catena-Poly[[[triaqua­europium(III)]-μ-(1H-benzimidazole-5,6-dicarboxyl­ato-κ2O5:O6)-μ-(1H,3H-benzimidazol-3-ium-5,6-dicarboxyl­ato-κ3O5:O6,O6′)] dihydrate]

Chen, X.-Y.; Huo, S.-M.; Lin, J.-J.; Cai, X.; Zeng, R.-H.

doi:10.1107/S1600536811033496

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 9| September 2011| Pages m1294-m1295

doi:10.1107/S1600536811033496

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catena-Poly[[[triaquaeuropium(III)]-μ-(1H-benzimidazole-5,6-dicarboxylato-κ²O⁵:O⁶)-μ-(1H,3H-benzimidazol-3-ium-5,6-dicarboxylato-κ³O⁵:O⁶,O^6′)] dihydrate]

Xiao-Ye Chen,^a Shu-Min Huo,^a Jing-Jun Lin,^a Xia Cai ^a and Rong-Hua Zeng ^a,^b ^*

^aSchool of Chemistry and the Environment, South China Normal University, Guangzhou 510006, People's Republic of China, and ^bKey Laboratory of Technology on Electrochemical Energy Storage and Power Generation in Guangdong Universities, South China Normal University, Guangzhou 510006, People's Republic of China
^*Correspondence e-mail: zrh321@yahoo.com.cn

(Received 11 August 2011; accepted 17 August 2011; online 27 August 2011)

In the title one-dimensional coordination polymer, {[Eu(C₉H₄N₂O₄)(C₉H₅N₂O₄)(H₂O)₃]·2H₂O}_n, one of the 1H-benzimidazole-5,6-dicarboxylate (Hbdc) ligands is protonated at the imidazole group (H₂bdc). The Eu^III ion is eight-coordinated by two O atoms from two Hbdc ligands, three O atoms from two H₂bdc ligands and three water molecules, showing a distorted square-antiprismatic geometry. The Eu^III ions are bridged by the carboxylate groups of the Hbdc and H₂bdc ligands, forming a chain along [110], with an Eu⋯Eu separation of 5.4594 (3) Å. These chains are further connected by intermolecular O—H⋯O, N—H⋯O and N—H⋯N hydrogen bonds, as well as π–π interactions between the imidazole and benzene rings [centroid–centroid distances = 3.558 (3), 3.906 (2), 3.397 (3), 3.796 (2) and 3.898 (2) Å], into a three-dimensional supramolecular network.

Related literature

For background to 1H-benzimidazole-5,6-dicarboxylate complexes, see: Fu et al. (2009 ); Huang et al. (2009 ); Pan et al. (2010 ); Wei et al. (2009 ); Yao et al. (2008 ).

Experimental

Crystal data

[Eu(C₉H₄N₂O₄)(C₉H₅N₂O₄)(H₂O)₃]·2H₂O
M_r = 651.33
Triclinic, $[P \overline 1]$
a = 8.4530 (4) Å
b = 10.9757 (6) Å
c = 12.7124 (7) Å
α = 112.112 (1)°
β = 91.614 (1)°
γ = 104.453 (1)°
V = 1048.25 (10) Å³
Z = 2
Mo Kα radiation
μ = 3.08 mm⁻¹
T = 298 K
0.24 × 0.22 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.526, T_max = 0.578
5435 measured reflections
3711 independent reflections
3454 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.057
S = 1.04
3711 reflections
328 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.63 e Å⁻³
Δρ_min = −0.67 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O1	0.85	1.95	2.727 (4)	152
O1W—H1WB⋯O4ⁱ	0.85	1.93	2.709 (4)	152
O2W—H2WA⋯O8	0.85	1.89	2.687 (4)	155
O2W—H2WB⋯O4W	0.85	2.23	2.608 (5)	107
O3W—H3WA⋯O7ⁱⁱ	0.85	2.01	2.815 (4)	159
O3W—H3WB⋯O5Wⁱⁱ	0.85	1.96	2.685 (4)	142
O4W—H4WA⋯O2ⁱⁱⁱ	0.85	2.19	2.968 (4)	153
O4W—H4WB⋯O1W^iv	0.85	2.49	3.022 (4)	122
O4W—H4WB⋯O4ⁱⁱⁱ	0.85	2.37	3.151 (4)	153
O5W—H5WA⋯O5	0.85	1.97	2.815 (4)	172
O5W—H5WB⋯O4^v	0.85	1.99	2.757 (4)	150
N1—H1⋯O1^vi	0.86	2.06	2.900 (4)	165
N3—H3A⋯N2^vii	0.86	1.88	2.725 (5)	168
N4—H4⋯O6^viii	0.86	1.98	2.750 (4)	148
Symmetry codes: (i) -x, -y, -z; (ii) x-1, y, z; (iii) -x, -y+1, -z; (iv) -x+1, -y+1, -z; (v) x+1, y, z; (vi) -x, -y, -z-1; (vii) x+2, y+1, z+1; (viii) -x+1, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, glogal. DOI: 10.1107/S1600536811033496/hy2459sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811033496/hy2459Isup2.hkl

