Tetra-kis(1,10-phenanthroline)bis-(μ-pyridine-2,6-dicarboxyl-ato)(pyridine-2,6-di-carboxyl-ato)dicopper(II)terbium(III) nitrate tetra-hydrate.

The asymmetric unit of the title compound, [Cu(2)Tb(C(7)H(3)NO(4))(3)(C(12)H(8)N(2))(4)]NO(3)·4H(2)O, consists of one-half of the C(2)-symmetric trinuclear coordination cation, one-half of the C(2)-symmetric nitrate anion and two water mol-ecules. In the coordination cation, the Cu(II) atom is coordinated by four N atoms from two 1,10-phenanthroline ligands and two O atoms from a bridging-chelating carboxyl-ate group of the pyridine-2,6-dicarboxyl-ate anion, completing a distorted N(4)O(2) octa-hedral coordination environment. The Tb(III) atom, located on a twofold rotation axis, is nine-coordinated by three tridentate pyridine-2,6-dicarboxyl-ate anions forming an N(3)O(6) donor set. The intra-molecular Cu⋯Tb distance of 5.0592 (11) Å indicates weak inter-actions between the Cu(II) and Tb(III) atoms. The coordination cations, nitrate anions and water mol-ecules are connected via O-H⋯O hydrogen bonds into layers parallel to the (001) plane. Moreover, there are extensive π-π stacking inter-actions [centroid-centroid distances = 4.332 (7) and 3.878 (5) Å] between the phenanthroline ligands and between phenanthroline and pyridine-2,6-dicarboxyl-ate ligands.

Related literature

For the photophysical properties of lanthanide(III) coordination compounds, see: Jüstel et al. (1998 ▶). For the Cu—O, Cu—N, Tb—O and Tb—N bond lengths in previously reported dinuclear copper(II)–terbium(III) coordination compounds, see: Sun et al. (2010 ▶); Yang et al. (2006 ▶).

Experimental

Crystal data

[Cu2Tb(C7H3NO4)3(C12H8N2)4]NO3·4H2O

M = 1636.20

Monoclinic,

a = 17.058 (4) Å

b = 19.574 (5) Å

c = 19.927 (5) Å

β = 97.289 (4)°

V = 6599 (3) Å3

Z = 4

Mo Kα radiation

μ = 1.78 mm−1

T = 296 K

0.19 × 0.17 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.728, T max = 0.776

17945 measured reflections

6454 independent reflections

4952 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.134

S = 1.04

6454 reflections

479 parameters

27 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.88 e Å−3

Δρmin = −1.09 e Å−3

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812031686/gk2483sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812031686/gk2483Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Cu2Tb(C7H3NO4)3(C12H8N2)4]NO3·4H2O	F(000) = 3288
Mr = 1636.20	Dx = 1.647 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5232 reflections
a = 17.058 (4) Å	θ = 2.3–25.0°
b = 19.574 (5) Å	µ = 1.78 mm−1
c = 19.927 (5) Å	T = 296 K
β = 97.289 (4)°	Block, blue
V = 6599 (3) Å3	0.19 × 0.17 × 0.15 mm
Z = 4

Bruker APEXII CCD diffractometer	6454 independent reflections
Radiation source: fine-focus sealed tube	4952 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
φ and ω scans	θmax = 26.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −21→11
Tmin = 0.728, Tmax = 0.776	k = −24→22
17945 measured reflections	l = −24→24

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.134	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0792P)2 + 8.9094P] where P = (Fo2 + 2Fc2)/3
6454 reflections	(Δ/σ)max = 0.001
479 parameters	Δρmax = 0.88 e Å−3
27 restraints	Δρmin = −1.09 e Å−3

Geometry. 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.

