# Electronic Supplementary Material for CrystEngComm
# This journal is (c) The Royal Society of Chemistry 2009

data_global
_journal_name_full               CrystEngComm

_journal_coden_Cambridge         1350

_publ_contact_author_name        'La-Sheng Long'
_publ_contact_author_email       LSLONG@XMU.EDU.CN

_publ_section_title              
;
Ionothermal Synthesis of 3d-4f and 4f layered
anionic metal-organic frameworks
;
loop_
_publ_author_name
'La-Sheng Long'
'Wen-Xian Chen'
'Rong-Bin Huang'
'Lan-Sun Zheng'

# Attachment 'complex11.cif'

data_complex1
_database_code_depnum_ccdc_archive 'CCDC 717557'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C38 H52 Co La2 N4 O24 S4'
_chemical_formula_weight         1413.83

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'
La La -0.2871 2.4523 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Co Co 0.3494 0.9721 '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                   10.444(2)
_cell_length_b                   11.213(2)
_cell_length_c                   12.233(2)
_cell_angle_alpha                79.66(3)
_cell_angle_beta                 71.61(3)
_cell_angle_gamma                87.54(3)
_cell_volume                     1337.2(5)
_cell_formula_units_Z            1
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       block
_exptl_crystal_colour            pink
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.20
_exptl_crystal_density_meas      'not measured'
_exptl_crystal_density_diffrn    1.756
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             705
_exptl_absorpt_coefficient_mu    2.114
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_correction_T_min  0.6201
_exptl_absorpt_correction_T_max  0.6772
_exptl_absorpt_process_details   Tompa_analytical

_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_type  'Rigaku RAXIS-CS Imaging Plate'
_diffrn_measurement_method       ω
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            11611
_diffrn_reflns_av_R_equivalents  0.0375
_diffrn_reflns_av_sigmaI/netI    0.0478
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_theta_min         3.09
_diffrn_reflns_theta_max         26.00
_reflns_number_total             5238
_reflns_number_gt                4749
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       R-AXIS-SPIDER
_computing_cell_refinement       RAPID
_computing_data_reduction        RAPID
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'SHELXTL V.5.0 (Sheldrick, 1997)'
_computing_publication_material  'SHELXL-97 (Sheldrick, 1997)'

