Poly[μ₆-(naphthalene-2,6-di­carboxyl­ato)-bis­(aqua­lithium)]

Abstract

The title compound, [Li₂(C₁₂H₆O₄)(H₂O)₂]_n, crystallizes with one half of the molecular entities in the asymmetric unit. The second half is gererated by inversion symmetry. The crystal structure has a layered arrangement built from distorted edge-sharing LiO₃(OH)₂ tetra­hedra parallel to (100), with naphthalenedi­carboxyl­ate bridging the LiO₃(OH)₂ layers along the [100] direction. Hydrogen bonding between the water molecule and adjacent carboxylate groups consolidates the packing.

Related literature  

For the synthesis and crystal structure of 2,6-naphthalenedi­carb­oxy­lic acid, see Kaduk & Golab (1999 ▶). For the synthesis and crystal structure of dilithium-2,6-naphthalene di­carboxyl­ate [Li₂(2,6-NDC)], see: Banerjee et al. (2009a ▶). For related compounds, see: Banerjee et al. (2009b ▶). [Li₂(2,6-NDC)] was recently reported to exhibit good electrochemical performance, see: Fédèle et al. (2014 ▶).

Experimental  

Crystal data  

• [Li₂(C₁₂H₆O₄)(H₂O)₂]

• M _r = 132.04

• Monoclinic,

• a = 23.5695 (18) Å

• b = 6.8115 (5) Å

• c = 7.5327 (6) Å

• β = 90.325 (3)°

• V = 1209.31 (16) ų

• Z = 8

• Mo Kα radiation

• μ = 0.11 mm⁻¹

• T = 293 K

• 0.12 × 0.05 × 0.03 mm

Data collection  

• Bruker D8 Venture diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T _min = 0.707, T _max = 0.746

• 12848 measured reflections

• 1388 independent reflections

• 1032 reflections with I > 2σ(I)

• R _int = 0.050

Refinement  

• R[F ² > 2σ(F ²)] = 0.043

• wR(F ²) = 0.109

• S = 1.06

• 1388 reflections

• 99 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.23 e Å⁻³

• Δρ_min = −0.24 e Å⁻³

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: SHELXLE (Hübschle et al., 2011 ▶); molecular graphics: VESTA (Momma & Izumi, 2011 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

CCDC reference: 1006973

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H1W⋯O1i	0.81 (3)	2.10 (3)	2.905 (2)	176 (3)
O2—H2W⋯O3ii	0.89 (3)	2.01 (3)	2.883 (2)	169 (3)

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

S1. Comment

For the last 30 years, inorganic compounds involving at least one transition metal as a redox center (such as LiCoO₂ or LiFePO₄) have been the traditional electrodes for Li-ion batteries. While they exhibit good performances in terms of cyclability, output voltage capacity, main drawbacks such as toxicity, sustainability and eco-conception still remain. In this context, organic based electrodes for Li-ion batteries recently regained attention. Among them, the dilithium 2,6-naphthalene dicarboxylate (Li₂-2,6-NDC) was recently reported to exhibit good electrochemical performances (Fédèle et al. 2014). The title compound (dilithium 2,6-naphthalene dicarboxylate dihydrate) is the hydrated form of the Li₂-2,6-NDC. In the former, pairs of edge-sharing LiO₄ tetrahedra are connected to each other by corners (Banerjee et al. 2009a). In the hydrated form, the corner sharing arrangement is no longer possible as one oxygen is replaced by a water molecule. Edge-sharing LiO₃(OH₂) tetrahedra are connected into sheets that extend in the yz plane. These are linked by the naphthalene dicarboxylate into a 3-D array. Crystal data, data collection and structure refinement details are summarized in Table 1.

S2. Experimental

Reagent and chemicals. The 2,6 naphthalene dicarboxylic acid (98+%) and lithium hydroxide were purchased from Alfa Aesar and Sigma-Aldrich, respectively. They were used as received without further purification. De-ionized water was utilized for the synthesis of the di-lithium salt.

Hydrothermal Lithiation procedure. 1 g of 2,6-naphthalene dicarboxylic acid (4.6 mmol) was added into 10 ml de-ionized water and added to a 23 ml autoclave. Two equivalents of anhydrous lithium hydroxide (222 mg, 9.3 mmol) were incorporated with the naphthalene derivative. The autoclave was then placed into a temperature controlled oven set at 150°C for 12 h duration before to be cooled down to room temperature with a ramp of 10°C/h. The resulting green solution was poured into a 50 ml beaker while the excess water was slowly evaporated under ambient conditions to form the colorless single crystals of the di-lithium-2,6-naphthalene dicarboxylate dihydrate.

S3. Refinement

All H-atoms were positioned geometrically and refined using a riding model with C—H = 0.90–0.93 Å and with U_iso(H) = 1.2Ueq(C). The H atoms of the aqua ligand (H1W and H2W) were found by Fourier difference map and further refined without any constrains.

