# Electronic Supplementary Material (ESI) for Chemical Science.
# This journal is © The Royal Society of Chemistry 2021

####################################################################### 
# 
# 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. 
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#######################################################################

data_orz237a
_database_code_depnum_ccdc_archive 'CCDC 2058759'
loop_
_audit_author_name
_audit_author_address
'Olivier Roubeau'
;Instituto de Ciencia de Materiales de Aragon (ICMA), CSIC and Universidad de Zaragoza
Spain
;
_audit_update_record             
;
2021-01-26 deposited with the CCDC.	2021-03-10 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C56 H46 N4 O8'
_chemical_formula_sum            'C56 H46 N4 O8'
_chemical_formula_weight         902.97

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'

_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                   9.0183(15)
_cell_length_b                   10.8486(18)
_cell_length_c                   22.331(3)
_cell_angle_alpha                90
_cell_angle_beta                 92.992(9)
_cell_angle_gamma                90
_cell_volume                     2181.8(6)
_cell_formula_units_Z            2
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    5611
_cell_measurement_theta_min      2.39
_cell_measurement_theta_max      26.39

_exptl_crystal_description       block
_exptl_crystal_colour            violet
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.374
_exptl_crystal_F_000             948
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.200
_exptl_crystal_size_mid          0.170
_exptl_crystal_size_min          0.160
_exptl_absorpt_coefficient_mu    0.093
_shelx_estimated_absorpt_T_min   0.982
_shelx_estimated_absorpt_T_max   0.985
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.659
_exptl_absorpt_correction_T_max  0.745
_exptl_absorpt_process_details   'SADABS-2008/1 - Bruker AXS'

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'multilayer monochromator ImuS'
_diffrn_measurement_device_type  'Bruker APEX II QUAZAR'
_diffrn_measurement_method       'φ and ω rotation with narrow frames'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            13440
_diffrn_reflns_av_unetI/netI     0.0291
_diffrn_reflns_av_R_equivalents  0.0299
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_theta_min         1.826
_diffrn_reflns_theta_max         24.712
_diffrn_reflns_theta_full        24.713
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measured_fraction_theta_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_point_group_measured_fraction_full 0.990
_reflns_number_total             3693
_reflns_number_gt                3304
_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       'Bruker APEX 2'
_computing_cell_refinement       'SAINT (Bruker)'
_computing_data_reduction        'SAINT (Bruker)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_computing_structure_refinement  'SHELXL-2014 (Sheldrick, 2015)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_refine_special_details          
;
 All non-hydrogens were refined anisotropically. Hydrogens were placed
 geometrically on their carrier atom and refined with a riding model,
 except those on the porphyrin nitrogens N1 and N2, which were refined
 with their thermal parameters 1.5 times of their carrier N and with
 half occupancy due to the symmetry of the molecule. One of the
 ethyl groups is disordered over two positions (C18-C19 A and B) 
 with relative occupancies refining to 0.733:0.267. Displacement
 parameters  restraints were used to refined these.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0586P)²+3.3746P] 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         3693
_refine_ls_number_parameters     326
_refine_ls_number_restraints     17
_refine_ls_R_factor_all          0.0660
_refine_ls_R_factor_gt           0.0601
_refine_ls_wR_factor_ref         0.1573
_refine_ls_wR_factor_gt          0.1536
_refine_ls_goodness_of_fit_ref   1.132
_refine_ls_restrained_S_all      1.137
_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
N1 N 0.4005(2) 0.1535(2) 0.46079(10) 0.0196(5) Uani 1 1 d D . . . .
H1 H 0.449(6) 0.096(4) 0.475(3) 0.029 Uiso 0.5 1 d D U P A 1
N2 N 0.4785(2) 0.0763(2) 0.58354(10) 0.0200(5) Uani 1 1 d D . . . .
H2 H 0.492(7) 0.048(6) 0.5502(15) 0.030 Uiso 0.5 1 d D U P B 2
O1 O 0.2140(2) 0.14970(19) 0.07101(9) 0.0328(5) Uani 1 1 d . . . . .
O2 O 0.3349(2) 0.32800(18) 0.09106(9) 0.0292(5) Uani 1 1 d . . . . .
O3 O 0.0202(2) 0.72800(18) 0.68101(9) 0.0288(5) Uani 1 1 d . . . . .
O4 O 0.2092(2) 0.82570(17) 0.63857(9) 0.0299(5) Uani 1 1 d . . . . .
C1 C 0.4012(3) 0.0887(2) 0.35487(12) 0.0196(6) Uani 1 1 d . . . . .
C2 C 0.3663(3) 0.1703(2) 0.40080(12) 0.0203(6) Uani 1 1 d . . . . .
C3 C 0.2881(3) 0.2856(2) 0.39244(13) 0.0217(6) Uani 1 1 d . . . . .
H3A H 0.2513 0.3192 0.3553 0.026 Uiso 1 1 calc R U . . .
C4 C 0.2768(3) 0.3371(2) 0.44707(12) 0.0219(6) Uani 1 1 d . . . . .
H4A H 0.2310 0.4136 0.4554 0.026 Uiso 1 1 calc R U . . .
C5 C 0.3471(3) 0.2542(2) 0.49041(12) 0.0190(6) Uani 1 1 d . . . . .
C6 C 0.3538(3) 0.2715(2) 0.55260(12) 0.0197(6) Uani 1 1 d . . . . .
C7 C 0.4141(3) 0.1881(2) 0.59485(12) 0.0196(6) Uani 1 1 d . . . . .
C8 C 0.4229(3) 0.2081(3) 0.65859(12) 0.0233(6) Uani 1 1 d . . . . .
H8A H 0.3867 0.2780 0.6789 0.028 Uiso 1 1 calc R U . . .
C9 C 0.4921(3) 0.1093(2) 0.68455(13) 0.0237(6) Uani 1 1 d . . . . .
H9A H 0.5135 0.0973 0.7263 0.028 Uiso 1 1 calc R U . . .
C10 C 0.5270(3) 0.0261(2) 0.63727(12) 0.0197(6) Uani 1 1 d . . . . .
C11 C 0.3629(3) 0.1262(2) 0.29136(12) 0.0205(6) Uani 1 1 d . . . . .
C12 C 0.2584(3) 0.0618(2) 0.25580(13) 0.0226(6) Uani 1 1 d . . . . .
H12A H 0.2056 -0.0045 0.2726 0.027 Uiso 1 1 calc R U . . .
C13 C 0.4372(3) 0.2255(2) 0.26615(12) 0.0215(6) Uani 1 1 d . . . . .
H13A H 0.5079 0.2713 0.2901 0.026 Uiso 1 1 calc R U . . .
C14 C 0.2301(3) 0.0927(2) 0.19631(13) 0.0222(6) Uani 1 1 d . . . . .
H14A H 0.1592 0.0472 0.1724 0.027 Uiso 1 1 calc R U . . .
C15 C 0.4081(3) 0.2574(2) 0.20672(12) 0.0210(6) Uani 1 1 d . . . . .
H15A H 0.4585 0.3251 0.1901 0.025 Uiso 1 1 calc R U . . .
C16 C 0.3055(3) 0.1907(2) 0.17121(12) 0.0207(6) Uani 1 1 d . . . . .
C17 C 0.2784(3) 0.2187(3) 0.10595(13) 0.0231(6) Uani 1 1 d . . . . .
C18 C 0.3247(4) 0.3617(4) 0.02794(16) 0.0475(9) Uani 1 1 d D U . . .
H18A H 0.3061 0.4512 0.0235 0.057 Uiso 0.733(8) 1 d R U P C 1
H18B H 0.2405 0.3172 0.0075 0.057 Uiso 0.733(8) 1 d R U P C 1
H18C H 0.4007 0.4274 0.0268 0.057 Uiso 0.267(8) 1 d R U P C 2
H18D H 0.3719 0.2890 0.0100 0.057 Uiso 0.267(8) 1 d R U P C 2
C19A C 0.4627(5) 0.3297(5) -0.0001(2) 0.0407(13) Uani 0.733(8) 1 d D U P C 1
H19A H 0.4600 0.3623 -0.0410 0.061 Uiso 0.733(8) 1 calc R U P C 1
H19B H 0.4733 0.2398 -0.0012 0.061 Uiso 0.733(8) 1 calc R U P C 1
H19C H 0.5471 0.3654 0.0233 0.061 Uiso 0.733(8) 1 calc R U P C 1
C19B C 0.2340(16) 0.3977(17) -0.0178(6) 0.062(5) Uani 0.267(8) 1 d D U P C 2
H19D H 0.2913 0.4101 -0.0534 0.092 Uiso 0.267(8) 1 calc R U P C 2
H19E H 0.1857 0.4752 -0.0074 0.092 Uiso 0.267(8) 1 calc R U P C 2
H19F H 0.1583 0.3344 -0.0261 0.092 Uiso 0.267(8) 1 calc R U P C 2
C21 C 0.2948(3) 0.3902(2) 0.57649(12) 0.0187(6) Uani 1 1 d . . . . .
C22 C 0.3754(3) 0.4988(3) 0.57199(13) 0.0234(6) Uani 1 1 d . . . . .
H22A H 0.4673 0.4978 0.5531 0.028 Uiso 1 1 calc R U . . .
C23 C 0.1605(3) 0.3933(3) 0.60533(14) 0.0266(6) Uani 1 1 d . . . . .
H23A H 0.1042 0.3198 0.6086 0.032 Uiso 1 1 calc R U . . .
C24 C 0.3230(3) 0.6083(2) 0.59483(13) 0.0230(6) Uani 1 1 d . . . . .
H24A H 0.3778 0.6822 0.5904 0.028 Uiso 1 1 calc R U . . .
C25 C 0.1085(3) 0.5023(3) 0.62925(13) 0.0256(6) Uani 1 1 d . . . . .
H25A H 0.0175 0.5030 0.6489 0.031 Uiso 1 1 calc R U . . .
C26 C 0.1898(3) 0.6107(2) 0.62448(12) 0.0208(6) Uani 1 1 d . . . . .
C27 C 0.1293(3) 0.7252(2) 0.65118(13) 0.0232(6) Uani 1 1 d . . . . .
C28 C 0.1491(4) 0.9435(3) 0.65918(15) 0.0349(7) Uani 1 1 d . . . . .
H28A H 0.0410 0.9459 0.6489 0.042 Uiso 1 1 calc R U . . .
H28B H 0.1956 1.0118 0.6375 0.042 Uiso 1 1 calc R U . . .
C29 C 0.1750(4) 0.9641(3) 0.72593(14) 0.0359(7) Uani 1 1 d . . . . .
H29A H 0.1667 1.0522 0.7348 0.054 Uiso 1 1 calc R U . . .
H29B H 0.2744 0.9350 0.7388 0.054 Uiso 1 1 calc R U . . .
H29C H 0.1005 0.9184 0.7474 0.054 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
N1 C2 1.371(4) . ?
N1 C5 1.377(3) . ?
N1 H1 0.82(2) . ?
N2 C10 1.368(3) . ?
N2 C7 1.374(3) . ?
N2 H2 0.82(2) . ?
O1 C17 1.208(3) . ?
O2 C17 1.340(3) . ?
O2 C18 1.454(4) . ?
O3 C27 1.217(3) . ?
O4 C27 1.345(3) . ?
O4 C28 1.472(3) . ?
C1 C2 1.403(4) . ?
C1 C10 1.409(4) 3_656 ?
C1 C11 1.499(4) . ?
C2 C3 1.444(4) . ?
C3 C4 1.350(4) . ?
C3 H3A 0.9500 . ?
C4 C5 1.443(4) . ?
C4 H4A 0.9500 . ?
C5 C6 1.400(4) . ?
C6 C7 1.397(4) . ?
C6 C21 1.502(4) . ?
C7 C8 1.438(4) . ?
C8 C9 1.355(4) . ?
C8 H8A 0.9500 . ?
C9 C10 1.437(4) . ?
C9 H9A 0.9500 . ?
C10 C1 1.409(4) 3_656 ?
C11 C12 1.389(4) . ?
C11 C13 1.402(4) . ?
C12 C14 1.381(4) . ?
C12 H12A 0.9500 . ?
C13 C15 1.383(4) . ?
C13 H13A 0.9500 . ?
C14 C16 1.395(4) . ?
C14 H14A 0.9500 . ?
C15 C16 1.390(4) . ?
C15 H15A 0.9500 . ?
C16 C17 1.496(4) . ?
C18 C19B 1.333(12) . ?
C18 C19A 1.463(5) . ?
C18 H18A 0.9899 . ?
C18 H18B 0.9902 . ?
C18 H18C 0.9900 . ?
C18 H18D 0.9902 . ?
C19A H19A 0.9800 . ?
C19A H19B 0.9800 . ?
C19A H19C 0.9800 . ?
C19B H19D 0.9800 . ?
C19B H19E 0.9800 . ?
C19B H19F 0.9800 . ?
C21 C22 1.390(4) . ?
C21 C23 1.401(4) . ?
C22 C24 1.386(4) . ?
C22 H22A 0.9500 . ?
C23 C25 1.389(4) . ?
C23 H23A 0.9500 . ?
C24 C26 1.402(4) . ?
C24 H24A 0.9500 . ?
C25 C26 1.393(4) . ?
C25 H25A 0.9500 . ?
C26 C27 1.493(4) . ?
C28 C29 1.513(4) . ?
C28 H28A 0.9900 . ?
C28 H28B 0.9900 . ?
C29 H29A 0.9800 . ?
C29 H29B 0.9800 . ?
C29 H29C 0.9800 . ?

