Poly[aqua­bis(μ-benzene-1,2-dicarboxyl­ato)ethano­ltetra­lithium]

Rodríguez-Cuamatzi, P.; Tlahuext, H.; Höpfl, H.

doi:10.1107/S1600536809003390

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 3| March 2009| Page m246

doi:10.1107/S1600536809003390

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Poly[aquabis(μ-benzene-1,2-dicarboxylato)ethanoltetralithium]

Patricia Rodríguez-Cuamatzi,^a Hugo Tlahuext ^b ^* and Herbert Höpfl ^b

^aUniversidad Politécnica de Tlaxcala, Carretera Federal Tlaxcala-Puebla Km 9.5, Tepeyanco, Tlaxcala, México, and ^bCentro de Investigaciones Químicas, Universidad Autónoma del Estado de Morelos, Av. Universidad 1001, Col. Chamilpa CP 62209, Cuernavaca Mor., México
^*Correspondence e-mail: tlahuext@ciq.uaem.mx

(Received 23 January 2009; accepted 27 January 2009; online 4 February 2009)

In the crystal structure of the title compound [Li₄(C₈H₄O₄)₂(C₂H₅OH)(H₂O)]_n, there are four crystallographically independent metal centers each of which is coordinated by four O atoms. The benzene-1,2-dicarboxylate groups act as bidentate–bridging ligands producing a two-dimensional coordination network parallel to the ab plane. The coordination polymer is further stabilized by coordination of water and ethanol molecules by the Li⁺ ions. Simultaneously, the water and ethanol molecules are involved in O—H⋯O and C—H⋯π interactions.

Related literature

For related literature, see: Łyszczek et al. (2008 ); Chae et al. (2004 ); García-Zarracino et al. (2003 ); García-Zarracino & Höpfl (2004 ); García-Zarracino et al. (2008 ). For analysis of hydrogen-bonding patterns, see: Hunter (1994 ); Desiraju (1991 ).

Experimental

Crystal data

[Li₄(C₈H₄O₄)₂(C₂H₆O)(H₂O)]
M_r = 420.07
Triclinic, $[P \overline 1]$
a = 7.5254 (7) Å
b = 10.0538 (10) Å
c = 13.5073 (13) Å
α = 106.460 (2)°
β = 91.185 (2)°
γ = 103.046 (2)°
V = 950.84 (16) Å³
Z = 2
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 293 (2) K
0.49 × 0.36 × 0.06 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.945, T_max = 1.000 (expected range = 0.938–0.993)
10069 measured reflections
3735 independent reflections
3110 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.129
S = 1.09
3735 reflections
299 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O9—H9⋯O10ⁱ	0.841 (13)	1.947 (17)	2.767 (2)	165 (2)
O10—H10A⋯O1	0.84 (2)	1.97 (2)	2.764 (2)	156 (2)
O10—H10B⋯O6ⁱ	0.84 (1)	1.984 (12)	2.797 (2)	163 (3)
C17—H17A⋯Cg2	0.97	2.86	3.584 (3)	132
C18—H18C⋯Cg1ⁱ	0.96	2.70	3.572 (3)	152
Symmetry code: (i) -x, -y+1, -z+1. Cg1 and Cg2 are the centroids of the C2–C7 and C10–C15 rings, respectively.

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT-Plus-NT (Bruker, 2001 ); data reduction: SAINT-Plus-NT; program(s) used to solve structure: SHELXTL-NT (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL-NT; molecular graphics: SHELXTL-NT; software used to prepare material for publication: PLATON (Spek, 2003 ) and publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809003390/bt2860sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809003390/bt2860Isup2.hkl

checkCIF report

Comment top

Metal-organic polymers are widely studied for their properties arising from the presence of a rigid framework with open channels and cavities. Frequently, such coordination polymers are constructed from metal ions and polycarboxylate linkers; however, systems containing main group elements are little explored so far (Łyszczek et al., 2008; García-Zarracino et al., 2008; Chae et al., 2004; García-Zarracino et al., 2003; García-Zarracino & Höpfl, 2004).