_refine_special_details          
;
Refinement of F² against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F², conventional R-factors R are based
on F, with F set to zero for negative F². The threshold expression of
F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F² 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/[σ²(Fo²)+(0.0616P)²+5.1978P] where P=(Fo²+2Fc²)/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         5238
_refine_ls_number_parameters     334
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0466
_refine_ls_R_factor_gt           0.0426
_refine_ls_wR_factor_ref         0.1255
_refine_ls_wR_factor_gt          0.1193
_refine_ls_goodness_of_fit_ref   1.088
_refine_ls_restrained_S_all      1.088
_refine_ls_shift/su_max          0.006
_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
La1 La 0.57604(3) 0.93872(3) 0.64678(2) 0.02241(12) Uani 1 1 d . . .
Co1 Co 0.0000 1.0000 0.5000 0.0274(2) Uani 1 2 d S . .
S1 S 0.48851(18) 1.26610(14) 0.54446(14) 0.0400(4) Uani 1 1 d . . .
S2 S 0.86930(16) 0.74099(14) 0.66938(14) 0.0397(4) Uani 1 1 d . . .
O1 O 0.4062(4) 0.7726(4) 0.7994(3) 0.0382(10) Uani 1 1 d . . .
O2 O 0.4449(5) 0.9367(4) 0.8592(4) 0.0436(11) Uani 1 1 d . . .
O3 O 0.0742(4) 0.8873(4) 1.3784(3) 0.0344(9) Uani 1 1 d . . .
O4 O 0.2806(4) 0.9595(4) 1.2760(4) 0.0409(11) Uani 1 1 d . . .
O5 O 0.7278(4) 0.7763(4) 0.7034(4) 0.0400(10) Uani 1 1 d . . .
O6 O 0.8981(6) 0.6556(6) 0.7591(5) 0.076(2) Uani 1 1 d . . .
O7 O 0.9602(4) 0.8452(4) 0.6309(4) 0.0402(10) Uani 1 1 d . . .
O8 O 0.5197(6) 1.1638(4) 0.6243(4) 0.0500(12) Uani 1 1 d . . .
O9 O 0.4215(5) 1.2268(4) 0.4684(4) 0.0393(10) Uani 1 1 d . . .
O10 O 0.4162(6) 1.3591(4) 0.6051(5) 0.0580(14) Uani 1 1 d . . .
O11 O 0.1941(4) 1.0165(4) 0.5222(3) 0.0306(8) Uani 1 1 d . . .
O12 O 0.3667(4) 0.9673(4) 0.5834(3) 0.0294(8) Uani 1 1 d . . .
N1 N 0.4911(6) 0.4251(5) 0.8262(5) 0.0450(13) Uani 1 1 d . . .
N2 N 0.3630(6) 0.2824(5) 0.9480(5) 0.0387(12) Uani 1 1 d . . .
C1 C 0.2810(5) 0.7980(5) 0.9957(5) 0.0276(11) Uani 1 1 d . . .
C2 C 0.2827(5) 0.8524(5) 1.0880(4) 0.0260(11) Uani 1 1 d . . .
H2 H 0.3519 0.9067 1.0783 0.031 Uiso 1 1 calc R . .
C3 C 0.1816(5) 0.8269(5) 1.1956(5) 0.0255(11) Uani 1 1 d . . .
C4 C 0.0813(5) 0.7414(5) 1.2090(5) 0.0303(12) Uani 1 1 d . . .
H4 H 0.0136 0.7233 1.2806 0.036 Uiso 1 1 calc R . .
C5 C 0.0802(6) 0.6835(5) 1.1188(5) 0.0319(12) Uani 1 1 d . . .
C6 C 0.1803(6) 0.7125(5) 1.0113(5) 0.0314(12) Uani 1 1 d . . .
H6 H 0.1802 0.6749 0.9495 0.038 Uiso 1 1 calc R . .
C7 C 0.3849(6) 0.8367(5) 0.8768(4) 0.0283(11) Uani 1 1 d . . .
C8 C 0.1791(5) 0.8947(5) 1.2906(5) 0.0280(11) Uani 1 1 d . . .
C9 C -0.0302(7) 0.5907(6) 1.1378(6) 0.0449(16) Uani 1 1 d . . .
H9A H -0.0416 0.5852 1.0640 0.067 Uiso 1 1 calc R . .
H9B H -0.1133 0.6153 1.1891 0.067 Uiso 1 1 calc R . .
H9C H -0.0053 0.5130 1.1722 0.067 Uiso 1 1 calc R . .
C10 C 0.6443(9) 1.3291(8) 0.4505(8) 0.066(2) Uani 1 1 d . . .
H10A H 0.6289 1.3971 0.3964 0.099 Uiso 1 1 calc R . .
H10B H 0.6948 1.2691 0.4081 0.099 Uiso 1 1 calc R . .
H10C H 0.6943 1.3555 0.4958 0.099 Uiso 1 1 calc R . .
C11 C 0.8928(10) 0.6717(8) 0.5448(8) 0.076(3) Uani 1 1 d . . .
H11A H 0.9845 0.6459 0.5178 0.114 Uiso 1 1 calc R . .
H11B H 0.8736 0.7291 0.4838 0.114 Uiso 1 1 calc R . .
H11C H 0.8331 0.6028 0.5655 0.114 Uiso 1 1 calc R . .
C12 C 0.2421(5) 0.9858(5) 0.6061(5) 0.0272(11) Uani 1 1 d . . .
C13 C 0.1541(7) 0.9728(9) 0.7303(6) 0.059(2) Uani 1 1 d . . .
H13A H 0.1648 0.8935 0.7714 0.089 Uiso 1 1 calc R . .
H13B H 0.0616 0.9833 0.7327 0.089 Uiso 1 1 calc R . .
H13C H 0.1792 1.0331 0.7667 0.089 Uiso 1 1 calc R . .
C14 C 0.4631(7) 0.3076(6) 0.8492(6) 0.0412(14) Uani 1 1 d . . .
H14 H 0.5071 0.2515 0.8031 0.049 Uiso 1 1 calc R . .
C15 C 0.3247(8) 0.3883(7) 0.9897(7) 0.0557(19) Uani 1 1 d . . .
H15 H 0.2567 0.3966 1.0583 0.067 Uiso 1 1 calc R . .
C16 C 0.4030(8) 0.4777(6) 0.9137(7) 0.0552(19) Uani 1 1 d . . .
H16 H 0.3988 0.5596 0.9189 0.066 Uiso 1 1 calc R . .
C17 C 0.6004(10) 0.4871(9) 0.7278(8) 0.074(3) Uani 1 1 d . . .
H17A H 0.6826 0.4435 0.7225 0.111 Uiso 1 1 calc R . .
H17B H 0.6116 0.5679 0.7397 0.111 Uiso 1 1 calc R . .
H17C H 0.5786 0.4908 0.6567 0.111 Uiso 1 1 calc R . .
C18 C 0.3050(8) 0.1606(6) 1.0031(6) 0.0484(16) Uani 1 1 d . . .
H18A H 0.3073 0.1433 1.0831 0.058 Uiso 1 1 calc R . .
H18B H 0.3600 0.1010 0.9614 0.058 Uiso 1 1 calc R . .
C19 C 0.1629(10) 0.1485(9) 1.0035(10) 0.080(3) Uani 1 1 d . . .
H19A H 0.1298 0.0677 1.0397 0.120 Uiso 1 1 calc R . .
H19B H 0.1602 0.1643 0.9245 0.120 Uiso 1 1 calc R . .
H19C H 0.1074 0.2057 1.0466 0.120 Uiso 1 1 calc R . .


