Br1 120.1(8) . . ?
C14 C15 Br1 119.2(8) . . ?
C15 C16 C17 120.0(10) . . ?
C15 C16 H16 120.0 . . ?
C17 C16 H16 120.0 . . ?
C16 C17 C12 119.2(10) . . ?
C16 C17 C18 118.4(9) . . ?
C12 C17 C18 122.3(9) . . ?
N19 C18 C17 123.4(9) . . ?
N19 C18 H18 118.3 . . ?
C17 C18 H18 118.3 . . ?
C18 N19 C20 117.3(8) . . ?
C18 N19 V1 124.6(7) . . ?
C20 N19 V1 116.8(7) . . ?
N19 C20 C21 107.3(9) . . ?
N19 C20 H20A 110.3 . . ?
C21 C20 H20A 110.3 . . ?
N19 C20 H20B 110.3 . . ?
C21 C20 H20B 110.3 . . ?
H20A C20 H20B 108.5 . . ?
C20 C21 N22 108.1(8) . . ?
C20 C21 H21A 110.1 . . ?
N22 C21 H21A 110.1 . . ?
C20 C21 H21B 110.1 . . ?
N22 C21 H21B 110.1 . . ?
H21A C21 H21B 108.4 . . ?
C23 N22 C21 116.1(8) . . ?
C23 N22 V1 112.2(6) . . ?
C21 N22 V1 111.7(7) . . ?
C23 N22 H22 105.3 . . ?
C21 N22 H22 105.3 . . ?
V1 N22 H22 105.3 . . ?
C24 C23 C28 119.3(10) . . ?
C24 C23 N22 119.6(9) . . ?
C28 C23 N22 121.0(9) . . ?
C25 C24 C23 121.6(11) . . ?
C25 C24 H24 119.2 . . ?
C23 C24 H24 119.2 . . ?
C24 C25 C26 119.6(12) . . ?
C24 C25 H25 120.2 . . ?
C26 C25 H25 120.2 . . ?
C27 C26 C25 119.2(11) . . ?
C27 C26 H26 120.4 . . ?
C25 C26 H26 120.4 . . ?
C26 C27 C28 120.8(12) . . ?
C26 C27 H27 119.6 . . ?
C28 C27 H27 119.6 . . ?
C23 C28 C27 119.4(11) . . ?
C23 C28 H28 120.3 . . ?
C27 C28 H28 120.3 . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
N22 H22 O2 0.98 1.90 2.869(11) 167.3 2_564

_refine_diff_density_max         1.014
_refine_diff_density_min         -0.772
_refine_diff_density_rms         0.134
####################################################################### 
# 
# 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_2
_database_code_depnum_ccdc_archive 'CCDC 1879192'
_audit_update_record             
;
2018-11-15 deposited with the CCDC.
2019-01-21 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2016/6
_shelx_SHELXL_version_number     2016/6
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C13 H18 Cl N2 O3 V'
_chemical_formula_weight         336.68

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'
V V 0.3005 0.5294 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/n'
_space_group_name_Hall           '-P 2yn'

_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+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, -y-1/2, z-1/2'

_cell_length_a                   14.1152(7)
_cell_length_b                   6.9353(3)
_cell_length_c                   15.1466(7)
_cell_angle_alpha                90
_cell_angle_beta                 106.842(5)
_cell_angle_gamma                90
_cell_volume                     1419.15(11)
_cell_formula_units_Z            4
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    9618
_cell_measurement_theta_min      3.41
_cell_measurement_theta_max      30.00

_exptl_crystal_description       block
_exptl_crystal_colour            black
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.576
_exptl_crystal_F_000             696
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.14
_exptl_absorpt_coefficient_mu    0.895
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details   'ABSPACK, Oxford Diffraction Ltd'
_exptl_absorpt_correction_T_min  0.912
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      150(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_measurement_device       'Oxford Diffaction X-Calibor System'
_diffrn_measurement_method       '321 frames, counting time 10 s.'
_diffrn_standards_interval_count n/a
_diffrn_standards_interval_time  n/a
_diffrn_standards_decay_%        n/a

_diffrn_reflns_number            9618
_diffrn_reflns_av_unetI/netI     0.0401
_diffrn_reflns_av_R_equivalents  0.0297
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_theta_min         3.413
_diffrn_reflns_theta_max         29.991
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measured_fraction_theta_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_point_group_measured_fraction_full 0.994
_reflns_number_total             4096
_reflns_number_gt                3498
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_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       'Crysalis, Oxford Diffraction'
_computing_cell_refinement       'Crysalis, Oxford Diffraction'
_computing_data_reduction        'Crysalis, Oxford Diffraction'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-2016/6 (Sheldrick, 2016)'
_computing_molecular_graphics    PLATON(Spek,2004)
_computing_publication_material  'SHELXL-2016/6, PLATON, WINGX (Ferrugia, 2012)'

