# Electronic Supplementary Material (ESI) for Chemical Science.
# 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 
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data_a31w
_database_code_depnum_ccdc_archive 'CCDC 1501174'
_audit_update_record             
;
2016-08-26 deposited with the CCDC.
2016-12-13 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7


_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C16 H32.72 N4 O12.36 Zr'
_chemical_formula_weight         570.16

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      tetragonal
_space_group_IT_number           103
_space_group_name_H-M_alt        'P 4 c c'
_space_group_name_Hall           'P 4 -2c'

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

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

_cell_length_a                   13.0201(18)
_cell_length_b                   13.0201(18)
_cell_length_c                   13.1802(19)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     2234.3(7)
_cell_formula_units_Z            4
_cell_measurement_temperature    173(2)
_cell_measurement_reflns_used    9915
_cell_measurement_theta_min      3.46
_cell_measurement_theta_max      30.04

_exptl_crystal_description       needle
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.695
_exptl_crystal_F_000             1182
_exptl_transmission_factor_min   0.693
_exptl_transmission_factor_max   0.746
_exptl_crystal_size_max          0.420
_exptl_crystal_size_mid          0.080
_exptl_crystal_size_min          0.070
_exptl_absorpt_coefficient_mu    0.565
_shelx_estimated_absorpt_T_min   0.797
_shelx_estimated_absorpt_T_max   0.962
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.693
_exptl_absorpt_correction_T_max  0.746
_exptl_absorpt_process_details   
;
 Data were corrected for scaling and absorption effects using the
 multi-scan technique (SADABS). The ratio of minimum
 to maximum apparent transmission was 0.929. The
 calculated minimum and maximum transmission
 coefficients (based on crystal size) are 0.797 and 0.962.
;
_diffrn_ambient_temperature      173(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Bruker APEX CCD'
_diffrn_reflns_reduction_process narrow-frame
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            39474
_diffrn_reflns_av_unetI/netI     0.0151
_diffrn_reflns_av_R_equivalents  0.0318
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_theta_min         3.465
_diffrn_reflns_theta_max         30.058
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measured_fraction_theta_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_point_group_measured_fraction_full 0.997
_reflns_number_total             3278
_reflns_number_gt                2866
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.916
_reflns_Friedel_fraction_max     0.998
_reflns_Friedel_fraction_full    0.998

_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 SMART'
_computing_cell_refinement       'Bruker APEX2 v2014.11-0'
_computing_data_reduction        'Bruker APEX2 v2014.11-0'
_computing_structure_solution    'SHELXL-2014 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2014 (Sheldrick, 2014)'
_computing_molecular_graphics    'Bruker APEX2 v2014.11-0'
_computing_publication_material  'Bruker APEX2 v2014.11-0'
_computing.bruker_data_scaling   'SADABS V2012/1 (Bruker AXS)'