_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
La1 O4 2.421(4) 2_677 ?
La1 O5 2.510(4) . ?
La1 O9 2.518(4) 2_676 ?
La1 O2 2.523(4) . ?
La1 O12 2.531(4) . ?
La1 O8 2.553(4) . ?
La1 O11 2.624(4) 2_676 ?
La1 O1 2.655(4) . ?
La1 O12 2.706(4) 2_676 ?
La1 C7 2.951(5) . ?
La1 C12 3.063(5) 2_676 ?
Co1 O3 2.067(4) 2_577 ?
Co1 O3 2.067(4) 1_554 ?
Co1 O7 2.096(4) 2_676 ?
Co1 O7 2.096(4) 1_455 ?
Co1 O11 2.149(4) 2_576 ?
Co1 O11 2.149(4) . ?
S1 O10 1.437(5) . ?
S1 O9 1.461(4) . ?
S1 O8 1.463(5) . ?
S1 C10 1.759(9) . ?
S2 O6 1.420(5) . ?
S2 O7 1.451(5) . ?
S2 O5 1.461(4) . ?
S2 C11 1.777(9) . ?
O1 C7 1.250(7) . ?
O2 C7 1.259(7) . ?
O3 C8 1.262(6) . ?
O3 Co1 2.067(4) 1_556 ?
O4 C8 1.259(7) . ?
O4 La1 2.421(4) 2_677 ?
O7 Co1 2.096(4) 1_655 ?
O9 La1 2.518(4) 2_676 ?
O11 C12 1.267(7) . ?
O11 La1 2.624(4) 2_676 ?
O12 C12 1.258(7) . ?
O12 La1 2.706(4) 2_676 ?
N1 C14 1.322(9) . ?
N1 C16 1.378(9) . ?
N1 C17 1.461(10) . ?
N2 C14 1.319(9) . ?
N2 C15 1.370(9) . ?
N2 C18 1.474(8) . ?
C1 C2 1.382(8) . ?
C1 C6 1.398(8) . ?
C1 C7 1.517(7) . ?
C2 C3 1.394(7) . ?
C3 C4 1.401(8) . ?
C3 C8 1.492(8) . ?
C4 C5 1.380(8) . ?
C5 C6 1.392(8) . ?
C5 C9 1.521(8) . ?
C12 C13 1.492(8) . ?
C12 La1 3.063(5) 2_676 ?
C15 C16 1.339(11) . ?
C18 C19 1.495(12) . ?