Refinement. 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.

	x	y	z	Uiso*/Ueq
Tb1	0.5000	0.828451 (16)	0.2500	0.04016 (14)
C1	0.3780 (4)	0.5559 (3)	0.2339 (3)	0.0657 (16)
H1A	0.4057	0.5538	0.2772	0.079*
C2	0.4024 (4)	0.5136 (3)	0.1828 (4)	0.0766 (19)
H2A	0.4466	0.4858	0.1921	0.092*
C3	0.3608 (4)	0.5140 (3)	0.1199 (4)	0.0725 (19)
H3A	0.3762	0.4862	0.0860	0.087*
C4	0.2954 (4)	0.5561 (3)	0.1064 (3)	0.0611 (16)
C5	0.2759 (3)	0.5984 (2)	0.1595 (3)	0.0461 (12)
C6	0.2115 (3)	0.6447 (3)	0.1487 (3)	0.0488 (12)
C7	0.1630 (4)	0.6464 (3)	0.0854 (3)	0.0569 (14)
C8	0.1825 (5)	0.6017 (4)	0.0330 (3)	0.0730 (19)
H8A	0.1509	0.6013	−0.0086	0.088*
C9	0.2464 (5)	0.5600 (4)	0.0431 (3)	0.0733 (19)
H9A	0.2586	0.5330	0.0075	0.088*
C10	0.0997 (4)	0.6915 (4)	0.0792 (3)	0.0674 (18)
H10A	0.0657	0.6939	0.0389	0.081*
C11	0.0872 (4)	0.7326 (3)	0.1327 (3)	0.0668 (16)
H11A	0.0444	0.7624	0.1290	0.080*
C12	0.1384 (3)	0.7293 (3)	0.1914 (3)	0.0573 (14)
H12A	0.1299	0.7587	0.2264	0.069*
C13	0.2621 (3)	0.8081 (3)	0.3376 (3)	0.0542 (14)
H13A	0.2924	0.8213	0.3041	0.065*
C14	0.2405 (4)	0.8578 (3)	0.3827 (3)	0.0639 (16)
H14A	0.2565	0.9030	0.3795	0.077*
C15	0.1954 (4)	0.8384 (3)	0.4313 (4)	0.0676 (18)
H15A	0.1799	0.8708	0.4612	0.081*
C16	0.1722 (3)	0.7695 (3)	0.4365 (3)	0.0527 (13)
C17	0.1964 (3)	0.7228 (3)	0.3895 (3)	0.0456 (12)
C18	0.1765 (3)	0.6513 (3)	0.3928 (3)	0.0445 (11)
C19	0.1323 (3)	0.6287 (3)	0.4433 (3)	0.0550 (14)
C20	0.1089 (4)	0.6773 (4)	0.4919 (3)	0.0637 (17)
H20A	0.0809	0.6624	0.5263	0.076*
C21	0.1273 (3)	0.7437 (4)	0.4877 (3)	0.0645 (17)
H21A	0.1105	0.7741	0.5188	0.077*
C22	0.1136 (4)	0.5585 (3)	0.4430 (3)	0.0642 (16)
H22A	0.0844	0.5409	0.4754	0.077*
C23	0.1379 (4)	0.5171 (3)	0.3959 (3)	0.0634 (16)
H23A	0.1245	0.4710	0.3950	0.076*
C24	0.1833 (3)	0.5435 (3)	0.3486 (3)	0.0542 (13)
H24A	0.2011	0.5140	0.3173	0.065*
C25	0.4261 (3)	0.6997 (2)	0.3338 (3)	0.0398 (11)
C26	0.5055 (3)	0.7063 (2)	0.3749 (2)	0.0413 (11)
C27	0.5311 (4)	0.6663 (3)	0.4298 (3)	0.0519 (14)
H27A	0.4987	0.6326	0.4444	0.062*
C28	0.6076 (4)	0.6775 (3)	0.4636 (3)	0.0631 (17)
H28A	0.6269	0.6517	0.5013	0.076*
C29	0.6531 (3)	0.7277 (3)	0.4394 (3)	0.0608 (16)
H29A	0.7041	0.7359	0.4605	0.073*
C30	0.6227 (3)	0.7663 (3)	0.3834 (3)	0.0476 (12)
C31	0.6681 (3)	0.8235 (3)	0.3539 (3)	0.0556 (15)
C32	0.4367 (3)	0.9434 (3)	0.3500 (3)	0.0543 (14)
C33	0.4679 (3)	0.9880 (2)	0.2977 (2)	0.0427 (11)
C34	0.4668 (3)	1.0585 (3)	0.2987 (3)	0.0540 (14)
H34A	0.4438	1.0817	0.3319	0.065*
Cu1	0.27722 (4)	0.66689 (3)	0.28488 (3)	0.04248 (18)
N1	0.3180 (3)	0.5977 (2)	0.2226 (2)	0.0490 (10)
N2	0.1994 (3)	0.6868 (2)	0.2016 (2)	0.0475 (10)
N3	0.2413 (2)	0.7437 (2)	0.3407 (2)	0.0454 (10)
N4	0.2020 (3)	0.6093 (2)	0.3464 (2)	0.0478 (10)
N5	0.5497 (2)	0.7559 (2)	0.3524 (2)	0.0411 (9)
N6	0.5000	0.9536 (3)	0.2500	0.0408 (13)
N7	1.0000	0.8539 (5)	0.2500	0.118 (4)
O1	0.41131 (19)	0.73634 (17)	0.28216 (17)	0.0446 (8)
O1W	0.3730 (5)	0.5423 (4)	0.4498 (4)	0.142 (3)
H1WA	0.371 (6)	0.5065 (12)	0.4206 (18)	0.170*
O2	0.3767 (2)	0.65755 (18)	0.35262 (19)	0.0489 (9)
O2W	0.8497 (6)	0.9270 (4)	0.3641 (7)	0.191 (4)
O3	0.6303 (2)	0.8570 (2)	0.3059 (2)	0.0581 (10)
O4	0.7371 (3)	0.8336 (2)	0.3812 (3)	0.0836 (15)
O5	0.4470 (2)	0.87888 (18)	0.34281 (19)	0.0547 (10)
O6	0.4060 (4)	0.9707 (2)	0.3959 (3)	0.105 (2)
C35	0.5000	1.0940 (4)	0.2500	0.056 (2)
H35	0.5000	1.1415	0.2500	0.067*
O8	1.0000	0.7900 (9)	0.2500	0.242 (6)
O7	0.9613 (7)	0.8826 (5)	0.2917 (6)	0.208 (4)
H2WB	0.814 (6)	0.900 (5)	0.372 (8)	0.250*
H2WA	0.882 (7)	0.905 (5)	0.343 (8)	0.250*
H1WB	0.385 (3)	0.575 (2)	0.425 (3)	0.250*

