catena-Poly[[(1,10-phenanthroline-κ2N,N′)lanthanum(III)]-μ-(5-bromo-2-hy­droxy­benzoato)-κ2O1:O1′-di-μ-chlorido]

Zhu, W.-Q.; Wang, J.-P.; Yuan, Y.-K.; Li, Z.

doi:10.1107/S1600536812025500

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Page m896

https://doi.org/10.1107/S1600536812025500

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catena-Poly[[(1,10-phenanthroline-κ²N,N′)lanthanum(III)]-μ-(5-bromo-2-hydroxybenzoato)-κ²O¹:O^1′-di-μ-chlorido]

Wen-Qing Zhu,^a ^* Jin-Ping Wang,^a Yu-Kun Yuan ^a and Zhuo Li ^a

^aCollege of Environment and Chemical Engineering, Xi'an Polytechnic University, Xi'an, Shaanxi 710048, People's Republic of China
^*Correspondence e-mail: wqzhu2008@163.com

(Received 14 May 2012; accepted 5 June 2012; online 13 June 2012)

In the title complex, [La(C₇H₄BrO₃)Cl₂(C₁₂H₈N₂)]_n, the La^III ion is eight-coordinated by two carboxylate O atoms from two 5-bromosalicylate ligands, two N atoms from a chelating 1,10-phenanthroline ligand and four bridging Cl atoms in a distorted square-antiprismatic geometry. The La^III ions are linked by bridging carboxylate groups and chloride anions into a chain along [100]. An intramolecular O—H⋯O hydrogen bond is formed in the 5-bromosalicylate ligand. π–π interactions between the pyridine and benzene rings and between the benzene rings are observed [centroid–centroid distances = 3.794 (5) and 3.804 (4) Å].

Related literature

For background to rare earth carboxylates, see: Ali et al. (2004 ); Costes et al. (2002 ); Kaur et al. (2010 ); Yin & Sun (2004 ). For complexes with salicylate ligands, see: Hu et al. (2005 ); Yin et al. (2004 ).

Experimental

Crystal data

[La(C₇H₄BrO₃)Cl₂(C₁₂H₈N₂)]
M_r = 606.02
Orthorhombic, P b c a
a = 8.2957 (10) Å
b = 22.104 (3) Å
c = 22.110 (3) Å
V = 4054.3 (9) Å³
Z = 8
Mo Kα radiation
μ = 4.36 mm⁻¹
T = 296 K
0.30 × 0.24 × 0.14 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.352, T_max = 0.584
19025 measured reflections
3598 independent reflections
2849 reflections with I > 2σ(I)
R_int = 0.065

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.125
S = 1.00
3598 reflections
254 parameters
H-atom parameters constrained
Δρ_max = 1.20 e Å⁻³
Δρ_min = −1.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O2	0.82	1.93	2.588 (6)	137

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: DIAMOND (Brandenburg, 1999 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812025500/hy2550sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812025500/hy2550Isup2.hkl

checkCIF report

Comment top

Over the past years, much attention has been paid to the rare earth carboxylates, owing to their novel structures and potential applications in a wide range of materials science, such as superconductor, magnetic materials and luminescent probes (Ali et al., 2004; Costes et al., 2002; Kaur et al., 2010; Yin & Sun, 2004). Because salicylic acid and its derivatives have been known for a long time to possess anti-inflammatory activity and have also been considered of interest from a structural point of view (Hu et al., 2005; Yin et al., 2004), a new lanthanum bromosalicylate complex was synthesized and its crystal structure is reported here.

Related literature top

For background to rare earth carboxylates, see: Ali et al. (2004); Costes et al. (2002); Kaur et al. (2010); Yin & Sun (2004). For complexes with salicylate ligands, see: Hu et al. (2005); Yin et al. (2004).