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
O4 La1 O5 75.31(16) 2_677 . ?
O4 La1 O9 141.77(15) 2_677 2_676 ?
O5 La1 O9 73.00(15) . 2_676 ?
O4 La1 O2 74.25(14) 2_677 . ?
O5 La1 O2 90.68(16) . . ?
O9 La1 O2 126.46(14) 2_676 . ?
O4 La1 O12 142.30(15) 2_677 . ?
O5 La1 O12 141.42(14) . . ?
O9 La1 O12 73.99(13) 2_676 . ?
O2 La1 O12 93.14(14) . . ?
O4 La1 O8 71.71(17) 2_677 . ?
O5 La1 O8 146.84(16) . . ?
O9 La1 O8 135.04(14) 2_676 . ?
O2 La1 O8 83.75(16) . . ?
O12 La1 O8 71.67(15) . . ?
O4 La1 O11 73.88(13) 2_677 2_676 ?
O5 La1 O11 76.53(13) . 2_676 ?
O9 La1 O11 78.39(14) 2_676 2_676 ?
O2 La1 O11 147.73(14) . 2_676 ?
O12 La1 O11 115.40(12) . 2_676 ?
O8 La1 O11 90.99(16) . 2_676 ?
O4 La1 O1 115.88(14) 2_677 . ?
O5 La1 O1 76.20(14) . . ?
O9 La1 O1 76.39(14) 2_676 . ?
O2 La1 O1 50.09(13) . . ?
O12 La1 O1 77.12(14) . . ?
O8 La1 O1 121.79(16) . . ?
O11 La1 O1 147.15(13) 2_676 . ?
O4 La1 O12 107.91(13) 2_677 2_676 ?
O5 La1 O12 117.35(13) . 2_676 ?
O9 La1 O12 69.69(13) 2_676 2_676 ?
O2 La1 O12 151.75(15) . 2_676 ?
O12 La1 O12 67.60(14) . 2_676 ?
O8 La1 O12 70.89(13) . 2_676 ?
O11 La1 O12 48.13(12) 2_676 2_676 ?
O1 La1 O12 136.20(13) . 2_676 ?
O4 La1 C7 95.55(15) 2_677 . ?
O5 La1 C7 83.38(15) . . ?
O9 La1 C7 101.44(15) 2_676 . ?
O2 La1 C7 25.06(15) . . ?
O12 La1 C7 84.11(14) . . ?
O8 La1 C7 102.96(16) . . ?
O11 La1 C7 159.08(14) 2_676 . ?
O1 La1 C7 25.05(14) . . ?
O12 La1 C7 151.64(14) 2_676 . ?
O4 La1 C12 92.71(14) 2_677 2_676 ?
O5 La1 C12 95.81(15) . 2_676 ?
O9 La1 C12 70.03(15) 2_676 2_676 ?
O2 La1 C12 163.49(14) . 2_676 ?
O12 La1 C12 91.21(13) . 2_676 ?
O8 La1 C12 82.52(16) . 2_676 ?
O11 La1 C12 24.19(13) 2_676 2_676 ?
O1 La1 C12 146.34(13) . 2_676 ?
O12 La1 C12 24.19(13) 2_676 2_676 ?
C7 La1 C12 171.20(15) . 2_676 ?
O3 Co1 O3 180.000(1) 2_577 1_554 ?
O3 Co1 O7 88.13(17) 2_577 2_676 ?
O3 Co1 O7 91.87(17) 1_554 2_676 ?
O3 Co1 O7 91.87(17) 2_577 1_455 ?
O3 Co1 O7 88.13(17) 1_554 1_455 ?
O7 Co1 O7 180.00(18) 2_676 1_455 ?
O3 Co1 O11 92.14(16) 2_577 2_576 ?
O3 Co1 O11 87.86(16) 1_554 2_576 ?
O7 Co1 O11 89.06(16) 2_676 2_576 ?
O7 Co1 O11 90.94(16) 1_455 2_576 ?
O3 Co1 O11 87.86(16) 2_577 . ?
O3 Co1 O11 92.14(16) 1_554 . ?
O7 Co1 O11 90.94(16) 2_676 . ?
O7 Co1 O11 89.06(16) 1_455 . ?
O11 Co1 O11 180.000(1) 2_576 . ?
O10 S1 O9 112.8(3) . . ?
O10 S1 O8 112.1(3) . . ?
O9 S1 O8 112.0(3) . . ?
O10 S1 C10 107.5(4) . . ?
O9 S1 C10 105.5(4) . . ?
O8 S1 C10 106.5(4) . . ?
O6 S2 O7 112.2(4) . . ?
O6 S2 O5 111.7(3) . . ?
O7 S2 O5 112.1(3) . . ?
O6 S2 C11 109.1(5) . . ?
O7 S2 C11 106.3(3) . . ?
O5 S2 C11 105.0(4) . . ?
C7 O1 La1 90.9(3) . . ?
C7 O2 La1 96.9(3) . . ?
C8 O3 Co1 131.5(4) . 1_556 ?
C8 O4 La1 151.0(4) . 2_677 ?
S2 O5 La1 140.6(3) . . ?
S2 O7 Co1 137.6(3) . 1_655 ?
S1 O8 La1 143.4(3) . . ?
S1 O9 La1 141.8(3) . 2_676 ?
C12 O11 Co1 134.9(3) . . ?
C12 O11 La1 97.7(3) . 2_676 ?
Co1 O11 La1 125.82(16) . 2_676 ?
C12 O12 La1 150.6(3) . . ?
C12 O12 La1 94.0(3) . 2_676 ?
La1 O12 La1 112.40(14) . 2_676 ?
C14 N1 C16 108.1(6) . . ?
C14 N1 C17 125.8(7) . . ?
C16 N1 C17 126.0(7) . . ?
C14 N2 C15 108.1(6) . . ?
C14 N2 C18 125.1(6) . . ?
C15 N2 C18 126.8(6) . . ?
C2 C1 C6 119.9(5) . . ?
C2 C1 C7 119.2(5) . . ?
C6 C1 C7 120.8(5) . . ?
C1 C2 C3 120.7(5) . . ?
C2 C3 C4 118.4(5) . . ?
C2 C3 C8 119.6(5) . . ?
C4 C3 C8 121.9(5) . . ?
C5 C4 C3 121.7(5) . . ?
C4 C5 C6 118.9(5) . . ?
C4 C5 C9 119.9(5) . . ?
C6 C5 C9 121.2(5) . . ?
C5 C6 C1 120.3(5) . . ?
O1 C7 O2 122.1(5) . . ?
O1 C7 C1 120.6(5) . . ?
O2 C7 C1 117.2(5) . . ?
O1 C7 La1 64.1(3) . . ?
O2 C7 La1 58.1(3) . . ?
C1 C7 La1 173.9(4) . . ?
O4 C8 O3 124.0(5) . . ?
O4 C8 C3 117.5(5) . . ?
O3 C8 C3 118.4(5) . . ?
O12 C12 O11 118.9(5) . . ?
O12 C12 C13 119.8(5) . . ?
O11 C12 C13 121.3(5) . . ?
O12 C12 La1 61.8(3) . 2_676 ?
O11 C12 La1 58.1(3) . 2_676 ?
C13 C12 La1 169.7(5) . 2_676 ?
N2 C14 N1 109.3(6) . . ?
C16 C15 N2 107.7(6) . . ?
C15 C16 N1 106.8(6) . . ?
N2 C18 C19 112.5(6) . . ?