_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0458P)²+0.2839P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         4096
_refine_ls_number_parameters     183
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0464
_refine_ls_R_factor_gt           0.0377
_refine_ls_wR_factor_ref         0.0947
_refine_ls_wR_factor_gt          0.0911
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_restrained_S_all      1.068
_refine_ls_shift/su_max          0.001
_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
V1 V 0.80839(2) 0.65632(4) 0.42769(2) 0.01218(8) Uani 1 1 d . . . . .
O1 O 0.73463(10) 0.78195(17) 0.34579(9) 0.0202(3) Uani 1 1 d . . . . .
O2 O 0.79728(10) 0.71932(18) 0.52731(9) 0.0191(3) Uani 1 1 d . . . . .
O11 O 0.93458(9) 0.77434(17) 0.44144(8) 0.0172(3) Uani 1 1 d . . . . .
C12 C 0.99137(12) 0.7714(2) 0.38590(11) 0.0132(3) Uani 1 1 d . . . . .
C13 C 1.04884(12) 0.9341(2) 0.38063(11) 0.0154(3) Uani 1 1 d . . . . .
H13 H 1.046447 1.041927 0.416430 0.018 Uiso 1 1 calc R U . . .
C14 C 1.10882(12) 0.9360(2) 0.32302(11) 0.0162(3) Uani 1 1 d . . . . .
H14 H 1.145581 1.045410 0.319274 0.019 Uiso 1 1 calc R U . . .
C15 C 1.11411(13) 0.7731(3) 0.27035(12) 0.0172(3) Uani 1 1 d . . . . .
Cl15 Cl 1.18798(4) 0.78049(7) 0.19590(3) 0.02570(12) Uani 1 1 d . . . . .
C16 C 1.06149(13) 0.6095(2) 0.27631(12) 0.0165(3) Uani 1 1 d . . . . .
H16 H 1.067388 0.500401 0.242574 0.020 Uiso 1 1 calc R U . . .
C17 C 0.99889(12) 0.6068(2) 0.33323(11) 0.0142(3) Uani 1 1 d . . . . .
C18 C 0.94480(13) 0.4334(2) 0.33872(11) 0.0158(3) Uani 1 1 d . . . . .
H18 H 0.960161 0.323433 0.310516 0.019 Uiso 1 1 calc R U . . .
N19 N 0.87679(10) 0.4185(2) 0.37963(9) 0.0144(3) Uani 1 1 d . . . . .
C20 C 0.82819(13) 0.2307(2) 0.37698(12) 0.0161(3) Uani 1 1 d . . . . .
H20A H 0.851113 0.166964 0.436384 0.019 Uiso 1 1 calc R U . . .
H20B H 0.842125 0.148278 0.330524 0.019 Uiso 1 1 calc R U . . .
C21 C 0.71925(13) 0.2729(2) 0.35350(12) 0.0162(3) Uani 1 1 d . . . . .
H21A H 0.695391 0.319338 0.290531 0.019 Uiso 1 1 calc R U . . .
H21B H 0.683557 0.155686 0.358307 0.019 Uiso 1 1 calc R U . . .
N22 N 0.70094(10) 0.42127(19) 0.41787(9) 0.0128(3) Uani 1 1 d . . . . .
C23 C 0.71741(13) 0.3387(2) 0.51319(11) 0.0159(3) Uani 1 1 d . . . . .
H23A H 0.696870 0.434263 0.550692 0.019 Uiso 1 1 calc R U . . .
H23B H 0.787887 0.318300 0.540069 0.019 Uiso 1 1 calc R U . . .
C24 C 0.66433(15) 0.1507(3) 0.51953(14) 0.0237(4) Uani 1 1 d . . . . .
H24A H 0.595764 0.162097 0.485204 0.036 Uiso 1 1 calc R U . . .
H24B H 0.669733 0.123639 0.582953 0.036 Uiso 1 1 calc R U . . .
H24C H 0.693982 0.047807 0.494427 0.036 Uiso 1 1 calc R U . . .
C25 C 0.59577(13) 0.4863(3) 0.37813(12) 0.0188(3) Uani 1 1 d . . . . .
H25A H 0.552784 0.376197 0.376065 0.023 Uiso 1 1 calc R U . . .
H25B H 0.586933 0.527375 0.315040 0.023 Uiso 1 1 calc R U . . .
C26 C 0.56207(15) 0.6477(3) 0.42885(16) 0.0278(4) Uani 1 1 d . . . . .
H26A H 0.569656 0.609121 0.491388 0.042 Uiso 1 1 calc R U . . .
H26B H 0.493735 0.676209 0.398896 0.042 Uiso 1 1 calc R U . . .
H26C H 0.601399 0.760521 0.428509 0.042 Uiso 1 1 calc R U . . .