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 N1 C5 107.3(2) . . ?
C2 N1 H1 125(5) . . ?
C5 N1 H1 128(5) . . ?
C10 N2 C7 108.0(2) . . ?
C10 N2 H2 126(5) . . ?
C7 N2 H2 126(5) . . ?
C17 O2 C18 117.2(2) . . ?
C27 O4 C28 115.4(2) . . ?
C2 C1 C10 125.8(2) . 3_656 ?
C2 C1 C11 118.1(2) . . ?
C10 C1 C11 116.1(2) 3_656 . ?
N1 C2 C1 125.7(2) . . ?
N1 C2 C3 109.0(2) . . ?
C1 C2 C3 125.4(2) . . ?
C4 C3 C2 107.5(2) . . ?
C4 C3 H3A 126.3 . . ?
C2 C3 H3A 126.3 . . ?
C3 C4 C5 107.3(2) . . ?
C3 C4 H4A 126.4 . . ?
C5 C4 H4A 126.4 . . ?
N1 C5 C6 125.8(2) . . ?
N1 C5 C4 108.9(2) . . ?
C6 C5 C4 125.2(2) . . ?
C7 C6 C5 125.3(2) . . ?
C7 C6 C21 116.6(2) . . ?
C5 C6 C21 118.0(2) . . ?
N2 C7 C6 127.0(2) . . ?
N2 C7 C8 108.2(2) . . ?
C6 C7 C8 124.8(2) . . ?
C9 C8 C7 107.7(2) . . ?
C9 C8 H8A 126.1 . . ?
C7 C8 H8A 126.1 . . ?
C8 C9 C10 107.2(2) . . ?
C8 C9 H9A 126.4 . . ?
C10 C9 H9A 126.4 . . ?
N2 C10 C1 125.7(2) . 3_656 ?
N2 C10 C9 108.8(2) . . ?
C1 C10 C9 125.5(2) 3_656 . ?
C12 C11 C13 118.8(2) . . ?
C12 C11 C1 121.3(2) . . ?
C13 C11 C1 119.8(2) . . ?
C14 C12 C11 120.9(2) . . ?
C14 C12 H12A 119.6 . . ?
C11 C12 H12A 119.6 . . ?
C15 C13 C11 120.4(2) . . ?
C15 C13 H13A 119.8 . . ?
C11 C13 H13A 119.8 . . ?
C12 C14 C16 120.2(2) . . ?
C12 C14 H14A 119.9 . . ?
C16 C14 H14A 119.9 . . ?
C13 C15 C16 120.3(2) . . ?
C13 C15 H15A 119.8 . . ?
C16 C15 H15A 119.8 . . ?
C15 C16 C14 119.4(2) . . ?
C15 C16 C17 121.3(2) . . ?
C14 C16 C17 119.2(2) . . ?
O1 C17 O2 124.4(3) . . ?
O1 C17 C16 123.5(3) . . ?
O2 C17 C16 112.1(2) . . ?
C19B C18 O2 145.2(8) . . ?
O2 C18 C19A 110.0(3) . . ?
O2 C18 H18A 110.2 . . ?
C19A C18 H18A 109.5 . . ?
O2 C18 H18B 109.4 . . ?
C19A C18 H18B 109.6 . . ?
H18A C18 H18B 108.1 . . ?
C19B C18 H18C 99.6 . . ?
O2 C18 H18C 101.4 . . ?
C19B C18 H18D 100.6 . . ?
O2 C18 H18D 100.7 . . ?
H18C C18 H18D 104.5 . . ?
C18 C19A H19A 109.5 . . ?
C18 C19A H19B 109.5 . . ?
H19A C19A H19B 109.5 . . ?
C18 C19A H19C 109.5 . . ?
H19A C19A H19C 109.5 . . ?
H19B C19A H19C 109.5 . . ?
C18 C19B H19D 109.5 . . ?
C18 C19B H19E 109.5 . . ?
H19D C19B H19E 109.5 . . ?
C18 C19B H19F 109.5 . . ?
H19D C19B H19F 109.5 . . ?
H19E C19B H19F 109.5 . . ?
C22 C21 C23 118.7(2) . . ?
C22 C21 C6 120.3(2) . . ?
C23 C21 C6 121.0(2) . . ?
C24 C22 C21 120.7(2) . . ?
C24 C22 H22A 119.7 . . ?
C21 C22 H22A 119.7 . . ?
C25 C23 C21 121.0(2) . . ?
C25 C23 H23A 119.5 . . ?
C21 C23 H23A 119.5 . . ?
C22 C24 C26 120.5(2) . . ?
C22 C24 H24A 119.8 . . ?
C26 C24 H24A 119.8 . . ?
C23 C25 C26 120.0(2) . . ?
C23 C25 H25A 120.0 . . ?
C26 C25 H25A 120.0 . . ?
C25 C26 C24 119.2(2) . . ?
C25 C26 C27 117.8(2) . . ?
C24 C26 C27 123.0(2) . . ?
O3 C27 O4 123.5(2) . . ?
O3 C27 C26 124.2(2) . . ?
O4 C27 C26 112.3(2) . . ?
O4 C28 C29 113.3(3) . . ?
O4 C28 H28A 108.9 . . ?
C29 C28 H28A 108.9 . . ?
O4 C28 H28B 108.9 . . ?
C29 C28 H28B 108.9 . . ?
H28A C28 H28B 107.7 . . ?
C28 C29 H29A 109.5 . . ?
C28 C29 H29B 109.5 . . ?
H29A C29 H29B 109.5 . . ?
C28 C29 H29C 109.5 . . ?
H29A C29 H29C 109.5 . . ?
H29B C29 H29C 109.5 . . ?