	U11	U22	U33	U12	U13	U23
Tb1	0.0415 (2)	0.0376 (2)	0.0439 (2)	0.000	0.01540 (15)	0.000
C1	0.069 (4)	0.053 (3)	0.077 (4)	0.010 (3)	0.014 (3)	−0.003 (3)
C2	0.078 (5)	0.054 (4)	0.101 (6)	0.009 (3)	0.027 (4)	−0.015 (4)
C3	0.085 (5)	0.054 (4)	0.085 (5)	−0.012 (3)	0.036 (4)	−0.021 (3)
C4	0.080 (4)	0.047 (3)	0.061 (4)	−0.019 (3)	0.027 (3)	−0.011 (3)
C5	0.060 (3)	0.037 (3)	0.044 (3)	−0.012 (2)	0.016 (2)	−0.005 (2)
C6	0.059 (3)	0.046 (3)	0.044 (3)	−0.010 (2)	0.018 (2)	0.002 (2)
C7	0.064 (4)	0.060 (3)	0.046 (3)	−0.022 (3)	0.005 (3)	0.006 (3)
C8	0.093 (5)	0.085 (5)	0.042 (3)	−0.034 (4)	0.010 (3)	−0.009 (3)
C9	0.096 (5)	0.073 (4)	0.053 (4)	−0.028 (4)	0.021 (4)	−0.021 (3)
C10	0.062 (4)	0.078 (4)	0.059 (4)	−0.022 (3)	−0.005 (3)	0.024 (3)
C11	0.054 (4)	0.070 (4)	0.074 (4)	0.004 (3)	0.000 (3)	0.015 (3)
C12	0.060 (4)	0.054 (3)	0.058 (4)	0.005 (3)	0.009 (3)	0.003 (3)
C13	0.052 (3)	0.048 (3)	0.066 (4)	0.003 (2)	0.022 (3)	0.002 (3)
C14	0.062 (4)	0.055 (3)	0.077 (4)	0.004 (3)	0.015 (3)	−0.012 (3)
C15	0.065 (4)	0.070 (4)	0.068 (4)	0.021 (3)	0.010 (3)	−0.020 (3)
C16	0.047 (3)	0.065 (4)	0.047 (3)	0.011 (3)	0.007 (2)	−0.007 (3)
C17	0.038 (3)	0.056 (3)	0.044 (3)	0.005 (2)	0.007 (2)	0.000 (2)
C18	0.040 (3)	0.055 (3)	0.037 (3)	−0.001 (2)	0.003 (2)	0.006 (2)
C19	0.041 (3)	0.076 (4)	0.048 (3)	0.003 (3)	0.007 (2)	0.012 (3)
C20	0.050 (3)	0.097 (5)	0.047 (3)	0.006 (3)	0.018 (3)	0.015 (3)
C21	0.060 (4)	0.090 (5)	0.047 (3)	0.018 (3)	0.020 (3)	−0.007 (3)
C22	0.060 (4)	0.076 (4)	0.056 (4)	−0.013 (3)	0.008 (3)	0.027 (3)
C23	0.068 (4)	0.062 (4)	0.059 (4)	−0.010 (3)	0.002 (3)	0.016 (3)
C24	0.060 (3)	0.050 (3)	0.050 (3)	−0.002 (3)	−0.001 (3)	0.007 (3)
C25	0.044 (3)	0.036 (2)	0.042 (3)	0.002 (2)	0.016 (2)	−0.001 (2)
C26	0.045 (3)	0.041 (3)	0.040 (3)	0.008 (2)	0.009 (2)	−0.003 (2)