We describe herein the crystal structure of dilithium phthalate solvate [(C₈H₄O₄)₂Li₄(H₂O)(C₂H₅OH)]_n. The asymmetric unit of the title compound contains two benzene-1,2-dicarboxylate ligands, four crystallographically independent lithium ions, an ethanol molecule and a water molecule. The four lithium ions have distorted tetrahedral coordination environments as shown in Fig. 1. The O—Li—O bond angles range from 96.90 (15) to 127.86 (19)°. The Li—O bond lengths vary from 1.901 (4) to 2.009 (4) Å, whereby it is interesting to note that the Li—O(H)Et bond is significantly shorter [1.910 (4) Å] than the remaining bonds, the only exception being Li—O1 [1.901 (4) Å]. Coordination of the crystallographically independent Li centers through bridging-bidentate benzene-1,2-dicarboxylate groups generates a two-dimensional network parallel to the ab plane (Fig. 2). In this two-dimensional coordination polymer four different Li_nO_nring structures can be identified: I (n= 4), II, III (n =6) and IV (n=8). It is notheworthy to mention that the COO groups in the benzene-1,2-dicarboxylate ligands adopt different coordination modes and torsion angles with respect to the corresponding aromatic ring plane: µ₃ and -72.2 (3)° for C(1)OO, µ₄ and -24.9 (3)° for C(8)OO, µ₃ and 21.0 (3)° for C(9)OO, µ₄ and 88.8 (2)° for C(16)OO.

Packing is further stabilized by ethanol and water molecules which are coordinated to Li(1) and Li(2), respectively. Both solvent molecules display O—H···O and C—H···π hydrogen bonds (Table 1, Fig. 3). The distances from the methylene (C17) and methyl (C18) groups to centroids Cg2 (C10—C15) and Cg1 (C2—C7) are 3.584 (3) and 3.572 (3) Å, respectively (Hunter, 1994; Desiraju, 1991).

Related literature top

For related literature, see: Łyszczek et al. (2008); Chae et al. (2004); García-Zarracino et al. (2003); García-Zarracino & Höpfl (2004); García-Zarracino et al. (2008). For analysis of hydrogen bonding patterns, see: Hunter (1994); Desiraju (1991). Cg1 and Cg2 are the centroids of the C2–C7 and C10–C15 rings, respectively.

Experimental top

Single crystals were obtained by slow evaporation of a solution (EtOH, 15 ml) containing benzene-1,2-dicarboxylic acid (0.50 g, 3.0 mmol) and lithium hydroxide dihydrate (0.36 g, 6.0 mmol).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT-Plus-NT (Bruker, 2001); data reduction: SAINT-Plus-NT (Bruker, 2001); program(s) used to solve structure: SHELXTL-NT (Sheldrick, 2008); program(s) used to refine structure: SHELXTL-NT (Sheldrick, 2008); molecular graphics: SHELXTL-NT (Sheldrick, 2008); software used to prepare material for publication: PLATON (Spek, 2003) and publCIF (Westrip, 2009).

Figures top

	Fig. 1. The asymmetric unit of the title compound, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. Crystal packing of the title compound, showing the two-dimensional network parallel to the ab plane. For clarity, hydrogen and carbon atoms are omitted.
	Fig. 3. View of O—H···O and the facial C—H···π hydrogen bonds. Dashed lines indicate the vectors from the methylene (C17) and methyl (C18) groups to centroids Cg2 (C10—C15) and Cg1 (C2—C7), respectively.

Poly[aquabis(µ-benzene-1,2-dicarboxylato)ethanoltetralithium] top

Crystal data top

[Li₄(C₈H₄O₄)₂(C₂H₆O)(H₂O)]	Z = 2
M_r = 420.07	F(000) = 432
Triclinic, P1	D_x = 1.467 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5254 (7) Å	Cell parameters from 5811 reflections
b = 10.0538 (10) Å	θ = 2.3–27.5°
c = 13.5073 (13) Å	µ = 0.12 mm⁻¹
α = 106.460 (2)°	T = 293 K
β = 91.185 (2)°	Plate, colourless
γ = 103.046 (2)°	0.49 × 0.36 × 0.06 mm
V = 950.84 (16) Å³

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	3735 independent reflections
Radiation source: fine-focus sealed tube	3110 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
Detector resolution: 8.3 pixels mm^-1	θ_max = 26.0°, θ_min = 1.6°
ϕ and ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −12→12
T_min = 0.945, T_max = 1.0	l = −16→16
10069 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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.129	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.0657P)² + 0.0955P] where P = (F_o² + 2F_c²)/3
3735 reflections	(Δ/σ)_max < 0.001
299 parameters	Δρ_max = 0.29 e Å⁻³
3 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

