Di-μ-benzoato-κ3O,O′:O′;κ3O:O,O′-bis[aqua­bis­(benzoato-κ2O,O′)(dimethylformamide-κO)europium(III)]

Wang, Z.; Zhou, X.

doi:10.1107/S1600536811042735

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Pages m1579-m1580

doi:10.1107/S1600536811042735

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Di-μ-benzoato-κ³O,O′:O′;κ³O:O,O′-bis[aquabis(benzoato-κ²O,O′)(dimethylformamide-κO)europium(III)]

Zhiliang Wang ^a ^* and Xianju Zhou ^b

^aCollege of Optoelectronic Engineering, Chongqing University of Post and Telecommunications, Chongqing 400065, People's Republic of China, and ^bDepartment of Mathematics and Physics, Chongqing University of Post and Telecommunications, Chongqing 400065, People's Republic of China
^*Correspondence e-mail: wzll-232612@163.com

(Received 21 September 2011; accepted 15 October 2011; online 22 October 2011)

The title dimeric complex, [Eu₂(C₇H₅O₂)₆(C₃H₇NO)₂(H₂O)₂], is centrosymmetric, implying that pairs of equivalent Eu³⁺ ions and ligands lie trans to each other and that the two Eu³⁺ ions have exactly the same coordination environment. Each Eu³⁺ ion is nine-coordinated by two bidentate benzoate ligands, two bridging tridentate chelating benzoate ligands, and one dimethylformamide and one water molecule. The coordination polyhedron of each Eu³⁺ ion can be described with a distorted monocapped square-antiprismatic geometry. The molecular structure is stabilized by intra- and intermolecular hydrogen bonds between the water molecules and benzoate O atoms.

Related literature

For properties of rare earth compounds derived from carboxylic acids, see: Chin et al. (1994 ); Singh et al. (2002 ). For related compounds, see: Jin et al. (1996 ); Gubina et al. (2000 ); Wang et al. (2003 ); Qiu et al. (2007 ); Ooi et al. (2010 ).

Experimental

Crystal data

[Eu₂(C₇H₅O₂)₆(C₃H₇NO)₂(H₂O)₂]
M_r = 1212.80
Monoclinic, P 2₁ /c
a = 11.6395 (2) Å
b = 8.3692 (1) Å
c = 25.5235 (4) Å
β = 101.460 (2)°
V = 2436.76 (6) Å³
Z = 2
Cu Kα radiation
μ = 18.84 mm⁻¹
T = 291 K
0.36 × 0.32 × 0.32 mm

Data collection

Oxford Gemini S Ultra diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction, Yarnton, Oxfordshire, England.]$ ) T_min = 0.056, T_max = 0.065
8782 measured reflections
4294 independent reflections
3860 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.120
S = 1.03
4294 reflections
315 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.20 e Å⁻³
Δρ_min = −1.92 e Å⁻³

Table 1
Selected bond lengths (Å)

Eu1—O8	2.368 (4)
Eu1—O4	2.368 (3)
Eu1—O7	2.404 (4)
Eu1—O2	2.416 (3)
Eu1—O3	2.416 (3)
Eu1—O5	2.420 (4)
Eu1—O6	2.500 (3)
Eu1—O1	2.584 (4)
Eu1—O4ⁱ	2.889 (4)
Symmetry code: (i) -x+1, -y+1, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7B⋯O6ⁱⁱ	0.86 (2)	1.90 (2)	2.756 (5)	174 (9)
O7—H7A⋯O2ⁱ	0.86 (2)	1.90 (4)	2.724 (5)	159 (9)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x+1, -y, -z+1.

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction, Yarnton, Oxfordshire, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811042735/vn2018sup1.cif

Supporting information file. DOI: 10.1107/S1600536811042735/vn2018Isup2.cdx

Structure factors: contains datablock I. DOI: 10.1107/S1600536811042735/vn2018Isup3.hkl

checkCIF report

Comment top

Because of their excellent luminescent properties (Chin et al., 1994; Singh et al., 2002), rare earth–carboxylic acid complexes have been widely studied and applied in many fields. Distinct structure features with various rare earths (Qiu et al., 2007; Gubina et al., 2000) or ligands (Jin et al., 1996; Wang et al., 2003) have been reported. The title compound, (I) was synthesized and its structure was determined. Similar crystal structure with benzoate as ligands have been reported recently (Ooi et al., 2010).

The centrosymmetric structure of the title complex (I) is shown in Fig. 1. The two Eu³⁺ ions are bridged by two tridentate bridging carboxylates. Each of the two Eu³⁺ ions is further coordinated by two chelating carboxlates, one DMF molecule and one water molecule, with an overall coordination number of nine. Eu—O bond distances are presented in Table 1.

In the crystal structure, intermolecular O7—H7B···O6ⁱⁱ hydrogen bonds (Table 2) link molecules into chains along the b axis (Fig. 2). The molecular structure is stabilized by intramolecular O7—H7A···O2ⁱ hydrogen bonds (Table 2).

Related literature top

For luminescence properties of rare earth–carboxylic acid complexes, see: Chin et al. (1994); Singh et al. (2002). For related compounds, see: Jin et al. (1996); Gubina et al. (2000); Wang et al. (2003); Qiu et al. (2007); Ooi et al. (2010).

