# Electronic Supplementary Material (ESI) for Journal of Materials Chemistry C
# This journal is © The Royal Society of Chemistry 2012


#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication 
#  deposited with the CCDC, and may include chemical, crystal,   
#  experimental, refinement, atomic coordinates, 
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted. 
# 
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material 
#  of the CCDC or of third parties, and may not be copied or further 
#  disseminated in any form, whether machine-readable or not,  
#  except for the purpose of generating routine backup copies 
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and 
#  data retrieval see:
#                         www.ccdc.cam.ac.uk 
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively. 
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data_1
_database_code_depnum_ccdc_archive 'CCDC 900650'


# Definition of non standard CIF items (Reliability indices used in FULLPROF)

_chemical_name_systematic        
; 'Tricalcium Phosphate:Mn'
;
_chemical_name_common            'Tricalcium Phosphate:Mn'
_chemical_formula_moiety         'Ca9.615 Mn0.885 P7 O28'
_chemical_formula_structural     Ca9.615Mn0.885(PO4)7
_chemical_formula_analytical     ?
_chemical_formula_iupac          ?
_chemical_formula_sum            'Ca28.85 Mn2.66 O84 P21'
_chemical_formula_weight         3296.34
_chemical_melting_point          ?
_chemical_compound_source        ? # for minerals and
# natural products

loop_
_atom_type_symbol
_atom_type_scat_length_neutron
_atom_type_scat_source
CA 0.47000 V.F._Sears_Neutron_News_3_26_(1992)
MN -0.37300 V.F._Sears_Neutron_News_3_26_(1992)
P 0.51300 V.F._Sears_Neutron_News_3_26_(1992)
O 0.58030 V.F._Sears_Neutron_News_3_26_(1992)

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

# 6. POWDER SPECIMEN AND CRYSTAL DATA

_symmetry_cell_setting           Hexagonal
_symmetry_space_group_name_H-M   'R 3 C'
_symmetry_space_group_name_Hall  'R 3 -2"c'

loop_
_symmetry_equiv_pos_as_xyz #<--must include 'x,y,z'
x,y,z
-y,x-y,z
-x+y,-x,z
-y,-x,z+1/2
-x+y,y,z+1/2
x,x-y,z+1/2
x+2/3,y+1/3,z+1/3
-y+2/3,x-y+1/3,z+1/3
-x+y+2/3,-x+1/3,z+1/3
-y+2/3,-x+1/3,z+5/6
-x+y+2/3,y+1/3,z+5/6
x+2/3,x-y+1/3,z+5/6
x+1/3,y+2/3,z+2/3
-y+1/3,x-y+2/3,z+2/3
-x+y+1/3,-x+2/3,z+2/3
-y+1/3,-x+2/3,z+1/6
-x+y+1/3,y+2/3,z+1/6
x+1/3,x-y+2/3,z+1/6

_cell_length_a                   10.3883(1)
_cell_length_b                   10.3883(1)
_cell_length_c                   37.2221(6)
_cell_angle_alpha                90.00000
_cell_angle_beta                 90.00000
_cell_angle_gamma                120.00000
_cell_volume                     3478.7(1)
_cell_formula_units_Z            2
_cell_measurement_temperature    293
_cell_special_details            
; ?
;
# The next three fields give the specimen dimensions in mm. The equatorial
# plane contains the incident and diffracted beam.

_pd_spec_size_axial              ? # perpendicular to
# equatorial plane
_pd_spec_size_equat              ? # parallel to
# scattering vector
# in transmission
_pd_spec_size_thick              ? # parallel to
# scattering vector
# in reflection

# The next five fields are character fields that describe the specimen.

_pd_spec_mounting                
# This field should be
# used to give details of the
# container.
; ?
;
_pd_spec_mount_mode              transmission
_pd_spec_shape                   cylinder
_pd_char_particle_morphology     powder
_pd_char_colour                  'pale grey'

_exptl_crystal_density_diffrn    3.147


# The following three fields describe the preparation of the specimen.
# The cooling rate is in K/min. The pressure at which the sample was
# prepared is in kPa. The temperature of preparation is in K.

