# Supplementary Material (ESI) for Dalton Transactions
# This journal is (c) The Royal Society of Chemistry 2009

data_global

_journal_coden_Cambridge         222
_journal_volume                  ?
_journal_page_first              ?
_journal_year                    ?

loop_
_publ_author_name
'Deanna Zubris'
'Karen P. Chiang'
'William G. Dougherty'
'Timothy J. Dudley'
'William S. Kassel'
'Margaret D. Kennedy'
'Janelle E. Steves'

_publ_contact_author_name        'Deanna Zubris'
_publ_contact_author_email       DEANNA.ZUBRIS@VILLANOVA.EDU

_publ_section_title              
;
Synthesis of a bulky bis(imino)pyridine ligand: A
methodology for systematic variation of steric bulk and energetic
implications for metallation.
;

# Attachment 'compound_3.cif'

data_zubr004
_database_code_depnum_ccdc_archive 'CCDC 702075'

_audit_creation_method           SHELXL-97

_chemical_name_systematic        
;

?

;

_chemical_name_common            ?

_chemical_melting_point          ?

_chemical_formula_moiety         ?

_chemical_formula_sum            'C18 H21 Br N2'

_chemical_formula_weight         345.28

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'
Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Monoclinic

_symmetry_space_group_name_H-M   P2(1)/n

loop_

_symmetry_equiv_pos_as_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                   9.5839(5)

_cell_length_b                   9.2243(5)

_cell_length_c                   18.6962(10)

_cell_angle_alpha                90.00

_cell_angle_beta                 91.4300(10)

_cell_angle_gamma                90.00

_cell_volume                     1652.32(15)

_cell_formula_units_Z            4

_cell_measurement_temperature    100(2)

_cell_measurement_reflns_used    8258

_cell_measurement_theta_min      2.18

_cell_measurement_theta_max      28.17

_exptl_crystal_description       block

_exptl_crystal_colour            colourless

_exptl_crystal_size_max          0.22

_exptl_crystal_size_mid          0.14

_exptl_crystal_size_min          0.07

_exptl_crystal_density_meas      ?

_exptl_crystal_density_diffrn    1.388

_exptl_crystal_density_method    'not measured'

_exptl_crystal_F_000             712

_exptl_absorpt_coefficient_mu    2.484

_exptl_absorpt_correction_type   none

_exptl_absorpt_correction_T_min  0.6086

_exptl_absorpt_correction_T_max  0.8473

_exptl_absorpt_process_details   ?

_exptl_special_details           
;

?

;

_diffrn_ambient_temperature      100(2)

_diffrn_radiation_wavelength     0.71073

_diffrn_radiation_type           MoK\a

_diffrn_radiation_source         'fine-focus sealed tube'

_diffrn_radiation_monochromator  graphite

_diffrn_measurement_device_type  'CCD area detector'

_diffrn_measurement_method       'phi and omega scans'

_diffrn_detector_area_resol_mean ?

_diffrn_standards_number         ?

_diffrn_standards_interval_count ?

_diffrn_standards_interval_time  ?

_diffrn_standards_decay_%        ?

_diffrn_reflns_number            11499

_diffrn_reflns_av_R_equivalents  0.0364

_diffrn_reflns_av_sigmaI/netI    0.0293

_diffrn_reflns_limit_h_min       -11

_diffrn_reflns_limit_h_max       12

_diffrn_reflns_limit_k_min       -12

_diffrn_reflns_limit_k_max       11

_diffrn_reflns_limit_l_min       -23

_diffrn_reflns_limit_l_max       24

_diffrn_reflns_theta_min         2.18

_diffrn_reflns_theta_max         28.37

_reflns_number_total             3812

_reflns_number_gt                3439

_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker SMART'

_computing_cell_refinement       'Bruker SMART'

_computing_data_reduction        'Bruker SAINT'

_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'

_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'

_computing_molecular_graphics    'Bruker SHELXTL'

_computing_publication_material  'Bruker SHELXTL'

_refine_special_details          
;

Refinement of F^2^ against ALL reflections. The weighted R-factor wR and

goodness of fit S are based on F^2^, conventional R-factors R are based

on F, with F set to zero for negative F^2^. The threshold expression of

F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is

not relevant to the choice of reflections for refinement. R-factors based

on F^2^ are statistically about twice as large as those based on F, and R-

factors based on ALL data will be even larger.

;

_refine_ls_structure_factor_coef Fsqd

_refine_ls_matrix_type           full

_refine_ls_weighting_scheme      calc

_refine_ls_weighting_details     
'calc w=1/[\s^2^(Fo^2^)+(0.0544P)^2^+0.6111P] where P=(Fo^2^+2Fc^2^)/3'

_atom_sites_solution_primary     direct

_atom_sites_solution_secondary   difmap

_atom_sites_solution_hydrogens   geom

_refine_ls_hydrogen_treatment    constr

_refine_ls_extinction_method     none

_refine_ls_extinction_coef       ?