Experimental top

0.5 g Eu₂O₃ (Strem, 99.99%) was dissolved in 5 ml 37% HCl and the solution was evaporated to dryness. 10 ml water was added to the residue and the pH was adjusted to 8 by the addition of NH₃ (aq). The ensuing precipitate was filtered, washed with water and dried. This precipitate was added to a solution containing 1 g C₆H₅COOH and 20 ml DMF with stirring. The mixture was vigorously stirred and filtered. The filtrate was put in a beaker covered with parafilm and left in a dark fume cupboard at room temperature to form colorless needle crystals.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms. The suffix A corresponds to the symmetry code [-x + 1, -y + 1, -z + 1].
	Fig. 2. The packing of (I), viewed along the a axis. C—H···O hydrogen bonds are shown as yellow dashed lines in bold.

Di-µ-benzoato- κ³O,O':O';κ³O:O,O'- bis[aquabis(benzoato-κ²O,O')(dimethylformamide- κO)europium(III)] top

Crystal data top

[Eu₂(C₇H₅O₂)₆(C₃H₇NO)₂(H₂O)₂]	F(000) = 1208
M_r = 1212.80	D_x = 1.653 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybc	Cell parameters from 5244 reflections
a = 11.6395 (2) Å	θ = 3.5–67.5°
b = 8.3692 (1) Å	µ = 18.84 mm⁻¹
c = 25.5235 (4) Å	T = 291 K
β = 101.460 (2)°	Block, colourless
V = 2436.76 (6) Å³	0.36 × 0.32 × 0.32 mm
Z = 2

Data collection top

Oxford Gemini S Ultra diffractometer	4294 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray source	3860 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.035
Detector resolution: 15.9149 pixels mm^-1	θ_max = 67.6°, θ_min = 3.5°
ω scans	h = −13→9
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −9→5
T_min = 0.056, T_max = 0.065	l = −30→30
8782 measured reflections

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0781P)²] where P = (F_o² + 2F_c²)/3
4294 reflections	(Δ/σ)_max = 0.003
315 parameters	Δρ_max = 1.20 e Å⁻³
3 restraints	Δρ_min = −1.92 e Å⁻³

Crystal data top

[Eu₂(C₇H₅O₂)₆(C₃H₇NO)₂(H₂O)₂]	V = 2436.76 (6) Å³
M_r = 1212.80	Z = 2
Monoclinic, P2₁/c	Cu Kα radiation
a = 11.6395 (2) Å	µ = 18.84 mm⁻¹
b = 8.3692 (1) Å	T = 291 K
c = 25.5235 (4) Å	0.36 × 0.32 × 0.32 mm
β = 101.460 (2)°

Data collection top

Oxford Gemini S Ultra diffractometer	4294 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	3860 reflections with I > 2σ(I)
T_min = 0.056, T_max = 0.065	R_int = 0.035
8782 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	3 restraints
wR(F²) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 1.20 e Å⁻³
4294 reflections	Δρ_min = −1.92 e Å⁻³
315 parameters

Special details top

Experimental. CrysAlisPro (Oxford Diffraction, 2010). Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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.