_pd_prep_cool_rate               ?
_pd_prep_pressure                ?
_pd_prep_temperature             293

# The next four fields are normally only needed for transmission experiments.

_exptl_absorpt_coefficient_mu    ?
_exptl_absorpt_correction_type   ?
_exptl_absorpt_process_details   ?
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?

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

# 7. EXPERIMENTAL DATA

_exptl_special_details           
; ?
;

# The following item is used to identify the equipment used to record
# the powder pattern when the diffractogram was measured at a laboratory
# other than the authors' home institution, e.g. when neutron or synchrotron
# radiation is used.

_pd_instr_location               
; 'ILL Grenoble'
;
_pd_calibration_special_details  
# description of the method used
# to calibrate the instrument
; ?
;

_diffrn_ambient_temperature      293
_diffrn_source                   'nuclear reactor'
_diffrn_radiation_type           'Constant Wavelength Neutron Diffraction'
_diffrn_radiation_wavelength     1.59438
_diffrn_source_type              ? # Put here the diffractometer and site

_diffrn_radiation_monochromator  ?
_diffrn_measurement_device_type  ?
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ? # Not in version 2.0.1
_diffrn_detector                 ?
_diffrn_detector_type            ? # make or model of detector
_pd_meas_scan_method             ? # options are 'step', 'cont',
# 'tof', 'fixed' or
# 'disp' (= dispersive)

_diffrn_reflns_limit_h_min       0
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_limit_l_max       45
_diffrn_reflns_theta_min         0.00
_diffrn_reflns_theta_max         79.975
_reflns_number_total             766
_reflns_number_observed          766
_pd_meas_special_details         
; ?
;

# The following four items give details of the measured (not processed)
# powder pattern. Angles are in degrees.

_pd_meas_number_of_points        3200
_pd_meas_2theta_range_min        0.00000
_pd_meas_2theta_range_max        159.95000
_pd_meas_2theta_range_inc        0.050016

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

# 8. REFINEMENT DATA

_refine_special_details          
; ?
;

# Use the next field to give any special details about the fitting of the
# powder pattern.

_pd_proc_ls_special_details      
; ?
;

# The next three items are given as text.

_pd_proc_ls_profile_function     ?
_pd_proc_ls_background_function  ?
_pd_proc_ls_pref_orient_corr     
; ?
;

# The following profile R-factors are NOT CORRECTED for background
# The sum is extended to all non-excluded points.
# These are the current CIF standard

_pd_proc_ls_prof_R_factor        2.8432
_pd_proc_ls_prof_wR_factor       3.5846
_pd_proc_ls_prof_wR_expected     2.0459

# The following profile R-factors are CORRECTED for background
# The sum is extended to all non-excluded points.
# These items are not in the current CIF standard, but are defined above

_pd_proc_ls_prof_cR_factor       7.3607
_pd_proc_ls_prof_cwR_factor      8.0720
_pd_proc_ls_prof_cwR_expected    4.6069

# The following items are not in the CIF standard, but are defined above

_pd_proc_ls_prof_chi2            3.0700
_pd_proc_ls_prof_echi2           3.0700

# Items related to LS refinement

_refine_ls_R_I_factor            2.9806
_refine_ls_number_reflns         782
_refine_ls_number_parameters     75
_refine_ls_number_restraints     0
_refine_ls_goodness_of_fit_all   3.11


# The following four items apply to angular dispersive measurements.
# 2theta minimum, maximum and increment (in degrees) are for the
# intensities used in the refinement.

_pd_proc_2theta_range_min        0.0884
_pd_proc_2theta_range_max        160.0384
_pd_proc_2theta_range_inc        0.050016
_pd_proc_wavelength              1.594384

_pd_block_diffractogram_id       ? # The id used for the block containing
# the powder pattern profile (section 11)

# Give appropriate details in the next two text fields.

_pd_proc_info_excluded_regions   ?
_pd_proc_info_data_reduction     ?

# The following items are used to identify the programs used.

_computing_data_collection       ?
_computing_structure_solution    ?
_computing_structure_refinement  FULLPROF
_computing_molecular_graphics    ?
_computing_publication_material  ?

