# Supplementary Material (ESI) for Dalton Transactions
# This journal is © The Royal Society of Chemistry 1999
# CCDC Number: 186/1717

data_global

#=======================================================================

_publ_contact_author
;
        Guido Pampaloni
        Dipartimento di Chimica e Chimica Industriale
        Universita' di Pisa
        Via Risorgimento, 35
        56126 Pisa
        Italy
;
_publ_contact_author_phone        '39 50 918221'
_publ_contact_author_fax          '39 50 20237'
_publ_contact_author_email        'pampa@dcci.unipi.it'
_publ_requested_journal           'Journal of Chemical Society, DaltonTrans.'
_publ_requested_coeditor_name     ?

_publ_contact_letter
;
  ?
;

#=======================================================================

# 3. TITLE AND AUTHOR LIST

_publ_section_title
;
      Coordination properties of 1,10-phenanthroline-5,6-dione
      towards group 4 and group 5 metals in low- and high
      oxidation states
;



data_fenqui2

_audit_creation_method            SHELXL-97
_chemical_name_systematic
;
1,10-Phenanthroline-5,6-dione
;
_chemical_name_common             ?
_chemical_melting_point           ?
_chemical_formula_moiety          ?
_chemical_formula_sum
 'C12 H6 N2 O2'
_chemical_formula_weight          210.19

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'

_symmetry_cell_setting            Triclinic
_symmetry_space_group_name_H-M    P-1

loop_
 _symmetry_equiv_pos_as_xyz
 'x, y, z'
 '-x, -y, -z'

_cell_length_a                    7.2720(10)
_cell_length_b                    9.3360(10)
_cell_length_c                    13.6050(10)
_cell_angle_alpha                 83.050(10)
_cell_angle_beta                  84.240(10)
_cell_angle_gamma                 83.450(10)
_cell_volume                      907.38(17)
_cell_formula_units_Z             4
_cell_measurement_temperature     293(2)
_cell_measurement_reflns_used     28
_cell_measurement_theta_min        9.993
_cell_measurement_theta_max       25.139

_exptl_crystal_description        'Prism'
_exptl_crystal_colour             'Orange'
_exptl_crystal_size_max          0.50 
_exptl_crystal_size_mid          0.28 
_exptl_crystal_size_min          0.08 
_exptl_crystal_density_diffrn     1.539
_exptl_crystal_density_meas       ?
_exptl_crystal_density_method     'not measured'
_exptl_crystal_F_000              432
_exptl_absorpt_coefficient_mu     0.108
_exptl_absorpt_correction_type    'not corrected'
_exptl_absorpt_correction_T_min   ?
_exptl_absorpt_correction_T_max   ?
_exptl_absorpt_process_details    ?

_exptl_special_details
;
 ?
;

_diffrn_ambient_temperature       293(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       'Siemens P4'
_diffrn_measurement_method       '2\q/\w scans'
_diffrn_detector_area_resol_mean  ?
_diffrn_standards_number            3
_diffrn_standards_interval_count   97
_diffrn_standards_interval_time   ?
_diffrn_standards_decay_%         ?
_diffrn_reflns_number             3028
_diffrn_reflns_av_R_equivalents   0.0163
_diffrn_reflns_av_sigmaI/netI     0.0287
_diffrn_reflns_limit_h_min        -1
_diffrn_reflns_limit_h_max        7
_diffrn_reflns_limit_k_min        -9
_diffrn_reflns_limit_k_max        9
_diffrn_reflns_limit_l_min        -14
_diffrn_reflns_limit_l_max        14
_diffrn_reflns_theta_min          2.21
_diffrn_reflns_theta_max          22.50
_reflns_number_total              2363
_reflns_number_gt                 1537
_reflns_threshold_expression      >2sigma(I)

