# Copyright The Royal Society of Chemistry, 1998
# CCDC Number: 182/1077


data_global

#1. Submission Details
_publ_contact_author
;
  Herbert Plenio
  Inst. Anorg. Chemie, Univ. Freiburg
  Albertstr.21, 79104 Freiburg, Germany
;
_publ_contact_author_phone   '049 761 203 6129'
_publ_contact_author_fax     '049 761 203 5987'
_publ_requested_journal      'Chem. Commun.'
_publ_contact_email          'plenio@uni-freiburg.de'

#2. Title and Author List

_publ_section_title
;
Synthesis of a ferrocene bridged cyclam - a new redox-activemacrocycle
and the structure of a Ni(II)-complex with strongly coupled metal centers.
;

loop_
_publ_author_name
_publ_author_adress
  
'Herbert Plenio'
; Inst. Anorg. Chemie, Univ. Freiburg
  Albertstr. 21, 79104 Freiburg, Germany
;
  'Clemens Aberle'
;
  Inst. Anorg. Chemie, Univ. Freiburg
  Albertstr. 21, 79104 Freiburg, Germany
;

#3 Results


data_ca4

_audit_creation_method            SHELXL-97
_chemical_name_systematic
;
 1,8-(1,1'-ferrocenedimethyldiyl),4,11-tetraaza-cyclotetradecane-
  Nickel(II)triflate complex'
;
_chemical_name_common             'ferrocene cyclam x Ni(II)triflate complex'
_chemical_formula_moiety          ?
_chemical_formula_sum
 'C13.50 H20 F3 Fe0.50 N2 Ni0.50 O3.50 S'
_chemical_formula_weight          412.65

loop_
 _atom_type_symbol
 _atom_type_description
 _atom_type_scat_dispersion_real
 _atom_type_scat_dispersion_imag
 _atom_type_scat_source
 'C'  'C'   0.0033   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'
 'S'  'S'   0.1246   0.1234
 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
 'Fe'  'Fe'   0.3463   0.8444
 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
 'Ni'  'Ni'   0.3393   1.1124
 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
 'F'  'F'   0.0171   0.0103
 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting            tetragonal
_symmetry_space_group_name_H-M    P4(3)2(1)2

loop_
 _symmetry_equiv_pos_as_xyz
 'x, y, z'
 '-x, -y, z+1/2'
 '-y+1/2, x+1/2, z+3/4'
 'y+1/2, -x+1/2, z+1/4'
 '-x+1/2, y+1/2, -z+3/4'
 'x+1/2, -y+1/2, -z+1/4'
 'y, x, -z'
 '-y, -x, -z+1/2'

_cell_length_a                    10.5735(15)
_cell_length_b                    10.5735(15)
_cell_length_c                    30.251(6)
_cell_angle_alpha                 90.00
_cell_angle_beta                  90.00
_cell_angle_gamma                 90.00
_cell_volume                      3382.0(10)
_cell_formula_units_Z             8
_cell_measurement_temperature     293(2)
_cell_measurement_reflns_used     20
_cell_measurement_theta_min       ?
_cell_measurement_theta_max       ?

_exptl_crystal_description        'plates'
_exptl_crystal_colour             yellow
_exptl_crystal_size_max           0.4
_exptl_crystal_size_mid           0.4
_exptl_crystal_size_min           0.2
_exptl_crystal_density_meas       ?
_exptl_crystal_density_diffrn     1.621
_exptl_crystal_density_method     'not measured'
_exptl_crystal_F_000              1704
_exptl_absorpt_coefficient_mu     1.192
_exptl_absorpt_correction_type    'empirical, psi-scans'
_exptl_absorpt_correction_T_min   ?
_exptl_absorpt_correction_T_max   ?

