Crystal structure and optical properties of a two-sited EuIII com­pound: an EuIII ion coordinated by two [EuIII(DOTA)]− com­plexes (DOTA is 1,4,7,10-tetra­azacyclo­dodecane-1,4,7,10-tetra­acetate)

Thomsen, M.S.; Madsen, A. Ø.; Sørensen, T.J.

doi:10.1107/S2053229621005647

Crystal structure and optical properties of a two-sited Eu^III compound: an Eu^III ion coordinated by two [Eu^III(DOTA)]⁻ complexes (DOTA is 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetate)

M. S. Thomsen, A. Ø. Madsen and T. J. Sørensen

The structure and solid-state luminescence properties of an Eu^III compound with two different lanthanide sites, [Eu(μ-O)₅(OH)(H₂O)₂][Eu(DOTA)(H₂O)]₂ (DOTA is 1,4,7,10-tetrazacyclododecane-1,4,7,10-tetraacetate, C₁₆H₂₄N₄O₈), were determined. The compound crystallizes in a laminar structure in the triclinic space group P $\overline{1}$ , where the two sites are a free europium(III) ion and an [Eu(DOTA)(H₂O)]⁻ complex. The crystal structure was determined using complex data treatment due to nonmerohedral twinning. Experimental data sets were recorded with large redundancy and separated according to scattering domains in order to obtain a reliable structure. In the first site, the [Eu(DOTA)(H₂O)]⁻ complex was found to adopt a capped twisted square-antiprismatic (cTSAP) conformation, where a capping water molecule increased the coordination number of the europium(III) site to nine (CN = 9). In the second site, the europium(III) ion was found to be coordinated by two water molecules, one hydroxide group and five oxide groups from neighbouring [Eu(DOTA)(H₂O)]⁻ complexes. The coordination geometry of this site was found to be a compressed square antiprism (SAP) and the coordination number of the europium(III) ion was found to be eight (CN = 8). A large increase in the rate constant of luminescence was observed for Eu^III in [Eu(DOTA)(H₂O)]⁻ in solid-state luminescence spectroscopy measurements compared to in solution, which led to investigations of single crystals in deuterated media to exclude additional effects of quenching. We conclude that the most probable cause of the decrease in the observed luminescence lifetimes is the high asymmetry of the coordination environment of [Eu(DOTA)(D₂O)]⁻ in the [Eu(μ-O)₅(OD)(D₂O)₂][Eu(DOTA)(D₂O)]₂ crystals.

Keywords: europium(III); luminescence; twinning; lanthanide chemistry; optical properties; crystal structure.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229621005647/yd3018sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229621005647/yd3018Isup2.hkl Contains datablock I
	Portable Document Format (PDF) file https://doi.org/10.1107/S2053229621005647/yd3018sup3.pdf Compilation of emission spectra, emission decay profiles, description of single-crystal spectroscopy set-up, crystal packing, powder XRD diffractogram, chart of structure of macrocyclic ligands and absorption spectrum

CCDC reference: 2055279

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXT2018 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009), CELL_NOW (Sheldrick, 2008) and TWINABS (Sheldrick, 2012).

Poly[sodium [tetraaquahydroxidopentaoxido\ bis(µ-1,4,7,10-tetrazacyclododecane-1,4,7,10-tetraacetato)trieuropium(III)] chloride hydrate] top

Crystal data top

Na[EuO₅(OH)(H₂O)₂][Eu(C₁₆H₂₄N₄O₈)(H₂O)]₂Cl·xH₂O	Z = 2
M_r = 1596.65	F(000) = 1587
Triclinic, P1	D_x = 1.980 Mg m⁻³
a = 9.2252 (18) Å	Mo Kα radiation, λ = 0.71073 Å
b = 16.937 (3) Å	Cell parameters from 5559 reflections
c = 17.274 (4) Å	θ = 2.2–32.1°
α = 96.37 (3)°	µ = 3.63 mm⁻¹
β = 92.39 (3)°	T = 100 K
γ = 93.26 (3)°	Plate, clear whiteish colourless
V = 2674.9 (9) Å³	1.20 × 0.71 × 0.12 mm

Data collection top

Bruker APEXII CCD diffractometer	8308 reflections with I > 2σ(I)
ω scans	R_int = 0.077
Absorption correction: empirical (using intensity measurements) (TWINABS; Sheldrick, 2012)	θ_max = 25.7°, θ_min = 1.6°
	h = −11→11
9966 measured reflections	k = −20→20
9966 independent reflections	l = 0→21

Refinement top

Refinement on F²	907 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.062	H-atom parameters constrained
wR(F²) = 0.171	w = 1/[σ²(F_o²) + (0.0915P)² + 70.0229P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
9966 reflections	Δρ_max = 3.47 e Å⁻³
759 parameters	Δρ_min = −1.94 e Å⁻³