checkCIF report

Comment top

There is currently much interest in employing N-heterocyclic carboxylic acids as multidentate ligands to design metal coordination polymers with intriguing structures and potential applications. Particular attention has been paid to 1H-benzimidazole-5,6-dicarboxylic acid (H₃bdc) ligand. It has rich coordination sites (two N atoms and four O atoms) and can be partially or fully deprotonated to produce [H₂bdc]^-, [Hbdc]^2- and [bdc]^3- anions at different pH values. Thus, H₃bdc can potentially afford different coordination modes in multicoordinated ways with transition metal ions (Fu et al., 2009; Wei et al., 2009) or rare earth metal ions (Huang et al., 2009; Pan et al., 2010; Yao et al., 2008) to form metal coordination polymers with various structures and interesting properties. In this paper, we report the crystal structure of the title compound, which was synthesized under hydrothermal conditions.

As shown in Fig. 1, the title compound has two forms of the ligands, [Hbdc]^2- and [H₂bdc]^- anions, and the latter is protonated at the imidazole group. The Eu^III ion is eight-coordinated by five O atoms from two Hbdc and two H₂bdc ligands and by three water molecules. The coordination geometry around the Eu^III ion can be described as distorted square-antiprismatic, with Eu—O bond lengths ranging from 2.343 (2) to 2.656 (3) Å and O—Eu—O bond angles varying from 68.99 (9) to 156.77 (9)°. In the crystal, the Eu^III ions are alternately bridged by the carboxylate groups of the Hbdc and H₂bdc ligands, forming chains along [1 1 0] (Fig. 2). These chains are further connected by intermolecular O—H···O, N—H···O and N—H···N hydrogen bonds (Table 1), as well as π–π interactions between the imidazole and benzene rings [centroid–centroid distances = 3.558 (3), 3.906 (2), 3.397 (3), 3.796 (2) and 3.898 (2) Å], into a three-dimensional supramolecular network (Fig. 3).

Related literature top

For background to 1H-benzimidazole-5,6-dicarboxylate complexes, see: Fu et al. (2009); Huang et al. (2009); Pan et al. (2010); Wei et al. (2009); Yao et al. (2008).

Experimental top

A mixture of Eu₂O₃ (0.352 g, 1 mmol), H₃bdc (0.206 g, 1 mmol), water (10 ml) in the presence of HClO₄ (0.039 g, 0.385 mmol) was stirred vigorously for 30 min and then sealed in a 20 ml Teflon-lined stainless-steel autoclave. The autoclave was heated and maintained at 443 K for 3 days, and then cooled to room temperature at 5K h^-1. Colorless block crystals of the title compound were obtained.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of the title compound, showing displacement ellipsoids drawn at the 30% probability level. [Symmetry codes: (i) 1-x, 1-y, -z; (ii) -x, -y, -z.]
	Fig. 2. The crystal packing of the title compound, showing the chain structure extending along [1 1 0].
	Fig. 3. The crystal packing of the title compound, showing the three-dimensional supramolecular network. Hydrogen bonds are shown as dashed lines.

catena-Poly[[[triaquaeuropium(III)]-µ-(1H- benzimidazole-5,6-dicarboxylato-κ²O⁵:O⁶)-µ- (1H,3H-benzimidazol-3-ium-5,6-dicarboxylato- κ³O⁵:O⁶,O^6')] dihydrate] top

Crystal data top

[Eu(C₉H₄N₂O₄)(C₉H₅N₂O₄)(H₂O)₃]·2H₂O	Z = 2
M_r = 651.33	F(000) = 644
Triclinic, P1	D_x = 2.064 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.4530 (4) Å	Cell parameters from 3764 reflections
b = 10.9757 (6) Å	θ = 2.8–25.2°
c = 12.7124 (7) Å	µ = 3.08 mm⁻¹
α = 112.112 (1)°	T = 298 K
β = 91.614 (1)°	Block, colorless
γ = 104.453 (1)°	0.24 × 0.22 × 0.20 mm
V = 1048.25 (10) Å³

Data collection top

Bruker APEXII CCD diffractometer	3711 independent reflections
Radiation source: fine-focus sealed tube	3454 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
ϕ and ω scans	θ_max = 25.2°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −10→10
T_min = 0.526, T_max = 0.578	k = −13→7
5435 measured reflections	l = −13→15

