Anion-directed assemblies of europium(III) coordination polymers based on 1H-benzimidazole-5,6-di­carboxyl­ate: structures and luminescence properties

Two europium(III) coordination polymers (CPs), namely, poly[[di­aqua­bis­(μ₄-1H-benzimidazole-5,6-di­carboxyl­ato-κ⁶N³:O⁵,O^5′:O⁵,O⁶:O^6′)(μ₂-oxalato-κ⁴O¹,O²:O^1′,O^2′)dieuropium(III)] dihydrate], {[Eu₂(C₉H₄N₂O₄)₂(C₂O₄)(H₂O)₂]·2H₂O}_n (1), and poly[(μ₃-1H-benzimidazol-3-ium-5,6-di­carboxyl­ato-κ⁵O⁵:O^5′,O⁶:O⁶,O^6′)(μ₃-sulfato-κ³O:O′:O′′)europium(III)], [Eu(C₉H₅N₂O₄)(SO₄)]_n (2), have been syn­thesized via the hydro­thermal method and structurally characterized. CP 1 shows a three-dimensional network, in which the oxalate ligand acts as a pillar, while CP 2 has a two-dimensional network based on a europium(III)–sulfate skeleton, further extended into a three-dimensional framework by hydrogen-bonding inter­actions. The structural diversity in the two com­pounds can be attributed to the different acidification abilities and geometries of the anionic ligands. The luminescence properties of 1 display the characteristic europium red emission with CIE chromaticity coordinates (2/3, 0.34). Inter­estingly, CP 2 shows the characteristic red emission with CIE chromaticity coordinates (0.60, 0.34) when excited at 280 nm and a near-white emission with CIE chromaticity coordinates (0.38, 0.29) when excited at 340 nm.

Computing details

Data collection: CrystalClear (Rigaku OD, 2005) for (1); SAINT (Bruker, 2012) for (2). Cell refinement: CrystalClear (Rigaku OD, 2005) for (1); APEX2 (Bruker, 2012) for (2). Data reduction: CrystalClear (Rigaku OD, 2005) for (1); SAINT (Bruker, 2012) for (2). For both structures, program(s) used to solve structure: olex2.solve (Bourhis et al., 2015); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Poly[[diaquabis(µ₄-1H-benzimidazole-5,6-dicarboxylato-κ⁶N³:O⁵,O^5':O⁵,O⁶:O^6')(µ₂-oxalato-κ⁴O¹,O²:O^1',O^2')dieuropium(III)] dihydrate] (1)

Crystal data

[Eu2(C9H4N2O4)2(C2O4)(H2O)2]·2H2O	Z = 1
Mr = 872.28	F(000) = 418
Triclinic, P1	Dx = 2.466 Mg m^−3
a = 7.4900 (15) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.4200 (19) Å	Cell parameters from 696 reflections
c = 9.6533 (19) Å	θ = 2.4–27.5°
α = 117.97 (3)°	µ = 5.39 mm^−1
β = 93.19 (3)°	T = 293 K
γ = 99.12 (3)°	Block, clear yellow
V = 587.3 (3) Å^3	0.2 × 0.2 × 0.15 mm

Data collection

Mercury2 (2x2 bin mode) diffractometer	2669 independent reflections
Radiation source: Sealed Tube	2403 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
ω scans	θmax = 27.4°, θmin = 2.5°
Absorption correction: multi-scan (CrystalClear; Rigaku OD, 2005)	h = −9→8
Tmin = 0.650, Tmax = 1.000	k = −10→12
4544 measured reflections	l = −12→12

Refinement

Refinement on F^2	Primary atom site location: iterative
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.080	w = 1/[σ^2(Fo^2) + (0.0284P)^2 + 1.6056P] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max < 0.001
2669 reflections	Δρmax = 2.17 e Å^−3
205 parameters	Δρmin = −1.98 e Å^−3
6 restraints