Special details top

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. Single-crystal X-ray diffraction data were collected on a Bruker D8 VENTURE diffractometer equipped with Mo Kα high brilliance IµS radiation X-ray tube (λ = 0.71073 Å), a multilayer X-ray mirror, a PHOTON 100 CMOS detector, and an Oxford Cryo Systems low-temperature device. The diffractometer was controlled using the SAINT program as implemented in the APEX2 software package (Bruker, 2009). Due to assumed nonmerohedral twinning, the unit-cell dimensions and orientation matrices were determined with CELL_NOW (Sheldrick, 2008), while absorption correction and generation of detwinned and summed intensity data files was done with TWINABS (Sheldrick, 2012). The structure was solved using OLEX2 (Dolomanov et al., 2009), with the SHELXT solution program (Sheldrick, 2015a) using direct methods and refined with the SHELXL refinement package (Sheldrick, 2015b) using least-squares minimization. Non-H atoms were refined anisotropically.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Eu11	0.79742 (5)	0.47249 (3)	0.69238 (3)	0.01010 (14)
Eu12	0.84781 (5)	0.02635 (3)	0.30758 (3)	0.00938 (14)
Eu2	0.32106 (5)	0.22322 (3)	0.46627 (3)	0.01105 (14)
Cl1	0.9991 (3)	0.74890 (15)	1.00401 (15)	0.0202 (5)
Na1	1.6602 (5)	0.9919 (3)	0.9788 (3)	0.0299 (10)
O1	0.6079 (8)	0.4136 (4)	0.6034 (4)	0.0178 (11)
O6	0.6621 (8)	0.0769 (4)	0.3858 (4)	0.0149 (10)
O10	0.9227 (8)	0.0456 (4)	0.4521 (4)	0.0161 (11)
H10A	0.975157	0.090150	0.461149	0.024*
H10B	0.848062	0.032416	0.474068	0.024*
O17	0.5748 (8)	0.6765 (4)	0.6087 (4)	0.0180 (14)
O3	1.0388 (7)	0.5314 (4)	0.6939 (4)	0.0179 (11)
O13	0.5500 (8)	0.1824 (4)	0.4334 (4)	0.0181 (14)
O8	1.0872 (7)	−0.0175 (4)	0.3180 (4)	0.0160 (10)
O2	0.7419 (7)	0.5959 (4)	0.6441 (4)	0.0156 (10)
O16	0.6074 (8)	−0.1523 (4)	0.4220 (5)	0.0229 (15)
O5	0.8743 (7)	0.4692 (4)	0.5533 (4)	0.0206 (12)
H5A	0.834349	0.428059	0.526160	0.031*
H5B	0.839985	0.508119	0.532689	0.031*
O23	1.2154 (9)	−0.1264 (5)	0.3115 (5)	0.0290 (17)
O19	1.3451 (8)	0.4995 (4)	0.9807 (5)	0.0236 (17)
O7	0.9778 (8)	0.1515 (4)	0.3457 (4)	0.0188 (11)
O20	1.1640 (9)	0.6489 (4)	0.7030 (5)	0.0267 (17)
O15	1.2015 (9)	0.2067 (5)	0.3382 (4)	0.0273 (17)
O9	0.7883 (8)	−0.0926 (4)	0.3662 (4)	0.0181 (11)
O4	0.9058 (8)	0.3514 (4)	0.6569 (5)	0.0264 (12)
O14	0.2917 (9)	0.0788 (5)	0.4154 (6)	0.033 (2)
H14	0.303222	0.058361	0.458846	0.049*
O12	0.1548 (10)	0.3280 (5)	0.4780 (6)	0.036 (2)
H12A	0.066589	0.312759	0.454574	0.055*
H12B	0.183319	0.369489	0.452303	0.055*
O18	0.0995 (9)	0.1722 (5)	0.5180 (6)	0.035 (2)
H18A	0.115760	0.137601	0.556717	0.053*
H18B	0.047533	0.211552	0.547371	0.053*
O21	0.7727 (11)	0.5443 (6)	0.4069 (6)	0.046 (3)
H21C	0.853930	0.525269	0.416632	0.069*
H21D	0.780492	0.594676	0.416728	0.069*
O22	1.7143 (9)	0.6630 (6)	1.0707 (5)	0.035 (2)
H22C	1.696344	0.711204	1.084205	0.052*
H22D	1.788823	0.666071	1.043679	0.052*
O11	0.4545 (10)	0.3132 (5)	0.5554 (5)	0.035 (2)
O24	1.2940 (10)	0.8451 (6)	1.0655 (6)	0.042 (2)
H24C	1.302028	0.860025	1.011801	0.063*
H24D	1.268319	0.898325	1.104070	0.063*
O25	1.0933 (10)	0.2766 (5)	0.6698 (6)	0.040 (2)
O26	1.5019 (9)	0.7476 (5)	1.0056 (7)	0.041 (2)
H26C	1.452881	0.786514	1.021813	0.061*
H26D	1.550551	0.764171	0.969271	0.061*
O27	1.7152 (10)	0.8301 (7)	0.9338 (5)	0.049 (3)
H27C	1.686663	0.801493	0.874445	0.074*
H27D	1.815642	0.807525	0.939840	0.074*
O29	1.2702 (10)	0.6452 (6)	0.9394 (6)	0.046 (3)
H29C	1.339871	0.672136	0.965652	0.069*
H29D	1.199591	0.675272	0.942475	0.069*
O30	−0.268 (2)	0.3612 (13)	0.4378 (10)	0.023 (6)	0.50 (5)
H30C	−0.326439	0.321937	0.444052	0.034*	0.77 (17)
H30D	−0.215836	0.343515	0.401124	0.034*	0.77 (17)
O30A	−0.224 (2)	0.3319 (13)	0.4523 (11)	0.024 (6)	0.50 (5)
O31	−0.500000	0.000000	0.500000	0.030 (5)	0.5
H31C	−0.443528	0.041239	0.498838	0.045*	0.5
H31D	−0.555484	−0.000789	0.459272	0.045*	0.5
O32	−0.3025 (17)	0.0760 (12)	0.5479 (10)	0.042 (4)	0.55
O33	−0.238 (2)	0.1602 (12)	0.5416 (12)	0.038 (5)	0.45
O34	0.563 (2)	0.4967 (11)	0.4808 (12)	0.056 (7)	0.61 (3)
O35	−0.0687 (11)	0.2677 (6)	0.5283 (6)	0.017 (3)	0.71 (3)
H35A	−0.127689	0.273876	0.490594	0.025*
H35B	−0.120082	0.270766	0.568083	0.025*
N5	0.6455 (9)	0.1087 (5)	0.2392 (5)	0.0131 (10)
N7	0.9221 (9)	−0.0725 (5)	0.1882 (5)	0.0133 (10)
N6	0.9477 (9)	0.1013 (5)	0.1928 (5)	0.0135 (10)
N8	0.6260 (9)	−0.0659 (5)	0.2426 (5)	0.0148 (10)
N1	0.5816 (11)	0.5511 (6)	0.7595 (6)	0.0248 (12)
N4	0.8831 (11)	0.5721 (5)	0.8178 (5)	0.0249 (12)
N2	0.5945 (10)	0.3763 (6)	0.7488 (6)	0.0241 (12)
N3	0.9009 (11)	0.3990 (6)	0.8089 (6)	0.0288 (12)
C1	0.5558 (11)	0.3123 (6)	0.6861 (6)	0.0189 (17)
H1A	0.464745	0.284714	0.696288	0.023*
H1B	0.630550	0.274223	0.683170	0.023*
C2	0.8516 (11)	0.1662 (6)	0.1768 (6)	0.0156 (15)
H2A	0.880254	0.187259	0.129344	0.019*
H2B	0.865714	0.209036	0.219123	0.019*
C3	0.6152 (10)	0.6219 (5)	0.6452 (6)	0.0119 (15)
C4	0.6206 (11)	0.1747 (6)	0.2996 (6)	0.0145 (16)
H4A	0.531766	0.199128	0.286324	0.017*
H4B	0.700467	0.214831	0.302136	0.017*
C5	0.6089 (11)	0.1432 (6)	0.3789 (6)	0.0129 (14)
C6	1.0176 (10)	−0.0317 (6)	0.1361 (6)	0.0143 (15)
H6A	1.023513	−0.065533	0.087380	0.017*
H6B	1.114819	−0.022788	0.160378	0.017*
C7	0.6935 (11)	0.1394 (6)	0.1681 (6)	0.0147 (15)
H7A	0.636813	0.183735	0.157301	0.018*
H7B	0.677673	0.098075	0.124468	0.018*
C8	1.0677 (11)	0.6030 (6)	0.7237 (6)	0.0150 (13)
C9	0.5279 (11)	−0.0256 (6)	0.1909 (6)	0.0156 (15)
H9A	0.434558	−0.055484	0.183618	0.019*
H9B	0.569225	−0.025181	0.140184	0.019*
C10	0.9610 (10)	0.0471 (6)	0.1197 (6)	0.0122 (14)
H10C	1.026407	0.072540	0.086130	0.015*
H10D	0.866529	0.037819	0.092355	0.015*
C11	0.5407 (12)	0.3487 (6)	0.6084 (7)	0.0213 (16)
C12	1.1136 (11)	−0.0888 (6)	0.2894 (6)	0.0174 (14)
C13	0.5054 (11)	0.0595 (6)	0.2245 (6)	0.0154 (16)
H13A	0.443010	0.083833	0.188519	0.018*
H13B	0.456562	0.058792	0.273124	0.018*
C14	0.5489 (11)	−0.0919 (6)	0.3089 (6)	0.0170 (15)
H14A	0.482363	−0.137279	0.290862	0.020*
H14B	0.492269	−0.049280	0.331218	0.020*
C15	0.7963 (11)	−0.1155 (6)	0.1430 (6)	0.0165 (16)
H15A	0.827811	−0.163815	0.114744	0.020*
H15B	0.759344	−0.082555	0.105094	0.020*
C16	1.0876 (12)	0.1684 (6)	0.3088 (6)	0.0176 (13)
C17	0.5057 (12)	0.5831 (7)	0.6942 (7)	0.0234 (18)
H17A	0.439366	0.621962	0.714279	0.028*
H17B	0.449522	0.540407	0.662321	0.028*
C18	0.6769 (11)	−0.1367 (6)	0.1949 (6)	0.0180 (17)
H18C	0.595522	−0.163173	0.162988	0.022*
H18D	0.711526	−0.173714	0.229396	0.022*
C19	0.6559 (12)	−0.1149 (6)	0.3715 (6)	0.0191 (14)
C20	1.0897 (11)	0.1366 (6)	0.2225 (6)	0.0147 (15)
H20A	1.118033	0.179861	0.192724	0.018*
H20B	1.161324	0.096967	0.215753	0.018*
C21	1.0091 (11)	−0.1299 (6)	0.2259 (6)	0.0170 (15)
H21A	1.063316	−0.159569	0.186826	0.020*
H21B	0.944103	−0.167427	0.248125	0.020*
C22	0.9728 (12)	0.6364 (6)	0.7881 (6)	0.0218 (18)