_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
V1 O2 1.6217(12) . ?
V1 O1 1.6228(13) . ?
V1 O11 1.9160(12) . ?
V1 N19 2.1423(14) . ?
V1 N22 2.2021(14) . ?
O11 C12 1.319(2) . ?
C12 C13 1.405(2) . ?
C12 C17 1.414(2) . ?
C13 C14 1.381(2) . ?
C13 H13 0.9300 . ?
C14 C15 1.398(2) . ?
C14 H14 0.9300 . ?
C15 C16 1.373(2) . ?
C15 Cl15 1.7444(18) . ?
C16 C17 1.402(2) . ?
C16 H16 0.9300 . ?
C17 C18 1.440(2) . ?
C18 N19 1.289(2) . ?
C18 H18 0.9300 . ?
N19 C20 1.467(2) . ?
C20 C21 1.503(2) . ?
C20 H20A 0.9700 . ?
C20 H20B 0.9700 . ?
C21 N22 1.491(2) . ?
C21 H21A 0.9700 . ?
C21 H21B 0.9700 . ?
N22 C25 1.500(2) . ?
N22 C23 1.507(2) . ?
C23 C24 1.521(2) . ?
C23 H23A 0.9700 . ?
C23 H23B 0.9700 . ?
C24 H24A 0.9600 . ?
C24 H24B 0.9600 . ?
C24 H24C 0.9600 . ?
C25 C26 1.511(3) . ?
C25 H25A 0.9700 . ?
C25 H25B 0.9700 . ?
C26 H26A 0.9600 . ?
C26 H26B 0.9600 . ?
C26 H26C 0.9600 . ?

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
O2 V1 O1 110.67(7) . . ?
O2 V1 O11 96.97(6) . . ?
O1 V1 O11 102.95(6) . . ?
O2 V1 N19 134.29(6) . . ?
O1 V1 N19 113.96(6) . . ?
O11 V1 N19 82.50(5) . . ?
O2 V1 N22 90.68(6) . . ?
O1 V1 N22 93.96(6) . . ?
O11 V1 N22 157.52(5) . . ?
N19 V1 N22 77.09(5) . . ?
C12 O11 V1 129.90(10) . . ?
O11 C12 C13 119.41(14) . . ?
O11 C12 C17 122.06(15) . . ?
C13 C12 C17 118.50(15) . . ?
C14 C13 C12 120.89(15) . . ?
C14 C13 H13 119.6 . . ?
C12 C13 H13 119.6 . . ?
C13 C14 C15 119.79(16) . . ?
C13 C14 H14 120.1 . . ?
C15 C14 H14 120.1 . . ?
C16 C15 C14 120.74(16) . . ?
C16 C15 Cl15 120.18(13) . . ?
C14 C15 Cl15 119.08(14) . . ?
C15 C16 C17 120.04(15) . . ?
C15 C16 H16 120.0 . . ?
C17 C16 H16 120.0 . . ?
C16 C17 C12 119.99(15) . . ?
C16 C17 C18 119.07(15) . . ?
C12 C17 C18 120.92(15) . . ?
N19 C18 C17 125.18(15) . . ?
N19 C18 H18 117.4 . . ?
C17 C18 H18 117.4 . . ?
C18 N19 C20 117.75(14) . . ?
C18 N19 V1 124.99(11) . . ?
C20 N19 V1 116.08(10) . . ?
N19 C20 C21 105.78(13) . . ?
N19 C20 H20A 110.6 . . ?
C21 C20 H20A 110.6 . . ?
N19 C20 H20B 110.6 . . ?
C21 C20 H20B 110.6 . . ?
H20A C20 H20B 108.7 . . ?
N22 C21 C20 109.81(13) . . ?
N22 C21 H21A 109.7 . . ?
C20 C21 H21A 109.7 . . ?
N22 C21 H21B 109.7 . . ?
C20 C21 H21B 109.7 . . ?
H21A C21 H21B 108.2 . . ?
C21 N22 C25 106.49(13) . . ?
C21 N22 C23 110.88(13) . . ?
C25 N22 C23 111.00(13) . . ?
C21 N22 V1 107.98(10) . . ?
C25 N22 V1 112.75(10) . . ?
C23 N22 V1 107.72(10) . . ?
N22 C23 C24 116.36(14) . . ?
N22 C23 H23A 108.2 . . ?
C24 C23 H23A 108.2 . . ?
N22 C23 H23B 108.2 . . ?
C24 C23 H23B 108.2 . . ?
H23A C23 H23B 107.3 . . ?
C23 C24 H24A 109.5 . . ?
C23 C24 H24B 109.5 . . ?
H24A C24 H24B 109.5 . . ?
C23 C24 H24C 109.5 . . ?
H24A C24 H24C 109.5 . . ?
H24B C24 H24C 109.5 . . ?
N22 C25 C26 116.06(15) . . ?
N22 C25 H25A 108.3 . . ?
C26 C25 H25A 108.3 . . ?
N22 C25 H25B 108.3 . . ?
C26 C25 H25B 108.3 . . ?
H25A C25 H25B 107.4 . . ?
C25 C26 H26A 109.5 . . ?
C25 C26 H26B 109.5 . . ?
H26A C26 H26B 109.5 . . ?
C25 C26 H26C 109.5 . . ?
H26A C26 H26C 109.5 . . ?
H26B C26 H26C 109.5 . . ?

