catena-Poly[1-butyl-3-methyl-imidazolium [[dichlorido(methanol-κO)(propan-2-ol-κO)lanthanate(III)]-di-μ-chlorido]].

The title compound, (C(8)H(15)N(2))[LaCl(4)(CH(3)OH)(C(3)H(7)OH)], consists of one 1-butyl-3-methyl-imidazolium (BMI(+)) cation and one hexa-hedral tetra-chlorido(methanol)(propan-2-ol)lanthanate anion. The La(III) ion is eight-coordinate, with the La(III) ion bridged by a pair of Cl atoms, so forming chains propagating along the a-axis direction. Each La(III) ion is further coordinated by two isolated Cl atoms, one methanol and one propan-2-ol mol-ecule. The coordinated methanol and propan-2-ol mol-ecules of the anion form O-H⋯Cl hydrogen bonds with the Cl atoms of inversion-related anions. The BMI(+) cation froms C-H⋯Cl hydrogen bonds with the Cl atoms of the anion. The anions are located in the C faces of the triclinic unit cell, with an inversion center in the middle of the La(2)Cl(2) ring of the polymeric chain.

Related literature

For related crystal structures, see: Binnemans (2007 ▶); Pellens et al. (2008 ▶); Matsumoto et al. (2002 ▶). For the synthesis of the title compound, see: Burrell et al. (2007 ▶). For the optical properties of lanthanides in ionic liquids, see: Brandner et al. (2011 ▶); Samikkanu et al. (2007 ▶).

Experimental

Crystal data

(C8H15N2)[LaCl4(CH4O)(C3H8O)]

M = 512.07

Triclinic,

a = 9.5035 (6) Å

b = 10.7413 (6) Å

c = 11.8625 (7) Å

α = 114.009 (1)°

β = 109.735 (1)°

γ = 92.857 (1)°

V = 1016.20 (10) Å3

Z = 2

Mo Kα radiation

μ = 2.63 mm−1

T = 100 K

0.30 × 0.15 × 0.05 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.506, T max = 0.880

11178 measured reflections

4155 independent reflections

3780 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.022

wR(F 2) = 0.049

S = 1.04

4155 reflections

198 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.71 e Å−3

Δρmin = −0.59 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681200517X/su2369sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681200517X/su2369Isup2.hkl

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

(C8H15N2)[LaCl4(CH4O)(C3H8O)]	Z = 2
Mr = 512.07	F(000) = 508
Triclinic, P1	Dx = 1.674 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.5035 (6) Å	Cell parameters from 8208 reflections
b = 10.7413 (6) Å	θ = 2.3–26.4°
c = 11.8625 (7) Å	µ = 2.63 mm−1
α = 114.009 (1)°	T = 100 K
β = 109.735 (1)°	Block, colourless
γ = 92.857 (1)°	0.30 × 0.15 × 0.05 mm
V = 1016.20 (10) Å3

Bruker APEXII CCD area-detector diffractometer	4155 independent reflections
Radiation source: fine-focus sealed tube	3780 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
φ and ω scans	θmax = 26.4°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
Tmin = 0.506, Tmax = 0.880	k = −13→13
11178 measured reflections	l = −14→14