Experimental top

An ethanol solution (5 ml) of LaCl₃.6H₂O (0.5 mmol, 0.177 g) was added dropwise to an ethanol solution (5 ml) of 5-bromosalicylic acid (0.5 mmol, 0.109 g) under stirring and then an ethanol solution (5 ml) of 1,10-phenanthroline (0.5 mmol, 0.084 g) was added dropwise. The mixture was stirred for about 13 min at room temperature and sealed in a Teflon-lined stainless autoclave and heated to 120°C for 60 h. After filtered, colorless flake-shaped crystals were obtained.

Structure description top

For background to rare earth carboxylates, see: Ali et al. (2004); Costes et al. (2002); Kaur et al. (2010); Yin & Sun (2004). For complexes with salicylate ligands, see: Hu et al. (2005); Yin et al. (2004).

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: DIAMOND (Brandenburg, 1999) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. [Symmetry codes: (a) x + 1/2, -y + 1/2, -z + 1; (b) x - 1/2, -y + 1/2, -z + 1.]
	Fig. 2. The one-dimensional chain structure in the title compound. Hydrogen bonds are shown as dashed lines.

catena-Poly[[(1,10-phenanthroline- κ²N,N')lanthanum(III)]-µ-(5-bromo-2-hydroxybenzoato)- κ²O¹:O^1'-di-µ-chlorido] top

Crystal data top

[La(C₇H₄BrO₃)Cl₂(C₁₂H₈N₂)]	F(000) = 2320
M_r = 606.02	D_x = 1.986 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3026 reflections
a = 8.2957 (10) Å	θ = 2.6–24.6°
b = 22.104 (3) Å	µ = 4.36 mm⁻¹
c = 22.110 (3) Å	T = 296 K
V = 4054.3 (9) Å³	Flake, colorless
Z = 8	0.30 × 0.24 × 0.14 mm

Data collection top

Bruker APEXII CCD diffractometer	3598 independent reflections
Radiation source: fine-focus sealed tube	2849 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.065
φ and ω scans	θ_max = 25.1°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→7
T_min = 0.352, T_max = 0.584	k = −26→26
19025 measured reflections	l = −26→26

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.125	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.080P)² + 0.7837P] where P = (F_o² + 2F_c²)/3
3598 reflections	(Δ/σ)_max = 0.002
254 parameters	Δρ_max = 1.20 e Å⁻³
0 restraints	Δρ_min = −1.34 e Å⁻³

Crystal data top

[La(C₇H₄BrO₃)Cl₂(C₁₂H₈N₂)]	V = 4054.3 (9) Å³
M_r = 606.02	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 8.2957 (10) Å	µ = 4.36 mm⁻¹
b = 22.104 (3) Å	T = 296 K
c = 22.110 (3) Å	0.30 × 0.24 × 0.14 mm

Data collection top

Bruker APEXII CCD diffractometer	3598 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2849 reflections with I > 2σ(I)
T_min = 0.352, T_max = 0.584	R_int = 0.065
19025 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.125	H-atom parameters constrained
S = 1.00	Δρ_max = 1.20 e Å⁻³
3598 reflections	Δρ_min = −1.34 e Å⁻³
254 parameters

