# Electronic Supplementary Material (ESI) for ChemComm.
# This journal is © The Royal Society of Chemistry 2016

####################################################################### 
# 
# 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_shelx
_database_code_depnum_ccdc_archive 'CCDC 1439012'
_audit_update_record             
;
2016-07-20 deposited with the CCDC.
2016-07-21 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          566
_chemical_formula_moiety         'C44 H60 N4 O4 Zr, C1 H2 Cl2'
_chemical_formula_sum            'C45 H62 Cl2 N4 O4 Zr'
_chemical_formula_weight         885.10

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'
Zr Zr -2.9673 0.5597 '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                   12.9667(6)
_cell_length_b                   18.0916(8)
_cell_length_c                   18.8976(9)
_cell_angle_alpha                90
_cell_angle_beta                 95.342(4)
_cell_angle_gamma                90
_cell_volume                     4413.9(4)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    32141
_cell_measurement_theta_min      1.83
_cell_measurement_theta_max      27.20

_exptl_crystal_description       block
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.332
_exptl_crystal_F_000             1864
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.400
_exptl_crystal_size_mid          0.300
_exptl_crystal_size_min          0.200
_exptl_absorpt_coefficient_mu    0.416
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_correction_T_min  0.6603
_exptl_absorpt_correction_T_max  0.9487
_exptl_absorpt_process_details   'STOE X-RED32'

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   
'sealed X-ray tube, 12 x 0.4 mm long-fine focus'
_diffrn_measurement_device_type  'STOE IPDS 2T'
_diffrn_measurement_method       'rotation method'
_diffrn_detector_area_resol_mean 6.67
_diffrn_reflns_number            52900
_diffrn_reflns_av_unetI/netI     0.0587
_diffrn_reflns_av_R_equivalents  0.1086
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_theta_min         1.561
_diffrn_reflns_theta_max         26.834
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             9388
_reflns_number_gt                7847
_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       'STOE X-AREA'
_computing_cell_refinement       'STOE X-AREA'
_computing_data_reduction        'STOE X-RED'
_computing_structure_solution    'SHELXS-2013 (Sheldrick, 2013)'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_molecular_graphics    'ORTEP-3 for Windows (Farrugia, 2012)'
_computing_publication_material  'WinGX publication routines (Farrugia, 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)+(0.0634P)²+5.9952P] 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         9388
_refine_ls_number_parameters     517
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0581
_refine_ls_R_factor_gt           0.0468
_refine_ls_wR_factor_ref         0.1306
_refine_ls_wR_factor_gt          0.1235
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_restrained_S_all      1.056
_refine_ls_shift/su_max          0.002
_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
C1 C 0.9659(2) 1.09085(14) 0.79413(15) 0.0170(5) Uani 1 1 d . . . . .
C2 C 0.9779(2) 1.13916(15) 0.85265(15) 0.0192(5) Uani 1 1 d . . . . .
C3 C 1.0471(2) 1.19789(15) 0.85156(16) 0.0218(6) Uani 1 1 d . . . . .
H3A H 1.0564 1.2294 0.8919 0.026 Uiso 1 1 calc R U . . .
C4 C 1.1033(2) 1.21242(15) 0.79393(16) 0.0233(6) Uani 1 1 d . . . . .
C5 C 1.0889(2) 1.16459(15) 0.73620(16) 0.0214(6) Uani 1 1 d . . . . .
H5A H 1.1254 1.1735 0.6958 0.026 Uiso 1 1 calc R U . . .
C6 C 1.0227(2) 1.10419(15) 0.73574(15) 0.0189(5) Uani 1 1 d . . . . .
C7 C 1.0181(2) 1.04963(15) 0.67523(15) 0.0207(6) Uani 1 1 d . . . . .
H7A H 0.9499 1.0539 0.6472 0.025 Uiso 1 1 calc R U . . .
H7B H 1.0722 1.0623 0.6436 0.025 Uiso 1 1 calc R U . . .
C8 C 0.9170(2) 1.12739(17) 0.91590(15) 0.0245(6) Uani 1 1 d . . . . .
H8A H 0.9143 1.0745 0.9266 0.029 Uiso 1 1 calc R U . . .
H8B H 0.8465 1.1463 0.9051 0.029 Uiso 1 1 calc R U . . .
H8C H 0.9507 1.1538 0.9571 0.029 Uiso 1 1 calc R U . . .
C9 C 1.1797(3) 1.27496(17) 0.79513(19) 0.0305(7) Uani 1 1 d . . . . .
H9A H 1.1928 1.2938 0.8437 0.037 Uiso 1 1 calc R U . . .
H9B H 1.1513 1.3147 0.7638 0.037 Uiso 1 1 calc R U . . .
H9C H 1.2447 1.2572 0.7786 0.037 Uiso 1 1 calc R U . . .
C10 C 1.0486(2) 0.92656(17) 0.63649(16) 0.0252(6) Uani 1 1 d . . . . .
H10A H 1.1077 0.9458 0.6134 0.030 Uiso 1 1 calc R U . . .
H10B H 0.9861 0.9287 0.6031 0.030 Uiso 1 1 calc R U . . .
H10C H 1.0621 0.8752 0.6510 0.030 Uiso 1 1 calc R U . . .
C11 C 1.1272(2) 0.96592(15) 0.75036(15) 0.0206(6) Uani 1 1 d . . . . .
H11A H 1.1309 1.0091 0.7826 0.025 Uiso 1 1 calc R U . . .
H11B H 1.1894 0.9666 0.7237 0.025 Uiso 1 1 calc R U . . .
C12 C 1.1266(2) 0.89608(16) 0.79361(16) 0.0216(6) Uani 1 1 d . . . . .
H12A H 1.1280 0.8528 0.7617 0.026 Uiso 1 1 calc R U . . .
H12B H 1.1896 0.8944 0.8275 0.026 Uiso 1 1 calc R U . . .
C13 C 1.0494(2) 0.94081(17) 0.89637(15) 0.0242(6) Uani 1 1 d . . . . .
H13C H 0.9876 0.9392 0.9225 0.029 Uiso 1 1 calc R U . . .
H13B H 1.0612 0.9917 0.8812 0.029 Uiso 1 1 calc R U . . .
H13A H 1.1096 0.9237 0.9272 0.029 Uiso 1 1 calc R U . . .
C14 C 1.0227(2) 0.81535(16) 0.85972(16) 0.0231(6) Uani 1 1 d . . . . .
H14A H 0.9561 0.8113 0.8812 0.028 Uiso 1 1 calc R U . . .
H14B H 1.0791 0.8054 0.8975 0.028 Uiso 1 1 calc R U . . .
C15 C 1.0256(2) 0.75779(16) 0.80266(16) 0.0219(6) Uani 1 1 d . . . . .
C16 C 1.0846(2) 0.69434(16) 0.81665(19) 0.0272(6) Uani 1 1 d . . . . .
H16A H 1.1186 0.6872 0.8629 0.033 Uiso 1 1 calc R U . . .
C17 C 1.0953(2) 0.64111(17) 0.7649(2) 0.0307(7) Uani 1 1 d . . . . .
C18 C 1.0467(2) 0.65420(16) 0.69764(19) 0.0293(7) Uani 1 1 d . . . . .
H18A H 1.0555 0.6193 0.6611 0.035 Uiso 1 1 calc R U . . .