[Li₄(C₈H₄O₄)₂(C₂H₆O)(H₂O)]	γ = 103.046 (2)°
M_r = 420.07	V = 950.84 (16) Å³
Triclinic, P1	Z = 2
a = 7.5254 (7) Å	Mo Kα radiation
b = 10.0538 (10) Å	µ = 0.12 mm⁻¹
c = 13.5073 (13) Å	T = 293 K
α = 106.460 (2)°	0.49 × 0.36 × 0.06 mm
β = 91.185 (2)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	3735 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3110 reflections with I > 2σ(I)
T_min = 0.945, T_max = 1.0	R_int = 0.039
10069 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	3 restraints
wR(F²) = 0.129	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.29 e Å⁻³
3735 reflections	Δρ_min = −0.20 e Å⁻³
299 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
Li1	0.3218 (5)	0.6867 (3)	0.6127 (3)	0.0274 (7)
Li2	0.1872 (5)	0.3690 (4)	0.4990 (3)	0.0287 (8)
Li3	0.1436 (5)	0.9010 (3)	0.4401 (3)	0.0271 (7)
Li4	0.4303 (5)	1.1686 (4)	0.5415 (3)	0.0277 (7)
O1	0.51646 (19)	0.40347 (14)	0.33549 (11)	0.0311 (4)
H9	0.0361 (13)	0.716 (3)	0.6978 (19)	0.047*
O2	0.60250 (18)	0.63805 (14)	0.41291 (11)	0.0277 (3)
O3	0.21664 (18)	0.55545 (14)	0.47330 (10)	0.0263 (3)
O4	0.05081 (18)	0.70170 (14)	0.44799 (11)	0.0277 (3)
O5	0.20599 (18)	1.05156 (15)	0.57359 (10)	0.0272 (3)
O6	−0.02639 (18)	1.04904 (15)	0.67106 (11)	0.0313 (4)
O7	0.60652 (17)	1.08648 (14)	0.60341 (10)	0.0251 (3)
O8	0.48228 (19)	0.86333 (14)	0.60088 (11)	0.0286 (3)
O9	0.1425 (2)	0.7081 (2)	0.71036 (12)	0.0434 (4)
O10	0.1786 (2)	0.24140 (16)	0.35725 (13)	0.0355 (4)
H10A	0.2810 (17)	0.269 (3)	0.3365 (19)	0.053*
H10B	0.155 (4)	0.1522 (4)	0.345 (2)	0.053*
C1	0.5022 (3)	0.5289 (2)	0.34916 (15)	0.0224 (4)
C2	0.3625 (3)	0.5497 (2)	0.27672 (15)	0.0236 (4)
C3	0.3998 (3)	0.5279 (2)	0.17410 (17)	0.0351 (5)
H3	0.5051	0.4983	0.1531	0.042*
C4	0.2845 (4)	0.5489 (3)	0.10264 (17)	0.0408 (6)
H4	0.3124	0.5345	0.0342	0.049*
C5	0.1273 (4)	0.5915 (2)	0.13316 (18)	0.0414 (6)
H5	0.0482	0.6052	0.0852	0.050*
C6	0.0877 (3)	0.6136 (2)	0.23443 (16)	0.0314 (5)
H6	−0.0179	0.6433	0.2545	0.038*
C7	0.2028 (3)	0.59242 (19)	0.30770 (15)	0.0227 (4)
C8	0.1526 (2)	0.6171 (2)	0.41697 (15)	0.0220 (4)
C9	0.1401 (3)	1.05967 (19)	0.65956 (15)	0.0226 (4)
C10	0.2681 (3)	1.0844 (2)	0.75287 (15)	0.0254 (4)
C11	0.2166 (3)	1.1396 (2)	0.85110 (17)	0.0360 (5)
H11	0.1030	1.1615	0.8579	0.043*
C12	0.3293 (4)	1.1626 (3)	0.93858 (18)	0.0446 (6)
H12	0.2924	1.1998	1.0038	0.054*
C13	0.4977 (4)	1.1299 (3)	0.92891 (18)	0.0453 (6)
H13	0.5747	1.1450	0.9878	0.054*
C14	0.5521 (3)	1.0751 (2)	0.83213 (17)	0.0348 (5)
H14	0.6654	1.0525	0.8262	0.042*
C15	0.4401 (3)	1.0531 (2)	0.74352 (15)	0.0237 (4)
C16	0.5114 (2)	0.9964 (2)	0.64110 (15)	0.0214 (4)
C17	0.1858 (3)	0.7394 (3)	0.81807 (18)	0.0484 (7)
