Poly[hexa-aqua-hexa-kis-(μ-pyridine-2,4-dicarboxyl-ato)tricopper(II)dieuropium(III)].

The asymmetric unit of the title heterometallic coordination polymer, [Cu(3)Eu(2)(C(7)H(3)NO(4))(6)(H(2)O)(6)](n), contains one Eu(III) and two Cu(II) atoms, three pyridine-2,4-dicarboxylate (pdc)(2-) anions and three water molecules. One Cu(II) atom is located on an inversion center and is N,O-chelated by two pdc(2-) anions in the equatorial plane and further coordinated by two carboxyl-ate O atoms from another two pdc anions in the axial positions, with an elongated octa-hedral geometry [Cu-O = 2.409 (3) Å in the axial direction]; the other Cu atom is N,O-chelated by two pdc anions in the coordination basal plane and coordinated by a carboxyl O atom at the apical position with a distorted square-pyramidal geometry [Cu-O = 2.359 (3) Å in the apical direction]. The Eu atom is eight-coordinated with a distorted square-anti-prismatic geometry formed by five carboxyl-ate O atoms from five pdc anions and three water mol-ecules. The carboxyl-ate anions bridge adjacent Eu and Cu atoms, forming the coordination polymer. Inter- and intra-molecular O-H⋯O hydrogen bonding occurs in the structure. π-π stacking further consolidates the crystal structure, the centroid-centroid distance between parallel pyridine rings being 3.367 (2) Å.

Related literature

For structures and applications of related heterometallic lanthanide-transition metal coordination polymers, see: Huang et al. (2008a ▶,b ▶). For the coordination modes of the pyridine-2,6-dicarboxyl­ate ligand, see: Ma et al. (2010 ▶); Zhao et al. (2007 ▶); Wang et al. (2007 ▶). For the coordination modes of the pyridine-2,5-dicarboxyl­ate ligand, see: Song et al. (2006 ▶); Wang et al. (2009 ▶). For the coordination modes of the pyridine-2,3-dicarboxyl­ate ligand, see: Wang et al. (2010 ▶).

Experimental

Crystal data

[Cu3Eu2(C7H3NO4)6(H2O)6]

M = 1593.29

Triclinic,

a = 9.4296 (10) Å

b = 10.7002 (11) Å

c = 12.2874 (13) Å

α = 86.186 (2)°

β = 81.556 (2)°

γ = 86.561 (2)°

V = 1222.0 (2) Å3

Z = 1

Mo Kα radiation

μ = 3.92 mm−1

T = 294 K

0.24 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.659, T max = 0.977

12982 measured reflections

5780 independent reflections

4828 reflections with I > 2σ(I)

R int = 0.044

Refinement

R[F 2 > 2σ(F 2)] = 0.028

wR(F 2) = 0.066

S = 0.98

5780 reflections

376 parameters

H-atom parameters constrained

Δρmax = 1.69 e Å−3

Δρmin = −0.94 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 1999 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810044594/xu5066sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810044594/xu5066Isup2.hkl

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

[Cu3Eu2(C7H3NO4)6(H2O)6]	Z = 1
Mr = 1593.29	F(000) = 777
Triclinic, P1	Dx = 2.165 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.4296 (10) Å	Cell parameters from 6583 reflections
b = 10.7002 (11) Å	θ = 2.5–25.0°
c = 12.2874 (13) Å	µ = 3.92 mm−1
α = 86.186 (2)°	T = 294 K
β = 81.556 (2)°	Equant, blue
γ = 86.561 (2)°	0.24 × 0.20 × 0.20 mm
V = 1222.0 (2) Å3

Bruker SMART CCD area-detector diffractometer	5780 independent reflections
Radiation source: fine-focus sealed tube	4828 reflections with I > 2σ(I)
graphite	Rint = 0.044
Detector resolution: 9 pixels mm-1	θmax = 28.3°, θmin = 1.7°
φ and ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Bruker, 2000)	k = −13→13
Tmin = 0.659, Tmax = 0.977	l = −15→16
12982 measured reflections