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

# 9. ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS

loop_
_atom_site_label
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_occupancy
_atom_site_adp_type # Not in version 2.0.1
_atom_site_type_symbol
Ca1 -0.2727(5) -0.1344(6) 0.1678(2) 0.0057(10) 1.00000 Uiso CA
Ca2 -0.3834(5) -0.2101(5) -0.0332(2) 0.0016(10) 1.00000 Uiso CA
Ca3 -0.2706(5) -0.1245(6) 0.0615(2) 0.0188(11) 1.00000 Uiso CA
Ca4 0.00000 0.00000 -0.0772(7) 0.039(6) 0.50000 Uiso CA
Ca5 0.00000 0.00000 -0.2643(5) 0.010(3) 0.115(10) Uiso CA
Mn5 0.00000 0.00000 -0.2643(5) 0.010(3) 0.885(10) Uiso MN
P1 0.00000 0.00000 0.00000 0.0117(16) 1.00000 Uiso P
P2 -0.3117(6) -0.1751(5) -0.1306(2) 0.0088(10) 1.00000 Uiso P
P3 -0.3449(6) -0.1924(6) -0.2329(2) 0.0113(11) 1.00000 Uiso P
O1 -0.2629(5) -0.1783(5) -0.0917(2) 0.0223(11) 1.00000 Uiso O
O2 -0.2733(5) -0.2766(5) -0.1522(2) 0.0094(9) 1.00000 Uiso O
O3 -0.2365(6) -0.0155(6) -0.1440(2) 0.0185(12) 1.00000 Uiso O
O4 -0.4845(5) -0.2427(5) -0.1342(2) 0.0126(9) 1.00000 Uiso O
O5 -0.4194(6) -0.1134(6) -0.2140(2) 0.0139(11) 1.00000 Uiso O
O6 -0.3976(5) -0.3541(5) -0.2209(2) 0.0104(10) 1.00000 Uiso O
O7 -0.1788(4) -0.1006(5) -0.2250(2) 0.0053(8) 1.00000 Uiso O
O8 -0.3761(4) -0.1970(5) -0.2735(2) 0.0087(8) 1.00000 Uiso O
O9 0.1367(5) -0.0070(7) -0.0111(2) 0.0183(9) 1.00000 Uiso O
O10 0.00000 0.00000 0.0427(3) 0.0121(17) 1.00000 Uiso O

# Note: if the displacement parameters were refined anisotropically
# the U matrices should be given as for single-crystal studies.

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

# 10. DISTANCES AND ANGLES / MOLECULAR GEOMETRY

_geom_special_details            ?