_refine_diff_density_max         0.323
_refine_diff_density_min         -0.572
_refine_diff_density_rms         0.105

####################################################################### 
# 
# 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_4
_database_code_depnum_ccdc_archive 'CCDC 1879194'
_audit_update_record             
;
2018-11-15 deposited with the CCDC.
2019-01-21 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2016/6
_shelx_SHELXL_version_number     2016/6
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C24 H38 N4 O8 V2'
_chemical_formula_weight         612.46

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'
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           14
_space_group_name_H-M_alt        'P 21/n'
_space_group_name_Hall           '-P 2yn'

_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+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, -y-1/2, z-1/2'

_cell_length_a                   8.9266(4)
_cell_length_b                   6.9648(3)
_cell_length_c                   21.9606(12)
_cell_angle_alpha                90
_cell_angle_beta                 96.547(4)
_cell_angle_gamma                90
_cell_volume                     1356.43(11)
_cell_formula_units_Z            2
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    8667
_cell_measurement_theta_min      3.41
_cell_measurement_theta_max      30.00

_exptl_crystal_description       block
_exptl_crystal_colour            brown
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.500
_exptl_crystal_F_000             640
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.18
_exptl_absorpt_coefficient_mu    0.743
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details   'ABSPACK, Oxford Diffraction Ltd'
_exptl_absorpt_correction_T_min  0.852
_exptl_absorpt_correction_T_max  0.875
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      150(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_measurement_device_type  'Oxford Diffaction X-Calibor System'
_diffrn_measurement_method       '321 frames, counting time 10 s.'
_diffrn_standards_interval_count n/a
_diffrn_standards_interval_time  n/a
_diffrn_standards_decay_%        n/a
_diffrn_reflns_number            8667
_diffrn_reflns_av_unetI/netI     0.0512
_diffrn_reflns_av_R_equivalents  0.0348
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_theta_min         3.414
_diffrn_reflns_theta_max         29.995
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.980
_diffrn_measured_fraction_theta_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_point_group_measured_fraction_full 0.990
_reflns_number_total             3873
_reflns_number_gt                3256
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_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       'Crysalis, Oxford Diffraction'
_computing_cell_refinement       'Crysalis, Oxford Diffraction'
_computing_data_reduction        'Crysalis, Oxford Diffraction'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-2016/6 (Sheldrick, 2016)'
_computing_molecular_graphics    PLATON(Spek,2004)
_computing_publication_material  'SHELXL-2016/6, PLATON, WINGX (Ferrugia, 2012)'
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0400P)²+0.9794P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         3950
_refine_ls_number_parameters     182
_refine_ls_number_restraints     3
_refine_ls_R_factor_all          0.0604
_refine_ls_R_factor_gt           0.0476
_refine_ls_wR_factor_ref         0.1072
_refine_ls_wR_factor_gt          0.1019
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_restrained_S_all      1.030
_refine_ls_shift/su_max          0.000
_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
V1 V 0.16982(4) 0.57862(5) 0.00630(2) 0.01620(10) Uani 1 1 d . . . . .
O1 O 0.00308(16) 0.6778(2) -0.01980(7) 0.0190(3) Uani 1 1 d . . . . .
O2 O 0.30002(16) 0.7245(2) -0.00934(7) 0.0240(3) Uani 1 1 d . . . . .
O11 O 0.15916(16) 0.6253(2) 0.09109(7) 0.0204(3) Uani 1 1 d . . . . .
C12 C 0.2634(2) 0.5999(3) 0.13911(9) 0.0186(4) Uani 1 1 d . . . . .
C13 C 0.2638(2) 0.7286(3) 0.18795(10) 0.0226(4) Uani 1 1 d . . . . .
H13 H 0.194445 0.828755 0.185393 0.027 Uiso 1 1 calc R U . . .
C14 C 0.3652(3) 0.7096(4) 0.23985(10) 0.0260(5) Uani 1 1 d . . . . .
H14 H 0.363816 0.796790 0.271865 0.031 Uiso 1 1 calc R U . . .
C15 C 0.4696(3) 0.5603(4) 0.24447(10) 0.0267(5) Uani 1 1 d . . . . .
H15 H 0.539501 0.548357 0.279058 0.032 Uiso 1 1 calc R U . . .
C16 C 0.4679(2) 0.4312(3) 0.19721(10) 0.0236(4) Uani 1 1 d . . . . .
H16 H 0.536545 0.330316 0.200814 0.028 Uiso 1 1 calc R U . . .
C17 C 0.3657(2) 0.4455(3) 0.14327(9) 0.0182(4) Uani 1 1 d . . . . .
C18 C 0.3687(2) 0.3011(3) 0.09458(10) 0.0179(4) Uani 1 1 d . . . . .
N19 N 0.31172(18) 0.3387(2) 0.03920(8) 0.0173(3) Uani 1 1 d . . . . .
C20 C 0.3255(3) 0.1955(3) -0.00917(10) 0.0237(4) Uani 1 1 d . . . . .
H20A H 0.244966 0.101773 -0.009810 0.028 Uiso 1 1 calc R U . . .
H20B H 0.421148 0.128703 -0.001477 0.028 Uiso 1 1 calc R U . . .
C21 C 0.3161(2) 0.2994(3) -0.06975(10) 0.0239(5) Uani 1 1 d . . . . .
H21A H 0.404234 0.379952 -0.071241 0.029 Uiso 1 1 calc R U . . .
H21B H 0.312050 0.207627 -0.103111 0.029 Uiso 1 1 calc R U . . .
N22 N 0.17849(19) 0.4183(2) -0.07582(8) 0.0173(3) Uani 1 1 d . . . . .
H22 H 0.092426 0.330021 -0.079380 0.021 Uiso 1 1 calc R U . . .
C23 C 0.1629(3) 0.5399(3) -0.13193(10) 0.0229(4) Uani 1 1 d . . . . .
H23A H 0.251113 0.621606 -0.131279 0.027 Uiso 1 1 calc R U . . .
H23B H 0.075680 0.622555 -0.131158 0.027 Uiso 1 1 calc R U . . .
C24 C 0.1457(3) 0.4257(4) -0.19123(11) 0.0305(5) Uani 1 1 d . . . . .
H24A H 0.234275 0.349219 -0.193587 0.046 Uiso 1 1 calc R U . . .
H24B H 0.132678 0.512328 -0.225437 0.046 Uiso 1 1 calc R U . . .
H24C H 0.059151 0.343471 -0.192152 0.046 Uiso 1 1 calc R U . . .
C181 C 0.4418(3) 0.1095(3) 0.11102(11) 0.0270(5) Uani 1 1 d . . . . .
H18A H 0.387217 0.009798 0.087870 0.041 Uiso 1 1 calc R U . . .
H18B H 0.440352 0.085786 0.154009 0.041 Uiso 1 1 calc R U . . .
H18C H 0.544190 0.111267 0.101618 0.041 Uiso 1 1 calc R U . . .
O1W O -0.0015(2) -0.0036(3) 0.09641(9) 0.0373(4) Uani 1 1 d D . . . .
H1 H -0.002(3) 0.087(3) 0.0707(12) 0.046(9) Uiso 1 1 d D . . . .
H2 H 0.070(3) -0.078(4) 0.0894(14) 0.047(9) Uiso 1 1 d 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
V1 O2 1.6098(15) . ?
V1 O1 1.6812(14) . ?
V1 O11 1.9033(15) . ?
V1 N22 2.1301(17) . ?
V1 N19 2.1702(17) . ?
V1 O1 2.4008(15) 3_565 ?
O11 C12 1.336(2) . ?
C12 C13 1.397(3) . ?
C12 C17 1.407(3) . ?
C13 C14 1.379(3) . ?
C13 H13 0.9300 . ?
C14 C15 1.393(3) . ?
C14 H14 0.9300 . ?
C15 C16 1.372(3) . ?
C15 H15 0.9300 . ?
C16 C17 1.414(3) . ?
C16 H16 0.9300 . ?
C17 C18 1.470(3) . ?
C18 N19 1.290(3) . ?
C18 C181 1.511(3) . ?
N19 C20 1.473(3) . ?
C20 C21 1.508(3) . ?
C20 H20A 0.9700 . ?
C20 H20B 0.9700 . ?
C21 N22 1.474(3) . ?
C21 H21A 0.9700 . ?
C21 H21B 0.9700 . ?
N22 C23 1.489(3) . ?
N22 H22 0.9800 . ?
C23 C24 1.519(3) . ?
C23 H23A 0.9700 . ?
C23 H23B 0.9700 . ?
C24 H24A 0.9600 . ?
C24 H24B 0.9600 . ?
C24 H24C 0.9600 . ?
C181 H18A 0.9600 . ?
C181 H18B 0.9600 . ?
C181 H18C 0.9600 . ?
O1W H1 0.846(16) . ?
O1W H2 0.846(16) . ?