C27	0.061 (4)	0.052 (3)	0.045 (3)	0.013 (2)	0.010 (3)	0.001 (2)
C28	0.067 (4)	0.072 (4)	0.048 (3)	0.024 (3)	−0.001 (3)	−0.003 (3)
C29	0.048 (3)	0.077 (4)	0.054 (4)	0.014 (3)	−0.007 (3)	−0.017 (3)
C30	0.042 (3)	0.052 (3)	0.049 (3)	0.004 (2)	0.007 (2)	−0.017 (2)
C31	0.043 (3)	0.065 (4)	0.060 (4)	−0.005 (3)	0.009 (3)	−0.025 (3)
C32	0.064 (4)	0.049 (3)	0.056 (3)	0.000 (3)	0.029 (3)	−0.004 (3)
C33	0.045 (3)	0.044 (3)	0.042 (3)	0.001 (2)	0.016 (2)	−0.006 (2)
C34	0.056 (3)	0.045 (3)	0.066 (4)	0.002 (2)	0.024 (3)	−0.010 (3)
Cu1	0.0467 (4)	0.0429 (4)	0.0393 (4)	0.0008 (2)	0.0111 (3)	0.0000 (2)
N1	0.055 (3)	0.041 (2)	0.053 (3)	0.0006 (19)	0.015 (2)	−0.0004 (19)
N2	0.054 (3)	0.048 (2)	0.041 (2)	−0.002 (2)	0.008 (2)	0.0044 (19)
N3	0.046 (2)	0.046 (2)	0.047 (2)	−0.0006 (18)	0.0144 (19)	−0.0005 (19)
N4	0.048 (2)	0.051 (3)	0.045 (2)	−0.0033 (19)	0.0078 (19)	0.005 (2)
N5	0.039 (2)	0.043 (2)	0.042 (2)	0.0025 (17)	0.0087 (18)	−0.0064 (18)
N6	0.043 (3)	0.039 (3)	0.044 (3)	0.000	0.018 (3)	0.000
N7	0.107 (8)	0.069 (6)	0.197 (13)	0.000	0.088 (8)	0.000
O1	0.0407 (18)	0.0471 (19)	0.046 (2)	−0.0036 (14)	0.0055 (15)	0.0081 (16)
O1W	0.189 (7)	0.125 (6)	0.113 (5)	−0.029 (5)	0.026 (5)	0.033 (4)
O2	0.052 (2)	0.046 (2)	0.049 (2)	−0.0056 (16)	0.0104 (17)	0.0090 (16)
O2W	0.183 (9)	0.088 (5)	0.324 (14)	−0.044 (5)	0.122 (9)	−0.032 (6)
O3	0.049 (2)	0.054 (2)	0.071 (3)	−0.0122 (18)	0.011 (2)	−0.009 (2)
O4	0.044 (2)	0.105 (4)	0.099 (4)	−0.019 (2)	−0.003 (2)	−0.013 (3)
O5	0.070 (3)	0.047 (2)	0.054 (2)	0.0024 (17)	0.0351 (19)	0.0037 (17)
O6	0.180 (6)	0.062 (3)	0.094 (4)	0.001 (3)	0.101 (4)	−0.005 (3)
C35	0.063 (5)	0.040 (4)	0.067 (5)	0.000	0.014 (4)	0.000
O8	0.242 (6)	0.241 (6)	0.243 (6)	0.000	0.0316 (14)	0.000
O7	0.208 (4)	0.208 (4)	0.209 (4)	0.0001 (11)	0.0291 (13)	−0.0002 (11)