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

	x	y	z	U_iso*/U_eq
Eu1	0.58936 (2)	0.32204 (3)	0.555114 (10)	0.02985 (13)
O1	0.7648 (3)	0.4223 (4)	0.62602 (15)	0.0471 (8)
O5	0.5539 (3)	0.2337 (5)	0.64080 (14)	0.0455 (8)
O8	0.7148 (3)	0.0976 (5)	0.55948 (16)	0.0499 (9)
O2	0.6119 (3)	0.5789 (4)	0.59914 (14)	0.0426 (8)
O7	0.5164 (4)	0.2066 (5)	0.46868 (15)	0.0460 (8)
O4	0.4078 (3)	0.4576 (4)	0.53174 (15)	0.0450 (8)
O6	0.4632 (3)	0.0941 (4)	0.57245 (14)	0.0442 (8)
O3	0.7419 (3)	0.4010 (5)	0.50855 (15)	0.0530 (10)
C1	0.7736 (4)	0.6905 (6)	0.65945 (19)	0.0347 (11)
N1	0.8798 (4)	−0.0405 (6)	0.5577 (2)	0.0521 (11)
C8	0.7618 (4)	0.5287 (6)	0.42852 (19)	0.0379 (10)
C15	0.4233 (4)	0.0286 (6)	0.6587 (2)	0.0414 (11)
C14	0.6945 (4)	0.4870 (6)	0.47094 (19)	0.0366 (10)
C16	0.4494 (5)	0.0601 (8)	0.7132 (2)	0.0546 (14)
H16	0.5050	0.1374	0.7265	0.065*
C9	0.8819 (5)	0.5075 (8)	0.4393 (2)	0.0503 (14)
H9	0.9175	0.4610	0.4716	0.060*
C22	0.8222 (5)	0.0822 (7)	0.5720 (3)	0.0530 (13)
H22	0.8650	0.1618	0.5926	0.064*
C21	0.4839 (4)	0.1220 (6)	0.62194 (19)	0.0378 (10)
C20	0.3412 (5)	−0.0855 (8)	0.6391 (3)	0.0540 (14)
H20	0.3239	−0.1083	0.6027	0.065*
C6	0.8917 (6)	0.6821 (7)	0.6827 (3)	0.0544 (16)
H6	0.9329	0.5878	0.6808	0.065*
C7	0.7149 (4)	0.5550 (6)	0.62677 (18)	0.0366 (10)
C10	0.9505 (6)	0.5531 (9)	0.4038 (3)	0.0681 (19)
H10	1.0315	0.5405	0.4122	0.082*
C19	0.2840 (6)	−0.1669 (8)	0.6742 (4)	0.070 (2)
H19	0.2274	−0.2430	0.6611	0.084*
C18	0.3111 (6)	−0.1349 (10)	0.7283 (3)	0.070 (2)
H18	0.2733	−0.1902	0.7516	0.084*
C13	0.7090 (6)	0.5896 (8)	0.3796 (2)	0.0622 (17)
H13	0.6281	0.6020	0.3713	0.075*
C17	0.3936 (6)	−0.0219 (9)	0.7476 (3)	0.0668 (18)
H17	0.4120	−0.0005	0.7841	0.080*
C24	1.0054 (6)	−0.0566 (11)	0.5768 (4)	0.088 (3)
H24B	1.0207	−0.1451	0.6011	0.132*
H24A	1.0358	0.0396	0.5949	0.132*
H24C	1.0428	−0.0750	0.5470	0.132*
C5	0.9487 (7)	0.8130 (9)	0.7088 (3)	0.071 (2)
H5	1.0283	0.8074	0.7237	0.085*
C4	0.8876 (7)	0.9514 (9)	0.7128 (3)	0.077 (2)
H4	0.9261	1.0399	0.7300	0.093*
C12	0.7762 (8)	0.6330 (10)	0.3423 (3)	0.085 (3)
H12	0.7403	0.6717	0.3089	0.102*
C23	0.8170 (8)	−0.1668 (8)	0.5251 (4)	0.078 (2)
H23B	0.8175	−0.2616	0.5463	0.118*
H23A	0.8545	−0.1886	0.4956	0.118*
H23C	0.7376	−0.1339	0.5119	0.118*
C2	0.7126 (6)	0.8298 (7)	0.6634 (3)	0.0581 (16)
H2	0.6336	0.8371	0.6475	0.070*
C11	0.8975 (8)	0.6176 (10)	0.3556 (3)	0.082 (2)
H11	0.9431	0.6514	0.3317	0.098*
C3	0.7697 (7)	0.9596 (8)	0.6914 (3)	0.078 (2)
H3	0.7280	1.0519	0.6955	0.093*
H7B	0.527 (8)	0.112 (5)	0.458 (4)	0.117*
H7A	0.470 (7)	0.253 (10)	0.443 (3)	0.117*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Eu1	0.03041 (19)	0.0315 (2)	0.02777 (18)	0.00101 (9)	0.00612 (12)	−0.00123 (9)
O1	0.0428 (19)	0.048 (2)	0.048 (2)	0.0050 (16)	0.0030 (15)	−0.0044 (17)
O5	0.050 (2)	0.047 (2)	0.0392 (18)	−0.0082 (17)	0.0086 (15)	−0.0080 (17)
O8	0.050 (2)	0.042 (2)	0.057 (2)	0.0100 (17)	0.0084 (17)	−0.0019 (18)
O2	0.0427 (18)	0.0357 (19)	0.0443 (18)	0.0032 (14)	−0.0039 (14)	−0.0070 (15)
O7	0.061 (2)	0.0381 (19)	0.0350 (18)	0.0043 (18)	−0.0003 (16)	−0.0049 (15)
O4	0.0327 (17)	0.053 (2)	0.051 (2)	0.0026 (15)	0.0118 (15)	−0.0110 (17)
O6	0.060 (2)	0.0393 (19)	0.0350 (18)	−0.0067 (16)	0.0138 (16)	0.0023 (15)
O3	0.0423 (19)	0.073 (3)	0.046 (2)	0.0038 (19)	0.0142 (16)	0.012 (2)
C1	0.037 (3)	0.040 (3)	0.025 (2)	0.0001 (19)	0.0017 (19)	−0.0030 (18)
N1	0.048 (2)	0.048 (3)	0.061 (3)	0.009 (2)	0.013 (2)	0.002 (2)
C8	0.037 (2)	0.045 (3)	0.035 (2)	0.004 (2)	0.0158 (19)	−0.004 (2)
C15	0.039 (3)	0.041 (3)	0.046 (3)	0.006 (2)	0.012 (2)	0.011 (2)
C14	0.029 (2)	0.044 (3)	0.038 (2)	−0.003 (2)	0.0085 (19)	−0.006 (2)
C16	0.064 (3)	0.062 (4)	0.040 (3)	0.000 (3)	0.015 (3)	0.006 (3)
C9	0.038 (3)	0.067 (4)	0.049 (3)	−0.004 (3)	0.016 (2)	−0.008 (3)
C22	0.055 (3)	0.044 (3)	0.058 (3)	−0.001 (3)	0.005 (3)	−0.001 (3)
C21	0.040 (3)	0.038 (3)	0.036 (2)	0.006 (2)	0.010 (2)	0.006 (2)
C20	0.052 (3)	0.058 (4)	0.054 (3)	−0.005 (3)	0.017 (3)	0.004 (3)
C6	0.049 (3)	0.058 (4)	0.049 (3)	0.005 (2)	−0.010 (3)	−0.010 (3)
C7	0.036 (2)	0.044 (3)	0.030 (2)	0.004 (2)	0.0063 (18)	−0.001 (2)
C10	0.059 (4)	0.078 (5)	0.078 (5)	−0.005 (3)	0.040 (4)	−0.005 (4)
C19	0.056 (4)	0.064 (4)	0.093 (6)	−0.011 (3)	0.022 (4)	0.019 (4)
C18	0.063 (4)	0.080 (5)	0.074 (5)	0.010 (4)	0.029 (4)	0.032 (4)
C13	0.069 (4)	0.076 (4)	0.046 (3)	0.036 (3)	0.022 (3)	0.012 (3)
C17	0.079 (4)	0.079 (5)	0.048 (3)	0.008 (4)	0.026 (3)	0.018 (3)
C24	0.061 (4)	0.100 (6)	0.101 (6)	0.029 (4)	0.011 (4)	0.014 (5)
C5	0.060 (4)	0.078 (5)	0.063 (4)	−0.008 (3)	−0.014 (3)	−0.008 (3)
C4	0.093 (5)	0.060 (4)	0.062 (4)	−0.017 (4)	−0.026 (4)	−0.009 (3)
C12	0.128 (7)	0.085 (5)	0.054 (4)	0.053 (5)	0.047 (4)	0.025 (4)
C23	0.083 (5)	0.060 (4)	0.095 (6)	0.006 (3)	0.024 (5)	−0.022 (4)
C2	0.054 (4)	0.059 (4)	0.053 (4)	0.008 (3)	−0.010 (3)	−0.013 (3)
C11	0.107 (6)	0.068 (5)	0.091 (6)	0.018 (4)	0.072 (5)	0.016 (4)
C3	0.099 (5)	0.051 (4)	0.066 (4)	0.012 (4)	−0.026 (4)	−0.027 (3)