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
O2 V1 O1 107.50(8) . . ?
O2 V1 O11 102.63(7) . . ?
O1 V1 O11 97.02(7) . . ?
O2 V1 N22 93.06(7) . . ?
O1 V1 N22 92.47(7) . . ?
O11 V1 N22 158.22(7) . . ?
O2 V1 N19 98.55(7) . . ?
O1 V1 N19 152.91(7) . . ?
O11 V1 N19 84.16(6) . . ?
N22 V1 N19 78.58(6) . . ?
O2 V1 O1 170.28(7) . 3_565 ?
O1 V1 O1 77.94(7) . 3_565 ?
O11 V1 O1 84.36(6) . 3_565 ?
N22 V1 O1 78.49(6) . 3_565 ?
N19 V1 O1 75.24(6) . 3_565 ?
V1 O1 V1 102.06(7) . 3_565 ?
C12 O11 V1 129.90(13) . . ?
O11 C12 C13 117.45(18) . . ?
O11 C12 C17 122.75(19) . . ?
C13 C12 C17 119.72(19) . . ?
C14 C13 C12 121.1(2) . . ?
C14 C13 H13 119.4 . . ?
C12 C13 H13 119.4 . . ?
C13 C14 C15 120.2(2) . . ?
C13 C14 H14 119.9 . . ?
C15 C14 H14 119.9 . . ?
C16 C15 C14 119.0(2) . . ?
C16 C15 H15 120.5 . . ?
C14 C15 H15 120.5 . . ?
C15 C16 C17 122.6(2) . . ?
C15 C16 H16 118.7 . . ?
C17 C16 H16 118.7 . . ?
C12 C17 C16 117.39(19) . . ?
C12 C17 C18 122.74(18) . . ?
C16 C17 C18 119.87(19) . . ?
N19 C18 C17 120.59(18) . . ?
N19 C18 C181 121.16(19) . . ?
C17 C18 C181 118.25(18) . . ?
C18 N19 C20 119.08(17) . . ?
C18 N19 V1 128.49(14) . . ?
C20 N19 V1 112.02(13) . . ?
N19 C20 C21 108.07(17) . . ?
N19 C20 H20A 110.1 . . ?
C21 C20 H20A 110.1 . . ?
N19 C20 H20B 110.1 . . ?
C21 C20 H20B 110.1 . . ?
H20A C20 H20B 108.4 . . ?
N22 C21 C20 108.14(18) . . ?
N22 C21 H21A 110.1 . . ?
C20 C21 H21A 110.1 . . ?
N22 C21 H21B 110.1 . . ?
C20 C21 H21B 110.1 . . ?
H21A C21 H21B 108.4 . . ?
C21 N22 C23 113.11(17) . . ?
C21 N22 V1 109.16(13) . . ?
C23 N22 V1 113.16(13) . . ?
C21 N22 H22 107.0 . . ?
C23 N22 H22 107.0 . . ?
V1 N22 H22 107.0 . . ?
N22 C23 C24 113.72(19) . . ?
N22 C23 H23A 108.8 . . ?
C24 C23 H23A 108.8 . . ?
N22 C23 H23B 108.8 . . ?
C24 C23 H23B 108.8 . . ?
H23A C23 H23B 107.7 . . ?
C23 C24 H24A 109.5 . . ?
C23 C24 H24B 109.5 . . ?
H24A C24 H24B 109.5 . . ?
C23 C24 H24C 109.5 . . ?
H24A C24 H24C 109.5 . . ?
H24B C24 H24C 109.5 . . ?
C18 C181 H18A 109.5 . . ?
C18 C181 H18B 109.5 . . ?
H18A C181 H18B 109.5 . . ?
C18 C181 H18C 109.5 . . ?
H18A C181 H18C 109.5 . . ?
H18B C181 H18C 109.5 . . ?
H1 O1W H2 106(2) . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
O1W H1 O1 0.846(16) 1.983(17) 2.824(2) 172(3) 3_565
N22 H22 O11 0.98 2.25 3.010(2) 133.2 3_565
N22 H22 O1W 0.98 2.43 3.298(3) 147.6 3
O1W H2 O11 0.846(16) 2.22(2) 2.964(2) 148(3) 1_545