_diffrn_measured_fraction_theta_max 0.998
_diffrn_reflns_theta_full        26.00
_diffrn_measured_fraction_theta_full 0.998
_refine_diff_density_max         2.692
_refine_diff_density_min         -0.961
_refine_diff_density_rms         0.154

# Attachment 'complex21.cif'

data_complex2
_database_code_depnum_ccdc_archive 'CCDC 717558'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C14 H14 Br Cl La N3 O6'
_chemical_formula_weight         574.55

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'
Cl Cl 0.1484 0.1585 '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'
La La -0.2871 2.4523 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           ORTHORHOMBIC
_symmetry_space_group_name_H-M   Pca2(1)

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

_cell_length_a                   24.509(6)
_cell_length_b                   9.835(2)
_cell_length_c                   7.5626(19)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     1822.8(8)
_cell_formula_units_Z            4
_cell_measurement_temperature    123(2)
_cell_measurement_reflns_used    3056
_cell_measurement_theta_min      2.23
_cell_measurement_theta_max      27.00

_exptl_crystal_description       needle
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.10
_exptl_crystal_size_min          0.10
_exptl_crystal_density_meas      'not measured'
_exptl_crystal_density_diffrn    2.094
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1104
_exptl_absorpt_coefficient_mu    4.718
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.3850
_exptl_absorpt_correction_T_max  0.6498
_exptl_absorpt_process_details   sadabs

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      123(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  'Bruker Smart Apex 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            9639
_diffrn_reflns_av_R_equivalents  0.0539
_diffrn_reflns_av_sigmaI/netI    0.0680
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_theta_min         1.66
_diffrn_reflns_theta_max         26.00
_reflns_number_total             3430
_reflns_number_gt                3006
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'SHELXTL-Plus (Sheldrick, 1990)'
_computing_cell_refinement       'SHELXTL-Plus (Sheldrick, 1990)'
_computing_data_reduction        'SHELXTL-Plus (Sheldrick, 1990)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'SHELXTL V.5.0 (Sheldrick, 1997)'
_computing_publication_material  'SHELXL-97 (Sheldrick, 1997)'

_refine_special_details          
;
Refinement of F² against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F², conventional R-factors R are based
on F, with F set to zero for negative F². The threshold expression of
F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F² 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/[σ²(Fo²)+(0.0727P)²+5.2175P] where P=(Fo²+2Fc²)/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_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.30(3)
_refine_ls_number_reflns         3430
_refine_ls_number_parameters     245
_refine_ls_number_restraints     7
_refine_ls_R_factor_all          0.0627
_refine_ls_R_factor_gt           0.0546
_refine_ls_wR_factor_ref         0.1380
_refine_ls_wR_factor_gt          0.1328
_refine_ls_goodness_of_fit_ref   1.100
_refine_ls_restrained_S_all      1.099
_refine_ls_shift/su_max          0.026
_refine_ls_shift/su_mean         0.002