Geometric parameters (Å, º) top

Eu1—O8	2.368 (4)	C16—C17	1.374 (8)
Eu1—O4	2.368 (3)	C16—H16	0.9300
Eu1—O7	2.404 (4)	C9—C10	1.377 (8)
Eu1—O2	2.416 (3)	C9—H9	0.9300
Eu1—O3	2.416 (3)	C22—H22	0.9300
Eu1—O5	2.420 (4)	C20—C19	1.395 (9)
Eu1—O6	2.500 (3)	C20—H20	0.9300
Eu1—O1	2.584 (4)	C6—C5	1.380 (10)
Eu1—C21	2.837 (5)	C6—H6	0.9300
Eu1—C7	2.867 (5)	C10—C11	1.371 (11)
Eu1—O4ⁱ	2.889 (4)	C10—H10	0.9300
Eu1—C14	3.011 (5)	C19—C18	1.380 (12)
O1—C7	1.255 (6)	C19—H19	0.9300
O5—C21	1.271 (6)	C18—C17	1.368 (11)
O8—C22	1.235 (7)	C18—H18	0.9300
O2—C7	1.280 (6)	C13—C12	1.394 (9)
O7—H7B	0.86 (2)	C13—H13	0.9300
O7—H7A	0.86 (2)	C17—H17	0.9300
O4—C14ⁱ	1.267 (5)	C24—H24B	0.9600
O4—Eu1ⁱ	2.889 (4)	C24—H24A	0.9600
O6—C21	1.260 (6)	C24—H24C	0.9600
O3—C14	1.238 (6)	C5—C4	1.373 (10)
C1—C2	1.379 (8)	C5—H5	0.9300
C1—C6	1.388 (8)	C4—C3	1.374 (10)
C1—C7	1.490 (7)	C4—H4	0.9300
N1—C22	1.316 (7)	C12—C11	1.392 (12)
N1—C23	1.450 (9)	C12—H12	0.9300
N1—C24	1.453 (8)	C23—H23B	0.9600
C8—C13	1.376 (8)	C23—H23A	0.9600
C8—C9	1.382 (7)	C23—H23C	0.9600
C8—C14	1.498 (6)	C2—C3	1.393 (9)
C15—C20	1.373 (8)	C2—H2	0.9300
C15—C16	1.388 (8)	C11—H11	0.9300
C15—C21	1.501 (7)	C3—H3	0.9300
C14—O4ⁱ	1.267 (5)