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)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.049	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0193P)2 + 0.4077P] where P = (Fo2 + 2Fc2)/3
4155 reflections	(Δ/σ)max = 0.001
198 parameters	Δρmax = 0.71 e Å−3
0 restraints	Δρmin = −0.59 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
La1	0.739307 (15)	0.491237 (15)	−0.023339 (14)	0.00964 (5)
Cl1	0.54404 (7)	0.24123 (7)	−0.24214 (6)	0.01713 (14)
Cl2	0.77665 (7)	0.64602 (7)	−0.16020 (7)	0.01686 (14)
Cl3	1.05144 (7)	0.63430 (7)	0.15869 (6)	0.01356 (13)
Cl4	0.56003 (7)	0.42798 (7)	0.11059 (6)	0.01393 (13)
O1	0.8605 (2)	0.3297 (2)	0.0650 (2)	0.0176 (4)
H1D	0.951 (4)	0.344 (4)	0.096 (4)	0.042 (11)*
O2	0.7406 (2)	0.7145 (2)	0.16709 (19)	0.0169 (4)
H2B	0.668 (4)	0.710 (4)	0.180 (4)	0.040 (12)*
N1	0.6581 (2)	0.1728 (2)	0.4667 (2)	0.0145 (5)
N2	0.6359 (2)	0.3591 (2)	0.4388 (2)	0.0148 (5)
C1	0.7807 (3)	0.8505 (3)	0.1784 (3)	0.0253 (7)
H1A	0.7734	0.9196	0.2577	0.038*
H1B	0.7118	0.8565	0.1010	0.038*
H1C	0.8837	0.8666	0.1841	0.038*
C2	0.7981 (3)	0.1900 (3)	0.0376 (3)	0.0218 (6)
H2A	0.6864	0.1766	0.0048	0.026*
C3	0.8374 (3)	0.0814 (3)	−0.0713 (3)	0.0297 (7)
H3A	0.7993	0.0941	−0.1509	0.045*
H3B	0.7911	−0.0104	−0.0907	0.045*
H3C	0.9465	0.0918	−0.0409	0.045*
C4	0.8534 (4)	0.1779 (4)	0.1663 (3)	0.0335 (8)
H4A	0.8255	0.2488	0.2310	0.050*
H4B	0.9628	0.1897	0.2001	0.050*
H4C	0.8073	0.0875	0.1502	0.050*
C5	0.6982 (3)	0.3114 (3)	0.5278 (3)	0.0152 (6)
H5A	0.7599	0.3662	0.6180	0.018*
C6	0.5659 (3)	0.1306 (3)	0.3339 (3)	0.0188 (6)
H6A	0.5214	0.0389	0.2686	0.023*
C7	0.5522 (3)	0.2461 (3)	0.3163 (3)	0.0195 (6)
H7A	0.4967	0.2492	0.2365	0.023*
C8	0.7080 (3)	0.0804 (3)	0.5284 (3)	0.0168 (6)
H8A	0.7713	0.1356	0.6219	0.025*
H8B	0.7654	0.0220	0.4847	0.025*
H8C	0.6199	0.0232	0.5191	0.025*
C9	0.6552 (3)	0.5071 (3)	0.4667 (3)	0.0167 (6)
H9A	0.6495	0.5616	0.5526	0.020*
H9B	0.5712	0.5167	0.3986	0.020*
C10	0.8046 (3)	0.5662 (3)	0.4693 (3)	0.0175 (6)
H10A	0.8113	0.5136	0.3833	0.021*
H10B	0.8899	0.5585	0.5378	0.021*
C11	0.8133 (3)	0.7191 (3)	0.4988 (3)	0.0199 (6)
H11A	0.8119	0.7717	0.5869	0.024*
H11B	0.7238	0.7264	0.4335	0.024*
C12	0.9580 (3)	0.7831 (3)	0.4944 (3)	0.0250 (7)
H12A	0.9588	0.8790	0.5135	0.038*
H12B	0.9588	0.7325	0.4068	0.038*
H12C	1.0469	0.7778	0.5601	0.038*