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
La1 La 0.216079(18) -0.28565(4) 0.13688(10) 0.01136(16) Uani 1 1 d . . .
Br1 Br 0.09749(5) -0.28523(13) 0.19803(19) 0.0386(4) Uani 1 1 d . . .
Cl1 Cl 0.17567(11) -0.2922(3) -0.2161(4) 0.0269(6) Uani 1 1 d . . .
O1 O 0.2832(3) -0.1434(7) -0.0845(9) 0.0177(15) Uani 1 1 d . . .
O2 O 0.2208(3) -0.0342(7) 0.0595(11) 0.0255(18) Uani 1 1 d . . .
O3 O 0.2232(3) 0.4633(7) 0.0654(11) 0.0238(17) Uani 1 1 d . . .
O4 O 0.2848(3) 0.5793(7) -0.0837(9) 0.0154(15) Uani 1 1 d . . .
O5 O 0.4460(4) 0.3148(10) -0.2741(18) 0.057(3) Uani 1 1 d . . .
O6 O 0.4415(3) 0.1056(10) -0.3072(16) 0.055(3) Uani 1 1 d . . .
N1 N 0.4241(4) 0.2107(10) -0.2538(15) 0.028(2) Uani 1 1 d . . .
N2 N 0.4204(4) 0.1161(12) -0.7116(18) 0.043(3) Uani 1 1 d . . .
N3 N 0.4276(5) 0.3319(14) -0.7130(17) 0.044(3) Uani 1 1 d . . .
C1 C 0.2930(4) 0.0899(11) -0.0665(14) 0.017(2) Uani 1 1 d . . .
C2 C 0.2692(4) 0.2124(9) -0.0243(14) 0.014(2) Uani 1 1 d . . .
H2 H 0.2351 0.2127 0.0358 0.016 Uiso 1 1 calc R . .
C3 C 0.2933(4) 0.3345(9) -0.0667(13) 0.012(2) Uani 1 1 d . . .
C4 C 0.3447(5) 0.3346(10) -0.1400(14) 0.019(2) Uani 1 1 d . . .
H4 H 0.3629 0.4174 -0.1664 0.023 Uiso 1 1 calc R . .
C5 C 0.3685(4) 0.2127(10) -0.1734(16) 0.017(2) Uani 1 1 d . . .
C6 C 0.3427(4) 0.0888(11) -0.1444(14) 0.018(2) Uani 1 1 d . . .
H6 H 0.3595 0.0057 -0.1783 0.022 Uiso 1 1 calc R . .
C7 C 0.2628(4) -0.0371(11) -0.0284(13) 0.020(2) Uani 1 1 d . . .
C8 C 0.2654(4) 0.4664(9) -0.0282(13) 0.015(2) Uani 1 1 d U . .
C9 C 0.4535(6) 0.2169(16) -0.740(2) 0.045(4) Uani 1 1 d . . .
H9 H 0.4906 0.2087 -0.7742 0.053 Uiso 1 1 calc R . .
C10 C 0.3718(5) 0.1702(16) -0.661(2) 0.044(4) Uani 1 1 d . . .
H10 H 0.3400 0.1201 -0.6298 0.053 Uiso 1 1 calc R . .
C11 C 0.3760(6) 0.2992(16) -0.662(2) 0.045(4) Uani 1 1 d . . .
H11 H 0.3480 0.3618 -0.6318 0.054 Uiso 1 1 calc R . .
C12 C 0.4338(8) -0.031(2) -0.719(3) 0.085(7) Uani 1 1 d . . .
H12A H 0.4713 -0.0438 -0.6730 0.101 Uiso 1 1 calc R . .
H12B H 0.4086 -0.0801 -0.6389 0.101 Uiso 1 1 calc R . .
H12C H 0.4308 -0.0633 -0.8378 0.101 Uiso 0.50 1 d PR . .
C13 C 0.4498(7) 0.4682(18) -0.734(3) 0.069(6) Uani 1 1 d . . .
H13A H 0.4351 0.5262 -0.6386 0.083 Uiso 1 1 calc R . .
H13B H 0.4898 0.4634 -0.7185 0.083 Uiso 1 1 calc R . .
H13C H 0.4408 0.5032 -0.8493 0.083 Uiso 0.50 1 d PR . .
C14 C 0.4403(11) 0.525(2) -0.877(5) 0.042(6) Uani 0.50 1 d P . .
H14A H 0.4572 0.6148 -0.8781 0.063 Uiso 0.50 1 calc PR . .
H14B H 0.4008 0.5337 -0.8930 0.063 Uiso 0.50 1 calc PR . .
H14C H 0.4554 0.4697 -0.9737 0.063 Uiso 0.50 1 calc PR . .
C15 C 0.4308(12) -0.082(3) -0.869(7) 0.057(7) Uani 0.50 1 d P . .
H15A H 0.4403 -0.1786 -0.8627 0.086 Uiso 0.50 1 calc PR . .
H15B H 0.4562 -0.0352 -0.9486 0.086 Uiso 0.50 1 calc PR . .
H15C H 0.3935 -0.0722 -0.9141 0.086 Uiso 0.50 1 calc PR . .