H22A	1.034082	0.664456	0.830557	0.026*
H22B	0.909892	0.674116	0.767999	0.026*
C23	1.0113 (12)	0.3267 (6)	0.6965 (8)	0.0277 (16)
C24	0.6535 (15)	0.6247 (7)	0.8153 (7)	0.0324 (19)
H24A	0.691126	0.664559	0.783904	0.039*
H24B	0.579766	0.648202	0.847267	0.039*
C25	1.0363 (13)	0.3657 (7)	0.7796 (8)	0.033 (2)
H25A	1.068167	0.326699	0.812682	0.039*
H25B	1.112357	0.407951	0.781629	0.039*
C26	0.9864 (16)	0.5250 (8)	0.8709 (8)	0.038 (2)
H26A	1.079411	0.520442	0.847068	0.045*
H26B	1.003635	0.555778	0.921537	0.045*
C27	0.7733 (14)	0.6018 (8)	0.8667 (7)	0.0330 (19)
H27A	0.812168	0.647688	0.901523	0.040*
H27B	0.737946	0.561229	0.897848	0.040*
C28	0.7918 (15)	0.3268 (8)	0.8183 (9)	0.040 (2)
H28A	0.801987	0.285505	0.775556	0.047*
H28B	0.817718	0.305279	0.866359	0.047*
C29	0.6413 (14)	0.3466 (8)	0.8195 (7)	0.034 (2)
H29A	0.580730	0.299552	0.826793	0.041*
H29B	0.629469	0.386480	0.863243	0.041*
C30	0.4554 (15)	0.4254 (8)	0.7638 (8)	0.037 (2)
H30A	0.405451	0.429659	0.713989	0.044*
H30B	0.389876	0.396078	0.794297	0.044*
C31	0.4863 (15)	0.5048 (7)	0.8038 (7)	0.033 (2)
H31A	0.396187	0.530873	0.811108	0.039*
H31B	0.531864	0.501265	0.854888	0.039*
C32	0.9271 (16)	0.4458 (8)	0.8817 (8)	0.039 (2)
H32A	0.994972	0.420398	0.913888	0.047*
H32B	0.836883	0.449861	0.908393	0.047*
O35A	−0.165 (3)	0.2420 (15)	0.5379 (15)	0.016 (8)	0.29 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Eu11	0.0097 (2)	0.0051 (2)	0.0145 (3)	0.00058 (17)	0.00180 (18)	−0.00420 (17)
Eu12	0.0116 (2)	0.0053 (2)	0.0111 (2)	0.00149 (17)	0.00497 (18)	−0.00183 (17)
Eu2	0.0128 (3)	0.0075 (2)	0.0118 (3)	−0.00343 (17)	0.00002 (18)	−0.00096 (18)
Cl1	0.0155 (12)	0.0227 (13)	0.0205 (13)	−0.0016 (10)	0.0044 (10)	−0.0054 (10)
Na1	0.023 (2)	0.028 (2)	0.038 (3)	−0.0006 (19)	−0.005 (2)	0.007 (2)
O1	0.019 (2)	0.013 (2)	0.020 (3)	−0.0031 (18)	0.000 (2)	−0.0002 (19)
O6	0.023 (2)	0.011 (2)	0.011 (2)	0.0073 (18)	0.006 (2)	−0.0013 (18)
O10	0.023 (3)	0.013 (3)	0.013 (2)	0.003 (2)	0.0020 (19)	0.0017 (18)
O17	0.018 (3)	0.013 (3)	0.023 (3)	0.000 (2)	0.001 (3)	0.001 (2)
O3	0.015 (2)	0.013 (2)	0.024 (3)	0.0013 (17)	0.0005 (19)	−0.0031 (19)
O13	0.029 (4)	0.010 (3)	0.017 (3)	0.008 (3)	0.011 (3)	0.000 (2)
O8	0.014 (2)	0.014 (2)	0.018 (3)	0.0029 (17)	0.0015 (18)	−0.0031 (19)
O2	0.014 (2)	0.011 (2)	0.021 (3)	0.0013 (17)	0.0031 (18)	−0.002 (2)
O16	0.028 (3)	0.015 (3)	0.026 (3)	−0.005 (3)	0.009 (3)	0.004 (2)
O5	0.016 (3)	0.018 (3)	0.025 (3)	0.000 (2)	0.004 (2)	−0.0098 (19)
O23	0.022 (3)	0.022 (3)	0.042 (4)	0.011 (3)	−0.001 (3)	0.001 (3)
O19	0.025 (4)	0.014 (4)	0.035 (5)	0.001 (3)	0.020 (3)	0.005 (3)
O7	0.030 (2)	0.008 (2)	0.017 (2)	−0.0041 (19)	0.003 (2)	−0.0015 (19)
O20	0.028 (3)	0.017 (3)	0.034 (4)	−0.004 (2)	0.007 (3)	0.001 (3)
O15	0.036 (3)	0.025 (4)	0.018 (3)	−0.017 (3)	−0.008 (3)	0.003 (3)
O9	0.021 (2)	0.009 (2)	0.025 (3)	0.0004 (17)	0.0081 (18)	0.002 (2)
O4	0.023 (2)	0.011 (2)	0.043 (3)	0.006 (2)	0.000 (2)	−0.008 (2)
O14	0.032 (5)	0.014 (4)	0.048 (6)	−0.004 (3)	−0.019 (4)	−0.005 (4)
O12	0.031 (5)	0.032 (5)	0.053 (6)	0.018 (4)	0.025 (4)	0.020 (4)
O18	0.027 (4)	0.018 (4)	0.064 (6)	−0.003 (3)	0.014 (4)	0.017 (4)
O21	0.053 (6)	0.025 (5)	0.053 (6)	0.002 (4)	0.003 (5)	−0.021 (5)
O22	0.025 (5)	0.048 (6)	0.031 (5)	0.000 (4)	0.011 (4)	0.004 (4)
O11	0.047 (4)	0.019 (4)	0.035 (3)	−0.009 (3)	−0.019 (3)	−0.001 (3)
O24	0.031 (5)	0.051 (6)	0.040 (6)	−0.008 (4)	0.015 (4)	−0.014 (5)
O25	0.038 (4)	0.022 (4)	0.062 (5)	0.017 (3)	0.005 (4)	−0.001 (3)
O26	0.019 (4)	0.027 (5)	0.077 (8)	0.002 (4)	0.007 (4)	0.012 (5)
O27	0.025 (5)	0.100 (9)	0.026 (5)	0.003 (5)	0.010 (4)	0.016 (5)
O29	0.025 (5)	0.051 (6)	0.056 (7)	0.014 (4)	−0.013 (4)	−0.016 (5)
O30	0.023 (7)	0.024 (7)	0.022 (7)	0.001 (2)	0.001 (2)	0.002 (2)
O30A	0.024 (7)	0.024 (7)	0.024 (7)	0.001 (2)	0.002 (2)	0.002 (2)
O31	0.031 (6)	0.031 (6)	0.030 (6)	0.004 (2)	0.003 (2)	0.004 (2)
O32	0.025 (7)	0.068 (8)	0.032 (7)	0.000 (6)	0.009 (6)	−0.002 (6)
O33	0.037 (6)	0.040 (6)	0.038 (6)	0.007 (5)	0.006 (5)	0.002 (5)
O34	0.055 (12)	0.048 (12)	0.067 (14)	0.014 (9)	0.027 (9)	0.005 (9)
O35	0.018 (4)	0.015 (4)	0.016 (4)	0.0004 (19)	0.0058 (18)	0.0001 (19)
N5	0.019 (2)	0.009 (2)	0.012 (2)	0.0025 (18)	0.0055 (18)	−0.0019 (18)
N7	0.013 (2)	0.009 (2)	0.017 (2)	0.0005 (18)	0.0049 (16)	−0.0053 (18)
N6	0.014 (2)	0.011 (2)	0.015 (2)	−0.0023 (17)	0.0020 (17)	−0.0011 (17)
N8	0.016 (2)	0.007 (2)	0.021 (2)	−0.0002 (18)	0.0075 (18)	−0.0032 (18)
N1	0.030 (2)	0.024 (3)	0.024 (3)	0.013 (2)	0.014 (2)	0.0038 (19)
N4	0.035 (3)	0.020 (2)	0.017 (3)	−0.010 (2)	0.0033 (19)	−0.009 (2)
N2	0.027 (2)	0.021 (2)	0.022 (2)	−0.009 (2)	0.003 (2)	−0.001 (2)
N3	0.028 (3)	0.026 (3)	0.034 (3)	0.009 (2)	−0.003 (2)	0.011 (2)
C1	0.017 (5)	0.015 (3)	0.023 (3)	−0.006 (3)	−0.002 (2)	0.002 (2)
C2	0.018 (3)	0.013 (3)	0.016 (4)	0.001 (2)	0.005 (2)	0.002 (3)
C3	0.014 (2)	0.008 (3)	0.012 (4)	0.000 (2)	0.002 (2)	−0.006 (2)
C4	0.020 (4)	0.010 (3)	0.013 (2)	0.006 (3)	0.004 (2)	−0.0015 (18)
C5	0.017 (3)	0.009 (2)	0.013 (2)	0.003 (2)	0.003 (2)	−0.003 (2)
C6	0.012 (3)	0.016 (3)	0.015 (4)	−0.001 (2)	0.002 (3)	−0.003 (2)
C7	0.017 (3)	0.014 (4)	0.013 (3)	0.002 (3)	0.005 (2)	0.001 (3)
C8	0.018 (2)	0.012 (2)	0.014 (3)	0.0013 (19)	−0.005 (2)	0.001 (2)
C9	0.015 (3)	0.010 (3)	0.022 (3)	−0.001 (2)	0.009 (3)	−0.001 (2)
C10	0.006 (4)	0.016 (3)	0.014 (3)	−0.003 (2)	0.004 (3)	−0.0013 (19)
C11	0.025 (3)	0.015 (3)	0.022 (3)	−0.006 (2)	−0.003 (2)	0.001 (2)
C12	0.016 (2)	0.014 (2)	0.022 (3)	0.0049 (19)	0.005 (2)	−0.001 (2)
C13	0.017 (3)	0.011 (3)	0.018 (4)	0.0023 (19)	0.006 (3)	−0.001 (2)
C14	0.021 (3)	0.009 (4)	0.020 (3)	−0.001 (3)	0.008 (2)	−0.003 (3)
C15	0.015 (3)	0.014 (4)	0.019 (3)	−0.002 (2)	0.0052 (19)	−0.008 (3)
C16	0.025 (2)	0.011 (2)	0.015 (3)	−0.006 (2)	−0.0016 (19)	0.000 (2)
C17	0.022 (3)	0.021 (5)	0.031 (3)	0.007 (3)	0.014 (2)	0.008 (3)
C18	0.017 (3)	0.008 (3)	0.027 (4)	−0.002 (2)	0.009 (3)	−0.007 (3)
C19	0.022 (2)	0.011 (3)	0.025 (3)	−0.001 (2)	0.009 (2)	0.002 (3)
C20	0.017 (3)	0.011 (4)	0.016 (3)	−0.005 (2)	−0.001 (2)	0.000 (2)
C21	0.018 (3)	0.011 (3)	0.022 (3)	0.005 (2)	0.006 (3)	−0.003 (2)
C22	0.024 (4)	0.016 (3)	0.021 (4)	−0.007 (3)	0.001 (3)	−0.010 (2)
C23	0.022 (3)	0.010 (3)	0.050 (3)	0.003 (2)	0.000 (3)	−0.001 (3)
C24	0.048 (4)	0.027 (4)	0.023 (4)	0.007 (3)	0.018 (3)	−0.001 (3)
C25	0.028 (3)	0.021 (5)	0.049 (4)	0.005 (3)	−0.004 (3)	0.000 (3)
C26	0.048 (5)	0.039 (4)	0.025 (5)	0.000 (3)	0.000 (4)	0.001 (3)
C27	0.045 (4)	0.027 (5)	0.026 (4)	−0.003 (3)	0.013 (2)	−0.002 (3)
C28	0.043 (3)	0.035 (4)	0.043 (7)	0.000 (3)	0.003 (3)	0.017 (4)
C29	0.040 (3)	0.036 (6)	0.026 (3)	−0.009 (3)	−0.004 (3)	0.003 (3)
C30	0.037 (4)	0.035 (3)	0.039 (6)	0.001 (3)	0.014 (4)	0.000 (3)
C31	0.042 (5)	0.031 (3)	0.026 (5)	0.005 (3)	0.015 (4)	0.006 (3)
C32	0.043 (6)	0.038 (3)	0.037 (3)	0.007 (3)	0.000 (3)	0.006 (2)
O35A	0.016 (8)	0.017 (8)	0.016 (8)	0.001 (2)	0.000 (2)	0.001 (2)