_refine_ls_number_reflns         3812

_refine_ls_number_parameters     195

_refine_ls_number_restraints     0

_refine_ls_R_factor_all          0.0360

_refine_ls_R_factor_gt           0.0320

_refine_ls_wR_factor_ref         0.0886

_refine_ls_wR_factor_gt          0.0859

_refine_ls_goodness_of_fit_ref   1.048

_refine_ls_restrained_S_all      1.048

_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_symmetry_multiplicity

_atom_site_calc_flag

_atom_site_refinement_flags

_atom_site_disorder_assembly

_atom_site_disorder_group

Br Br 0.682965(19) 0.06744(2) 0.024776(10) 0.02818(9) Uani 1 1 d . . .
N1 N 0.88107(14) 0.11622(15) 0.13105(7) 0.0163(3) Uani 1 1 d . . .
N2 N 1.12455(15) 0.29166(14) 0.22264(7) 0.0168(3) Uani 1 1 d . . .
C1 C 0.84794(17) 0.02375(18) 0.07932(9) 0.0168(3) Uani 1 1 d . . .
C2 C 0.92217(18) -0.10026(18) 0.06178(9) 0.0195(3) Uani 1 1 d . . .
H2B H 0.8932 -0.1617 0.0234 0.023 Uiso 1 1 calc R . .
C3 C 1.04054(18) -0.12943(17) 0.10316(9) 0.0202(3) Uani 1 1 d . . .
H3A H 1.0951 -0.2130 0.0938 0.024 Uiso 1 1 calc R . .
C4 C 1.07923(18) -0.03605(17) 0.15841(9) 0.0183(3) Uani 1 1 d . . .
H4A H 1.1597 -0.0552 0.1876 0.022 Uiso 1 1 calc R . .
C5 C 0.99776(17) 0.08610(16) 0.17010(9) 0.0149(3) Uani 1 1 d . . .
C6 C 1.03659(17) 0.18980(16) 0.22987(8) 0.0147(3) Uani 1 1 d . . .
C7 C 0.96322(18) 0.17253(17) 0.30111(9) 0.0169(3) Uani 1 1 d . . .
C8 C 0.8360(2) 0.2743(2) 0.29851(11) 0.0292(4) Uani 1 1 d . . .
H8A H 0.7764 0.2505 0.2568 0.044 Uiso 1 1 calc R . .
H8B H 0.8677 0.3750 0.2949 0.044 Uiso 1 1 calc R . .
H8C H 0.7828 0.2623 0.3422 0.044 Uiso 1 1 calc R . .
C9 C 1.0617(2) 0.2152(2) 0.36315(9) 0.0274(4) Uani 1 1 d . . .
H9A H 1.0948 0.3145 0.3560 0.041 Uiso 1 1 calc R . .
H9B H 1.1415 0.1488 0.3650 0.041 Uiso 1 1 calc R . .
H9C H 1.0118 0.2096 0.4082 0.041 Uiso 1 1 calc R . .
C10 C 0.9120(2) 0.01675(19) 0.31121(9) 0.0230(4) Uani 1 1 d . . .
H10A H 0.8434 -0.0072 0.2733 0.035 Uiso 1 1 calc R . .
H10B H 0.8687 0.0078 0.3579 0.035 Uiso 1 1 calc R . .
H10C H 0.9913 -0.0500 0.3089 0.035 Uiso 1 1 calc R . .
C11 C 1.17989(17) 0.32459(16) 0.15434(9) 0.0164(3) Uani 1 1 d . . .
C12 C 1.30974(18) 0.27003(17) 0.13445(9) 0.0196(3) Uani 1 1 d . . .
C13 C 1.3916(2) 0.16761(19) 0.18211(11) 0.0268(4) Uani 1 1 d . . .
H13A H 1.4904 0.1713 0.1700 0.040 Uiso 1 1 calc R . .
H13B H 1.3564 0.0687 0.1752 0.040 Uiso 1 1 calc R . .
H13C H 1.3813 0.1962 0.2322 0.040 Uiso 1 1 calc R . .
C14 C 1.36302(19) 0.31657(19) 0.06959(10) 0.0236(4) Uani 1 1 d . . .
H14A H 1.4496 0.2787 0.0545 0.028 Uiso 1 1 calc R . .
C15 C 1.2933(2) 0.41613(19) 0.02679(10) 0.0239(4) Uani 1 1 d . . .
H15A H 1.3320 0.4467 -0.0170 0.029 Uiso 1 1 calc R . .
C16 C 1.16579(19) 0.47144(19) 0.04829(9) 0.0202(3) Uani 1 1 d . . .
H16A H 1.1185 0.5409 0.0191 0.024 Uiso 1 1 calc R . .
C17 C 1.10656(18) 0.42683(16) 0.11168(9) 0.0170(3) Uani 1 1 d . . .
C18 C 0.96822(18) 0.48509(18) 0.13524(9) 0.0193(3) Uani 1 1 d . . .
H18A H 0.9372 0.5624 0.1026 0.029 Uiso 1 1 calc R . .
H18B H 0.9785 0.5239 0.1839 0.029 Uiso 1 1 calc R . .
H18C H 0.8991 0.4068 0.1346 0.029 Uiso 1 1 calc R . .