H17A	0.2974	0.8148	0.8391	0.058*
H17B	0.2091	0.6552	0.8322	0.058*
C18	0.0380 (4)	0.7851 (3)	0.8815 (2)	0.0621 (8)
H18A	0.0126	0.8675	0.8671	0.093*
H18B	0.0772	0.8085	0.9538	0.093*
H18C	−0.0708	0.7087	0.8644	0.093*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Li1	0.0269 (18)	0.0260 (18)	0.0314 (19)	0.0084 (14)	0.0015 (14)	0.0105 (15)
Li2	0.0232 (18)	0.0280 (18)	0.036 (2)	0.0073 (14)	−0.0001 (14)	0.0106 (15)
Li3	0.0244 (18)	0.0259 (17)	0.0326 (19)	0.0064 (14)	0.0026 (14)	0.0107 (15)
Li4	0.0256 (18)	0.0272 (18)	0.0328 (19)	0.0062 (14)	0.0019 (15)	0.0129 (15)
O1	0.0299 (8)	0.0243 (8)	0.0430 (9)	0.0112 (6)	0.0011 (7)	0.0123 (6)
O2	0.0221 (7)	0.0252 (7)	0.0357 (8)	0.0050 (6)	−0.0027 (6)	0.0096 (6)
O3	0.0260 (8)	0.0268 (7)	0.0299 (8)	0.0089 (6)	0.0005 (6)	0.0126 (6)
O4	0.0228 (7)	0.0253 (7)	0.0397 (9)	0.0102 (6)	0.0086 (6)	0.0131 (6)
O5	0.0222 (7)	0.0308 (8)	0.0277 (8)	0.0048 (6)	0.0016 (6)	0.0088 (6)
O6	0.0184 (8)	0.0384 (9)	0.0428 (9)	0.0116 (6)	0.0064 (6)	0.0167 (7)
O7	0.0162 (7)	0.0272 (7)	0.0345 (8)	0.0047 (6)	0.0019 (6)	0.0137 (6)
O8	0.0335 (8)	0.0217 (7)	0.0341 (8)	0.0109 (6)	0.0055 (6)	0.0101 (6)
O9	0.0273 (9)	0.0688 (12)	0.0372 (9)	0.0183 (8)	0.0039 (7)	0.0150 (8)
O10	0.0246 (8)	0.0303 (8)	0.0503 (10)	0.0066 (7)	0.0062 (7)	0.0095 (8)
C1	0.0175 (10)	0.0254 (10)	0.0279 (11)	0.0076 (8)	0.0073 (8)	0.0111 (8)
C2	0.0238 (10)	0.0194 (10)	0.0271 (11)	0.0040 (8)	0.0005 (8)	0.0071 (8)
C3	0.0369 (13)	0.0377 (12)	0.0337 (12)	0.0132 (10)	0.0081 (10)	0.0117 (10)
C4	0.0558 (16)	0.0444 (14)	0.0243 (12)	0.0123 (12)	0.0024 (11)	0.0132 (10)
C5	0.0521 (15)	0.0398 (13)	0.0336 (13)	0.0143 (12)	−0.0121 (11)	0.0113 (10)
C6	0.0301 (12)	0.0278 (11)	0.0365 (13)	0.0114 (9)	−0.0063 (9)	0.0071 (9)
C7	0.0223 (10)	0.0177 (9)	0.0280 (11)	0.0045 (8)	−0.0026 (8)	0.0071 (8)
C8	0.0154 (9)	0.0192 (9)	0.0305 (11)	0.0019 (7)	−0.0009 (8)	0.0077 (8)
C9	0.0212 (10)	0.0172 (9)	0.0317 (11)	0.0069 (8)	0.0034 (8)	0.0093 (8)
C10	0.0259 (11)	0.0226 (10)	0.0294 (11)	0.0067 (8)	0.0040 (8)	0.0097 (8)
C11	0.0340 (13)	0.0394 (13)	0.0346 (13)	0.0120 (10)	0.0089 (10)	0.0083 (10)
C12	0.0504 (16)	0.0543 (15)	0.0258 (12)	0.0130 (12)	0.0097 (11)	0.0061 (11)
C13	0.0450 (15)	0.0578 (16)	0.0295 (13)	0.0053 (12)	−0.0079 (11)	0.0136 (11)
C14	0.0294 (12)	0.0409 (13)	0.0337 (12)	0.0083 (10)	−0.0037 (9)	0.0110 (10)
C15	0.0243 (10)	0.0202 (10)	0.0270 (10)	0.0035 (8)	0.0006 (8)	0.0094 (8)
C16	0.0148 (9)	0.0247 (10)	0.0281 (11)	0.0085 (8)	−0.0033 (8)	0.0105 (8)
C17	0.0380 (14)	0.0637 (17)	0.0381 (14)	0.0000 (12)	0.0020 (11)	0.0162 (12)
C18	0.067 (2)	0.0632 (19)	0.0450 (16)	0.0023 (15)	0.0195 (14)	0.0077 (14)