Refinement top

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.057	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0269P)² + 1.5288P] where P = (F_o² + 2F_c²)/3
3711 reflections	(Δ/σ)_max = 0.001
328 parameters	Δρ_max = 0.63 e Å⁻³
0 restraints	Δρ_min = −0.67 e Å⁻³

Crystal data top

[Eu(C₉H₄N₂O₄)(C₉H₅N₂O₄)(H₂O)₃]·2H₂O	γ = 104.453 (1)°
M_r = 651.33	V = 1048.25 (10) Å³
Triclinic, P1	Z = 2
a = 8.4530 (4) Å	Mo Kα radiation
b = 10.9757 (6) Å	µ = 3.08 mm⁻¹
c = 12.7124 (7) Å	T = 298 K
α = 112.112 (1)°	0.24 × 0.22 × 0.20 mm
β = 91.614 (1)°

Data collection top

Bruker APEXII CCD diffractometer	3711 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	3454 reflections with I > 2σ(I)
T_min = 0.526, T_max = 0.578	R_int = 0.016
5435 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	0 restraints
wR(F²) = 0.057	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.63 e Å⁻³
3711 reflections	Δρ_min = −0.67 e Å⁻³
328 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.0343 (4)	0.0408 (4)	−0.2244 (3)	0.0189 (8)
C2	−0.1313 (4)	−0.0377 (4)	−0.2964 (3)	0.0187 (8)
C3	−0.1457 (5)	−0.0513 (4)	−0.4085 (3)	0.0244 (9)
H3	−0.051 (5)	−0.019 (4)	−0.434 (3)	0.029*
C4	−0.3019 (5)	−0.1056 (4)	−0.4725 (3)	0.0232 (8)
C5	−0.5240 (5)	−0.1795 (4)	−0.5977 (3)	0.0299 (9)
H5	−0.5915	−0.2033	−0.6655	0.036*
C6	−0.4412 (4)	−0.1460 (4)	−0.4248 (3)	0.0213 (8)
C7	−0.4269 (4)	−0.1359 (4)	−0.3119 (3)	0.0210 (8)
H7	−0.5196	−0.1642	−0.2801	0.025*
C8	−0.2722 (4)	−0.0831 (4)	−0.2488 (3)	0.0171 (7)
C9	−0.2606 (4)	−0.0819 (4)	−0.1297 (3)	0.0185 (8)
C10	0.5024 (4)	0.4467 (4)	0.2501 (3)	0.0198 (8)
C11	0.6702 (4)	0.5243 (4)	0.3216 (3)	0.0174 (7)
C12	0.6891 (4)	0.5302 (4)	0.4319 (3)	0.0219 (8)
H12	0.6019	0.4883	0.4609	0.026*
C13	0.8420 (4)	0.6003 (4)	0.4979 (3)	0.0198 (8)
C14	1.0585 (5)	0.7001 (4)	0.6311 (3)	0.0271 (9)
H14	1.1247	0.7334	0.7012	0.033*
C15	0.9760 (4)	0.6562 (4)	0.4530 (3)	0.0190 (8)
C16	0.9601 (4)	0.6502 (4)	0.3422 (3)	0.0198 (8)
H16	1.0501	0.6869	0.3122	0.024*
C17	0.8053 (4)	0.5876 (4)	0.2777 (3)	0.0174 (7)
C18	0.7878 (4)	0.6050 (4)	0.1667 (3)	0.0174 (7)
Eu1	0.24165 (2)	0.308010 (18)	0.021383 (14)	0.01508 (7)
N1	−0.3591 (4)	−0.1283 (4)	−0.5833 (3)	0.0302 (8)
H1	−0.3003	−0.1126	−0.6334	0.036*
N2	−0.5797 (4)	−0.1922 (4)	−0.5056 (3)	0.0271 (8)
N3	1.1094 (4)	0.7157 (3)	0.5386 (3)	0.0239 (7)
H3A	1.2081	0.7556	0.5326	0.029*
N4	0.8992 (4)	0.6303 (3)	0.6108 (3)	0.0248 (7)
H4	0.8422	0.6080	0.6591	0.030*
O1	0.1619 (3)	0.0246 (3)	−0.2694 (2)	0.0282 (6)
O2	0.0329 (3)	0.1254 (3)	−0.1235 (2)	0.0218 (6)
O3	−0.1766 (3)	−0.1539 (3)	−0.1112 (2)	0.0232 (6)
O4	−0.3436 (3)	−0.0182 (3)	−0.0613 (2)	0.0286 (6)
O5	0.5008 (3)	0.3761 (3)	0.1434 (2)	0.0233 (6)
O6	0.3781 (3)	0.4550 (3)	0.2988 (3)	0.0357 (7)
O7	0.8941 (3)	0.5849 (3)	0.1007 (2)	0.0251 (6)
O8	0.6729 (3)	0.6529 (3)	0.1488 (2)	0.0217 (6)
O1W	0.3986 (3)	0.1495 (3)	−0.0826 (2)	0.0225 (6)
H1WA	0.3469	0.0936	−0.1481	0.027*
H1WB	0.4122	0.1032	−0.0442	0.027*
O2W	0.3436 (3)	0.5492 (3)	0.1002 (3)	0.0327 (7)
H2WA	0.4404	0.5907	0.1361	0.039*
H2WB	0.3295	0.5815	0.0506	0.039*
O3W	0.0181 (3)	0.3743 (3)	0.1123 (2)	0.0277 (6)