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.066	H-atom parameters constrained
S = 0.98	w = 1/[σ2(Fo2) + (0.0323P)2] where P = (Fo2 + 2Fc2)/3
5780 reflections	(Δ/σ)max = 0.001
376 parameters	Δρmax = 1.69 e Å−3
0 restraints	Δρmin = −0.94 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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
Eu1	0.42924 (2)	0.65169 (1)	0.35169 (1)	0.0161 (1)
Cu1	−0.04296 (4)	0.81387 (4)	0.11987 (3)	0.0220 (1)
Cu2	0.50000	1.00000	0.00000	0.0188 (2)
O1	0.1188 (3)	0.8879 (2)	0.0288 (2)	0.0274 (8)
O2	0.2474 (3)	1.0583 (2)	0.0150 (2)	0.0272 (8)
O3	0.1716 (3)	1.3256 (3)	0.3467 (2)	0.0406 (10)
O4	−0.0222 (3)	1.2972 (3)	0.4696 (3)	0.0524 (11)
O5	0.2216 (2)	0.2480 (2)	−0.19845 (19)	0.0238 (7)
O6	0.3969 (2)	0.3742 (2)	−0.18098 (19)	0.0236 (8)
O7	0.0882 (3)	0.6635 (2)	0.2196 (2)	0.0313 (8)
O8	0.3149 (3)	0.5865 (2)	0.2057 (2)	0.0258 (8)
O9	0.5336 (3)	1.1177 (2)	−0.13010 (19)	0.0230 (7)
O10	0.5037 (3)	1.1358 (2)	−0.30699 (19)	0.0235 (7)
O11	0.3895 (3)	0.7209 (2)	−0.46529 (19)	0.0254 (8)
O12	0.4790 (3)	0.5533 (2)	−0.3775 (2)	0.0269 (8)
O13	0.6647 (3)	0.6702 (3)	0.4101 (2)	0.0318 (9)
O14	0.2105 (3)	0.7873 (2)	0.3621 (2)	0.0285 (8)
O15	0.2311 (3)	0.5207 (2)	0.4481 (2)	0.0262 (8)
N1	−0.0265 (3)	0.9489 (3)	0.2186 (2)	0.0222 (9)
N2	0.0738 (3)	0.3055 (3)	−0.0108 (2)	0.0190 (8)
N3	0.4749 (3)	0.8802 (3)	−0.1097 (2)	0.0179 (8)
C1	0.0834 (3)	1.0218 (3)	0.1776 (3)	0.0193 (10)
C2	0.1182 (4)	1.1211 (3)	0.2322 (3)	0.0232 (10)
C3	0.0356 (4)	1.1510 (3)	0.3314 (3)	0.0260 (11)
C4	−0.0795 (4)	1.0771 (4)	0.3712 (3)	0.0344 (12)
C5	−0.1064 (4)	0.9764 (4)	0.3138 (3)	0.0314 (12)
C6	0.1590 (4)	0.9878 (3)	0.0650 (3)	0.0213 (10)
C7	0.0646 (4)	1.2678 (4)	0.3881 (3)	0.0282 (12)
C8	−0.0144 (4)	0.3380 (3)	0.0799 (3)	0.0214 (10)
C9	0.0190 (4)	0.4295 (3)	0.1443 (3)	0.0225 (10)
C10	0.1511 (4)	0.4835 (3)	0.1200 (3)	0.0200 (10)
C11	0.2450 (3)	0.4447 (3)	0.0287 (3)	0.0199 (10)
C12	0.2009 (3)	0.3591 (3)	−0.0364 (3)	0.0177 (9)
C13	0.2824 (3)	0.3236 (3)	−0.1467 (3)	0.0187 (10)
C14	0.1878 (4)	0.5861 (3)	0.1875 (3)	0.0209 (10)
C15	0.4789 (3)	0.9361 (3)	−0.2116 (3)	0.0177 (9)
C16	0.4629 (4)	0.8712 (3)	−0.3016 (3)	0.0195 (10)
C17	0.4471 (4)	0.7427 (3)	−0.2868 (3)	0.0193 (10)
C18	0.4458 (4)	0.6855 (3)	−0.1819 (3)	0.0248 (10)
C19	0.4564 (4)	0.7580 (3)	−0.0948 (3)	0.0233 (10)
C20	0.5063 (3)	1.0751 (3)	−0.2176 (3)	0.0178 (9)
C21	0.4380 (4)	0.6657 (3)	−0.3837 (3)	0.0195 (10)
H2A	0.19630	1.16800	0.20320	0.0280*
H4A	−0.13820	1.09550	0.43650	0.0410*
H5A	−0.18220	0.92660	0.34220	0.0380*
H8A	−0.10000	0.29790	0.09970	0.0260*
H9A	−0.04660	0.45500	0.20380	0.0270*
H11A	0.33600	0.47600	0.01220	0.0240*
H13A	0.71830	0.70010	0.35740	0.0480*
H13B	0.70360	0.60960	0.44030	0.0480*
H14A	0.16690	0.76300	0.31500	0.0430*
H14B	0.15520	0.77690	0.41960	0.0430*
H15A	0.19680	0.46590	0.41800	0.0390*
H15B	0.15630	0.55220	0.48000	0.0390*
H16A	0.46260	0.91230	−0.37070	0.0230*
H18A	0.43800	0.59920	−0.17040	0.0300*
H19A	0.45030	0.72020	−0.02400	0.0280*