	U11	U22	U33	U12	U13	U23
La1	0.00730 (8)	0.00983 (8)	0.01066 (8)	0.00150 (5)	0.00309 (6)	0.00398 (6)
Cl1	0.0115 (3)	0.0139 (3)	0.0183 (3)	0.0012 (2)	0.0051 (3)	0.0010 (3)
Cl2	0.0131 (3)	0.0205 (4)	0.0221 (3)	0.0054 (3)	0.0073 (3)	0.0138 (3)
Cl3	0.0089 (3)	0.0143 (3)	0.0129 (3)	0.0018 (2)	0.0032 (2)	0.0029 (3)
Cl4	0.0113 (3)	0.0179 (3)	0.0158 (3)	0.0046 (2)	0.0060 (2)	0.0099 (3)
O1	0.0107 (10)	0.0165 (10)	0.0292 (11)	0.0036 (8)	0.0068 (9)	0.0143 (9)
O2	0.0120 (10)	0.0131 (10)	0.0206 (11)	−0.0001 (8)	0.0072 (8)	0.0027 (8)
N1	0.0128 (11)	0.0147 (12)	0.0153 (11)	0.0024 (9)	0.0057 (9)	0.0061 (10)
N2	0.0118 (11)	0.0168 (12)	0.0173 (12)	0.0046 (9)	0.0077 (9)	0.0073 (10)
C1	0.0278 (16)	0.0136 (15)	0.0324 (18)	0.0036 (12)	0.0152 (14)	0.0059 (13)
C2	0.0188 (14)	0.0170 (15)	0.0346 (17)	0.0055 (12)	0.0112 (13)	0.0156 (14)
C3	0.0246 (16)	0.0244 (17)	0.0350 (19)	0.0063 (13)	0.0079 (14)	0.0117 (15)
C4	0.041 (2)	0.0298 (19)	0.038 (2)	0.0069 (15)	0.0174 (16)	0.0215 (16)
C5	0.0124 (13)	0.0172 (14)	0.0124 (13)	0.0032 (11)	0.0039 (10)	0.0042 (11)
C6	0.0169 (14)	0.0161 (15)	0.0153 (14)	0.0017 (11)	0.0034 (11)	0.0023 (12)
C7	0.0173 (14)	0.0205 (15)	0.0132 (14)	0.0036 (11)	0.0013 (11)	0.0045 (12)
C8	0.0179 (14)	0.0158 (14)	0.0165 (14)	0.0034 (11)	0.0080 (11)	0.0061 (12)
C9	0.0163 (14)	0.0162 (14)	0.0207 (15)	0.0066 (11)	0.0081 (11)	0.0102 (12)
C10	0.0136 (13)	0.0188 (15)	0.0173 (14)	0.0029 (11)	0.0052 (11)	0.0065 (12)
C11	0.0174 (14)	0.0189 (15)	0.0231 (15)	0.0046 (11)	0.0066 (12)	0.0101 (13)
C12	0.0231 (15)	0.0249 (17)	0.0271 (17)	0.0023 (13)	0.0089 (13)	0.0128 (14)