H3WA	−0.0036	0.4498	0.1257	0.033*
H3WB	−0.0456	0.3322	0.1459	0.033*
O4W	0.2568 (4)	0.7730 (3)	0.1413 (3)	0.0389 (7)
H4WA	0.1577	0.7772	0.1398	0.047*
H4WB	0.3140	0.8382	0.1259	0.047*
O5W	0.7262 (3)	0.2225 (3)	0.1315 (2)	0.0302 (6)
H5WA	0.6621	0.2706	0.1300	0.036*
H5WB	0.7262	0.1686	0.0628	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0164 (18)	0.0202 (19)	0.0207 (19)	−0.0007 (15)	−0.0012 (14)	0.0129 (16)
C2	0.0184 (18)	0.0187 (19)	0.0173 (18)	0.0028 (15)	0.0028 (14)	0.0067 (15)
C3	0.0187 (19)	0.033 (2)	0.0191 (19)	0.0015 (17)	0.0035 (15)	0.0109 (17)
C4	0.0226 (19)	0.032 (2)	0.0153 (18)	0.0067 (17)	0.0029 (15)	0.0101 (16)
C5	0.025 (2)	0.041 (3)	0.019 (2)	0.0059 (18)	−0.0054 (16)	0.0098 (18)
C6	0.0217 (19)	0.022 (2)	0.0167 (18)	0.0034 (16)	−0.0014 (14)	0.0063 (15)
C7	0.0173 (18)	0.025 (2)	0.0215 (19)	0.0038 (16)	0.0048 (15)	0.0121 (16)
C8	0.0197 (18)	0.0151 (18)	0.0170 (18)	0.0041 (14)	0.0004 (14)	0.0077 (15)
C9	0.0188 (18)	0.0167 (18)	0.0170 (18)	−0.0018 (15)	−0.0015 (14)	0.0080 (15)
C10	0.0157 (18)	0.0199 (19)	0.023 (2)	0.0002 (15)	−0.0022 (15)	0.0109 (16)
C11	0.0139 (17)	0.0192 (19)	0.0152 (17)	0.0018 (14)	−0.0015 (13)	0.0046 (15)
C12	0.0168 (18)	0.026 (2)	0.023 (2)	0.0023 (16)	0.0042 (15)	0.0119 (17)
C13	0.0201 (18)	0.025 (2)	0.0155 (18)	0.0077 (16)	0.0029 (14)	0.0082 (16)
C14	0.029 (2)	0.028 (2)	0.018 (2)	0.0055 (18)	−0.0055 (16)	0.0060 (17)
C15	0.0159 (17)	0.0169 (19)	0.0201 (19)	0.0034 (15)	−0.0010 (14)	0.0038 (15)
C16	0.0170 (18)	0.0217 (19)	0.0204 (19)	0.0017 (15)	0.0030 (14)	0.0102 (16)
C17	0.0189 (18)	0.0171 (18)	0.0168 (18)	0.0042 (15)	0.0017 (14)	0.0080 (15)
C18	0.0144 (17)	0.0149 (18)	0.0190 (18)	−0.0025 (14)	−0.0023 (14)	0.0071 (15)
Eu1	0.01417 (10)	0.01681 (11)	0.01459 (10)	0.00295 (7)	0.00063 (6)	0.00757 (7)
N1	0.0256 (18)	0.049 (2)	0.0148 (16)	0.0055 (16)	0.0020 (13)	0.0141 (16)
N2	0.0207 (16)	0.035 (2)	0.0213 (17)	0.0029 (15)	−0.0044 (13)	0.0102 (15)
N3	0.0139 (15)	0.0304 (19)	0.0211 (17)	0.0001 (13)	−0.0064 (12)	0.0079 (14)
N4	0.0252 (17)	0.0329 (19)	0.0171 (16)	0.0051 (15)	0.0009 (13)	0.0129 (15)
O1	0.0166 (13)	0.0372 (17)	0.0244 (14)	0.0037 (12)	0.0034 (11)	0.0075 (13)
O2	0.0195 (13)	0.0199 (14)	0.0184 (13)	−0.0001 (11)	−0.0002 (10)	0.0032 (11)
O3	0.0231 (14)	0.0250 (14)	0.0281 (14)	0.0046 (11)	0.0029 (11)	0.0191 (12)
O4	0.0384 (16)	0.0338 (16)	0.0204 (14)	0.0179 (13)	0.0094 (12)	0.0128 (12)
O5	0.0226 (13)	0.0224 (14)	0.0220 (14)	0.0039 (11)	−0.0043 (11)	0.0077 (12)
O6	0.0157 (14)	0.052 (2)	0.0389 (17)	0.0044 (13)	0.0067 (12)	0.0197 (15)
O7	0.0228 (14)	0.0356 (16)	0.0224 (14)	0.0111 (12)	0.0055 (11)	0.0155 (12)
O8	0.0192 (13)	0.0260 (14)	0.0260 (14)	0.0080 (11)	0.0040 (10)	0.0160 (12)
O1W	0.0239 (14)	0.0249 (14)	0.0194 (13)	0.0065 (11)	0.0000 (10)	0.0099 (11)
O2W	0.0279 (15)	0.0213 (15)	0.0426 (18)	0.0016 (12)	−0.0120 (13)	0.0103 (13)
O3W	0.0262 (14)	0.0305 (16)	0.0355 (16)	0.0138 (12)	0.0128 (12)	0.0187 (13)
O4W	0.0299 (16)	0.0295 (17)	0.061 (2)	0.0109 (13)	0.0063 (14)	0.0200 (15)
O5W	0.0301 (15)	0.0324 (16)	0.0254 (15)	0.0093 (13)	0.0014 (12)	0.0084 (13)