loop_

_atom_site_aniso_label

_atom_site_aniso_U_11

_atom_site_aniso_U_22

_atom_site_aniso_U_33

_atom_site_aniso_U_23

_atom_site_aniso_U_13

_atom_site_aniso_U_12

Br 0.02101(13) 0.03880(13) 0.02428(12) -0.00739(7) -0.00825(8) 0.00561(7)
N1 0.0158(7) 0.0173(6) 0.0159(6) -0.0002(5) 0.0002(5) 0.0002(5)
N2 0.0159(7) 0.0166(6) 0.0178(6) 0.0004(5) -0.0005(5) 0.0009(5)
C1 0.0126(8) 0.0212(7) 0.0164(7) 0.0009(6) -0.0003(6) -0.0015(6)
C2 0.0196(9) 0.0191(7) 0.0198(8) -0.0045(6) 0.0045(7) -0.0038(6)
C3 0.0184(8) 0.0159(7) 0.0264(9) -0.0025(6) 0.0050(7) 0.0001(6)
C4 0.0149(8) 0.0169(7) 0.0231(8) 0.0007(6) 0.0000(7) 0.0009(6)
C5 0.0137(8) 0.0154(7) 0.0157(7) 0.0011(5) 0.0017(6) -0.0021(5)
C6 0.0135(7) 0.0144(7) 0.0160(7) 0.0002(5) -0.0023(6) 0.0036(5)
C7 0.0161(8) 0.0183(7) 0.0163(7) 0.0002(6) 0.0006(6) 0.0002(6)
C8 0.0275(10) 0.0319(9) 0.0287(9) 0.0022(8) 0.0084(8) 0.0106(8)
C9 0.0326(10) 0.0327(9) 0.0167(8) 0.0020(7) -0.0031(7) -0.0127(8)
C10 0.0248(9) 0.0231(8) 0.0212(8) 0.0006(7) 0.0026(7) -0.0066(7)
C11 0.0165(8) 0.0149(7) 0.0178(7) -0.0032(6) 0.0004(6) -0.0034(6)
C12 0.0174(8) 0.0174(7) 0.0240(8) -0.0039(6) 0.0004(7) -0.0013(6)
C13 0.0204(9) 0.0212(8) 0.0389(11) 0.0030(7) 0.0018(8) 0.0038(7)
C14 0.0188(9) 0.0260(8) 0.0261(9) -0.0084(7) 0.0050(7) -0.0012(6)
C15 0.0249(10) 0.0292(9) 0.0178(8) -0.0037(6) 0.0038(7) -0.0055(7)
C16 0.0208(9) 0.0226(8) 0.0171(7) -0.0014(6) -0.0023(6) -0.0028(6)
C17 0.0168(9) 0.0158(7) 0.0183(8) -0.0039(6) -0.0020(7) -0.0027(5)
C18 0.0189(9) 0.0197(7) 0.0193(8) 0.0005(6) -0.0002(6) 0.0018(6)

_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

Br C1 1.9032(16) . ?
N1 C1 1.322(2) . ?
N1 C5 1.349(2) . ?
N2 C6 1.272(2) . ?
N2 C11 1.427(2) . ?
C1 C2 1.391(2) . ?
C2 C3 1.384(3) . ?
C3 C4 1.388(2) . ?
C4 C5 1.391(2) . ?
C5 C6 1.510(2) . ?
C6 C7 1.530(2) . ?
C7 C9 1.528(2) . ?
C7 C10 1.532(2) . ?
C7 C8 1.539(2) . ?
C11 C12 1.401(2) . ?
C11 C17 1.411(2) . ?
C12 C14 1.395(3) . ?
C12 C13 1.506(2) . ?
C14 C15 1.380(3) . ?
C15 C16 1.393(3) . ?
C16 C17 1.389(2) . ?
C17 C18 1.507(2) . ?

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

C1 N1 C5 116.33(14) . . ?
C6 N2 C11 120.95(14) . . ?
N1 C1 C2 126.04(15) . . ?
N1 C1 Br 115.88(12) . . ?
C2 C1 Br 118.09(12) . . ?
C3 C2 C1 116.43(15) . . ?
C2 C3 C4 119.70(15) . . ?
C3 C4 C5 118.61(16) . . ?
N1 C5 C4 122.86(15) . . ?
N1 C5 C6 117.10(13) . . ?
C4 C5 C6 120.02(15) . . ?
N2 C6 C5 122.75(15) . . ?
N2 C6 C7 119.32(15) . . ?
C5 C6 C7 117.91(13) . . ?
C9 C7 C6 110.21(14) . . ?
C9 C7 C10 109.96(14) . . ?
C6 C7 C10 111.14(13) . . ?
C9 C7 C8 109.91(15) . . ?
C6 C7 C8 106.86(13) . . ?
C10 C7 C8 108.69(15) . . ?
C12 C11 C17 121.53(16) . . ?
C12 C11 N2 120.88(15) . . ?
C17 C11 N2 117.19(15) . . ?
C14 C12 C11 117.84(16) . . ?
C14 C12 C13 120.72(16) . . ?
C11 C12 C13 121.42(16) . . ?
C15 C14 C12 121.77(17) . . ?
C14 C15 C16 119.48(17) . . ?
C17 C16 C15 121.19(17) . . ?
C16 C17 C11 118.15(16) . . ?
C16 C17 C18 121.68(15) . . ?
C11 C17 C18 120.17(15) . . ?