_refine_special_details          
;The contents of the asymmetric unit for the refined model,
 Zr0.5O4N2C8H12 - 2.18 H2O, included 1 ordered (site occupancy 0.25)
 and 1 disordered (site occupancies: 0.17/0.08) Zr center.  For the
 disordered Zr site, the 2 partial-occupancy O8N4C16H24 ligands, DOTA,
 are rotated about the c axis by ∼ 45° with respect to each other.
 The final model includes 6 partial occupancy water molecules for which
 2 oxygens were refined anisotropically and 4 oxygens were refined
 isotropically; only 3 water hydrogens were included in structural model
 (only 2 of which appear to make reasonable hydrogen-bonded contacts)., asymmetric unit contains 1 ordered and 1 disordered Zr center
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0493P)²+3.3847P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
;
 Flack x determined using 1231 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.032(14)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         3278
_refine_ls_number_parameters     240
_refine_ls_number_restraints     5
_refine_ls_R_factor_all          0.0500
_refine_ls_R_factor_gt           0.0432
_refine_ls_wR_factor_ref         0.1119
_refine_ls_wR_factor_gt          0.1061
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_restrained_S_all      1.067
_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
Zr1 Zr 0.0000 0.0000 0.64073(11) 0.01366(17) Uani 1 4 d S T P . .
O1 O 0.0273(3) 0.1420(2) 0.7169(3) 0.0289(7) Uani 1 1 d . . . . .
O2 O 0.1290(3) 0.2733(3) 0.7516(3) 0.0374(8) Uani 1 1 d . . . . .
N1 N 0.1234(3) 0.0951(3) 0.5413(3) 0.0263(8) Uani 1 1 d . . . . .
C1 C 0.0725(3) 0.1523(4) 0.4566(3) 0.0256(8) Uani 1 1 d . . . . .
H1A H 0.0554 0.1041 0.4010 0.031 Uiso 1 1 calc R U . . .
H1B H 0.1199 0.2050 0.4295 0.031 Uiso 1 1 calc R U . . .
C2 C 0.2028(4) 0.0237(4) 0.4948(4) 0.0320(10) Uani 1 1 d . . . . .
H2A H 0.2378 0.0590 0.4380 0.038 Uiso 1 1 calc R U . . .
H2B H 0.2551 0.0058 0.5464 0.038 Uiso 1 1 calc R U . . .
C3 C 0.1757(4) 0.1679(4) 0.6113(3) 0.0294(10) Uani 1 1 d . . . . .
H3A H 0.1963 0.2301 0.5731 0.035 Uiso 1 1 calc R U . . .
H3B H 0.2387 0.1354 0.6384 0.035 Uiso 1 1 calc R U . . .
C4 C 0.1061(4) 0.1992(3) 0.6996(3) 0.0249(8) Uani 1 1 d . . . . .
Zr2 Zr 0.5000 0.5000 0.40214(15) 0.0196(6) Uani 0.68 4 d S T P A 1
O3 O 0.3572(4) 0.4804(4) 0.4811(4) 0.0317(12) Uani 0.68 1 d . . P A 1
O4 O 0.2211(5) 0.3841(5) 0.5157(5) 0.0450(15) Uani 0.68 1 d . . P A 1
N2 N 0.3985(5) 0.3809(5) 0.3051(5) 0.0283(13) Uani 0.68 1 d . . P A 1
C5 C 0.3441(6) 0.4358(8) 0.2217(6) 0.0323(16) Uani 0.68 1 d . . P A 1
H5A H 0.3931 0.4508 0.1662 0.039 Uiso 0.68 1 calc R U P A 1
H5B H 0.2890 0.3914 0.1942 0.039 Uiso 0.68 1 calc R U P A 1
C6 C 0.4667(7) 0.2989(6) 0.2596(6) 0.0321(15) Uani 0.68 1 d . . P A 1
H6A H 0.4822 0.2463 0.3117 0.039 Uiso 0.68 1 calc R U P A 1
H6B H 0.4303 0.2648 0.2030 0.039 Uiso 0.68 1 calc R U P A 1
C7 C 0.3232(5) 0.3326(5) 0.3747(7) 0.035(2) Uani 0.68 1 d . . P A 1
H7A H 0.3519 0.2674 0.4008 0.042 Uiso 0.68 1 calc R U P A 1
H7B H 0.2597 0.3164 0.3366 0.042 Uiso 0.68 1 calc R U P A 1
C8 C 0.2964(6) 0.4034(6) 0.4648(5) 0.0323(15) Uani 0.68 1 d . . P A 1
Zr2' Zr 0.5000 0.5000 0.3626(3) 0.0126(8) Uani 0.32 4 d S T P B 2
O3' O 0.4128(8) 0.3849(8) 0.4402(7) 0.025(2) Uani 0.32 1 d . . P B 2
O4' O 0.3906(10) 0.2214(8) 0.4844(7) 0.034(3) Uani 0.32 1 d . . P B 2
N2' N 0.5099(9) 0.3431(10) 0.2616(8) 0.020(2) Uani 0.32 1 d . . P B 2
C5' C 0.6152(11) 0.3306(10) 0.2184(11) 0.019(2) Uani 0.32 1 d . . P B 2
H5'A H 0.6622 0.3032 0.2709 0.023 Uiso 0.32 1 calc R U P B 2
H5'B H 0.6135 0.2814 0.1611 0.023 Uiso 0.32 1 calc R U P B 2
C6' C 0.4309(9) 0.3476(8) 0.1829(8) 0.015(2) Uani 0.32 1 d . . P B 2
H6'A H 0.4220 0.2781 0.1539 0.018 Uiso 0.32 1 calc R U P B 2
H6'B H 0.4552 0.3932 0.1278 0.018 Uiso 0.32 1 calc R U P B 2
C7' C 0.4885(10) 0.2560(10) 0.3326(10) 0.023(2) Uani 0.32 1 d . . P B 2
H7'A H 0.5545 0.2273 0.3567 0.027 Uiso 0.32 1 calc R U P B 2
H7'B H 0.4519 0.2011 0.2953 0.027 Uiso 0.32 1 calc R U P B 2
C8' C 0.4209(11) 0.2895(10) 0.4287(9) 0.022(2) Uani 0.32 1 d . . P B 2
O5 O 0.1122(9) 0.5580(8) 0.5822(11) 0.100(4) Uani 0.68 1 d D . P C 1
H51 H 0.101(11) 0.565(12) 0.495(3) 0.120 Uiso 0.68 1 d D U P D 1
H52 H 0.052(8) 0.591(10) 0.636(7) 0.120 Uiso 0.68 1 d D U P E 1
O6 O 0.0630(6) 0.6214(7) 0.7872(7) 0.101(3) Uani 0.9 1 d D . P F 1
H61 H -0.024(3) 0.622(9) 0.798(10) 0.121 Uiso 0.9 1 d D U P G 1
O5' O 0.0000 0.5000 0.640(8) 0.076(14) Uiso 0.14 2 d S . P H 2
O6' O -0.028(5) 0.571(5) 0.873(5) 0.076(16) Uiso 0.1 1 d . . P I 2
O7' O 0.093(2) 0.433(2) 0.5030(18) 0.080(7) Uiso 0.25 1 d . . P J 2
O7" O 0.025(3) 0.499(4) 0.436(2) 0.081(11) Uiso 0.18 1 d . . P K 3