Geometric parameters (Å, º) top

C1—O1	1.256 (4)	C14—H14	0.9300
C1—O2	1.272 (4)	C15—N3	1.382 (4)
C1—C2	1.507 (5)	C15—C16	1.386 (5)
C2—C3	1.374 (5)	C16—C17	1.387 (5)
C2—C8	1.416 (5)	C16—H16	0.9300
C3—C4	1.394 (5)	C17—C18	1.502 (5)
C3—H3	0.91 (4)	C18—O7	1.249 (4)
C4—N1	1.385 (5)	C18—O8	1.267 (4)
C4—C6	1.391 (5)	Eu1—O3ⁱ	2.344 (2)
C5—N2	1.318 (5)	Eu1—O2W	2.360 (3)
C5—N1	1.345 (5)	Eu1—O3W	2.369 (3)
C5—H5	0.9300	Eu1—O2	2.407 (2)
C6—N2	1.388 (5)	Eu1—O5	2.425 (2)
C6—C7	1.396 (5)	Eu1—O8ⁱⁱ	2.453 (2)
C7—C8	1.379 (5)	Eu1—O1W	2.460 (2)
C7—H7	0.9300	Eu1—O7ⁱⁱ	2.656 (3)
C8—C9	1.509 (5)	N1—H1	0.8600
C9—O4	1.248 (4)	N3—H3A	0.8600
C9—O3	1.263 (4)	N4—H4	0.8600
C10—O6	1.239 (4)	O1W—H1WA	0.8500
C10—O5	1.282 (4)	O1W—H1WB	0.8500
C10—C11	1.518 (5)	O2W—H2WA	0.8500
C11—C12	1.382 (5)	O2W—H2WB	0.8498
C11—C17	1.424 (5)	O3W—H3WA	0.8500
C12—C13	1.387 (5)	O3W—H3WB	0.8500
C12—H12	0.9300	O4W—H4WA	0.8500
C13—N4	1.388 (5)	O4W—H4WB	0.8500
C13—C15	1.393 (5)	O5W—H5WA	0.8499
C14—N3	1.319 (5)	O5W—H5WB	0.8500
C14—N4	1.335 (5)