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

C5 N1 C1 C2 -0.1(2) . . . . ?
C5 N1 C1 Br 179.92(11) . . . . ?
N1 C1 C2 C3 0.8(3) . . . . ?
Br C1 C2 C3 -179.23(12) . . . . ?
C1 C2 C3 C4 -0.4(2) . . . . ?
C2 C3 C4 C5 -0.7(2) . . . . ?
C1 N1 C5 C4 -1.0(2) . . . . ?
C1 N1 C5 C6 -179.47(14) . . . . ?
C3 C4 C5 N1 1.5(2) . . . . ?
C3 C4 C5 C6 179.84(15) . . . . ?
C11 N2 C6 C5 7.5(2) . . . . ?
C11 N2 C6 C7 -170.80(13) . . . . ?
N1 C5 C6 N2 -96.65(19) . . . . ?
C4 C5 C6 N2 84.9(2) . . . . ?
N1 C5 C6 C7 81.70(18) . . . . ?
C4 C5 C6 C7 -96.77(18) . . . . ?
N2 C6 C7 C9 -34.2(2) . . . . ?
C5 C6 C7 C9 147.42(15) . . . . ?
N2 C6 C7 C10 -156.33(15) . . . . ?
C5 C6 C7 C10 25.3(2) . . . . ?
N2 C6 C7 C8 85.23(18) . . . . ?
C5 C6 C7 C8 -93.18(17) . . . . ?
C6 N2 C11 C12 -97.36(19) . . . . ?
C6 N2 C11 C17 89.75(18) . . . . ?
C17 C11 C12 C14 -2.0(2) . . . . ?
N2 C11 C12 C14 -174.55(14) . . . . ?
C17 C11 C12 C13 176.40(15) . . . . ?
N2 C11 C12 C13 3.8(2) . . . . ?
C11 C12 C14 C15 1.8(2) . . . . ?
C13 C12 C14 C15 -176.58(17) . . . . ?
C12 C14 C15 C16 -0.4(3) . . . . ?
C14 C15 C16 C17 -0.8(3) . . . . ?
C15 C16 C17 C11 0.6(2) . . . . ?
C15 C16 C17 C18 -179.56(15) . . . . ?
C12 C11 C17 C16 0.8(2) . . . . ?
N2 C11 C17 C16 173.63(14) . . . . ?
C12 C11 C17 C18 -179.02(14) . . . . ?
N2 C11 C17 C18 -6.2(2) . . . . ?

_diffrn_measured_fraction_theta_max 0.922

_diffrn_reflns_theta_full        25.00

_diffrn_measured_fraction_theta_full 0.992

_refine_diff_density_max         1.041

_refine_diff_density_min         -0.331

_refine_diff_density_rms         0.079

# Attachment 'compound_6.cif'

data_zubr009
_database_code_depnum_ccdc_archive 'CCDC 702076'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C31 H39 N3'
_chemical_formula_weight         453.65

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 '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 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Monoclinic
_symmetry_space_group_name_H-M   P2(1)/c

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

_cell_length_a                   11.5027(4)
_cell_length_b                   11.6244(4)
_cell_length_c                   20.8562(7)
_cell_angle_alpha                90.00
_cell_angle_beta                 105.5970(10)
_cell_angle_gamma                90.00
_cell_volume                     2686.03(16)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    9914
_cell_measurement_theta_min      3.99
_cell_measurement_theta_max      67.96

_exptl_crystal_description       block
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          0.27
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.15
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.122
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             984
_exptl_absorpt_coefficient_mu    0.496
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.8785
_exptl_absorpt_correction_T_max  0.9297
_exptl_absorpt_process_details   SADABS