Special details

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 for 1 was collected on a Mercury70 CCD diffractometer (Mo Kα = 0.71073 Å) at room temperature. The structure was solved by a direct methods and refined on F² by full-matrix least-squares methods using the OLEX2 program package. All non-hydrogen atoms were refined anisotropically.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Eu1	0.12225 (4)	0.34001 (3)	0.31736 (3)	0.01315 (11)
O1	−0.0767 (5)	0.1837 (5)	0.0597 (5)	0.0189 (9)
C7	0.4084 (7)	0.3471 (7)	−0.2893 (7)	0.0134 (11)
C2	−0.0549 (7)	0.0403 (7)	−0.0355 (7)	0.0135 (11)
O3	−0.0414 (6)	0.4683 (5)	−0.2261 (5)	0.0195 (9)
O2	−0.1136 (6)	−0.0382 (5)	−0.1801 (5)	0.0201 (9)
O1W	−0.1517 (7)	0.2013 (5)	0.3770 (6)	0.0272 (11)
H1WA	−0.222 (8)	0.266 (7)	0.423 (8)	0.041*
H1WB	−0.163 (10)	0.133 (7)	0.412 (8)	0.041*
O4	0.1354 (5)	0.4942 (5)	−0.3894 (5)	0.0180 (9)
O6	0.6220 (5)	0.4190 (5)	−0.4316 (5)	0.0196 (9)
O5	0.3463 (5)	0.2691 (5)	−0.5621 (5)	0.0160 (8)
N2	0.5840 (7)	0.2290 (6)	0.0010 (6)	0.0192 (11)
H2	0.692 (10)	0.202 (8)	−0.011 (8)	0.029*
C9	0.4628 (8)	0.3513 (7)	−0.4363 (7)	0.0145 (12)
C1	0.4795 (8)	0.2333 (7)	0.1134 (7)	0.0195 (13)
H1	0.5147	0.2079	0.1916	0.023*
C3	0.1984 (8)	0.3534 (7)	−0.1001 (7)	0.0162 (12)
H3	0.0885	0.3712	−0.0614	0.019*
N1	0.3234 (7)	0.2772 (6)	0.1004 (6)	0.0164 (10)
C6	0.3242 (8)	0.3039 (7)	−0.0316 (7)	0.0138 (11)
C10	0.1033 (7)	0.4467 (6)	−0.2863 (7)	0.0128 (11)
C4	0.5347 (8)	0.2975 (7)	−0.2195 (7)	0.0168 (12)
H4	0.6460	0.2810	−0.2559	0.020*
C5	0.4889 (8)	0.2735 (7)	−0.0939 (7)	0.0140 (11)
C8	0.2391 (8)	0.3765 (7)	−0.2294 (7)	0.0136 (11)
O2W	0.8217 (11)	0.0418 (8)	0.5565 (8)	0.0605 (18)
H2WA	0.872 (13)	0.091 (11)	0.652 (4)	0.091*
H2WB	0.750 (12)	−0.044 (7)	0.543 (11)	0.091*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Eu1	0.01403 (16)	0.01565 (16)	0.00958 (17)	0.00388 (11)	0.00171 (11)	0.00573 (13)
O1	0.020 (2)	0.018 (2)	0.017 (2)	0.0093 (17)	−0.0011 (18)	0.0064 (19)
C7	0.012 (3)	0.017 (3)	0.011 (3)	0.003 (2)	0.001 (2)	0.007 (2)
C2	0.012 (3)	0.020 (3)	0.010 (3)	0.004 (2)	0.002 (2)	0.008 (2)
O3	0.019 (2)	0.026 (2)	0.017 (2)	0.0088 (18)	0.0033 (18)	0.012 (2)
O2	0.025 (2)	0.016 (2)	0.016 (2)	0.0008 (17)	−0.0059 (18)	0.0067 (19)
O1W	0.031 (3)	0.024 (2)	0.031 (3)	0.008 (2)	0.016 (2)	0.014 (2)
O4	0.019 (2)	0.024 (2)	0.016 (2)	0.0072 (18)	0.0047 (17)	0.0124 (19)
O6	0.015 (2)	0.023 (2)	0.022 (2)	0.0029 (17)	0.0065 (18)	0.012 (2)
O5	0.015 (2)	0.022 (2)	0.012 (2)	0.0022 (17)	0.0010 (16)	0.0085 (18)
N2	0.018 (3)	0.027 (3)	0.020 (3)	0.010 (2)	0.006 (2)	0.015 (2)
C9	0.019 (3)	0.014 (3)	0.013 (3)	0.009 (2)	0.004 (2)	0.006 (2)
C1	0.025 (3)	0.022 (3)	0.016 (3)	0.007 (3)	0.006 (3)	0.012 (3)
C3	0.013 (3)	0.018 (3)	0.018 (3)	0.002 (2)	0.007 (2)	0.009 (3)
N1	0.018 (3)	0.024 (3)	0.011 (3)	0.006 (2)	0.002 (2)	0.011 (2)
C6	0.016 (3)	0.018 (3)	0.011 (3)	0.007 (2)	0.004 (2)	0.009 (2)
C10	0.012 (3)	0.012 (3)	0.009 (3)	−0.001 (2)	−0.004 (2)	0.003 (2)
C4	0.016 (3)	0.020 (3)	0.015 (3)	0.005 (2)	0.005 (2)	0.009 (3)
C5	0.016 (3)	0.017 (3)	0.009 (3)	0.004 (2)	−0.001 (2)	0.007 (2)
C8	0.013 (3)	0.016 (3)	0.008 (3)	0.002 (2)	0.002 (2)	0.004 (2)
O2W	0.092 (6)	0.042 (4)	0.051 (4)	0.000 (3)	0.002 (4)	0.030 (3)