C19 C 0.9854(2) 0.71637(16) 0.68121(17) 0.0246(6) Uani 1 1 d . . . . .
C20 C 0.9733(2) 0.76888(15) 0.73459(16) 0.0207(6) Uani 1 1 d . . . . .
C21 C 1.1588(3) 0.57267(19) 0.7811(3) 0.0477(10) Uani 1 1 d . . . . .
H21A H 1.1219 0.5397 0.8112 0.057 Uiso 1 1 calc R U . . .
H21B H 1.2257 0.5864 0.8059 0.057 Uiso 1 1 calc R U . . .
H21C H 1.1700 0.5473 0.7366 0.057 Uiso 1 1 calc R U . . .
C22 C 0.9319(3) 0.72643(18) 0.60786(18) 0.0320(7) Uani 1 1 d . . . . .
H22A H 0.8607 0.7080 0.6067 0.038 Uiso 1 1 calc R U . . .
H22B H 0.9692 0.6988 0.5736 0.038 Uiso 1 1 calc R U . . .
H22C H 0.9308 0.7790 0.5955 0.038 Uiso 1 1 calc R U . . .
C23 C 0.7568(2) 0.99719(16) 0.60653(15) 0.0221(6) Uani 1 1 d . . . . .
C24 C 0.7467(3) 0.97945(18) 0.53369(16) 0.0280(7) Uani 1 1 d . . . . .
C25 C 0.6769(3) 1.0194(2) 0.48865(18) 0.0348(8) Uani 1 1 d . . . . .
H25A H 0.6699 1.0074 0.4395 0.042 Uiso 1 1 calc R U . . .
C26 C 0.6168(3) 1.07619(19) 0.51211(19) 0.0350(8) Uani 1 1 d . . . . .
C27 C 0.6280(2) 1.09296(18) 0.58432(18) 0.0301(7) Uani 1 1 d . . . . .
H27A H 0.5878 1.1317 0.6017 0.036 Uiso 1 1 calc R U . . .
C28 C 0.6968(2) 1.05413(16) 0.63175(16) 0.0233(6) Uani 1 1 d . . . . .
C29 C 0.8090(3) 0.9180(2) 0.50511(17) 0.0365(8) Uani 1 1 d . . . . .
H29A H 0.8155 0.8773 0.5394 0.044 Uiso 1 1 calc R U . . .
H29B H 0.8781 0.9364 0.4972 0.044 Uiso 1 1 calc R U . . .
H29C H 0.7740 0.9003 0.4601 0.044 Uiso 1 1 calc R U . . .
C30 C 0.5380(3) 1.1157(2) 0.4617(2) 0.0496(10) Uani 1 1 d . . . . .
H30C H 0.5252 1.1651 0.4802 0.060 Uiso 1 1 calc R U . . .
H30B H 0.4731 1.0875 0.4572 0.060 Uiso 1 1 calc R U . . .
H30A H 0.5644 1.1201 0.4150 0.060 Uiso 1 1 calc R U . . .
C31 C 0.7016(2) 1.07064(15) 0.70992(16) 0.0235(6) Uani 1 1 d . . . . .
H31A H 0.7678 1.0959 0.7247 0.028 Uiso 1 1 calc R U . . .
H31B H 0.6445 1.1049 0.7186 0.028 Uiso 1 1 calc R U . . .
C32 C 0.6798(2) 1.02759(17) 0.82781(16) 0.0243(6) Uani 1 1 d . . . . .
H32A H 0.6217 1.0623 0.8268 0.029 Uiso 1 1 calc R U . . .
H32B H 0.7432 1.0521 0.8481 0.029 Uiso 1 1 calc R U . . .
H32C H 0.6655 0.9847 0.8570 0.029 Uiso 1 1 calc R U . . .
C33 C 0.6008(2) 0.96028(16) 0.72675(16) 0.0224(6) Uani 1 1 d . . . . .
H33A H 0.5948 0.9610 0.6741 0.027 Uiso 1 1 calc R U . . .
H33B H 0.5379 0.9837 0.7427 0.027 Uiso 1 1 calc R U . . .
C34 C 0.6077(2) 0.88137(16) 0.75256(16) 0.0210(6) Uani 1 1 d . . . . .
H34B H 0.6084 0.8806 0.8050 0.025 Uiso 1 1 calc R U . . .
H34A H 0.5460 0.8537 0.7324 0.025 Uiso 1 1 calc R U . . .
C35 C 0.6867(2) 0.82405(16) 0.65564(15) 0.0230(6) Uani 1 1 d . . . . .
H35C H 0.7500 0.8012 0.6414 0.028 Uiso 1 1 calc R U . . .
H35B H 0.6705 0.8683 0.6268 0.028 Uiso 1 1 calc R U . . .
H35A H 0.6292 0.7888 0.6485 0.028 Uiso 1 1 calc R U . . .
C36 C 0.7184(2) 0.77514(15) 0.77257(15) 0.0204(6) Uani 1 1 d . . . . .
H36A H 0.7843 0.7525 0.7610 0.025 Uiso 1 1 calc R U . . .
H36B H 0.6618 0.7404 0.7570 0.025 Uiso 1 1 calc R U . . .
C37 C 0.7219(2) 0.78466(15) 0.85195(15) 0.0199(5) Uani 1 1 d . . . . .
C38 C 0.6756(2) 0.73131(16) 0.89108(16) 0.0228(6) Uani 1 1 d . . . . .
H38A H 0.6440 0.6899 0.8670 0.027 Uiso 1 1 calc R U . . .
C39 C 0.6739(2) 0.73636(17) 0.96418(17) 0.0270(6) Uani 1 1 d . . . . .
C40 C 0.7160(2) 0.79959(17) 0.99723(16) 0.0262(6) Uani 1 1 d . . . . .
H40A H 0.7129 0.8052 1.0470 0.031 Uiso 1 1 calc R U . . .
C41 C 0.7628(2) 0.85516(16) 0.96000(15) 0.0229(6) Uani 1 1 d . . . . .
C42 C 0.7687(2) 0.84641(15) 0.88682(15) 0.0187(5) Uani 1 1 d . . . . .
C43 C 0.6267(3) 0.67563(19) 1.0054(2) 0.0369(8) Uani 1 1 d . . . . .
H43A H 0.6621 0.6289 0.9976 0.044 Uiso 1 1 calc R U . . .
H43B H 0.5530 0.6708 0.9892 0.044 Uiso 1 1 calc R U . . .
H43C H 0.6345 0.6877 1.0562 0.044 Uiso 1 1 calc R U . . .
C44 C 0.8047(3) 0.92326(18) 0.99820(16) 0.0293(7) Uani 1 1 d . . . . .
H44A H 0.8787 0.9167 1.0123 0.035 Uiso 1 1 calc R U . . .
H44B H 0.7679 0.9313 1.0406 0.035 Uiso 1 1 calc R U . . .
H44C H 0.7946 0.9661 0.9666 0.035 Uiso 1 1 calc R U . . .
C45 C 1.4433(4) 0.8342(3) 0.9000(3) 0.0710(15) Uani 1 1 d . . . . .
H45B H 1.5006 0.8300 0.9383 0.085 Uiso 1 1 calc R U . . .
H45A H 1.4670 0.8114 0.8568 0.085 Uiso 1 1 calc R U . . .
N1 N 1.03329(18) 0.97178(12) 0.69980(12) 0.0184(5) Uani 1 1 d . . . . .