O8—Eu1—O4	154.52 (13)	C13—C8—C9	118.7 (5)
O8—Eu1—O7	80.01 (13)	C13—C8—C14	122.6 (5)
O4—Eu1—O7	80.00 (13)	C9—C8—C14	118.6 (5)
O8—Eu1—O2	132.46 (13)	C20—C15—C16	119.7 (5)
O4—Eu1—O2	72.54 (12)	C20—C15—C21	120.9 (5)
O7—Eu1—O2	140.39 (13)	C16—C15—C21	119.4 (5)
O8—Eu1—O3	74.58 (14)	O3—C14—O4ⁱ	121.6 (4)
O4—Eu1—O3	116.81 (13)	O3—C14—C8	118.7 (4)
O7—Eu1—O3	79.55 (15)	O4ⁱ—C14—C8	119.8 (4)
O2—Eu1—O3	87.86 (14)	O3—C14—Eu1	50.3 (2)
O8—Eu1—O5	85.94 (14)	O4ⁱ—C14—Eu1	72.3 (3)
O4—Eu1—O5	94.03 (13)	C8—C14—Eu1	165.4 (3)
O7—Eu1—O5	127.89 (13)	C17—C16—C15	120.5 (6)
O2—Eu1—O5	82.75 (13)	C17—C16—H16	119.7
O3—Eu1—O5	143.29 (13)	C15—C16—H16	119.7
O8—Eu1—O6	76.39 (14)	C10—C9—C8	121.9 (6)
O4—Eu1—O6	83.33 (13)	C10—C9—H9	119.0
O7—Eu1—O6	75.10 (13)	C8—C9—H9	119.0
O2—Eu1—O6	127.60 (12)	O8—C22—N1	123.7 (6)
O3—Eu1—O6	144.16 (14)	O8—C22—H22	118.2
O5—Eu1—O6	52.81 (12)	N1—C22—H22	118.2
O8—Eu1—O1	80.26 (13)	O6—C21—O5	119.8 (4)
O4—Eu1—O1	124.21 (12)	O6—C21—C15	120.7 (5)
O7—Eu1—O1	149.22 (13)	O5—C21—C15	119.5 (4)
O2—Eu1—O1	52.24 (11)	O6—C21—Eu1	61.7 (3)
O3—Eu1—O1	72.56 (13)	O5—C21—Eu1	58.1 (2)
O5—Eu1—O1	73.68 (12)	C15—C21—Eu1	175.2 (4)
O6—Eu1—O1	122.27 (12)	C15—C20—C19	119.5 (6)
O8—Eu1—C21	80.78 (14)	C15—C20—H20	120.3
O4—Eu1—C21	87.89 (13)	C19—C20—H20	120.3
O7—Eu1—C21	101.45 (15)	C5—C6—C1	120.5 (6)
O2—Eu1—C21	105.40 (14)	C5—C6—H6	119.8
O3—Eu1—C21	154.81 (14)	C1—C6—H6	119.8
O5—Eu1—C21	26.48 (14)	O1—C7—O2	121.0 (5)
O6—Eu1—C21	26.34 (13)	O1—C7—C1	121.3 (4)
O1—Eu1—C21	98.42 (13)	O2—C7—C1	117.7 (4)
O8—Eu1—C7	106.16 (14)	O1—C7—Eu1	64.3 (3)
O4—Eu1—C7	98.69 (13)	O2—C7—Eu1	56.8 (2)
O7—Eu1—C7	154.32 (14)	C1—C7—Eu1	173.3 (3)
O2—Eu1—C7	26.30 (12)	C11—C10—C9	118.9 (7)
O3—Eu1—C7	78.27 (14)	C11—C10—H10	120.5
O5—Eu1—C7	77.76 (13)	C9—C10—H10	120.5
O6—Eu1—C7	130.46 (12)	C18—C19—C20	120.3 (7)
O1—Eu1—C7	25.97 (12)	C18—C19—H19	119.9
C21—Eu1—C7	104.14 (14)	C20—C19—H19	119.9
O8—Eu1—O4ⁱ	116.21 (12)	C17—C18—C19	119.9 (6)
O4—Eu1—O4ⁱ	69.30 (12)	C17—C18—H18	120.0
O7—Eu1—O4ⁱ	66.92 (12)	C19—C18—H18	120.0
O2—Eu1—O4ⁱ	76.82 (11)	C8—C13—C12	120.5 (6)
O3—Eu1—O4ⁱ	47.66 (11)	C8—C13—H13	119.8
O5—Eu1—O4ⁱ	156.69 (11)	C12—C13—H13	119.8
O6—Eu1—O4ⁱ	136.02 (11)	C18—C17—C16	120.1 (7)
O1—Eu1—O4ⁱ	101.67 (11)	C18—C17—H17	119.9
C21—Eu1—O4ⁱ	155.54 (12)	C16—C17—H17	119.9
C7—Eu1—O4ⁱ	88.47 (12)	N1—C24—H24B	109.5
O8—Eu1—C14	93.62 (13)	N1—C24—H24A	109.5
O4—Eu1—C14	93.99 (13)	H24B—C24—H24A	109.5
O7—Eu1—C14	69.44 (14)	N1—C24—H24C	109.5
O2—Eu1—C14	84.36 (13)	H24B—C24—H24C	109.5
O3—Eu1—C14	23.22 (13)	H24A—C24—H24C	109.5
O5—Eu1—C14	162.04 (12)	C4—C5—C6	119.9 (7)
O6—Eu1—C14	144.35 (12)	C4—C5—H5	120.1
O1—Eu1—C14	88.52 (12)	C6—C5—H5	120.1
C21—Eu1—C14	170.15 (14)	C5—C4—C3	120.2 (6)
C7—Eu1—C14	85.15 (13)	C5—C4—H4	119.9
O4ⁱ—Eu1—C14	24.70 (11)	C3—C4—H4	119.9
C7—O1—Eu1	89.7 (3)	C11—C12—C13	119.2 (7)
C21—O5—Eu1	95.4 (3)	C11—C12—H12	120.4
C22—O8—Eu1	132.7 (4)	C13—C12—H12	120.4
C7—O2—Eu1	96.9 (3)	N1—C23—H23B	109.5
Eu1—O7—H7B	128 (6)	N1—C23—H23A	109.5
Eu1—O7—H7A	126 (6)	H23B—C23—H23A	109.5
H7B—O7—H7A	106 (5)	N1—C23—H23C	109.5
C14ⁱ—O4—Eu1	166.2 (3)	H23B—C23—H23C	109.5
C14ⁱ—O4—Eu1ⁱ	83.0 (3)	H23A—C23—H23C	109.5
Eu1—O4—Eu1ⁱ	110.70 (12)	C1—C2—C3	119.8 (6)
C21—O6—Eu1	92.0 (3)	C1—C2—H2	120.1
C14—O3—Eu1	106.4 (3)	C3—C2—H2	120.1
C2—C1—C6	119.4 (5)	C10—C11—C12	120.7 (6)
C2—C1—C7	119.9 (5)	C10—C11—H11	119.7
C6—C1—C7	120.5 (5)	C12—C11—H11	119.7
C22—N1—C23	120.1 (5)	C4—C3—C2	120.1 (7)
C22—N1—C24	120.9 (6)	C4—C3—H3	119.9
C23—N1—C24	118.9 (6)	C2—C3—H3	119.9