_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 O1 2.133(3) . ?
Zr1 O1 2.133(3) 4 ?
Zr1 O1 2.133(3) 2 ?
Zr1 O1 2.133(3) 3 ?
Zr1 N1 2.415(4) 2 ?
Zr1 N1 2.415(4) 4 ?
Zr1 N1 2.415(4) . ?
Zr1 N1 2.415(4) 3 ?
O1 C4 1.287(5) . ?
O2 C4 1.221(5) . ?
N1 C3 1.488(6) . ?
N1 C1 1.496(5) . ?
N1 C2 1.519(6) . ?
C1 C2 1.503(7) 3 ?
C1 H1A 0.9900 . ?
C1 H1B 0.9900 . ?
C2 C1 1.503(7) 4 ?
C2 H2A 0.9900 . ?
C2 H2B 0.9900 . ?
C3 C4 1.531(6) . ?
C3 H3A 0.9900 . ?
C3 H3B 0.9900 . ?
Zr2 O3 2.146(5) 2_665 ?
Zr2 O3 2.146(5) 4_565 ?
Zr2 O3 2.146(5) 3_655 ?
Zr2 O3 2.146(5) . ?
Zr2 N2 2.406(6) . ?
Zr2 N2 2.406(6) 2_665 ?
Zr2 N2 2.406(6) 4_565 ?
Zr2 N2 2.406(6) 3_655 ?
O3 C8 1.295(9) . ?
O4 C8 1.215(9) . ?
N2 C7 1.482(9) . ?
N2 C5 1.490(10) . ?
N2 C6 1.512(9) . ?
C5 C6 1.486(12) 4_565 ?
C5 H5A 0.9900 . ?
C5 H5B 0.9900 . ?
C6 C5 1.486(12) 3_655 ?
C6 H6A 0.9900 . ?
C6 H6B 0.9900 . ?
C7 C8 1.543(11) . ?
C7 H7A 0.9900 . ?
C7 H7B 0.9900 . ?
Zr2' O3' 2.140(10) 2_665 ?
Zr2' O3' 2.140(10) 3_655 ?
Zr2' O3' 2.140(10) . ?
Zr2' O3' 2.140(10) 4_565 ?
Zr2' N2' 2.443(13) 4_565 ?
Zr2' N2' 2.443(13) . ?
Zr2' N2' 2.443(13) 3_655 ?
Zr2' N2' 2.443(13) 2_665 ?
O3' C8' 1.255(17) . ?
O4' C8' 1.217(14) . ?
N2' C6' 1.461(15) . ?
N2' C5' 1.493(17) . ?
N2' C7' 1.496(17) . ?
C5' C6' 1.469(17) 3_655 ?
C5' H5'A 0.9900 . ?
C5' H5'B 0.9900 . ?
C6' C5' 1.469(17) 4_565 ?
C6' H6'A 0.9900 . ?
C6' H6'B 0.9900 . ?
C7' C8' 1.603(19) . ?
C7' H7'A 0.9900 . ?
C7' H7'B 0.9900 . ?
O5 H51 1.16(3) . ?
O5 H52 1.14(3) . ?
O6 H61 1.14(3) . ?
O7" O7" 0.65(7) 2_565 ?