_refine_diff_density_max         0.842
_refine_diff_density_min         -0.389
_refine_diff_density_rms         0.062

_shelxl_version_number           2014-3



####################################################################### 
# 
# 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_orz233a-TiOTCPPEt
_database_code_depnum_ccdc_archive 'CCDC 2058761'
loop_
_audit_author_name
_audit_author_address
'Olivier Roubeau'
;Instituto de Ciencia de Materiales de Aragon (ICMA), CSIC and Universidad de Zaragoza
Spain
;
_audit_update_record             
;
2021-01-26 deposited with the CCDC.	2021-03-10 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C56 H45 N4 O8.50 Ti0.50'
_chemical_formula_sum            'C56 H45 N4 O8.50 Ti0.50'
_chemical_formula_weight         933.91

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'
Ti Ti 0.2776 0.4457 '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                   9.4036(14)
_cell_length_b                   10.8957(13)
_cell_length_c                   22.319(3)
_cell_angle_alpha                90
_cell_angle_beta                 90.524(13)
_cell_angle_gamma                90
_cell_volume                     2286.7(5)
_cell_formula_units_Z            2
_cell_measurement_temperature    295(2)
_cell_measurement_reflns_used    1218
_cell_measurement_theta_min      3.3710
_cell_measurement_theta_max      13.8360

_exptl_crystal_description       rod
_exptl_crystal_colour            violet
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.356
_exptl_crystal_F_000             976
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.220
_exptl_crystal_size_mid          0.060
_exptl_crystal_size_min          0.030
_exptl_absorpt_coefficient_mu    0.171
_shelx_estimated_absorpt_T_min   0.963
_shelx_estimated_absorpt_T_max   0.995
_exptl_absorpt_correction_T_min  0.58288
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.38.41r (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      295(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Sapphire3'
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            Sapphire3
_diffrn_detector_area_resol_mean 16.3990
_diffrn_reflns_number            14032
_diffrn_reflns_av_unetI/netI     0.0664
_diffrn_reflns_av_R_equivalents  0.1029
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_theta_min         3.316
_diffrn_reflns_theta_max         17.219
_diffrn_reflns_theta_full        17.219
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measured_fraction_theta_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_point_group_measured_fraction_full 0.990
_reflns_number_total             1359
_reflns_number_gt                817
_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       'CrysAlisPro 1.171.38.41r (Rigaku OD, 2015)'
_computing_cell_refinement       'CrysAlisPro 1.171.38.41r (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41r (Rigaku OD, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2015)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_refine_special_details          
;
 All non-hydrogens were refined anisotropically, except the two
 components of the disordered ester ethyl group (C18-C19 A and B). The 
 titanyl moeity is disordered by symmetry over two equivalent positions
 on each side of the porphyrin deck. In addition, refinement with
 occupancy >0.7 for the Ti and O sites did not converge properly.
 The occupancy was first refined, and eventually fixed to 0.5
 (taking into account the two positions, i.e. the site occupancy is
 0.25). One of the two unique esther ethyl groups is also disordered
 over two positions, with relative occupancies of respectively 
 0.43:0.57 (C18-C19 A and B). These were refined with restrained 
 distance and displacement parameters. Hydrogens were placed 
 geometrically on their carrier atom and refined with a riding model.
;

_vrf_THETM01_orz233a-TiOTCPPEt   
;
PROBLEM:  The value of sine(theta_max)/wavelength is less than 0.550
            Calculated sin(theta_max)/wavelength =    0.4165
RESPONSE: Although large, crystals were not strongly diffracting. There
was only significant diffraction up to ca. 1.2 angstrom resolution where
the mean I/sigma(I) was already only 1.9. Data were thus cut at 1.20
angstrom. This results in a poor themax, and also ma poor data over
parameters ratio and an overall low bond precision. 
;

_vrf_PLAT088_orz233a-TiOTCPPEt   
;
PROBLEM:  Poor Data / Parameter Ratio ....................       4.19 Note
RESPONSE: Although large, crystals were not strongly diffracting. There
was only significant diffraction up to ca. 1.2 angstrom resolution where
the mean I/sigma(I) was already only 1.9. Data were thus cut at 1.20
angstrom. This results in a poor themax, and also a poor data over
parameters ratio and an overall low bond precision. 
;

_vrf_PLAT341_orz233a-TiOTCPPEt   
;
PROBLEM:  Low Bond Precision on  C-C Bonds ...............    0.02048 Ang. 
RESPONSE: Although large, crystals were not strongly diffracting. There
was only significant diffraction up to ca. 1.2 angstrom resolution where
the mean I/sigma(I) was already only 1.9. Data were thus cut at 1.20
angstrom. This results in a poor themax, and also a poor data over
parameters ratio and an overall low bond precision. 
;