Geometric parameters (Å, º) top

Li1—O1ⁱ	1.901 (4)	O10—H10A	0.84 (2)
Li1—O9	1.910 (4)	O10—H10B	0.840 (10)
Li1—O8	1.959 (4)	C1—C2	1.510 (3)
Li1—O3	1.993 (4)	C2—C3	1.385 (3)
Li2—O3	1.967 (4)	C2—C7	1.398 (3)
Li2—O10	1.970 (4)	C3—C4	1.376 (3)
Li2—O2ⁱ	1.986 (4)	C3—H3	0.9300
Li2—O4ⁱⁱ	1.998 (4)	C4—C5	1.379 (3)
Li3—O6ⁱⁱⁱ	1.964 (4)	C4—H4	0.9300
Li3—O5	1.965 (4)	C5—C6	1.373 (3)
Li3—O7^iv	1.970 (4)	C5—H5	0.9300
Li3—O4	2.002 (3)	C6—C7	1.394 (3)
Li4—O2^iv	1.940 (4)	C6—H6	0.9300
Li4—O5	1.961 (4)	C7—C8	1.497 (3)
Li4—O7	1.995 (4)	C9—C10	1.498 (3)
Li4—O8^iv	2.009 (4)	C10—C11	1.386 (3)
O1—C1	1.251 (2)	C10—C15	1.400 (3)
O1—Li1ⁱ	1.901 (4)	C11—C12	1.373 (3)
O2—C1	1.257 (2)	C11—H11	0.9300
O2—Li4^iv	1.940 (4)	C12—C13	1.379 (4)
O2—Li2ⁱ	1.986 (4)	C12—H12	0.9300
O3—C8	1.258 (2)	C13—C14	1.377 (3)
O4—C8	1.261 (2)	C13—H13	0.9300
O4—Li2ⁱⁱ	1.998 (4)	C14—C15	1.384 (3)
O5—C9	1.261 (2)	C14—H14	0.9300
O6—C9	1.250 (2)	C15—C16	1.499 (3)
O6—Li3ⁱⁱⁱ	1.964 (4)	C17—C18	1.493 (4)
O7—C16	1.255 (2)	C17—H17A	0.9700
O7—Li3^iv	1.970 (4)	C17—H17B	0.9700
O8—C16	1.258 (2)	C18—H18A	0.9600
O8—Li4^iv	2.009 (4)	C18—H18B	0.9600
O9—C17	1.413 (3)	C18—H18C	0.9600
O9—H9	0.841 (13)