N2 N 1.03392(18) 0.89223(13) 0.83311(13) 0.0188(5) Uani 1 1 d . . . . .
N3 N 0.69336(18) 1.00294(13) 0.75442(13) 0.0194(5) Uani 1 1 d . . . . .
N4 N 0.70214(18) 0.84503(13) 0.73149(12) 0.0183(5) Uani 1 1 d . . . . .
O1 O 0.90449(14) 1.03135(10) 0.79528(10) 0.0169(4) Uani 1 1 d . . . . .
O2 O 0.91532(15) 0.82908(10) 0.72052(10) 0.0193(4) Uani 1 1 d . . . . .
O3 O 0.82214(15) 0.95836(11) 0.65190(10) 0.0196(4) Uani 1 1 d . . . . .
O4 O 0.81840(14) 0.89720(10) 0.85059(10) 0.0179(4) Uani 1 1 d . . . . .
Zr1 Zr 0.86451(2) 0.92882(2) 0.75483(2) 0.01390(9) Uani 1 1 d . . . . .
Cl1 Cl 1.33786(11) 0.78395(8) 0.92495(7) 0.0690(3) Uani 1 1 d . . . . .
Cl2 Cl 1.41917(13) 0.92573(10) 0.88359(14) 0.1072(7) 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
C1 O1 1.340(3) . ?
C1 C6 1.404(4) . ?
C1 C2 1.407(4) . ?
C2 C3 1.392(4) . ?
C2 C8 1.508(4) . ?
C3 C4 1.391(4) . ?
C4 C5 1.391(4) . ?
C4 C9 1.502(4) . ?
C5 C6 1.389(4) . ?
C6 C7 1.508(4) . ?
C7 N1 1.490(4) . ?
C10 N1 1.478(3) . ?
C11 N1 1.480(4) . ?
C11 C12 1.505(4) . ?
C12 N2 1.475(4) . ?
C13 N2 1.482(4) . ?
C14 N2 1.491(4) . ?
C14 C15 1.502(4) . ?
C15 C16 1.392(4) . ?
C15 C20 1.412(4) . ?
C16 C17 1.389(5) . ?
C17 C18 1.385(5) . ?
C17 C21 1.503(4) . ?
C18 C19 1.395(4) . ?
C19 C20 1.405(4) . ?
C19 C22 1.502(5) . ?
C20 O2 1.336(3) . ?
C23 O3 1.346(3) . ?
C23 C28 1.401(4) . ?
C23 C24 1.408(4) . ?
C24 C25 1.387(5) . ?
C24 C29 1.503(5) . ?
C25 C26 1.386(5) . ?
C26 C27 1.392(5) . ?
C26 C30 1.511(5) . ?
C27 C28 1.395(4) . ?
C28 C31 1.503(4) . ?
C31 N3 1.495(3) . ?
C32 N3 1.483(4) . ?
C33 N3 1.481(4) . ?
C33 C34 1.509(4) . ?
C34 N4 1.477(4) . ?
C35 N4 1.478(4) . ?
C36 N4 1.488(3) . ?
C36 C37 1.507(4) . ?
C37 C38 1.386(4) . ?
C37 C42 1.406(4) . ?
C38 C39 1.387(4) . ?
C39 C40 1.391(5) . ?
C39 C43 1.509(4) . ?
C40 C41 1.397(4) . ?
C41 C42 1.401(4) . ?
C41 C44 1.504(4) . ?
C42 O4 1.345(3) . ?
C45 Cl2 1.709(6) . ?
C45 Cl1 1.742(5) . ?
N1 Zr1 2.627(2) . ?
N2 Zr1 2.617(2) . ?
N3 Zr1 2.592(2) . ?
N4 Zr1 2.599(2) . ?
O1 Zr1 2.0542(18) . ?
O2 Zr1 2.0470(19) . ?
O3 Zr1 2.0424(19) . ?
O4 Zr1 2.0400(19) . ?

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 C1 C6 120.5(2) . . ?
O1 C1 C2 120.6(2) . . ?
C6 C1 C2 118.9(2) . . ?
C3 C2 C1 119.2(3) . . ?
C3 C2 C8 120.4(3) . . ?
C1 C2 C8 120.5(3) . . ?
C4 C3 C2 122.8(3) . . ?
C3 C4 C5 117.0(3) . . ?
C3 C4 C9 121.5(3) . . ?
C5 C4 C9 121.4(3) . . ?
C6 C5 C4 122.2(3) . . ?
C5 C6 C1 120.0(3) . . ?
C5 C6 C7 120.1(3) . . ?
C1 C6 C7 119.8(2) . . ?
N1 C7 C6 112.8(2) . . ?
N1 C11 C12 111.5(2) . . ?
N2 C12 C11 111.1(2) . . ?
N2 C14 C15 113.3(2) . . ?
C16 C15 C20 120.0(3) . . ?
C16 C15 C14 119.1(3) . . ?
C20 C15 C14 120.9(2) . . ?
C17 C16 C15 121.8(3) . . ?
C18 C17 C16 117.5(3) . . ?
C18 C17 C21 121.4(3) . . ?
C16 C17 C21 121.1(3) . . ?
C17 C18 C19 122.9(3) . . ?
C18 C19 C20 119.0(3) . . ?
C18 C19 C22 120.5(3) . . ?
C20 C19 C22 120.5(3) . . ?
O2 C20 C19 120.4(3) . . ?
O2 C20 C15 120.7(3) . . ?
C19 C20 C15 118.8(3) . . ?
O3 C23 C28 120.2(3) . . ?
O3 C23 C24 120.0(3) . . ?
C28 C23 C24 119.8(3) . . ?
C25 C24 C23 118.5(3) . . ?
C25 C24 C29 120.5(3) . . ?
C23 C24 C29 121.1(3) . . ?
C26 C25 C24 123.0(3) . . ?
C25 C26 C27 117.7(3) . . ?
C25 C26 C30 121.1(4) . . ?
C27 C26 C30 121.1(4) . . ?
C26 C27 C28 121.5(3) . . ?
C27 C28 C23 119.6(3) . . ?
C27 C28 C31 119.8(3) . . ?
C23 C28 C31 120.5(3) . . ?
N3 C31 C28 113.0(2) . . ?
N3 C33 C34 110.9(2) . . ?
N4 C34 C33 111.1(2) . . ?
N4 C36 C37 114.3(2) . . ?
C38 C37 C42 119.5(3) . . ?
C38 C37 C36 118.5(3) . . ?
C42 C37 C36 121.9(2) . . ?
C37 C38 C39 122.3(3) . . ?
C38 C39 C40 117.4(3) . . ?
C38 C39 C43 120.8(3) . . ?
C40 C39 C43 121.9(3) . . ?
C39 C40 C41 122.4(3) . . ?
C40 C41 C42 118.8(3) . . ?
C40 C41 C44 120.1(3) . . ?
C42 C41 C44 121.0(3) . . ?
O4 C42 C41 119.9(3) . . ?
O4 C42 C37 120.7(2) . . ?
C41 C42 C37 119.4(3) . . ?
Cl2 C45 Cl1 114.8(3) . . ?
C10 N1 C11 108.6(2) . . ?
C10 N1 C7 107.2(2) . . ?
C11 N1 C7 110.3(2) . . ?
C10 N1 Zr1 109.66(16) . . ?
C11 N1 Zr1 112.88(16) . . ?
C7 N1 Zr1 108.17(16) . . ?