_refine_diff_density_max         0.453
_refine_diff_density_min         -0.347
_refine_diff_density_rms         0.071

####################################################################### 
# 
# 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_3
_database_code_depnum_ccdc_archive 'CCDC 1879193'
_audit_update_record             
;
2018-11-15 deposited with the CCDC.
2019-01-21 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2016/6
_shelx_SHELXL_version_number     2016/6
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C22 H28 Cl2 N4 O6 V2'
_chemical_formula_weight         617.26

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'
V V 0.3005 0.5294 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_H-M_alt        'I 2/a'
_space_group_name_Hall           '-I 2ya'

_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+1/2, y, -z'
'x+1/2, y+1/2, z+1/2'
'-x+1, y+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, -y, z'
'-x+1/2, -y+1/2, -z+1/2'
'x, -y+1/2, z+1/2'

_cell_length_a                   22.194(2)
_cell_length_b                   7.5879(7)
_cell_length_c                   15.5112(12)
_cell_angle_alpha                90
_cell_angle_beta                 97.479(10)
_cell_angle_gamma                90
_cell_volume                     2589.9(4)
_cell_formula_units_Z            4
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    7844
_cell_measurement_theta_min      3.424
_cell_measurement_theta_max      30.00

_exptl_crystal_description       needle
_exptl_crystal_colour            black
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.06
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.583
_exptl_crystal_F_000             1264
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_absorpt_coefficient_mu    0.973
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details   'ABSPACK, Oxford Diffraction Ltd'
_exptl_absorpt_correction_T_min  0.912
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      150(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_measurement_device       'Oxford Diffaction X-Calibor System'
_diffrn_measurement_method       '321 frames, counting time 10 s.'
_diffrn_standards_interval_count n/a
_diffrn_standards_interval_time  n/a
_diffrn_standards_decay_%        n/a

