# Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A.
# This journal is © The Royal Society of Chemistry 2018


data_Hf-Ni-L_He-RT-d500

_publ_requested_journal          'Journal of the American Chemical Society'
_publ_contact_author_name        'Amanda J. Morris'
_publ_contact_author_address     
;Virginia Tech - College of Science
Dept. of Chemistry
3109 Hahn Hall South
Blacksburg, VA 24061
;
_publ_contact_author_email       ajmorris@vt.edu
_publ_contact_author_phone       1(540)2315585
loop_
_publ_author_name
_publ_author_address
'Morris, Amanda'
;Virginia Tech - College of Science
Dept. of Chemistry
3109 Hahn Hall South
Blacksburg, VA 24061
;
_chemical_name_systematic        
'6,13-dicarboxy-1,4,8,11-tetrazacyclotetradecan nickel Hafnium oxide'
_chemical_name_common            'Hafnium nickel cyclam carboxylate'
_chemical_formula_moiety         
'(Hf 4+)6, (O 2-)8, (Ni N4 C12 H22 O4 Cl0.82 2-)4'
_chemical_formula_sum            'C24 H44 Cl1.64 Hf3 N8 Ni2 O16'
_chemical_formula_weight         1411.67
_cell_formula_units_Z            4
_chemical_compound_source        synthetic
_diffrn_ambient_temperature      298
_diffrn_ambient_pressure         101
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Synchrotron mono-beam'
_diffrn_radiation_wavelength     0.45260
_diffrn_source                   synchrotron
_diffrn_source_type              'APS Beamline 17-BM'
_diffrn_measurement_device_type  'Debye-scherrer geometry diffractometer with area detector at Beamline 17-BM'
_chemical_name_mineral           none
_cell_measurement_temperature    298
_cell_length_a 				16.5939(12)
_cell_length_b 				16.5939(12)
_cell_length_c 				18.661(2)
_cell_angle_alpha 			90
_cell_angle_beta 			90
_cell_angle_gamma 			90
_cell_volume 				5138.5(10)
_space_group_crystal_system      tetragonal
_space_group_IT_number           87
_space_group_name_H-M_alt        'I 4/m'
_space_group_name_Hall           '-I 4'
_chemical_absolute_configuration .
_pd_proc_ls_prof_R_factor              0.0537
_pd_proc_ls_prof_wR_factor             0.0746
_pd_proc_ls_prof_wR_expected           0.0109
_refine_ls_R_Fsqd_factor               0.0523
_reflns_number_total                   442
_reflns_limit_h_min                    0
_reflns_limit_h_max                    12
_reflns_limit_k_min                    0
_reflns_limit_k_max                    12
_reflns_limit_l_min                    0
_reflns_limit_l_max                    14
_reflns_d_resolution_high              1.483
_reflns_d_resolution_low               12.400
_refine_ls_goodness_of_fit_all         7.83

loop_
	_symmetry_equiv_pos_as_xyz
	 'x, y, z '
	 '-x, -y, z '
	 '-y, x, -z '
	 '-y, x, z '
	 'y, -x, -z '
	 'y, -x, z '
	 'x, y, -z '
	 '-x, -y, -z '
	 'x+1/2, y+1/2, z+1/2 '
	 '-x+1/2, -y+1/2, z+1/2 '
	 '-y+1/2, x+1/2, -z+1/2 '
	 '-y+1/2, x+1/2, z+1/2 '
	 'y+1/2, -x+1/2, -z+1/2 '
	 'y+1/2, -x+1/2, z+1/2 '
	 'x+1/2, y+1/2, -z+1/2 '
	 '-x+1/2, -y+1/2, -z+1/2 '
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_symmetry_multiplicity
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_occupancy
_atom_site_B_iso_or_equiv
Hf1 Hf   8 -0.1450(6) 0.0363(6) 0 1 1.36(11)
Hf2 Hf   4 0 0 0.1223(9) 1 1.36(11)
O3 O  16 -0.0483(17) 0.081(3) 0.070(3) 1 2.5(10)
O5 O   8 -0.221(6) 0.156(7) 0 1 2.5(10)
O4 O   8 -0.263(6) -0.041(7) 0 1 2.5(10)
Ni1 Ni   8 0.25 0.25 0.25 1 8.0(12)
Cl1 Cl  16 0.114(6) 0.194(8) 0.280(5) 0.41(3) 8
O1 O  16 0.201(12) -0.045(2) 0.1004(19) 1 2.5(10)
O2 O  16 0.120(11) 0.004(6) 0.184(2) 1 2.5(10)
N1 N  16 0.281(5) 0.1455(14) 0.2875(9) 1 8.0(18)
H1 H  16 0.339(5) 0.139(4) 0.2766(16) 1 12(3)
N2 N  16 0.2395(13) 0.2103(8) 0.1529(3) 1 8.0(18)
H2 H  16 0.2948(14) 0.209(3) 0.1331(7) 1 12(3)
C1 C  16 0.274(6) 0.1477(13) 0.3670(8) 1 8.0(18)
H1A H  16 0.307(9) 0.104(3) 0.3886(14) 1 12(3)