Tb1—O5	2.374 (3)	C20—C21	1.342 (9)
Tb1—O5i	2.374 (3)	C20—H20A	0.9300
Tb1—O3	2.422 (4)	C21—H21A	0.9300
Tb1—O3i	2.422 (4)	C22—C23	1.346 (9)
Tb1—N6	2.450 (5)	C22—H22A	0.9300
Tb1—O1	2.489 (3)	C23—C24	1.393 (8)
Tb1—O1i	2.489 (3)	C23—H23A	0.9300
Tb1—N5i	2.542 (4)	C24—N4	1.328 (7)
Tb1—N5	2.542 (4)	C24—H24A	0.9300
C1—N1	1.308 (7)	C25—O1	1.254 (6)
C1—C2	1.415 (9)	C25—O2	1.269 (6)
C1—H1A	0.9300	C25—C26	1.497 (7)
C2—C3	1.360 (10)	C26—N5	1.340 (6)
C2—H2A	0.9300	C26—C27	1.373 (7)
C3—C4	1.386 (9)	C27—C28	1.408 (9)
C3—H3A	0.9300	C27—H27A	0.9300
C4—C5	1.416 (7)	C28—C29	1.378 (9)
C4—C9	1.424 (9)	C28—H28A	0.9300
C5—N1	1.366 (7)	C29—C30	1.392 (8)
C5—C6	1.419 (8)	C29—H29A	0.9300
C6—N2	1.374 (7)	C30—N5	1.332 (6)
C6—C7	1.418 (8)	C30—C31	1.522 (8)
C7—C10	1.389 (9)	C31—O4	1.248 (7)
C7—C8	1.433 (9)	C31—O3	1.265 (7)
C8—C9	1.356 (10)	C32—O6	1.233 (7)
C8—H8A	0.9300	C32—O5	1.285 (6)
C9—H9A	0.9300	C32—C33	1.507 (7)
C10—C11	1.372 (9)	C33—N6	1.338 (5)
C10—H10A	0.9300	C33—C34	1.380 (7)
C11—C12	1.371 (8)	C34—C35	1.372 (7)
C11—H11A	0.9300	C34—H34A	0.9300
C12—N2	1.328 (7)	Cu1—N3	2.011 (4)
C12—H12A	0.9300	Cu1—N1	2.019 (4)
C13—N3	1.314 (7)	Cu1—N2	2.027 (4)
C13—C14	1.407 (8)	Cu1—O2	2.038 (4)
C13—H13A	0.9300	Cu1—N4	2.195 (4)
C14—C15	1.364 (9)	Cu1—O1	2.667 (3)
C14—H14A	0.9300	N6—C33i	1.338 (5)
C15—C16	1.414 (8)	N7—O8	1.250 (15)
C15—H15A	0.9300	N7—O7	1.258 (10)
C16—C17	1.407 (7)	N7—O7ii	1.258 (10)
C16—C21	1.441 (8)	O1W—H1WA	0.908 (19)
C17—N3	1.374 (6)	O1W—H1WB	0.85 (2)
C17—C18	1.444 (7)	O2W—H2WB	0.84 (2)
C18—N4	1.351 (7)	O2W—H2WA	0.86 (2)
C18—C19	1.402 (7)	C35—C34i	1.372 (7)
C19—C22	1.410 (8)	C35—H35	0.9300
C19—C20	1.450 (9)
O5—Tb1—O5i	130.87 (17)	C19—C18—C17	119.3 (5)
O5—Tb1—O3	87.91 (14)	C18—C19—C22	116.6 (6)
O5i—Tb1—O3	81.06 (14)	C18—C19—C20	119.4 (5)
O5—Tb1—O3i	81.06 (14)	C22—C19—C20	124.1 (5)
O5i—Tb1—O3i	87.91 (14)	C21—C20—C19	120.4 (5)
O3—Tb1—O3i	153.3 (2)	C21—C20—H20A	119.8
O5—Tb1—N6	65.43 (9)	C19—C20—H20A	119.8
O5i—Tb1—N6	65.43 (8)	C20—C21—C16	122.2 (6)
O3—Tb1—N6	76.67 (10)	C20—C21—H21A	118.9
O3i—Tb1—N6	76.67 (10)	C16—C21—H21A	118.9
O5—Tb1—O1	78.26 (12)	C23—C22—C19	120.0 (5)
O5i—Tb1—O1	143.68 (12)	C23—C22—H22A	120.0
O3—Tb1—O1	126.92 (13)	C19—C22—H22A	120.0
O3i—Tb1—O1	74.53 (13)	C22—C23—C24	119.6 (6)
N6—Tb1—O1	136.41 (8)	C22—C23—H23A	120.2
O5—Tb1—O1i	143.68 (12)	C24—C23—H23A	120.2
O5i—Tb1—O1i	78.26 (12)	N4—C24—C23	122.7 (6)
O3—Tb1—O1i	74.53 (13)	N4—C24—H24A	118.7
O3i—Tb1—O1i	126.92 (13)	C23—C24—H24A	118.7
N6—Tb1—O1i	136.41 (8)	O1—C25—O2	122.9 (5)
O1—Tb1—O1i	87.18 (16)	O1—C25—C26	118.2 (4)
O5—Tb1—N5i	137.42 (13)	O2—C25—C26	118.9 (4)
O5i—Tb1—N5i	74.24 (12)	N5—C26—C27	123.0 (5)
O3—Tb1—N5i	133.76 (13)	N5—C26—C25	112.9 (4)