O8—Eu1—O1—C7	175.9 (3)	O8—Eu1—C14—O4ⁱ	157.2 (3)
O4—Eu1—O1—C7	−11.9 (3)	O4—Eu1—C14—O4ⁱ	1.5 (3)
O7—Eu1—O1—C7	125.1 (3)	O7—Eu1—C14—O4ⁱ	79.3 (3)
O2—Eu1—O1—C7	−2.1 (3)	O2—Eu1—C14—O4ⁱ	−70.5 (3)
O3—Eu1—O1—C7	99.1 (3)	O3—Eu1—C14—O4ⁱ	−168.3 (5)
O5—Eu1—O1—C7	−95.5 (3)	O5—Eu1—C14—O4ⁱ	−114.8 (4)
O6—Eu1—O1—C7	−117.1 (3)	O6—Eu1—C14—O4ⁱ	85.6 (3)
C21—Eu1—O1—C7	−105.1 (3)	O1—Eu1—C14—O4ⁱ	−122.7 (3)
O4ⁱ—Eu1—O1—C7	60.9 (3)	C7—Eu1—C14—O4ⁱ	−96.9 (3)
C14—Eu1—O1—C7	81.9 (3)	O8—Eu1—C14—C8	10.2 (13)
O8—Eu1—O5—C21	−77.4 (3)	O4—Eu1—C14—C8	−145.4 (13)
O4—Eu1—O5—C21	77.0 (3)	O7—Eu1—C14—C8	−67.7 (13)
O7—Eu1—O5—C21	−3.4 (4)	O2—Eu1—C14—C8	142.6 (13)
O2—Eu1—O5—C21	148.8 (3)	O3—Eu1—C14—C8	44.8 (12)
O3—Eu1—O5—C21	−134.7 (3)	O5—Eu1—C14—C8	98.2 (13)
O6—Eu1—O5—C21	−1.4 (3)	O6—Eu1—C14—C8	−61.3 (13)
O1—Eu1—O5—C21	−158.4 (3)	O1—Eu1—C14—C8	90.4 (13)
C7—Eu1—O5—C21	175.1 (3)	C7—Eu1—C14—C8	116.2 (13)
O4ⁱ—Eu1—O5—C21	120.0 (3)	O4ⁱ—Eu1—C14—C8	−146.9 (14)
C14—Eu1—O5—C21	−166.6 (4)	C20—C15—C16—C17	0.0 (9)
O4—Eu1—O8—C22	169.1 (5)	C21—C15—C16—C17	178.9 (5)
O7—Eu1—O8—C22	130.3 (5)	C13—C8—C9—C10	3.4 (10)
O2—Eu1—O8—C22	−23.8 (6)	C14—C8—C9—C10	−175.5 (6)
O3—Eu1—O8—C22	48.5 (5)	Eu1—O8—C22—N1	−159.4 (4)
O5—Eu1—O8—C22	−100.1 (5)	C23—N1—C22—O8	0.5 (10)
O6—Eu1—O8—C22	−152.8 (5)	C24—N1—C22—O8	−175.8 (6)
O1—Eu1—O8—C22	−26.0 (5)	Eu1—O6—C21—O5	−2.5 (5)
C21—Eu1—O8—C22	−126.2 (5)	Eu1—O6—C21—C15	175.2 (4)
C7—Eu1—O8—C22	−24.1 (5)	Eu1—O5—C21—O6	2.6 (5)
O4ⁱ—Eu1—O8—C22	72.3 (5)	Eu1—O5—C21—C15	−175.1 (4)
C14—Eu1—O8—C22	61.9 (5)	C20—C15—C21—O6	−2.2 (8)
O8—Eu1—O2—C7	−0.7 (4)	C16—C15—C21—O6	179.0 (5)
O4—Eu1—O2—C7	173.6 (3)	C20—C15—C21—O5	175.5 (5)
O7—Eu1—O2—C7	−138.2 (3)	C16—C15—C21—O5	−3.3 (8)
O3—Eu1—O2—C7	−67.4 (3)	O8—Eu1—C21—O6	−77.9 (3)
O5—Eu1—O2—C7	77.0 (3)	O4—Eu1—C21—O6	79.2 (3)
O6—Eu1—O2—C7	106.9 (3)	O7—Eu1—C21—O6	−0.2 (3)
O1—Eu1—O2—C7	2.1 (3)	O2—Eu1—C21—O6	150.4 (3)
C21—Eu1—O2—C7	90.8 (3)	O3—Eu1—C21—O6	−89.9 (4)
O4ⁱ—Eu1—O2—C7	−114.3 (3)	O5—Eu1—C21—O6	−177.4 (5)
C14—Eu1—O2—C7	−90.5 (3)	O1—Eu1—C21—O6	−156.5 (3)
O8—Eu1—O4—C14ⁱ	78.9 (14)	C7—Eu1—C21—O6	177.6 (3)
O7—Eu1—O4—C14ⁱ	117.7 (14)	O4ⁱ—Eu1—C21—O6	58.5 (5)
O2—Eu1—O4—C14ⁱ	−91.2 (14)	O8—Eu1—C21—O5	99.5 (3)
O3—Eu1—O4—C14ⁱ	−169.5 (14)	O4—Eu1—C21—O5	−103.4 (3)
O5—Eu1—O4—C14ⁱ	−10.1 (14)	O7—Eu1—C21—O5	177.2 (3)
O6—Eu1—O4—C14ⁱ	41.7 (14)	O2—Eu1—C21—O5	−32.2 (3)
O1—Eu1—O4—C14ⁱ	−83.1 (14)	O3—Eu1—C21—O5	87.5 (5)
C21—Eu1—O4—C14ⁱ	15.6 (14)	O6—Eu1—C21—O5	177.4 (5)
C7—Eu1—O4—C14ⁱ	−88.3 (14)	O1—Eu1—C21—O5	20.9 (3)
O4ⁱ—Eu1—O4—C14ⁱ	−173.4 (15)	C7—Eu1—C21—O5	−5.0 (3)