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 Zr1 O1 77.22(8) . 4 ?
O1 Zr1 O1 123.88(18) . 2 ?
O1 Zr1 O1 77.22(8) 4 2 ?
O1 Zr1 O1 77.22(8) . 3 ?
O1 Zr1 O1 123.88(18) 4 3 ?
O1 Zr1 O1 77.22(8) 2 3 ?
O1 Zr1 N1 144.16(13) . 2 ?
O1 Zr1 N1 138.26(13) 4 2 ?
O1 Zr1 N1 72.53(13) 2 2 ?
O1 Zr1 N1 76.37(13) 3 2 ?
O1 Zr1 N1 138.26(13) . 4 ?
O1 Zr1 N1 72.53(13) 4 4 ?
O1 Zr1 N1 76.37(13) 2 4 ?
O1 Zr1 N1 144.16(13) 3 4 ?
N1 Zr1 N1 72.88(9) 2 4 ?
O1 Zr1 N1 72.53(13) . . ?
O1 Zr1 N1 76.37(13) 4 . ?
O1 Zr1 N1 144.16(13) 2 . ?
O1 Zr1 N1 138.26(13) 3 . ?
N1 Zr1 N1 114.28(18) 2 . ?
N1 Zr1 N1 72.88(9) 4 . ?
O1 Zr1 N1 76.37(13) . 3 ?
O1 Zr1 N1 144.16(13) 4 3 ?
O1 Zr1 N1 138.26(13) 2 3 ?
O1 Zr1 N1 72.53(13) 3 3 ?
N1 Zr1 N1 72.88(9) 2 3 ?
N1 Zr1 N1 114.28(18) 4 3 ?
N1 Zr1 N1 72.88(9) . 3 ?
C4 O1 Zr1 123.4(3) . . ?
C3 N1 C1 110.4(4) . . ?
C3 N1 C2 109.2(4) . . ?
C1 N1 C2 107.7(3) . . ?
C3 N1 Zr1 107.2(3) . . ?
C1 N1 Zr1 111.4(3) . . ?
C2 N1 Zr1 111.0(3) . . ?
N1 C1 C2 109.7(3) . 3 ?
N1 C1 H1A 109.7 . . ?
C2 C1 H1A 109.7 3 . ?
N1 C1 H1B 109.7 . . ?
C2 C1 H1B 109.7 3 . ?
H1A C1 H1B 108.2 . . ?
C1 C2 N1 110.4(4) 4 . ?
C1 C2 H2A 109.6 4 . ?
N1 C2 H2A 109.6 . . ?
C1 C2 H2B 109.6 4 . ?
N1 C2 H2B 109.6 . . ?
H2A C2 H2B 108.1 . . ?
N1 C3 C4 111.7(4) . . ?
N1 C3 H3A 109.3 . . ?
C4 C3 H3A 109.3 . . ?
N1 C3 H3B 109.3 . . ?
C4 C3 H3B 109.3 . . ?
H3A C3 H3B 107.9 . . ?
O2 C4 O1 123.6(4) . . ?
O2 C4 C3 119.5(4) . . ?
O1 C4 C3 116.9(4) . . ?
O3 Zr2 O3 76.39(13) 2_665 4_565 ?
O3 Zr2 O3 76.39(13) 2_665 3_655 ?
O3 Zr2 O3 122.0(3) 4_565 3_655 ?
O3 Zr2 O3 122.0(3) 2_665 . ?
O3 Zr2 O3 76.39(13) 4_565 . ?
O3 Zr2 O3 76.39(13) 3_655 . ?
O3 Zr2 N2 144.1(2) 2_665 . ?
O3 Zr2 N2 138.7(2) 4_565 . ?
O3 Zr2 N2 76.4(2) 3_655 . ?
O3 Zr2 N2 72.9(2) . . ?
O3 Zr2 N2 72.9(2) 2_665 2_665 ?
O3 Zr2 N2 76.4(2) 4_565 2_665 ?
O3 Zr2 N2 138.7(2) 3_655 2_665 ?
O3 Zr2 N2 144.1(2) . 2_665 ?
N2 Zr2 N2 115.8(3) . 2_665 ?
O3 Zr2 N2 138.7(2) 2_665 4_565 ?
O3 Zr2 N2 72.9(2) 4_565 4_565 ?
O3 Zr2 N2 144.1(2) 3_655 4_565 ?
O3 Zr2 N2 76.4(2) . 4_565 ?
N2 Zr2 N2 73.58(15) . 4_565 ?
N2 Zr2 N2 73.58(15) 2_665 4_565 ?
O3 Zr2 N2 76.4(2) 2_665 3_655 ?
O3 Zr2 N2 144.1(2) 4_565 3_655 ?
O3 Zr2 N2 72.9(2) 3_655 3_655 ?
O3 Zr2 N2 138.7(2) . 3_655 ?
N2 Zr2 N2 73.58(15) . 3_655 ?
N2 Zr2 N2 73.58(15) 2_665 3_655 ?
N2 Zr2 N2 115.8(3) 4_565 3_655 ?
C8 O3 Zr2 122.7(5) . . ?
C7 N2 C5 110.2(6) . . ?