Special details top

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
La1	0.78367 (4)	0.242463 (15)	0.537359 (15)	0.02456 (15)
Br1	0.86777 (13)	−0.05046 (5)	0.66282 (5)	0.0877 (4)
Cl1	0.57034 (19)	0.18099 (7)	0.45631 (7)	0.0352 (4)
Cl2	0.46216 (18)	0.27765 (8)	0.57361 (7)	0.0365 (4)
N1	0.6683 (7)	0.1654 (3)	0.6202 (2)	0.0401 (14)
N2	0.8088 (7)	0.2724 (3)	0.6548 (2)	0.0396 (14)
O1	0.9829 (5)	0.16436 (19)	0.5594 (2)	0.0389 (11)
O2	1.2182 (5)	0.1607 (2)	0.5117 (2)	0.0423 (12)
O3	1.3579 (7)	0.0573 (2)	0.4954 (3)	0.0615 (15)
H3	1.3282	0.0899	0.4818	0.092*
C1	0.5984 (9)	0.1136 (3)	0.6047 (4)	0.0510 (19)
H1	0.5907	0.1048	0.5637	0.061*
C2	0.5357 (10)	0.0711 (4)	0.6451 (4)	0.067 (2)
H2	0.4911	0.0349	0.6317	0.080*
C3	0.5428 (11)	0.0852 (5)	0.7052 (4)	0.075 (3)
H3A	0.5001	0.0585	0.7334	0.090*
C4	0.6131 (10)	0.1391 (4)	0.7249 (3)	0.059 (2)
C5	0.6262 (12)	0.1591 (5)	0.7881 (3)	0.082 (3)
H5	0.5853	0.1341	0.8184	0.098*
C6	0.6954 (12)	0.2124 (5)	0.8043 (4)	0.077 (3)
H6	0.7022	0.2228	0.8450	0.093*
C7	0.7564 (11)	0.2516 (4)	0.7606 (4)	0.056 (2)
C8	0.8293 (11)	0.3067 (4)	0.7754 (4)	0.065 (2)
H8	0.8383	0.3182	0.8157	0.078*
C9	0.8855 (11)	0.3424 (4)	0.7323 (4)	0.062 (2)
H9	0.9332	0.3792	0.7419	0.074*
C10	0.8721 (9)	0.3240 (3)	0.6727 (3)	0.0482 (19)
H10	0.9107	0.3501	0.6431	0.058*
C11	0.7488 (9)	0.2351 (3)	0.6985 (3)	0.0417 (17)
C12	0.6755 (8)	0.1795 (3)	0.6812 (3)	0.0417 (17)
C13	1.0177 (9)	−0.0158 (3)	0.6085 (3)	0.0481 (18)
C14	1.1393 (10)	−0.0516 (3)	0.5865 (4)	0.056 (2)
H14	1.1465	−0.0922	0.5971	0.067*
C15	1.2497 (11)	−0.0257 (4)	0.5485 (4)	0.060 (2)
H15	1.3323	−0.0496	0.5331	0.072*
C16	1.2430 (9)	0.0348 (3)	0.5321 (3)	0.0442 (18)
C17	1.1162 (8)	0.0710 (3)	0.5553 (3)	0.0316 (14)
C18	1.0040 (8)	0.0436 (3)	0.5932 (3)	0.0397 (16)
H18	0.9185	0.0662	0.6083	0.048*
C19	1.1035 (8)	0.1364 (3)	0.5407 (3)	0.0352 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
La1	0.0211 (2)	0.0260 (2)	0.0266 (2)	0.00183 (13)	−0.00042 (14)	0.00254 (13)
Br1	0.0732 (7)	0.0716 (7)	0.1182 (9)	−0.0105 (5)	0.0171 (6)	0.0530 (6)
Cl1	0.0248 (8)	0.0350 (9)	0.0459 (9)	0.0010 (6)	−0.0002 (7)	−0.0084 (7)
Cl2	0.0264 (8)	0.0551 (10)	0.0282 (8)	0.0097 (7)	−0.0002 (6)	−0.0023 (7)
N1	0.031 (3)	0.045 (3)	0.044 (3)	0.003 (3)	0.000 (3)	0.012 (3)
N2	0.032 (3)	0.052 (4)	0.035 (3)	0.011 (3)	−0.001 (2)	0.004 (3)
O1	0.034 (3)	0.039 (3)	0.043 (3)	0.012 (2)	0.009 (2)	0.012 (2)
O2	0.031 (3)	0.032 (3)	0.064 (3)	0.001 (2)	0.010 (2)	0.018 (2)
O3	0.051 (3)	0.045 (3)	0.088 (4)	0.017 (3)	0.032 (3)	0.013 (3)
C1	0.051 (5)	0.048 (4)	0.054 (4)	−0.001 (4)	−0.003 (4)	0.013 (4)
C2	0.059 (6)	0.061 (5)	0.081 (6)	−0.013 (4)	−0.005 (5)	0.032 (5)
C3	0.059 (6)	0.095 (7)	0.071 (6)	−0.014 (5)	0.005 (5)	0.050 (5)
C4	0.046 (5)	0.077 (6)	0.054 (5)	0.007 (4)	0.011 (4)	0.030 (4)
C5	0.077 (7)	0.137 (10)	0.032 (5)	0.018 (7)	0.012 (4)	0.044 (5)
C6	0.076 (7)	0.111 (9)	0.044 (5)	0.008 (6)	−0.004 (5)	0.010 (6)
C7	0.057 (6)	0.085 (7)	0.027 (4)	0.026 (4)	0.002 (4)	0.010 (4)
C8	0.074 (6)	0.079 (7)	0.043 (5)	0.020 (5)	−0.020 (4)	−0.022 (5)
C9	0.071 (6)	0.068 (6)	0.045 (5)	0.013 (5)	−0.016 (4)	−0.011 (4)
C10	0.046 (5)	0.055 (5)	0.043 (4)	0.008 (4)	−0.002 (3)	−0.013 (3)
C11	0.031 (4)	0.058 (5)	0.036 (4)	0.016 (3)	0.000 (3)	0.005 (3)
C12	0.023 (3)	0.064 (5)	0.038 (4)	0.017 (3)	0.007 (3)	0.018 (3)
C13	0.047 (5)	0.039 (4)	0.058 (5)	−0.008 (3)	−0.002 (4)	0.014 (3)
C14	0.060 (5)	0.032 (4)	0.076 (6)	0.000 (4)	0.000 (5)	0.010 (4)
C15	0.063 (5)	0.033 (4)	0.084 (6)	0.020 (4)	0.000 (5)	−0.004 (4)
C16	0.038 (4)	0.032 (4)	0.062 (5)	0.004 (3)	−0.001 (4)	−0.004 (3)
C17	0.030 (4)	0.024 (3)	0.041 (4)	0.002 (3)	−0.007 (3)	0.002 (3)
C18	0.034 (4)	0.036 (4)	0.048 (4)	0.001 (3)	−0.001 (3)	0.010 (3)
C19	0.032 (4)	0.037 (4)	0.037 (4)	0.004 (3)	−0.007 (3)	0.002 (3)