_diffrn_reflns_number            7844
_diffrn_reflns_av_unetI/netI     0.0447
_diffrn_reflns_av_R_equivalents  0.0295
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_theta_min         3.424
_diffrn_reflns_theta_max         29.999
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measured_fraction_theta_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_point_group_measured_fraction_full 0.985
_reflns_number_total             3726
_reflns_number_gt                3036
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_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       'Crysalis, Oxford Diffraction'
_computing_cell_refinement       'Crysalis, Oxford Diffraction'
_computing_data_reduction        'Crysalis, Oxford Diffraction'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-2016/6 (Sheldrick, 2016)'
_computing_molecular_graphics    PLATON(Spek,2004)
_computing_publication_material  'SHELXL-2016/6, PLATON, WINGX (Ferrugia, 2012)'
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0509P)²+0.8673P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         3726
_refine_ls_number_parameters     167
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0595
_refine_ls_R_factor_gt           0.0443
_refine_ls_wR_factor_ref         0.1075
_refine_ls_wR_factor_gt          0.1015
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_restrained_S_all      1.060
_refine_ls_shift/su_max          0.001
_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
V1 V 0.52251(2) 0.93922(4) 0.09435(2) 0.01654(10) Uani 1 1 d . . . . .
O1 O 0.54357(7) 0.9756(2) 0.19647(9) 0.0240(3) Uani 1 1 d . . . . .
O2 O 0.52289(7) 1.13418(19) 0.04346(9) 0.0184(3) Uani 1 1 d . . . . .
O11 O 0.59481(7) 0.8394(2) 0.05947(9) 0.0215(3) Uani 1 1 d . . . . .
C12 C 0.62382(10) 0.6911(3) 0.08238(13) 0.0203(4) Uani 1 1 d . . . . .
C13 C 0.68678(10) 0.6818(3) 0.07899(15) 0.0271(5) Uani 1 1 d . . . . .
H13 H 0.707381 0.782173 0.064607 0.033 Uiso 1 1 calc R U . . .
C14 C 0.71849(11) 0.5275(3) 0.09652(16) 0.0307(5) Uani 1 1 d . . . . .
H14 H 0.760075 0.524023 0.093736 0.037 Uiso 1 1 calc R U . . .
C15 C 0.68833(11) 0.3767(3) 0.11841(15) 0.0259(5) Uani 1 1 d . . . . .
Cl15 Cl 0.72818(3) 0.17899(9) 0.13608(5) 0.04336(18) Uani 1 1 d . . . . .
C16 C 0.62742(10) 0.3813(3) 0.12429(13) 0.0220(4) Uani 1 1 d . . . . .
H16 H 0.607759 0.279866 0.139485 0.026 Uiso 1 1 calc R U . . .
C17 C 0.59438(10) 0.5378(3) 0.10757(12) 0.0184(4) Uani 1 1 d . . . . .
C18 C 0.52971(10) 0.5323(3) 0.11279(12) 0.0182(4) Uani 1 1 d . . . . .
H18 H 0.512202 0.423196 0.120865 0.022 Uiso 1 1 calc R U . . .
N19 N 0.49509(8) 0.6678(2) 0.10702(10) 0.0167(3) Uani 1 1 d . . . . .
C20 C 0.43007(10) 0.6446(3) 0.11166(13) 0.0192(4) Uani 1 1 d . . . . .
H20A H 0.423253 0.539342 0.144540 0.023 Uiso 1 1 calc R U . . .
H20B H 0.408012 0.633009 0.053708 0.023 Uiso 1 1 calc R U . . .
C21 C 0.40879(10) 0.8058(3) 0.15619(13) 0.0204(4) Uani 1 1 d . . . . .
H21A H 0.364887 0.804120 0.153578 0.024 Uiso 1 1 calc R U . . .
H21B H 0.426347 0.807252 0.216817 0.024 Uiso 1 1 calc R U . . .
N22 N 0.42805(8) 0.9638(2) 0.11149(11) 0.0181(4) Uani 1 1 d D . . . .
H22 H 0.4075(10) 0.965(3) 0.0624(11) 0.022 Uiso 1 1 d D U . . .
C23 C 0.41515(10) 1.1317(3) 0.15459(14) 0.0223(4) Uani 1 1 d . . . . .
H23A H 0.428622 1.228617 0.121067 0.027 Uiso 1 1 calc R U . . .
H23B H 0.438928 1.134863 0.211655 0.027 Uiso 1 1 calc R U . . .
C24 C 0.34886(11) 1.1607(3) 0.16508(16) 0.0310(5) Uani 1 1 d . . . . .
H24A H 0.324706 1.156632 0.109082 0.046 Uiso 1 1 calc R U . . .
H24B H 0.344235 1.273710 0.191248 0.046 Uiso 1 1 calc R U . . .
H24C H 0.335687 1.070050 0.201559 0.046 Uiso 1 1 calc R U . . .


_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
V1 O1 1.6158(15) . ?
V1 O2 1.6773(14) . ?
V1 O11 1.9151(15) . ?
V1 N22 2.1552(18) . ?
V1 N19 2.1637(17) . ?
V1 O2 2.3097(14) 5_675 ?
V1 V1 3.1072(7) 5_675 ?
O11 C12 1.322(3) . ?
C12 C13 1.407(3) . ?
C12 C17 1.414(3) . ?
C13 C14 1.375(3) . ?
C13 H13 0.9300 . ?
C14 C15 1.390(3) . ?
C14 H14 0.9300 . ?
C15 C16 1.367(3) . ?
C15 Cl15 1.745(2) . ?
C16 C17 1.402(3) . ?
C16 H16 0.9300 . ?
C17 C18 1.449(3) . ?
C18 N19 1.280(3) . ?
C18 H18 0.9300 . ?
N19 C20 1.465(3) . ?
C20 C21 1.511(3) . ?
C20 H20A 0.9700 . ?
C20 H20B 0.9700 . ?
C21 N22 1.476(2) . ?
C21 H21A 0.9700 . ?
C21 H21B 0.9700 . ?
N22 C23 1.484(3) . ?
N22 H22 0.835(16) . ?
C23 C24 1.517(3) . ?
C23 H23A 0.9700 . ?
C23 H23B 0.9700 . ?
C24 H24A 0.9600 . ?
C24 H24B 0.9600 . ?
C24 H24C 0.9600 . ?