O1ⁱ—Li1—O9	105.47 (17)	C4—C3—C2	121.5 (2)
O1ⁱ—Li1—O8	103.97 (17)	C4—C3—H3	119.3
O9—Li1—O8	116.44 (18)	C2—C3—H3	119.3
O1ⁱ—Li1—O3	106.04 (16)	C3—C4—C5	119.6 (2)
O9—Li1—O3	112.98 (18)	C3—C4—H4	120.2
O8—Li1—O3	110.81 (17)	C5—C4—H4	120.2
O3—Li2—O10	101.37 (17)	C6—C5—C4	119.9 (2)
O3—Li2—O2ⁱ	112.47 (17)	C6—C5—H5	120.0
O10—Li2—O2ⁱ	110.56 (17)	C4—C5—H5	120.0
O3—Li2—O4ⁱⁱ	114.83 (17)	C5—C6—C7	121.2 (2)
O10—Li2—O4ⁱⁱ	105.75 (17)	C5—C6—H6	119.4
O2ⁱ—Li2—O4ⁱⁱ	111.15 (18)	C7—C6—H6	119.4
O6ⁱⁱⁱ—Li3—O5	115.79 (17)	C6—C7—C2	118.77 (19)
O6ⁱⁱⁱ—Li3—O7^iv	100.67 (16)	C6—C7—C8	119.09 (18)
O5—Li3—O7^iv	97.71 (16)	C2—C7—C8	122.15 (17)
O6ⁱⁱⁱ—Li3—O4	116.55 (17)	O3—C8—O4	123.65 (18)
O5—Li3—O4	115.86 (17)	O3—C8—C7	118.68 (17)
O7^iv—Li3—O4	106.30 (16)	O4—C8—C7	117.65 (17)
O2^iv—Li4—O5	104.30 (17)	O6—C9—O5	123.40 (18)
O2^iv—Li4—O7	127.86 (19)	O6—C9—C10	118.31 (17)
O5—Li4—O7	96.90 (15)	O5—C9—C10	118.29 (17)
O2^iv—Li4—O8^iv	107.63 (16)	O6—C9—Li3ⁱⁱⁱ	43.92 (12)
O5—Li4—O8^iv	123.76 (18)	C11—C10—C15	118.73 (19)
O7—Li4—O8^iv	98.37 (15)	C11—C10—C9	119.75 (19)
C1—O1—Li1ⁱ	136.25 (17)	C15—C10—C9	121.52 (17)
C1—O2—Li4^iv	129.06 (16)	C12—C11—C10	121.5 (2)
C1—O2—Li2ⁱ	123.07 (16)	C12—C11—H11	119.2
Li4^iv—O2—Li2ⁱ	107.38 (16)	C10—C11—H11	119.2
C8—O3—Li2	142.29 (16)	C11—C12—C13	119.5 (2)
C8—O3—Li1	112.98 (15)	C11—C12—H12	120.3
Li2—O3—Li1	100.59 (15)	C13—C12—H12	120.3
C8—O4—Li2ⁱⁱ	119.14 (16)	C14—C13—C12	120.1 (2)
C8—O4—Li3	116.27 (15)	C14—C13—H13	120.0
Li2ⁱⁱ—O4—Li3	124.59 (15)	C12—C13—H13	120.0
C9—O5—Li4	129.30 (16)	C13—C14—C15	120.8 (2)
C9—O5—Li3	130.62 (16)	C13—C14—H14	119.6
Li4—O5—Li3	99.23 (15)	C15—C14—H14	119.6
C9—O6—Li3ⁱⁱⁱ	109.88 (16)	C14—C15—C10	119.38 (19)
C16—O7—Li3^iv	128.87 (15)	C14—C15—C16	117.46 (18)
C16—O7—Li4	106.10 (15)	C10—C15—C16	123.16 (17)
Li3^iv—O7—Li4	121.08 (15)	O7—C16—O8	123.81 (18)
C16—O8—Li1	139.52 (17)	O7—C16—C15	116.96 (17)
C16—O8—Li4^iv	106.87 (16)	O8—C16—C15	119.11 (17)
Li1—O8—Li4^iv	110.21 (15)	O9—C17—C18	113.4 (2)
C17—O9—Li1	122.55 (17)	O9—C17—H17A	108.9
C17—O9—H9	110.9 (17)	C18—C17—H17A	108.9
Li1—O9—H9	125.6 (17)	O9—C17—H17B	108.9
Li2—O10—H10A	105.3 (19)	C18—C17—H17B	108.9
Li2—O10—H10B	121.2 (18)	H17A—C17—H17B	107.7
H10A—O10—H10B	109 (3)	C17—C18—H18A	109.5
O1—C1—O2	125.25 (18)	C17—C18—H18B	109.5
O1—C1—C2	116.45 (17)	H18A—C18—H18B	109.5
O2—C1—C2	118.11 (16)	C17—C18—H18C	109.5
C3—C2—C7	119.07 (19)	H18A—C18—H18C	109.5
C3—C2—C1	116.90 (18)	H18B—C18—H18C	109.5
C7—C2—C1	124.02 (17)