O1—C1—O2	125.0 (3)	O2W—Eu1—O5	70.78 (9)
O1—C1—C2	118.5 (3)	O3W—Eu1—O5	116.75 (9)
O2—C1—C2	116.3 (3)	O2—Eu1—O5	147.35 (9)
C3—C2—C8	120.3 (3)	O3ⁱ—Eu1—O8ⁱⁱ	147.47 (9)
C3—C2—C1	117.4 (3)	O2W—Eu1—O8ⁱⁱ	79.57 (10)
C8—C2—C1	122.0 (3)	O3W—Eu1—O8ⁱⁱ	123.60 (9)
C2—C3—C4	118.8 (3)	O2—Eu1—O8ⁱⁱ	80.30 (8)
C2—C3—H3	116 (3)	O5—Eu1—O8ⁱⁱ	103.24 (8)
C4—C3—H3	125 (3)	O3ⁱ—Eu1—O1W	81.33 (9)
N1—C4—C6	105.6 (3)	O2W—Eu1—O1W	124.88 (9)
N1—C4—C3	133.3 (3)	O3W—Eu1—O1W	156.77 (9)
C6—C4—C3	121.0 (3)	O2—Eu1—O1W	77.56 (8)
N2—C5—N1	112.8 (3)	O5—Eu1—O1W	73.73 (8)
N2—C5—H5	123.6	O8ⁱⁱ—Eu1—O1W	69.16 (8)
N1—C5—H5	123.6	O3ⁱ—Eu1—O7ⁱⁱ	142.44 (8)
N2—C6—C4	109.1 (3)	O2W—Eu1—O7ⁱⁱ	68.99 (9)
N2—C6—C7	130.4 (3)	O3W—Eu1—O7ⁱⁱ	72.82 (8)
C4—C6—C7	120.5 (3)	O2—Eu1—O7ⁱⁱ	71.98 (9)
C8—C7—C6	118.5 (3)	O5—Eu1—O7ⁱⁱ	135.26 (8)
C8—C7—H7	120.8	O8ⁱⁱ—Eu1—O7ⁱⁱ	50.84 (8)
C6—C7—H7	120.8	O1W—Eu1—O7ⁱⁱ	115.56 (8)
C7—C8—C2	120.9 (3)	O3ⁱ—Eu1—C18ⁱⁱ	154.10 (9)
C7—C8—C9	116.8 (3)	O2W—Eu1—C18ⁱⁱ	73.39 (10)
C2—C8—C9	122.2 (3)	O3W—Eu1—C18ⁱⁱ	98.19 (10)
O4—C9—O3	125.9 (3)	O2—Eu1—C18ⁱⁱ	73.86 (9)
O4—C9—C8	117.4 (3)	O5—Eu1—C18ⁱⁱ	121.97 (9)
O3—C9—C8	116.5 (3)	O8ⁱⁱ—Eu1—C18ⁱⁱ	25.48 (9)
O6—C10—O5	125.0 (3)	O1W—Eu1—C18ⁱⁱ	92.14 (9)
O6—C10—C11	118.1 (3)	O7ⁱⁱ—Eu1—C18ⁱⁱ	25.38 (9)
O5—C10—C11	116.9 (3)	O3ⁱ—Eu1—H2WB	146.1
C12—C11—C17	120.4 (3)	O2W—Eu1—H2WB	16.6
C12—C11—C10	117.4 (3)	O3W—Eu1—H2WB	80.6
C17—C11—C10	122.2 (3)	O2—Eu1—H2WB	125.6
C11—C12—C13	118.0 (3)	O5—Eu1—H2WB	83.6
C11—C12—H12	121.0	O8ⁱⁱ—Eu1—H2WB	65.6
C13—C12—H12	121.0	O1W—Eu1—H2WB	122.2
C12—C13—N4	132.5 (3)	O7ⁱⁱ—Eu1—H2WB	53.7
C12—C13—C15	121.4 (3)	C18ⁱⁱ—Eu1—H2WB	56.9
N4—C13—C15	106.1 (3)	C5—N1—C4	107.0 (3)
N3—C14—N4	111.0 (3)	C5—N1—H1	126.5
N3—C14—H14	124.5	C4—N1—H1	126.5
N4—C14—H14	124.5	C5—N2—C6	105.5 (3)
N3—C15—C16	131.3 (3)	C14—N3—C15	107.8 (3)
N3—C15—C13	107.3 (3)	C14—N3—H3A	126.1
C16—C15—C13	121.4 (3)	C15—N3—H3A	126.1
C15—C16—C17	117.6 (3)	C14—N4—C13	107.8 (3)
C15—C16—H16	121.2	C14—N4—H4	126.1
C17—C16—H16	121.2	C13—N4—H4	126.1
C16—C17—C11	121.0 (3)	C1—O2—Eu1	133.9 (2)
C16—C17—C18	115.4 (3)	C9—O3—Eu1ⁱ	129.4 (2)
C11—C17—C18	123.3 (3)	C10—O5—Eu1	116.1 (2)
O7—C18—O8	122.0 (3)	C18—O7—Eu1ⁱⁱ	88.9 (2)
O7—C18—C17	119.8 (3)	C18—O8—Eu1ⁱⁱ	98.1 (2)
O8—C18—C17	117.8 (3)	Eu1—O1W—H1WA	111.5
O7—C18—Eu1ⁱⁱ	65.67 (19)	Eu1—O1W—H1WB	108.5
O8—C18—Eu1ⁱⁱ	56.45 (17)	H1WA—O1W—H1WB	107.7
C17—C18—Eu1ⁱⁱ	169.2 (2)	Eu1—O2W—H2WA	122.2
O3ⁱ—Eu1—O2W	130.52 (10)	Eu1—O2W—H2WB	111.0
O3ⁱ—Eu1—O3W	80.33 (9)	H2WA—O2W—H2WB	107.7
O2W—Eu1—O3W	78.17 (10)	Eu1—O3W—H3WA	125.9
O3ⁱ—Eu1—O2	80.26 (9)	Eu1—O3W—H3WB	125.9
O2W—Eu1—O2	140.57 (9)	H3WA—O3W—H3WB	107.7
O3W—Eu1—O2	85.39 (9)	H4WA—O4W—H4WB	107.7
O3ⁱ—Eu1—O5	80.37 (9)	H5WA—O5W—H5WB	107.7