_vrf_PLAT201_orz233a-TiOTCPPEt   
;
PROBLEM:  Isotropic non-H Atoms in Main Residue(s) .......          2 Report
              C18B    C19B
RESPONSE: One of the two unique esther ethyl groups is disordered over 
two positions, and both its components were refined isotropically 
(C18-C19 A and B).
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1217P)²+0.1909P] 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         1359
_refine_ls_number_parameters     324
_refine_ls_number_restraints     7
_refine_ls_R_factor_all          0.1054
_refine_ls_R_factor_gt           0.0672
_refine_ls_wR_factor_ref         0.2071
_refine_ls_wR_factor_gt          0.1724
_refine_ls_goodness_of_fit_ref   1.016
_refine_ls_restrained_S_all      1.041
_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
Ti1 Ti 0.5570(11) 0.0239(9) 0.5025(5) 0.122(4) Uani 0.25 1 d . . P A 2
O1 O 0.715(3) 0.088(2) 0.5142(12) 0.119(9) Uani 0.25 1 d . . P A 2
O2 O 0.2142(9) 0.1348(8) 0.9228(4) 0.127(3) Uani 1 1 d . . . . .
O3 O 0.3417(8) 0.3033(9) 0.9069(3) 0.120(3) Uani 1 1 d . . . . .
O4 O 0.0206(9) 0.7282(7) 0.3267(3) 0.112(3) Uani 1 1 d . . . . .
O5 O 0.2210(9) 0.8161(8) 0.3567(3) 0.131(3) Uani 1 1 d . U . . .
N1 N 0.4017(8) 0.1459(8) 0.5393(6) 0.076(3) Uani 1 1 d . . . . .
H1 H 0.446530 0.084394 0.524422 0.091 Uiso 0.5 1 calc R U P B 1
N2 N 0.4852(9) 0.0802(10) 0.4206(4) 0.077(2) Uani 1 1 d . . . . .
C1 C 0.3969(11) 0.0784(13) 0.6450(7) 0.074(3) Uani 1 1 d . . . . .
C2 C 0.3647(11) 0.1622(13) 0.5993(7) 0.073(3) Uani 1 1 d . . . . .
C3 C 0.2887(11) 0.2770(13) 0.6042(6) 0.082(3) Uani 1 1 d . . . . .
H3A H 0.251334 0.310202 0.639066 0.098 Uiso 1 1 calc R U . . .
C4 C 0.2818(12) 0.3262(10) 0.5501(8) 0.087(4) Uani 1 1 d . . . . .
H4A H 0.237840 0.400332 0.540797 0.104 Uiso 1 1 calc R U . . .
C5 C 0.3519(11) 0.2487(12) 0.5081(8) 0.074(3) Uani 1 1 d . . . . .
C6 C 0.3623(11) 0.2733(12) 0.4476(8) 0.074(4) Uani 1 1 d . . . . .
C7 C 0.4209(11) 0.1957(13) 0.4075(7) 0.070(3) Uani 1 1 d . . . . .
C8 C 0.4336(11) 0.2167(10) 0.3445(8) 0.092(3) Uani 1 1 d . . . . .
H8A H 0.401355 0.286902 0.325040 0.110 Uiso 1 1 calc R U . . .
C9 C 0.4984(12) 0.1217(14) 0.3168(5) 0.090(3) Uani 1 1 d . . . . .
H9A H 0.517251 0.112754 0.276223 0.108 Uiso 1 1 calc R U . . .
C10 C 0.5315(12) 0.0375(12) 0.3651(7) 0.076(3) Uani 1 1 d . . . . .
C11 C 0.3621(16) 0.1124(13) 0.7072(6) 0.077(3) Uani 1 1 d . . . . .
C12 C 0.2640(15) 0.0501(10) 0.7397(9) 0.091(3) Uani 1 1 d . . . . .
H12A H 0.215125 -0.014791 0.721921 0.109 Uiso 1 1 calc R U . . .
C13 C 0.4349(11) 0.2081(12) 0.7340(8) 0.083(3) Uani 1 1 d . . . . .
H13A H 0.501765 0.252291 0.712424 0.100 Uiso 1 1 calc R U . . .
C14 C 0.2352(11) 0.0800(12) 0.7977(8) 0.085(3) Uani 1 1 d . . . . .
H14A H 0.166241 0.037159 0.818727 0.103 Uiso 1 1 calc R U . . .
C15 C 0.4082(15) 0.2377(9) 0.7926(9) 0.086(3) Uani 1 1 d . . . . .
H15A H 0.457918 0.301663 0.810778 0.103 Uiso 1 1 calc R U . . .
C16 C 0.3092(17) 0.1740(15) 0.8246(6) 0.076(3) Uani 1 1 d . . . . .
C17 C 0.2823(12) 0.1967(12) 0.8903(7) 0.084(3) Uani 1 1 d . . . . .
C18A C 0.331(5) 0.317(5) 0.973(3) 0.174(7) Uiso 0.429(14) 1 d D U P C 1
H18A H 0.365881 0.244266 0.993687 0.209 Uiso 0.429(14) 1 calc R U P C 1
H18B H 0.233800 0.332181 0.985115 0.209 Uiso 0.429(14) 1 calc R U P C 1
C19A C 0.429(3) 0.432(3) 0.9882(13) 0.174(7) Uiso 0.429(14) 1 d D U P C 1
H19A H 0.524033 0.415339 0.975606 0.261 Uiso 0.429(14) 1 calc R U P C 1
H19B H 0.428123 0.446527 1.030635 0.261 Uiso 0.429(14) 1 calc R U P C 1
H19C H 0.392643 0.502543 0.967551 0.261 Uiso 0.429(14) 1 calc R U P C 1
C18B C 0.319(4) 0.347(4) 0.969(2) 0.174(7) Uiso 0.571(14) 1 d D U P C 2
H18C H 0.238587 0.305741 0.987485 0.209 Uiso 0.571(14) 1 calc R U P C 2
H18D H 0.303958 0.434884 0.970537 0.209 Uiso 0.571(14) 1 calc R U P C 2
C19B C 0.462(2) 0.310(3) 0.9999(10) 0.174(7) Uiso 0.571(14) 1 d D U P C 2
H19D H 0.476437 0.222645 0.995824 0.261 Uiso 0.571(14) 1 calc R U P C 2
H19E H 0.459800 0.330629 1.041645 0.261 Uiso 0.571(14) 1 calc R U P C 2
H19F H 0.539319 0.352340 0.981134 0.261 Uiso 0.571(14) 1 calc R U P C 2
C21 C 0.3029(18) 0.3939(11) 0.4236(4) 0.073(3) Uani 1 1 d . . . . .
C22 C 0.1708(19) 0.3981(13) 0.3993(6) 0.109(4) Uani 1 1 d . . . . .
H22A H 0.116229 0.326924 0.398292 0.131 Uiso 1 1 calc R U . . .
C23 C 0.3831(12) 0.4981(16) 0.4248(4) 0.093(3) Uani 1 1 d . . . . .
H23A H 0.474525 0.496826 0.441019 0.112 Uiso 1 1 calc R U . . .
C24 C 0.1159(12) 0.5033(17) 0.3765(5) 0.101(4) Uani 1 1 d . . . . .
H24A H 0.024240 0.504214 0.360559 0.121 Uiso 1 1 calc R U . . .
C25 C 0.3278(18) 0.6054(11) 0.4016(5) 0.094(3) Uani 1 1 d . . . . .
H25A H 0.381754 0.676948 0.402915 0.112 Uiso 1 1 calc R U . . .
C26 C 0.1954(18) 0.6077(14) 0.3770(5) 0.081(3) Uani 1 1 d . . . . .
C27 C 0.1328(14) 0.7216(14) 0.3489(5) 0.100(4) Uani 1 1 d . . . . .
C28 C 0.1547(13) 0.9507(11) 0.3409(6) 0.144(5) Uani 1 1 d . . . . .
H28A H 0.054305 0.954044 0.350412 0.173 Uiso 1 1 calc R U . . .
H28B H 0.204091 1.014763 0.362992 0.173 Uiso 1 1 calc R U . . .
C29 C 0.1770(15) 0.9640(11) 0.2757(6) 0.165(5) Uani 1 1 d . . . . .
