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


data_Hf-Cu-L_He-RT-d900

_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 copper Hafnium oxide'
_chemical_name_common            'Hafnium copper cyclam carboxylate'
_chemical_formula_moiety         
'(Hf 4+)6, (O 2-)8, (Cu N4 C12 H22 O4 Cl1.34 2-)4'
_chemical_formula_sum            'C24 H44 Cl2.68 Cu2 Hf3 N8 O16'
_chemical_formula_weight         1458.23
_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 				16.7929(14)
_cell_length_b 				16.7929(14)
_cell_length_c 				19.020(3)
_cell_angle_alpha 			90
_cell_angle_beta 			90
_cell_angle_gamma 			90
_cell_volume 				5363.7(12)
_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              0.0529
_pd_proc_ls_prof_wR_factor             0.0767
_pd_proc_ls_prof_wR_expected           0.0173
_refine_ls_R_Fsqd_factor               0.0786
_reflns_number_total                   378
_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              1.591
_reflns_d_resolution_low               12.588
_refine_ls_goodness_of_fit_all         4.88

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 -0.1441(5) 0.0384(5) 0 1 2.39(12)
Hf2 Hf   4 0 0 0.1232(7) 1 2.39(12)
O3 O  16 -0.0458(14) 0.079(2) 0.068(2) 1 2.5(8)
O5 O   8 -0.197(5) 0.155(5) 0 1 2.5(8)
O4 O   8 -0.248(5) -0.031(5) 0 1 2.5(8)
Cu1 Cu   8 0.25 0.25 0.25 1 8.0(9)
Cl1 Cl  16 0.097(3) 0.191(6) 0.275(3) 0.67(3) 8
O1 O  16 0.228(9) -0.0478(13) 0.0999(17) 1 2.5(8)
O2 O  16 0.141(8) -0.006(4) 0.1844(19) 1 2.5(8)
N1 N  16 0.287(4) 0.1460(14) 0.2925(7) 1 8.0(15)
H1 H  16 0.345(4) 0.143(3) 0.2852(11) 1 12(2)
N2 N  16 0.2511(10) 0.2067(7) 0.1511(2) 1 8.0(15)
H2 H  16 0.3074(11) 0.206(2) 0.1356(6) 1 12(2)
C1 C  16 0.270(5) 0.1518(12) 0.3691(6) 1 8.0(15)
H1A H  16 0.301(6) 0.111(2) 0.3952(9) 1 12(2)
H1B H  16 0.213(5) 0.1428(15) 0.3783(7) 1 12(2)
C2 C  16 0.254(6) 0.0701(2) 0.2639(10) 1 8.0(15)
H2A H  16 0.275(8) 0.0246(10) 0.2911(13) 1 12(2)
H2B H  16 0.195(6) 0.0703(18) 0.2689(12) 1 12(2)
C3 C  16 0.264(6) 0.0627(7) 0.1839(10) 1 8.0(15)
H3 H  16 0.322(6) 0.067(3) 0.1735(12) 1 12(2)
C4 C  16 0.220(3) 0.1248(13) 0.1391(8) 1 8.0(15)
H4A H  16 0.224(3) 0.1119(15) 0.0884(8) 1 12(2)
H4B H  16 0.164(4) 0.122(3) 0.1532(12) 1 12(2)
C5 C  16 0.207(2) 0.2652(19) 0.1066(4) 1 8.0(15)
H5A H  16 0.220(3) 0.2565(18) 0.0563(3) 1 12(2)
H5B H  16 0.149(2) 0.260(4) 0.1136(10) 1 12(2)
C6 C  16 0.209(8) -0.0022(16) 0.1524(15) 1 8.0(15)

# 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       O4        2.10000 1_555   1_555
	Hf1       O5        2.15721 1_555   1_555
	Hf1       O3        2.20140 1_555   7_555
	Hf1       O3        2.20140 1_555   4_555
	Hf1       O3        2.20140 1_555   1_555
	Hf1       O3        2.20140 1_555   3_555
	Hf1       O1        2.37(10) 1_555   2_555
	Hf1       O1        2.37(10) 1_555   8_555
	Hf2       O3        1.86208 1_555   1_555
	Hf2       O3        1.86208 1_555   4_555
	Hf2       O3        1.86208 1_555   2_555
	Hf2       O3        1.86208 1_555   6_555
	Hf2       O2        2.64(14) 1_555   2_555
	Hf2       O2        2.64(14) 1_555   6_555
	Hf2       O2        2.64(14) 1_555   1_555
	Hf2       O2        2.64(14) 1_555   4_555
	O3        Hf2       1.86208 1_555   1_555
	O3        Hf1       2.20140 1_555   1_555
	O3        Hf1       2.20140 1_555   5_555
	Cu1       N2        2.01700 1_555  16_555
	Cu1       N2        2.01700 1_555   1_555
	Cu1       N1        2.02200 1_555  16_555
	Cu1       N1        2.02200 1_555   1_555
	Cu1       Cl1       2.80000 1_555  16_555
	Cu1       Cl1       2.80000 1_555   1_555
	Cl1       Cu1       2.80000 1_555   1_555
	O1        C6        1.30000 1_555   1_555
	O1        Hf1       2.37(10) 1_555   2_555
	O2        C6        1.30000 1_555   1_555
	O2        Hf2       2.64(14) 1_555   1_555
	N1        H1        0.99000 1_555   1_555
	N1        C1        1.48800 1_555   1_555
	N1        C2        1.49300 1_555   1_555
	N1        Cu1       2.02200 1_555   1_555
	H1        N1        0.99000 1_555   1_555
	N2        H2        0.99000 1_555   1_555
	N2        C4        1.48600 1_555   1_555