H1B H  16 0.218(7) 0.140(2) 0.3820(7) 1 12(3)
C2 C  16 0.240(8) 0.0717(4) 0.2601(12) 1 8.0(18)
H2A H  16 0.264(11) 0.0236(7) 0.2839(16) 1 12(3)
H2B H  16 0.182(8) 0.074(3) 0.2717(12) 1 12(3)
C3 C  16 0.251(8) 0.0641(6) 0.1791(12) 1 8.0(18)
H3 H  16 0.309(7) 0.069(3) 0.1674(16) 1 12(3)
C4 C  16 0.205(4) 0.130(2) 0.1390(8) 1 8.0(18)
H4A H  16 0.206(4) 0.119(2) 0.0869(9) 1 12(3)
H4B H  16 0.148(5) 0.129(5) 0.1545(14) 1 12(3)
C5 C  16 0.195(3) 0.271(3) 0.1094(8) 1 8.0(18)
H5A H  16 0.206(4) 0.263(2) 0.0577(6) 1 12(3)
H5B H  16 0.136(3) 0.267(5) 0.1179(16) 1 12(3)
C6 C  16 0.189(10) 0.003(3) 0.1506(16) 1 8.0(18)

# MOLECULAR GEOMETRY

loop_
	_geom_bond_atom_site_label_1
	_geom_bond_atom_site_label_2
	_geom_bond_distance
	_geom_bond_site_symmetry_1
	_geom_bond_site_symmetry_2
	Hf1       O1        2.10(10) 1_555   2_555
	Hf1       O1        2.10(10) 1_555   8_555
	Hf1       O3        2.19668 1_555   7_555
	Hf1       O3        2.19668 1_555   1_555
	Hf1       O3        2.19668 1_555   3_555
	Hf1       O3        2.19668 1_555   4_555
	Hf1       O5        2.35000 1_555   1_555
	Hf1       O4        2.35000 1_555   1_555
	Hf2       O3        1.83865 1_555   1_555
	Hf2       O3        1.83865 1_555   6_555
	Hf2       O3        1.83865 1_555   2_555
	Hf2       O3        1.83865 1_555   4_555
	Hf2       O2        2.30(16) 1_555   2_555
	Hf2       O2        2.30(16) 1_555   4_555
	Hf2       O2        2.30(16) 1_555   1_555
	Hf2       O2        2.30(16) 1_555   6_555
	O3        Hf2       1.83865 1_555   1_555
	O3        Hf1       2.19668 1_555   1_555
	O3        Hf1       2.19668 1_555   5_555
	Ni1       N2        1.93600 1_555   1_555
	Ni1       N2        1.93600 1_555  16_555
	Ni1       N1        1.93900 1_555   1_555
	Ni1       N1        1.93900 1_555  16_555
	Ni1       Cl1       2.49694 1_555  16_555
	Ni1       Cl1       2.49694 1_555   1_555
	Cl1       Ni1       2.49694 1_555   1_555
	O1        C6        1.23930 1_555   1_555
	O1        Hf1       2.10(10) 1_555   2_555
	O2        C6        1.30000 1_555   1_555
	O2        Hf2       2.30(16) 1_555   1_555
	N1        H1        0.99000 1_555   1_555
	N1        C2        1.48800 1_555   1_555
	N1        C1        1.48800 1_555   1_555
	N1        Ni1       1.93900 1_555   1_555
	H1        N1        0.99000 1_555   1_555
	N2        H2        0.99000 1_555   1_555
	N2        C4        1.47900 1_555   1_555
	N2        C5        1.49000 1_555   1_555
	N2        Ni1       1.93600 1_555   1_555
	H2        N2        0.99000 1_555   1_555
	C1        H1A       0.99000 1_555   1_555
	C1        H1B       0.99000 1_555   1_555
	C1        N1        1.48800 1_555   1_555
	C1        C5        1.50159 1_555  16_555
	H1A       C1        0.99000 1_555   1_555
	H1B       C1        0.99000 1_555   1_555
	C2        H2A       0.99000 1_555   1_555
	C2        H2B       0.99000 1_555   1_555
	C2        N1        1.48800 1_555   1_555
	C2        C3        1.52700 1_555   1_555
	H2A       C2        0.99000 1_555   1_555
	H2B       C2        0.99000 1_555   1_555
	C3        H3        0.99000 1_555   1_555
	C3        C2        1.52700 1_555   1_555
	C3        C4        1.53045 1_555   1_555
	C3        C6        1.55000 1_555   1_555
	H3        C3        0.99000 1_555   1_555
	C4        H4B       0.99000 1_555   1_555
	C4        H4A       0.99000 1_555   1_555
	C4        N2        1.47900 1_555   1_555
	C4        C3        1.53045 1_555   1_555
	H4A       C4        0.99000 1_555   1_555
	H4B       C4        0.99000 1_555   1_555
	C5        H5B       0.99000 1_555   1_555
	C5        H5A       0.99000 1_555   1_555
	C5        N2        1.49000 1_555   1_555
	C5        C1        1.50159 1_555  16_555
	H5A       C5        0.99000 1_555   1_555
	H5B       C5        0.99000 1_555   1_555
	C6        O1        1.23930 1_555   1_555