C14—Eu1—O4—C14ⁱ	−174.0 (13)	O4ⁱ—Eu1—C21—O5	−124.1 (3)
O8—Eu1—O4—Eu1ⁱ	−107.7 (3)	C16—C15—C20—C19	0.7 (9)
O7—Eu1—O4—Eu1ⁱ	−68.97 (14)	C21—C15—C20—C19	−178.1 (5)
O2—Eu1—O4—Eu1ⁱ	82.15 (14)	C2—C1—C6—C5	−1.3 (11)
O3—Eu1—O4—Eu1ⁱ	3.84 (19)	C7—C1—C6—C5	174.0 (7)
O5—Eu1—O4—Eu1ⁱ	163.24 (13)	Eu1—O1—C7—O2	3.6 (5)
O6—Eu1—O4—Eu1ⁱ	−144.95 (14)	Eu1—O1—C7—C1	−175.9 (4)
O1—Eu1—O4—Eu1ⁱ	90.26 (16)	Eu1—O2—C7—O1	−3.9 (5)
C21—Eu1—O4—Eu1ⁱ	−170.98 (15)	Eu1—O2—C7—C1	175.7 (4)
C7—Eu1—O4—Eu1ⁱ	85.03 (14)	C2—C1—C7—O1	−173.9 (5)
O4ⁱ—Eu1—O4—Eu1ⁱ	0.0	C6—C1—C7—O1	10.8 (8)
C14—Eu1—O4—Eu1ⁱ	−0.67 (15)	C2—C1—C7—O2	6.5 (7)
O8—Eu1—O6—C21	96.7 (3)	C6—C1—C7—O2	−168.7 (5)
O4—Eu1—O6—C21	−98.8 (3)	O8—Eu1—C7—O1	−4.2 (3)
O7—Eu1—O6—C21	179.8 (3)	O4—Eu1—C7—O1	170.1 (3)
O2—Eu1—O6—C21	−36.9 (3)	O7—Eu1—C7—O1	−104.9 (4)
O3—Eu1—O6—C21	133.4 (3)	O2—Eu1—C7—O1	176.3 (5)
O5—Eu1—O6—C21	1.5 (3)	O3—Eu1—C7—O1	−74.2 (3)
O1—Eu1—O6—C21	27.8 (3)	O5—Eu1—C7—O1	77.8 (3)
C7—Eu1—O6—C21	−3.0 (4)	O6—Eu1—C7—O1	81.5 (3)
O4ⁱ—Eu1—O6—C21	−149.5 (3)	C21—Eu1—C7—O1	80.1 (3)
C14—Eu1—O6—C21	173.7 (3)	O4ⁱ—Eu1—C7—O1	−121.1 (3)
O8—Eu1—O3—C14	144.0 (4)	C14—Eu1—C7—O1	−96.6 (3)
O4—Eu1—O3—C14	−11.5 (4)	O8—Eu1—C7—O2	179.5 (3)
O7—Eu1—O3—C14	61.6 (4)	O4—Eu1—C7—O2	−6.2 (3)
O2—Eu1—O3—C14	−80.7 (4)	O7—Eu1—C7—O2	78.8 (4)
O5—Eu1—O3—C14	−155.5 (3)	O3—Eu1—C7—O2	109.5 (3)
O6—Eu1—O3—C14	107.0 (4)	O5—Eu1—C7—O2	−98.5 (3)
O1—Eu1—O3—C14	−131.6 (4)	O6—Eu1—C7—O2	−94.8 (3)
C21—Eu1—O3—C14	156.3 (3)	O1—Eu1—C7—O2	−176.3 (5)
C7—Eu1—O3—C14	−105.4 (4)	C21—Eu1—C7—O2	−96.2 (3)
O4ⁱ—Eu1—O3—C14	−6.6 (3)	O4ⁱ—Eu1—C7—O2	62.6 (3)
Eu1—O3—C14—O4ⁱ	13.2 (6)	C14—Eu1—C7—O2	87.1 (3)
Eu1—O3—C14—C8	−168.3 (4)	C8—C9—C10—C11	−1.8 (11)
C13—C8—C14—O3	164.0 (6)	C15—C20—C19—C18	−1.1 (10)
C9—C8—C14—O3	−17.0 (8)	C20—C19—C18—C17	0.6 (11)
C13—C8—C14—O4ⁱ	−17.4 (8)	C9—C8—C13—C12	−1.7 (10)
C9—C8—C14—O4ⁱ	161.5 (5)	C14—C8—C13—C12	177.2 (6)
C13—C8—C14—Eu1	125.8 (12)	C19—C18—C17—C16	0.2 (11)
C9—C8—C14—Eu1	−55.2 (15)	C15—C16—C17—C18	−0.5 (10)
O8—Eu1—C14—O3	−34.6 (4)	C1—C6—C5—C4	1.4 (13)
O4—Eu1—C14—O3	169.7 (4)	C6—C5—C4—C3	0.7 (14)
O7—Eu1—C14—O3	−112.5 (4)	C8—C13—C12—C11	−1.6 (12)
O2—Eu1—C14—O3	97.8 (4)	C6—C1—C2—C3	−0.9 (10)
O5—Eu1—C14—O3	53.4 (6)	C7—C1—C2—C3	−176.2 (6)
O6—Eu1—C14—O3	−106.1 (4)	C9—C10—C11—C12	−1.6 (12)
O1—Eu1—C14—O3	45.6 (4)	C13—C12—C11—C10	3.3 (13)
C7—Eu1—C14—O3	71.3 (4)	C5—C4—C3—C2	−2.9 (13)
O4ⁱ—Eu1—C14—O3	168.3 (5)	C1—C2—C3—C4	3.0 (12)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7B···O6ⁱⁱ	0.86 (2)	1.90 (2)	2.756 (5)	174 (9)
O7—H7A···O2ⁱ	0.86 (2)	1.90 (4)	2.724 (5)	159 (9)