La1—O1	2.5102 (19)	C3—H3A	0.9600
La1—O2	2.5348 (19)	C3—H3B	0.9600
La1—Cl1	2.8232 (6)	C3—H3C	0.9600
La1—Cl2	2.8378 (7)	C4—H4A	0.9600
La1—Cl3	2.8884 (6)	C4—H4B	0.9600
La1—Cl4	2.9119 (6)	C4—H4C	0.9600
La1—Cl4i	2.9841 (6)	C5—H5A	0.9300
La1—Cl3ii	3.0021 (6)	C6—C7	1.346 (4)
Cl3—La1ii	3.0021 (6)	C6—H6A	0.9300
Cl4—La1i	2.9841 (6)	C7—H7A	0.9300
O1—C2	1.446 (3)	C8—H8A	0.9600
O1—H1D	0.79 (4)	C8—H8B	0.9600
O2—C1	1.431 (3)	C8—H8C	0.9600
O2—H2B	0.75 (4)	C9—C10	1.512 (4)
N1—C5	1.329 (3)	C9—H9A	0.9700
N1—C6	1.378 (3)	C9—H9B	0.9700
N1—C8	1.466 (3)	C10—C11	1.525 (4)
N2—C5	1.332 (3)	C10—H10A	0.9700
N2—C7	1.381 (3)	C10—H10B	0.9700
N2—C9	1.474 (3)	C11—C12	1.533 (4)
C1—H1A	0.9600	C11—H11A	0.9700
C1—H1B	0.9600	C11—H11B	0.9700
C1—H1C	0.9600	C12—H12A	0.9600
C2—C4	1.500 (4)	C12—H12B	0.9600
C2—C3	1.520 (4)	C12—H12C	0.9600
C2—H2A	0.9800
O1—La1—O2	110.49 (6)	C3—C2—H2A	107.9
O1—La1—Cl1	83.72 (5)	C2—C3—H3A	109.5
O2—La1—Cl1	142.48 (5)	C2—C3—H3B	109.5
O1—La1—Cl2	141.74 (5)	H3A—C3—H3B	109.5
O2—La1—Cl2	89.42 (5)	C2—C3—H3C	109.5
Cl1—La1—Cl2	100.30 (2)	H3A—C3—H3C	109.5
O1—La1—Cl3	72.67 (5)	H3B—C3—H3C	109.5
O2—La1—Cl3	70.43 (5)	C2—C4—H4A	109.5
Cl1—La1—Cl3	146.015 (18)	C2—C4—H4B	109.5
Cl2—La1—Cl3	84.745 (19)	H4A—C4—H4B	109.5
O1—La1—Cl4	72.72 (5)	C2—C4—H4C	109.5
O2—La1—Cl4	70.12 (5)	H4A—C4—H4C	109.5
Cl1—La1—Cl4	82.364 (19)	H4B—C4—H4C	109.5
Cl2—La1—Cl4	145.479 (18)	N1—C5—N2	109.0 (2)
Cl3—La1—Cl4	112.230 (18)	N1—C5—H5A	125.5
O1—La1—Cl4i	141.39 (5)	N2—C5—H5A	125.5
O2—La1—Cl4i	71.22 (5)	C7—C6—N1	107.5 (2)
Cl1—La1—Cl4i	76.418 (18)	C7—C6—H6A	126.3
Cl2—La1—Cl4i	75.142 (17)	N1—C6—H6A	126.3
Cl3—La1—Cl4i	136.524 (19)	C6—C7—N2	107.1 (2)
Cl4—La1—Cl4i	72.078 (19)	C6—C7—H7A	126.5
O1—La1—Cl3ii	70.16 (5)	N2—C7—H7A	126.5
O2—La1—Cl3ii	139.40 (5)	N1—C8—H8A	109.5
Cl1—La1—Cl3ii	77.752 (18)	N1—C8—H8B	109.5
Cl2—La1—Cl3ii	73.582 (18)	H8A—C8—H8B	109.5
Cl3—La1—Cl3ii	71.48 (2)	N1—C8—H8C	109.5
Cl4—La1—Cl3ii	139.352 (18)	H8A—C8—H8C	109.5
Cl4i—La1—Cl3ii	134.605 (17)	H8B—C8—H8C	109.5
La1—Cl3—La1ii	108.52 (2)	N2—C9—C10	113.7 (2)
La1—Cl4—La1i	107.922 (19)	N2—C9—H9A	108.8
C2—O1—La1	130.59 (16)	C10—C9—H9A	108.8
C2—O1—H1D	109 (3)	N2—C9—H9B	108.8
La1—O1—H1D	118 (3)	C10—C9—H9B	108.8
C1—O2—La1	123.48 (17)	H9A—C9—H9B	107.7
C1—O2—H2B	108 (3)	C9—C10—C11	109.5 (2)