	N2        C5        1.49000 1_555   1_555
	N2        Cu1       2.01700 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        1.51634 1_555  16_555
	H1A       C1        0.99000 1_555   1_555
	H1B       C1        0.99000 1_555   1_555
	C2        H2B       0.99000 1_555   1_555
	C2        H2A       0.99000 1_555   1_555
	C2        N1        1.49300 1_555   1_555
	C2        C3        1.53500 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        1.53500 1_555   1_555
	C3        C4        1.53630 1_555   1_555
	C3        C6        1.55000 1_555   1_555
	H3        C3        0.99000 1_555   1_555
	C4        H4A       0.99000 1_555   1_555
	C4        H4B       0.99000 1_555   1_555
	C4        N2        1.48600 1_555   1_555
	C4        C3        1.53630 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        1.51634 1_555  16_555
	H5A       C5        0.99000 1_555   1_555
	H5B       C5        0.99000 1_555   1_555
	C6        O1        1.30000 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
	O5        Hf1       O4         99.311    1_555 1_555   1_555
	O3        Hf1       O5         91.585    7_555 1_555   1_555
	O3        Hf1       O4         142.762   7_555 1_555   1_555
	O3        Hf1       O3         99.580    4_555 1_555   7_555
	O3        Hf1       O5         142.151   4_555 1_555   1_555
	O3        Hf1       O4         93.328    4_555 1_555   1_555
	O3        Hf1       O3         58.960    1_555 1_555   4_555
	O3        Hf1       O3         71.462    1_555 1_555   7_555
	O3        Hf1       O5         91.585    1_555 1_555   1_555
	O3        Hf1       O4         142.762   1_555 1_555   1_555
	O3        Hf1       O3         99.580    3_555 1_555   1_555
	O3        Hf1       O3         71.462    3_555 1_555   4_555
	O3        Hf1       O3         58.960    3_555 1_555   7_555
	O3        Hf1       O5         142.151   3_555 1_555   1_555
	O3        Hf1       O4         93.328    3_555 1_555   1_555
	O1        Hf1       O3         143.8(6)  2_555 1_555   3_555
	O1        Hf1       O3         88(3)  2_555 1_555   1_555
	O1        Hf1       O3         83(2)  2_555 1_555   4_555
	O1        Hf1       O3         153.4(15)  2_555 1_555   7_555
	O1        Hf1       O5         72.1(11)  2_555 1_555   1_555
	O1        Hf1       O4         63(2)  2_555 1_555   1_555
	O1        Hf1       O1         106(6)  8_555 1_555   2_555
	O1        Hf1       O3         83(2)  8_555 1_555   3_555
	O1        Hf1       O3         153.4(15)  8_555 1_555   1_555
	O1        Hf1       O3         143.8(6)  8_555 1_555   4_555
	O1        Hf1       O3         88(3)  8_555 1_555   7_555
	O1        Hf1       O5         72.1(11)  8_555 1_555   1_555
	O1        Hf1       O4         63(2)  8_555 1_555   1_555
	O3        Hf2       O3         71.154    4_555 1_555   1_555
	O3        Hf2       O3         71.154    2_555 1_555   4_555
	O3        Hf2       O3         110.729   2_555 1_555   1_555
	O3        Hf2       O3         71.154    6_555 1_555   2_555
	O3        Hf2       O3         110.729   6_555 1_555   4_555
	O3        Hf2       O3         71.154    6_555 1_555   1_555
	O2        Hf2       O3         150.7(15)  2_555 1_555   6_555
	O2        Hf2       O3         130.5(8)  2_555 1_555   2_555
	O2        Hf2       O3         68.2(7)  2_555 1_555   4_555
	O2        Hf2       O3         81.5(16)  2_555 1_555   1_555
	O2        Hf2       O2         78.8(9)  6_555 1_555   2_555
	O2        Hf2       O3         130.5(8)  6_555 1_555   6_555
	O2        Hf2       O3         68.2(7)  6_555 1_555   2_555
	O2        Hf2       O3         81.5(16)  6_555 1_555   4_555
	O2        Hf2       O3         150.7(15)  6_555 1_555   1_555
	O2        Hf2       O2         78.8(9)  1_555 1_555   6_555
	O2        Hf2       O2         128(2)  1_555 1_555   2_555
	O2        Hf2       O3         68.2(7)  1_555 1_555   6_555
	O2        Hf2       O3         81.5(16)  1_555 1_555   2_555
	O2        Hf2       O3         150.7(15)  1_555 1_555   4_555
	O2        Hf2       O3         130.5(8)  1_555 1_555   1_555
	O2        Hf2       O2         78.8(9)  4_555 1_555   1_555