_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   'enraf-nonius cad4f'
_diffrn_measurement_method        'omega-2theta'
_diffrn_detector_area_resol_mean  ?
_diffrn_standards_number          2
_diffrn_standards_interval_count  'every 100 refl.'
_diffrn_standards_interval_time   'every 60 min'
_diffrn_standards_decay_%         none
_diffrn_reflns_number             3524
_diffrn_reflns_av_R_equivalents   0.0594
_diffrn_reflns_av_sigmaI/netI     0.0787
_diffrn_reflns_limit_h_min        0
_diffrn_reflns_limit_h_max        12
_diffrn_reflns_limit_k_min        -13
_diffrn_reflns_limit_k_max        0
_diffrn_reflns_limit_l_min        -37
_diffrn_reflns_limit_l_max        0
_diffrn_reflns_theta_min          2.69
_diffrn_reflns_theta_max          25.97
_reflns_number_total              3137
_reflns_number_gt                 2152
_reflns_threshold_expression      >2sigma(I)

_computing_data_collection        'turbo-mol, enraf-nonius'
_computing_cell_refinement        'turbo-mol, enraf-nonius'
_computing_data_reduction         'cadfor, cadsex, E. Keller, Freiburg 1993'
_computing_structure_solution     'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement   'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics     'Schakal, E. Keller, Freiburg 1995'
_computing_publication_material   'CIFTAB, G.M. Sheldirck'