Geometric parameters (Å, º) top

Eu11—O1	2.377 (7)	N7—C6	1.482 (12)
Eu11—O3	2.386 (7)	N7—C15	1.480 (12)
Eu11—O2	2.408 (7)	N7—C21	1.484 (13)
Eu11—O5	2.529 (7)	N6—C2	1.493 (13)
Eu11—O4	2.364 (7)	N6—C10	1.490 (12)
Eu11—N1	2.690 (9)	N6—C20	1.458 (12)
Eu11—N4	2.657 (9)	N8—C9	1.490 (14)
Eu11—N2	2.695 (9)	N8—C14	1.469 (13)
Eu11—N3	2.653 (10)	N8—C18	1.488 (12)
Eu11—C8	3.223 (10)	N1—C17	1.473 (15)
Eu11—C11	3.254 (10)	N1—C24	1.583 (16)
Eu11—C23	3.251 (11)	N1—C31	1.445 (15)
Eu12—O6	2.365 (7)	N4—C22	1.480 (14)
Eu12—O10	2.542 (7)	N4—C26	1.600 (17)
Eu12—O8	2.376 (7)	N4—C27	1.424 (16)
Eu12—O7	2.387 (7)	N2—C1	1.463 (14)
Eu12—O9	2.399 (7)	N2—C29	1.431 (16)
Eu12—N5	2.702 (8)	N2—C30	1.583 (16)
Eu12—N7	2.647 (8)	N3—C25	1.484 (16)
Eu12—N6	2.639 (8)	N3—C28	1.566 (16)
Eu12—N8	2.635 (8)	N3—C32	1.415 (17)
Eu12—C12	3.224 (10)	C1—H1A	0.9700
Eu12—C16	3.172 (10)	C1—H1B	0.9700
Eu12—C19	3.217 (10)	C1—C11	1.542 (15)
Eu2—O17ⁱ	2.427 (7)	C2—H2A	0.9700
Eu2—O13	2.333 (7)	C2—H2B	0.9700
Eu2—O16ⁱⁱ	2.470 (8)	C2—C7	1.499 (14)
Eu2—O15ⁱⁱⁱ	2.411 (8)	C3—C17	1.512 (14)
Eu2—O14	2.501 (8)	C4—H4A	0.9700
Eu2—H14	2.7762	C4—H4B	0.9700
Eu2—O12	2.409 (8)	C4—C5	1.530 (14)
Eu2—O18	2.418 (8)	C6—H6A	0.9700
Eu2—O11	2.306 (8)	C6—H6B	0.9700
Na1—Na1^iv	3.096 (9)	C6—C10	1.513 (14)
Na1—O24^iv	2.958 (11)	C7—H7A	0.9700
Na1—O27	2.845 (13)	C7—H7B	0.9700
O1—C11	1.245 (12)	C8—C22	1.523 (15)
O6—C5	1.267 (12)	C9—H9A	0.9700
O10—H10A	0.8683	C9—H9B	0.9700
O10—H10B	0.8314	C9—C13	1.523 (13)
O17—C3	1.241 (12)	C10—H10C	0.9700
O3—C8	1.272 (12)	C10—H10D	0.9700
O13—C5	1.251 (12)	C12—C21	1.510 (15)
O8—C12	1.294 (12)	C13—H13A	0.9700
O2—C3	1.273 (12)	C13—H13B	0.9700
O16—C19	1.219 (13)	C14—H14A	0.9700
O5—H5A	0.8510	C14—H14B	0.9700
O5—H5B	0.8534	C14—C19	1.531 (15)
O23—C12	1.235 (13)	C15—H15A	0.9700
O7—C16	1.256 (13)	C15—H15B	0.9700
O20—C8	1.238 (13)	C15—C18	1.502 (14)
O15—C16	1.260 (13)	C16—C20	1.529 (14)
O9—C19	1.268 (13)	C17—H17A	0.9700
O4—C23	1.283 (14)	C17—H17B	0.9700
O14—H14	0.8656	C18—H18C	0.9700
O12—H12A	0.9045	C18—H18D	0.9700
O12—H12B	0.9033	C20—H20A	0.9700
O18—H18A	0.9493	C20—H20B	0.9700
O18—H18B	0.9559	C21—H21A	0.9700
O21—H21C	0.8498	C21—H21B	0.9700
O21—H21D	0.8502	C22—H22A	0.9700
O22—H22C	0.8507	C22—H22B	0.9700
O22—H22D	0.8492	C23—C25	1.514 (18)
O11—C11	1.261 (13)	C24—H24A	0.9700
O24—H24C	0.9935	C24—H24B	0.9700
O24—H24D	1.1032	C24—C27	1.484 (19)
O25—C23	1.233 (14)	C25—H25A	0.9700
O26—H26C	0.8497	C25—H25B	0.9700
O26—H26D	0.8495	C26—H26A	0.9700
O27—H27C	1.0984	C26—H26B	0.9700
O27—H27D	1.0274	C26—C32	1.455 (19)
O29—H29C	0.8501	C27—H27A	0.9700
O29—H29D	0.8493	C27—H27B	0.9700
O30—H30C	0.8500	C28—H28A	0.9700
O30—H30D	0.8504	C28—H28B	0.9700
O31—H31C^v	0.8498	C28—C29	1.448 (19)
O31—H31C	0.8499	C29—H29A	0.9700
O31—H31D^v	0.8510 (10)	C29—H29B	0.9700
O31—H31D	0.8510	C30—H30A	0.9700
O32—O33	1.53 (3)	C30—H30B	0.9700
O33—O35A	1.51 (3)	C30—C31	1.449 (18)
O34—O34ⁱ	1.36 (3)	C31—H31A	0.9700
O35—H35A	0.8506	C31—H31B	0.9700
O35—H35B	0.8497	C32—H32A	0.9700
N5—C4	1.477 (12)	C32—H32B	0.9700
N5—C7	1.461 (12)	O35A—H35A	1.0868
N5—C13	1.494 (13)	O35A—H35B	0.7653