_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
La1 O4 2.496(7) 4_545 ?
La1 O1 2.529(7) 4 ?
La1 O3 2.533(6) 1_545 ?
La1 O2 2.544(7) . ?
La1 O4 2.718(7) 1_545 ?
La1 O1 2.733(8) . ?
La1 Cl1 2.848(3) . ?
La1 Cl1 2.877(3) 4 ?
La1 Br1 2.9429(15) . ?
La1 C7 2.975(11) . ?
La1 C8 2.995(9) 1_545 ?
La1 La1 4.1307(9) 4 ?
Cl1 La1 2.877(3) 4_554 ?
O1 C7 1.234(12) . ?
O1 La1 2.529(7) 4_554 ?
O2 C7 1.226(13) . ?
O3 C8 1.254(12) . ?
O3 La1 2.533(6) 1_565 ?
O4 C8 1.279(12) . ?
O4 La1 2.496(7) 4_564 ?
O4 La1 2.718(7) 1_565 ?
O5 N1 1.166(13) . ?
O6 N1 1.188(13) . ?
N1 C5 1.494(14) . ?
N2 C9 1.297(19) . ?
N2 C10 1.361(17) . ?
N2 C12 1.48(2) . ?
N3 C9 1.313(19) . ?
N3 C11 1.361(18) . ?
N3 C13 1.45(2) . ?
C1 C6 1.353(15) . ?
C1 C2 1.376(15) . ?
C1 C7 1.480(15) . ?
C2 C3 1.377(14) . ?
C2 H2 0.9500 . ?
C3 C4 1.374(15) . ?
C3 C8 1.494(12) . ?
C4 C5 1.357(15) . ?
C4 H4 0.9500 . ?
C5 C6 1.390(15) . ?
C6 H6 0.9500 . ?
C8 La1 2.995(9) 1_565 ?
C9 H9 0.9500 . ?
C10 C11 1.27(2) . ?
C10 H10 0.9500 . ?
C11 H11 0.9500 . ?
C12 C15 1.25(5) . ?
C12 H12A 0.9900 . ?
C12 H12B 0.9900 . ?
C12 H12C 0.9601 . ?
C13 C14 1.24(4) . ?
C13 H13A 0.9900 . ?
C13 H13B 0.9900 . ?
C13 H13C 0.9601 . ?
C14 H13C 0.2977 . ?
C14 H14A 0.9800 . ?
C14 H14B 0.9800 . ?
C14 H14C 0.9800 . ?
C15 H12C 0.2986 . ?
C15 H15A 0.9800 . ?
C15 H15B 0.9800 . ?
C15 H15C 0.9800 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O4 La1 O1 65.7(2) 4_545 4 ?
O4 La1 O3 70.3(2) 4_545 1_545 ?
O1 La1 O3 135.8(3) 4 1_545 ?
O4 La1 O2 135.4(2) 4_545 . ?
O1 La1 O2 69.7(3) 4 . ?
O3 La1 O2 153.5(3) 1_545 . ?
O4 La1 O4 105.4(2) 4_545 1_545 ?
O1 La1 O4 141.0(2) 4 1_545 ?
O3 La1 O4 49.5(2) 1_545 1_545 ?
O2 La1 O4 107.8(2) . 1_545 ?
O4 La1 O1 142.8(2) 4_545 . ?
O1 La1 O1 102.9(2) 4 . ?
O3 La1 O1 109.1(2) 1_545 . ?
O2 La1 O1 48.2(2) . . ?
O4 La1 O1 60.1(2) 1_545 . ?
O4 La1 Cl1 141.12(16) 4_545 . ?
O1 La1 Cl1 142.72(18) 4 . ?
O3 La1 Cl1 78.6(2) 1_545 . ?
O2 La1 Cl1 79.8(2) . . ?
O4 La1 Cl1 68.25(16) 1_545 . ?
O1 La1 Cl1 69.30(16) . . ?
O4 La1 Cl1 70.69(17) 4_545 4 ?
O1 La1 Cl1 71.58(17) 4 4 ?
O3 La1 Cl1 89.83(18) 1_545 4 ?
O2 La1 Cl1 93.94(19) . 4 ?
O4 La1 Cl1 69.79(15) 1_545 4 ?
O1 La1 Cl1 72.13(15) . 4 ?
Cl1 La1 Cl1 133.03(8) . 4 ?
O4 La1 Br1 81.88(16) 4_545 . ?
O1 La1 Br1 82.83(15) 4 . ?
O3 La1 Br1 95.91(17) 1_545 . ?
O2 La1 Br1 94.57(17) . . ?
O4 La1 Br1 135.20(14) 1_545 . ?
O1 La1 Br1 133.64(14) . . ?
Cl1 La1 Br1 78.69(7) . . ?
Cl1 La1 Br1 148.20(7) 4 . ?
O4 La1 C7 142.8(2) 4_545 . ?
O1 La1 C7 83.8(2) 4 . ?
O3 La1 C7 133.2(3) 1_545 . ?
O2 La1 C7 24.1(2) . . ?
O4 La1 C7 84.5(2) 1_545 . ?
O1 La1 C7 24.5(2) . . ?
Cl1 La1 C7 76.02(18) . . ?
Cl1 La1 C7 79.98(19) 4 . ?
Br1 La1 C7 116.42(19) . . ?
O4 La1 C8 85.6(2) 4_545 1_545 ?
O1 La1 C8 142.6(3) 4 1_545 ?
O3 La1 C8 24.4(3) 1_545 1_545 ?
O2 La1 C8 132.6(3) . 1_545 ?
O4 La1 C8 25.3(2) 1_545 1_545 ?
O1 La1 C8 85.3(2) . 1_545 ?
Cl1 La1 C8 74.4(2) . 1_545 ?
Cl1 La1 C8 76.73(19) 4 1_545 ?
Br1 La1 C8 117.75(19) . 1_545 ?
C7 La1 C8 109.8(3) . 1_545 ?
O4 La1 La1 39.52(15) 4_545 4 ?