_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 w=1/[\s^2^(Fo^2^)+(0.0671P)^2^+2.0909P] 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        no
_refine_ls_abs_structure_details
 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack    0.00(3)
_refine_ls_number_reflns          3137
_refine_ls_number_parameters      219
_refine_ls_number_restraints      0
_refine_ls_R_factor_all           0.1175
_refine_ls_R_factor_gt            0.0452
_refine_ls_wR_factor_ref          0.1323
_refine_ls_wR_factor_gt           0.1101
_refine_ls_goodness_of_fit_ref    1.057
_refine_ls_restrained_S_all       1.057
_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_calc_flag
 _atom_site_refinement_flags
 _atom_site_disorder_assembly
 _atom_site_disorder_group
Fe1 Fe 0.42124(7) 1.42124(7) 0.0000 0.0462(3) Uani 1 d S . .
Ni1 Ni 0.16348(6) 1.16348(6) 0.0000 0.0339(2) Uani 1 d S . .
C1 C 0.4206(6) 1.2828(5) 0.04857(18) 0.0442(13) Uani 1 d . . .
C2 C 0.5463(6) 1.3209(8) 0.0387(2) 0.0611(18) Uani 1 d . . .
H2 H 0.6113 1.2694 0.0285 0.073 Uiso 1 calc R . .
C3 C 0.5539(7) 1.4544(8) 0.0474(2) 0.075(2) Uani 1 d . . .
H3 H 0.6257 1.5042 0.0441 0.090 Uiso 1 calc R . .
C4 C 0.4352(8) 1.4970(7) 0.0618(2) 0.068(2) Uani 1 d . . .
H4 H 0.4143 1.5797 0.0693 0.082 Uiso 1 calc R . .
C5 C 0.3534(6) 1.3918(6) 0.06273(18) 0.0495(16) Uani 1 d . . .
H5 H 0.2689 1.3935 0.0713 0.059 Uiso 1 calc R . .
C6 C 0.3940(5) 1.1425(5) 0.04919(18) 0.0435(14) Uani 1 d . . .
H6A H 0.4327 1.1058 0.0231 0.052 Uiso 1 calc R . .
H6B H 0.4369 1.1069 0.0747 0.052 Uiso 1 calc R . .
C7 C 0.1970(5) 1.1410(6) 0.09267(17) 0.0482(15) Uani 1 d . . .
H7A H 0.2081 1.0773 0.1154 0.058 Uiso 1 calc R . .
H7B H 0.2346 1.2193 0.1029 0.058 Uiso 1 calc R . .
C8 C 0.0592(6) 1.1601(6) 0.08343(19) 0.0525(15) Uani 1 d . . .
H8A H 0.0180 1.0791 0.0790 0.063 Uiso 1 calc R . .
H8B H 0.0191 1.2024 0.1082 0.063 Uiso 1 calc R . .
C9 C -0.0869(6) 1.2451(7) 0.0301(2) 0.0606(17) Uani 1 d . . .
H9A H -0.1341 1.2854 0.0537 0.073 Uiso 1 calc R . .
H9B H -0.1191 1.1597 0.0267 0.073 Uiso 1 calc R . .
C10 C 0.3174(7) 0.8914(6) 0.01260(19) 0.0575(16) Uani 1 d . . .
H10A H 0.3224 0.8012 0.0181 0.069 Uiso 1 calc R . .
H10B H 0.4031 0.9226 0.0090 0.069 Uiso 1 calc R . .
C11 C 0.2587(7) 0.9550(6) 0.0522(2) 0.0538(16) Uani 1 d . . .
H11A H 0.3036 0.9279 0.0785 0.065 Uiso 1 calc R . .
H11B H 0.1719 0.9264 0.0550 0.065 Uiso 1 calc R . .
C12 C 0.0538(8) 0.6950(8) 0.1138(3) 0.081(3) Uani 1 d . . .
C13 C -0.1318(9) 0.8682(9) 0.0000 0.098(4) Uani 1 d S . .
C14 C -0.2382(11) 0.8732(13) 0.0323(4) 0.165(6) Uani 1 d . . .
H14A H -0.2173 0.8231 0.0578 0.248 Uiso 1 calc R . .
H14B H -0.3135 0.8404 0.0188 0.248 Uiso 1 calc R . .
H14C H -0.2522 0.9592 0.0412 0.248 Uiso 1 calc R . .
N1 N 0.2594(4) 1.0992(4) 0.05064(14) 0.0393(11) Uani 1 d . . .
N2 N 0.0481(5) 1.2390(5) 0.04270(15) 0.0465(12) Uani 1 d . . .
H22A H 0.0753 1.3187 0.0490 0.056 Uiso 1 calc R . .