O1—Eu11—O3	140.7 (2)	C2—N6—Eu12	110.1 (6)
O1—Eu11—O2	85.6 (2)	C10—N6—Eu12	112.8 (5)
O1—Eu11—O5	69.2 (2)	C10—N6—C2	109.4 (8)
O1—Eu11—N1	83.7 (3)	C20—N6—Eu12	104.7 (6)
O1—Eu11—N4	149.5 (3)	C20—N6—C2	108.9 (7)
O1—Eu11—N2	63.0 (3)	C20—N6—C10	110.7 (7)
O1—Eu11—N3	122.3 (3)	C9—N8—Eu12	114.0 (5)
O1—Eu11—C8	146.6 (2)	C14—N8—Eu12	104.2 (6)
O1—Eu11—C11	18.3 (3)	C14—N8—C9	111.1 (8)
O1—Eu11—C23	101.3 (3)	C14—N8—C18	109.3 (8)
O3—Eu11—O2	81.5 (2)	C18—N8—Eu12	110.9 (6)
O3—Eu11—O5	71.5 (2)	C18—N8—C9	107.2 (8)
O3—Eu11—N1	121.6 (3)	C17—N1—Eu11	104.0 (6)
O3—Eu11—N4	63.8 (3)	C17—N1—C24	107.2 (9)
O3—Eu11—N2	151.4 (3)	C24—N1—Eu11	107.6 (7)
O3—Eu11—N3	84.2 (3)	C31—N1—Eu11	115.3 (7)
O3—Eu11—C8	19.9 (2)	C31—N1—C17	113.3 (10)
O3—Eu11—C11	149.7 (3)	C31—N1—C24	108.9 (9)
O3—Eu11—C23	74.1 (3)	C22—N4—Eu11	105.2 (6)
O2—Eu11—O5	71.2 (2)	C22—N4—C26	108.2 (9)
O2—Eu11—N1	63.2 (3)	C26—N4—Eu11	107.0 (7)
O2—Eu11—N4	81.0 (3)	C27—N4—Eu11	117.3 (7)
O2—Eu11—N2	122.7 (3)	C27—N4—C22	112.6 (9)
O2—Eu11—N3	148.1 (3)	C27—N4—C26	106.3 (9)
O2—Eu11—C8	68.6 (2)	C1—N2—Eu11	105.9 (6)
O2—Eu11—C11	102.6 (3)	C1—N2—C30	107.8 (9)
O2—Eu11—C23	149.0 (3)	C29—N2—Eu11	113.5 (7)
O5—Eu11—N1	128.2 (3)	C29—N2—C1	112.2 (9)
O5—Eu11—N4	130.1 (3)	C29—N2—C30	109.4 (10)
O5—Eu11—N2	127.6 (3)	C30—N2—Eu11	107.7 (7)
O5—Eu11—N3	130.0 (3)	C25—N3—Eu11	104.2 (7)
O5—Eu11—C8	82.3 (2)	C25—N3—C28	107.1 (9)
O5—Eu11—C11	81.3 (3)	C28—N3—Eu11	107.6 (7)
O5—Eu11—C23	82.9 (3)	C32—N3—Eu11	116.5 (8)
O4—Eu11—O1	82.9 (3)	C32—N3—C25	111.5 (10)
O4—Eu11—O3	85.0 (3)	C32—N3—C28	109.5 (11)
O4—Eu11—O2	142.1 (3)	N2—C1—H1A	109.9
O4—Eu11—O5	70.9 (3)	N2—C1—H1B	109.9
O4—Eu11—N1	149.6 (3)	N2—C1—C11	108.8 (8)
O4—Eu11—N4	123.5 (3)	H1A—C1—H1B	108.3
O4—Eu11—N2	83.1 (3)	C11—C1—H1A	109.9
O4—Eu11—N3	63.8 (3)	C11—C1—H1B	109.9
O4—Eu11—C8	104.4 (3)	N6—C2—H2A	108.9
O4—Eu11—C11	73.4 (3)	N6—C2—H2B	108.9
O4—Eu11—C23	19.2 (3)	N6—C2—C7	113.3 (8)
N1—Eu11—N2	66.6 (3)	H2A—C2—H2B	107.7
N1—Eu11—C8	101.8 (3)	C7—C2—H2A	108.9
N1—Eu11—C11	85.7 (3)	C7—C2—H2B	108.9
N1—Eu11—C23	147.1 (3)	O17—C3—O2	124.7 (9)
N4—Eu11—N1	65.9 (3)	O17—C3—C17	117.7 (9)
N4—Eu11—N2	102.2 (3)	O2—C3—C17	117.6 (9)
N4—Eu11—C8	48.6 (3)	N5—C4—H4A	109.7
N4—Eu11—C11	146.3 (3)	N5—C4—H4B	109.7
N4—Eu11—C23	104.3 (3)	N5—C4—C5	109.9 (8)
N2—Eu11—C8	149.3 (3)	H4A—C4—H4B	108.2
N2—Eu11—C11	47.4 (3)	C5—C4—H4A	109.7
N2—Eu11—C23	86.6 (3)	C5—C4—H4B	109.7
N3—Eu11—N1	101.8 (3)	O6—C5—Eu12	37.7 (4)
N3—Eu11—N4	67.1 (3)	O6—C5—C4	116.5 (8)
N3—Eu11—N2	67.2 (3)	O13—C5—Eu12	153.7 (7)
N3—Eu11—C8	89.2 (3)	O13—C5—O6	123.0 (9)
N3—Eu11—C11	104.1 (3)	O13—C5—C4	120.5 (8)
N3—Eu11—C23	48.0 (3)	C4—C5—Eu12	81.6 (5)
C8—Eu11—C11	163.3 (3)	N7—C6—H6A	109.4
C8—Eu11—C23	91.7 (3)	N7—C6—H6B	109.4
C23—Eu11—C11	89.7 (3)	N7—C6—C10	111.3 (8)
O6—Eu12—O10	67.3 (2)	H6A—C6—H6B	108.0
O6—Eu12—O8	141.1 (2)	C10—C6—H6A	109.4
O6—Eu12—O7	86.0 (2)	C10—C6—H6B	109.4
O6—Eu12—O9	82.7 (2)	N5—C7—C2	110.5 (8)
O6—Eu12—N5	62.6 (2)	N5—C7—H7A	109.5
O6—Eu12—N7	148.3 (2)	N5—C7—H7B	109.5
O6—Eu12—N6	121.8 (2)	C2—C7—H7A	109.5
O6—Eu12—N8	81.0 (2)	C2—C7—H7B	109.5
O6—Eu12—C12	147.7 (3)	H7A—C7—H7B	108.1
O6—Eu12—C16	105.9 (3)	O3—C8—Eu11	39.6 (5)
O6—Eu12—C19	68.7 (2)	O3—C8—C22	117.7 (9)
O10—Eu12—N5	124.8 (2)	O20—C8—Eu11	153.7 (7)
O10—Eu12—N7	133.6 (2)	O20—C8—O3	125.4 (10)
O10—Eu12—N6	129.7 (2)	O20—C8—C22	116.9 (9)
O10—Eu12—N8	125.7 (2)	C22—C8—Eu11	81.8 (6)
O10—Eu12—C12	85.8 (2)	N8—C9—H9A	109.2
O10—Eu12—C16	80.5 (2)	N8—C9—H9B	109.2
O10—Eu12—C19	78.3 (3)	N8—C9—C13	112.0 (8)
O8—Eu12—O10	73.8 (2)	H9A—C9—H9B	107.9
O8—Eu12—O7	80.7 (2)	C13—C9—H9A	109.2
O8—Eu12—O9	82.6 (2)	C13—C9—H9B	109.2
O8—Eu12—N5	151.2 (2)	N6—C10—C6	111.7 (8)
O8—Eu12—N7	64.8 (2)	N6—C10—H10C	109.3
O8—Eu12—N6	84.5 (2)	N6—C10—H10D	109.3
O8—Eu12—N8	122.8 (2)	C6—C10—H10C	109.3
O8—Eu12—C12	20.3 (2)	C6—C10—H10D	109.3
O8—Eu12—C16	68.0 (3)	H10C—C10—H10D	107.9
O8—Eu12—C19	102.5 (3)	O1—C11—Eu11	36.8 (5)
O7—Eu12—O10	67.7 (2)	O1—C11—O11	124.0 (10)
O7—Eu12—O9	136.9 (3)	O1—C11—C1	117.8 (9)
O7—Eu12—N5	86.8 (2)	O11—C11—Eu11	159.5 (8)
O7—Eu12—N7	122.1 (2)	O11—C11—C1	118.0 (9)
O7—Eu12—N6	64.2 (2)	C1—C11—Eu11	82.0 (5)
O7—Eu12—N8	154.1 (3)	O8—C12—Eu12	39.7 (4)
O7—Eu12—C12	100.5 (3)	O8—C12—C21	117.3 (9)
O7—Eu12—C16	20.5 (3)	O23—C12—Eu12	156.5 (8)
O7—Eu12—C19	143.6 (3)	O23—C12—O8	124.9 (10)
O9—Eu12—O10	69.6 (2)	O23—C12—C21	117.8 (9)
O9—Eu12—N5	122.9 (2)	C21—C12—Eu12	80.1 (5)
O9—Eu12—N7	84.7 (2)	N5—C13—C9	112.2 (8)
O9—Eu12—N6	152.0 (2)	N5—C13—H13A	109.2
O9—Eu12—N8	63.4 (3)	N5—C13—H13B	109.2
O9—Eu12—C12	71.0 (2)	C9—C13—H13A	109.2
O9—Eu12—C16	142.9 (3)	C9—C13—H13B	109.2
O9—Eu12—C19	20.1 (3)	H13A—C13—H13B	107.9
N5—Eu12—C12	148.6 (3)	N8—C14—H14A	109.4
N5—Eu12—C16	92.0 (3)	N8—C14—H14B	109.4
N5—Eu12—C19	102.9 (3)	N8—C14—C19	111.0 (8)
N7—Eu12—N5	101.6 (2)	H14A—C14—H14B	108.0