Geometric parameters (Å, º) top

La1—O1	2.439 (4)	C3—H3A	0.9300
La1—O2ⁱ	2.461 (4)	C4—C12	1.415 (10)
La1—N1	2.678 (5)	C4—C5	1.469 (12)
La1—N2	2.687 (6)	C5—C6	1.359 (14)
La1—Cl1	2.8618 (16)	C5—H5	0.9300
La1—Cl2	2.8915 (16)	C6—C7	1.393 (14)
La1—Cl2ⁱⁱ	2.9001 (16)	C6—H6	0.9300
La1—Cl1ⁱⁱ	2.9219 (16)	C7—C8	1.397 (12)
Br1—C13	1.891 (7)	C7—C11	1.422 (11)
Cl1—La1ⁱ	2.9219 (16)	C8—C9	1.321 (12)
Cl2—La1ⁱ	2.9001 (16)	C8—H8	0.9300
N1—C1	1.328 (9)	C9—C10	1.383 (10)
N1—C12	1.386 (9)	C9—H9	0.9300
N2—C10	1.317 (9)	C10—H10	0.9300
N2—C11	1.365 (10)	C11—C12	1.424 (11)
O1—C19	1.246 (8)	C13—C18	1.361 (9)
O2—C19	1.266 (8)	C13—C14	1.369 (10)
O2—La1ⁱⁱ	2.461 (4)	C14—C15	1.368 (12)
O3—C16	1.348 (9)	C14—H14	0.9300
O3—H3	0.8200	C15—C16	1.386 (12)
C1—C2	1.395 (10)	C15—H15	0.9300
C1—H1	0.9300	C16—C17	1.418 (9)
C2—C3	1.365 (13)	C17—C18	1.392 (9)
C2—H2	0.9300	C17—C19	1.485 (8)
C3—C4	1.396 (13)	C18—H18	0.9300