O2 O -0.0511(5) 0.9489(5) 0.0000 0.098(2) Uani 1 d S . .
O3 O -0.1355(5) 0.5719(6) 0.0847(2) 0.0942(17) Uani 1 d . . .
O4 O 0.0517(6) 0.5799(7) 0.03883(18) 0.112(2) Uani 1 d . . .
O5 O 0.0504(6) 0.4560(5) 0.1045(2) 0.1022(19) Uani 1 d . . .
S1 S -0.0023(2) 0.56429(19) 0.08112(6) 0.0708(5) Uani 1 d . . .
F1 F 0.1799(5) 0.7030(5) 0.11194(19) 0.1153(18) Uani 1 d . . .
F2 F 0.0081(6) 0.8031(5) 0.0960(2) 0.121(2) Uani 1 d . . .
F3 F 0.0209(5) 0.6862(5) 0.15462(14) 0.1009(16) Uani 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
Fe1 0.0470(4) 0.0470(4) 0.0446(6) 0.0051(5) -0.0051(5) -0.0126(5)
Ni1 0.0359(3) 0.0359(3) 0.0301(4) 0.0005(3) -0.0005(3) 0.0027(4)
C1 0.045(3) 0.048(3) 0.039(3) 0.007(3) -0.007(3) -0.006(3)
C2 0.045(4) 0.077(5) 0.061(4) 0.019(4) -0.008(3) -0.006(3)
C3 0.065(5) 0.089(6) 0.070(4) 0.017(4) -0.031(4) -0.041(4)
C4 0.096(6) 0.059(4) 0.051(4) -0.001(3) -0.021(4) -0.020(4)
C5 0.059(4) 0.050(3) 0.040(3) -0.002(3) 0.001(3) -0.013(3)
C6 0.045(3) 0.047(4) 0.038(3) 0.007(3) -0.003(2) 0.001(3)
C7 0.057(4) 0.057(4) 0.031(2) 0.005(2) 0.001(2) 0.000(3)
C8 0.056(4) 0.057(4) 0.045(3) 0.005(3) 0.004(3) 0.000(3)
C9 0.039(4) 0.080(5) 0.062(4) -0.001(4) 0.006(3) 0.006(3)
C10 0.069(4) 0.038(3) 0.065(4) -0.002(3) -0.010(3) 0.008(3)
C11 0.063(4) 0.043(4) 0.055(4) 0.012(3) -0.008(3) 0.002(3)
C12 0.086(6) 0.072(5) 0.086(6) 0.018(4) 0.031(4) -0.012(4)
C13 0.098(6) 0.098(6) 0.099(9) 0.036(6) -0.036(6) -0.013(7)
C14 0.093(8) 0.210(15) 0.193(13) 0.114(11) -0.003(8) -0.014(9)
N1 0.042(3) 0.039(3) 0.037(2) 0.010(2) 0.002(2) -0.002(2)
N2 0.047(3) 0.048(3) 0.044(3) -0.001(2) 0.001(2) 0.001(2)
O2 0.093(4) 0.093(4) 0.109(6) -0.005(4) 0.005(4) -0.027(5)
O3 0.076(4) 0.100(5) 0.107(4) -0.018(4) 0.011(3) -0.010(3)
O4 0.110(5) 0.158(6) 0.067(3) -0.024(4) 0.030(3) 0.001(4)
O5 0.126(5) 0.062(3) 0.118(5) 0.000(3) 0.022(4) 0.021(3)
S1 0.0810(14) 0.0683(12) 0.0631(10) -0.0138(9) 0.0161(10) 0.0075(10)
F1 0.094(4) 0.130(5) 0.122(4) 0.004(3) 0.013(3) -0.041(3)
F2 0.133(5) 0.060(3) 0.171(5) 0.026(3) 0.006(4) -0.005(3)
F3 0.128(4) 0.109(4) 0.066(3) -0.027(3) 0.026(3) -0.029(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
Fe1 C3 2.036(6) . ?
Fe1 C3 2.036(6) 7_465 ?
Fe1 C4 2.039(6) 7_465 ?
Fe1 C4 2.039(6) . ?
Fe1 C5 2.052(6) . ?
Fe1 C5 2.052(6) 7_465 ?
Fe1 C2 2.060(6) . ?
Fe1 C2 2.060(6) 7_465 ?
Fe1 C1 2.074(5) 7_465 ?
Fe1 C1 2.074(5) . ?
Ni1 N2 1.948(5) 7_465 ?
Ni1 N2 1.948(5) . ?
Ni1 N1 1.959(4) . ?
Ni1 N1 1.959(4) 7_465 ?
C1 C2 1.420(9) . ?
C1 C5 1.420(9) . ?
C1 C6 1.510(8) . ?
C2 C3 1.438(11) . ?
C3 C4 1.402(11) . ?
C4 C5 1.409(9) . ?
C6 N1 1.495(7) . ?
C7 C8 1.497(8) . ?
C7 N1 1.499(7) . ?
C8 N2 1.493(7) . ?
C9 N2 1.479(8) . ?
C9 C10 1.518(8) 7_465 ?
C10 C11 1.508(9) . ?
C10 C9 1.518(8) 7_465 ?
C11 N1 1.525(8) . ?
C12 F3 1.286(9) . ?
C12 F1 1.337(9) . ?
C12 F2 1.353(9) . ?
C12 S1 1.801(9) . ?
C13 O2 1.207(14) . ?
C13 C14 1.491(12) 7_465 ?
C13 C14 1.491(12) . ?
O3 S1 1.415(6) . ?
O4 S1 1.411(5) . ?
O5 S1 1.457(6) . ?