_computing_data_collection      'Siemens XSCANS'
_computing_cell_refinement      'Siemens XSCANS'
_computing_data_reduction       'Siemens XSCANS'
_computing_structure_solution     'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement   'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics   'Siemens SHELXTL'
_computing_publication_material 'Siemens 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^)+(0.0578P)^2^+0.0734P] 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     mixed
_refine_ls_extinction_method      none
_refine_ls_extinction_coef        ?
_refine_ls_number_reflns          2363
_refine_ls_number_parameters      289
_refine_ls_number_restraints      0
_refine_ls_R_factor_all           0.0774
_refine_ls_R_factor_gt            0.0436
_refine_ls_wR_factor_ref          0.1154
_refine_ls_wR_factor_gt           0.1003
_refine_ls_goodness_of_fit_ref    1.049
_refine_ls_restrained_S_all       1.049
_refine_ls_shift/su_max           0.003
_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
O1 O 0.4073(3) -0.3330(2) 0.09104(15) 0.0719(7) Uani 1 1 d . . .
C1 C 0.3512(4) -0.2202(3) 0.0442(2) 0.0458(7) Uani 1 1 d . . .
C2 C 0.3069(4) -0.2105(3) -0.06010(19) 0.0402(7) Uani 1 1 d . . .
C3 C 0.3399(4) -0.3326(3) -0.1111(2) 0.0546(8) Uani 1 1 d . . .
H3 H 0.3926 -0.4202 -0.0807 0.071 Uiso 1 1 calc R . .
C4 C 0.2933(4) -0.3215(3) -0.2070(2) 0.0634(9) Uani 1 1 d . . .
H4 H 0.3151 -0.4006 -0.2436 0.082 Uiso 1 1 calc R . .
C5 C 0.2129(4) -0.1896(3) -0.2477(2) 0.0619(9) Uani 1 1 d . . .
H5 H 0.1778 -0.1838 -0.3120 0.080 Uiso 1 1 calc R . .
N1 N 0.1815(3) -0.0694(2) -0.20181(15) 0.0502(7) Uani 1 1 d . . .
C6 C 0.2312(3) -0.0801(3) -0.10854(17) 0.0356(7) Uani 1 1 d . . .
C7 C 0.2020(3) 0.0552(3) -0.05868(18) 0.0345(6) Uani 1 1 d . . .
N2 N 0.1320(3) 0.1763(2) -0.11106(15) 0.0434(6) Uani 1 1 d . . .
C8 C 0.1152(4) 0.2990(3) -0.0676(2) 0.0504(8) Uani 1 1 d . . .
H8 H 0.0706 0.3842 -0.1042 0.065 Uiso 1 1 calc R . .
C9 C 0.1590(4) 0.3079(3) 0.0269(2) 0.0479(8) Uani 1 1 d . . .
H9 H 0.1438 0.3964 0.0532 0.062 Uiso 1 1 calc R . .
C10 C 0.2258(4) 0.1835(3) 0.0819(2) 0.0434(7) Uani 1 1 d . . .
H10 H 0.2540 0.1853 0.1469 0.056 Uiso 1 1 calc R . .
C11 C 0.2505(3) 0.0544(3) 0.03851(17) 0.0336(6) Uani 1 1 d . . .
C12 C 0.3271(4) -0.0807(3) 0.09469(19) 0.0398(7) Uani 1 1 d . . .
O2 O 0.3722(3) -0.0840(2) 0.17807(14) 0.0626(6) Uani 1 1 d . . .
O3 O 0.1310(3) 0.4489(2) 0.23788(15) 0.0785(8) Uani 1 1 d . . .
C13 C 0.1751(4) 0.4477(3) 0.3212(2) 0.0480(8) Uani 1 1 d . . .
C14 C 0.1624(3) 0.5797(3) 0.37241(18) 0.0361(7) Uani 1 1 d . . .
C15 C 0.1007(4) 0.7133(3) 0.32441(19) 0.0455(7) Uani 1 1 d . . .
H15 H 0.0656 0.7206 0.2600 0.059 Uiso 1 1 calc R . .
C16 C 0.0918(4) 0.8347(3) 0.3729(2) 0.0504(8) Uani 1 1 d . . .
H16 H 0.0536 0.9260 0.3418 0.066 Uiso 1 1 calc R . .
C17 C 0.1410(4) 0.8172(3) 0.4685(2) 0.0492(8) Uani 1 1 d . . .
H17 H 0.1334 0.8999 0.5011 0.064 Uiso 1 1 calc R . .
N3 N 0.1992(3) 0.6908(2) 0.51850(15) 0.0435(6) Uani 1 1 d . . .
C18 C 0.2123(3) 0.5732(2) 0.46986(18) 0.0332(6) Uani 1 1 d . . .
C19 C 0.2834(3) 0.4321(3) 0.52404(18) 0.0343(6) Uani 1 1 d . . .
N4 N 0.3315(3) 0.4345(2) 0.61655(15) 0.0401(6) Uani 1 1 d . . .
C20 C 0.3936(4) 0.3080(3) 0.6654(2) 0.0474(8) Uani 1 1 d . . .
H20 H 0.4279 0.3088 0.7293 0.062 Uiso 1 1 calc R . .
C21 C 0.4100(4) 0.1768(3) 0.6271(2) 0.0505(8) Uani 1 1 d . . .
H21 H 0.4529 0.0917 0.6645 0.066 Uiso 1 1 calc R . .
C22 C 0.3617(4) 0.1749(3) 0.5329(2) 0.0490(8) Uani 1 1 d . . .
H22 H 0.3716 0.0880 0.5049 0.064 Uiso 1 1 calc R . .
C23 C 0.2976(3) 0.3041(3) 0.47948(18) 0.0388(7) Uani 1 1 d . . .
C24 C 0.2459(4) 0.3024(3) 0.3780(2) 0.0495(8) Uani 1 1 d . . .
O4 O 0.2541(4) 0.1928(2) 0.33793(16) 0.0855(8) Uani 1 1 d . . .