N7—Eu12—C12	48.8 (3)	C19—C14—H14A	109.4
N7—Eu12—C16	101.6 (3)	C19—C14—H14B	109.4
N7—Eu12—C19	90.6 (3)	N7—C15—H15A	109.3
N6—Eu12—N5	66.7 (2)	N7—C15—H15B	109.3
N6—Eu12—N7	67.3 (2)	N7—C15—C18	111.6 (8)
N6—Eu12—C12	88.9 (3)	H15A—C15—H15B	108.0
N6—Eu12—C16	49.2 (3)	C18—C15—H15A	109.3
N6—Eu12—C19	151.7 (3)	C18—C15—H15B	109.3
N8—Eu12—N5	67.3 (2)	O7—C16—Eu12	41.8 (5)
N8—Eu12—N7	67.4 (2)	O7—C16—O15	125.0 (10)
N8—Eu12—N6	104.4 (3)	O7—C16—C20	118.7 (9)
N8—Eu12—C12	102.5 (3)	O15—C16—Eu12	150.7 (7)
N8—Eu12—C16	152.6 (3)	O15—C16—C20	116.2 (9)
N8—Eu12—C19	48.7 (3)	C20—C16—Eu12	82.0 (5)
C16—Eu12—C12	85.8 (3)	N1—C17—C3	109.8 (9)
C16—Eu12—C19	158.5 (3)	N1—C17—H17A	109.7
C19—Eu12—C12	89.2 (3)	N1—C17—H17B	109.7
O17ⁱ—Eu2—O16ⁱⁱ	138.4 (2)	C3—C17—H17A	109.7
O17ⁱ—Eu2—O14	122.7 (3)	C3—C17—H17B	109.7
O17ⁱ—Eu2—H14	137.2	H17A—C17—H17B	108.2
O13—Eu2—O17ⁱ	73.9 (2)	N8—C18—C15	112.7 (8)
O13—Eu2—O16ⁱⁱ	77.8 (2)	N8—C18—H18C	109.1
O13—Eu2—O15ⁱⁱⁱ	99.3 (3)	N8—C18—H18D	109.1
O13—Eu2—O14	72.5 (3)	C15—C18—H18C	109.1
O13—Eu2—H14	73.8	C15—C18—H18D	109.1
O13—Eu2—O12	148.3 (3)	H18C—C18—H18D	107.8
O13—Eu2—O18	139.9 (3)	O16—C19—Eu12	154.5 (8)
O16ⁱⁱ—Eu2—O14	75.1 (3)	O16—C19—O9	125.8 (11)
O16ⁱⁱ—Eu2—H14	57.4	O16—C19—C14	117.8 (9)
O15ⁱⁱⁱ—Eu2—O17ⁱ	71.5 (2)	O9—C19—Eu12	40.5 (5)
O15ⁱⁱⁱ—Eu2—O16ⁱⁱ	143.9 (3)	O9—C19—C14	116.4 (9)
O15ⁱⁱⁱ—Eu2—O14	69.9 (3)	C14—C19—Eu12	80.1 (5)
O15ⁱⁱⁱ—Eu2—H14	86.9	N6—C20—C16	111.3 (8)
O15ⁱⁱⁱ—Eu2—O18	89.0 (3)	N6—C20—H20A	109.4
O14—Eu2—H14	17.9	N6—C20—H20B	109.4
O12—Eu2—O17ⁱ	75.6 (3)	C16—C20—H20A	109.4
O12—Eu2—O16ⁱⁱ	122.1 (3)	C16—C20—H20B	109.4
O12—Eu2—O15ⁱⁱⁱ	78.6 (3)	H20A—C20—H20B	108.0
O12—Eu2—O14	133.1 (3)	N7—C21—C12	112.0 (8)
O12—Eu2—H14	136.8	N7—C21—H21A	109.2
O12—Eu2—O18	71.7 (3)	N7—C21—H21B	109.2
O18—Eu2—O17ⁱ	144.6 (3)	C12—C21—H21A	109.2
O18—Eu2—O16ⁱⁱ	73.0 (3)	C12—C21—H21B	109.2
O18—Eu2—O14	73.9 (3)	H21A—C21—H21B	107.9
O18—Eu2—H14	67.6	N4—C22—C8	111.1 (8)
O11—Eu2—O17ⁱ	74.4 (3)	N4—C22—H22A	109.4
O11—Eu2—O13	83.1 (3)	N4—C22—H22B	109.4
O11—Eu2—O16ⁱⁱ	72.5 (3)	C8—C22—H22A	109.4
O11—Eu2—O15ⁱⁱⁱ	143.5 (3)	C8—C22—H22B	109.4
O11—Eu2—O14	142.7 (3)	H22A—C22—H22B	108.0
O11—Eu2—H14	127.9	O4—C23—Eu11	37.4 (5)
O11—Eu2—O12	80.8 (3)	O4—C23—C25	116.1 (10)
O11—Eu2—O18	112.6 (3)	O25—C23—Eu11	156.3 (10)
O24^iv—Na1—Na1^iv	95.7 (3)	O25—C23—O4	123.8 (12)
O27—Na1—Na1^iv	111.0 (3)	O25—C23—C25	120.1 (11)
O27—Na1—O24^iv	143.2 (3)	C25—C23—Eu11	80.2 (6)
C11—O1—Eu11	124.9 (7)	N1—C24—H24A	109.1
C5—O6—Eu12	123.2 (6)	N1—C24—H24B	109.1
Eu12—O10—H10A	107.5	H24A—C24—H24B	107.9
Eu12—O10—H10B	104.5	C27—C24—N1	112.3 (10)
H10A—O10—H10B	127.3	C27—C24—H24A	109.1
C3—O17—Eu2ⁱ	139.0 (6)	C27—C24—H24B	109.1
C8—O3—Eu11	120.5 (6)	N3—C25—C23	110.6 (10)
C5—O13—Eu2	139.6 (7)	N3—C25—H25A	109.5
C12—O8—Eu12	120.0 (6)	N3—C25—H25B	109.5
C3—O2—Eu11	122.6 (6)	C23—C25—H25A	109.5
C19—O16—Eu2ⁱⁱ	143.0 (7)	C23—C25—H25B	109.5
Eu11—O5—H5A	109.5	H25A—C25—H25B	108.1
Eu11—O5—H5B	109.4	N4—C26—H26A	108.8
H5A—O5—H5B	104.3	N4—C26—H26B	108.8
C16—O7—Eu12	117.7 (6)	H26A—C26—H26B	107.7
C16—O15—Eu2^vi	134.1 (7)	C32—C26—N4	113.7 (11)
C19—O9—Eu12	119.4 (6)	C32—C26—H26A	108.8
C23—O4—Eu11	123.4 (7)	C32—C26—H26B	108.8
Eu2—O14—H14	99.3	N4—C27—C24	107.4 (10)
Eu2—O12—H12A	112.5	N4—C27—H27A	110.2
Eu2—O12—H12B	112.4	N4—C27—H27B	110.2
H12A—O12—H12B	102.2	C24—C27—H27A	110.2
Eu2—O18—H18A	113.4	C24—C27—H27B	110.2
Eu2—O18—H18B	114.4	H27A—C27—H27B	108.5
H18A—O18—H18B	99.6	N3—C28—H28A	108.8
H21C—O21—H21D	109.7	N3—C28—H28B	108.8
H22C—O22—H22D	104.5	H28A—C28—H28B	107.7
C11—O11—Eu2	167.1 (8)	C29—C28—N3	114.0 (11)
Na1^iv—O24—H24C	53.5	C29—C28—H28A	108.8
Na1^iv—O24—H24D	57.6	C29—C28—H28B	108.8
H24C—O24—H24D	108.3	N2—C29—C28	111.6 (11)
H26C—O26—H26D	104.7	N2—C29—H29A	109.3
Na1—O27—H27C	121.3	N2—C29—H29B	109.3
Na1—O27—H27D	123.6	C28—C29—H29A	109.3
H27C—O27—H27D	97.3	C28—C29—H29B	109.3
H29C—O29—H29D	104.6	H29A—C29—H29B	108.0
H30C—O30—H30D	104.4	N2—C30—H30A	108.7
H31C—O31—H31C^v	180.0	N2—C30—H30B	108.7
H31C^v—O31—H31D^v	103.7	H30A—C30—H30B	107.6
H31C—O31—H31D	103.7	C31—C30—N2	114.4 (11)
H31C—O31—H31D^v	76.3	C31—C30—H30A	108.7
H31D—O31—H31C^v	76.3	C31—C30—H30B	108.7
H31D—O31—H31D^v	180.0	N1—C31—C30	110.5 (10)
O35A—O33—O32	176 (2)	N1—C31—H31A	109.5
H35A—O35—H35B	104.5	N1—C31—H31B	109.5
C4—N5—Eu12	103.7 (6)	C30—C31—H31A	109.5
C4—N5—C13	107.0 (7)	C30—C31—H31B	109.5
C7—N5—Eu12	113.2 (6)	H31A—C31—H31B	108.1
C7—N5—C4	110.7 (7)	N3—C32—C26	110.5 (11)
C7—N5—C13	111.4 (8)	N3—C32—H32A	109.6
C13—N5—Eu12	110.5 (6)	N3—C32—H32B	109.6
C6—N7—Eu12	111.7 (5)	C26—C32—H32A	109.6
C6—N7—C21	107.8 (7)	C26—C32—H32B	109.6
C15—N7—Eu12	113.6 (5)	H32A—C32—H32B	108.1
C15—N7—C6	110.5 (8)	O33—O35A—H35A	133.8
C15—N7—C21	109.6 (8)	O33—O35A—H35B	132.4
C21—N7—Eu12	103.2 (6)	H35A—O35A—H35B	91.4