Geometric parameters (Å, º)

Eu1—O1	2.456 (4)	O4—Eu1^ii	2.595 (4)
Eu1—C2	3.259 (6)	O4—Eu1^v	2.489 (4)
Eu1—C2^i	3.260 (6)	O4—C10	1.288 (7)
Eu1—O3^ii	2.486 (4)	O6—Eu1^iv	2.465 (4)
Eu1—O2^i	2.498 (4)	O6—C9	1.248 (7)
Eu1—O1W	2.497 (4)	O5—Eu1^v	2.342 (4)
Eu1—O4^ii	2.595 (4)	O5—C9	1.274 (7)
Eu1—O4^iii	2.489 (4)	N2—H2	0.88 (7)
Eu1—O6^iv	2.465 (4)	N2—C1	1.361 (7)
Eu1—O5^iii	2.342 (4)	N2—C5	1.381 (7)
Eu1—N1	2.545 (5)	C1—H1	0.9300
Eu1—C10^ii	2.926 (5)	C1—N1	1.318 (8)
O1—C2	1.272 (7)	C3—H3	0.9300
C7—C9	1.514 (7)	C3—C6	1.380 (8)
C7—C4	1.390 (8)	C3—C8	1.404 (8)
C7—C8	1.436 (7)	N1—C6	1.410 (7)
C2—Eu1^i	3.260 (6)	C6—C5	1.413 (8)
C2—C2^i	1.532 (11)	C10—Eu1^ii	2.926 (5)
C2—O2	1.244 (7)	C10—C8	1.506 (8)
O3—Eu1^ii	2.486 (4)	C4—H4	0.9300
O3—C10	1.259 (7)	C4—C5	1.385 (8)
O2—Eu1^i	2.498 (4)	O2W—H2WA	0.848 (10)
O1W—H1WA	0.846 (10)	O2W—H2WB	0.847 (10)
O1W—H1WB	0.847 (10)
O1—Eu1—C2	20.06 (13)	N1—Eu1—O4^ii	131.76 (13)
O1—Eu1—C2^i	46.83 (13)	N1—Eu1—C10^ii	105.79 (15)
O1—Eu1—O3^ii	70.28 (13)	C10^ii—Eu1—C2^i	118.38 (15)
O1—Eu1—O2^i	65.52 (13)	C10^ii—Eu1—C2	91.63 (15)
O1—Eu1—O1W	76.81 (15)	C2—O1—Eu1	118.4 (4)
O1—Eu1—O4^iii	145.90 (13)	C4—C7—C9	113.2 (5)
O1—Eu1—O4^ii	82.28 (13)	C4—C7—C8	120.7 (5)
O1—Eu1—O6^iv	133.81 (14)	C8—C7—C9	125.9 (5)
O1—Eu1—N1	71.86 (15)	Eu1—C2—Eu1^i	152.81 (19)
O1—Eu1—C10^ii	71.66 (14)	O1—C2—Eu1	41.5 (3)
C2—Eu1—C2^i	27.19 (19)	O1—C2—Eu1^i	163.4 (4)
O3^ii—Eu1—C2	87.50 (14)	O1—C2—C2^i	116.5 (6)
O3^ii—Eu1—C2^i	113.71 (14)	C2^i—C2—Eu1	76.4 (4)
O3^ii—Eu1—O2^i	133.56 (14)	C2^i—C2—Eu1^i	76.4 (4)
O3^ii—Eu1—O1W	111.46 (15)	O2—C2—Eu1^i	43.0 (3)
O3^ii—Eu1—O4^iii	104.18 (13)	O2—C2—Eu1	162.0 (4)
O3^ii—Eu1—O4^ii	50.97 (12)	O2—C2—O1	125.7 (5)
O3^ii—Eu1—N1	81.74 (14)	O2—C2—C2^i	117.8 (6)
O3^ii—Eu1—C10^ii	25.25 (14)	C10—O3—Eu1^ii	97.3 (3)