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     1.54178
_diffrn_radiation_type           CuK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            19187
_diffrn_reflns_av_R_equivalents  0.0226
_diffrn_reflns_av_sigmaI/netI    0.0228
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_theta_min         3.99
_diffrn_reflns_theta_max         68.15
_reflns_number_total             4836
_reflns_number_gt                4604
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_refine_special_details          
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ are statistically about twice as large as those based on F, and R-
factors based on ALL data will be even larger.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[\s^2^(Fo^2^)+(0.0411P)^2^+1.0911P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         4836
_refine_ls_number_parameters     317
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0419
_refine_ls_R_factor_gt           0.0402
_refine_ls_wR_factor_ref         0.1014
_refine_ls_wR_factor_gt          0.1003
_refine_ls_goodness_of_fit_ref   1.066
_refine_ls_restrained_S_all      1.066
_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_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
N1 N 0.65054(9) 0.71032(8) 0.14122(5) 0.0209(2) Uani 1 1 d . . .
N2 N 0.39269(9) 0.88292(9) 0.09403(5) 0.0229(2) Uani 1 1 d . . .
N3 N 0.89684(9) 0.64081(9) 0.10695(5) 0.0232(2) Uani 1 1 d . . .
C1 C 0.52945(10) 0.71813(10) 0.12562(5) 0.0206(2) Uani 1 1 d . . .
C2 C 0.45413(11) 0.62617(11) 0.09941(6) 0.0232(3) Uani 1 1 d . . .
H2B H 0.3690 0.6336 0.0901 0.028 Uiso 1 1 calc R . .
C3 C 0.50565(11) 0.52358(10) 0.08719(6) 0.0244(3) Uani 1 1 d . . .
H3B H 0.4562 0.4596 0.0693 0.029 Uiso 1 1 calc R . .
C4 C 0.63042(11) 0.51550(10) 0.10145(6) 0.0241(3) Uani 1 1 d . . .
H4A H 0.6678 0.4465 0.0928 0.029 Uiso 1 1 calc R . .
C5 C 0.69963(10) 0.61096(10) 0.12872(5) 0.0209(2) Uani 1 1 d . . .
C6 C 0.47791(10) 0.83339(10) 0.13710(6) 0.0217(2) Uani 1 1 d . . .
C7 C 0.52419(11) 0.89258(11) 0.20512(6) 0.0248(3) Uani 1 1 d . . .
C8 C 0.44095(13) 0.99292(12) 0.21004(7) 0.0365(3) Uani 1 1 d . . .
H8A H 0.4662 1.0261 0.2549 0.055 Uiso 1 1 calc R . .
H8B H 0.3577 0.9651 0.2012 0.055 Uiso 1 1 calc R . .
H8C H 0.4456 1.0519 0.1772 0.055 Uiso 1 1 calc R . .
C9 C 0.65273(12) 0.93976(12) 0.21567(7) 0.0328(3) Uani 1 1 d . . .
H9A H 0.6757 0.9837 0.2573 0.049 Uiso 1 1 calc R . .
H9B H 0.6554 0.9900 0.1784 0.049 Uiso 1 1 calc R . .
H9C H 0.7091 0.8756 0.2181 0.049 Uiso 1 1 calc R . .
C10 C 0.52251(13) 0.80450(12) 0.25954(6) 0.0335(3) Uani 1 1 d . . .
H10A H 0.5484 0.8417 0.3032 0.050 Uiso 1 1 calc R . .
H10B H 0.5776 0.7411 0.2575 0.050 Uiso 1 1 calc R . .
H10C H 0.4405 0.7744 0.2527 0.050 Uiso 1 1 calc R . .
C11 C 0.33147(11) 0.84152(10) 0.03003(6) 0.0245(3) Uani 1 1 d . . .
C12 C 0.20662(12) 0.82246(11) 0.01984(7) 0.0325(3) Uani 1 1 d . . .
C13 C 0.13643(13) 0.79755(12) -0.04363(8) 0.0409(4) Uani 1 1 d . . .
H13A H 0.0524 0.7840 -0.0510 0.049 Uiso 1 1 calc R . .
C14 C 0.18760(15) 0.79220(12) -0.09636(8) 0.0445(4) Uani 1 1 d . . .
H14A H 0.1383 0.7768 -0.1399 0.053 Uiso 1 1 calc R . .
C15 C 0.31015(15) 0.80918(12) -0.08596(7) 0.0383(3) Uani 1 1 d . . .
H15A H 0.3443 0.8038 -0.1226 0.046 Uiso 1 1 calc R . .
C16 C 0.38531(12) 0.83414(11) -0.02253(6) 0.0285(3) Uani 1 1 d . . .
C17 C 0.15248(13) 0.82816(14) 0.07769(9) 0.0440(4) Uani 1 1 d . . .
H17A H 0.0664 0.8094 0.0626 0.066 Uiso 1 1 calc R . .
H17B H 0.1625 0.9059 0.0965 0.066 Uiso 1 1 calc R . .
H17C H 0.1933 0.7728 0.1118 0.066 Uiso 1 1 calc R . .
C18 C 0.51823(12) 0.85128(13) -0.01288(7) 0.0346(3) Uani 1 1 d . . .
H18A H 0.5497 0.9034 0.0247 0.052 Uiso 1 1 calc R . .
H18B H 0.5321 0.8847 -0.0533 0.052 Uiso 1 1 calc R . .
H18C H 0.5596 0.7770 -0.0038 0.052 Uiso 1 1 calc R . .
C19 C 0.83655(10) 0.60866(10) 0.14659(6) 0.0222(3) Uani 1 1 d . . .
C20 C 0.90461(11) 0.56688(11) 0.21631(6) 0.0272(3) Uani 1 1 d . . .
C21 C 0.86570(18) 0.44382(14) 0.22656(8) 0.0522(4) Uani 1 1 d . . .
H21A H 0.9078 0.4179 0.2715 0.078 Uiso 1 1 calc R . .
H21B H 0.8860 0.3929 0.1937 0.078 Uiso 1 1 calc R . .
H21C H 0.7784 0.4419 0.2210 0.078 Uiso 1 1 calc R . .
C22 C 0.87310(13) 0.64445(14) 0.26831(7) 0.0378(3) Uani 1 1 d . . .
H22A H 0.9150 0.6171 0.3130 0.057 Uiso 1 1 calc R . .
H22B H 0.7858 0.6426 0.2627 0.057 Uiso 1 1 calc R . .
H22C H 0.8983 0.7235 0.2626 0.057 Uiso 1 1 calc R . .
C23 C 1.04069(13) 0.57068(18) 0.22525(7) 0.0478(4) Uani 1 1 d . . .
H23A H 1.0827 0.5455 0.2704 0.072 Uiso 1 1 calc R . .
H23B H 1.0651 0.6495 0.2184 0.072 Uiso 1 1 calc R . .
H23C H 1.0617 0.5195 0.1927 0.072 Uiso 1 1 calc R . .
C24 C 0.84407(10) 0.68291(11) 0.04168(6) 0.0223(3) Uani 1 1 d . . .
C25 C 0.82756(10) 0.60670(11) -0.01227(6) 0.0248(3) Uani 1 1 d . . .
C26 C 0.79091(11) 0.65188(12) -0.07637(6) 0.0303(3) Uani 1 1 d . . .
H26A H 0.7787 0.6017 -0.1135 0.036 Uiso 1 1 calc R . .
C27 C 0.77192(12) 0.76888(13) -0.08688(7) 0.0339(3) Uani 1 1 d . . .
H27A H 0.7465 0.7983 -0.1309 0.041 Uiso 1 1 calc R . .
C28 C 0.79008(12) 0.84281(12) -0.03315(7) 0.0323(3) Uani 1 1 d . . .
H28A H 0.7776 0.9230 -0.0408 0.039 Uiso 1 1 calc R . .
C29 C 0.82635(11) 0.80176(11) 0.03184(6) 0.0265(3) Uani 1 1 d . . .
C30 C 0.85046(12) 0.48009(11) -0.00057(7) 0.0298(3) Uani 1 1 d . . .
H30A H 0.8586 0.4438 -0.0415 0.045 Uiso 1 1 calc R . .
H30B H 0.7827 0.4451 0.0125 0.045 Uiso 1 1 calc R . .
H30C H 0.9250 0.4688 0.0350 0.045 Uiso 1 1 calc R . .
C31 C 0.84601(13) 0.88254(12) 0.09002(7) 0.0338(3) Uani 1 1 d . . .
H31A H 0.8411 0.9622 0.0741 0.051 Uiso 1 1 calc R . .
H31B H 0.9259 0.8687 0.1205 0.051 Uiso 1 1 calc R . .
H31C H 0.7839 0.8694 0.1134 0.051 Uiso 1 1 calc R . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
N1 0.0225(5) 0.0210(5) 0.0186(5) 0.0006(4) 0.0045(4) 0.0006(4)
N2 0.0205(5) 0.0231(5) 0.0253(5) -0.0001(4) 0.0064(4) 0.0000(4)
N3 0.0223(5) 0.0239(5) 0.0224(5) -0.0025(4) 0.0042(4) 0.0021(4)
C1 0.0218(5) 0.0224(6) 0.0172(5) 0.0015(4) 0.0046(4) 0.0003(5)
C2 0.0218(6) 0.0255(6) 0.0219(6) 0.0013(5) 0.0050(5) -0.0013(5)
C3 0.0282(6) 0.0220(6) 0.0220(6) -0.0012(5) 0.0048(5) -0.0051(5)
C4 0.0304(6) 0.0203(6) 0.0224(6) -0.0007(5) 0.0084(5) 0.0017(5)
C5 0.0244(6) 0.0223(6) 0.0162(5) 0.0018(4) 0.0057(4) 0.0017(5)
C6 0.0192(5) 0.0219(6) 0.0251(6) 0.0003(5) 0.0078(5) -0.0021(5)
C7 0.0273(6) 0.0235(6) 0.0231(6) -0.0024(5) 0.0060(5) 0.0020(5)
C8 0.0423(8) 0.0342(7) 0.0303(7) -0.0079(6) 0.0053(6) 0.0109(6)
C9 0.0336(7) 0.0313(7) 0.0321(7) -0.0099(5) 0.0065(5) -0.0060(6)
C10 0.0441(8) 0.0319(7) 0.0244(6) -0.0010(5) 0.0090(6) -0.0003(6)
C11 0.0255(6) 0.0175(6) 0.0275(6) 0.0009(5) 0.0015(5) 0.0029(5)
C12 0.0258(6) 0.0212(6) 0.0457(8) 0.0008(5) 0.0011(6) 0.0015(5)
C13 0.0313(7) 0.0244(7) 0.0546(9) -0.0016(6) -0.0101(7) 0.0004(6)
C14 0.0538(9) 0.0232(7) 0.0384(8) -0.0040(6) -0.0190(7) 0.0066(6)
C15 0.0592(9) 0.0246(7) 0.0260(7) 0.0007(5) 0.0026(6) 0.0112(6)
C16 0.0357(7) 0.0206(6) 0.0268(6) 0.0021(5) 0.0044(5) 0.0065(5)
C17 0.0259(7) 0.0423(9) 0.0655(10) -0.0013(7) 0.0153(7) -0.0039(6)
C18 0.0394(8) 0.0358(7) 0.0325(7) 0.0054(6) 0.0165(6) 0.0080(6)
C19 0.0245(6) 0.0197(6) 0.0218(6) -0.0031(4) 0.0054(5) 0.0029(5)
C20 0.0276(6) 0.0317(7) 0.0205(6) -0.0002(5) 0.0035(5) 0.0062(5)
C21 0.0757(12) 0.0363(8) 0.0309(8) 0.0092(6) -0.0091(8) 0.0007(8)
C22 0.0348(7) 0.0506(9) 0.0237(7) -0.0070(6) 0.0006(5) 0.0099(6)
C23 0.0298(7) 0.0836(13) 0.0274(7) 0.0079(7) 0.0031(6) 0.0207(8)
C24 0.0162(5) 0.0277(6) 0.0234(6) 0.0012(5) 0.0060(4) -0.0005(5)
C25 0.0181(5) 0.0302(7) 0.0262(6) -0.0014(5) 0.0064(5) -0.0019(5)
C26 0.0240(6) 0.0431(8) 0.0237(6) -0.0021(5) 0.0064(5) -0.0031(6)
C27 0.0270(6) 0.0482(8) 0.0271(7) 0.0124(6) 0.0086(5) 0.0035(6)
C28 0.0291(7) 0.0310(7) 0.0399(8) 0.0113(6) 0.0147(6) 0.0052(5)
C29 0.0216(6) 0.0277(6) 0.0323(7) 0.0019(5) 0.0111(5) 0.0003(5)
C30 0.0308(7) 0.0290(7) 0.0307(7) -0.0058(5) 0.0101(5) -0.0028(5)
C31 0.0376(7) 0.0252(7) 0.0430(8) -0.0029(6) 0.0186(6) -0.0009(6)