O1—La1—O2ⁱ	148.59 (15)	C3—C4—C12	118.5 (8)
O1—La1—N1	69.84 (15)	C3—C4—C5	125.7 (8)
O2ⁱ—La1—N1	140.90 (16)	C12—C4—C5	115.7 (9)
O1—La1—N2	85.91 (16)	C6—C5—C4	122.8 (8)
O2ⁱ—La1—N2	103.23 (17)	C6—C5—H5	118.6
N1—La1—N2	61.55 (19)	C4—C5—H5	118.6
O1—La1—Cl1	102.01 (12)	C5—C6—C7	120.7 (9)
O2ⁱ—La1—Cl1	90.03 (11)	C5—C6—H6	119.6
N1—La1—Cl1	84.55 (13)	C7—C6—H6	119.6
N2—La1—Cl1	140.34 (13)	C6—C7—C8	122.5 (9)
O1—La1—Cl2	139.46 (11)	C6—C7—C11	119.6 (9)
O2ⁱ—La1—Cl2	71.62 (11)	C8—C7—C11	117.8 (8)
N1—La1—Cl2	69.63 (12)	C9—C8—C7	120.4 (8)
N2—La1—Cl2	74.78 (12)	C9—C8—H8	119.8
Cl1—La1—Cl2	74.39 (4)	C7—C8—H8	119.8
O1—La1—Cl2ⁱⁱ	73.42 (11)	C8—C9—C10	118.8 (8)
O2ⁱ—La1—Cl2ⁱⁱ	82.71 (12)	C8—C9—H9	120.6
N1—La1—Cl2ⁱⁱ	131.57 (13)	C10—C9—H9	120.6
N2—La1—Cl2ⁱⁱ	144.64 (13)	N2—C10—C9	125.0 (8)
Cl1—La1—Cl2ⁱⁱ	73.33 (4)	N2—C10—H10	117.5
Cl2—La1—Cl2ⁱⁱ	138.31 (4)	C9—C10—H10	117.5
O1—La1—Cl1ⁱⁱ	81.30 (11)	N2—C11—C7	120.9 (8)
O2ⁱ—La1—Cl1ⁱⁱ	72.36 (11)	N2—C11—C12	119.0 (7)
N1—La1—Cl1ⁱⁱ	128.79 (13)	C7—C11—C12	120.0 (7)
N2—La1—Cl1ⁱⁱ	75.41 (13)	N1—C12—C4	120.5 (7)
Cl1—La1—Cl1ⁱⁱ	143.93 (3)	N1—C12—C11	118.4 (6)
Cl2—La1—Cl1ⁱⁱ	125.57 (5)	C4—C12—C11	121.1 (7)
Cl2ⁱⁱ—La1—Cl1ⁱⁱ	73.37 (4)	C18—C13—C14	122.0 (7)
La1—Cl1—La1ⁱ	101.44 (5)	C18—C13—Br1	119.5 (6)
La1—Cl2—La1ⁱ	101.25 (5)	C14—C13—Br1	118.4 (5)
C1—N1—C12	117.6 (6)	C15—C14—C13	118.0 (7)
C1—N1—La1	121.9 (5)	C15—C14—H14	121.0
C12—N1—La1	120.4 (4)	C13—C14—H14	121.0
C10—N2—C11	117.0 (7)	C14—C15—C16	122.4 (8)
C10—N2—La1	122.4 (5)	C14—C15—H15	118.8
C11—N2—La1	120.6 (5)	C16—C15—H15	118.8
C19—O1—La1	146.0 (4)	O3—C16—C15	119.0 (7)
C19—O2—La1ⁱⁱ	139.2 (4)	O3—C16—C17	122.2 (6)
C16—O3—H3	109.5	C15—C16—C17	118.7 (8)
N1—C1—C2	125.3 (8)	C18—C17—C16	117.9 (6)
N1—C1—H1	117.4	C18—C17—C19	120.5 (6)
C2—C1—H1	117.4	C16—C17—C19	121.7 (6)
C3—C2—C1	116.9 (8)	C13—C18—C17	120.9 (7)
C3—C2—H2	121.5	C13—C18—H18	119.5
C1—C2—H2	121.5	C17—C18—H18	119.5
C2—C3—C4	121.1 (8)	O1—C19—O2	124.2 (6)
C2—C3—H3A	119.5	O1—C19—C17	117.9 (6)
C4—C3—H3A	119.5	O2—C19—C17	117.9 (6)