O2^i—Eu1—C2	46.62 (13)	C2—O2—Eu1^i	117.2 (3)
O2^i—Eu1—C2^i	19.86 (13)	Eu1—O1W—H1WA	112 (4)
O2^i—Eu1—O4^ii	131.93 (14)	Eu1—O1W—H1WB	131 (5)
O2^i—Eu1—N1	71.89 (15)	H1WA—O1W—H1WB	105.8 (17)
O2^i—Eu1—C10^ii	135.58 (15)	Eu1^v—O4—Eu1^ii	110.09 (15)
O1W—Eu1—C2	78.76 (15)	C10—O4—Eu1^v	132.2 (4)
O1W—Eu1—C2^i	76.60 (14)	C10—O4—Eu1^ii	91.5 (3)
O1W—Eu1—O2^i	71.75 (14)	C9—O6—Eu1^iv	151.5 (4)
O1W—Eu1—O4^ii	66.60 (14)	C9—O5—Eu1^v	133.0 (3)
O1W—Eu1—N1	139.25 (16)	C1—N2—H2	127 (5)
O1W—Eu1—C10^ii	87.91 (15)	C1—N2—C5	107.1 (5)
O4^ii—Eu1—C2^i	122.92 (14)	C5—N2—H2	126 (5)
O4^iii—Eu1—C2	152.96 (13)	O6—C9—C7	119.0 (5)
O4^ii—Eu1—C2	101.26 (14)	O6—C9—O5	124.2 (5)
O4^iii—Eu1—C2^i	138.51 (13)	O5—C9—C7	116.4 (5)
O4^iii—Eu1—O2^i	120.25 (13)	N2—C1—H1	123.3
O4^iii—Eu1—O1W	74.28 (15)	N1—C1—N2	113.4 (5)
O4^iii—Eu1—O4^ii	69.91 (15)	N1—C1—H1	123.3
O4^iii—Eu1—N1	141.95 (15)	C6—C3—H3	120.6
O4^iii—Eu1—C10^ii	89.49 (14)	C6—C3—C8	118.9 (5)
O4^ii—Eu1—C10^ii	26.10 (13)	C8—C3—H3	120.6
O6^iv—Eu1—C2^i	135.80 (13)	C1—N1—Eu1	120.6 (4)
O6^iv—Eu1—C2	136.64 (13)	C1—N1—C6	105.0 (5)
O6^iv—Eu1—O3^ii	73.19 (14)	C6—N1—Eu1	133.5 (3)
O6^iv—Eu1—O2^i	132.08 (14)	C3—C6—N1	131.2 (5)
O6^iv—Eu1—O1W	144.30 (14)	C3—C6—C5	120.0 (5)
O6^iv—Eu1—O4^ii	95.99 (13)	N1—C6—C5	108.8 (5)
O6^iv—Eu1—O4^iii	70.39 (14)	O3—C10—Eu1^ii	57.4 (3)
O6^iv—Eu1—N1	75.83 (15)	O3—C10—O4	118.5 (5)
O6^iv—Eu1—C10^ii	86.76 (14)	O3—C10—C8	119.6 (5)
O5^iii—Eu1—O1	131.67 (13)	O4—C10—Eu1^ii	62.4 (3)
O5^iii—Eu1—C2^i	84.95 (14)	O4—C10—C8	121.8 (5)
O5^iii—Eu1—C2	111.65 (14)	C8—C10—Eu1^ii	165.0 (4)
O5^iii—Eu1—O3^ii	147.90 (14)	C7—C4—H4	121.2
O5^iii—Eu1—O2^i	67.25 (14)	C5—C4—C7	117.6 (5)
O5^iii—Eu1—O1W	97.83 (15)	C5—C4—H4	121.2
O5^iii—Eu1—O4^ii	140.17 (13)	N2—C5—C6	105.7 (5)
O5^iii—Eu1—O4^iii	70.60 (13)	N2—C5—C4	131.6 (5)