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

Experimental details

Crystal data
Chemical formula	[Eu₂(C₇H₅O₂)₆(C₃H₇NO)₂(H₂O)₂]
M_r	1212.80
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	291
a, b, c (Å)	11.6395 (2), 8.3692 (1), 25.5235 (4)
β (°)	101.460 (2)
V (Å³)	2436.76 (6)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	18.84
Crystal size (mm)	0.36 × 0.32 × 0.32

Data collection
Diffractometer	Oxford Gemini S Ultra diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)
T_min, T_max	0.056, 0.065
No. of measured, independent and observed [I > 2σ(I)] reflections	8782, 4294, 3860
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.120, 1.03
No. of reflections	4294
No. of parameters	315
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.20, −1.92

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999).

Selected bond lengths (Å) top

Eu1—O8	2.368 (4)	Eu1—O5	2.420 (4)
Eu1—O4	2.368 (3)	Eu1—O6	2.500 (3)
Eu1—O7	2.404 (4)	Eu1—O1	2.584 (4)
Eu1—O2	2.416 (3)	Eu1—O4ⁱ	2.889 (4)
Eu1—O3	2.416 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7B···O6ⁱⁱ	0.86 (2)	1.90 (2)	2.756 (5)	174 (9)
O7—H7A···O2ⁱ	0.86 (2)	1.90 (4)	2.724 (5)	159 (9)

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

Acknowledgements

This work was supported by the National Natural Science Foundation of China (grant Nos. 10704090 and 20903123), the Key Project of the Chinese Ministry of Education (grant No. KJ110532) and the Natural Science Foundation Project of Chongqing (grant Nos. CSTC2010BA4009, KJTD201016 and CSTC2011jjA1425). ZXJ thanks Dr Shiming Zhou and Dr Xiantao Wei from the University of Science and Technology of China for helpful discussions and assistance with the X-ray diffraction measurements.

References

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