H29A H 0.166508 1.048620 0.264580 0.248 Uiso 1 1 calc R U . . .
H29B H 0.107959 0.915467 0.254368 0.248 Uiso 1 1 calc R U . . .
H29C H 0.270866 0.936429 0.265868 0.248 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
Ti1 Ti1 1.195(17) 3_656 ?
Ti1 O1 1.66(3) . ?
Ti1 N2 2.037(14) . ?
Ti1 N2 2.099(14) 3_656 ?
Ti1 N1 2.109(13) 3_656 ?
O1 C18B 1.57(5) 4_665 ?
O2 C17 1.183(12) . ?
O3 C17 1.341(11) . ?
O3 C18B 1.49(5) . ?
O3 C18A 1.49(6) . ?
O4 C27 1.164(11) . ?
O5 C27 1.332(11) . ?
O5 C28 1.631(12) . ?
N1 C5 1.397(12) . ?
N1 C2 1.399(10) . ?
N1 H1 0.8600 . ?
N2 C10 1.397(11) . ?
N2 C7 1.425(11) . ?
C1 C2 1.399(12) . ?
C1 C10 1.449(13) 3_656 ?
C1 C11 1.476(13) . ?
C2 C3 1.445(13) . ?
C3 C4 1.322(10) . ?
C3 H3A 0.9300 . ?
C4 C5 1.428(13) . ?
C4 H4A 0.9300 . ?
C5 C6 1.380(13) . ?
C6 C7 1.353(13) . ?
C6 C21 1.523(13) . ?
C7 C8 1.431(13) . ?
C8 C9 1.353(11) . ?
C8 H8A 0.9300 . ?
C9 C10 1.447(12) . ?
C9 H9A 0.9300 . ?
C11 C12 1.361(12) . ?
C11 C13 1.381(11) . ?
C12 C14 1.363(12) . ?
C12 H12A 0.9300 . ?
C13 C15 1.374(11) . ?
C13 H13A 0.9300 . ?
C14 C16 1.374(12) . ?
C14 H14A 0.9300 . ?
C15 C16 1.367(12) . ?
C15 H15A 0.9300 . ?
C16 C17 1.509(14) . ?
C18A C19A 1.58(3) . ?
C18A H18A 0.9700 . ?
C18A H18B 0.9700 . ?
C19A H19A 0.9600 . ?
C19A H19B 0.9600 . ?
C19A H19C 0.9600 . ?
C18B C19B 1.56(3) . ?
C18B H18C 0.9700 . ?
C18B H18D 0.9700 . ?
C19B H19D 0.9600 . ?
C19B H19E 0.9600 . ?
C19B H19F 0.9600 . ?
C21 C22 1.351(12) . ?
C21 C23 1.364(11) . ?
C22 C24 1.355(13) . ?
C22 H22A 0.9300 . ?
C23 C25 1.378(12) . ?
C23 H23A 0.9300 . ?
C24 C26 1.360(12) . ?
C24 H24A 0.9300 . ?
C25 C26 1.357(11) . ?
C25 H25A 0.9300 . ?
C26 C27 1.508(15) . ?
C28 C29 1.480(12) . ?
C28 H28A 0.9700 . ?
C28 H28B 0.9700 . ?
C29 H29A 0.9600 . ?
C29 H29B 0.9600 . ?
C29 H29C 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
Ti1 Ti1 O1 176.2(17) 3_656 . ?
Ti1 Ti1 N2 76.0(11) 3_656 . ?
O1 Ti1 N2 107.6(10) . . ?
N2 Ti1 N2 146.4(5) . 3_656 ?
N2 Ti1 N1 85.9(6) . 3_656 ?
N2 Ti1 N1 85.7(6) 3_656 3_656 ?
C18B O1 Ti1 130(2) 4_665 . ?
C17 O3 C18B 118.2(17) . . ?
C17 O3 C18A 109.4(19) . . ?
C27 O5 C28 115.5(10) . . ?
C5 N1 C2 106.9(10) . . ?
C5 N1 H1 126.6 . . ?
C2 N1 H1 126.6 . . ?
C10 N2 C7 104.3(9) . . ?
C10 N2 Ti1 126.3(9) . . ?
C7 N2 Ti1 125.8(10) . . ?
C10 N2 Ti1 127.5(9) . 3_656 ?
C7 N2 Ti1 124.1(10) . 3_656 ?
C2 C1 C10 123.7(12) . 3_656 ?
C2 C1 C11 118.2(12) . . ?
C10 C1 C11 118.1(13) 3_656 . ?
C1 C2 N1 124.1(13) . . ?
C1 C2 C3 127.9(14) . . ?
N1 C2 C3 108.0(10) . . ?
C4 C3 C2 107.6(10) . . ?
C4 C3 H3A 126.2 . . ?
C2 C3 H3A 126.2 . . ?
C3 C4 C5 109.9(11) . . ?
C3 C4 H4A 125.0 . . ?
C5 C4 H4A 125.0 . . ?
C6 C5 N1 128.1(13) . . ?
C6 C5 C4 124.3(14) . . ?
N1 C5 C4 107.6(12) . . ?
C7 C6 C5 123.9(12) . . ?
C7 C6 C21 117.2(12) . . ?
C5 C6 C21 118.9(11) . . ?
C6 C7 N2 126.3(12) . . ?
C6 C7 C8 126.1(13) . . ?
N2 C7 C8 107.6(10) . . ?
C9 C8 C7 111.7(11) . . ?
C9 C8 H8A 124.2 . . ?
C7 C8 H8A 124.2 . . ?
C8 C9 C10 103.9(10) . . ?
C8 C9 H9A 128.1 . . ?
C10 C9 H9A 128.1 . . ?
N2 C10 C9 112.5(10) . . ?
N2 C10 C1 125.2(12) . 3_656 ?
C9 C10 C1 122.4(15) . 3_656 ?
C12 C11 C13 118.7(11) . . ?
C12 C11 C1 122.3(16) . . ?
C13 C11 C1 118.9(16) . . ?
C11 C12 C14 121.9(11) . . ?
C11 C12 H12A 119.0 . . ?
C14 C12 H12A 119.0 . . ?
C15 C13 C11 119.8(10) . . ?
C15 C13 H13A 120.1 . . ?
C11 C13 H13A 120.1 . . ?
C12 C14 C16 119.3(10) . . ?
C12 C14 H14A 120.3 . . ?
C16 C14 H14A 120.3 . . ?
C16 C15 C13 120.6(10) . . ?
C16 C15 H15A 119.7 . . ?
C13 C15 H15A 119.7 . . ?
C15 C16 C14 119.6(10) . . ?
C15 C16 C17 123.0(17) . . ?
C14 C16 C17 117.3(17) . . ?
O2 C17 O3 123.4(14) . . ?
O2 C17 C16 126.8(13) . . ?
O3 C17 C16 109.7(13) . . ?
O3 C18A C19A 104(3) . . ?
O3 C18A H18A 110.9 . . ?
C19A C18A H18A 110.9 . . ?
O3 C18A H18B 110.9 . . ?
C19A C18A H18B 110.9 . . ?
H18A C18A H18B 108.9 . . ?
C18A C19A H19A 109.5 . . ?
C18A C19A H19B 109.5 . . ?
H19A C19A H19B 109.5 . . ?
C18A C19A H19C 109.5 . . ?
H19A C19A H19C 109.5 . . ?
H19B C19A H19C 109.5 . . ?
O3 C18B C19B 101(3) . . ?
O3 C18B H18C 111.5 . . ?
C19B C18B H18C 111.5 . . ?
O3 C18B H18D 111.5 . . ?
C19B C18B H18D 111.5 . . ?
H18C C18B H18D 109.3 . . ?
C18B C19B H19D 109.5 . . ?
C18B C19B H19E 109.5 . . ?
H19D C19B H19E 109.5 . . ?
C18B C19B H19F 109.5 . . ?
H19D C19B H19F 109.5 . . ?
H19E C19B H19F 109.5 . . ?
C22 C21 C23 119.1(9) . . ?
C22 C21 C6 120.2(14) . . ?
C23 C21 C6 120.7(14) . . ?
C21 C22 C24 121.7(10) . . ?
C21 C22 H22A 119.2 . . ?
C24 C22 H22A 119.2 . . ?
C21 C23 C25 119.5(9) . . ?
C21 C23 H23A 120.2 . . ?
C25 C23 H23A 120.2 . . ?
C22 C24 C26 119.8(11) . . ?
C22 C24 H24A 120.1 . . ?
C26 C24 H24A 120.1 . . ?
C26 C25 C23 120.6(10) . . ?
C26 C25 H25A 119.7 . . ?
C23 C25 H25A 119.7 . . ?
C25 C26 C24 119.3(10) . . ?
C25 C26 C27 122.4(14) . . ?
C24 C26 C27 118.2(15) . . ?
O4 C27 O5 124.7(14) . . ?
O4 C27 C26 125.2(12) . . ?
O5 C27 C26 110.0(11) . . ?
C29 C28 O5 104.0(10) . . ?
C29 C28 H28A 110.9 . . ?
O5 C28 H28A 110.9 . . ?
C29 C28 H28B 110.9 . . ?
O5 C28 H28B 110.9 . . ?
H28A C28 H28B 109.0 . . ?
C28 C29 H29A 109.5 . . ?
C28 C29 H29B 109.5 . . ?
H29A C29 H29B 109.5 . . ?
C28 C29 H29C 109.5 . . ?
H29A C29 H29C 109.5 . . ?
H29B C29 H29C 109.5 . . ?