O5^iii—Eu1—O6^iv	75.36 (14)	C4—C5—C6	122.6 (5)
O5^iii—Eu1—N1	84.53 (14)	C7—C8—C10	124.3 (5)
O5^iii—Eu1—C10^ii	156.66 (15)	C3—C8—C7	120.2 (5)
N1—Eu1—C2	62.99 (15)	C3—C8—C10	115.3 (5)
N1—Eu1—C2^i	63.03 (15)	H2WA—O2W—H2WB	105.8 (17)
Eu1—O1—C2—Eu1^i	155.2 (11)	O4—C10—C8—C3	170.7 (5)
Eu1—O1—C2—C2^i	16.5 (7)	N2—C1—N1—Eu1	−170.3 (4)
Eu1—O1—C2—O2	−162.9 (4)	N2—C1—N1—C6	0.1 (7)
Eu1—C2—O2—Eu1^i	157.0 (10)	C9—C7—C4—C5	−173.6 (5)
Eu1^ii—O3—C10—O4	−13.4 (5)	C9—C7—C8—C3	173.9 (5)
Eu1^ii—O3—C10—C8	162.8 (4)	C9—C7—C8—C10	−11.9 (9)
Eu1^v—O4—C10—Eu1^ii	−119.2 (4)	C1—N2—C5—C6	0.0 (6)
Eu1^ii—O4—C10—O3	12.8 (5)	C1—N2—C5—C4	176.2 (6)
Eu1^v—O4—C10—O3	−106.4 (5)	C1—N1—C6—C3	−179.1 (6)
Eu1^ii—O4—C10—C8	−163.4 (5)	C1—N1—C6—C5	−0.1 (6)
Eu1^v—O4—C10—C8	77.5 (7)	C3—C6—C5—N2	179.2 (5)
Eu1^iv—O6—C9—C7	−58.0 (10)	C3—C6—C5—C4	2.6 (9)
Eu1^iv—O6—C9—O5	129.9 (7)	N1—C6—C5—N2	0.1 (6)
Eu1^v—O5—C9—C7	96.1 (5)	N1—C6—C5—C4	−176.6 (5)
Eu1^v—O5—C9—O6	−91.6 (6)	C6—C3—C8—C7	0.6 (8)
Eu1—N1—C6—C3	−10.5 (10)	C6—C3—C8—C10	−174.1 (5)
Eu1—N1—C6—C5	168.5 (4)	C4—C7—C9—O6	−47.3 (7)
Eu1^ii—C10—C8—C7	−105.7 (14)	C4—C7—C9—O5	125.4 (5)
Eu1^ii—C10—C8—C3	68.8 (15)	C4—C7—C8—C3	−0.7 (8)
O1—C2—O2—Eu1^i	−163.8 (4)	C4—C7—C8—C10	173.5 (5)
C7—C4—C5—N2	−178.3 (6)	C5—N2—C1—N1	−0.1 (7)
C7—C4—C5—C6	−2.6 (9)	C8—C7—C9—O6	137.7 (6)
C2^i—C2—O2—Eu1^i	16.8 (7)	C8—C7—C9—O5	−49.6 (8)
O3—C10—C8—C7	−179.8 (5)	C8—C7—C4—C5	1.7 (8)
O3—C10—C8—C3	−5.4 (8)	C8—C3—C6—N1	177.4 (6)
O4—C10—C8—C7	−3.7 (9)	C8—C3—C6—C5	−1.5 (9)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O6^vi	0.85 (1)	2.06 (2)	2.896 (6)	170 (6)
O1W—H1WB···O2W^vii	0.85 (1)	1.96 (3)	2.771 (7)	161 (7)
N2—H2···O1^viii	0.88 (7)	1.89 (7)	2.715 (6)	155 (7)
O2W—H2WA···O2^ix	0.85 (1)	2.44 (8)	3.008 (7)	125 (8)
O2W—H2WB···O5^x	0.85 (1)	2.22 (4)	3.025 (7)	159 (9)