C12 N2 C13 109.0(2) . . ?
C12 N2 C14 109.0(2) . . ?
C13 N2 C14 106.9(2) . . ?
C12 N2 Zr1 112.51(17) . . ?
C13 N2 Zr1 110.45(16) . . ?
C14 N2 Zr1 108.87(16) . . ?
C33 N3 C32 108.9(2) . . ?
C33 N3 C31 109.0(2) . . ?
C32 N3 C31 107.5(2) . . ?
C33 N3 Zr1 113.40(17) . . ?
C32 N3 Zr1 109.20(16) . . ?
C31 N3 Zr1 108.64(16) . . ?
C34 N4 C35 109.6(2) . . ?
C34 N4 C36 108.6(2) . . ?
C35 N4 C36 106.7(2) . . ?
C34 N4 Zr1 111.93(16) . . ?
C35 N4 Zr1 110.42(16) . . ?
C36 N4 Zr1 109.51(16) . . ?
C1 O1 Zr1 148.10(17) . . ?
C20 O2 Zr1 147.93(18) . . ?
C23 O3 Zr1 147.23(19) . . ?
C42 O4 Zr1 146.80(18) . . ?
O4 Zr1 O3 147.48(8) . . ?
O4 Zr1 O2 99.40(8) . . ?
O3 Zr1 O2 89.71(8) . . ?
O4 Zr1 O1 90.44(7) . . ?
O3 Zr1 O1 98.88(8) . . ?
O2 Zr1 O1 146.76(8) . . ?
O4 Zr1 N3 79.99(7) . . ?
O3 Zr1 N3 73.00(8) . . ?
O2 Zr1 N3 139.09(8) . . ?
O1 Zr1 N3 73.76(7) . . ?
O4 Zr1 N4 71.77(7) . . ?
O3 Zr1 N4 81.33(7) . . ?
O2 Zr1 N4 73.23(8) . . ?
O1 Zr1 N4 139.67(7) . . ?
N3 Zr1 N4 67.75(7) . . ?
O4 Zr1 N2 74.18(7) . . ?
O3 Zr1 N2 137.88(8) . . ?
O2 Zr1 N2 71.22(8) . . ?
O1 Zr1 N2 81.29(7) . . ?
N3 Zr1 N2 143.70(7) . . ?
N4 Zr1 N2 124.93(7) . . ?
O4 Zr1 N1 139.29(7) . . ?
O3 Zr1 N1 72.88(8) . . ?
O2 Zr1 N1 80.26(7) . . ?
O1 Zr1 N1 71.91(7) . . ?
N3 Zr1 N1 126.19(7) . . ?
N4 Zr1 N1 142.87(7) . . ?
N2 Zr1 N1 67.18(7) . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
O1 C1 C2 C3 176.1(2) . . . . ?
C6 C1 C2 C3 -1.2(4) . . . . ?
O1 C1 C2 C8 -3.7(4) . . . . ?
C6 C1 C2 C8 179.0(3) . . . . ?
C1 C2 C3 C4 1.9(4) . . . . ?
C8 C2 C3 C4 -178.4(3) . . . . ?
C2 C3 C4 C5 -0.8(4) . . . . ?
C2 C3 C4 C9 -178.3(3) . . . . ?
C3 C4 C5 C6 -0.9(4) . . . . ?
C9 C4 C5 C6 176.5(3) . . . . ?
C4 C5 C6 C1 1.6(4) . . . . ?
C4 C5 C6 C7 -173.7(3) . . . . ?
O1 C1 C6 C5 -177.7(2) . . . . ?
C2 C1 C6 C5 -0.5(4) . . . . ?
O1 C1 C6 C7 -2.5(4) . . . . ?
C2 C1 C6 C7 174.7(2) . . . . ?
C5 C6 C7 N1 127.3(3) . . . . ?
C1 C6 C7 N1 -47.9(3) . . . . ?
N1 C11 C12 N2 -57.9(3) . . . . ?
N2 C14 C15 C16 135.5(3) . . . . ?
N2 C14 C15 C20 -41.7(4) . . . . ?
C20 C15 C16 C17 0.9(4) . . . . ?
C14 C15 C16 C17 -176.3(3) . . . . ?
C15 C16 C17 C18 1.5(5) . . . . ?
C15 C16 C17 C21 -179.6(3) . . . . ?
C16 C17 C18 C19 -2.5(5) . . . . ?
C21 C17 C18 C19 178.6(3) . . . . ?
C17 C18 C19 C20 1.0(4) . . . . ?
C17 C18 C19 C22 -178.1(3) . . . . ?
C18 C19 C20 O2 179.8(3) . . . . ?
C22 C19 C20 O2 -1.1(4) . . . . ?
C18 C19 C20 C15 1.5(4) . . . . ?
C22 C19 C20 C15 -179.4(3) . . . . ?
C16 C15 C20 O2 179.2(3) . . . . ?
C14 C15 C20 O2 -3.7(4) . . . . ?
C16 C15 C20 C19 -2.4(4) . . . . ?
C14 C15 C20 C19 174.7(3) . . . . ?
O3 C23 C24 C25 178.5(3) . . . . ?
C28 C23 C24 C25 0.0(4) . . . . ?
O3 C23 C24 C29 -0.8(4) . . . . ?
C28 C23 C24 C29 -179.2(3) . . . . ?
C23 C24 C25 C26 0.2(5) . . . . ?
C29 C24 C25 C26 179.5(3) . . . . ?
C24 C25 C26 C27 -0.2(5) . . . . ?
C24 C25 C26 C30 -177.0(3) . . . . ?
C25 C26 C27 C28 -0.1(5) . . . . ?
C30 C26 C27 C28 176.7(3) . . . . ?
C26 C27 C28 C23 0.4(4) . . . . ?
C26 C27 C28 C31 -176.1(3) . . . . ?
O3 C23 C28 C27 -178.8(3) . . . . ?
C24 C23 C28 C27 -0.3(4) . . . . ?
O3 C23 C28 C31 -2.3(4) . . . . ?
C24 C23 C28 C31 176.1(3) . . . . ?
C27 C28 C31 N3 129.2(3) . . . . ?
C23 C28 C31 N3 -47.2(4) . . . . ?
N3 C33 C34 N4 -57.6(3) . . . . ?
N4 C36 C37 C38 141.4(3) . . . . ?
N4 C36 C37 C42 -37.4(4) . . . . ?
C42 C37 C38 C39 -0.2(4) . . . . ?
C36 C37 C38 C39 -179.0(3) . . . . ?
C37 C38 C39 C40 3.3(4) . . . . ?
C37 C38 C39 C43 -177.4(3) . . . . ?
C38 C39 C40 C41 -2.7(5) . . . . ?
C43 C39 C40 C41 178.0(3) . . . . ?
C39 C40 C41 C42 -0.9(5) . . . . ?
C39 C40 C41 C44 178.4(3) . . . . ?
C40 C41 C42 O4 -176.3(3) . . . . ?
C44 C41 C42 O4 4.3(4) . . . . ?
C40 C41 C42 C37 4.1(4) . . . . ?
C44 C41 C42 C37 -175.3(3) . . . . ?
C38 C37 C42 O4 176.8(2) . . . . ?
C36 C37 C42 O4 -4.4(4) . . . . ?
C38 C37 C42 C41 -3.6(4) . . . . ?
C36 C37 C42 C41 175.2(3) . . . . ?