C7 N2 C6 109.6(6) . . ?
C5 N2 C6 109.0(6) . . ?
C7 N2 Zr2 107.9(5) . . ?
C5 N2 Zr2 110.1(5) . . ?
C6 N2 Zr2 110.0(4) . . ?
C6 C5 N2 110.5(6) 4_565 . ?
C6 C5 H5A 109.6 4_565 . ?
N2 C5 H5A 109.6 . . ?
C6 C5 H5B 109.6 4_565 . ?
N2 C5 H5B 109.6 . . ?
H5A C5 H5B 108.1 . . ?
C5 C6 N2 110.8(6) 3_655 . ?
C5 C6 H6A 109.5 3_655 . ?
N2 C6 H6A 109.5 . . ?
C5 C6 H6B 109.5 3_655 . ?
N2 C6 H6B 109.5 . . ?
H6A C6 H6B 108.1 . . ?
N2 C7 C8 111.9(6) . . ?
N2 C7 H7A 109.2 . . ?
C8 C7 H7A 109.2 . . ?
N2 C7 H7B 109.2 . . ?
C8 C7 H7B 109.2 . . ?
H7A C7 H7B 107.9 . . ?
O4 C8 O3 124.2(7) . . ?
O4 C8 C7 118.9(7) . . ?
O3 C8 C7 116.9(6) . . ?
O3' Zr2' O3' 76.8(2) 2_665 3_655 ?
O3' Zr2' O3' 123.0(5) 2_665 . ?
O3' Zr2' O3' 76.8(2) 3_655 . ?
O3' Zr2' O3' 76.8(2) 2_665 4_565 ?
O3' Zr2' O3' 123.0(5) 3_655 4_565 ?
O3' Zr2' O3' 76.8(2) . 4_565 ?
O3' Zr2' N2' 137.8(4) 2_665 4_565 ?
O3' Zr2' N2' 144.9(4) 3_655 4_565 ?
O3' Zr2' N2' 77.3(4) . 4_565 ?
O3' Zr2' N2' 72.7(4) 4_565 4_565 ?
O3' Zr2' N2' 144.9(4) 2_665 . ?
O3' Zr2' N2' 77.3(4) 3_655 . ?
O3' Zr2' N2' 72.7(4) . . ?
O3' Zr2' N2' 137.8(4) 4_565 . ?
N2' Zr2' N2' 72.7(3) 4_565 . ?
O3' Zr2' N2' 77.3(4) 2_665 3_655 ?
O3' Zr2' N2' 72.7(4) 3_655 3_655 ?
O3' Zr2' N2' 137.8(4) . 3_655 ?
O3' Zr2' N2' 144.9(4) 4_565 3_655 ?
N2' Zr2' N2' 113.9(5) 4_565 3_655 ?
N2' Zr2' N2' 72.7(3) . 3_655 ?
O3' Zr2' N2' 72.7(4) 2_665 2_665 ?
O3' Zr2' N2' 137.8(4) 3_655 2_665 ?
O3' Zr2' N2' 144.9(4) . 2_665 ?
O3' Zr2' N2' 77.3(4) 4_565 2_665 ?
N2' Zr2' N2' 72.7(3) 4_565 2_665 ?
N2' Zr2' N2' 113.9(5) . 2_665 ?
N2' Zr2' N2' 72.7(3) 3_655 2_665 ?
C8' O3' Zr2' 126.2(9) . . ?
C6' N2' C5' 112.4(10) . . ?
C6' N2' C7' 110.1(10) . . ?
C5' N2' C7' 109.1(11) . . ?
C6' N2' Zr2' 108.4(8) . . ?
C5' N2' Zr2' 110.3(8) . . ?
C7' N2' Zr2' 106.4(8) . . ?
C6' C5' N2' 109.1(11) 3_655 . ?
C6' C5' H5'A 109.9 3_655 . ?
N2' C5' H5'A 109.9 . . ?
C6' C5' H5'B 109.9 3_655 . ?
N2' C5' H5'B 109.9 . . ?
H5'A C5' H5'B 108.3 . . ?
N2' C6' C5' 114.4(10) . 4_565 ?
N2' C6' H6'A 108.7 . . ?
C5' C6' H6'A 108.7 4_565 . ?
N2' C6' H6'B 108.7 . . ?
C5' C6' H6'B 108.7 4_565 . ?
H6'A C6' H6'B 107.6 . . ?
N2' C7' C8' 113.0(10) . . ?
N2' C7' H7'A 109.0 . . ?
C8' C7' H7'A 109.0 . . ?
N2' C7' H7'B 109.0 . . ?
C8' C7' H7'B 109.0 . . ?
H7'A C7' H7'B 107.8 . . ?
O4' C8' O3' 128.4(13) . . ?
O4' C8' C7' 117.1(12) . . ?
O3' C8' C7' 114.2(10) . . ?
H51 O5 H52 120(4) . . ?