O1—La1—Cl1—La1ⁱ	161.75 (11)	C2—C3—C4—C5	179.5 (9)
O2ⁱ—La1—Cl1—La1ⁱ	−47.48 (12)	C3—C4—C5—C6	−179.6 (10)
N1—La1—Cl1—La1ⁱ	93.73 (13)	C12—C4—C5—C6	−0.9 (14)
N2—La1—Cl1—La1ⁱ	63.6 (2)	C4—C5—C6—C7	0.9 (16)
Cl2—La1—Cl1—La1ⁱ	23.40 (5)	C5—C6—C7—C8	−179.7 (10)
Cl2ⁱⁱ—La1—Cl1—La1ⁱ	−129.86 (6)	C5—C6—C7—C11	−1.2 (14)
Cl1ⁱⁱ—La1—Cl1—La1ⁱ	−106.56 (8)	C6—C7—C8—C9	180.0 (9)
O1—La1—Cl2—La1ⁱ	−113.89 (18)	C11—C7—C8—C9	1.5 (13)
O2ⁱ—La1—Cl2—La1ⁱ	71.80 (13)	C7—C8—C9—C10	−0.6 (13)
N1—La1—Cl2—La1ⁱ	−113.49 (14)	C11—N2—C10—C9	1.6 (11)
N2—La1—Cl2—La1ⁱ	−178.30 (15)	La1—N2—C10—C9	178.7 (6)
Cl1—La1—Cl2—La1ⁱ	−23.57 (5)	C8—C9—C10—N2	−1.0 (13)
Cl2ⁱⁱ—La1—Cl2—La1ⁱ	16.84 (4)	C10—N2—C11—C7	−0.5 (10)
Cl1ⁱⁱ—La1—Cl2—La1ⁱ	122.73 (5)	La1—N2—C11—C7	−177.7 (5)
O1—La1—N1—C1	−84.2 (5)	C10—N2—C11—C12	178.4 (6)
O2ⁱ—La1—N1—C1	104.1 (6)	La1—N2—C11—C12	1.2 (8)
N2—La1—N1—C1	179.4 (6)	C6—C7—C11—N2	−179.5 (8)
Cl1—La1—N1—C1	20.8 (5)	C8—C7—C11—N2	−0.9 (12)
Cl2—La1—N1—C1	96.1 (5)	C6—C7—C11—C12	1.6 (12)
Cl2ⁱⁱ—La1—N1—C1	−41.2 (6)	C8—C7—C11—C12	−179.9 (7)
Cl1ⁱⁱ—La1—N1—C1	−144.0 (5)	C1—N1—C12—C4	1.2 (9)
O1—La1—N1—C12	97.8 (5)	La1—N1—C12—C4	179.3 (5)
O2ⁱ—La1—N1—C12	−73.9 (5)	C1—N1—C12—C11	−179.5 (6)
N2—La1—N1—C12	1.4 (4)	La1—N1—C12—C11	−1.4 (8)
Cl1—La1—N1—C12	−157.2 (5)	C3—C4—C12—N1	−0.7 (11)
Cl2—La1—N1—C12	−81.9 (4)	C5—C4—C12—N1	−179.5 (7)
Cl2ⁱⁱ—La1—N1—C12	140.8 (4)	C3—C4—C12—C11	−179.9 (7)
Cl1ⁱⁱ—La1—N1—C12	38.0 (5)	C5—C4—C12—C11	1.3 (11)
O1—La1—N2—C10	112.4 (5)	N2—C11—C12—N1	0.2 (10)
O2ⁱ—La1—N2—C10	−37.2 (5)	C7—C11—C12—N1	179.1 (6)
N1—La1—N2—C10	−178.4 (6)	N2—C11—C12—C4	179.4 (6)
Cl1—La1—N2—C10	−143.7 (5)	C7—C11—C12—C4	−1.7 (11)
Cl2—La1—N2—C10	−103.6 (5)	C18—C13—C14—C15	0.5 (12)
Cl2ⁱⁱ—La1—N2—C10	58.9 (6)	Br1—C13—C14—C15	−178.3 (6)
Cl1ⁱⁱ—La1—N2—C10	30.3 (5)	C13—C14—C15—C16	0.5 (13)
O1—La1—N2—C11	−70.6 (5)	C14—C15—C16—O3	178.7 (8)
O2ⁱ—La1—N2—C11	139.9 (5)	C14—C15—C16—C17	−0.5 (13)
N1—La1—N2—C11	−1.3 (5)	O3—C16—C17—C18	−179.6 (7)
Cl1—La1—N2—C11	33.4 (6)	C15—C16—C17—C18	−0.4 (10)