Figures

Fig. 1.

Molecular view of the title compound. Li, O, C, and H atoms are represented by light green, red, brown and white spheres respectively

Fig. 2.

Crystal structure of the title compound view along the b axis. Layers of LiO3(OH2) edge-sharing tetrahedra in the (yz) plane are connected via naphthalene dicarboxylate molecules.

Crystal data

[Li2(C12H6O4)(H2O)2]	Z = 8
Mr = 132.04	F(000) = 544
Monoclinic, C2/c	Dx = 1.450 Mg m−3
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 23.5695 (18) Å	µ = 0.11 mm−1
b = 6.8115 (5) Å	T = 293 K
c = 7.5327 (6) Å	Prism, colourless
β = 90.325 (3)°	0.12 × 0.05 × 0.03 mm
V = 1209.31 (16) Å3

Data collection

Bruker D8 Venture diffractometer	1388 independent reflections
Radiation source: fine-focus sealed tube	1032 reflections with I > 2σ(I)
Multilayer optics monochromator	Rint = 0.050
phi scan	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −30→29
Tmin = 0.707, Tmax = 0.746	k = −8→8
12848 measured reflections	l = −9→9

Refinement

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0452P)2 + 1.0165P] where P = (Fo2 + 2Fc2)/3
1388 reflections	(Δ/σ)max = 0.010
99 parameters	Δρmax = 0.23 e Å−3
0 restraints	Δρmin = −0.24 e Å−3

Special details

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·A single gross outlier (reflection 3 3 3)was omitted from the final refinement.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.06322 (5)	0.42265 (18)	0.41860 (17)	0.0357 (3)
H1W	0.0611 (12)	0.761 (5)	0.695 (4)	0.082 (10)*
H2W	0.0553 (11)	0.949 (5)	0.635 (4)	0.089 (10)*
O2	0.05985 (7)	0.8245 (3)	0.6045 (2)	0.0496 (4)
O3	−0.05040 (4)	0.75789 (19)	0.34106 (15)	0.0323 (3)
C1	0.08206 (6)	0.3193 (2)	0.5432 (2)	0.0252 (4)
C2	0.14481 (6)	0.2809 (2)	0.5548 (2)	0.0251 (4)
C3	0.17876 (6)	0.3237 (2)	0.4137 (2)	0.0261 (4)
H3	0.1627	0.3764	0.3112	0.031*
C4	0.23825 (6)	0.2893 (2)	0.4209 (2)	0.0245 (4)
C5	0.22574 (7)	0.1697 (3)	0.7239 (2)	0.0300 (4)
H4	0.2412	0.1206	0.8288	0.036*
C6	0.16892 (7)	0.2010 (3)	0.7120 (2)	0.0303 (4)
H5	0.1457	0.1700	0.8074	0.036*
Li1	0.03075 (12)	0.6849 (4)	0.4040 (4)	0.0305 (6)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0262 (6)	0.0378 (7)	0.0432 (7)	0.0097 (5)	−0.0039 (5)	0.0041 (6)
O2	0.0714 (11)	0.0404 (9)	0.0367 (8)	−0.0102 (8)	−0.0102 (7)	−0.0003 (7)
O3	0.0197 (5)	0.0452 (7)	0.0322 (6)	−0.0007 (5)	0.0075 (5)	−0.0052 (6)
C1	0.0190 (7)	0.0253 (8)	0.0313 (9)	0.0018 (6)	0.0016 (6)	−0.0084 (7)
C2	0.0180 (7)	0.0241 (8)	0.0333 (9)	0.0019 (6)	0.0022 (6)	−0.0009 (7)
C3	0.0208 (8)	0.0285 (8)	0.0290 (8)	0.0037 (7)	−0.0011 (6)	0.0035 (7)
C4	0.0215 (8)	0.0236 (8)	0.0283 (8)	0.0021 (6)	0.0010 (6)	0.0023 (7)
C5	0.0241 (8)	0.0365 (9)	0.0293 (9)	0.0035 (7)	0.0005 (6)	0.0096 (8)
C6	0.0239 (8)	0.0366 (9)	0.0304 (9)	0.0016 (7)	0.0063 (6)	0.0053 (7)
Li1	0.0275 (14)	0.0337 (15)	0.0302 (14)	0.0016 (12)	−0.0007 (11)	0.0021 (12)

Geometric parameters (Å, º)