	C6        O2        1.30000 1_555   1_555
	C6        C3        1.55000 1_555   1_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_2
		_geom_angle_site_symmetry_3
	O1        Hf1       O1         127(10)  8_555 1_555   2_555
	O3        Hf1       O1         77(4)  7_555 1_555   8_555
	O3        Hf1       O1         147(3)  7_555 1_555   2_555
	O3        Hf1       O3         73.124    1_555 1_555   7_555
	O3        Hf1       O1         147(3)  1_555 1_555   8_555
	O3        Hf1       O1         77(4)  1_555 1_555   2_555
	O3        Hf1       O3         102.339   3_555 1_555   1_555
	O3        Hf1       O3         60.264    3_555 1_555   7_555
	O3        Hf1       O1         74(4)  3_555 1_555   8_555
	O3        Hf1       O1         142.2(19)  3_555 1_555   2_555
	O3        Hf1       O3         73.124    4_555 1_555   3_555
	O3        Hf1       O3         60.264    4_555 1_555   1_555
	O3        Hf1       O3         102.339   4_555 1_555   7_555
	O3        Hf1       O1         142.2(19)  4_555 1_555   8_555
	O3        Hf1       O1         74(4)  4_555 1_555   2_555
	O5        Hf1       O3         143.172   1_555 1_555   4_555
	O5        Hf1       O3         143.172   1_555 1_555   3_555
	O5        Hf1       O3         96.319    1_555 1_555   1_555
	O5        Hf1       O3         96.319    1_555 1_555   7_555
	O5        Hf1       O1         73(3)  1_555 1_555   8_555
	O5        Hf1       O1         73(3)  1_555 1_555   2_555
	O4        Hf1       O5         90.828    1_555 1_555   1_555
	O4        Hf1       O3         93.160    1_555 1_555   4_555
	O4        Hf1       O3         93.160    1_555 1_555   3_555
	O4        Hf1       O3         142.557   1_555 1_555   1_555
	O4        Hf1       O3         142.557   1_555 1_555   7_555
	O4        Hf1       O1         70(3)  1_555 1_555   8_555
	O4        Hf1       O1         70(3)  1_555 1_555   2_555
	O3        Hf2       O3         73.702    6_555 1_555   1_555
	O3        Hf2       O3         73.702    2_555 1_555   6_555
	O3        Hf2       O3         116.024   2_555 1_555   1_555
	O3        Hf2       O3         73.702    4_555 1_555   2_555
	O3        Hf2       O3         116.024   4_555 1_555   6_555
	O3        Hf2       O3         73.702    4_555 1_555   1_555
	O2        Hf2       O3         67.9(9)  2_555 1_555   4_555
	O2        Hf2       O3         128.4(18)  2_555 1_555   2_555
	O2        Hf2       O3         155(3)  2_555 1_555   6_555
	O2        Hf2       O3         85(3)  2_555 1_555   1_555
	O2        Hf2       O2         75.5(18)  4_555 1_555   2_555
	O2        Hf2       O3         128.4(18)  4_555 1_555   4_555
	O2        Hf2       O3         155(3)  4_555 1_555   2_555
	O2        Hf2       O3         85(3)  4_555 1_555   6_555
	O2        Hf2       O3         67.9(9)  4_555 1_555   1_555
	O2        Hf2       O2         75.5(18)  1_555 1_555   4_555
	O2        Hf2       O2         120(4)  1_555 1_555   2_555
	O2        Hf2       O3         155(3)  1_555 1_555   4_555
	O2        Hf2       O3         85(3)  1_555 1_555   2_555
	O2        Hf2       O3         67.9(9)  1_555 1_555   6_555
	O2        Hf2       O3         128.4(18)  1_555 1_555   1_555
	O2        Hf2       O2         75.5(18)  6_555 1_555   1_555
	O2        Hf2       O2         120(4)  6_555 1_555   4_555
	O2        Hf2       O2         75.5(18)  6_555 1_555   2_555
	O2        Hf2       O3         85(3)  6_555 1_555   4_555
	O2        Hf2       O3         67.9(9)  6_555 1_555   2_555
	O2        Hf2       O3         128.4(18)  6_555 1_555   6_555
	O2        Hf2       O3         155(3)  6_555 1_555   1_555
	Hf1       O3        Hf2        112.989   1_555 1_555   1_555
	Hf1       O3        Hf1        105.942   5_555 1_555   1_555
	Hf1       O3        Hf2        112.989   5_555 1_555   1_555
	N2        Ni1       N2         180.000  16_555 1_555   1_555