Cl2—La1—N2—C11	73.4 (5)	O3—C16—C17—C19	−0.6 (11)
Cl2ⁱⁱ—La1—N2—C11	−124.0 (5)	C15—C16—C17—C19	178.6 (7)
Cl1ⁱⁱ—La1—N2—C11	−152.6 (5)	C14—C13—C18—C17	−1.4 (11)
O2ⁱ—La1—O1—C19	−32.9 (9)	Br1—C13—C18—C17	177.4 (5)
N1—La1—O1—C19	157.1 (8)	C16—C17—C18—C13	1.3 (10)
N2—La1—O1—C19	−141.8 (8)	C19—C17—C18—C13	−177.7 (6)
Cl1—La1—O1—C19	77.5 (8)	La1—O1—C19—O2	39.6 (12)
Cl2—La1—O1—C19	157.5 (7)	La1—O1—C19—C17	−142.6 (6)
Cl2ⁱⁱ—La1—O1—C19	9.2 (8)	La1ⁱⁱ—O2—C19—O1	−9.6 (11)
Cl1ⁱⁱ—La1—O1—C19	−65.9 (8)	La1ⁱⁱ—O2—C19—C17	172.6 (4)
C12—N1—C1—C2	−2.0 (11)	C18—C17—C19—O1	−5.8 (9)
La1—N1—C1—C2	179.9 (6)	C16—C17—C19—O1	175.2 (6)
N1—C1—C2—C3	2.1 (13)	C18—C17—C19—O2	172.2 (6)
C1—C2—C3—C4	−1.4 (14)	C16—C17—C19—O2	−6.8 (9)
C2—C3—C4—C12	0.8 (13)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2	0.82	1.93	2.588 (6)	137

Experimental details

Crystal data
Chemical formula	[La(C₇H₄BrO₃)Cl₂(C₁₂H₈N₂)]
M_r	606.02
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	296
a, b, c (Å)	8.2957 (10), 22.104 (3), 22.110 (3)
V (Å³)	4054.3 (9)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	4.36
Crystal size (mm)	0.30 × 0.24 × 0.14

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.352, 0.584
No. of measured, independent and observed [I > 2σ(I)] reflections	19025, 3598, 2849
R_int	0.065
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.125, 1.00
No. of reflections	3598
No. of parameters	254
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.20, −1.34

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999) and Mercury (Macrae et al., 2006), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2	0.82	1.93	2.588 (6)	137

Acknowledgements

This project was supported by the Shaanxi Science Research Project (No. 2011 K07–23), the Scientific Research Special Plan of Shaanxi Department of Education (No. 11 J K0566) and the Foundation of Xi'an Polytechnic University (No. BS1013).

References

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