C12 C11 N1 C10 -81.3(3) . . . . ?
C12 C11 N1 C7 161.6(2) . . . . ?
C12 C11 N1 Zr1 40.5(3) . . . . ?
C6 C7 N1 C10 -168.6(2) . . . . ?
C6 C7 N1 C11 -50.6(3) . . . . ?
C6 C7 N1 Zr1 73.3(2) . . . . ?
C11 C12 N2 C13 -78.0(3) . . . . ?
C11 C12 N2 C14 165.7(2) . . . . ?
C11 C12 N2 Zr1 44.8(3) . . . . ?
C15 C14 N2 C12 -52.0(3) . . . . ?
C15 C14 N2 C13 -169.6(2) . . . . ?
C15 C14 N2 Zr1 71.1(2) . . . . ?
C34 C33 N3 C32 -81.9(3) . . . . ?
C34 C33 N3 C31 161.1(2) . . . . ?
C34 C33 N3 Zr1 39.9(3) . . . . ?
C28 C31 N3 C33 -52.0(3) . . . . ?
C28 C31 N3 C32 -169.9(2) . . . . ?
C28 C31 N3 Zr1 72.1(2) . . . . ?
C33 C34 N4 C35 -77.5(3) . . . . ?
C33 C34 N4 C36 166.3(2) . . . . ?
C33 C34 N4 Zr1 45.3(3) . . . . ?
C37 C36 N4 C34 -54.5(3) . . . . ?
C37 C36 N4 C35 -172.5(2) . . . . ?
C37 C36 N4 Zr1 68.0(2) . . . . ?
C6 C1 O1 Zr1 17.3(5) . . . . ?
C2 C1 O1 Zr1 -159.9(2) . . . . ?
C19 C20 O2 Zr1 -173.5(2) . . . . ?
C15 C20 O2 Zr1 4.9(5) . . . . ?
C28 C23 O3 Zr1 17.3(5) . . . . ?
C24 C23 O3 Zr1 -161.2(2) . . . . ?
C41 C42 O4 Zr1 179.0(2) . . . . ?
C37 C42 O4 Zr1 -1.4(5) . . . . ?

_refine_diff_density_max         1.084
_refine_diff_density_min         -1.501
_refine_diff_density_rms         0.100

_shelxl_version_number           2013-4


_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: methylenchloride, hexane'
_chemical_properties_physical    ', Moisture-sensitive'
####################################################################### 
# 
# 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_shelx
_database_code_depnum_ccdc_archive 'CCDC 1439014'
_audit_update_record             
;
2015-11-25 deposited with the CCDC.
2016-07-21 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          >573
_chemical_formula_moiety         'C29 H33 N3 O6 Zr'
_chemical_formula_sum            'C29 H33 N3 O6 Zr'
_chemical_formula_weight         610.80

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'
Zr Zr -2.9673 0.5597 '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                   9.4729(14)
_cell_length_b                   22.863(5)
_cell_length_c                   12.408(2)
_cell_angle_alpha                90
_cell_angle_beta                 93.774(14)
_cell_angle_gamma                90
_cell_volume                     2681.5(8)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    3067
_cell_measurement_theta_min      1.79
_cell_measurement_theta_max      27.22

_exptl_crystal_description       fragment
_exptl_crystal_colour            'pale yellow'
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.513
_exptl_crystal_F_000             1264
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.500
_exptl_crystal_size_mid          0.387
_exptl_crystal_size_min          0.280
_exptl_absorpt_coefficient_mu    0.459
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   integration
_exptl_absorpt_correction_T_min  0.8625
_exptl_absorpt_correction_T_max  0.9353
_exptl_absorpt_process_details   
;
'X-SHAPE 2.07 (03-Aug-2005) Stoe & Cie, Darmstadt, Germany'
;

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   
'sealed X-ray tube, 12 x 0.4 mm long-fine focus'
_diffrn_measurement_device_type  'STOE IPDS 2T'
_diffrn_measurement_method       'rotation method'
_diffrn_detector_area_resol_mean 6.67
_diffrn_reflns_number            39090
_diffrn_reflns_av_unetI/netI     0.0190
_diffrn_reflns_av_R_equivalents  0.0388
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_theta_min         1.781
_diffrn_reflns_theta_max         26.828
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             5682
_reflns_number_gt                5006
_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       'STOE X-AREA'
_computing_cell_refinement       'STOE X-AREA'
_computing_data_reduction        'STOE X-RED'
_computing_structure_solution    'SHELXS-2013 (Sheldrick, 2013)'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_molecular_graphics    'ORTEP-3 for Windows (Farrugia, 2012)'
_computing_publication_material  'WinGX publication routines (Farrugia, 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)+(0.0386P)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_number_reflns         5682
_refine_ls_number_parameters     358
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0285
_refine_ls_R_factor_gt           0.0230
_refine_ls_wR_factor_ref         0.0665
_refine_ls_wR_factor_gt          0.0652
_refine_ls_goodness_of_fit_ref   1.243
_refine_ls_restrained_S_all      1.243
_refine_ls_shift/su_max          0.002
_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
Zr1 Zr 0.25904(2) -0.07687(2) 0.78561(2) 0.01840(6) Uani 1 1 d . . . . .
O1 O 0.17453(11) -0.14900(4) 0.84426(9) 0.0219(2) Uani 1 1 d . . . . .
O2 O 0.28840(11) -0.00163(4) 0.70978(9) 0.0215(2) Uani 1 1 d . . . . .
O3 O 0.26681(11) -0.03792(5) 0.94403(9) 0.0232(2) Uani 1 1 d . . . . .
O4 O 0.40142(11) -0.12178(5) 0.68628(9) 0.0242(2) Uani 1 1 d . . . . .
O5 O 0.36380(14) -0.02725(5) 1.11295(10) 0.0343(3) Uani 1 1 d . . . . .
O6 O 0.60691(13) -0.16788(5) 0.66166(10) 0.0345(3) Uani 1 1 d . . . . .
N1 N 0.10399(14) -0.11182(5) 0.63234(11) 0.0226(3) Uani 1 1 d . . . . .
N2 N 0.03124(13) -0.02790(5) 0.79360(10) 0.0210(3) Uani 1 1 d . . . . .
N3 N 0.46648(13) -0.09934(5) 0.88244(11) 0.0210(3) Uani 1 1 d . . . . .
C1 C 0.36321(17) -0.04709(7) 1.02193(13) 0.0244(3) Uani 1 1 d . . . . .
C2 C 0.48122(16) -0.08570(6) 0.98733(14) 0.0232(3) Uani 1 1 d . . . . .
C3 C 0.59474(17) -0.10650(7) 1.05301(15) 0.0299(4) Uani 1 1 d . . . . .
H3A H 0.6054 -0.0966 1.1258 0.036 Uiso 1 1 calc R U . . .
C4 C 0.69175(17) -0.14256(8) 1.00611(16) 0.0317(4) Uani 1 1 d . . . . .
H4A H 0.7672 -0.1581 1.0485 0.038 Uiso 1 1 calc R U . . .
C5 C 0.67727(16) -0.15555(7) 0.89697(15) 0.0287(4) Uani 1 1 d . . . . .
H5A H 0.7431 -0.1789 0.8651 0.034 Uiso 1 1 calc R U . . .
C6 C 0.56186(15) -0.13271(6) 0.83654(14) 0.0230(3) Uani 1 1 d . . . . .