Symmetry codes: (vi) x−1, y, z+1; (vii) x−1, y, z; (viii) x+1, y, z; (ix) x+1, y, z+1; (x) −x+1, −y, −z.

Poly[(µ₃-1H-benzimidazol-3-ium-5,6-dicarboxylato-κ⁵O⁵:O^5',O⁶:O⁶,O^6')(µ₃-sulfato-κ³O,O',O'')europium(III)] (2)

Crystal data

[Eu(C9H5N2O4)(SO4)]	Z = 2
Mr = 453.17	F(000) = 432
Triclinic, P1	Dx = 2.676 Mg m^−3
a = 6.9610 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.9482 (9) Å	Cell parameters from 6853 reflections
c = 10.9901 (13) Å	θ = 2.7–25.7°
α = 101.579 (4)°	µ = 5.81 mm^−1
β = 106.761 (4)°	T = 298 K
γ = 95.588 (4)°	Block, clear brown
V = 562.51 (11) Å^3	0.14 × 0.12 × 0.1 mm

Data collection

Bruker APEXII CCD diffractometer	1954 reflections with I > 2σ(I)
Radiation source: 6853	Rint = 0.058
φ and ω scans	θmax = 25.7°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −8→8
Tmin = 0.058, Tmax = 0.092	k = −9→9
10824 measured reflections	l = −13→13
2149 independent reflections

Refinement

Refinement on F^2	Primary atom site location: iterative
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.028	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.058	w = 1/[σ^2(Fo^2) + (0.0103P)^2 + 1.9181P] where P = (Fo^2 + 2Fc^2)/3
S = 1.11	(Δ/σ)max < 0.001
2149 reflections	Δρmax = 0.94 e Å^−3
196 parameters	Δρmin = −1.08 e Å^−3
2 restraints

Special details

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 for 2 was collected on Bruker APEXII CCD with graphite-monochromated (Mo Kα = 0.71073 Å) at room temperature. The structure was solved by a direct methods and refined on F² by full-matrix least-squares methods using the OLEX2 program package. All non-hydrogen atoms were refined anisotropically.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Eu1	0.33734 (4)	0.67677 (3)	0.94671 (3)	0.01456 (9)
S1	0.78370 (19)	0.59927 (16)	0.84882 (12)	0.0155 (3)
O5	0.5768 (5)	0.0810 (4)	0.8835 (3)	0.0165 (8)
O8	0.3747 (5)	0.3640 (4)	0.8773 (3)	0.0169 (8)
O3	0.9841 (5)	0.7182 (5)	0.8962 (4)	0.0190 (8)
O2	0.8014 (5)	0.4562 (4)	0.9175 (3)	0.0174 (8)
O4	0.7307 (6)	0.5265 (5)	0.7078 (3)	0.0224 (8)
O1	0.6310 (5)	0.7017 (4)	0.8793 (3)	0.0180 (8)
O6	0.2928 (5)	−0.1123 (4)	0.8251 (3)	0.0173 (8)
O7	0.2161 (6)	0.4874 (5)	0.7245 (4)	0.0218 (8)