_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 C5 1.3417(15) . ?
N1 C1 1.3455(15) . ?
N2 C6 1.2750(16) . ?
N2 C11 1.4155(15) . ?
N3 C19 1.2698(16) . ?
N3 C24 1.4200(15) . ?
C1 C2 1.3920(17) . ?
C1 C6 1.5101(16) . ?
C2 C3 1.3855(18) . ?
C3 C4 1.3883(17) . ?
C4 C5 1.3947(17) . ?
C5 C19 1.5179(16) . ?
C6 C7 1.5373(16) . ?
C7 C8 1.5300(18) . ?
C7 C10 1.5325(18) . ?
C7 C9 1.5362(18) . ?
C11 C16 1.3992(18) . ?
C11 C12 1.4116(18) . ?
C12 C13 1.383(2) . ?
C12 C17 1.501(2) . ?
C13 C14 1.381(2) . ?
C14 C15 1.382(2) . ?
C15 C16 1.4024(19) . ?
C16 C18 1.5008(19) . ?
C19 C20 1.5333(16) . ?
C20 C23 1.5263(19) . ?
C20 C22 1.5272(18) . ?
C20 C21 1.531(2) . ?
C24 C25 1.4044(17) . ?
C24 C29 1.4035(18) . ?
C25 C26 1.3921(18) . ?
C25 C30 1.5035(18) . ?
C26 C27 1.385(2) . ?
C27 C28 1.383(2) . ?
C28 C29 1.3910(18) . ?
C29 C31 1.5027(18) . ?