C7 C 0.52571(16) -0.14275(6) 0.71787(14) 0.0247(3) Uani 1 1 d . . . . .
C8 C 0.08558(15) -0.19421(6) 0.82349(13) 0.0209(3) Uani 1 1 d . . . . .
C9 C 0.03061(15) -0.22456(7) 0.90974(13) 0.0229(3) Uani 1 1 d . . . . .
C10 C -0.05678(16) -0.27242(7) 0.88626(13) 0.0245(3) Uani 1 1 d . . . . .
H10A H -0.0931 -0.2930 0.9429 0.029 Uiso 1 1 calc R U . . .
C11 C -0.09151(16) -0.29040(7) 0.78082(14) 0.0265(3) Uani 1 1 d . . . . .
C12 C -0.03874(16) -0.25813(7) 0.69669(13) 0.0250(3) Uani 1 1 d . . . . .
H12A H -0.0632 -0.2691 0.6257 0.030 Uiso 1 1 calc R U . . .
C13 C 0.04950(15) -0.21008(7) 0.71619(13) 0.0228(3) Uani 1 1 d . . . . .
C14 C 0.07159(18) -0.20650(7) 1.02378(14) 0.0283(3) Uani 1 1 d . . . . .
H14A H 0.0554 -0.1653 1.0317 0.042 Uiso 1 1 calc R U . . .
H14B H 0.1700 -0.2149 1.0403 0.042 Uiso 1 1 calc R U . . .
H14C H 0.0157 -0.2277 1.0723 0.042 Uiso 1 1 calc R U . . .
C15 C -0.1797(2) -0.34464(8) 0.75843(16) 0.0368(4) Uani 1 1 d . . . . .
H15A H -0.2425 -0.3501 0.8152 0.055 Uiso 1 1 calc R U . . .
H15B H -0.1187 -0.3780 0.7551 0.055 Uiso 1 1 calc R U . . .
H15C H -0.2339 -0.3403 0.6908 0.055 Uiso 1 1 calc R U . . .
C16 C 0.11006(17) -0.17750(7) 0.62377(13) 0.0250(3) Uani 1 1 d . . . . .
H16A H 0.2080 -0.1891 0.6195 0.030 Uiso 1 1 calc R U . . .
H16B H 0.0590 -0.1893 0.5570 0.030 Uiso 1 1 calc R U . . .
C17 C -0.04496(16) -0.09321(7) 0.64274(14) 0.0259(3) Uani 1 1 d . . . . .
H17A H -0.0904 -0.1199 0.6903 0.031 Uiso 1 1 calc R U . . .
H17B H -0.0962 -0.0946 0.5725 0.031 Uiso 1 1 calc R U . . .
C18 C -0.05028(16) -0.03188(7) 0.68747(14) 0.0251(3) Uani 1 1 d . . . . .
H18A H -0.0113 -0.0048 0.6372 0.030 Uiso 1 1 calc R U . . .
H18B H -0.1479 -0.0209 0.6958 0.030 Uiso 1 1 calc R U . . .
C19 C 0.04977(16) 0.03499(6) 0.82487(13) 0.0225(3) Uani 1 1 d . . . . .
H19A H 0.1045 0.0368 0.8937 0.027 Uiso 1 1 calc R U . . .
H19B H -0.0427 0.0514 0.8354 0.027 Uiso 1 1 calc R U . . .
C20 C 0.12143(15) 0.07272(6) 0.74516(12) 0.0204(3) Uani 1 1 d . . . . .
C21 C 0.23788(15) 0.05286(6) 0.69085(12) 0.0195(3) Uani 1 1 d . . . . .
C22 C 0.30214(16) 0.08911(7) 0.61728(13) 0.0221(3) Uani 1 1 d . . . . .
C23 C 0.25285(16) 0.14618(6) 0.60335(13) 0.0235(3) Uani 1 1 d . . . . .
H23A H 0.2954 0.1705 0.5549 0.028 Uiso 1 1 calc R U . . .
C24 C 0.14165(16) 0.16791(6) 0.65981(13) 0.0231(3) Uani 1 1 d . . . . .
C25 C 0.07637(16) 0.13005(6) 0.72882(13) 0.0220(3) Uani 1 1 d . . . . .
H25A H 0.0001 0.1436 0.7652 0.026 Uiso 1 1 calc R U . . .
C26 C 0.42187(18) 0.06583(7) 0.55553(15) 0.0294(4) Uani 1 1 d . . . . .
H26A H 0.3879 0.0345 0.5093 0.044 Uiso 1 1 calc R U . . .
H26B H 0.4958 0.0516 0.6054 0.044 Uiso 1 1 calc R U . . .
H26C H 0.4582 0.0966 0.5126 0.044 Uiso 1 1 calc R U . . .
C27 C 0.09222(18) 0.23076(7) 0.64832(14) 0.0278(3) Uani 1 1 d . . . . .
H27A H 0.1287 0.2477 0.5850 0.042 Uiso 1 1 calc R U . . .
H27B H 0.1260 0.2526 0.7109 0.042 Uiso 1 1 calc R U . . .
H27C H -0.0093 0.2318 0.6418 0.042 Uiso 1 1 calc R U . . .
C28 C 0.15493(19) -0.08765(7) 0.53020(13) 0.0281(3) Uani 1 1 d . . . . .
H28A H 0.0945 -0.1010 0.4700 0.042 Uiso 1 1 calc R U . . .
H28B H 0.2499 -0.1007 0.5219 0.042 Uiso 1 1 calc R U . . .
H28C H 0.1532 -0.0457 0.5329 0.042 Uiso 1 1 calc R U . . .
C29 C -0.05060(17) -0.05550(7) 0.87863(14) 0.0269(3) Uani 1 1 d . . . . .
H29A H -0.0695 -0.0956 0.8601 0.040 Uiso 1 1 calc R U . . .
H29B H -0.1384 -0.0350 0.8837 0.040 Uiso 1 1 calc R U . . .
H29C H 0.0034 -0.0536 0.9468 0.040 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
Zr1 O2 1.9890(11) . ?
Zr1 O1 1.9917(11) . ?
Zr1 O4 2.1473(11) . ?
Zr1 O3 2.1549(11) . ?
Zr1 N3 2.2931(13) . ?
Zr1 N2 2.4389(13) . ?
Zr1 N1 2.4586(13) . ?
O1 C8 1.3477(18) . ?
O2 C21 1.3497(18) . ?
O3 C1 1.3023(19) . ?
O4 C7 1.3073(19) . ?
O5 C1 1.217(2) . ?
O6 C7 1.216(2) . ?
N1 C17 1.487(2) . ?
N1 C28 1.492(2) . ?
N1 C16 1.5067(19) . ?
N2 C18 1.485(2) . ?
N2 C29 1.490(2) . ?
N2 C19 1.4966(19) . ?
N3 C2 1.337(2) . ?
N3 C6 1.338(2) . ?
C1 C2 1.509(2) . ?
C2 C3 1.390(2) . ?
C3 C4 1.390(3) . ?
C3 H3A 0.9300 . ?
C4 C5 1.384(3) . ?
C4 H4A 0.9300 . ?
C5 C6 1.386(2) . ?
C5 H5A 0.9300 . ?
C6 C7 1.507(2) . ?
C8 C13 1.400(2) . ?
C8 C9 1.404(2) . ?
C9 C10 1.391(2) . ?