O1 La1 La1 40.06(17) 4 4 ?
O3 La1 La1 99.65(19) 1_545 4 ?
O2 La1 La1 101.08(19) . 4 ?
O4 La1 La1 108.19(15) 1_545 4 ?
O1 La1 La1 108.58(14) . 4 ?
Cl1 La1 La1 176.38(6) . 4 ?
Cl1 La1 La1 43.54(6) 4 4 ?
Br1 La1 La1 104.70(3) . 4 ?
C7 La1 La1 103.28(17) . 4 ?
C8 La1 La1 102.65(19) 1_545 4 ?
La1 Cl1 La1 92.36(8) . 4_554 ?
C7 O1 La1 139.3(6) . 4_554 ?
C7 O1 La1 88.8(7) . . ?
La1 O1 La1 103.4(2) 4_554 . ?
C7 O2 La1 98.0(6) . . ?
C8 O3 La1 98.9(6) . 1_565 ?
C8 O4 La1 137.4(6) . 4_564 ?
C8 O4 La1 89.6(6) . 1_565 ?
La1 O4 La1 104.7(2) 4_564 1_565 ?
O5 N1 O6 123.7(11) . . ?
O5 N1 C5 117.5(9) . . ?
O6 N1 C5 118.4(10) . . ?
C9 N2 C10 107.2(13) . . ?
C9 N2 C12 126.9(13) . . ?
C10 N2 C12 125.7(14) . . ?
C9 N3 C11 106.8(13) . . ?
C9 N3 C13 126.6(13) . . ?
C11 N3 C13 126.6(14) . . ?
C6 C1 C2 119.3(10) . . ?
C6 C1 C7 121.9(10) . . ?
C2 C1 C7 118.8(9) . . ?
C1 C2 C3 121.8(11) . . ?
C1 C2 H2 119.1 . . ?
C3 C2 H2 119.1 . . ?
C4 C3 C2 119.2(9) . . ?
C4 C3 C8 119.8(9) . . ?
C2 C3 C8 121.0(10) . . ?
C5 C4 C3 117.9(10) . . ?
C5 C4 H4 121.0 . . ?
C3 C4 H4 121.0 . . ?
C4 C5 C6 123.3(11) . . ?
C4 C5 N1 118.7(9) . . ?
C6 C5 N1 117.9(9) . . ?
C1 C6 C5 118.1(10) . . ?
C1 C6 H6 120.9 . . ?
C5 C6 H6 120.9 . . ?
O2 C7 O1 123.2(11) . . ?
O2 C7 C1 120.4(9) . . ?
O1 C7 C1 116.4(10) . . ?
O2 C7 La1 57.9(6) . . ?
O1 C7 La1 66.7(6) . . ?
C1 C7 La1 165.4(6) . . ?
O3 C8 O4 120.8(8) . . ?
O3 C8 C3 117.8(9) . . ?
O4 C8 C3 121.3(9) . . ?
O3 C8 La1 56.7(5) . 1_565 ?
O4 C8 La1 65.1(5) . 1_565 ?
C3 C8 La1 166.5(7) . 1_565 ?
N2 C9 N3 109.4(13) . . ?
N2 C9 H9 125.3 . . ?
N3 C9 H9 125.3 . . ?
C11 C10 N2 108.4(12) . . ?
C11 C10 H10 125.8 . . ?
N2 C10 H10 125.8 . . ?
C10 C11 N3 108.3(13) . . ?
C10 C11 H11 125.9 . . ?
N3 C11 H11 125.9 . . ?
C15 C12 N2 114(2) . . ?
C15 C12 H12A 108.7 . . ?
N2 C12 H12A 108.7 . . ?
C15 C12 H12B 108.7 . . ?
N2 C12 H12B 108.7 . . ?
H12A C12 H12B 107.6 . . ?
C15 C12 H12C 4.4 . . ?
N2 C12 H12C 110.0 . . ?
H12A C12 H12C 110.8 . . ?
H12B C12 H12C 111.0 . . ?
C14 C13 N3 116.1(18) . . ?
C14 C13 H13A 108.3 . . ?
N3 C13 H13A 108.3 . . ?
C14 C13 H13B 108.3 . . ?
N3 C13 H13B 108.3 . . ?
H13A C13 H13B 107.4 . . ?
C14 C13 H13C 6.0 . . ?
N3 C13 H13C 110.2 . . ?
H13A C13 H13C 111.8 . . ?
H13B C13 H13C 110.8 . . ?
C13 C14 H13C 19.6 . . ?
C13 C14 H14A 109.5 . . ?
H13C C14 H14A 128.9 . . ?
C13 C14 H14B 109.5 . . ?
H13C C14 H14B 100.8 . . ?
H14A C14 H14B 109.5 . . ?
C13 C14 H14C 109.5 . . ?
H13C C14 H14C 97.3 . . ?
H14A C14 H14C 109.5 . . ?
H14B C14 H14C 109.5 . . ?
C12 C15 H12C 14.2 . . ?
C12 C15 H15A 109.5 . . ?
H12C C15 H15A 123.7 . . ?
C12 C15 H15B 109.5 . . ?
H12C C15 H15B 101.5 . . ?
H15A C15 H15B 109.5 . . ?
C12 C15 H15C 109.5 . . ?
H12C C15 H15C 102.4 . . ?
H15A C15 H15C 109.5 . . ?
H15B C15 H15C 109.5 . . ?

_diffrn_measured_fraction_theta_max 0.998
_diffrn_reflns_theta_full        26.00
_diffrn_measured_fraction_theta_full 0.998
_refine_diff_density_max         4.938
_refine_diff_density_min         -0.868
_refine_diff_density_rms         0.248