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
O1 0.0996(19) 0.0480(12) 0.0605(14) 0.0090(11) -0.0175(13) 0.0181(12)
C1 0.0456(19) 0.0418(17) 0.0470(17) 0.0050(14) -0.0088(15) 0.0024(14)
C2 0.0410(18) 0.0348(15) 0.0444(16) -0.0044(13) -0.0058(14) -0.0001(13)
C3 0.060(2) 0.0377(16) 0.066(2) -0.0086(15) -0.0051(17) 0.0013(15)
C4 0.078(3) 0.053(2) 0.064(2) -0.0250(17) -0.0053(19) -0.0075(18)
C5 0.083(3) 0.065(2) 0.0423(18) -0.0167(16) -0.0142(17) -0.0085(19)
N1 0.0716(18) 0.0476(14) 0.0343(14) -0.0116(11) -0.0132(12) -0.0034(13)
C6 0.0398(17) 0.0388(15) 0.0289(15) -0.0049(12) -0.0035(13) -0.0061(13)
C7 0.0336(16) 0.0353(15) 0.0336(15) 0.0001(12) -0.0046(12) -0.0014(12)
N2 0.0577(16) 0.0353(13) 0.0371(13) -0.0031(11) -0.0156(12) 0.0049(11)
C8 0.064(2) 0.0377(16) 0.0483(18) -0.0032(14) -0.0132(16) 0.0065(14)
C9 0.059(2) 0.0398(15) 0.0452(17) -0.0117(13) -0.0090(15) 0.0034(14)
C10 0.0472(19) 0.0500(18) 0.0346(15) -0.0108(13) -0.0049(14) -0.0045(14)
C11 0.0357(16) 0.0389(15) 0.0261(14) -0.0002(12) -0.0050(12) -0.0043(12)
C12 0.0375(17) 0.0521(17) 0.0291(15) 0.0024(13) -0.0072(13) -0.0052(14)
O2 0.0827(16) 0.0672(14) 0.0376(12) 0.0023(10) -0.0234(11) 0.0017(11)
O3 0.124(2) 0.0741(15) 0.0413(13) -0.0103(11) -0.0335(13) -0.0024(14)
C13 0.054(2) 0.0587(19) 0.0332(17) -0.0069(14) -0.0076(15) -0.0078(15)
C14 0.0337(17) 0.0452(16) 0.0297(14) -0.0005(12) -0.0060(12) -0.0063(13)
C15 0.0452(18) 0.0555(18) 0.0341(15) 0.0072(14) -0.0103(14) -0.0049(14)
C16 0.050(2) 0.0457(17) 0.0516(18) 0.0071(15) -0.0061(15) 0.0019(14)
C17 0.059(2) 0.0374(16) 0.0512(18) -0.0055(14) -0.0117(16) 0.0033(15)
N3 0.0507(16) 0.0365(13) 0.0435(14) -0.0039(11) -0.0151(12) 0.0030(11)
C18 0.0291(16) 0.0357(15) 0.0347(15) -0.0015(12) -0.0060(13) -0.0018(12)
C19 0.0296(16) 0.0411(16) 0.0315(15) 0.0007(12) -0.0054(12) -0.0033(12)
N4 0.0468(15) 0.0429(13) 0.0302(12) 0.0006(10) -0.0112(11) -0.0007(11)
C20 0.0479(19) 0.0565(19) 0.0363(16) 0.0065(14) -0.0130(14) -0.0035(15)
C21 0.049(2) 0.0418(17) 0.0575(19) 0.0102(15) -0.0154(16) 0.0011(14)
C22 0.050(2) 0.0383(16) 0.059(2) -0.0059(14) -0.0108(16) 0.0017(14)
C23 0.0380(18) 0.0405(16) 0.0376(16) -0.0021(13) -0.0066(13) -0.0024(13)
C24 0.059(2) 0.0464(17) 0.0453(17) -0.0134(15) -0.0100(15) -0.0021(15)
O4 0.143(2) 0.0562(14) 0.0635(15) -0.0270(12) -0.0326(15) 0.0067(14)