O10—Li2—O3—C8	48.3 (3)	C7—C2—C3—C4	0.8 (3)
O2ⁱ—Li2—O3—C8	166.4 (2)	C1—C2—C3—C4	−177.7 (2)
O4ⁱⁱ—Li2—O3—C8	−65.1 (3)	C2—C3—C4—C5	−0.6 (4)
O10—Li2—O3—Li1	−158.66 (16)	C3—C4—C5—C6	0.5 (4)
O2ⁱ—Li2—O3—Li1	−40.6 (2)	C4—C5—C6—C7	−0.7 (3)
O4ⁱⁱ—Li2—O3—Li1	87.9 (2)	C5—C6—C7—C2	0.9 (3)
O1ⁱ—Li1—O3—C8	−159.63 (16)	C5—C6—C7—C8	−179.59 (19)
O9—Li1—O3—C8	85.3 (2)	C3—C2—C7—C6	−1.0 (3)
O8—Li1—O3—C8	−47.4 (2)	C1—C2—C7—C6	177.47 (18)
O1ⁱ—Li1—O3—Li2	37.91 (19)	C3—C2—C7—C8	179.55 (18)
O9—Li1—O3—Li2	−77.1 (2)	C1—C2—C7—C8	−2.0 (3)
O8—Li1—O3—Li2	150.12 (17)	Li2—O3—C8—O4	105.0 (3)
O6ⁱⁱⁱ—Li3—O4—C8	105.3 (2)	Li1—O3—C8—O4	−46.0 (2)
O5—Li3—O4—C8	−113.2 (2)	Li2—O3—C8—C7	−76.6 (3)
O7^iv—Li3—O4—C8	−5.9 (2)	Li1—O3—C8—C7	132.36 (18)
C9ⁱⁱⁱ—Li3—O4—C8	128.77 (16)	Li2ⁱⁱ—O4—C8—O3	−59.5 (3)
O6ⁱⁱⁱ—Li3—O4—Li2ⁱⁱ	−74.8 (2)	Li3—O4—C8—O3	120.4 (2)
O5—Li3—O4—Li2ⁱⁱ	66.7 (2)	Li2ⁱⁱ—O4—C8—C7	122.07 (19)
O7^iv—Li3—O4—Li2ⁱⁱ	173.99 (16)	Li3—O4—C8—C7	−58.0 (2)
C9ⁱⁱⁱ—Li3—O4—Li2ⁱⁱ	−51.4 (2)	C6—C7—C8—O3	156.66 (18)
Li4^iv—Li3—O4—Li2ⁱⁱ	153.92 (16)	C2—C7—C8—O3	−23.8 (3)
O2^iv—Li4—O5—C9	−58.5 (2)	C6—C7—C8—O4	−24.8 (3)
O7—Li4—O5—C9	73.5 (2)	C2—C7—C8—O4	154.65 (18)
O8^iv—Li4—O5—C9	178.40 (18)	Li3ⁱⁱⁱ—O6—C9—O5	−23.6 (3)
C16^iv—Li4—O5—C9	161.14 (16)	Li3ⁱⁱⁱ—O6—C9—C10	155.94 (17)
O2^iv—Li4—O5—Li3	131.37 (17)	Li4—O5—C9—O6	137.2 (2)
O7—Li4—O5—Li3	−96.65 (16)	Li3—O5—C9—O6	−55.7 (3)
O8^iv—Li4—O5—Li3	8.3 (2)	Li4—O5—C9—C10	−42.3 (3)
C16^iv—Li4—O5—Li3	−9.01 (16)	Li3—O5—C9—C10	124.8 (2)
O6ⁱⁱⁱ—Li3—O5—C9	111.4 (2)	Li4—O5—C9—Li3ⁱⁱⁱ	120.91 (19)
O7^iv—Li3—O5—C9	−142.81 (18)	Li3—O5—C9—Li3ⁱⁱⁱ	−71.9 (2)
O4—Li3—O5—C9	−30.4 (3)	O6—C9—C10—C11	−20.6 (3)
C9ⁱⁱⁱ—Li3—O5—C9	84.1 (2)	O5—C9—C10—C11	158.97 (19)
O6ⁱⁱⁱ—Li3—O5—Li4	−78.7 (2)	Li3ⁱⁱⁱ—C9—C10—C11	19.7 (4)
O7^iv—Li3—O5—Li4	27.15 (17)	O6—C9—C10—C15	159.43 (18)
O4—Li3—O5—Li4	139.50 (18)	O5—C9—C10—C15	−21.0 (3)
C9ⁱⁱⁱ—Li3—O5—Li4	−105.99 (16)	Li3ⁱⁱⁱ—C9—C10—C15	−160.3 (3)
Li3ⁱⁱⁱ—Li3—O5—Li4	−125.95 (13)	C15—C10—C11—C12	−0.6 (3)
Li4^iv—Li3—O5—Li4	55.88 (16)	C9—C10—C11—C12	179.4 (2)
O2^iv—Li4—O7—C16	112.4 (2)	C10—C11—C12—C13	−0.1 (4)
O5—Li4—O7—C16	−1.76 (19)	C11—C12—C13—C14	0.2 (4)
O8^iv—Li4—O7—C16	−127.46 (16)	C12—C13—C14—C15	0.6 (4)
C16^iv—Li4—O7—C16	−103.37 (14)	C13—C14—C15—C10	−1.3 (3)
O2^iv—Li4—O7—Li3^iv	−88.1 (3)	C13—C14—C15—C16	178.5 (2)
O5—Li4—O7—Li3^iv	157.75 (15)	C11—C10—C15—C14	1.3 (3)
O8^iv—Li4—O7—Li3^iv	32.0 (2)	C9—C10—C15—C14	−178.69 (18)
C16^iv—Li4—O7—Li3^iv	56.14 (18)	C11—C10—C15—C16	−178.52 (18)
O1ⁱ—Li1—O8—C16	−113.1 (2)	C9—C10—C15—C16	1.5 (3)
O9—Li1—O8—C16	2.4 (3)	Li3^iv—O7—C16—O8	−51.7 (3)
O3—Li1—O8—C16	133.4 (2)	Li4—O7—C16—O8	105.6 (2)
O1ⁱ—Li1—O8—Li4^iv	91.69 (18)	Li3^iv—O7—C16—C15	124.2 (2)
O9—Li1—O8—Li4^iv	−152.80 (18)	Li4—O7—C16—C15	−78.46 (19)
O3—Li1—O8—Li4^iv	−21.8 (2)	Li3^iv—O7—C16—Li4^iv	−59.9 (2)
O1ⁱ—Li1—O9—C17	36.1 (3)	Li4—O7—C16—Li4^iv	97.41 (14)
O8—Li1—O9—C17	−78.6 (3)	Li1—O8—C16—O7	−166.9 (2)
O3—Li1—O9—C17	151.5 (2)	Li4^iv—O8—C16—O7	−11.2 (2)
Li1ⁱ—O1—C1—O2	−3.7 (4)	Li1—O8—C16—C15	17.3 (3)
Li1ⁱ—O1—C1—C2	171.2 (2)	Li4^iv—O8—C16—C15	172.99 (17)
Li4^iv—O2—C1—O1	−168.20 (19)	Li1—O8—C16—Li4^iv	−155.7 (3)
Li2ⁱ—O2—C1—O1	2.7 (3)	C14—C15—C16—O7	−87.3 (2)
Li4^iv—O2—C1—C2	17.0 (3)	C10—C15—C16—O7	92.6 (2)
Li2ⁱ—O2—C1—C2	−172.08 (17)	C14—C15—C16—O8	88.8 (2)
O1—C1—C2—C3	−69.0 (2)	C10—C15—C16—O8	−91.3 (2)
O2—C1—C2—C3	106.2 (2)	C14—C15—C16—Li4^iv	107.8 (5)
O1—C1—C2—C7	112.5 (2)	C10—C15—C16—Li4^iv	−72.3 (6)
O2—C1—C2—C7	−72.2 (2)	Li1—O9—C17—C18	166.4 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9···O10ⁱⁱ	0.84 (1)	1.95 (2)	2.767 (2)	165 (2)
O10—H10A···O1	0.84 (2)	1.97 (2)	2.764 (2)	156 (2)
O10—H10B···O6ⁱⁱ	0.84 (1)	1.98 (1)	2.797 (2)	163 (3)
C17—H17A···Cg2	0.97	2.86	3.584 (3)	132
C18—H18C···Cg1ⁱⁱ	0.96	2.70	3.572 (3)	152