O1—C1—C2—C3	−39.6 (5)	C16—C17—C18—O7	47.4 (5)
O2—C1—C2—C3	136.4 (4)	C11—C17—C18—O7	−139.2 (4)
O1—C1—C2—C8	147.3 (4)	C16—C17—C18—O8	−125.8 (4)
O2—C1—C2—C8	−36.7 (5)	C11—C17—C18—O8	47.7 (5)
C8—C2—C3—C4	2.4 (6)	C16—C17—C18—Eu1ⁱⁱ	−70.7 (14)
C1—C2—C3—C4	−170.8 (4)	C11—C17—C18—Eu1ⁱⁱ	102.8 (12)
C2—C3—C4—N1	177.5 (4)	N2—C5—N1—C4	0.0 (5)
C2—C3—C4—C6	−0.2 (6)	C6—C4—N1—C5	0.0 (5)
N1—C4—C6—N2	0.0 (4)	C3—C4—N1—C5	−178.0 (5)
C3—C4—C6—N2	178.3 (4)	N1—C5—N2—C6	0.0 (5)
N1—C4—C6—C7	−179.8 (4)	C4—C6—N2—C5	0.0 (5)
C3—C4—C6—C7	−1.5 (6)	C7—C6—N2—C5	179.7 (4)
N2—C6—C7—C8	−178.7 (4)	N4—C14—N3—C15	1.6 (5)
C4—C6—C7—C8	1.0 (6)	C16—C15—N3—C14	176.2 (4)
C6—C7—C8—C2	1.1 (5)	C13—C15—N3—C14	−1.6 (4)
C6—C7—C8—C9	−176.4 (3)	N3—C14—N4—C13	−1.0 (5)
C3—C2—C8—C7	−2.9 (6)	C12—C13—N4—C14	179.4 (4)
C1—C2—C8—C7	170.0 (3)	C15—C13—N4—C14	0.0 (4)
C3—C2—C8—C9	174.5 (4)	O1—C1—O2—Eu1	8.7 (6)
C1—C2—C8—C9	−12.6 (5)	C2—C1—O2—Eu1	−166.9 (2)
C7—C8—C9—O4	−58.4 (5)	O3ⁱ—Eu1—O2—C1	−112.6 (3)
C2—C8—C9—O4	124.1 (4)	O2W—Eu1—O2—C1	101.4 (3)
C7—C8—C9—O3	116.7 (4)	O3W—Eu1—O2—C1	166.5 (3)
C2—C8—C9—O3	−60.7 (5)	O5—Eu1—O2—C1	−58.2 (4)
O6—C10—C11—C12	37.3 (5)	O8ⁱⁱ—Eu1—O2—C1	41.2 (3)
O5—C10—C11—C12	−142.0 (4)	O1W—Eu1—O2—C1	−29.4 (3)
O6—C10—C11—C17	−143.7 (4)	O7ⁱⁱ—Eu1—O2—C1	93.1 (3)
O5—C10—C11—C17	37.0 (5)	C18ⁱⁱ—Eu1—O2—C1	66.6 (3)
C17—C11—C12—C13	0.7 (6)	O4—C9—O3—Eu1ⁱ	41.5 (5)
C10—C11—C12—C13	179.8 (3)	C8—C9—O3—Eu1ⁱ	−133.1 (3)
C11—C12—C13—N4	176.6 (4)	O6—C10—O5—Eu1	17.8 (5)
C11—C12—C13—C15	−4.0 (6)	C11—C10—O5—Eu1	−163.0 (2)
C12—C13—C15—N3	−178.6 (3)	O3ⁱ—Eu1—O5—C10	−75.4 (2)
N4—C13—C15—N3	1.0 (4)	O2W—Eu1—O5—C10	63.8 (2)
C12—C13—C15—C16	3.4 (6)	O3W—Eu1—O5—C10	−1.4 (3)
N4—C13—C15—C16	−177.1 (3)	O2—Eu1—O5—C10	−129.7 (2)
N3—C15—C16—C17	−176.9 (4)	O8ⁱⁱ—Eu1—O5—C10	137.6 (2)
C13—C15—C16—C17	0.6 (5)	O1W—Eu1—O5—C10	−159.1 (3)
C15—C16—C17—C11	−3.8 (5)	O7ⁱⁱ—Eu1—O5—C10	90.8 (3)
C15—C16—C17—C18	169.9 (3)	C18ⁱⁱ—Eu1—O5—C10	118.8 (2)
C12—C11—C17—C16	3.2 (6)	O8—C18—O7—Eu1ⁱⁱ	3.3 (3)
C10—C11—C17—C16	−175.8 (3)	C17—C18—O7—Eu1ⁱⁱ	−169.6 (3)
C12—C11—C17—C18	−169.9 (3)	O7—C18—O8—Eu1ⁱⁱ	−3.6 (4)
C10—C11—C17—C18	11.1 (5)	C17—C18—O8—Eu1ⁱⁱ	169.4 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O1	0.85	1.95	2.727 (4)	152
O1W—H1WB···O4ⁱ	0.85	1.93	2.709 (4)	152
O2W—H2WA···O8	0.85	1.89	2.687 (4)	155
O2W—H2WB···O4W	0.85	2.23	2.608 (5)	107
O3W—H3WA···O7ⁱⁱⁱ	0.85	2.01	2.815 (4)	159
O3W—H3WB···O5Wⁱⁱⁱ	0.85	1.96	2.685 (4)	142
O4W—H4WA···O2^iv	0.85	2.19	2.968 (4)	153
O4W—H4WB···O1Wⁱⁱ	0.85	2.49	3.022 (4)	122
O4W—H4WB···O4^iv	0.85	2.37	3.151 (4)	153
O5W—H5WA···O5	0.85	1.97	2.815 (4)	172
O5W—H5WB···O4^v	0.85	1.99	2.757 (4)	150
N1—H1···O1^vi	0.86	2.06	2.900 (4)	165
N3—H3A···N2^vii	0.86	1.88	2.725 (5)	168
N4—H4···O6^viii	0.86	1.98	2.750 (4)	148