N1	0.1856 (7)	−0.1924 (6)	0.3237 (4)	0.0188 (10)
C7	0.1927 (7)	0.0841 (7)	0.4208 (5)	0.0166 (11)
N2	0.1171 (7)	0.0561 (6)	0.2854 (4)	0.0176 (9)
C1	0.2952 (7)	0.3604 (7)	0.7553 (5)	0.0151 (11)
C8	0.3338 (7)	0.0418 (7)	0.6723 (5)	0.0169 (11)
C3	0.1139 (8)	−0.1086 (7)	0.2314 (5)	0.0179 (11)
H3	0.0682	−0.1587	0.1419	0.022*
C5	0.2175 (7)	0.2269 (7)	0.5223 (5)	0.0172 (11)
H5	0.1871	0.3333	0.5061	0.021*
C6	0.2351 (8)	−0.0777 (7)	0.4438 (5)	0.0164 (11)
C4	0.3050 (8)	−0.0999 (7)	0.5702 (5)	0.0182 (11)
H4	0.3316	−0.2075	0.5853	0.022*
C2	0.4068 (8)	0.0038 (6)	0.8063 (5)	0.0145 (11)
C9	0.2896 (7)	0.2066 (6)	0.6501 (5)	0.0147 (11)
H1	0.196 (9)	−0.301 (2)	0.307 (5)	0.022*
H2	0.071 (8)	0.124 (6)	0.236 (5)	0.022*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Eu1	0.01161 (14)	0.01631 (14)	0.01529 (14)	0.00305 (10)	0.00343 (10)	0.00361 (10)
S1	0.0116 (6)	0.0176 (6)	0.0177 (7)	0.0030 (5)	0.0042 (5)	0.0052 (5)
O5	0.0152 (18)	0.0178 (18)	0.0151 (18)	0.0035 (15)	0.0039 (15)	0.0018 (15)
O8	0.0187 (19)	0.0156 (18)	0.0137 (18)	0.0040 (15)	0.0025 (15)	0.0010 (14)
O3	0.0118 (18)	0.0196 (19)	0.026 (2)	0.0034 (15)	0.0048 (15)	0.0077 (16)
O2	0.0142 (18)	0.0215 (19)	0.0192 (19)	0.0043 (15)	0.0069 (15)	0.0084 (16)
O4	0.024 (2)	0.026 (2)	0.017 (2)	0.0067 (17)	0.0054 (16)	0.0035 (16)
O1	0.0151 (18)	0.0182 (19)	0.023 (2)	0.0052 (15)	0.0075 (15)	0.0067 (16)
O6	0.0139 (18)	0.0203 (19)	0.0198 (19)	0.0051 (15)	0.0052 (15)	0.0086 (16)
O7	0.023 (2)	0.020 (2)	0.020 (2)	0.0077 (16)	0.0036 (16)	0.0030 (16)
N1	0.020 (2)	0.018 (2)	0.016 (2)	0.002 (2)	0.0056 (19)	0.0014 (19)
C7	0.012 (2)	0.020 (3)	0.017 (3)	0.000 (2)	0.004 (2)	0.003 (2)
N2	0.016 (2)	0.022 (2)	0.016 (2)	0.0038 (19)	0.0060 (19)	0.0053 (19)
C1	0.005 (2)	0.023 (3)	0.016 (3)	0.002 (2)	0.003 (2)	0.003 (2)
C8	0.011 (2)	0.021 (3)	0.018 (3)	0.001 (2)	0.004 (2)	0.005 (2)
C3	0.013 (3)	0.021 (3)	0.018 (3)	0.001 (2)	0.004 (2)	0.003 (2)
C5	0.014 (3)	0.019 (3)	0.020 (3)	0.007 (2)	0.006 (2)	0.007 (2)
C6	0.016 (3)	0.021 (3)	0.014 (3)	0.004 (2)	0.009 (2)	0.000 (2)
C4	0.013 (3)	0.019 (3)	0.020 (3)	0.003 (2)	0.003 (2)	0.006 (2)
C2	0.016 (3)	0.013 (3)	0.014 (3)	0.004 (2)	0.005 (2)	−0.001 (2)
C9	0.010 (2)	0.017 (3)	0.017 (3)	0.002 (2)	0.007 (2)	0.003 (2)