O3i—Tb1—N5i	64.29 (13)	C27—C26—C25	124.1 (5)
N6—Tb1—N5i	123.98 (9)	C26—C27—C28	118.2 (6)
O1—Tb1—N5i	69.51 (12)	C26—C27—H27A	120.9
O1i—Tb1—N5i	62.63 (12)	C28—C27—H27A	120.9
O5—Tb1—N5	74.24 (12)	C29—C28—C27	118.3 (6)
O5i—Tb1—N5	137.42 (13)	C29—C28—H28A	120.8
O3—Tb1—N5	64.29 (13)	C27—C28—H28A	120.8
O3i—Tb1—N5	133.76 (13)	C28—C29—C30	119.9 (5)
N6—Tb1—N5	123.98 (9)	C28—C29—H29A	120.1
O1—Tb1—N5	62.63 (12)	C30—C29—H29A	120.1
O1i—Tb1—N5	69.51 (12)	N5—C30—C29	121.3 (5)
N5i—Tb1—N5	112.04 (17)	N5—C30—C31	115.1 (5)
N1—C1—C2	122.5 (6)	C29—C30—C31	123.5 (5)
N1—C1—H1A	118.7	O4—C31—O3	127.6 (6)
C2—C1—H1A	118.7	O4—C31—C30	116.5 (6)
C3—C2—C1	119.6 (6)	O3—C31—C30	115.9 (5)
C3—C2—H2A	120.2	O6—C32—O5	125.9 (5)
C1—C2—H2A	120.2	O6—C32—C33	118.8 (5)
C2—C3—C4	119.7 (6)	O5—C32—C33	115.3 (4)
C2—C3—H3A	120.2	N6—C33—C34	121.3 (5)
C4—C3—H3A	120.2	N6—C33—C32	114.3 (4)
C3—C4—C5	117.6 (6)	C34—C33—C32	124.3 (4)
C3—C4—C9	124.8 (6)	C35—C34—C33	119.3 (5)
C5—C4—C9	117.6 (6)	C35—C34—H34A	120.4
N1—C5—C4	122.4 (5)	C33—C34—H34A	120.4
N1—C5—C6	116.9 (4)	N3—Cu1—N1	173.77 (17)
C4—C5—C6	120.7 (5)	N3—Cu1—N2	95.52 (18)
N2—C6—C7	122.8 (5)	N1—Cu1—N2	82.30 (18)
N2—C6—C5	117.0 (5)	N3—Cu1—O2	89.25 (16)
C7—C6—C5	120.2 (5)	N1—Cu1—O2	91.39 (17)
C10—C7—C6	116.9 (6)	N2—Cu1—O2	164.39 (16)
C10—C7—C8	125.0 (6)	N3—Cu1—N4	80.47 (17)
C6—C7—C8	118.1 (6)	N1—Cu1—N4	105.65 (17)
C9—C8—C7	121.0 (6)	N2—Cu1—N4	100.79 (17)
C9—C8—H8A	119.5	O2—Cu1—N4	94.65 (15)
C7—C8—H8A	119.5	C1—N1—C5	118.2 (5)
C8—C9—C4	122.3 (6)	C1—N1—Cu1	129.6 (4)
C8—C9—H9A	118.9	C5—N1—Cu1	112.2 (3)
C4—C9—H9A	118.9	C12—N2—C6	116.7 (5)
C11—C10—C7	119.9 (6)	C12—N2—Cu1	131.6 (4)
C11—C10—H10A	120.0	C6—N2—Cu1	111.6 (4)
C7—C10—H10A	120.0	C13—N3—C17	119.8 (5)
C12—C11—C10	119.4 (6)	C13—N3—Cu1	126.0 (4)
C12—C11—H11A	120.3	C17—N3—Cu1	114.0 (3)
C10—C11—H11A	120.3	C24—N4—C18	117.8 (5)
N2—C12—C11	124.2 (6)	C24—N4—Cu1	132.6 (4)
N2—C12—H12A	117.9	C18—N4—Cu1	109.4 (3)
C11—C12—H12A	117.9	C30—N5—C26	119.2 (4)
N3—C13—C14	122.6 (5)	C30—N5—Tb1	118.9 (3)
N3—C13—H13A	118.7	C26—N5—Tb1	121.9 (3)
C14—C13—H13A	118.7	C33—N6—C33i	119.6 (6)
C15—C14—C13	118.6 (6)	C33—N6—Tb1	120.2 (3)
C15—C14—H14A	120.7	C33i—N6—Tb1	120.2 (3)
C13—C14—H14A	120.7	O8—N7—O7	116.6 (7)
C14—C15—C16	120.4 (6)	O8—N7—O7ii	116.6 (7)
C14—C15—H15A	119.8	O7—N7—O7ii	126.9 (14)
C16—C15—H15A	119.8	C25—O1—Tb1	124.1 (3)
C17—C16—C15	117.5 (5)	H1WA—O1W—H1WB	102 (3)
C17—C16—C21	118.0 (5)	C25—O2—Cu1	105.9 (3)
C15—C16—C21	124.4 (5)	H2WB—O2W—H2WA	108 (4)
N3—C17—C16	121.0 (5)	C31—O3—Tb1	125.3 (4)
N3—C17—C18	118.4 (4)	C32—O5—Tb1	124.5 (3)
C16—C17—C18	120.5 (5)	C34i—C35—C34	119.2 (7)
N4—C18—C19	123.2 (5)	C34i—C35—H35	120.4
N4—C18—C17	117.4 (4)	C34—C35—H35	120.4