	U11	U22	U33	U12	U13	U23
Eu1	0.0202 (1)	0.0122 (1)	0.0166 (1)	−0.0010 (1)	−0.0040 (1)	−0.0033 (1)
Cu1	0.0214 (2)	0.0212 (2)	0.0238 (2)	−0.0061 (2)	0.0003 (2)	−0.0088 (2)
Cu2	0.0269 (3)	0.0140 (3)	0.0167 (3)	−0.0032 (2)	−0.0048 (2)	−0.0041 (2)
O1	0.0258 (13)	0.0283 (15)	0.0280 (14)	−0.0073 (11)	0.0036 (11)	−0.0125 (11)
O2	0.0224 (13)	0.0206 (14)	0.0364 (15)	−0.0039 (10)	0.0047 (11)	−0.0022 (11)
O3	0.0470 (18)	0.0376 (17)	0.0378 (16)	−0.0199 (14)	0.0054 (14)	−0.0160 (13)
O4	0.0512 (19)	0.046 (2)	0.057 (2)	−0.0178 (15)	0.0228 (16)	−0.0343 (16)
O5	0.0226 (12)	0.0271 (14)	0.0222 (12)	−0.0056 (10)	−0.0001 (10)	−0.0089 (10)
O6	0.0211 (12)	0.0235 (14)	0.0258 (13)	−0.0055 (10)	0.0027 (10)	−0.0073 (10)
O7	0.0308 (14)	0.0296 (15)	0.0369 (15)	0.0100 (12)	−0.0139 (12)	−0.0169 (12)
O8	0.0222 (13)	0.0320 (15)	0.0250 (13)	−0.0017 (11)	−0.0061 (11)	−0.0095 (11)
O9	0.0349 (14)	0.0140 (12)	0.0215 (12)	−0.0062 (10)	−0.0067 (11)	−0.0016 (10)
O10	0.0352 (14)	0.0145 (12)	0.0207 (12)	−0.0031 (10)	−0.0032 (11)	−0.0002 (10)
O11	0.0367 (14)	0.0211 (13)	0.0190 (12)	0.0028 (11)	−0.0064 (11)	−0.0042 (10)
O12	0.0392 (15)	0.0133 (13)	0.0285 (14)	0.0033 (11)	−0.0062 (12)	−0.0056 (10)
O13	0.0287 (14)	0.0401 (17)	0.0280 (14)	−0.0078 (12)	−0.0103 (11)	0.0068 (12)
O14	0.0282 (14)	0.0287 (15)	0.0301 (14)	0.0032 (11)	−0.0076 (11)	−0.0084 (11)
O15	0.0264 (13)	0.0219 (13)	0.0304 (14)	−0.0060 (10)	0.0002 (11)	−0.0076 (11)
N1	0.0215 (15)	0.0211 (16)	0.0239 (15)	−0.0018 (12)	0.0000 (12)	−0.0070 (12)
N2	0.0182 (14)	0.0165 (14)	0.0220 (15)	0.0014 (11)	−0.0025 (12)	−0.0018 (11)
N3	0.0223 (14)	0.0156 (14)	0.0159 (14)	−0.0019 (11)	−0.0018 (11)	−0.0034 (11)
C1	0.0178 (16)	0.0178 (17)	0.0229 (17)	0.0008 (13)	−0.0037 (14)	−0.0049 (13)
C2	0.0240 (18)	0.0167 (17)	0.0295 (19)	−0.0045 (14)	−0.0036 (15)	−0.0030 (14)
C3	0.0252 (19)	0.024 (2)	0.029 (2)	−0.0025 (15)	−0.0016 (16)	−0.0078 (16)
C4	0.037 (2)	0.034 (2)	0.031 (2)	−0.0092 (18)	0.0076 (17)	−0.0137 (17)
C5	0.029 (2)	0.032 (2)	0.032 (2)	−0.0102 (17)	0.0068 (17)	−0.0101 (17)
C6	0.0179 (17)	0.0220 (18)	0.0242 (18)	0.0047 (14)	−0.0054 (14)	−0.0030 (14)
C7	0.035 (2)	0.022 (2)	0.029 (2)	−0.0021 (16)	−0.0053 (17)	−0.0090 (16)
C8	0.0175 (16)	0.0229 (19)	0.0233 (17)	−0.0030 (13)	−0.0005 (14)	−0.0022 (14)
C9	0.0218 (17)	0.0253 (19)	0.0202 (17)	0.0024 (14)	−0.0017 (14)	−0.0061 (14)
C10	0.0215 (17)	0.0199 (18)	0.0197 (17)	0.0032 (14)	−0.0074 (14)	−0.0040 (13)
C11	0.0157 (16)	0.0218 (18)	0.0229 (17)	−0.0012 (13)	−0.0040 (14)	−0.0040 (14)
C12	0.0167 (16)	0.0178 (17)	0.0187 (16)	0.0004 (13)	−0.0027 (13)	−0.0021 (13)
C13	0.0188 (16)	0.0173 (17)	0.0207 (17)	0.0024 (13)	−0.0050 (14)	−0.0037 (13)
C14	0.0253 (18)	0.0232 (18)	0.0147 (16)	0.0010 (14)	−0.0046 (14)	−0.0036 (13)
C15	0.0205 (16)	0.0133 (16)	0.0195 (16)	−0.0003 (13)	−0.0030 (13)	−0.0026 (13)
C16	0.0272 (18)	0.0164 (17)	0.0154 (16)	0.0005 (13)	−0.0056 (14)	−0.0010 (13)
C17	0.0216 (17)	0.0158 (17)	0.0208 (17)	0.0016 (13)	−0.0033 (14)	−0.0048 (13)
C18	0.040 (2)	0.0151 (17)	0.0200 (17)	−0.0041 (15)	−0.0046 (16)	−0.0028 (13)
C19	0.036 (2)	0.0182 (18)	0.0160 (16)	−0.0015 (15)	−0.0051 (15)	0.0006 (13)
C20	0.0169 (16)	0.0136 (16)	0.0220 (17)	−0.0005 (12)	0.0009 (13)	−0.0031 (13)
C21	0.0209 (17)	0.0193 (18)	0.0184 (16)	−0.0049 (13)	−0.0001 (14)	−0.0043 (13)

Eu1—O6i	2.485 (2)	O15—H15B	0.8200
Eu1—O8	2.386 (3)	O15—H15A	0.8200
Eu1—O10ii	2.404 (2)	N1—C5	1.335 (5)
Eu1—O11iii	2.385 (2)	N1—C1	1.352 (4)
Eu1—O12i	2.328 (2)	N2—C8	1.341 (4)
Eu1—O13	2.454 (3)	N2—C12	1.346 (4)
Eu1—O14	2.442 (3)	N3—C15	1.348 (4)
Eu1—O15	2.510 (3)	N3—C19	1.327 (5)
Cu1—O1	1.932 (3)	C1—C6	1.517 (5)
Cu1—O5iv	1.944 (2)	C1—C2	1.374 (5)
Cu1—O7	2.359 (3)	C2—C3	1.392 (5)
Cu1—N1	1.975 (3)	C3—C7	1.528 (5)
Cu1—N2iv	1.975 (3)	C3—C4	1.392 (5)
Cu2—O2	2.409 (3)	C4—C5	1.382 (6)
Cu2—O9	1.968 (2)	C8—C9	1.377 (5)
Cu2—N3	1.969 (3)	C9—C10	1.389 (5)
Cu2—O2ii	2.409 (3)	C10—C11	1.393 (5)
Cu2—O9ii	1.968 (2)	C10—C14	1.505 (5)
Cu2—N3ii	1.969 (3)	C11—C12	1.376 (5)
O1—C6	1.283 (4)	C12—C13	1.516 (5)
O2—C6	1.227 (4)	C15—C20	1.520 (5)
O3—C7	1.242 (5)	C15—C16	1.375 (5)
O4—C7	1.242 (5)	C16—C17	1.389 (5)
O5—C13	1.272 (4)	C17—C21	1.508 (5)
O6—C13	1.242 (4)	C17—C18	1.388 (5)
O7—C14	1.251 (4)	C18—C19	1.381 (5)
O8—C14	1.251 (5)	C2—H2A	0.9300
O9—C20	1.261 (4)	C4—H4A	0.9300
O10—C20	1.241 (4)	C5—H5A	0.9300
O11—C21	1.260 (4)	C8—H8A	0.9300
O12—C21	1.242 (4)	C9—H9A	0.9300
O13—H13B	0.8200	C11—H11A	0.9300
O13—H13A	0.8200	C16—H16A	0.9300
O14—H14A	0.8200	C18—H18A	0.9300
O14—H14B	0.8200	C19—H19A	0.9300
O8—Eu1—O13	143.07 (9)	H15A—O15—H15B	99.00
O8—Eu1—O14	76.92 (8)	Eu1—O15—H15A	123.00
O8—Eu1—O15	75.96 (8)	Eu1—O15—H15B	122.00
O8—Eu1—O11iii	144.45 (9)	C1—N1—C5	118.9 (3)
O6i—Eu1—O8	68.55 (8)	Cu1—N1—C1	111.1 (2)
O8—Eu1—O12i	88.94 (8)	Cu1—N1—C5	130.0 (3)
O8—Eu1—O10ii	108.10 (8)	Cu1iv—N2—C8	128.5 (2)
O13—Eu1—O14	133.64 (9)	C8—N2—C12	119.2 (3)
O13—Eu1—O15	126.29 (9)	Cu1iv—N2—C12	112.3 (2)
O11iii—Eu1—O13	72.28 (9)	Cu2—N3—C19	128.7 (2)
O6i—Eu1—O13	75.67 (8)	Cu2—N3—C15	111.9 (2)
O12i—Eu1—O13	74.51 (10)	C15—N3—C19	119.4 (3)
O10ii—Eu1—O13	72.65 (10)	N1—C1—C6	114.2 (3)
O14—Eu1—O15	73.99 (8)	C2—C1—C6	123.6 (3)
O11iii—Eu1—O14	74.60 (9)	N1—C1—C2	122.2 (3)
O6i—Eu1—O14	124.22 (8)	C1—C2—C3	119.5 (3)
O12i—Eu1—O14	144.83 (9)	C2—C3—C4	117.7 (3)
O10ii—Eu1—O14	71.70 (9)	C2—C3—C7	120.2 (3)
O11iii—Eu1—O15	76.07 (8)	C4—C3—C7	122.0 (3)
O6i—Eu1—O15	132.71 (7)	C3—C4—C5	120.0 (3)
O12i—Eu1—O15	71.37 (9)	N1—C5—C4	121.7 (4)
O10ii—Eu1—O15	143.28 (8)	O1—C6—C1	115.5 (3)
O6i—Eu1—O11iii	146.55 (8)	O1—C6—O2	125.7 (3)
O11iii—Eu1—O12i	102.40 (8)	O2—C6—C1	118.8 (3)
O10ii—Eu1—O11iii	82.57 (8)	O3—C7—C3	116.6 (3)
O6i—Eu1—O12i	77.62 (8)	O3—C7—O4	126.3 (4)
O6i—Eu1—O10ii	79.02 (8)	O4—C7—C3	117.1 (3)
O10ii—Eu1—O12i	143.40 (10)	N2—C8—C9	121.5 (3)
O1—Cu1—O7	97.47 (10)	C8—C9—C10	119.7 (3)
O1—Cu1—N1	84.50 (11)	C9—C10—C11	118.4 (3)
O1—Cu1—O5iv	172.30 (10)	C9—C10—C14	120.4 (3)
O1—Cu1—N2iv	94.73 (11)	C11—C10—C14	121.1 (3)
O1—Cu1—O2v	92.14 (9)	C10—C11—C12	118.9 (3)
O7—Cu1—N1	93.91 (10)	C11—C12—C13	124.3 (3)
O5iv—Cu1—O7	90.08 (9)	N2—C12—C13	113.4 (3)
O7—Cu1—N2iv	93.32 (10)	N2—C12—C11	122.1 (3)
O2v—Cu1—O7	164.52 (8)	O5—C13—C12	115.7 (3)
O5iv—Cu1—N1	96.55 (10)	O6—C13—C12	118.4 (3)
N1—Cu1—N2iv	172.76 (12)	O5—C13—O6	125.9 (3)
O2v—Cu1—N1	99.09 (10)	O8—C14—C10	117.1 (3)
O5iv—Cu1—N2iv	83.28 (10)	O7—C14—O8	126.2 (3)
O2v—Cu1—O5iv	80.16 (8)	O7—C14—C10	116.7 (3)
O2v—Cu1—N2iv	73.73 (10)	N3—C15—C20	113.9 (3)
O2—Cu2—O9	88.97 (10)	C16—C15—C20	123.7 (3)
O2—Cu2—N3	88.99 (10)	N3—C15—C16	122.4 (3)
O2—Cu2—O2ii	180.00	C15—C16—C17	118.4 (3)
O2—Cu2—O9ii	91.03 (10)	C16—C17—C21	120.6 (3)
O2—Cu2—N3ii	91.01 (10)	C18—C17—C21	120.5 (3)
O9—Cu2—N3	83.49 (11)	C16—C17—C18	118.9 (3)
O2ii—Cu2—O9	91.03 (10)	C17—C18—C19	119.3 (3)
O9—Cu2—O9ii	180.00	N3—C19—C18	121.6 (3)
O9—Cu2—N3ii	96.51 (10)	O9—C20—C15	115.9 (3)
O2ii—Cu2—N3	91.01 (10)	O10—C20—C15	118.3 (3)
O9ii—Cu2—N3	96.51 (11)	O9—C20—O10	125.7 (3)
N3—Cu2—N3ii	180.00	O12—C21—C17	117.9 (3)
O2ii—Cu2—O9ii	88.97 (10)	O11—C21—O12	124.9 (3)
O2ii—Cu2—N3ii	88.99 (10)	O11—C21—C17	117.2 (3)
O9ii—Cu2—N3ii	83.49 (10)	C1—C2—H2A	120.00
Cu1—O1—C6	114.4 (2)	C3—C2—H2A	120.00
Cu2—O2—C6	120.1 (2)	C3—C4—H4A	120.00
Cu1v—O2—Cu2	138.98 (10)	C5—C4—H4A	120.00
Cu1v—O2—C6	94.1 (2)	N1—C5—H5A	119.00
Cu1iv—O5—C13	115.0 (2)	C4—C5—H5A	119.00
Eu1i—O6—C13	131.3 (2)	N2—C8—H8A	119.00
Cu1—O7—C14	130.9 (2)	C9—C8—H8A	119.00
Eu1—O8—C14	134.9 (2)	C8—C9—H9A	120.00
Cu2—O9—C20	113.9 (2)	C10—C9—H9A	120.00
Eu1ii—O10—C20	127.0 (2)	C10—C11—H11A	121.00
Eu1vi—O11—C21	125.3 (2)	C12—C11—H11A	121.00
Eu1i—O12—C21	173.8 (3)	C15—C16—H16A	121.00
H13A—O13—H13B	112.00	C17—C16—H16A	121.00
Eu1—O13—H13A	108.00	C17—C18—H18A	120.00
Eu1—O13—H13B	120.00	C19—C18—H18A	120.00
H14A—O14—H14B	104.00	N3—C19—H19A	119.00
Eu1—O14—H14A	105.00	C18—C19—H19A	119.00
Eu1—O14—H14B	114.00
O13—Eu1—O8—C14	−178.0 (3)	Cu1—O7—C14—C10	−65.8 (4)
O14—Eu1—O8—C14	−27.5 (3)	Eu1—O8—C14—O7	31.0 (5)
O15—Eu1—O8—C14	49.0 (3)	Eu1—O8—C14—C10	−149.5 (2)
O11iii—Eu1—O8—C14	9.9 (4)	Cu2—O9—C20—O10	171.5 (3)
O6i—Eu1—O8—C14	−162.9 (3)	Cu2—O9—C20—C15	−10.4 (3)
O12i—Eu1—O8—C14	120.0 (3)	Eu1ii—O10—C20—O9	6.3 (5)
O10ii—Eu1—O8—C14	−93.0 (3)	Eu1ii—O10—C20—C15	−171.72 (19)
O8—Eu1—O11iii—C21iii	119.5 (3)	Eu1vi—O11—C21—O12	−20.8 (5)
O13—Eu1—O11iii—C21iii	−55.5 (3)	Eu1vi—O11—C21—C17	159.0 (2)
O14—Eu1—O11iii—C21iii	157.4 (3)	Cu1—N1—C1—C2	−179.0 (3)
O15—Eu1—O11iii—C21iii	80.5 (3)	Cu1—N1—C1—C6	3.7 (3)
O8—Eu1—O6i—C13i	152.9 (3)	C5—N1—C1—C2	1.9 (5)
O13—Eu1—O6i—C13i	−36.4 (3)	C5—N1—C1—C6	−175.5 (3)
O14—Eu1—O6i—C13i	97.0 (3)	Cu1—N1—C5—C4	−179.0 (3)
O15—Eu1—O6i—C13i	−163.0 (3)	C1—N1—C5—C4	0.0 (5)
O8—Eu1—O10ii—C20ii	−10.3 (3)	C12—N2—C8—C9	3.3 (5)
O13—Eu1—O10ii—C20ii	130.9 (3)	Cu1iv—N2—C8—C9	−175.7 (3)
O14—Eu1—O10ii—C20ii	−79.3 (3)	C8—N2—C12—C11	1.3 (5)
O15—Eu1—O10ii—C20ii	−100.9 (3)	C8—N2—C12—C13	−174.1 (3)
O7—Cu1—O1—C6	−96.6 (2)	Cu1iv—N2—C12—C11	−179.6 (3)
N1—Cu1—O1—C6	−3.3 (2)	Cu1iv—N2—C12—C13	5.0 (3)
N2iv—Cu1—O1—C6	169.5 (3)	Cu2—N3—C15—C16	−179.6 (3)
O2v—Cu1—O1—C6	95.6 (2)	Cu2—N3—C15—C20	1.9 (3)
O1—Cu1—O7—C14	−48.9 (3)	C19—N3—C15—C16	0.7 (5)
N1—Cu1—O7—C14	−133.9 (3)	C19—N3—C15—C20	−177.8 (3)
O5iv—Cu1—O7—C14	129.6 (3)	Cu2—N3—C19—C18	−177.5 (3)
N2iv—Cu1—O7—C14	46.3 (3)	C15—N3—C19—C18	2.2 (5)
O1—Cu1—N1—C1	−0.5 (2)	N1—C1—C2—C3	−2.1 (5)
O1—Cu1—N1—C5	178.5 (3)	C6—C1—C2—C3	175.1 (3)
O7—Cu1—N1—C1	96.6 (2)	N1—C1—C6—O1	−6.7 (4)
O7—Cu1—N1—C5	−84.4 (3)	N1—C1—C6—O2	170.7 (3)
O5iv—Cu1—N1—C1	−172.9 (2)	C2—C1—C6—O1	176.0 (3)
O5iv—Cu1—N1—C5	6.2 (3)	C2—C1—C6—O2	−6.7 (5)
O2v—Cu1—N1—C1	−91.8 (2)	C1—C2—C3—C4	0.4 (5)
O2v—Cu1—N1—C5	87.2 (3)	C1—C2—C3—C7	−174.7 (3)
O7—Cu1—O5iv—C13iv	−98.6 (2)	C2—C3—C4—C5	1.4 (6)
N1—Cu1—O5iv—C13iv	167.5 (2)	C7—C3—C4—C5	176.3 (4)
O1—Cu1—N2iv—C8iv	14.0 (3)	C2—C3—C7—O3	−6.4 (5)
O1—Cu1—N2iv—C12iv	−166.9 (2)	C2—C3—C7—O4	172.3 (4)
O7—Cu1—N2iv—C8iv	−83.8 (3)	C4—C3—C7—O3	178.8 (4)
O7—Cu1—N2iv—C12iv	95.3 (2)	C4—C3—C7—O4	−2.5 (6)
O1—Cu1—O2v—C6v	−12.3 (2)	C3—C4—C5—N1	−1.6 (6)
N1—Cu1—O2v—C6v	72.5 (2)	N2—C8—C9—C10	−4.7 (5)
O9—Cu2—O2—C6	158.3 (3)	C8—C9—C10—C11	1.4 (5)
O9—Cu2—O2—Cu1v	15.88 (14)	C8—C9—C10—C14	178.3 (3)
N3—Cu2—O2—C6	74.8 (3)	C9—C10—C11—C12	2.9 (5)
N3—Cu2—O2—Cu1v	−67.63 (15)	C14—C10—C11—C12	−173.9 (3)
O9ii—Cu2—O2—C6	−21.7 (3)	C9—C10—C14—O7	−37.3 (5)
N3ii—Cu2—O2—C6	−105.2 (3)	C9—C10—C14—O8	143.1 (3)
O2—Cu2—O9—C20	−80.0 (2)	C11—C10—C14—O7	139.4 (3)
N3—Cu2—O9—C20	9.1 (2)	C11—C10—C14—O8	−40.2 (5)
O2ii—Cu2—O9—C20	100.0 (2)	C10—C11—C12—N2	−4.4 (5)
N3ii—Cu2—O9—C20	−170.9 (2)	C10—C11—C12—C13	170.5 (3)
O2—Cu2—N3—C15	83.5 (2)	N2—C12—C13—O5	−0.9 (4)
O2—Cu2—N3—C19	−96.9 (3)	N2—C12—C13—O6	175.6 (3)
O9—Cu2—N3—C15	−5.6 (2)	C11—C12—C13—O5	−176.2 (3)
O9—Cu2—N3—C19	174.1 (3)	C11—C12—C13—O6	0.3 (5)
O2ii—Cu2—N3—C15	−96.5 (2)	N3—C15—C16—C17	−2.3 (5)
O2ii—Cu2—N3—C19	83.1 (3)	C20—C15—C16—C17	176.1 (3)
O9ii—Cu2—N3—C15	174.4 (2)	N3—C15—C20—O9	5.8 (4)
O9ii—Cu2—N3—C19	−6.0 (3)	N3—C15—C20—O10	−176.0 (3)
Cu1—O1—C6—O2	−171.0 (3)	C16—C15—C20—O9	−172.7 (3)
Cu1—O1—C6—C1	6.1 (4)	C16—C15—C20—O10	5.5 (5)
Cu2—O2—C6—O1	−76.7 (4)	C15—C16—C17—C18	1.0 (5)
Cu2—O2—C6—C1	106.3 (3)	C15—C16—C17—C21	−176.4 (3)
Cu1v—O2—C6—O1	79.6 (4)	C16—C17—C18—C19	1.7 (6)
Cu1v—O2—C6—C1	−97.4 (3)	C21—C17—C18—C19	179.1 (3)
Cu1iv—O5—C13—O6	179.9 (3)	C16—C17—C21—O11	−27.2 (5)
Cu1iv—O5—C13—C12	−3.9 (3)	C16—C17—C21—O12	152.6 (4)
Eu1i—O6—C13—O5	−4.7 (5)	C18—C17—C21—O11	155.5 (4)
Eu1i—O6—C13—C12	179.13 (19)	C18—C17—C21—O12	−24.7 (5)
Cu1—O7—C14—O8	113.8 (4)	C17—C18—C19—N3	−3.4 (6)

D—H···A	D—H	H···A	D···A	D—H···A
O13—H13A···O5i	0.82	2.00	2.769 (3)	155
O13—H13B···O15vii	0.82	2.02	2.822 (4)	164
O14—H14A···O7	0.82	1.89	2.690 (4)	164
O14—H14B···O4viii	0.82	1.88	2.667 (4)	161
O15—H15A···O3ix	0.82	1.83	2.630 (4)	164
O15—H15B···O4viii	0.82	2.06	2.814 (4)	153
C18—H18A···O6	0.93	2.48	3.389 (4)	167

Table 1

Selected bond lengths (Å)

Eu1—O6i	2.485 (2)
Eu1—O8	2.386 (3)
Eu1—O10ii	2.404 (2)
Eu1—O11iii	2.385 (2)
Eu1—O12i	2.328 (2)
Eu1—O13	2.454 (3)
Eu1—O14	2.442 (3)
Eu1—O15	2.510 (3)
Cu1—O1	1.932 (3)
Cu1—O5iv	1.944 (2)
Cu1—O7	2.359 (3)
Cu1—N1	1.975 (3)
Cu1—N2iv	1.975 (3)
Cu2—O2	2.409 (3)
Cu2—O9	1.968 (2)
Cu2—N3	1.969 (3)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O13—H13A⋯O5i	0.82	2.00	2.769 (3)	155
O13—H13B⋯O15v	0.82	2.02	2.822 (4)	164
O14—H14A⋯O7	0.82	1.89	2.690 (4)	164
O14—H14B⋯O4vi	0.82	1.88	2.667 (4)	161
O15—H15A⋯O3vii	0.82	1.83	2.630 (4)	164
O15—H15B⋯O4vi	0.82	2.06	2.814 (4)	153

Symmetry codes: (i) ; (v) ; (vi) ; (vii) .