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
C5 N1 C1 118.27(10) . . ?
C6 N2 C11 127.17(10) . . ?
C19 N3 C24 123.92(10) . . ?
N1 C1 C2 122.53(11) . . ?
N1 C1 C6 116.53(10) . . ?
C2 C1 C6 120.94(10) . . ?
C3 C2 C1 118.78(11) . . ?
C2 C3 C4 119.18(11) . . ?
C3 C4 C5 118.51(11) . . ?
N1 C5 C4 122.70(11) . . ?
N1 C5 C19 115.50(10) . . ?
C4 C5 C19 121.80(10) . . ?
N2 C6 C1 123.31(11) . . ?
N2 C6 C7 117.25(10) . . ?
C1 C6 C7 119.35(10) . . ?
C8 C7 C10 109.08(11) . . ?
C8 C7 C9 108.29(11) . . ?
C10 C7 C9 109.62(11) . . ?
C8 C7 C6 109.60(10) . . ?
C10 C7 C6 108.31(10) . . ?
C9 C7 C6 111.91(10) . . ?
C16 C11 C12 121.27(12) . . ?
C16 C11 N2 123.15(11) . . ?
C12 C11 N2 115.05(11) . . ?
C13 C12 C11 119.04(14) . . ?
C13 C12 C17 121.14(13) . . ?
C11 C12 C17 119.82(12) . . ?
C14 C13 C12 120.49(14) . . ?
C13 C14 C15 120.25(13) . . ?
C14 C15 C16 121.46(14) . . ?
C11 C16 C15 117.47(13) . . ?
C11 C16 C18 122.44(11) . . ?
C15 C16 C18 120.09(13) . . ?
N3 C19 C5 123.17(10) . . ?
N3 C19 C20 118.79(10) . . ?
C5 C19 C20 118.03(10) . . ?
C23 C20 C22 109.12(11) . . ?
C23 C20 C21 109.80(13) . . ?
C22 C20 C21 108.56(12) . . ?
C23 C20 C19 110.61(10) . . ?
C22 C20 C19 109.16(10) . . ?
C21 C20 C19 109.54(11) . . ?
C25 C24 C29 121.38(11) . . ?
C25 C24 N3 118.78(11) . . ?
C29 C24 N3 119.16(11) . . ?
C26 C25 C24 118.18(12) . . ?
C26 C25 C30 121.32(12) . . ?
C24 C25 C30 120.49(11) . . ?
C27 C26 C25 121.09(12) . . ?
C28 C27 C26 119.93(12) . . ?
C27 C28 C29 121.12(13) . . ?
C28 C29 C24 118.29(12) . . ?
C28 C29 C31 120.87(12) . . ?
C24 C29 C31 120.84(12) . . ?