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

Experimental details

Crystal data
Chemical formula	[Eu(C₉H₄N₂O₄)(C₉H₅N₂O₄)(H₂O)₃]·2H₂O
M_r	651.33
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	8.4530 (4), 10.9757 (6), 12.7124 (7)
α, β, γ (°)	112.112 (1), 91.614 (1), 104.453 (1)
V (Å³)	1048.25 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.08
Crystal size (mm)	0.24 × 0.22 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.526, 0.578
No. of measured, independent and observed [I > 2σ(I)] reflections	5435, 3711, 3454
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.057, 1.04
No. of reflections	3711
No. of parameters	328
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.63, −0.67

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O1	0.85	1.95	2.727 (4)	152
O1W—H1WB···O4ⁱ	0.85	1.93	2.709 (4)	152
O2W—H2WA···O8	0.85	1.89	2.687 (4)	155
O2W—H2WB···O4W	0.85	2.23	2.608 (5)	107
O3W—H3WA···O7ⁱⁱ	0.85	2.01	2.815 (4)	159
O3W—H3WB···O5Wⁱⁱ	0.85	1.96	2.685 (4)	142
O4W—H4WA···O2ⁱⁱⁱ	0.85	2.19	2.968 (4)	153
O4W—H4WB···O1W^iv	0.85	2.49	3.022 (4)	122
O4W—H4WB···O4ⁱⁱⁱ	0.85	2.37	3.151 (4)	153
O5W—H5WA···O5	0.85	1.97	2.815 (4)	172
O5W—H5WB···O4^v	0.85	1.99	2.757 (4)	150
N1—H1···O1^vi	0.86	2.06	2.900 (4)	165
N3—H3A···N2^vii	0.86	1.88	2.725 (5)	168
N4—H4···O6^viii	0.86	1.98	2.750 (4)	148

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

Acknowledgements

The authors acknowledge the Undergraduates Innovating Experimentation Project of Guangdong Province, the Undergraduates Innovating Experimentation Project of South China Normal University and the Students Extracurricular Scientific Research Project of South China Normal University for supporting this work.

References

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