La1—O2—H2B	112 (3)	C9—C10—H10A	109.8
C5—N1—C6	108.2 (2)	C11—C10—H10A	109.8
C5—N1—C8	125.9 (2)	C9—C10—H10B	109.8
C6—N1—C8	125.8 (2)	C11—C10—H10B	109.8
C5—N2—C7	108.2 (2)	H10A—C10—H10B	108.2
C5—N2—C9	125.7 (2)	C10—C11—C12	112.2 (2)
C7—N2—C9	126.1 (2)	C10—C11—H11A	109.2
O2—C1—H1A	109.5	C12—C11—H11A	109.2
O2—C1—H1B	109.5	C10—C11—H11B	109.2
H1A—C1—H1B	109.5	C12—C11—H11B	109.2
O2—C1—H1C	109.5	H11A—C11—H11B	107.9
H1A—C1—H1C	109.5	C11—C12—H12A	109.5
H1B—C1—H1C	109.5	C11—C12—H12B	109.5
O1—C2—C4	108.9 (2)	H12A—C12—H12B	109.5
O1—C2—C3	110.9 (2)	C11—C12—H12C	109.5
C4—C2—C3	113.2 (3)	H12A—C12—H12C	109.5
O1—C2—H2A	107.9	H12B—C12—H12C	109.5
C4—C2—H2A	107.9
O1—La1—Cl3—La1ii	74.31 (5)	Cl1—La1—O2—C1	−116.57 (19)
O2—La1—Cl3—La1ii	−165.68 (5)	Cl2—La1—O2—C1	−10.28 (19)
Cl1—La1—Cl3—La1ii	26.22 (4)	Cl3—La1—O2—C1	74.35 (19)
Cl2—La1—Cl3—La1ii	−74.42 (2)	Cl4—La1—O2—C1	−161.9 (2)
Cl4—La1—Cl3—La1ii	136.68 (2)	Cl4i—La1—O2—C1	−84.77 (19)
Cl4i—La1—Cl3—La1ii	−136.31 (2)	Cl3ii—La1—O2—C1	53.2 (2)
Cl3ii—La1—Cl3—La1ii	0.0	La1—O1—C2—C4	−139.1 (2)
O1—La1—Cl4—La1i	−163.89 (5)	La1—O1—C2—C3	95.8 (2)
O2—La1—Cl4—La1i	75.95 (5)	C6—N1—C5—N2	−0.4 (3)
Cl1—La1—Cl4—La1i	−78.13 (2)	C8—N1—C5—N2	177.5 (2)
Cl2—La1—Cl4—La1i	18.96 (4)	C7—N2—C5—N1	0.3 (3)
Cl3—La1—Cl4—La1i	133.77 (2)	C9—N2—C5—N1	−178.9 (2)
Cl4i—La1—Cl4—La1i	0.0	C5—N1—C6—C7	0.4 (3)
Cl3ii—La1—Cl4—La1i	−139.14 (2)	C8—N1—C6—C7	−177.5 (2)
O2—La1—O1—C2	119.5 (2)	N1—C6—C7—N2	−0.2 (3)
Cl1—La1—O1—C2	−24.7 (2)	C5—N2—C7—C6	0.0 (3)
Cl2—La1—O1—C2	−123.36 (19)	C9—N2—C7—C6	179.1 (2)
Cl3—La1—O1—C2	−179.9 (2)	C5—N2—C9—C10	80.0 (3)
Cl4—La1—O1—C2	59.3 (2)	C7—N2—C9—C10	−99.1 (3)
Cl4i—La1—O1—C2	34.2 (2)	N2—C9—C10—C11	−180.0 (2)
Cl3ii—La1—O1—C2	−103.9 (2)	C9—C10—C11—C12	−176.5 (2)
O1—La1—O2—C1	136.28 (19)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1D···Cl2ii	0.79 (4)	2.42 (4)	3.206 (2)	171 (4)
O2—H2B···Cl1i	0.75 (4)	2.39 (4)	3.122 (2)	166 (4)
C5—H5A···Cl3iii	0.93	2.65	3.458 (3)	145
C8—H8A···Cl3iii	0.96	2.67	3.565 (3)	156

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1D⋯Cl2i	0.79 (4)	2.42 (4)	3.206 (2)	171 (4)
O2—H2B⋯Cl1ii	0.75 (4)	2.39 (4)	3.122 (2)	166 (4)
C5—H5A⋯Cl3iii	0.93	2.65	3.458 (3)	145
C8—H8A⋯Cl3iii	0.96	2.67	3.565 (3)	156

Symmetry codes: (i) ; (ii) ; (iii) .