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
Ca1 P2 3.061(10) 9_445 ?
Ca1 O2 2.478(8) 9_445 ?
Ca1 O3 2.938(10) 8_455 ?
Ca1 O4 2.451(7) 8_455 ?
Ca1 O4 2.466(9) 9_445 ?
Ca1 O5 2.336(10) 8_455 ?
Ca1 O6 2.447(10) 9_445 ?
Ca1 O8 2.376(10) 6_555 ?
Ca1 O9 2.479(8) 18_445 ?
Ca2 P3 3.143(10) 16_445 ?
Ca2 P3 3.107(8) 17_445 ?
Ca2 O1 2.450(10) . ?
Ca2 O2 2.386(10) 16_445 ?
Ca2 O3 2.426(10) 17_445 ?
Ca2 O5 2.637(9) 17_445 ?
Ca2 O6 2.680(8) 16_445 ?
Ca2 O7 2.430(9) 16_445 ?
Ca2 O7 2.422(6) 17_445 ?
Ca2 O9 2.358(8) 3_555 ?
Ca3 P2 3.124(10) 16_445 ?
Ca3 P3 3.115(9) 8_455 ?
Ca3 P3 3.013(10) 9_445 ?
Ca3 O1 2.637(9) 16_445 ?
Ca3 O2 2.426(10) 16_445 ?
Ca3 O3 2.567(8) 17_445 ?
Ca3 O5 2.563(10) 8_455 ?
Ca3 O6 2.364(10) 9_445 ?
Ca3 O8 2.509(7) 8_455 ?
Ca3 O8 2.555(9) 9_445 ?
Ca3 O9 3.037(10) 3_555 ?
Ca3 O10 2.536(6) . ?
Ca4 P1 2.87(3) . ?
Ca4 O1 2.474(7) . ?
Ca4 O1 2.474(9) 2_555 ?
Ca4 O1 2.474(8) 3_555 ?
Ca4 O9 2.86(2) . ?
Ca4 O9 2.86(2) 2_555 ?
Ca4 O9 2.86(2) 3_555 ?
Ca5 O4 2.130(13) 10_444 ?
Ca5 O4 2.130(14) 11_454 ?
Ca5 O4 2.130(13) 12_554 ?
Ca5 O7 2.177(14) . ?
Ca5 O7 2.177(14) 2_555 ?
Ca5 O7 2.177(14) 3_555 ?
Mn5 O4 2.130(13) 10_444 ?
Mn5 O4 2.130(14) 11_454 ?
Mn5 O4 2.130(13) 12_554 ?
Mn5 O7 2.177(14) . ?
Mn5 O7 2.177(14) 2_555 ?
Mn5 O7 2.177(14) 3_555 ?
P1 Ca4 2.87(3) . ?
P1 O9 1.515(7) . ?
P1 O9 1.515(8) 2_555 ?
P1 O9 1.515(5) 3_555 ?
P1 O10 1.589(11) . ?
P2 Ca1 3.061(7) 14_444 ?
P2 Ca3 3.124(10) 10_444 ?
P2 O1 1.540(10) . ?
P2 O2 1.529(10) . ?
P2 O3 1.521(8) . ?
P2 O4 1.573(8) . ?
P3 Ca2 3.143(10) 10_444 ?
P3 Ca2 3.107(7) 11_454 ?
P3 Ca3 3.013(8) 14_444 ?
P3 Ca3 3.115(10) 15_444 ?
P3 O5 1.550(11) . ?
P3 O6 1.550(8) . ?
P3 O7 1.526(6) . ?
P3 O8 1.541(10) . ?
O1 Ca2 2.450(10) . ?
O1 Ca3 2.637(9) 10_444 ?
O1 Ca4 2.474(7) . ?
O1 P2 1.540(10) . ?
O1 O2 2.453(10) . ?
O1 O3 2.502(10) . ?
O1 O4 2.590(9) . ?
O1 O5 2.950(9) 17_445 ?
O1 O6 3.140(9) 16_445 ?
O1 O9 3.191(10) 3_555 ?
O2 Ca1 2.478(6) 14_444 ?
O2 Ca2 2.386(10) 10_444 ?
O2 Ca3 2.426(10) 10_444 ?
O2 P2 1.529(10) . ?
O2 O1 2.453(10) . ?
O2 O3 2.561(9) . ?
O2 O3 2.774(8) 2_555 ?
O2 O4 2.482(9) . ?
O2 O6 2.796(10) . ?
O2 O7 3.139(10) . ?
O2 O8 2.981(7) 17_445 ?
O2 O9 3.183(10) 12_444 ?
O3 Ca1 2.938(9) 15_444 ?
O3 Ca2 2.426(10) 11_454 ?
O3 Ca3 2.567(9) 11_454 ?
O3 P2 1.521(8) . ?
O3 O1 2.502(10) . ?
O3 O2 2.561(9) . ?
O3 O2 2.774(6) 3_555 ?
O3 O4 2.502(6) . ?
O3 O5 3.082(10) . ?
O3 O8 3.101(9) 16_445 ?
O3 O9 3.060(11) 10_454 ?
O4 Ca1 2.466(9) 14_444 ?
O4 Ca1 2.451(10) 15_444 ?
O4 Ca5 2.130(13) 16_445 ?
O4 Mn5 2.130(13) 16_445 ?
O4 P2 1.573(8) . ?
O4 O1 2.590(9) . ?
O4 O2 2.482(9) . ?
O4 O3 2.502(6) . ?
O4 O4 2.839(8) 2_455 ?
O4 O4 2.839(5) 3_445 ?
O4 O5 3.190(10) . ?
O4 O8 3.066(8) 16_445 ?
O4 O8 3.142(8) 17_445 ?
O5 Ca1 2.336(10) 15_444 ?
O5 Ca2 2.637(6) 11_454 ?
O5 Ca3 2.563(10) 15_444 ?
O5 P3 1.550(11) . ?
O5 O1 2.950(8) 11_454 ?
O5 O3 3.082(10) . ?
O5 O4 3.190(10) . ?
O5 O6 2.634(9) . ?
O5 O6 2.800(10) 2_455 ?
O5 O7 2.470(8) . ?
O5 O8 2.500(10) . ?
O5 O9 3.164(10) 10_454 ?
O6 Ca1 2.447(9) 14_444 ?
O6 Ca2 2.680(8) 10_444 ?
O6 Ca3 2.364(9) 14_444 ?
O6 P3 1.550(8) . ?
O6 O1 3.140(9) 10_444 ?
O6 O2 2.796(10) . ?
O6 O5 2.634(9) . ?
O6 O5 2.800(6) 3_445 ?
O6 O7 2.478(5) . ?
O6 O8 2.486(10) . ?
O7 Ca2 2.430(9) 10_444 ?
O7 Ca2 2.422(8) 11_454 ?
O7 Ca5 2.177(14) . ?
O7 Mn5 2.177(14) . ?
O7 P3 1.526(6) . ?
O7 O2 3.139(10) . ?
O7 O5 2.470(8) . ?
O7 O6 2.478(5) . ?
O7 O7 2.793(7) 2_555 ?
O7 O7 2.793(5) 3_555 ?
O7 O8 2.532(8) . ?
O8 Ca1 2.376(10) 6_554 ?
O8 Ca3 2.555(7) 14_444 ?
O8 Ca3 2.509(9) 15_444 ?
O8 P3 1.541(10) . ?
O8 O2 2.981(9) 11_454 ?
O8 O3 3.101(10) 10_444 ?
O8 O4 3.066(8) 10_444 ?
O8 O4 3.142(6) 11_454 ?
O8 O5 2.500(10) . ?
O8 O6 2.486(10) . ?
O8 O7 2.532(8) . ?
O8 O9 3.060(9) 13_444 ?
O8 O10 2.692(5) 13_444 ?
O9 Ca1 2.479(6) 12_554 ?
O9 Ca2 2.358(10) 2_555 ?
O9 Ca3 3.037(10) 2_555 ?
O9 Ca4 2.86(2) . ?
O9 P1 1.515(7) . ?
O9 O1 3.191(10) 2_555 ?
O9 O2 3.183(9) 18_545 ?
O9 O3 3.060(10) 16_545 ?
O9 O5 3.164(9) 16_545 ?
O9 O8 3.060(9) 7_555 ?
O9 O9 2.525(11) 2_555 ?
O9 O9 2.525(7) 3_555 ?
O9 O10 2.477(12) . ?
O10 Ca3 2.536(6) . ?
O10 Ca3 2.536(8) 2_555 ?
O10 Ca3 2.536(6) 3_555 ?
O10 P1 1.589(11) . ?
O10 O8 2.692(5) 7_555 ?
O10 O8 2.692(6) 8_455 ?
O10 O8 2.692(5) 9_445 ?
O10 O9 2.477(12) . ?
O10 O9 2.477(12) 2_555 ?
O10 O9 2.477(11) 3_555 ?