	N1        Ni1       N2         86.690    1_555 1_555  16_555
	N1        Ni1       N2         93.310    1_555 1_555   1_555
	N1        Ni1       N1         180.000  16_555 1_555   1_555
	N1        Ni1       N2         93.310   16_555 1_555  16_555
	N1        Ni1       N2         86.690   16_555 1_555   1_555
	Cl1       Ni1       N1         80.000   16_555 1_555  16_555
	Cl1       Ni1       N1         100.000  16_555 1_555   1_555
	Cl1       Ni1       N2         90.229   16_555 1_555  16_555
	Cl1       Ni1       N2         89.771   16_555 1_555   1_555
	Cl1       Ni1       Cl1        180.000   1_555 1_555  16_555
	Cl1       Ni1       N1         100.000   1_555 1_555  16_555
	Cl1       Ni1       N1         80.000    1_555 1_555   1_555
	Cl1       Ni1       N2         89.771    1_555 1_555  16_555
	Cl1       Ni1       N2         90.229    1_555 1_555   1_555
	Hf1       O1        C6         124(4)  2_555 1_555   1_555
	Hf2       O2        C6         121.1(18)  1_555 1_555   1_555
	C2        N1        H1         106.210   1_555 1_555   1_555
	C1        N1        C2         109.300   1_555 1_555   1_555
	C1        N1        H1         106.232   1_555 1_555   1_555
	Ni1       N1        C1         108.553   1_555 1_555   1_555
	Ni1       N1        C2         119.528   1_555 1_555   1_555
	Ni1       N1        H1         106.210   1_555 1_555   1_555
	C4        N2        H2         105.850   1_555 1_555   1_555
	C5        N2        C4         109.010   1_555 1_555   1_555
	C5        N2        H2         105.850   1_555 1_555   1_555
	Ni1       N2        C5         108.867   1_555 1_555   1_555
	Ni1       N2        C4         120.406   1_555 1_555   1_555
	Ni1       N2        H2         105.878   1_555 1_555   1_555
	H1B       C1        H1A        108.632   1_555 1_555   1_555
	N1        C1        H1B        110.400   1_555 1_555   1_555
	N1        C1        H1A        110.320   1_555 1_555   1_555
	C5        C1        N1         106.856  16_555 1_555   1_555
	C5        C1        H1B        110.331  16_555 1_555   1_555
	C5        C1        H1A        110.301  16_555 1_555   1_555
	H2B       C2        H2A        108.060   1_555 1_555   1_555
	N1        C2        H2B        109.430   1_555 1_555   1_555
	N1        C2        H2A        109.480   1_555 1_555   1_555
	C3        C2        N1         110.779   1_555 1_555   1_555
	C3        C2        H2B        109.554   1_555 1_555   1_555
	C3        C2        H2A        109.490   1_555 1_555   1_555
	C2        C3        H3         109.010   1_555 1_555   1_555
	C4        C3        C2         111.468   1_555 1_555   1_555
	C4        C3        H3         108.948   1_555 1_555   1_555
	C6        C3        C4         87.880    1_555 1_555   1_555
	C6        C3        C2         108.335   1_555 1_555   1_555
	C6        C3        H3         129.000   1_555 1_555   1_555
	H4A       C4        H4B        108.028   1_555 1_555   1_555
	N2        C4        H4A        109.380   1_555 1_555   1_555
	N2        C4        H4B        109.410   1_555 1_555   1_555
	C3        C4        N2         111.169   1_555 1_555   1_555
	C3        C4        H4A        109.407   1_555 1_555   1_555
	C3        C4        H4B        109.388   1_555 1_555   1_555
	H5A       C5        H5B        108.692   1_555 1_555   1_555
	N2        C5        H5A        110.460   1_555 1_555   1_555
	N2        C5        H5B        110.470   1_555 1_555   1_555
	C1        C5        N2         106.369  16_555 1_555   1_555
	C1        C5        H5A        110.425  16_555 1_555   1_555
	C1        C5        H5B        110.422  16_555 1_555   1_555
	O2        C6        O1         121.470   1_555 1_555   1_555
	C3        C6        O2         114.150   1_555 1_555   1_555
	C3        C6        O1         124.380   1_555 1_555   1_555