C9 C14 1.500(2) . ?
C10 C11 1.390(2) . ?
C10 H10A 0.9300 . ?
C11 C12 1.397(2) . ?
C11 C15 1.511(2) . ?
C12 C13 1.392(2) . ?
C12 H12A 0.9300 . ?
C13 C16 1.512(2) . ?
C14 H14A 0.9600 . ?
C14 H14B 0.9600 . ?
C14 H14C 0.9600 . ?
C15 H15A 0.9600 . ?
C15 H15B 0.9600 . ?
C15 H15C 0.9600 . ?
C16 H16A 0.9700 . ?
C16 H16B 0.9700 . ?
C17 C18 1.510(2) . ?
C17 H17A 0.9700 . ?
C17 H17B 0.9700 . ?
C18 H18A 0.9700 . ?
C18 H18B 0.9700 . ?
C19 C20 1.507(2) . ?
C19 H19A 0.9700 . ?
C19 H19B 0.9700 . ?
C20 C25 1.389(2) . ?
C20 C21 1.405(2) . ?
C21 C22 1.401(2) . ?
C22 C23 1.393(2) . ?
C22 C26 1.507(2) . ?
C23 C24 1.394(2) . ?
C23 H23A 0.9300 . ?
C24 C25 1.391(2) . ?
C24 C27 1.515(2) . ?
C25 H25A 0.9300 . ?
C26 H26A 0.9600 . ?
C26 H26B 0.9600 . ?
C26 H26C 0.9600 . ?
C27 H27A 0.9600 . ?
C27 H27B 0.9600 . ?
C27 H27C 0.9600 . ?
C28 H28A 0.9600 . ?
C28 H28B 0.9600 . ?
C28 H28C 0.9600 . ?
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
O2 Zr1 O1 163.95(4) . . ?
O2 Zr1 O4 91.68(4) . . ?
O1 Zr1 O4 95.55(4) . . ?
O2 Zr1 O3 94.39(4) . . ?
O1 Zr1 O3 89.96(4) . . ?
O4 Zr1 O3 137.40(4) . . ?
O2 Zr1 N3 107.45(4) . . ?
O1 Zr1 N3 88.53(4) . . ?
O4 Zr1 N3 69.19(5) . . ?
O3 Zr1 N3 68.77(4) . . ?
O2 Zr1 N2 76.93(4) . . ?
O1 Zr1 N2 89.27(4) . . ?
O4 Zr1 N2 146.48(4) . . ?
O3 Zr1 N2 75.55(4) . . ?
N3 Zr1 N2 144.24(5) . . ?
O2 Zr1 N1 90.58(4) . . ?
O1 Zr1 N1 77.26(4) . . ?
O4 Zr1 N1 76.50(4) . . ?
O3 Zr1 N1 145.36(4) . . ?
N3 Zr1 N1 141.28(5) . . ?
N2 Zr1 N1 72.27(4) . . ?
C8 O1 Zr1 145.74(10) . . ?
C21 O2 Zr1 145.25(10) . . ?
C1 O3 Zr1 126.21(10) . . ?
C7 O4 Zr1 126.21(10) . . ?
C17 N1 C28 109.24(12) . . ?
C17 N1 C16 109.40(12) . . ?
C28 N1 C16 107.05(12) . . ?
C17 N1 Zr1 111.20(9) . . ?
C28 N1 Zr1 109.06(9) . . ?
C16 N1 Zr1 110.79(9) . . ?
C18 N2 C29 109.73(12) . . ?
C18 N2 C19 109.52(12) . . ?
C29 N2 C19 106.31(12) . . ?
C18 N2 Zr1 110.22(9) . . ?
C29 N2 Zr1 109.72(9) . . ?
C19 N2 Zr1 111.26(9) . . ?
C2 N3 C6 121.15(13) . . ?
C2 N3 Zr1 119.27(10) . . ?
C6 N3 Zr1 118.95(10) . . ?
O5 C1 O3 126.10(15) . . ?
O5 C1 C2 121.60(14) . . ?
O3 C1 C2 112.29(13) . . ?
N3 C2 C3 121.22(15) . . ?
N3 C2 C1 112.44(13) . . ?
C3 C2 C1 126.33(16) . . ?
C2 C3 C4 117.69(16) . . ?
C2 C3 H3A 121.2 . . ?
C4 C3 H3A 121.2 . . ?
C5 C4 C3 120.73(15) . . ?
C5 C4 H4A 119.6 . . ?
C3 C4 H4A 119.6 . . ?
C6 C5 C4 118.17(16) . . ?
C6 C5 H5A 120.9 . . ?
C4 C5 H5A 120.9 . . ?
N3 C6 C5 121.00(16) . . ?
N3 C6 C7 112.73(13) . . ?
C5 C6 C7 126.26(15) . . ?
O6 C7 O4 126.34(16) . . ?
O6 C7 C6 121.37(14) . . ?
O4 C7 C6 112.29(13) . . ?
O1 C8 C13 119.40(14) . . ?
O1 C8 C9 119.46(14) . . ?
C13 C8 C9 121.14(14) . . ?
C10 C9 C8 118.33(15) . . ?
C10 C9 C14 121.83(14) . . ?
C8 C9 C14 119.80(14) . . ?
C11 C10 C9 122.03(15) . . ?
C11 C10 H10A 119.0 . . ?
C9 C10 H10A 119.0 . . ?
C10 C11 C12 118.21(14) . . ?
C10 C11 C15 120.64(15) . . ?
C12 C11 C15 121.11(16) . . ?
C13 C12 C11 121.81(15) . . ?
C13 C12 H12A 119.1 . . ?
C11 C12 H12A 119.1 . . ?
C12 C13 C8 118.42(14) . . ?
C12 C13 C16 120.69(14) . . ?
C8 C13 C16 120.83(13) . . ?
C9 C14 H14A 109.5 . . ?
C9 C14 H14B 109.5 . . ?
H14A C14 H14B 109.5 . . ?
C9 C14 H14C 109.5 . . ?
H14A C14 H14C 109.5 . . ?
H14B C14 H14C 109.5 . . ?
C11 C15 H15A 109.5 . . ?
C11 C15 H15B 109.5 . . ?
H15A C15 H15B 109.5 . . ?
C11 C15 H15C 109.5 . . ?
H15A C15 H15C 109.5 . . ?
H15B C15 H15C 109.5 . . ?
N1 C16 C13 114.79(13) . . ?
N1 C16 H16A 108.6 . . ?
C13 C16 H16A 108.6 . . ?
N1 C16 H16B 108.6 . . ?
C13 C16 H16B 108.6 . . ?
H16A C16 H16B 107.5 . . ?
N1 C17 C18 110.63(12) . . ?
N1 C17 H17A 109.5 . . ?
C18 C17 H17A 109.5 . . ?
N1 C17 H17B 109.5 . . ?
C18 C17 H17B 109.5 . . ?
H17A C17 H17B 108.1 . . ?
N2 C18 C17 110.78(12) . . ?
N2 C18 H18A 109.5 . . ?
C17 C18 H18A 109.5 . . ?
N2 C18 H18B 109.5 . . ?
C17 C18 H18B 109.5 . . ?
H18A C18 H18B 108.1 . . ?
N2 C19 C20 115.46(13) . . ?
N2 C19 H19A 108.4 . . ?
C20 C19 H19A 108.4 . . ?
N2 C19 H19B 108.4 . . ?