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
C3 Fe1 C3 105.0(4) . 7_465 ?
C3 Fe1 C4 111.2(3) . 7_465 ?
C3 Fe1 C4 40.2(3) 7_465 7_465 ?
C3 Fe1 C4 40.2(3) . . ?
C3 Fe1 C4 111.2(3) 7_465 . ?
C4 Fe1 C4 141.5(4) 7_465 . ?
C3 Fe1 C5 67.4(3) . . ?
C3 Fe1 C5 144.7(3) 7_465 . ?
C4 Fe1 C5 174.8(3) 7_465 . ?
C4 Fe1 C5 40.3(2) . . ?
C3 Fe1 C5 144.7(3) . 7_465 ?
C3 Fe1 C5 67.4(3) 7_465 7_465 ?
C4 Fe1 C5 40.3(2) 7_465 7_465 ?
C4 Fe1 C5 174.8(3) . 7_465 ?
C5 Fe1 C5 138.5(3) . 7_465 ?
C3 Fe1 C2 41.1(3) . . ?
C3 Fe1 C2 130.1(3) 7_465 . ?
C4 Fe1 C2 107.8(3) 7_465 . ?
C4 Fe1 C2 68.6(3) . . ?
C5 Fe1 C2 67.7(3) . . ?
C5 Fe1 C2 116.3(3) 7_465 . ?
C3 Fe1 C2 130.1(3) . 7_465 ?
C3 Fe1 C2 41.1(3) 7_465 7_465 ?
C4 Fe1 C2 68.6(3) 7_465 7_465 ?
C4 Fe1 C2 107.8(3) . 7_465 ?
C5 Fe1 C2 116.3(3) . 7_465 ?
C5 Fe1 C2 67.7(3) 7_465 7_465 ?
C2 Fe1 C2 169.7(4) . 7_465 ?
C3 Fe1 C1 170.3(3) . 7_465 ?
C3 Fe1 C1 67.9(3) 7_465 7_465 ?
C4 Fe1 C1 68.2(3) 7_465 7_465 ?
C4 Fe1 C1 134.6(3) . 7_465 ?
C5 Fe1 C1 114.1(2) . 7_465 ?
C5 Fe1 C1 40.3(2) 7_465 7_465 ?
C2 Fe1 C1 148.6(3) . 7_465 ?
C2 Fe1 C1 40.2(2) 7_465 7_465 ?
C3 Fe1 C1 67.9(3) . . ?
C3 Fe1 C1 170.3(3) 7_465 . ?
C4 Fe1 C1 134.6(3) 7_465 . ?
C4 Fe1 C1 68.2(3) . . ?
C5 Fe1 C1 40.3(2) . . ?
C5 Fe1 C1 114.1(2) 7_465 . ?
C2 Fe1 C1 40.2(2) . . ?
C2 Fe1 C1 148.6(3) 7_465 . ?
C1 Fe1 C1 119.8(3) 7_465 . ?
N2 Ni1 N2 162.4(3) 7_465 . ?
N2 Ni1 N1 95.1(2) 7_465 . ?
N2 Ni1 N1 87.0(2) . . ?
N2 Ni1 N1 87.0(2) 7_465 7_465 ?
N2 Ni1 N1 95.1(2) . 7_465 ?
N1 Ni1 N1 166.1(3) . 7_465 ?
C2 C1 C5 107.5(6) . . ?
C2 C1 C6 117.1(6) . . ?
C5 C1 C6 134.4(6) . . ?
C2 C1 Fe1 69.3(3) . . ?
C5 C1 Fe1 69.0(3) . . ?
C6 C1 Fe1 134.6(4) . . ?
C1 C2 C3 107.0(6) . . ?
C1 C2 Fe1 70.5(3) . . ?
C3 C2 Fe1 68.6(4) . . ?
C4 C3 C2 108.8(6) . . ?
C4 C3 Fe1 70.0(4) . . ?
C2 C3 Fe1 70.3(4) . . ?
C3 C4 C5 107.5(7) . . ?
C3 C4 Fe1 69.8(4) . . ?
C5 C4 Fe1 70.4(4) . . ?
C4 C5 C1 109.1(6) . . ?
C4 C5 Fe1 69.3(4) . . ?
C1 C5 Fe1 70.7(3) . . ?
N1 C6 C1 118.6(5) . . ?
C8 C7 N1 108.0(4) . . ?
N2 C8 C7 107.8(5) . . ?
N2 C9 C10 112.8(5) . 7_465 ?
C11 C10 C9 113.6(6) . 7_465 ?
C10 C11 N1 114.7(5) . . ?
F3 C12 F1 108.4(8) . . ?
F3 C12 F2 110.4(8) . . ?
F1 C12 F2 106.6(6) . . ?
F3 C12 S1 112.5(5) . . ?
F1 C12 S1 110.7(6) . . ?
F2 C12 S1 108.1(6) . . ?
O2 C13 C14 120.5(7) . 7_465 ?
O2 C13 C14 120.5(7) . . ?
C14 C13 C14 118.9(14) 7_465 . ?
C6 N1 C7 110.7(4) . . ?
C6 N1 C11 108.2(5) . . ?
C7 N1 C11 105.4(4) . . ?
C6 N1 Ni1 111.3(3) . . ?
C7 N1 Ni1 109.4(3) . . ?
C11 N1 Ni1 111.7(4) . . ?
C9 N2 C8 108.3(5) . . ?
C9 N2 Ni1 116.8(4) . . ?
C8 N2 Ni1 105.6(4) . . ?
O4 S1 O3 117.7(4) . . ?
O4 S1 O5 112.2(4) . . ?
O3 S1 O5 112.9(4) . . ?
O4 S1 C12 105.9(4) . . ?
O3 S1 C12 104.0(4) . . ?
O5 S1 C12 102.2(4) . . ?

_diffrn_measured_fraction_theta_max    0.995
_diffrn_reflns_theta_full              25.97
_diffrn_measured_fraction_theta_full   0.995
_refine_diff_density_max    0.419
_refine_diff_density_min   -0.370
_refine_diff_density_rms    0.069