Eu11—O1—C11—O11	−170.0 (9)	O25—C23—C25—N3	−158.8 (11)
Eu11—O1—C11—C1	14.3 (14)	N5—C4—C5—Eu12	34.6 (7)
Eu11—O3—C8—O20	−150.1 (8)	N5—C4—C5—O6	19.9 (12)
Eu11—O3—C8—C22	27.4 (12)	N5—C4—C5—O13	−160.5 (9)
Eu11—O2—C3—O17	−166.1 (7)	N7—C6—C10—N6	58.2 (10)
Eu11—O2—C3—C17	13.6 (12)	N7—C15—C18—N8	56.9 (12)
Eu11—O4—C23—O25	−160.0 (9)	N6—C2—C7—N5	59.8 (11)
Eu11—O4—C23—C25	17.3 (14)	N8—C9—C13—N5	57.5 (11)
Eu11—N1—C17—C3	−47.0 (9)	N8—C14—C19—Eu12	33.5 (6)
Eu11—N1—C24—C27	−48.4 (10)	N8—C14—C19—O16	−165.7 (9)
Eu11—N1—C31—C30	−40.5 (13)	N8—C14—C19—O9	14.9 (12)
Eu11—N4—C22—C8	−39.6 (10)	N1—C24—C27—N4	62.3 (12)
Eu11—N4—C26—C32	−47.2 (12)	N4—C26—C32—N3	58.7 (15)
Eu11—N4—C27—C24	−44.2 (12)	N2—C1—C11—Eu11	33.2 (7)
Eu11—N2—C1—C11	−42.9 (9)	N2—C1—C11—O1	24.6 (14)
Eu11—N2—C29—C28	−39.0 (13)	N2—C1—C11—O11	−151.4 (10)
Eu11—N2—C30—C31	−46.2 (12)	N2—C30—C31—N1	59.5 (15)
Eu11—N3—C25—C23	−44.7 (10)	N3—C28—C29—N2	60.4 (15)
Eu11—N3—C28—C29	−47.8 (13)	C1—N2—C29—C28	81.0 (13)
Eu11—N3—C32—C26	−38.7 (14)	C1—N2—C30—C31	−160.1 (10)
Eu11—C8—C22—N4	30.8 (8)	C2—N6—C10—C6	−162.9 (7)
Eu11—C23—C25—N3	34.4 (8)	C2—N6—C20—C16	79.0 (10)
Eu12—O6—C5—O13	−155.3 (7)	C4—N5—C7—C2	78.5 (10)
Eu12—O6—C5—C4	24.3 (11)	C4—N5—C13—C9	−156.4 (8)
Eu12—O8—C12—O23	−155.6 (9)	C6—N7—C15—C18	−163.2 (8)
Eu12—O8—C12—C21	22.3 (12)	C6—N7—C21—C12	75.0 (10)
Eu12—O7—C16—O15	−144.4 (9)	C7—N5—C4—C5	−165.6 (8)
Eu12—O7—C16—C20	31.6 (12)	C7—N5—C13—C9	82.5 (10)
Eu12—O9—C19—O16	−150.4 (9)	C9—N8—C14—C19	−166.5 (8)
Eu12—O9—C19—C14	29.0 (11)	C9—N8—C18—C15	78.6 (10)
Eu12—N5—C4—C5	−43.9 (8)	C10—N6—C2—C7	75.2 (10)
Eu12—N5—C7—C2	−37.4 (9)	C10—N6—C20—C16	−160.6 (8)
Eu12—N5—C13—C9	−44.2 (9)	C13—N5—C4—C5	72.9 (10)
Eu12—N7—C6—C10	−45.4 (9)	C13—N5—C7—C2	−162.5 (8)
Eu12—N7—C15—C18	−36.6 (10)	C14—N8—C9—C13	77.9 (10)
Eu12—N7—C21—C12	−43.3 (8)	C14—N8—C18—C15	−160.9 (9)
Eu12—N6—C2—C7	−49.3 (9)	C15—N7—C6—C10	82.1 (9)
Eu12—N6—C10—C6	−40.0 (8)	C15—N7—C21—C12	−164.6 (8)
Eu12—N6—C20—C16	−38.7 (9)	C17—N1—C24—C27	−159.8 (9)
Eu12—N8—C9—C13	−39.5 (9)	C17—N1—C31—C30	79.2 (13)
Eu12—N8—C14—C19	−43.2 (8)	C18—N8—C9—C13	−162.7 (8)
Eu12—N8—C18—C15	−46.5 (10)	C18—N8—C14—C19	75.4 (10)
Eu12—C12—C21—N7	33.8 (7)	C20—N6—C2—C7	−163.6 (8)
Eu12—C16—C20—N6	30.5 (7)	C20—N6—C10—C6	77.0 (9)
Eu2ⁱ—O17—C3—O2	−9.8 (16)	C21—N7—C6—C10	−158.1 (8)
Eu2ⁱ—O17—C3—C17	170.4 (7)	C21—N7—C15—C18	78.2 (10)
Eu2—O13—C5—Eu12	−147.8 (10)	C22—N4—C26—C32	−160.0 (11)
Eu2—O13—C5—O6	−112.5 (11)	C22—N4—C27—C24	78.0 (12)
Eu2—O13—C5—C4	67.9 (13)	C24—N1—C17—C3	66.8 (10)
Eu2ⁱⁱ—O16—C19—Eu12	−56 (2)	C24—N1—C31—C30	−161.6 (11)
Eu2ⁱⁱ—O16—C19—O9	−7.6 (19)	C25—N3—C28—C29	−159.4 (11)
Eu2ⁱⁱ—O16—C19—C14	172.9 (7)	C25—N3—C32—C26	80.7 (14)
Eu2^vi—O15—C16—Eu12	−24 (2)	C26—N4—C22—C8	74.4 (11)
Eu2^vi—O15—C16—O7	28.2 (17)	C26—N4—C27—C24	−163.7 (10)
Eu2^vi—O15—C16—C20	−148.0 (8)	C27—N4—C22—C8	−168.5 (10)
Eu2—O11—C11—Eu11	122 (3)	C27—N4—C26—C32	78.9 (13)
Eu2—O11—C11—O1	140 (3)	C28—N3—C25—C23	69.1 (12)
Eu2—O11—C11—C1	−45 (4)	C28—N3—C32—C26	−161.0 (11)
O17—C3—C17—N1	−152.5 (9)	C29—N2—C1—C11	−167.3 (9)
O3—C8—C22—N4	13.5 (14)	C29—N2—C30—C31	77.7 (13)
O8—C12—C21—N7	19.6 (13)	C30—N2—C1—C11	72.2 (11)
O2—C3—C17—N1	27.7 (13)	C30—N2—C29—C28	−159.4 (11)
O23—C12—C21—N7	−162.4 (9)	C31—N1—C17—C3	−173.0 (9)
O7—C16—C20—N6	9.9 (13)	C31—N1—C24—C27	77.3 (12)
O20—C8—C22—N4	−168.7 (9)	C32—N3—C25—C23	−171.2 (10)
O15—C16—C20—N6	−173.7 (9)	C32—N3—C28—C29	79.6 (14)
O4—C23—C25—N3	23.8 (15)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z+1; (iii) x−1, y, z; (iv) −x+3, −y+2, −z+2; (v) −x−1, −y, −z+1; (vi) x+1, y, z.