Symmetry code: (ii) −x, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Li₄(C₈H₄O₄)₂(C₂H₆O)(H₂O)]
M_r	420.07
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.5254 (7), 10.0538 (10), 13.5073 (13)
α, β, γ (°)	106.460 (2), 91.185 (2), 103.046 (2)
V (Å³)	950.84 (16)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.49 × 0.36 × 0.06

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.945, 1.0
No. of measured, independent and observed [I > 2σ(I)] reflections	10069, 3735, 3110
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.129, 1.09
No. of reflections	3735
No. of parameters	299
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)	0.29, −0.20

Computer programs: SMART (Bruker, 2000), SAINT-Plus-NT (Bruker, 2001), SHELXTL-NT (Sheldrick, 2008), PLATON (Spek, 2003) and publCIF (Westrip, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9···O10ⁱ	0.841 (13)	1.947 (17)	2.767 (2)	165 (2)
O10—H10A···O1	0.84 (2)	1.97 (2)	2.764 (2)	156 (2)
O10—H10B···O6ⁱ	0.84 (1)	1.984 (12)	2.797 (2)	163 (3)
C17—H17A···Cg2	0.97	2.86	3.584 (3)	132
C18—H18C···Cg1ⁱ	0.96	2.70	3.572 (3)	152

Symmetry code: (i) −x, −y+1, −z+1.

Acknowledgements

This work was supported by Consejo Nacional de Ciencia y Tecnología (CIAM-59213 for HH).

References

Bruker (2000). SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2001). SAINT-Plus-NT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chae, H. K., Siberio-Perez, D. Y., Kim, J., Go, Y., Eddaoudi, M., Matzger, A. J., O'Keeffe, M. & Yaghi, O. M. (2004). Nature (London), 427, 523–527. Web of Science CSD CrossRef PubMed CAS Google Scholar
Desiraju, G. R. (1991). Acc. Chem. Res. 24, 290–296. CrossRef CAS Web of Science Google Scholar
García-Zarracino, R. & Höpfl, H. (2004). Angew. Chem. Int. Ed. 43, 1507–1511. Google Scholar
García-Zarracino, R., Ramos-Quiñones, J. & Höpfl, H. (2003). Inorg. Chem. 42, 3835–3845. Web of Science CSD CrossRef PubMed Google Scholar
García-Zarracino, R., Rangel-Marrón, M., Tlahuext, H. & Höpfl, H. (2008). Acta Cryst. E64, m1626. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hunter, C. A. (1994). Chem. Soc. Rev. pp. 101–109. CrossRef Web of Science Google Scholar
Łyszczek, R., Mazur, L. & Rzączyńsk, Z. (2008). Inorg. Chem. Commun. 11, 1091–1093. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2009). publCIF. In preparation. Google Scholar