	O2        Hf2       O2         128(2)  4_555 1_555   6_555
	O2        Hf2       O2         78.8(9)  4_555 1_555   2_555
	O2        Hf2       O3         81.5(16)  4_555 1_555   6_555
	O2        Hf2       O3         150.7(15)  4_555 1_555   2_555
	O2        Hf2       O3         130.5(8)  4_555 1_555   4_555
	O2        Hf2       O3         68.2(7)  4_555 1_555   1_555
	Hf1       O3        Hf2        114.910   1_555 1_555   1_555
	Hf1       O3        Hf1        107.120   5_555 1_555   1_555
	Hf1       O3        Hf2        114.910   5_555 1_555   1_555
	N2        Cu1       N2         180.000   1_555 1_555  16_555
	N1        Cu1       N2         86.640   16_555 1_555   1_555
	N1        Cu1       N2         93.360   16_555 1_555  16_555
	N1        Cu1       N1         180.000   1_555 1_555  16_555
	N1        Cu1       N2         93.360    1_555 1_555   1_555
	N1        Cu1       N2         86.640    1_555 1_555  16_555
	Cl1       Cu1       N1         95.085   16_555 1_555   1_555
	Cl1       Cu1       N1         84.915   16_555 1_555  16_555
	Cl1       Cu1       N2         87.637   16_555 1_555   1_555
	Cl1       Cu1       N2         92.363   16_555 1_555  16_555
	Cl1       Cu1       Cl1        180.000   1_555 1_555  16_555
	Cl1       Cu1       N1         84.915    1_555 1_555   1_555
	Cl1       Cu1       N1         95.085    1_555 1_555  16_555
	Cl1       Cu1       N2         92.363    1_555 1_555   1_555
	Cl1       Cu1       N2         87.637    1_555 1_555  16_555
	Hf1       O1        C6         115(3)  2_555 1_555   1_555
	Hf2       O2        C6         125.6(10)  1_555 1_555   1_555
	C1        N1        H1         109.123   1_555 1_555   1_555
	C2        N1        C1         109.960   1_555 1_555   1_555
	C2        N1        H1         106.210   1_555 1_555   1_555
	Cu1       N1        C2         118.508   1_555 1_555   1_555
	Cu1       N1        C1         106.050   1_555 1_555   1_555
	Cu1       N1        H1         106.717   1_555 1_555   1_555
	C4        N2        H2         105.850   1_555 1_555   1_555
	C5        N2        C4         110.640   1_555 1_555   1_555
	C5        N2        H2         108.062   1_555 1_555   1_555
	Cu1       N2        C5         106.698   1_555 1_555   1_555
	Cu1       N2        C4         118.224   1_555 1_555   1_555
	Cu1       N2        H2         106.952   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         108.097  16_555 1_555   1_555
	C5        C1        H1B        109.178  16_555 1_555   1_555
	C5        C1        H1A        110.205  16_555 1_555   1_555
	H2A       C2        H2B        108.060   1_555 1_555   1_555
	N1        C2        H2A        109.480   1_555 1_555   1_555
	N1        C2        H2B        109.430   1_555 1_555   1_555
	C3        C2        N1         112.788   1_555 1_555   1_555
	C3        C2        H2A        114.510   1_555 1_555   1_555
	C3        C2        H2B        102.167   1_555 1_555   1_555
	C2        C3        H3         107.660   1_555 1_555   1_555
	C4        C3        C2         116.070   1_555 1_555   1_555
	C4        C3        H3         107.624   1_555 1_555   1_555
	C6        C3        C4         88.635    1_555 1_555   1_555
	C6        C3        C2         111.818   1_555 1_555   1_555
	C6        C3        H3         124.216   1_555 1_555   1_555
	H4B       C4        H4A        108.028   1_555 1_555   1_555
	N2        C4        H4B        109.410   1_555 1_555   1_555
	N2        C4        H4A        109.380   1_555 1_555   1_555
	C3        C4        N2         112.168   1_555 1_555   1_555
	C3        C4        H4B        106.390   1_555 1_555   1_555
	C3        C4        H4A        111.331   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         108.068  16_555 1_555   1_555
	C1        C5        H5A        112.245  16_555 1_555   1_555
	C1        C5        H5B        106.850  16_555 1_555   1_555
	O2        C6        O1         123.110   1_555 1_555   1_555
	C3        C6        O2         112.510   1_555 1_555   1_555
	C3        C6        O1         124.380   1_555 1_555   1_555