_refine_diff_density_max         0.152
_refine_diff_density_min         -0.187
_refine_diff_density_rms         0.043



####################################################################### 
# 
# 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_ORZ178-VOTCPPEt-150K
_database_code_depnum_ccdc_archive 'CCDC 2058760'
loop_
_audit_author_name
_audit_author_address
'Olivier Roubeau'
;Instituto de Ciencia de Materiales de Aragon (ICMA), CSIC and Universidad de Zaragoza
Spain
;
_audit_update_record             
;
2021-01-26 deposited with the CCDC.	2021-03-10 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C56 H44 N4 O9 V'
_chemical_formula_sum            'C56 H44 N4 O9 V'
_chemical_formula_weight         967.89

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                   9.3937(6)
_cell_length_b                   10.8559(6)
_cell_length_c                   22.317(2)
_cell_angle_alpha                90
_cell_angle_beta                 93.508(8)
_cell_angle_gamma                90
_cell_volume                     2271.6(3)
_cell_formula_units_Z            2
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    3348
_cell_measurement_theta_min      4.05
_cell_measurement_theta_max      26.21

_exptl_crystal_description       block
_exptl_crystal_colour            violet
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.415
_exptl_crystal_F_000             1006
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.880
_exptl_crystal_size_mid          0.470
_exptl_crystal_size_min          0.190
_exptl_absorpt_coefficient_mu    0.285
_shelx_estimated_absorpt_T_min   0.787
_shelx_estimated_absorpt_T_max   0.948
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.783
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.38.41r (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_oxdiff_exptl_absorpt_empirical_full_min 0.659
_oxdiff_exptl_absorpt_empirical_full_max 1.269
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      150(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Sapphire3'
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            Sapphire3
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean 16.3990
_diffrn_reflns_number            16887
_diffrn_reflns_av_unetI/netI     0.0434
_diffrn_reflns_av_R_equivalents  0.0418
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_theta_min         3.324
_diffrn_reflns_theta_max         25.026
_diffrn_reflns_theta_full        25.025
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             3997
_reflns_number_gt                2786
_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       'CrysAlisPro 1.171.38.41r (Rigaku OD, 2015)'
_computing_cell_refinement       'CrysAlisPro 1.171.38.41r (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41r (Rigaku OD, 2015)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_computing_structure_refinement  'SHELXL-2014 (Sheldrick, 2015)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_refine_special_details          
;
 All non-hydrogens were refined anisotropically. The vanadyl
 moeity is disordered by symmetry over two equivalent positions
 on each side of the porphyrin deck. Both unique ester functions
 are also disordered over two positions, with relative occupancies
 of respectively 0.68:0.32 (O3:O3B) and 0.82:0.18 (O5:O5B). The 
 disordered ester moeities were refined with distance and 
 displacement parameters restraints. Hydrogens were placed 
 geometrically on their carrier atom and refined with a riding 
 model.
;

_vrf_PLAT430_ORZ178-VOTCPPEt-150K 
;
PROBLEM:  Short Inter D...A Contact  O1     ..  O5      ..       2.74 Ang.
RESPONSE: This short contact involves one of the components of
one of the ester groups (O5) and the O1 atom which is
disordered over two equivalent positions by symmetry. The
short contact is therefore likely not present as the two atoms
can pertain to different parts of the disorder model.
;