Geometric parameters (Å, º)

Eu1—Eu1^i	3.9278 (6)	O3—Eu1^iv	2.430 (3)
Eu1—O5^i	2.288 (3)	O2—Eu1^i	2.354 (3)
Eu1—O8	2.512 (3)	O6—Eu1^v	2.335 (3)
Eu1—O8^i	2.451 (3)	O6—C2	1.246 (6)
Eu1—O3^ii	2.430 (3)	O7—C1	1.255 (6)
Eu1—O2^i	2.354 (3)	N1—C3	1.329 (6)
Eu1—O1	2.371 (3)	N1—C6	1.374 (7)
Eu1—O6^iii	2.335 (3)	C7—N2	1.390 (6)
Eu1—O7	2.456 (4)	C7—C5	1.380 (7)
Eu1—C1	2.865 (5)	C7—C6	1.402 (7)
Eu1—C2^i	3.248 (5)	N2—C3	1.320 (7)
S1—O3	1.496 (4)	C1—C9	1.494 (7)
S1—O2	1.482 (3)	C8—C4	1.373 (7)
S1—O4	1.463 (4)	C8—C2	1.515 (7)
S1—O1	1.473 (4)	C8—C9	1.426 (7)
O5—Eu1^i	2.288 (3)	C5—C9	1.396 (7)
O5—C2	1.252 (6)	C6—C4	1.386 (7)
O8—Eu1^i	2.451 (3)	C2—Eu1^i	3.248 (5)
O8—C1	1.288 (6)
O5^i—Eu1—Eu1^i	109.17 (8)	O7—Eu1—C1	25.84 (12)
O5^i—Eu1—O8^i	71.40 (12)	O7—Eu1—C2^i	160.19 (13)
O5^i—Eu1—O8	145.56 (11)	C1—Eu1—Eu1^i	61.97 (10)
O5^i—Eu1—O3^ii	89.18 (12)	C1—Eu1—C2^i	153.87 (13)
O5^i—Eu1—O2^i	84.71 (12)	C2^i—Eu1—Eu1^i	96.45 (9)
O5^i—Eu1—O1	99.90 (12)	O2—S1—O3	108.8 (2)
O5^i—Eu1—O6^iii	81.45 (12)	O4—S1—O3	109.3 (2)
O5^i—Eu1—O7	161.57 (12)	O4—S1—O2	109.4 (2)
O5^i—Eu1—C1	170.40 (13)	O4—S1—O1	111.1 (2)
O5^i—Eu1—C2^i	16.94 (12)	O1—S1—O3	107.8 (2)
O8—Eu1—Eu1^i	37.13 (8)	O1—S1—O2	110.3 (2)
O8^i—Eu1—Eu1^i	38.22 (8)	C2—O5—Eu1^i	130.9 (3)
O8^i—Eu1—O8	75.35 (12)	Eu1^i—O8—Eu1	104.65 (12)
O8^i—Eu1—O7	123.85 (12)	C1—O8—Eu1	92.1 (3)
O8^i—Eu1—C1	99.35 (13)	C1—O8—Eu1^i	148.7 (3)
O8—Eu1—C1	26.69 (12)	S1—O3—Eu1^iv	134.8 (2)
O8—Eu1—C2^i	133.54 (12)	S1—O2—Eu1^i	142.6 (2)
O8^i—Eu1—C2^i	58.27 (12)	S1—O1—Eu1	141.1 (2)
O3^ii—Eu1—Eu1^i	137.94 (8)	C2—O6—Eu1^v	135.6 (3)
O3^ii—Eu1—O8	112.78 (12)	C1—O7—Eu1	95.6 (3)
O3^ii—Eu1—O8^i	142.48 (12)	C3—N1—C6	108.6 (4)
O3^ii—Eu1—O7	82.99 (12)	N2—C7—C6	105.3 (4)
O3^ii—Eu1—C1	100.02 (13)	C5—C7—N2	133.0 (5)
O3^ii—Eu1—C2^i	106.07 (12)	C5—C7—C6	121.6 (5)
O2^i—Eu1—Eu1^i	71.45 (8)	C3—N2—C7	109.1 (4)
O2^i—Eu1—O8	77.39 (12)	O8—C1—Eu1	61.2 (3)
O2^i—Eu1—O8^i	73.37 (12)	O8—C1—C9	121.5 (4)
O2^i—Eu1—O3^ii	73.11 (12)	O7—C1—Eu1	58.5 (3)
O2^i—Eu1—O1	141.40 (12)	O7—C1—O8	119.1 (5)
O2^i—Eu1—O7	108.68 (12)	O7—C1—C9	119.3 (4)
O2^i—Eu1—C1	95.25 (13)	C9—C1—Eu1	173.5 (3)
O2^i—Eu1—C2^i	90.93 (12)	C4—C8—C2	114.1 (4)
O1—Eu1—Eu1^i	70.88 (8)	C4—C8—C9	121.4 (5)
O1—Eu1—O8	77.80 (11)	C9—C8—C2	124.4 (5)
O1—Eu1—O8^i	72.04 (12)	N2—C3—N1	110.0 (5)
O1—Eu1—O3^ii	144.58 (12)	C7—C5—C9	117.9 (5)
O1—Eu1—O7	77.77 (12)	N1—C6—C7	107.0 (4)
O1—Eu1—C1	74.17 (13)	N1—C6—C4	131.9 (5)
O1—Eu1—C2^i	85.20 (13)	C4—C6—C7	121.0 (5)
O6^iii—Eu1—Eu1^i	145.98 (9)	C8—C4—C6	118.1 (5)
O6^iii—Eu1—O8	129.42 (12)	O5—C2—Eu1^i	32.2 (2)
O6^iii—Eu1—O8^i	132.65 (12)	O5—C2—C8	118.8 (4)
O6^iii—Eu1—O3^ii	72.09 (12)	O6—C2—Eu1^i	118.4 (3)
O6^iii—Eu1—O2^i	142.57 (12)	O6—C2—O5	126.2 (5)
O6^iii—Eu1—O1	75.51 (12)	O6—C2—C8	114.9 (4)
O6^iii—Eu1—O7	80.27 (12)	C8—C2—Eu1^i	118.2 (3)
O6^iii—Eu1—C1	103.91 (13)	C8—C9—C1	124.3 (4)
O6^iii—Eu1—C2^i	85.78 (12)	C5—C9—C1	115.5 (4)
O7—Eu1—Eu1^i	87.53 (8)	C5—C9—C8	120.0 (5)
O7—Eu1—O8	52.36 (11)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2^vi	0.86 (1)	2.54 (5)	3.062 (6)	120 (4)
N1—H1···O4^vi	0.86 (1)	1.90 (2)	2.750 (6)	169 (6)
N2—H2···O3^vii	0.86 (1)	2.09 (2)	2.927 (5)	168 (5)
N2—H2···O6^viii	0.86 (1)	2.41 (5)	2.878 (6)	115 (4)

Symmetry codes: (vi) −x+1, −y, −z+1; (vii) −x+1, −y+1, −z+1; (viii) −x, −y, −z+1.