O1—C1	1.253 (2)	C3—C4	1.422 (2)
O1—Li1	1.946 (3)	C3—H3	0.9300
O2—Li1	1.910 (3)	C4—C5iii	1.414 (2)
O2—H1W	0.81 (3)	C4—C4iii	1.417 (3)
O2—H2W	0.89 (3)	C5—C6	1.359 (2)
O3—C1i	1.265 (2)	C5—C4iii	1.414 (2)
O3—Li1ii	1.969 (3)	C5—H4	0.9300
O3—Li1	2.030 (3)	C6—H5	0.9300
C1—O3i	1.265 (2)	Li1—O3ii	1.969 (3)
C1—C2	1.504 (2)	Li1—C1i	2.691 (3)
C1—Li1i	2.691 (3)	Li1—Li1ii	2.728 (6)
C2—C3	1.365 (2)	Li1—Li1i	3.250 (6)
C2—C6	1.419 (2)
C1—O1—Li1	134.09 (14)	C5—C6—C2	120.35 (15)
Li1—O2—H1W	114 (2)	C5—C6—H5	119.8
Li1—O2—H2W	129.8 (19)	C2—C6—H5	119.8
H1W—O2—H2W	107 (3)	O2—Li1—O1	105.84 (15)
C1i—O3—Li1ii	133.11 (14)	O2—Li1—O3ii	122.04 (16)
C1i—O3—Li1	107.22 (13)	O1—Li1—O3ii	100.98 (14)
Li1ii—O3—Li1	86.02 (13)	O2—Li1—O3	113.35 (15)
O1—C1—O3i	122.81 (14)	O1—Li1—O3	127.43 (16)
O1—C1—C2	119.05 (14)	O3ii—Li1—O3	86.88 (12)
O3i—C1—C2	118.13 (14)	O2—Li1—C1i	103.83 (13)
O1—C1—Li1i	76.73 (11)	O1—Li1—C1i	111.74 (13)
O3i—C1—Li1i	46.09 (10)	O3ii—Li1—C1i	112.28 (13)
C2—C1—Li1i	164.10 (13)	O3—Li1—C1i	26.69 (6)
C3—C2—C6	119.84 (14)	O2—Li1—Li1ii	149.25 (11)
C3—C2—C1	119.89 (14)	O1—Li1—Li1ii	104.78 (10)
C6—C2—C1	120.27 (14)	O3ii—Li1—Li1ii	47.92 (9)
C2—C3—C4	121.15 (15)	O3—Li1—Li1ii	46.06 (9)
C2—C3—H3	119.4	C1i—Li1—Li1ii	66.74 (11)
C4—C3—H3	119.4	O2—Li1—Li1i	101.12 (15)
C5iii—C4—C4iii	119.35 (17)	O1—Li1—Li1i	55.92 (10)
C5iii—C4—C3	122.30 (14)	O3ii—Li1—Li1i	136.12 (18)
C4iii—C4—C3	118.35 (17)	O3—Li1—Li1i	82.63 (12)
C6—C5—C4iii	120.93 (15)	C1i—Li1—Li1i	58.82 (9)
C6—C5—H4	119.5	Li1ii—Li1—Li1i	98.18 (13)
C4iii—C5—H4	119.5
Li1—O1—C1—O3i	71.7 (2)	C1—O1—Li1—O2	24.8 (2)
Li1—O1—C1—C2	−109.69 (19)	C1—O1—Li1—O3ii	152.87 (15)
Li1—O1—C1—Li1i	72.46 (19)	C1—O1—Li1—O3	−112.6 (2)
O1—C1—C2—C3	−13.1 (2)	C1—O1—Li1—C1i	−87.6 (2)
O3i—C1—C2—C3	165.63 (15)	C1—O1—Li1—Li1ii	−158.04 (16)
Li1i—C1—C2—C3	159.3 (4)	C1—O1—Li1—Li1i	−68.08 (18)
O1—C1—C2—C6	166.67 (15)	C1i—O3—Li1—O2	−73.79 (18)
O3i—C1—C2—C6	−14.6 (2)	Li1ii—O3—Li1—O2	152.12 (13)
Li1i—C1—C2—C6	−21.0 (5)	C1i—O3—Li1—O1	61.0 (2)
C6—C2—C3—C4	0.2 (3)	Li1ii—O3—Li1—O1	−73.05 (18)
C1—C2—C3—C4	179.88 (14)	C1i—O3—Li1—O3ii	162.48 (11)
C2—C3—C4—C5iii	179.28 (16)	Li1ii—O3—Li1—O3ii	28.40 (17)
C2—C3—C4—C4iii	−0.5 (3)	Li1ii—O3—Li1—C1i	−134.08 (16)
C4iii—C5—C6—C2	−1.7 (3)	C1i—O3—Li1—Li1ii	134.08 (16)
C3—C2—C6—C5	1.0 (3)	C1i—O3—Li1—Li1i	25.18 (15)
C1—C2—C6—C5	−178.74 (15)	Li1ii—O3—Li1—Li1i	−108.90 (8)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1W···O1iv	0.81 (3)	2.10 (3)	2.905 (2)	176 (3)
O2—H2W···O3v	0.89 (3)	2.01 (3)	2.883 (2)	169 (3)

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