_vrf_PLAT413_ORZ178-VOTCPPEt-150K 
;
PROBLEM:  Short Inter XH3 .. XHn     H15A   ..  H29D    ..       1.97 Ang.
RESPONSE: This short contact involves an hydrogen
atom from one of the partial disordered ester groups (H39D)
and is therefore likely due to ill-defined calculated H position
due to this disorder.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0941P)²+6.7889P] 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         3997
_refine_ls_number_parameters     385
_refine_ls_number_restraints     156
_refine_ls_R_factor_all          0.1210
_refine_ls_R_factor_gt           0.0895
_refine_ls_wR_factor_ref         0.2496
_refine_ls_wR_factor_gt          0.2274
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_restrained_S_all      1.018
_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 0.4562(2) 0.01958(18) 0.49005(12) 0.0729(7) Uani 0.5 1 d . . P . .
O1 O 0.3084(10) 0.0798(8) 0.4718(5) 0.095(3) Uani 0.5 1 d . . P . .
O2 O 0.7766(5) 0.1227(4) 0.0804(2) 0.0772(13) Uani 1 1 d . . . . .
O3 O 0.6608(8) 0.3082(7) 0.0948(3) 0.0611(17) Uani 0.684(10) 1 d D U P A 1
O3B O 0.6144(19) 0.2568(17) 0.0884(7) 0.067(3) Uani 0.316(10) 1 d D U P A 2
O4 O 0.9819(3) 0.7443(3) 0.67422(16) 0.0506(9) Uani 1 1 d . . . . .
O5 O 0.7777(5) 0.8341(4) 0.6401(3) 0.0489(15) Uani 0.820(9) 1 d D U P B 1
O5B O 0.755(2) 0.8051(18) 0.6726(12) 0.046(3) Uani 0.180(9) 1 d D U P B 2
N1 N 0.6000(4) 0.1451(3) 0.46370(19) 0.0405(9) Uani 1 1 d . . . . .
N2 N 0.4920(4) -0.0861(3) 0.41946(18) 0.0405(10) Uani 1 1 d . . . . .
C1 C 0.6072(5) 0.0721(4) 0.3580(2) 0.0423(11) Uani 1 1 d . . . . .
C2 C 0.6375(5) 0.1578(4) 0.4052(2) 0.0434(12) Uani 1 1 d . . . . .
C3 C 0.7123(5) 0.2718(4) 0.3980(3) 0.0470(12) Uani 1 1 d . . . . .
H3A H 0.7502 0.3016 0.3622 0.056 Uiso 1 1 calc R U . . .
C4 C 0.7183(5) 0.3286(4) 0.4521(2) 0.0484(13) Uani 1 1 d . . . . .
H4A H 0.7610 0.4063 0.4612 0.058 Uiso 1 1 calc R U . . .
C5 C 0.6490(5) 0.2513(4) 0.4933(2) 0.0418(12) Uani 1 1 d . . . . .
C6 C 0.6345(5) 0.2774(4) 0.5535(2) 0.0428(12) Uani 1 1 d . . . . .
C7 C 0.5697(5) 0.1993(4) 0.5943(2) 0.0429(12) Uani 1 1 d . . . . .
C8 C 0.5594(5) 0.2246(4) 0.6567(2) 0.0497(13) Uani 1 1 d . . . . .
H8A H 0.5932 0.2967 0.6771 0.060 Uiso 1 1 calc R U . . .
C9 C 0.4934(5) 0.1286(4) 0.6818(2) 0.0467(12) Uani 1 1 d . . . . .
H9A H 0.4727 0.1196 0.7227 0.056 Uiso 1 1 calc R U . . .
C10 C 0.5392(5) -0.0422(4) 0.3664(2) 0.0440(12) Uani 1 1 d . . . . .
C11 C 0.6414(5) 0.1069(4) 0.2968(2) 0.0444(12) Uani 1 1 d . . . . .
C12 C 0.7433(5) 0.0429(4) 0.2651(3) 0.0520(14) Uani 1 1 d . . . . .
H12A H 0.7967 -0.0214 0.2846 0.062 Uiso 1 1 calc R U . . .
C13 C 0.5682(5) 0.2029(4) 0.2673(2) 0.0464(12) Uani 1 1 d . . . . .
H13A H 0.5006 0.2491 0.2879 0.056 Uiso 1 1 calc R U . . .
C14 C 0.7671(5) 0.0716(5) 0.2067(3) 0.0522(14) Uani 1 1 d . . . . .
H14A H 0.8361 0.0263 0.1863 0.063 Uiso 1 1 calc R U . . .
C15 C 0.5924(5) 0.2322(4) 0.2083(3) 0.0481(12) Uani 1 1 d . . . . .
H15A H 0.5410 0.2981 0.1891 0.058 Uiso 1 1 calc R U . . .
C16 C 0.6913(5) 0.1664(4) 0.1765(2) 0.0489(13) Uani 1 1 d . . . . .
C17 C 0.7111(6) 0.1901(6) 0.1122(3) 0.0607(15) Uani 1 1 d . . . . .
C18 C 0.6699(10) 0.3395(10) 0.0321(4) 0.075(2) Uani 0.684(10) 1 d D U P A 1
H18A H 0.7527 0.2975 0.0158 0.090 Uiso 0.684(10) 1 calc R U P A 1
H18B H 0.6829 0.4295 0.0278 0.090 Uiso 0.684(10) 1 calc R U P A 1
C19 C 0.5358(15) 0.3000(16) -0.0018(6) 0.105(4) Uani 0.684(10) 1 d D U P A 1
H19A H 0.5396 0.3235 -0.0441 0.157 Uiso 0.684(10) 1 calc R U P A 1
H19B H 0.4540 0.3402 0.0152 0.157 Uiso 0.684(10) 1 calc R U P A 1
H19C H 0.5256 0.2104 0.0012 0.157 Uiso 0.684(10) 1 calc R U P A 1
C18B C 0.597(3) 0.2520(19) 0.0228(8) 0.078(3) Uani 0.316(10) 1 d D U P A 2
H18C H 0.5357 0.1823 0.0090 0.094 Uiso 0.316(10) 1 calc R U P A 2
H18D H 0.6906 0.2450 0.0047 0.094 Uiso 0.316(10) 1 calc R U P A 2
C19B C 0.526(3) 0.375(2) 0.0080(13) 0.094(6) Uani 0.316(10) 1 d D U P A 2
H19D H 0.5066 0.3818 -0.0355 0.142 Uiso 0.316(10) 1 calc R U P A 2
H19E H 0.5902 0.4422 0.0218 0.142 Uiso 0.316(10) 1 calc R U P A 2
H19F H 0.4369 0.3810 0.0281 0.142 Uiso 0.316(10) 1 calc R U P A 2
C21 C 0.6918(5) 0.3972(4) 0.5779(2) 0.0412(11) Uani 1 1 d . . . . .
C22 C 0.8295(5) 0.4059(4) 0.6037(3) 0.0604(16) Uani 1 1 d . . . . .
H22A H 0.8884 0.3347 0.6052 0.072 Uiso 1 1 calc R U . . .
C23 C 0.6089(5) 0.5023(4) 0.5771(3) 0.0548(14) Uani 1 1 d . . . . .
H23A H 0.5134 0.4991 0.5605 0.066 Uiso 1 1 calc R U . . .
C24 C 0.8832(5) 0.5145(4) 0.6270(3) 0.0566(15) Uani 1 1 d . . . . .
H24A H 0.9780 0.5175 0.6444 0.068 Uiso 1 1 calc R U . . .
C25 C 0.6634(5) 0.6119(4) 0.6000(3) 0.0522(14) Uani 1 1 d . . . . .
H25A H 0.6052 0.6836 0.5982 0.063 Uiso 1 1 calc R U . . .
C26 C 0.8003(4) 0.6190(4) 0.6253(2) 0.0366(10) Uani 1 1 d . . . . .
C27 C 0.8645(5) 0.7355(4) 0.6511(2) 0.0402(11) Uani 1 1 d . . . . .
C28 C 0.8336(8) 0.9552(6) 0.6583(3) 0.0447(15) Uani 0.820(9) 1 d D U P B 1
H28A H 0.7793 1.0197 0.6354 0.054 Uiso 0.820(9) 1 calc R U P B 1
H28B H 0.9345 0.9612 0.6482 0.054 Uiso 0.820(9) 1 calc R U P B 1
C29 C 0.8242(7) 0.9786(6) 0.7244(3) 0.0524(16) Uani 0.820(9) 1 d D U P B 1
H29A H 0.8423 1.0659 0.7329 0.079 Uiso 0.820(9) 1 calc R U P B 1
H29B H 0.8955 0.9283 0.7470 0.079 Uiso 0.820(9) 1 calc R U P B 1
H29C H 0.7287 0.9567 0.7362 0.079 Uiso 0.820(9) 1 calc R U P B 1
C28B C 0.801(3) 0.922(2) 0.7003(14) 0.049(3) Uani 0.180(9) 1 d D U P B 2
H28C H 0.8785 0.9064 0.7315 0.059 Uiso 0.180(9) 1 calc R U P B 2
H28D H 0.7203 0.9600 0.7200 0.059 Uiso 0.180(9) 1 calc R U P B 2
C29B C 0.853(4) 1.009(3) 0.6544(15) 0.055(6) Uani 0.180(9) 1 d D U P B 2
H29D H 0.8797 1.0879 0.6737 0.083 Uiso 0.180(9) 1 calc R U P B 2
H29E H 0.7774 1.0234 0.6230 0.083 Uiso 0.180(9) 1 calc R U P B 2
H29F H 0.9366 0.9740 0.6364 0.083 Uiso 0.180(9) 1 calc R U P B 2


_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 V1 1.004(4) 3_656 ?
V1 O1 1.566(9) . ?
V1 N2 1.994(4) . ?
V1 N1 2.031(4) . ?
V1 N1 2.146(4) 3_656 ?
V1 N2 2.172(5) 3_656 ?
O2 C17 1.212(7) . ?
O3 C17 1.412(10) . ?
O3 C18 1.450(9) . ?
O3B C17 1.254(18) . ?
O3B C18B 1.464(15) . ?
O4 C27 1.192(5) . ?
O5 C27 1.360(6) . ?
O5 C28 1.464(7) . ?
O5B C27 1.39(2) . ?
O5B C28B 1.466(16) . ?
N1 C2 1.380(7) . ?
N1 C5 1.392(5) . ?
N1 V1 2.146(4) 3_656 ?
N2 C10 1.374(6) . ?
N2 C7 1.385(5) 3_656 ?
N2 V1 2.172(5) 3_656 ?
C1 C10 1.413(6) . ?
C1 C2 1.420(7) . ?
C1 C11 1.472(7) . ?
C2 C3 1.437(6) . ?
C3 C4 1.354(7) . ?
C3 H3A 0.9500 . ?
C4 C5 1.430(7) . ?
C4 H4A 0.9500 . ?
C5 C6 1.388(7) . ?
C6 C7 1.409(7) . ?
C6 C21 1.498(6) . ?
C7 N2 1.385(5) 3_656 ?
C7 C8 1.428(7) . ?
C8 C9 1.352(7) . ?
C8 H8A 0.9500 . ?
C9 C10 1.446(7) 3_656 ?
C9 H9A 0.9500 . ?
C10 C9 1.446(7) 3_656 ?
C11 C13 1.391(7) . ?
C11 C12 1.408(7) . ?
C12 C14 1.372(8) . ?
C12 H12A 0.9500 . ?
C13 C15 1.387(7) . ?
C13 H13A 0.9500 . ?
C14 C16 1.400(7) . ?
C14 H14A 0.9500 . ?
C15 C16 1.398(7) . ?
C15 H15A 0.9500 . ?
C16 C17 1.482(8) . ?
C18 C19 1.491(12) . ?
C18 H18A 0.9900 . ?
C18 H18B 0.9900 . ?
C19 H19A 0.9800 . ?
C19 H19B 0.9800 . ?
C19 H19C 0.9800 . ?
C18B C19B 1.521(17) . ?
C18B H18C 0.9900 . ?
C18B H18D 0.9900 . ?
C19B H19D 0.9800 . ?
C19B H19E 0.9800 . ?
C19B H19F 0.9800 . ?
C21 C23 1.380(6) . ?
C21 C22 1.386(6) . ?
C22 C24 1.372(6) . ?
C22 H22A 0.9500 . ?
C23 C25 1.381(6) . ?
C23 H23A 0.9500 . ?
C24 C26 1.375(6) . ?
C24 H24A 0.9500 . ?
C25 C26 1.375(6) . ?
C25 H25A 0.9500 . ?
C26 C27 1.500(6) . ?
C28 C29 1.504(8) . ?
C28 H28A 0.9900 . ?
C28 H28B 0.9900 . ?
C29 H29A 0.9800 . ?
C29 H29B 0.9800 . ?
C29 H29C 0.9800 . ?
C28B C29B 1.500(17) . ?
C28B H28C 0.9900 . ?
C28B H28D 0.9900 . ?
C29B H29D 0.9800 . ?
C29B H29E 0.9800 . ?
C29B H29F 0.9800 . ?