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WB···O2	0.85 (2)	2.16 (2)	2.979 (7)	162 (4)
O2W—H2WB···O4	0.84 (2)	1.87 (3)	2.705 (9)	174 (11)
O2W—H2WA···O7	0.86 (2)	1.84 (2)	2.675 (14)	164 (10)
O1W—H1WA···O2Wiii	0.91 (2)	1.93 (2)	2.827 (12)	171 (10)

Table 1

Selected bond lengths (Å)

Tb1—O5	2.374 (3)
Tb1—O3	2.422 (4)
Tb1—N6	2.450 (5)
Tb1—O1	2.489 (3)
Tb1—N5	2.542 (4)
Cu1—N3	2.011 (4)
Cu1—N1	2.019 (4)
Cu1—N2	2.027 (4)
Cu1—O2	2.038 (4)
Cu1—N4	2.195 (4)
Cu1—O1	2.667 (3)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WB⋯O2	0.85 (2)	2.16 (2)	2.979 (7)	162 (4)
O2W—H2WB⋯O4	0.84 (2)	1.87 (3)	2.705 (9)	174 (11)
O2W—H2WA⋯O7	0.86 (2)	1.84 (2)	2.675 (14)	164 (10)
O1W—H1WA⋯O2W i	0.91 (2)	1.93 (2)	2.827 (12)	171 (10)

Symmetry code: (i) .