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
C5 N1 C1 C2 2.36(16) . . . . ?
C5 N1 C1 C6 -176.84(10) . . . . ?
N1 C1 C2 C3 -1.84(17) . . . . ?
C6 C1 C2 C3 177.33(10) . . . . ?
C1 C2 C3 C4 0.08(17) . . . . ?
C2 C3 C4 C5 1.03(17) . . . . ?
C1 N1 C5 C4 -1.17(16) . . . . ?
C1 N1 C5 C19 179.14(10) . . . . ?
C3 C4 C5 N1 -0.50(17) . . . . ?
C3 C4 C5 C19 179.17(10) . . . . ?
C11 N2 C6 C1 0.49(18) . . . . ?
C11 N2 C6 C7 -176.07(11) . . . . ?
N1 C1 C6 N2 132.53(12) . . . . ?
C2 C1 C6 N2 -46.68(16) . . . . ?
N1 C1 C6 C7 -50.98(14) . . . . ?
C2 C1 C6 C7 129.81(12) . . . . ?
N2 C6 C7 C8 9.05(15) . . . . ?
C1 C6 C7 C8 -167.65(11) . . . . ?
N2 C6 C7 C10 127.95(12) . . . . ?
C1 C6 C7 C10 -48.75(14) . . . . ?
N2 C6 C7 C9 -111.10(12) . . . . ?
C1 C6 C7 C9 72.20(14) . . . . ?
C6 N2 C11 C16 -70.32(17) . . . . ?
C6 N2 C11 C12 117.90(13) . . . . ?
C16 C11 C12 C13 -0.87(19) . . . . ?
N2 C11 C12 C13 171.07(11) . . . . ?
C16 C11 C12 C17 178.46(12) . . . . ?
N2 C11 C12 C17 -9.60(17) . . . . ?
C11 C12 C13 C14 -0.5(2) . . . . ?
C17 C12 C13 C14 -179.77(13) . . . . ?
C12 C13 C14 C15 1.5(2) . . . . ?
C13 C14 C15 C16 -1.2(2) . . . . ?
C12 C11 C16 C15 1.16(18) . . . . ?
N2 C11 C16 C15 -170.12(11) . . . . ?
C12 C11 C16 C18 -178.56(12) . . . . ?
N2 C11 C16 C18 10.16(19) . . . . ?
C14 C15 C16 C11 -0.15(19) . . . . ?
C14 C15 C16 C18 179.57(12) . . . . ?
C24 N3 C19 C5 0.25(18) . . . . ?
C24 N3 C19 C20 -178.91(11) . . . . ?
N1 C5 C19 N3 -87.71(14) . . . . ?
C4 C5 C19 N3 92.59(15) . . . . ?
N1 C5 C19 C20 91.46(13) . . . . ?
C4 C5 C19 C20 -88.24(14) . . . . ?
N3 C19 C20 C23 -0.71(17) . . . . ?
C5 C19 C20 C23 -179.92(12) . . . . ?
N3 C19 C20 C22 119.37(13) . . . . ?
C5 C19 C20 C22 -59.83(15) . . . . ?
N3 C19 C20 C21 -121.88(14) . . . . ?
C5 C19 C20 C21 58.91(15) . . . . ?
C19 N3 C24 C25 -96.91(14) . . . . ?
C19 N3 C24 C29 92.35(15) . . . . ?
C29 C24 C25 C26 -1.07(17) . . . . ?
N3 C24 C25 C26 -171.59(10) . . . . ?
C29 C24 C25 C30 178.25(11) . . . . ?
N3 C24 C25 C30 7.73(16) . . . . ?
C24 C25 C26 C27 0.43(18) . . . . ?
C30 C25 C26 C27 -178.89(12) . . . . ?
C25 C26 C27 C28 0.37(19) . . . . ?
C26 C27 C28 C29 -0.56(19) . . . . ?
C27 C28 C29 C24 -0.07(18) . . . . ?
C27 C28 C29 C31 179.96(12) . . . . ?
C25 C24 C29 C28 0.90(17) . . . . ?
N3 C24 C29 C28 171.38(10) . . . . ?
C25 C24 C29 C31 -179.14(11) . . . . ?
N3 C24 C29 C31 -8.65(17) . . . . ?

_diffrn_measured_fraction_theta_max 0.987
_diffrn_reflns_theta_full        67.00
_diffrn_measured_fraction_theta_full 0.995
_refine_diff_density_max         0.211
_refine_diff_density_min         -0.198
_refine_diff_density_rms         0.034