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
V1 V1 O1 168.6(6) 3_656 . ?
V1 V1 N2 86.1(3) 3_656 . ?
O1 V1 N2 103.0(4) . . ?
V1 V1 N1 82.6(3) 3_656 . ?
O1 V1 N1 103.9(4) . . ?
N2 V1 N1 90.58(19) . . ?
V1 V1 N1 69.8(3) 3_656 3_656 ?
O1 V1 N1 103.4(4) . 3_656 ?
N2 V1 N1 87.65(17) . 3_656 ?
N1 V1 N1 152.35(11) . 3_656 ?
V1 V1 N2 66.4(3) 3_656 3_656 ?
O1 V1 N2 104.3(4) . 3_656 ?
N2 V1 N2 152.52(11) . 3_656 ?
N1 V1 N2 86.05(17) . 3_656 ?
N1 V1 N2 82.97(17) 3_656 3_656 ?
C17 O3 C18 116.1(7) . . ?
C17 O3B C18B 115.8(15) . . ?
C27 O5 C28 117.1(4) . . ?
C27 O5B C28B 114(2) . . ?
C2 N1 C5 105.7(4) . . ?
C2 N1 V1 123.6(3) . . ?
C5 N1 V1 128.6(4) . . ?
C2 N1 V1 128.5(3) . 3_656 ?
C5 N1 V1 123.1(3) . 3_656 ?
V1 N1 V1 27.65(11) . 3_656 ?
C10 N2 C7 105.6(4) . 3_656 ?
C10 N2 V1 124.0(3) . . ?
C7 N2 V1 126.7(3) 3_656 . ?
C10 N2 V1 128.3(3) . 3_656 ?
C7 N2 V1 124.6(3) 3_656 3_656 ?
V1 N2 V1 27.48(11) . 3_656 ?
C10 C1 C2 123.3(5) . . ?
C10 C1 C11 118.3(4) . . ?
C2 C1 C11 118.3(4) . . ?
N1 C2 C1 125.8(4) . . ?
N1 C2 C3 110.3(4) . . ?
C1 C2 C3 124.0(5) . . ?
C4 C3 C2 106.7(5) . . ?
C4 C3 H3A 126.7 . . ?
C2 C3 H3A 126.7 . . ?
C3 C4 C5 108.0(4) . . ?
C3 C4 H4A 126.0 . . ?
C5 C4 H4A 126.0 . . ?
C6 C5 N1 125.4(4) . . ?
C6 C5 C4 125.3(4) . . ?
N1 C5 C4 109.4(4) . . ?
C5 C6 C7 125.1(4) . . ?
C5 C6 C21 118.4(4) . . ?
C7 C6 C21 116.5(5) . . ?
N2 C7 C6 125.6(5) 3_656 . ?
N2 C7 C8 109.6(4) 3_656 . ?
C6 C7 C8 124.9(4) . . ?
C9 C8 C7 108.4(4) . . ?
C9 C8 H8A 125.8 . . ?
C7 C8 H8A 125.8 . . ?
C8 C9 C10 105.9(5) . 3_656 ?
C8 C9 H9A 127.1 . . ?
C10 C9 H9A 127.1 3_656 . ?
N2 C10 C1 126.2(4) . . ?
N2 C10 C9 110.6(4) . 3_656 ?
C1 C10 C9 123.2(5) . 3_656 ?
C13 C11 C12 117.6(5) . . ?
C13 C11 C1 120.1(4) . . ?
C12 C11 C1 122.2(4) . . ?
C14 C12 C11 121.4(5) . . ?
C14 C12 H12A 119.3 . . ?
C11 C12 H12A 119.3 . . ?
C15 C13 C11 121.1(5) . . ?
C15 C13 H13A 119.5 . . ?
C11 C13 H13A 119.5 . . ?
C12 C14 C16 121.0(5) . . ?
C12 C14 H14A 119.5 . . ?
C16 C14 H14A 119.5 . . ?
C13 C15 C16 121.1(5) . . ?
C13 C15 H15A 119.5 . . ?
C16 C15 H15A 119.5 . . ?
C14 C16 C15 117.8(5) . . ?
C14 C16 C17 120.2(5) . . ?
C15 C16 C17 121.9(5) . . ?
O2 C17 O3B 118.8(9) . . ?
O2 C17 O3 124.1(6) . . ?
O2 C17 C16 124.1(6) . . ?
O3B C17 C16 112.3(9) . . ?
O3 C17 C16 111.3(5) . . ?
O3 C18 C19 108.9(9) . . ?
O3 C18 H18A 109.9 . . ?
C19 C18 H18A 109.9 . . ?
O3 C18 H18B 109.9 . . ?
C19 C18 H18B 109.9 . . ?
H18A C18 H18B 108.3 . . ?
C18 C19 H19A 109.5 . . ?
C18 C19 H19B 109.5 . . ?
H19A C19 H19B 109.5 . . ?
C18 C19 H19C 109.5 . . ?
H19A C19 H19C 109.5 . . ?
H19B C19 H19C 109.5 . . ?
O3B C18B C19B 101.9(18) . . ?
O3B C18B H18C 111.4 . . ?
C19B C18B H18C 111.4 . . ?
O3B C18B H18D 111.4 . . ?
C19B C18B H18D 111.4 . . ?
H18C C18B H18D 109.3 . . ?
C18B C19B H19D 109.5 . . ?
C18B C19B H19E 109.5 . . ?
H19D C19B H19E 109.5 . . ?
C18B C19B H19F 109.5 . . ?
H19D C19B H19F 109.5 . . ?
H19E C19B H19F 109.5 . . ?
C23 C21 C22 117.5(4) . . ?
C23 C21 C6 121.5(4) . . ?
C22 C21 C6 121.0(4) . . ?
C24 C22 C21 121.8(4) . . ?
C24 C22 H22A 119.1 . . ?
C21 C22 H22A 119.1 . . ?
C21 C23 C25 120.7(4) . . ?
C21 C23 H23A 119.6 . . ?
C25 C23 H23A 119.6 . . ?
C22 C24 C26 120.3(4) . . ?
C22 C24 H24A 119.9 . . ?
C26 C24 H24A 119.9 . . ?
C26 C25 C23 121.1(4) . . ?
C26 C25 H25A 119.4 . . ?
C23 C25 H25A 119.4 . . ?
C25 C26 C24 118.6(4) . . ?
C25 C26 C27 123.3(4) . . ?
C24 C26 C27 118.1(4) . . ?
O4 C27 O5 123.0(4) . . ?
O4 C27 O5B 119.6(9) . . ?
O4 C27 C26 125.0(4) . . ?
O5 C27 C26 111.8(4) . . ?
O5B C27 C26 107.6(9) . . ?
O5 C28 C29 112.4(7) . . ?
O5 C28 H28A 109.1 . . ?
C29 C28 H28A 109.1 . . ?
O5 C28 H28B 109.1 . . ?
C29 C28 H28B 109.1 . . ?
H28A C28 H28B 107.9 . . ?
C28 C29 H29A 109.5 . . ?
C28 C29 H29B 109.5 . . ?
H29A C29 H29B 109.5 . . ?
C28 C29 H29C 109.5 . . ?
H29A C29 H29C 109.5 . . ?
H29B C29 H29C 109.5 . . ?
O5B C28B C29B 111(3) . . ?
O5B C28B H28C 109.4 . . ?
C29B C28B H28C 109.4 . . ?
O5B C28B H28D 109.4 . . ?
C29B C28B H28D 109.4 . . ?
H28C C28B H28D 108.0 . . ?
C28B C29B H29D 109.5 . . ?
C28B C29B H29E 109.5 . . ?
H29D C29B H29E 109.5 . . ?
C28B C29B H29F 109.5 . . ?
H29D C29B H29F 109.5 . . ?
H29E C29B H29F 109.5 . . ?

_refine_diff_density_max         0.359
_refine_diff_density_min         -1.111
_refine_diff_density_rms         0.091

_shelxl_version_number           2014-3



_exptl_crystal_preparation       'Magnetic properties'