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
O1 V1 O2 106.97(7) . . ?
O1 V1 O11 101.44(8) . . ?
O2 V1 O11 99.21(7) . . ?
O1 V1 N22 91.50(7) . . ?
O2 V1 N22 92.66(7) . . ?
O11 V1 N22 158.96(7) . . ?
O1 V1 N19 97.05(7) . . ?
O2 V1 N19 154.28(7) . . ?
O11 V1 N19 84.55(6) . . ?
N22 V1 N19 77.38(6) . . ?
O1 V1 O2 169.80(7) . 5_675 ?
O2 V1 O2 78.78(7) . 5_675 ?
O11 V1 O2 85.63(6) . 5_675 ?
N22 V1 O2 79.68(6) . 5_675 ?
N19 V1 O2 76.15(6) . 5_675 ?
O1 V1 V1 152.77(6) . 5_675 ?
O2 V1 V1 46.81(5) . 5_675 ?
O11 V1 V1 91.71(5) . 5_675 ?
N22 V1 V1 83.79(5) . 5_675 ?
N19 V1 V1 107.96(5) . 5_675 ?
O2 V1 V1 31.97(4) 5_675 5_675 ?
V1 O2 V1 101.22(7) . 5_675 ?
C12 O11 V1 131.11(12) . . ?
O11 C12 C13 118.93(19) . . ?
O11 C12 C17 123.24(19) . . ?
C13 C12 C17 117.8(2) . . ?
C14 C13 C12 121.4(2) . . ?
C14 C13 H13 119.3 . . ?
C12 C13 H13 119.3 . . ?
C13 C14 C15 120.0(2) . . ?
C13 C14 H14 120.0 . . ?
C15 C14 H14 120.0 . . ?
C16 C15 C14 120.5(2) . . ?
C16 C15 Cl15 119.80(18) . . ?
C14 C15 Cl15 119.72(18) . . ?
C15 C16 C17 120.5(2) . . ?
C15 C16 H16 119.8 . . ?
C17 C16 H16 119.8 . . ?
C16 C17 C12 119.90(19) . . ?
C16 C17 C18 117.62(19) . . ?
C12 C17 C18 122.40(19) . . ?
N19 C18 C17 124.29(19) . . ?
N19 C18 H18 117.9 . . ?
C17 C18 H18 117.9 . . ?
C18 N19 C20 119.10(17) . . ?
C18 N19 V1 126.70(14) . . ?
C20 N19 V1 114.17(12) . . ?
N19 C20 C21 107.08(16) . . ?
N19 C20 H20A 110.3 . . ?
C21 C20 H20A 110.3 . . ?
N19 C20 H20B 110.3 . . ?
C21 C20 H20B 110.3 . . ?
H20A C20 H20B 108.6 . . ?
N22 C21 C20 108.43(15) . . ?
N22 C21 H21A 110.0 . . ?
C20 C21 H21A 110.0 . . ?
N22 C21 H21B 110.0 . . ?
C20 C21 H21B 110.0 . . ?
H21A C21 H21B 108.4 . . ?
C21 N22 C23 113.64(15) . . ?
C21 N22 V1 109.49(13) . . ?
C23 N22 V1 112.19(13) . . ?
C21 N22 H22 106.2(17) . . ?
C23 N22 H22 106.8(17) . . ?
V1 N22 H22 108.2(17) . . ?
N22 C23 C24 114.80(19) . . ?
N22 C23 H23A 108.6 . . ?
C24 C23 H23A 108.6 . . ?
N22 C23 H23B 108.6 . . ?
C24 C23 H23B 108.6 . . ?
H23A C23 H23B 107.5 . . ?
C23 C24 H24A 109.5 . . ?
C23 C24 H24B 109.5 . . ?
H24A C24 H24B 109.5 . . ?
C23 C24 H24C 109.5 . . ?
H24A C24 H24C 109.5 . . ?
H24B C24 H24C 109.5 . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
C16 H16 O2 0.93 2.50 3.116(3) 123.8 1_545
C18 H18 O2 0.93 2.53 3.204(3) 130.0 1_545
C20 H20A O1 0.97 2.53 3.223(3) 128.7 4_545
C23 H23A O2 0.97 2.64 3.124(2) 110.8 .
N22 H22 O11 0.835(16) 2.40(2) 3.028(2) 133(2) 5_675

_refine_diff_density_max         1.233
_refine_diff_density_min         -0.436
_refine_diff_density_rms         0.087