C20 C19 H19B 108.4 . . ?
H19A C19 H19B 107.5 . . ?
C25 C20 C21 118.56(14) . . ?
C25 C20 C19 119.24(14) . . ?
C21 C20 C19 122.11(13) . . ?
O2 C21 C22 119.67(13) . . ?
O2 C21 C20 119.69(13) . . ?
C22 C21 C20 120.64(14) . . ?
C23 C22 C21 118.58(14) . . ?
C23 C22 C26 121.69(14) . . ?
C21 C22 C26 119.73(14) . . ?
C22 C23 C24 121.99(14) . . ?
C22 C23 H23A 119.0 . . ?
C24 C23 H23A 119.0 . . ?
C25 C24 C23 117.94(14) . . ?
C25 C24 C27 120.07(14) . . ?
C23 C24 C27 121.99(14) . . ?
C20 C25 C24 122.16(14) . . ?
C20 C25 H25A 118.9 . . ?
C24 C25 H25A 118.9 . . ?
C22 C26 H26A 109.5 . . ?
C22 C26 H26B 109.5 . . ?
H26A C26 H26B 109.5 . . ?
C22 C26 H26C 109.5 . . ?
H26A C26 H26C 109.5 . . ?
H26B C26 H26C 109.5 . . ?
C24 C27 H27A 109.5 . . ?
C24 C27 H27B 109.5 . . ?
H27A C27 H27B 109.5 . . ?
C24 C27 H27C 109.5 . . ?
H27A C27 H27C 109.5 . . ?
H27B C27 H27C 109.5 . . ?
N1 C28 H28A 109.5 . . ?
N1 C28 H28B 109.5 . . ?
H28A C28 H28B 109.5 . . ?
N1 C28 H28C 109.5 . . ?
H28A C28 H28C 109.5 . . ?
H28B C28 H28C 109.5 . . ?
N2 C29 H29A 109.5 . . ?
N2 C29 H29B 109.5 . . ?
H29A C29 H29B 109.5 . . ?
N2 C29 H29C 109.5 . . ?
H29A C29 H29C 109.5 . . ?
H29B C29 H29C 109.5 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
Zr1 O3 C1 O5 -176.22(12) . . . . ?
Zr1 O3 C1 C2 4.66(18) . . . . ?
C6 N3 C2 C3 -1.2(2) . . . . ?
Zr1 N3 C2 C3 169.63(11) . . . . ?
C6 N3 C2 C1 179.20(13) . . . . ?
Zr1 N3 C2 C1 -10.01(16) . . . . ?
O5 C1 C2 N3 -175.26(14) . . . . ?
O3 C1 C2 N3 3.90(19) . . . . ?
O5 C1 C2 C3 5.1(3) . . . . ?
O3 C1 C2 C3 -175.72(15) . . . . ?
N3 C2 C3 C4 -0.7(2) . . . . ?
C1 C2 C3 C4 178.89(15) . . . . ?
C2 C3 C4 C5 2.0(2) . . . . ?
C3 C4 C5 C6 -1.4(2) . . . . ?
C2 N3 C6 C5 1.7(2) . . . . ?
Zr1 N3 C6 C5 -169.08(11) . . . . ?
C2 N3 C6 C7 -179.89(13) . . . . ?
Zr1 N3 C6 C7 9.29(16) . . . . ?
C4 C5 C6 N3 -0.4(2) . . . . ?
C4 C5 C6 C7 -178.57(15) . . . . ?
Zr1 O4 C7 O6 -179.52(12) . . . . ?
Zr1 O4 C7 C6 0.59(17) . . . . ?
N3 C6 C7 O6 173.65(14) . . . . ?
C5 C6 C7 O6 -8.1(2) . . . . ?
N3 C6 C7 O4 -6.45(18) . . . . ?
C5 C6 C7 O4 171.82(14) . . . . ?
Zr1 O1 C8 C13 20.4(2) . . . . ?
Zr1 O1 C8 C9 -159.58(12) . . . . ?
O1 C8 C9 C10 -177.63(13) . . . . ?
C13 C8 C9 C10 2.4(2) . . . . ?
O1 C8 C9 C14 -0.1(2) . . . . ?
C13 C8 C9 C14 179.90(14) . . . . ?
C8 C9 C10 C11 -0.5(2) . . . . ?
C14 C9 C10 C11 -177.98(14) . . . . ?
C9 C10 C11 C12 -1.5(2) . . . . ?
C9 C10 C11 C15 176.41(15) . . . . ?
C10 C11 C12 C13 1.7(2) . . . . ?
C15 C11 C12 C13 -176.15(15) . . . . ?
C11 C12 C13 C8 0.1(2) . . . . ?
C11 C12 C13 C16 177.40(14) . . . . ?
O1 C8 C13 C12 177.86(13) . . . . ?
C9 C8 C13 C12 -2.2(2) . . . . ?
O1 C8 C13 C16 0.5(2) . . . . ?
C9 C8 C13 C16 -179.50(14) . . . . ?
C17 N1 C16 C13 -56.43(17) . . . . ?
C28 N1 C16 C13 -174.68(13) . . . . ?
Zr1 N1 C16 C13 66.52(14) . . . . ?
C12 C13 C16 N1 135.79(14) . . . . ?
C8 C13 C16 N1 -46.95(19) . . . . ?
C28 N1 C17 C18 -81.72(16) . . . . ?
C16 N1 C17 C18 161.40(13) . . . . ?
Zr1 N1 C17 C18 38.71(15) . . . . ?
C29 N2 C18 C17 -75.44(16) . . . . ?
C19 N2 C18 C17 168.22(13) . . . . ?
Zr1 N2 C18 C17 45.50(14) . . . . ?
N1 C17 C18 N2 -57.39(17) . . . . ?
C18 N2 C19 C20 -57.26(16) . . . . ?
C29 N2 C19 C20 -175.75(12) . . . . ?
Zr1 N2 C19 C20 64.84(14) . . . . ?
N2 C19 C20 C25 142.97(14) . . . . ?
N2 C19 C20 C21 -40.6(2) . . . . ?
Zr1 O2 C21 C22 -174.69(12) . . . . ?
Zr1 O2 C21 C20 5.3(2) . . . . ?
C25 C20 C21 O2 176.48(13) . . . . ?
C19 C20 C21 O2 0.0(2) . . . . ?
C25 C20 C21 C22 -3.5(2) . . . . ?
C19 C20 C21 C22 -179.94(14) . . . . ?
O2 C21 C22 C23 -176.68(13) . . . . ?
C20 C21 C22 C23 3.3(2) . . . . ?
O2 C21 C22 C26 3.3(2) . . . . ?
C20 C21 C22 C26 -176.74(14) . . . . ?
C21 C22 C23 C24 -0.4(2) . . . . ?
C26 C22 C23 C24 179.67(15) . . . . ?
C22 C23 C24 C25 -2.3(2) . . . . ?
C22 C23 C24 C27 177.29(14) . . . . ?
C21 C20 C25 C24 0.8(2) . . . . ?
C19 C20 C25 C24 177.31(14) . . . . ?
C23 C24 C25 C20 2.1(2) . . . . ?
C27 C24 C25 C20 -177.50(14) . . . . ?

_refine_diff_density_max         0.348
_refine_diff_density_min         -0.426
_refine_diff_density_rms         0.048

_shelxl_version_number           2013-4


_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent: '