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
C3 N1 C1 C2 -75.4(5) . . . 3 ?
C2 N1 C1 C2 165.5(4) . . . 3 ?
Zr1 N1 C1 C2 43.5(4) . . . 3 ?
C3 N1 C2 C1 158.8(4) . . . 4 ?
C1 N1 C2 C1 -81.3(5) . . . 4 ?
Zr1 N1 C2 C1 40.9(4) . . . 4 ?
C1 N1 C3 C4 92.9(4) . . . . ?
C2 N1 C3 C4 -148.8(4) . . . . ?
Zr1 N1 C3 C4 -28.6(5) . . . . ?
Zr1 O1 C4 O2 -170.2(4) . . . . ?
Zr1 O1 C4 C3 7.2(5) . . . . ?
N1 C3 C4 O2 -165.2(4) . . . . ?
N1 C3 C4 O1 17.3(6) . . . . ?
C7 N2 C5 C6 74.9(8) . . . 4_565 ?
C6 N2 C5 C6 -164.8(7) . . . 4_565 ?
Zr2 N2 C5 C6 -44.1(7) . . . 4_565 ?
C7 N2 C6 C5 -159.0(6) . . . 3_655 ?
C5 N2 C6 C5 80.3(9) . . . 3_655 ?
Zr2 N2 C6 C5 -40.5(7) . . . 3_655 ?
C5 N2 C7 C8 -93.0(8) . . . . ?
C6 N2 C7 C8 147.1(6) . . . . ?
Zr2 N2 C7 C8 27.3(7) . . . . ?
Zr2 O3 C8 O4 171.5(6) . . . . ?
Zr2 O3 C8 C7 -8.3(9) . . . . ?
N2 C7 C8 O4 164.7(7) . . . . ?
N2 C7 C8 O3 -15.5(10) . . . . ?
C6' N2' C5' C6' 79.8(14) . . . 3_655 ?
C7' N2' C5' C6' -157.8(10) . . . 3_655 ?
Zr2' N2' C5' C6' -41.3(11) . . . 3_655 ?
C5' N2' C6' C5' -165.7(12) . . . 4_565 ?
C7' N2' C6' C5' 72.5(14) . . . 4_565 ?
Zr2' N2' C6' C5' -43.5(12) . . . 4_565 ?
C6' N2' C7' C8' -91.9(12) . . . . ?
C5' N2' C7' C8' 144.3(10) . . . . ?
Zr2' N2' C7' C8' 25.4(11) . . . . ?
Zr2' O3' C8' O4' 162.6(12) . . . . ?
Zr2' O3' C8' C7' -11.7(16) . . . . ?
N2' C7' C8' O4' 172.2(12) . . . . ?
N2' C7' C8' O3' -12.8(16) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
O5 H52 O6 1.14(3) 2.04(10) 2.897(15) 129(9) .
O6 H61 O2 1.14(3) 2.03(10) 2.890(8) 129(9) 2_565

_refine_diff_density_max         0.863
_refine_diff_density_min         -0.816
_refine_diff_density_rms         0.090