_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
O1 C1 1.213(3) . ?
C1 C2 1.477(4) . ?
C1 C12 1.529(4) . ?
C2 C3 1.391(4) . ?
C2 C6 1.395(3) . ?
C3 C4 1.369(4) . ?
C4 C5 1.379(4) . ?
C5 N1 1.335(3) . ?
N1 C6 1.343(3) . ?
C6 C7 1.489(3) . ?
C7 N2 1.339(3) . ?
C7 C11 1.401(3) . ?
N2 C8 1.339(3) . ?
C8 C9 1.370(4) . ?
C9 C10 1.371(4) . ?
C10 C11 1.391(3) . ?
C11 C12 1.476(3) . ?
C12 O2 1.208(3) . ?
O3 C13 1.207(3) . ?
C13 C14 1.477(3) . ?
C13 C24 1.539(4) . ?
C14 C15 1.385(3) . ?
C14 C18 1.402(3) . ?
C15 C16 1.371(4) . ?
C16 C17 1.369(4) . ?
C17 N3 1.336(3) . ?
N3 C18 1.338(3) . ?
C18 C19 1.494(3) . ?
C19 N4 1.343(3) . ?
C19 C23 1.393(3) . ?
N4 C20 1.337(3) . ?
C20 C21 1.376(4) . ?
C21 C22 1.365(4) . ?
C22 C23 1.388(3) . ?
C23 C24 1.469(3) . ?
C24 O4 1.209(3) . ?

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 C2 123.1(3) . . ?
O1 C1 C12 118.8(2) . . ?
C2 C1 C12 118.1(2) . . ?
C3 C2 C6 119.2(2) . . ?
C3 C2 C1 120.0(2) . . ?
C6 C2 C1 120.9(2) . . ?
C4 C3 C2 118.7(3) . . ?
C3 C4 C5 118.0(3) . . ?
N1 C5 C4 125.0(3) . . ?
C5 N1 C6 116.7(2) . . ?
N1 C6 C2 122.2(2) . . ?
N1 C6 C7 116.6(2) . . ?
C2 C6 C7 121.1(2) . . ?
N2 C7 C11 122.0(2) . . ?
N2 C7 C6 117.4(2) . . ?
C11 C7 C6 120.6(2) . . ?
C7 N2 C8 117.0(2) . . ?
N2 C8 C9 124.7(3) . . ?
C8 C9 C10 118.5(2) . . ?
C9 C10 C11 118.6(2) . . ?
C10 C11 C7 119.1(2) . . ?
C10 C11 C12 120.0(2) . . ?
C7 C11 C12 120.9(2) . . ?
O2 C12 C11 122.3(2) . . ?
O2 C12 C1 119.5(2) . . ?
C11 C12 C1 118.2(2) . . ?
O3 C13 C14 123.0(3) . . ?
O3 C13 C24 119.1(2) . . ?
C14 C13 C24 117.9(2) . . ?
C15 C14 C18 118.5(2) . . ?
C15 C14 C13 120.2(2) . . ?
C18 C14 C13 121.2(2) . . ?
C16 C15 C14 119.3(3) . . ?
C17 C16 C15 117.9(3) . . ?
N3 C17 C16 125.2(3) . . ?
C17 N3 C18 116.7(2) . . ?
N3 C18 C14 122.4(2) . . ?
N3 C18 C19 117.0(2) . . ?
C14 C18 C19 120.6(2) . . ?
N4 C19 C23 122.1(2) . . ?
N4 C19 C18 117.3(2) . . ?
C23 C19 C18 120.6(2) . . ?
C20 N4 C19 117.3(2) . . ?
N4 C20 C21 124.3(3) . . ?
C22 C21 C20 118.2(3) . . ?
C21 C22 C23 119.3(3) . . ?
C22 C23 C19 118.8(2) . . ?
C22 C23 C24 119.4(2) . . ?
C19 C23 C24 121.7(2) . . ?
O4 C24 C23 123.2(3) . . ?
O4 C24 C13 118.9(2) . . ?
C23 C24 C13 117.9(2) . . ?

_diffrn_measured_fraction_theta_max    0.998
_diffrn_reflns_theta_full              22.50
_diffrn_measured_fraction_theta_full   0.998
_refine_diff_density_max    0.133
_refine_diff_density_min   -0.222
_refine_diff_density_rms    0.044
#===END