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
O9 P1 O9 112.9(8) . 2_555 ?
O9 P1 O9 112.9(5) . 3_555 ?
O9 P1 O9 112.9(6) 2_555 3_555 ?
O9 P1 O10 105.8(3) . . ?
O9 P1 O10 105.8(3) . 5_555 ?
O9 P1 O10 105.8(3) . 5_555 ?
O1 P2 O2 106.1(8) . . ?
O1 P2 O3 109.7(8) . . ?
O1 P2 O4 112.6(7) . . ?
O2 P2 O3 114.2(7) . . ?
O2 P2 O4 106.3(7) . . ?
O3 P2 O4 108.0(5) . . ?
O5 P3 O6 116.3(8) . . ?
O5 P3 O7 106.8(7) . . ?
O5 P3 O8 108.0(8) . . ?
O6 P3 O7 107.3(5) . . ?
O6 P3 O8 107.1(8) . . ?
O7 P3 O8 111.3(7) . . ?


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

#=============================================================================
# Additional structures (last six sections and associated data_? identifiers)
# may be added at this point.
#=============================================================================

# The following lines are used to test the character set of files sent by
# network email or other means. They are not part of the CIF data set.
# abcdefghijklmnopqrstuvwxyzABCDEFGHIJKLMNOPQRSTUVWXYZ0123456789
# !@#$%^&*()_+{}:"~<>?|\-=[];'`,./