Eu—O and Eu—N bond lengths (Å) in the 1-H crystal structure top

Eu(III) site	Atom1	Atom2	Distance (Å)
Site 1.1^a	Eu11	N1	2.690 (9)
Site 1.1	Eu11	N2	2.695 (9)
Site 1.1	Eu11	N3	2.653 (10)
Site 1.1	Eu11	N4	2.657 (9)
Site 1.1	Eu11	O1	2.377 (7)
Site 1.1	Eu11	O2	2.408 (7)
Site 1.1	Eu11	O3	2.386 (7)
Site 1.1	Eu11	O4	2.364 (7)
Site 1.1	Eu11	O5^b	2.529 (7)
Site 1.2	Eu12	N5	2.702 (8)
Site 1.2	Eu12	N6	2.639 (8)
Site 1.2	Eu12	N7	2.647 (8)
Site 1.2	Eu12	N8	2.635 (8)
Site 1.2	Eu12	O6	2.365 (7)
Site 1.2	Eu12	O7	2.387 (7)
Site 1.2	Eu12	O8	2.376 (7)
Site 1.2	Eu12	O9	2.399 (7)
Site 1.2	Eu12	O10^b	2.542 (7)
Site 2	Eu2	O11	2.306 (8)
Site 2	Eu2	O12^b	2.409 (8)
Site 2	Eu2	O13	2.333 (7)
Site 2	Eu2	O14^b	2.501 (8)
Site 2	Eu2	O15	2.411 (8)
Site 2	Eu2	O16	2.470 (8)
Site 2	Eu2	O17	2.427 (7)
Site 2	Eu2	O18^b	2.418 (8)

Notes: (a) sites 1.1 and 1.2 refer to the two Eu.DOTA centres in the asymmetric unit; (b) water molecule.

Luminescence lifetimes of Eu^III in a 1-H crystal, 1-H powder and a 1-D crystal at two different positions top

	Temperature (K)	τ₁ (µs)	τ₂ (µs)
1-H	293	88.3	460.3
Powder 1-H	77	267.2	558.5
1-D @Position 1	293	-	880.7
1-D @Position 2	293	559.1	962.2

Luminescence lifetimes of Eu^III in 4N-4O-1O coordination geometries (CN = 9) in deuterated media at 293 K top

Complex	Structure	τ_lm (µs)
[Eu(DOTA)(D₂O)]^- in 1-D	cTSAP	962
[Eu.L(D₂O)]³⁺	cTSAP	769
[Eu(DOTA)(D₂O)]^-	cSAP	2.174
[Eu(DOTAM)(D₂O)]³⁺	cTSAP	2.439

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Crystal structure and optical properties of a two-sited EuIII com­pound: an EuIII ion coordinated by two [EuIII(DOTA)]− com­plexes (DOTA is 1,4,7,10-tetra­azacyclo­dodecane-1,4,7,10-tetra­acetate)

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Crystal structure and optical properties of a two-sited Eu^III compound: an Eu^III ion coordinated by two [Eu^III(DOTA)]⁻ complexes (DOTA is 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetate)