Poly[[dodeca-aqua-bis-(μ(3)-pyridine-2,6-dicarboxyl-ato)tetra-kis-(μ(2)-pyridine-2,6-dicarboxyl-ato)tri-calciumdieuropium(III)] 10.5-hydrate].

In the title compound, {[Ca(3)Eu(2)(C(7)H(3)NO(4))(6)(H(2)O)(12)]·10.5H(2)O}(n), the Eu(III) ion is nine-coordinated by three tridentate pyridine-2,6-dicarboxyl-ate (PDA) ligands, forming a [Eu(PDA)(3)](3-) building block. The Ca(2+) ions adopt two types of coordination geometries. One Ca(2+) ion, lying on a twofold rotation axis, is eight-coordinated by four carboxyl-ate O atoms from four PDA ligands and four water mol-ecules, and the other two Ca(2+) ions, each lying on an inversion center, are six-coordinated by two carboxyl-ate O atoms from two PDA ligands and four water mol-ecules. The carboxyl-ate groups bridge the Eu(III) and Ca(2+) ions into a three-dimensional porous framework, with channels extending along [010] and [001] in which lattice water mol-ecules are located. Two of the lattice water mol-ecules are disordered over two sets of sites with equal occupancy and one water mol-ecule is 0.25-occupied. Numerous O-H⋯O hydrogen bonds involving the water mol-ecules and carboxyl-ate O atoms are present.

Related literature

For 3d–4f and 4d–4f metal complexes with pyridine-2,6-dicarboxyl­ate ligands, see: Zhao et al. (2006 ▶, 2007 ▶, 2011 ▶); Zhao, Zhao et al. (2009 ▶). For Ln–Ba (Ln = lanthanide) complexes with pyridine-2,6-dicarboxyl­ate ligands, see: Zhao, Zuo et al. (2009 ▶).

Experimental

Crystal data

[Ca3Eu2(C7H3NO4)6(H2O)12]·10.5H2O

M = 1820.14

Monoclinic,

a = 16.070 (4) Å

b = 9.471 (2) Å

c = 23.540 (6) Å

β = 107.685 (4)°

V = 3413.5 (14) Å3

Z = 2

Mo Kα radiation

μ = 2.16 mm−1

T = 113 K

0.20 × 0.19 × 0.16 mm

Data collection

Rigaku Saturn724 CCD diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2009 ▶) T min = 0.672, T max = 0.724

27531 measured reflections

6015 independent reflections

4964 reflections with I > 2σ(I)

R int = 0.054

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.094

S = 1.14

6015 reflections

531 parameters

30 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.31 e Å−3

Δρmin = −1.29 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2009 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812018028/hy2534sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812018028/hy2534Isup2.hkl

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

[Ca3Eu2(C7H3NO4)6(H2O)12]·10.5H2O	F(000) = 1830
Mr = 1820.14	Dx = 1.771 Mg m−3
Monoclinic, P2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yc	Cell parameters from 11834 reflections
a = 16.070 (4) Å	θ = 1.3–27.9°
b = 9.471 (2) Å	µ = 2.16 mm−1
c = 23.540 (6) Å	T = 113 K
β = 107.685 (4)°	Prism, colorless
V = 3413.5 (14) Å3	0.20 × 0.19 × 0.16 mm
Z = 2

Rigaku Saturn724 CCD diffractometer	6015 independent reflections
Radiation source: rotating anode	4964 reflections with I > 2σ(I)
Multilayer monochromator	Rint = 0.054
Detector resolution: 14.22 pixels mm-1	θmax = 25.0°, θmin = 1.3°
ω and φ scans	h = −18→19
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2009)	k = −10→11
Tmin = 0.672, Tmax = 0.724	l = −28→28
27531 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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	w = 1/[σ2(Fo2) + (0.0212P)2 + 16.8621P] where P = (Fo2 + 2Fc2)/3
6015 reflections	(Δ/σ)max = 0.002
531 parameters	Δρmax = 1.31 e Å−3
30 restraints	Δρmin = −1.29 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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	Occ. (<1)
Eu1	0.296251 (16)	0.50554 (3)	0.097315 (11)	0.00952 (9)
Ca1	0.5000	0.0000	0.0000	0.0113 (3)
Ca2	0.5000	1.00350 (17)	0.2500	0.0138 (3)
Ca3	0.0000	0.0000	0.0000	0.0198 (4)
O1	0.3736 (2)	0.3233 (4)	0.16621 (16)	0.0151 (8)
O2	0.4013 (3)	0.2000 (4)	0.25127 (16)	0.0182 (9)
O3	0.1929 (2)	0.6789 (4)	0.11297 (16)	0.0174 (9)
O4	0.1130 (3)	0.7722 (5)	0.16683 (18)	0.0282 (11)
O5	0.3886 (2)	0.6872 (4)	0.15705 (16)	0.0149 (8)
O6	0.5155 (2)	0.8058 (4)	0.18919 (16)	0.0158 (9)
O7	0.3344 (2)	0.3313 (4)	0.03339 (16)	0.0140 (8)
O8	0.4335 (2)	0.2095 (4)	0.00428 (16)	0.0169 (9)
O9	0.2999 (2)	0.6871 (4)	0.02212 (16)	0.0162 (9)
O10	0.2495 (3)	0.7858 (4)	−0.06830 (18)	0.0243 (10)
O11	0.1823 (2)	0.3273 (4)	0.08688 (16)	0.0159 (9)
O12	0.0604 (3)	0.2142 (4)	0.03527 (18)	0.0205 (9)
O13	0.6116 (2)	0.0662 (4)	0.08852 (17)	0.0185 (9)
H13A	0.647 (2)	0.113 (5)	0.075 (2)	0.022*
H13B	0.639 (3)	0.012 (5)	0.1167 (18)	0.022*
O14	0.4145 (3)	−0.0939 (4)	0.05348 (17)	0.0222 (10)
H14A	0.419 (4)	−0.043 (5)	0.0840 (16)	0.027*
H14B	0.380 (3)	−0.162 (4)	0.052 (2)	0.027*
O15	0.3478 (3)	0.9194 (4)	0.21233 (17)	0.0204 (9)
H15A	0.306 (3)	0.974 (5)	0.194 (2)	0.025*
H15B	0.354 (4)	0.854 (4)	0.1894 (18)	0.025*
O16	0.4648 (3)	1.0983 (4)	0.14661 (18)	0.0165 (9)
H16A	0.504 (4)	1.121 (7)	0.135 (3)	0.020*
H16B	0.437 (4)	1.172 (7)	0.148 (3)	0.020*
O17	0.1405 (3)	−0.0914 (5)	0.0396 (2)	0.0314 (11)
H17A	0.164 (3)	−0.161 (4)	0.061 (3)	0.038*
H17B	0.179 (3)	−0.033 (5)	0.036 (3)	0.038*
O18	−0.0140 (3)	−0.0554 (5)	0.0933 (2)	0.0391 (12)
H18A	−0.0678 (13)	−0.048 (7)	0.090 (3)	0.047*
H18B	0.011 (3)	−0.118 (6)	0.118 (3)	0.047*
N1	0.2624 (3)	0.4885 (5)	0.19488 (18)	0.0125 (9)
N2	0.4526 (3)	0.5088 (4)	0.09633 (18)	0.0106 (9)
N3	0.1693 (3)	0.5085 (5)	0.00041 (19)	0.0132 (9)
C1	0.3627 (4)	0.2941 (6)	0.2164 (2)	0.0140 (12)
C2	0.2960 (4)	0.3823 (6)	0.2330 (2)	0.0158 (12)
C3	0.2680 (4)	0.3533 (7)	0.2820 (2)	0.0227 (14)
H3	0.2916	0.2765	0.3078	0.027*
C4	0.2045 (4)	0.4396 (8)	0.2922 (3)	0.0292 (16)
H4	0.1838	0.4223	0.3253	0.035*
C5	0.1711 (4)	0.5518 (7)	0.2539 (3)	0.0281 (16)
H5	0.1283	0.6128	0.2608	0.034*
C6	0.2015 (4)	0.5727 (6)	0.2057 (2)	0.0184 (13)
C7	0.1659 (4)	0.6849 (6)	0.1585 (2)	0.0170 (13)
C8	0.4686 (4)	0.7088 (6)	0.1610 (2)	0.0124 (12)
C9	0.5084 (3)	0.6070 (5)	0.1267 (2)	0.0119 (12)
C10	0.5932 (4)	0.6158 (6)	0.1249 (2)	0.0169 (12)
H10	0.6311	0.6876	0.1464	0.020*
C11	0.6218 (4)	0.5190 (6)	0.0915 (2)	0.0182 (13)
H11	0.6800	0.5233	0.0896	0.022*
C12	0.5646 (4)	0.4142 (6)	0.0603 (2)	0.0165 (12)
H12	0.5832	0.3458	0.0372	0.020*
C13	0.4797 (3)	0.4130 (5)	0.0640 (2)	0.0116 (12)
C14	0.4114 (4)	0.3098 (6)	0.0316 (2)	0.0134 (12)
C15	0.2437 (4)	0.7017 (6)	−0.0285 (3)	0.0172 (13)
C16	0.1646 (4)	0.6081 (6)	−0.0416 (2)	0.0147 (12)
C17	0.0927 (4)	0.6196 (6)	−0.0923 (2)	0.0192 (13)
H17	0.0898	0.6920	−0.1207	0.023*
C18	0.0254 (4)	0.5236 (7)	−0.1002 (3)	0.0258 (15)
H18	−0.0243	0.5285	−0.1346	0.031*
C19	0.0312 (4)	0.4197 (6)	−0.0574 (3)	0.0207 (14)
H19	−0.0142	0.3524	−0.0622	0.025*
C20	0.1038 (3)	0.4157 (6)	−0.0079 (2)	0.0137 (12)
C21	0.1156 (4)	0.3100 (6)	0.0415 (2)	0.0149 (12)
O19	0.2379 (3)	0.0820 (5)	0.9928 (2)	0.0386 (12)
H19A	0.211 (4)	0.121 (6)	0.9594 (17)	0.046*
H19B	0.282 (3)	0.132 (6)	1.011 (2)	0.046*
O20	0.2972 (3)	0.9062 (5)	0.3187 (2)	0.0351 (12)
H20A	0.314 (4)	0.890 (7)	0.2883 (16)	0.042*
H20B	0.253 (3)	0.960 (6)	0.309 (2)	0.042*
O21	0.1986 (3)	0.0862 (5)	0.15634 (18)	0.0290 (11)
H21A	0.196 (4)	0.152 (4)	0.1311 (18)	0.035*
H21B	0.176 (4)	0.011 (3)	0.139 (2)	0.035*
O22	0.1015 (10)	0.9136 (14)	0.8459 (6)	0.049 (4)	0.50
O23	0.1373 (5)	0.9971 (10)	0.2459 (3)	0.030 (2)	0.50
O22'	0.1367 (9)	0.9633 (14)	0.8406 (7)	0.049 (4)	0.50
O23'	0.0826 (8)	1.1594 (14)	0.2299 (5)	0.066 (4)	0.50
O24	0.8088 (12)	0.744 (2)	0.1251 (9)	0.039 (5)	0.25

	U11	U22	U33	U12	U13	U23
Eu1	0.00769 (14)	0.00855 (14)	0.01199 (14)	−0.00043 (12)	0.00250 (10)	−0.00100 (12)
Ca1	0.0110 (7)	0.0095 (7)	0.0141 (7)	0.0012 (7)	0.0049 (6)	−0.0014 (7)
Ca2	0.0153 (8)	0.0103 (8)	0.0120 (7)	0.000	−0.0018 (6)	0.000
Ca3	0.0147 (8)	0.0103 (8)	0.0264 (9)	−0.0014 (7)	−0.0059 (7)	−0.0002 (7)
O1	0.015 (2)	0.014 (2)	0.016 (2)	0.0042 (16)	0.0041 (16)	−0.0006 (16)
O2	0.021 (2)	0.014 (2)	0.015 (2)	0.0040 (17)	−0.0005 (17)	0.0014 (17)
O3	0.014 (2)	0.018 (2)	0.020 (2)	0.0036 (17)	0.0044 (17)	−0.0012 (17)
O4	0.023 (2)	0.036 (3)	0.025 (2)	0.016 (2)	0.0068 (19)	−0.003 (2)
O5	0.009 (2)	0.014 (2)	0.021 (2)	−0.0012 (16)	0.0038 (16)	−0.0036 (16)
O6	0.010 (2)	0.013 (2)	0.022 (2)	−0.0035 (16)	0.0008 (16)	−0.0036 (17)
O7	0.012 (2)	0.013 (2)	0.018 (2)	−0.0009 (16)	0.0071 (16)	−0.0035 (16)
O8	0.023 (2)	0.013 (2)	0.017 (2)	0.0045 (17)	0.0090 (17)	−0.0017 (16)
O9	0.014 (2)	0.016 (2)	0.018 (2)	0.0002 (17)	0.0050 (17)	0.0032 (16)
O10	0.021 (2)	0.026 (2)	0.027 (2)	0.0012 (19)	0.0096 (19)	0.0131 (19)
O11	0.010 (2)	0.015 (2)	0.020 (2)	−0.0034 (16)	0.0012 (17)	−0.0025 (16)
O12	0.015 (2)	0.013 (2)	0.032 (2)	−0.0064 (17)	0.0043 (18)	−0.0052 (17)
O13	0.015 (2)	0.021 (2)	0.018 (2)	−0.0004 (18)	0.0024 (17)	0.0034 (17)
O14	0.033 (3)	0.018 (2)	0.019 (2)	−0.0128 (19)	0.014 (2)	−0.0057 (17)
O15	0.019 (2)	0.013 (2)	0.023 (2)	0.0057 (18)	−0.0025 (18)	−0.0045 (17)
O16	0.019 (2)	0.010 (2)	0.020 (2)	0.0020 (18)	0.0057 (18)	−0.0018 (17)
O17	0.015 (2)	0.016 (2)	0.061 (3)	0.0024 (18)	0.007 (2)	0.014 (2)
O18	0.042 (3)	0.028 (3)	0.046 (3)	0.007 (2)	0.012 (3)	0.005 (2)
N1	0.010 (2)	0.013 (2)	0.014 (2)	−0.001 (2)	0.0023 (18)	−0.005 (2)
N2	0.012 (2)	0.006 (2)	0.014 (2)	−0.001 (2)	0.0042 (18)	0.0029 (19)
N3	0.011 (2)	0.013 (2)	0.017 (2)	0.000 (2)	0.0055 (18)	−0.004 (2)
C1	0.017 (3)	0.012 (3)	0.011 (3)	−0.008 (2)	0.001 (2)	−0.003 (2)
C2	0.011 (3)	0.018 (3)	0.015 (3)	−0.003 (2)	−0.002 (2)	−0.006 (2)
C3	0.019 (3)	0.034 (4)	0.014 (3)	−0.003 (3)	0.003 (3)	0.003 (3)
C4	0.017 (3)	0.052 (4)	0.019 (3)	0.004 (3)	0.008 (3)	0.005 (3)
C5	0.016 (3)	0.052 (4)	0.019 (3)	0.001 (3)	0.009 (3)	−0.010 (3)
C6	0.009 (3)	0.023 (3)	0.019 (3)	−0.001 (2)	−0.003 (2)	−0.007 (2)
C7	0.010 (3)	0.022 (3)	0.017 (3)	0.001 (3)	0.001 (2)	−0.007 (2)
C8	0.014 (3)	0.010 (3)	0.011 (3)	0.000 (2)	0.001 (2)	0.002 (2)
C9	0.010 (3)	0.009 (3)	0.016 (3)	0.002 (2)	0.002 (2)	0.005 (2)
C10	0.013 (3)	0.018 (3)	0.020 (3)	−0.001 (2)	0.004 (2)	0.005 (2)
C11	0.012 (3)	0.020 (3)	0.022 (3)	0.005 (2)	0.005 (2)	0.008 (2)
C12	0.015 (3)	0.015 (3)	0.021 (3)	0.004 (2)	0.009 (2)	0.003 (2)
C13	0.012 (3)	0.008 (3)	0.015 (3)	0.004 (2)	0.005 (2)	0.006 (2)
C14	0.017 (3)	0.010 (3)	0.013 (3)	0.002 (2)	0.006 (2)	0.005 (2)
C15	0.020 (3)	0.012 (3)	0.023 (3)	0.007 (2)	0.010 (3)	0.001 (2)
C16	0.015 (3)	0.014 (3)	0.019 (3)	0.006 (2)	0.012 (2)	0.001 (2)
C17	0.015 (3)	0.025 (3)	0.020 (3)	0.004 (3)	0.008 (3)	0.003 (3)
C18	0.014 (3)	0.039 (4)	0.020 (3)	0.007 (3)	−0.002 (2)	−0.002 (3)
C19	0.013 (3)	0.018 (3)	0.025 (3)	0.000 (3)	−0.002 (3)	−0.009 (3)
C20	0.011 (3)	0.013 (3)	0.019 (3)	0.000 (2)	0.006 (2)	−0.006 (2)
C21	0.013 (3)	0.010 (3)	0.023 (3)	0.000 (2)	0.008 (3)	−0.004 (2)
O19	0.032 (3)	0.038 (3)	0.048 (3)	−0.013 (2)	0.014 (2)	−0.013 (2)
O20	0.038 (3)	0.035 (3)	0.031 (3)	0.010 (2)	0.008 (2)	−0.011 (2)
O21	0.029 (3)	0.016 (2)	0.031 (3)	−0.002 (2)	−0.007 (2)	0.0055 (19)
O22	0.070 (11)	0.046 (9)	0.048 (7)	0.012 (7)	0.041 (7)	0.017 (6)
O23	0.023 (5)	0.048 (6)	0.017 (4)	−0.007 (5)	0.003 (4)	−0.005 (4)
O22'	0.040 (8)	0.041 (8)	0.071 (9)	−0.001 (6)	0.025 (6)	0.026 (6)
O23'	0.068 (8)	0.085 (10)	0.045 (7)	−0.036 (7)	0.018 (6)	−0.015 (6)
O24	0.034 (6)	0.040 (6)	0.043 (6)	0.003 (5)	0.013 (5)	0.003 (5)

Eu1—O5	2.423 (4)	O14—H14A	0.85 (1)
Eu1—O7	2.434 (4)	O14—H14B	0.85 (1)
Eu1—O1	2.435 (4)	O15—H15A	0.85 (1)
Eu1—O3	2.441 (4)	O15—H15B	0.85 (1)
Eu1—O11	2.447 (4)	O16—H16A	0.78 (6)
Eu1—O9	2.481 (4)	O16—H16B	0.84 (6)
Eu1—N2	2.520 (4)	O17—H17A	0.85 (1)
Eu1—N1	2.521 (4)	O17—H17B	0.85 (1)
Eu1—N3	2.557 (4)	O18—H18A	0.85 (1)
Ca1—O8i	2.270 (4)	O18—H18B	0.85 (1)
Ca1—O8	2.270 (4)	N1—C6	1.345 (7)
Ca1—O14i	2.305 (4)	N1—C2	1.347 (7)
Ca1—O14	2.305 (4)	N2—C9	1.338 (7)
Ca1—O13i	2.383 (4)	N2—C13	1.340 (7)
Ca1—O13	2.383 (4)	N3—C20	1.339 (7)
Ca1—H13A	2.70 (5)	N3—C16	1.353 (7)
Ca1—H14A	2.70 (4)	C1—C2	1.501 (8)
Ca2—O6ii	2.415 (4)	C2—C3	1.387 (8)
Ca2—O6	2.415 (4)	C3—C4	1.383 (9)
Ca2—O2iii	2.451 (4)	C3—H3	0.9500
Ca2—O2iv	2.451 (4)	C4—C5	1.391 (9)
Ca2—O15ii	2.466 (4)	C4—H4	0.9500
Ca2—O15	2.466 (4)	C5—C6	1.379 (8)
Ca2—O16ii	2.493 (4)	C5—H5	0.9500
Ca2—O16	2.493 (4)	C6—C7	1.519 (8)
Ca2—H15B	2.74 (5)	C8—C9	1.519 (7)
Ca3—O12	2.292 (4)	C9—C10	1.378 (8)
Ca3—O12v	2.292 (4)	C10—C11	1.375 (8)
Ca3—O17v	2.332 (4)	C10—H10	0.9500
Ca3—O17	2.332 (4)	C11—C12	1.400 (8)
Ca3—O18	2.334 (5)	C11—H11	0.9500
Ca3—O18v	2.334 (5)	C12—C13	1.392 (8)
Ca3—H17B	2.76 (4)	C12—H12	0.9500
Ca3—H18A	2.70 (5)	C13—C14	1.495 (8)
O1—C1	1.276 (6)	C15—C16	1.502 (8)
O2—C1	1.243 (6)	C16—C17	1.390 (8)
O2—Ca2vi	2.451 (4)	C17—C18	1.381 (8)
O3—C7	1.274 (7)	C17—H17	0.9500
O4—C7	1.243 (7)	C18—C19	1.392 (9)
O5—C8	1.277 (6)	C18—H18	0.9500
O6—C8	1.244 (6)	C19—C20	1.375 (8)
O7—C14	1.267 (6)	C19—H19	0.9500
O8—C14	1.257 (6)	C20—C21	1.501 (8)
O9—C15	1.266 (7)	O19—H19A	0.86 (1)
O10—C15	1.254 (7)	O19—H19B	0.85 (1)
O11—C21	1.274 (6)	O20—H20A	0.85 (1)
O12—C21	1.247 (7)	O20—H20B	0.85 (1)
O13—H13A	0.85 (1)	O21—H21A	0.85 (1)
O13—H13B	0.85 (1)	O21—H21B	0.85 (1)
O5—Eu1—O7	127.97 (12)	O12v—Ca3—H17B	107.2 (11)
O5—Eu1—O1	91.03 (12)	O17v—Ca3—H17B	163.3 (7)
O7—Eu1—O1	75.97 (12)	O17—Ca3—H17B	16.7 (7)
O5—Eu1—O3	76.07 (12)	O18—Ca3—H17B	94.3 (12)
O7—Eu1—O3	149.31 (12)	O18v—Ca3—H17B	85.7 (12)
O1—Eu1—O3	127.54 (13)	O12—Ca3—H18A	95.3 (15)
O5—Eu1—O11	148.83 (13)	O12v—Ca3—H18A	84.7 (15)
O7—Eu1—O11	77.98 (12)	O17v—Ca3—H18A	78.7 (7)
O1—Eu1—O11	78.07 (12)	O17—Ca3—H18A	101.3 (7)
O3—Eu1—O11	87.52 (13)	O18—Ca3—H18A	17.5 (8)
O5—Eu1—O9	77.22 (12)	O18v—Ca3—H18A	162.5 (8)
O7—Eu1—O9	87.93 (12)	H17B—Ca3—H18A	111.7 (14)
O1—Eu1—O9	148.04 (13)	C1—O1—Eu1	125.7 (3)
O3—Eu1—O9	78.80 (13)	C1—O2—Ca2vi	137.0 (4)
O11—Eu1—O9	125.83 (12)	C7—O3—Eu1	125.3 (3)
O5—Eu1—N2	63.91 (13)	C8—O5—Eu1	125.6 (3)
O7—Eu1—N2	64.10 (13)	C8—O6—Ca2	137.2 (4)
O1—Eu1—N2	72.89 (13)	C14—O7—Eu1	124.2 (3)
O3—Eu1—N2	135.96 (13)	C14—O8—Ca1	153.3 (3)
O11—Eu1—N2	136.48 (13)	C15—O9—Eu1	125.7 (4)
O9—Eu1—N2	75.26 (13)	C21—O11—Eu1	125.9 (3)
O5—Eu1—N1	77.31 (13)	C21—O12—Ca3	153.5 (4)
O7—Eu1—N1	133.20 (13)	Ca1—O13—H13A	103 (4)
O1—Eu1—N1	63.64 (13)	Ca1—O13—H13B	127 (4)
O3—Eu1—N1	63.93 (13)	H13A—O13—H13B	111 (4)
O11—Eu1—N1	71.66 (13)	Ca1—O14—H14A	109 (3)
O9—Eu1—N1	138.80 (13)	Ca1—O14—H14B	141 (3)
N2—Eu1—N1	120.06 (13)	H14A—O14—H14B	111 (5)
O5—Eu1—N3	133.78 (14)	Ca2—O15—H15A	122 (4)
O7—Eu1—N3	74.84 (13)	Ca2—O15—H15B	99 (4)
O1—Eu1—N3	135.19 (13)	H15A—O15—H15B	110 (5)
O3—Eu1—N3	74.49 (13)	Ca2—O16—H16A	118 (5)
O11—Eu1—N3	63.13 (13)	Ca2—O16—H16B	103 (4)
O9—Eu1—N3	62.70 (13)	H16A—O16—H16B	106 (6)
N2—Eu1—N3	121.28 (13)	Ca3—O17—H17A	137 (4)
N1—Eu1—N3	118.61 (14)	Ca3—O17—H17B	111 (4)
O8i—Ca1—O8	179.999 (2)	H17A—O17—H17B	111 (5)
O8i—Ca1—O14i	86.94 (14)	Ca3—O18—H18A	107 (4)
O8—Ca1—O14i	93.06 (14)	Ca3—O18—H18B	131 (5)
O8i—Ca1—O14	93.07 (14)	H18A—O18—H18B	112 (6)
O8—Ca1—O14	86.93 (14)	C6—N1—C2	119.0 (5)
O14i—Ca1—O14	180.0	C6—N1—Eu1	120.3 (4)
O8i—Ca1—O13i	88.30 (14)	C2—N1—Eu1	120.0 (4)
O8—Ca1—O13i	91.70 (14)	C9—N2—C13	119.5 (5)
O14i—Ca1—O13i	92.24 (14)	C9—N2—Eu1	120.8 (3)
O14—Ca1—O13i	87.76 (14)	C13—N2—Eu1	119.7 (3)
O8i—Ca1—O13	91.70 (14)	C20—N3—C16	119.0 (5)
O8—Ca1—O13	88.30 (14)	C20—N3—Eu1	120.1 (3)
O14i—Ca1—O13	87.76 (14)	C16—N3—Eu1	120.8 (3)
O14—Ca1—O13	92.24 (14)	O2—C1—O1	125.8 (5)
O13i—Ca1—O13	180.0	O2—C1—C2	118.6 (5)
O8i—Ca1—H13A	92.6 (12)	O1—C1—C2	115.5 (5)
O8—Ca1—H13A	87.4 (12)	N1—C2—C3	122.4 (5)
O14i—Ca1—H13A	70.1 (6)	N1—C2—C1	114.5 (5)
O14—Ca1—H13A	109.9 (6)	C3—C2—C1	123.0 (5)
O13i—Ca1—H13A	162.2 (6)	C4—C3—C2	118.0 (6)
O13—Ca1—H13A	17.8 (6)	C4—C3—H3	121.0
O8i—Ca1—H14A	103.8 (11)	C2—C3—H3	121.0
O8—Ca1—H14A	76.2 (11)	C3—C4—C5	119.9 (6)
O14i—Ca1—H14A	162.7 (6)	C3—C4—H4	120.0
O14—Ca1—H14A	17.3 (6)	C5—C4—H4	120.0
O13i—Ca1—H14A	101.5 (10)	C6—C5—C4	118.6 (6)
O13—Ca1—H14A	78.5 (10)	C6—C5—H5	120.7
H13A—Ca1—H14A	95.5 (12)	C4—C5—H5	120.7
O6ii—Ca2—O6	78.34 (19)	N1—C6—C5	122.0 (6)
O6ii—Ca2—O2iii	113.44 (13)	N1—C6—C7	114.2 (5)
O6—Ca2—O2iii	141.21 (12)	C5—C6—C7	123.6 (5)
O6ii—Ca2—O2iv	141.21 (12)	O4—C7—O3	126.0 (5)
O6—Ca2—O2iv	113.44 (13)	O4—C7—C6	118.2 (5)
O2iii—Ca2—O2iv	81.20 (19)	O3—C7—C6	115.8 (5)
O6ii—Ca2—O15ii	78.83 (13)	O6—C8—O5	126.2 (5)
O6—Ca2—O15ii	72.14 (13)	O6—C8—C9	117.9 (5)
O2iii—Ca2—O15ii	144.61 (14)	O5—C8—C9	115.9 (5)
O2iv—Ca2—O15ii	71.03 (13)	N2—C9—C10	122.3 (5)
O6ii—Ca2—O15	72.14 (13)	N2—C9—C8	113.8 (5)
O6—Ca2—O15	78.83 (13)	C10—C9—C8	123.9 (5)
O2iii—Ca2—O15	71.03 (13)	C11—C10—C9	118.8 (5)
O2iv—Ca2—O15	144.61 (14)	C11—C10—H10	120.6
O15ii—Ca2—O15	142.3 (2)	C9—C10—H10	120.6
O6ii—Ca2—O16ii	74.59 (13)	C10—C11—C12	119.5 (5)
O6—Ca2—O16ii	145.52 (14)	C10—C11—H11	120.3
O2iii—Ca2—O16ii	70.74 (13)	C12—C11—H11	120.3
O2iv—Ca2—O16ii	77.45 (14)	C13—C12—C11	118.2 (5)
O15ii—Ca2—O16ii	81.92 (14)	C13—C12—H12	120.9
O15—Ca2—O16ii	111.92 (14)	C11—C12—H12	120.9
O6ii—Ca2—O16	145.52 (14)	N2—C13—C12	121.6 (5)
O6—Ca2—O16	74.59 (13)	N2—C13—C14	114.7 (5)
O2iii—Ca2—O16	77.45 (14)	C12—C13—C14	123.7 (5)
O2iv—Ca2—O16	70.74 (13)	O8—C14—O7	124.7 (5)
O15ii—Ca2—O16	111.91 (14)	O8—C14—C13	118.5 (5)
O15—Ca2—O16	81.92 (14)	O7—C14—C13	116.8 (5)
O16ii—Ca2—O16	137.8 (2)	O10—C15—O9	125.4 (5)
O6ii—Ca2—H15B	71.4 (11)	O10—C15—C16	118.1 (5)
O6—Ca2—H15B	61.0 (6)	O9—C15—C16	116.5 (5)
O2iii—Ca2—H15B	86.9 (6)	N3—C16—C17	121.9 (5)
O2iv—Ca2—H15B	147.2 (11)	N3—C16—C15	114.0 (5)
O15ii—Ca2—H15B	128.1 (6)	C17—C16—C15	124.1 (5)
O15—Ca2—H15B	17.9 (6)	C18—C17—C16	118.5 (6)
O16ii—Ca2—H15B	126.9 (9)	C18—C17—H17	120.7
O16—Ca2—H15B	76.9 (12)	C16—C17—H17	120.7
O12—Ca3—O12v	180.00 (9)	C17—C18—C19	119.3 (5)
O12—Ca3—O17v	93.91 (15)	C17—C18—H18	120.3
O12v—Ca3—O17v	86.09 (15)	C19—C18—H18	120.3
O12—Ca3—O17	86.09 (15)	C20—C19—C18	119.1 (6)
O12v—Ca3—O17	93.91 (15)	C20—C19—H19	120.5
O17v—Ca3—O17	180.0 (3)	C18—C19—H19	120.5
O12—Ca3—O18	90.53 (16)	N3—C20—C19	122.1 (5)
O12v—Ca3—O18	89.48 (16)	N3—C20—C21	114.6 (5)
O17v—Ca3—O18	95.84 (18)	C19—C20—C21	123.3 (5)
O17—Ca3—O18	84.16 (18)	O12—C21—O11	125.4 (5)
O12—Ca3—O18v	89.47 (16)	O12—C21—C20	118.5 (5)
O12v—Ca3—O18v	90.53 (16)	O11—C21—C20	116.1 (5)
O17v—Ca3—O18v	84.16 (18)	H19A—O19—H19B	109 (5)
O17—Ca3—O18v	95.84 (18)	H20A—O20—H20B	110 (5)
O18—Ca3—O18v	180.0	H21A—O21—H21B	111 (4)
O12—Ca3—H17B	72.8 (11)
O5—Eu1—O1—C1	78.5 (4)	O11—Eu1—N3—C20	1.3 (4)
O7—Eu1—O1—C1	−152.5 (4)	O9—Eu1—N3—C20	−179.1 (4)
O3—Eu1—O1—C1	5.4 (5)	N2—Eu1—N3—C20	131.3 (4)
O11—Eu1—O1—C1	−72.0 (4)	N1—Eu1—N3—C20	−46.0 (4)
O9—Eu1—O1—C1	145.6 (4)	O5—Eu1—N3—C16	30.0 (5)
N2—Eu1—O1—C1	140.8 (4)	O7—Eu1—N3—C16	−98.5 (4)
N1—Eu1—O1—C1	3.2 (4)	O1—Eu1—N3—C16	−149.5 (4)
N3—Eu1—O1—C1	−101.8 (4)	O3—Eu1—N3—C16	82.3 (4)
O5—Eu1—O3—C7	−84.6 (4)	O11—Eu1—N3—C16	177.5 (4)
O7—Eu1—O3—C7	129.9 (4)	O9—Eu1—N3—C16	−2.9 (4)
O1—Eu1—O3—C7	−4.2 (5)	N2—Eu1—N3—C16	−52.5 (4)
O11—Eu1—O3—C7	68.7 (4)	N1—Eu1—N3—C16	130.2 (4)
O9—Eu1—O3—C7	−164.0 (4)	Ca2vi—O2—C1—O1	−8.5 (9)
N2—Eu1—O3—C7	−109.3 (4)	Ca2vi—O2—C1—C2	170.7 (3)
N1—Eu1—O3—C7	−2.1 (4)	Eu1—O1—C1—O2	179.0 (4)
N3—Eu1—O3—C7	131.4 (4)	Eu1—O1—C1—C2	−0.2 (6)
O7—Eu1—O5—C8	−0.5 (5)	C6—N1—C2—C3	2.3 (8)
O1—Eu1—O5—C8	72.5 (4)	Eu1—N1—C2—C3	−168.5 (4)
O3—Eu1—O5—C8	−159.0 (4)	C6—N1—C2—C1	179.4 (5)
O11—Eu1—O5—C8	140.8 (4)	Eu1—N1—C2—C1	8.6 (6)
O9—Eu1—O5—C8	−77.5 (4)	O2—C1—C2—N1	175.2 (5)
N2—Eu1—O5—C8	2.1 (4)	O1—C1—C2—N1	−5.5 (7)
N1—Eu1—O5—C8	135.1 (4)	O2—C1—C2—C3	−7.8 (8)
N3—Eu1—O5—C8	−107.2 (4)	O1—C1—C2—C3	171.5 (5)
O6ii—Ca2—O6—C8	66.7 (5)	N1—C2—C3—C4	−1.5 (9)
O2iii—Ca2—O6—C8	−46.3 (6)	C1—C2—C3—C4	−178.3 (5)
O2iv—Ca2—O6—C8	−152.2 (5)	C2—C3—C4—C5	−0.2 (9)
O15ii—Ca2—O6—C8	148.6 (5)	C3—C4—C5—C6	1.1 (10)
O15—Ca2—O6—C8	−7.1 (5)	C2—N1—C6—C5	−1.3 (8)
O16ii—Ca2—O6—C8	105.5 (5)	Eu1—N1—C6—C5	169.5 (4)
O16—Ca2—O6—C8	−91.7 (5)	C2—N1—C6—C7	−177.7 (5)
O5—Eu1—O7—C14	9.2 (4)	Eu1—N1—C6—C7	−7.0 (6)
O1—Eu1—O7—C14	−71.0 (4)	C4—C5—C6—N1	−0.4 (9)
O3—Eu1—O7—C14	145.0 (4)	C4—C5—C6—C7	175.7 (6)
O11—Eu1—O7—C14	−151.5 (4)	Eu1—O3—C7—O4	−179.7 (4)
O9—Eu1—O7—C14	81.2 (4)	Eu1—O3—C7—C6	−0.5 (7)
N2—Eu1—O7—C14	6.6 (4)	N1—C6—C7—O4	−175.9 (5)
N1—Eu1—O7—C14	−101.4 (4)	C5—C6—C7—O4	7.8 (9)
N3—Eu1—O7—C14	143.4 (4)	N1—C6—C7—O3	4.9 (7)
O14i—Ca1—O8—C14	−123.5 (8)	C5—C6—C7—O3	−171.4 (5)
O14—Ca1—O8—C14	56.5 (8)	Ca2—O6—C8—O5	−0.2 (9)
O13i—Ca1—O8—C14	144.1 (8)	Ca2—O6—C8—C9	178.4 (3)
O13—Ca1—O8—C14	−35.9 (8)	Eu1—O5—C8—O6	176.3 (4)
O5—Eu1—O9—C15	−157.9 (4)	Eu1—O5—C8—C9	−2.3 (6)
O7—Eu1—O9—C15	72.4 (4)	C13—N2—C9—C10	1.6 (8)
O1—Eu1—O9—C15	131.3 (4)	Eu1—N2—C9—C10	−176.9 (4)
O3—Eu1—O9—C15	−79.8 (4)	C13—N2—C9—C8	179.7 (4)
O11—Eu1—O9—C15	−1.2 (5)	Eu1—N2—C9—C8	1.2 (6)
N2—Eu1—O9—C15	136.1 (4)	O6—C8—C9—N2	−178.1 (4)
N1—Eu1—O9—C15	−104.8 (4)	O5—C8—C9—N2	0.6 (7)
N3—Eu1—O9—C15	−1.6 (4)	O6—C8—C9—C10	−0.1 (8)
O5—Eu1—O11—C21	133.3 (4)	O5—C8—C9—C10	178.7 (5)
O7—Eu1—O11—C21	−77.0 (4)	N2—C9—C10—C11	−1.0 (8)
O1—Eu1—O11—C21	−155.0 (4)	C8—C9—C10—C11	−178.9 (5)
O3—Eu1—O11—C21	75.8 (4)	C9—C10—C11—C12	−0.1 (8)
O9—Eu1—O11—C21	1.5 (5)	C10—C11—C12—C13	0.6 (8)
N2—Eu1—O11—C21	−106.3 (4)	C9—N2—C13—C12	−1.0 (7)
N1—Eu1—O11—C21	139.1 (4)	Eu1—N2—C13—C12	177.5 (4)
N3—Eu1—O11—C21	1.9 (4)	C9—N2—C13—C14	−179.4 (4)
O17v—Ca3—O12—C21	−129.5 (8)	Eu1—N2—C13—C14	−0.9 (6)
O17—Ca3—O12—C21	50.5 (8)	C11—C12—C13—N2	0.0 (8)
O18—Ca3—O12—C21	134.6 (8)	C11—C12—C13—C14	178.2 (5)
O18v—Ca3—O12—C21	−45.4 (8)	Ca1—O8—C14—O7	−107.4 (8)
O5—Eu1—N1—C6	85.5 (4)	Ca1—O8—C14—C13	73.3 (9)
O7—Eu1—N1—C6	−143.7 (4)	Eu1—O7—C14—O8	171.1 (4)
O1—Eu1—N1—C6	−176.9 (4)	Eu1—O7—C14—C13	−9.5 (6)
O3—Eu1—N1—C6	4.9 (4)	N2—C13—C14—O8	−174.2 (5)
O11—Eu1—N1—C6	−91.5 (4)	C12—C13—C14—O8	7.5 (8)
O9—Eu1—N1—C6	32.4 (5)	N2—C13—C14—O7	6.5 (7)
N2—Eu1—N1—C6	134.8 (4)	C12—C13—C14—O7	−171.9 (5)
N3—Eu1—N1—C6	−47.8 (4)	Eu1—O9—C15—O10	−173.7 (4)
O5—Eu1—N1—C2	−103.9 (4)	Eu1—O9—C15—C16	5.3 (7)
O7—Eu1—N1—C2	26.9 (5)	C20—N3—C16—C17	2.0 (8)
O1—Eu1—N1—C2	−6.3 (4)	Eu1—N3—C16—C17	−174.3 (4)
O3—Eu1—N1—C2	175.6 (4)	C20—N3—C16—C15	−177.5 (5)
O11—Eu1—N1—C2	79.2 (4)	Eu1—N3—C16—C15	6.3 (6)
O9—Eu1—N1—C2	−156.9 (3)	O10—C15—C16—N3	171.7 (5)
N2—Eu1—N1—C2	−54.5 (4)	O9—C15—C16—N3	−7.4 (7)
N3—Eu1—N1—C2	122.9 (4)	O10—C15—C16—C17	−7.7 (8)
O5—Eu1—N2—C9	−1.6 (3)	O9—C15—C16—C17	173.2 (5)
O7—Eu1—N2—C9	176.1 (4)	N3—C16—C17—C18	−1.8 (9)
O1—Eu1—N2—C9	−101.5 (4)	C15—C16—C17—C18	177.6 (5)
O3—Eu1—N2—C9	25.3 (4)	C16—C17—C18—C19	0.6 (9)
O11—Eu1—N2—C9	−151.8 (3)	C17—C18—C19—C20	0.4 (9)
O9—Eu1—N2—C9	81.1 (4)	C16—N3—C20—C19	−1.0 (8)
N1—Eu1—N2—C9	−57.2 (4)	Eu1—N3—C20—C19	175.3 (4)
N3—Eu1—N2—C9	125.5 (4)	C16—N3—C20—C21	−180.0 (5)
O5—Eu1—N2—C13	179.9 (4)	Eu1—N3—C20—C21	−3.7 (6)
O7—Eu1—N2—C13	−2.4 (3)	C18—C19—C20—N3	−0.2 (9)
O1—Eu1—N2—C13	80.0 (4)	C18—C19—C20—C21	178.7 (5)
O3—Eu1—N2—C13	−153.2 (3)	Ca3—O12—C21—O11	−98.7 (9)
O11—Eu1—N2—C13	29.7 (4)	Ca3—O12—C21—C20	81.6 (9)
O9—Eu1—N2—C13	−97.3 (4)	Eu1—O11—C21—O12	175.9 (4)
N1—Eu1—N2—C13	124.4 (4)	Eu1—O11—C21—C20	−4.4 (7)
N3—Eu1—N2—C13	−53.0 (4)	N3—C20—C21—O12	−175.2 (5)
O5—Eu1—N3—C20	−146.2 (4)	C19—C20—C21—O12	5.8 (8)
O7—Eu1—N3—C20	85.3 (4)	N3—C20—C21—O11	5.1 (7)
O1—Eu1—N3—C20	34.3 (5)	C19—C20—C21—O11	−173.9 (5)
O3—Eu1—N3—C20	−93.9 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O13—H13A···O10vii	0.85 (1)	1.97 (2)	2.796 (6)	163 (5)
O13—H13B···O20viii	0.85 (1)	1.85 (1)	2.696 (6)	175 (6)
O14—H14A···O16vi	0.85 (1)	1.96 (2)	2.774 (6)	160 (5)
O14—H14B···O9vi	0.85 (1)	1.91 (2)	2.723 (5)	160 (5)
O15—H15A···O21iii	0.85 (1)	1.99 (1)	2.839 (6)	172 (6)
O15—H15B···O5	0.85 (1)	1.90 (1)	2.734 (5)	165 (5)
O16—H16A···O13iii	0.78 (6)	2.38 (7)	3.079 (6)	150 (6)
O16—H16B···O1iii	0.84 (6)	1.88 (7)	2.704 (6)	169 (6)
O17—H17A···O3vi	0.85 (1)	1.91 (1)	2.745 (6)	167 (5)
O17—H17B···O19ix	0.85 (1)	1.93 (3)	2.722 (7)	155 (6)
O18—H18A···O22′x	0.85 (1)	2.37 (6)	2.990 (15)	130 (6)
O18—H18A···O22x	0.85 (1)	2.16 (7)	2.657 (14)	117 (6)
O18—H18B···O4vi	0.85 (1)	1.98 (2)	2.772 (6)	155 (5)
O19—H19A···O24xi	0.86 (1)	2.31 (3)	3.12 (2)	159 (6)
O19—H19B···O7xii	0.85 (1)	2.07 (4)	2.828 (6)	148 (6)
O20—H20A···O15	0.85 (1)	2.04 (2)	2.862 (6)	161 (6)
O20—H20B···O23	0.85 (1)	2.03 (4)	2.758 (10)	143 (6)
O20—H20B···O22′xiii	0.85 (1)	2.32 (4)	3.042 (13)	143 (5)
O21—H21A···O11	0.85 (1)	1.94 (2)	2.774 (6)	167 (6)
O21—H21B···O17	0.85 (1)	2.42 (4)	3.113 (7)	138 (5)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O13—H13A⋯O10i	0.85 (1)	1.97 (2)	2.796 (6)	163 (5)
O13—H13B⋯O20ii	0.85 (1)	1.85 (1)	2.696 (6)	175 (6)
O14—H14A⋯O16iii	0.85 (1)	1.96 (2)	2.774 (6)	160 (5)
O14—H14B⋯O9iii	0.85 (1)	1.91 (2)	2.723 (5)	160 (5)
O15—H15A⋯O21iv	0.85 (1)	1.99 (1)	2.839 (6)	172 (6)
O15—H15B⋯O5	0.85 (1)	1.90 (1)	2.734 (5)	165 (5)
O16—H16A⋯O13iv	0.78 (6)	2.38 (7)	3.079 (6)	150 (6)
O16—H16B⋯O1iv	0.84 (6)	1.88 (7)	2.704 (6)	169 (6)
O17—H17A⋯O3iii	0.85 (1)	1.91 (1)	2.745 (6)	167 (5)
O17—H17B⋯O19v	0.85 (1)	1.93 (3)	2.722 (7)	155 (6)
O18—H18A⋯O22′vi	0.85 (1)	2.37 (6)	2.990 (15)	130 (6)
O18—H18A⋯O22vi	0.85 (1)	2.16 (7)	2.657 (14)	117 (6)
O18—H18B⋯O4iii	0.85 (1)	1.98 (2)	2.772 (6)	155 (5)
O19—H19A⋯O24vii	0.86 (1)	2.31 (3)	3.12 (2)	159 (6)
O19—H19B⋯O7viii	0.85 (1)	2.07 (4)	2.828 (6)	148 (6)
O20—H20A⋯O15	0.85 (1)	2.04 (2)	2.862 (6)	161 (6)
O20—H20B⋯O23	0.85 (1)	2.03 (4)	2.758 (10)	143 (6)
O20—H20B⋯O22′ix	0.85 (1)	2.32 (4)	3.042 (13)	143 (5)
O21—H21A⋯O11	0.85 (1)	1.94 (2)	2.774 (6)	167 (6)
O21—H21B⋯O17	0.85 (1)	2.42 (4)	3.113 (7)	138 (5)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) ; (ix) .