Di-μ-aqua-bis­[aqua­(5-carboxyl­ato-1H-1,2,3-triazole-4-carb­oxy­lic acid-κ2N3,O4)lithium]

Starosta, W.; Leciejewicz, J.

doi:10.1107/S1600536813023167

metal-organic compounds

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Volume 69| Part 9| September 2013| Pages m515-m516

doi:10.1107/S1600536813023167

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Di-μ-aqua-bis[aqua(5-carboxylato-1H-1,2,3-triazole-4-carboxylic acid-κ²N³,O⁴)lithium]

Wojciech Starosta ^a and Janusz Leciejewicz ^a ^*

^aInstitute of Nuclear Chemistry and Technology, ul.Dorodna 16, 03-195 Warszawa, Poland
^*Correspondence e-mail: j.leciejewicz@ichtj.waw.pl

(Received 13 August 2013; accepted 18 August 2013; online 23 August 2013)

The crystal structure of the title compound, [Li₂(C₄H₂N₃O₄)₂(H₂O)₄], contains centrosymmetric dinuclear molecules in which two Li^I ions are bridged by two water O atoms. The metal ion is coordinated by one N,O-bidentate ligand and three water O atoms (one of them is symmetry generated), with one of the bridging water O atoms in the apical position of a distorted square pyramid. The carboxylate group that participates in coordination to the metal ion remains protonated; the other is deprotonated and coordination inactive. An intramolecular O—H⋯O hydrogen bond between carboxylate groups is observed. In the crystal, dimers are linked by O—H⋯O, O—H⋯N and N—H⋯O hydrogen bonds, generating a three-dimensional network.

Related literature

For the structures of Co and Ni complexes with the 1,2,3-trizole-4,5-dicarboxylate ligand, see: Tong et al. (2011 ).

Experimental

Crystal data

[Li₂(C₄H₂N₃O₄)₂(H₂O)₄]
M_r = 398.12
Triclinic, $[P \overline 1]$
a = 5.1264 (10) Å
b = 8.0350 (16) Å
c = 10.040 (2) Å
α = 68.60 (3)°
β = 77.64 (3)°
γ = 85.16 (3)°
V = 376.12 (13) Å³
Z = 1
Mo Kα radiation
μ = 0.16 mm⁻¹
T = 293 K
0.45 × 0.26 × 0.22 mm

Data collection

Kuma KM-4 four-circle diffractometer
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.951, T_max = 0.966
2414 measured reflections
2185 independent reflections
1695 reflections with I > 2σ(I)
R_int = 0.110
3 standard reflections every 200 reflections intensity decay: 3.7%

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.151
S = 1.04
2185 reflections
151 parameters
All H-atom parameters refined
Δρ_max = 0.62 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Table 1
Selected bond lengths (Å)

Li1—O1	2.156 (3)
Li1—O5	2.089 (3)
Li1—O5ⁱ	2.029 (3)
Li1—O6	1.916 (3)
Li1—N3	2.234 (3)
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
O5—H52⋯O1ⁱⁱ	0.86 (2)	1.93 (2)	2.7873 (16)	172 (2)
O6—H61⋯N2ⁱⁱⁱ	0.84 (4)	2.30 (4)	3.0545 (19)	150 (4)
O5—H51⋯O3^iv	0.90 (2)	1.98 (3)	2.8834 (16)	174 (2)
O6—H62⋯O4^v	0.91 (5)	1.83 (5)	2.7343 (16)	176 (4)
N1—H1⋯O4^vi	0.86 (2)	1.92 (2)	2.7522 (17)	162 (2)
O2—H2⋯O3	0.93 (5)	1.63 (5)	2.5380 (16)	167 (4)
Symmetry codes: (ii) x+1, y, z; (iii) -x+2, -y, -z+1; (iv) -x+1, -y+1, -z; (v) x, y, z+1; (vi) -x+2, -y, -z.

Data collection: KM-4 Software (Kuma, 1996 $[Kuma (1996). KM-4 Software. Kuma Diffraction Ltd, Wrocław, Poland.]$ ); cell refinement: KM-4 Software; data reduction: DATAPROC (Kuma, 2001 $[Kuma (2001). DATAPROC. Kuma Diffraction Ltd, Wrocław, Poland.]$ ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536813023167/hb7130sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813023167/hb7130Isup2.hkl

checkCIF report

Comment top

The triclinic unit cell of the title compound comprises two Li(C₄H₂N₃O₄)(H₂O)₂ molecules related by an inversion centre to form a dimeric moiety in which two Li^I ions are bridged by an aqua O atom donated by each molecule {Fig.1). The coordination of the Li^I ion is distorted square-pyramidal: carboxylate O1, hetero-ring N1, aquua O6 and O5⁽ⁱ⁾ atoms constitute its base [r.m.s. 0.0798 (2) Å], the Li1 ion is 0.1995 (2) Å out of it, the aqua O5⁽ⁱ⁾ is at the apex. Li—O and Li—N bond distances are usual (Table 2). The ligand triazole ring is almost planar [r.m.s. 0.0006 (1) Å]. The carboxylate C6/O1/O2 and C7/O3/O4 groups make with it dihedral angles of 2.0 (1)° and 5.5 (1)°, respectively. The Fourier map indicates clearly that the O2 atom is protonated and acts as a donor in a fairly short intra-molecular hydrogen bond of 2.538 (2) Å to the O3 atom as an acceptor. The C7/O3/O4 carboxylic group remains deprotonated and coordination inactive. The bond distances and bond angles within the triazole ring do not differ from those reported in the structures of other complexes, for example, with Co and Ni (Tong et al., 2011). The dimers form molecular sheets (Fig. 2) in which they interact via an extensive hydrogen bond network; coordinated water molecules are as donors a hetero-ring N atom and carboxylate O atoms as acceptors (Table 3).

Related literature top

For the structures of Co and Ni complexes with the 1,2,3-trizole-4,5-dicarboxylate ligand, see: Tong et al. (2011).

Experimental top

1 mmol of 1,2,3-triazole-4,5-dicarboxylic acid and ca2 mmol s of lithium hydroxide dissolved in 50 ml of hot, doubly distilled water were boiled under reflux with stirring for ten hours and then left to crystallize at room temperature. Colourless blocks deposited after a week among polycrystalline material. After extraction, the crystals were washed with cold ethanol and dried in the air.

Computing details top

Data collection: KM-4 Software (Kuma, 1996); cell refinement: KM-4 Software (Kuma, 1996); data reduction: DATAPROC (Kuma, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A dimeric molecule of the title complex with 50% probability displacement ellipsoids. Symmetry code: (i): -x + 1, -y + 1, -z + 1.
	Fig. 2. The packing of the dimers with hydrogen bonds shown as dashed lines.

Di-µ-aqua-bis[aqua(5-carboxylato-1H-1,2,3-triazole-4-carboxylic acid-κ²N³,O⁴)lithium] top

Crystal data top

[Li₂(C₄H₂N₃O₄)₂(H₂O)₄]	Z = 1
M_r = 398.12	F(000) = 204
Triclinic, P1	D_x = 1.758 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.1264 (10) Å	Cell parameters from 25 reflections
b = 8.0350 (16) Å	θ = 6–15°
c = 10.040 (2) Å	µ = 0.16 mm⁻¹
α = 68.60 (3)°	T = 293 K
β = 77.64 (3)°	Blocks, colourless
γ = 85.16 (3)°	0.45 × 0.26 × 0.22 mm
V = 376.12 (13) Å³

Data collection top

Kuma KM-4 four-circle diffractometer	1695 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.110
Graphite monochromator	θ_max = 30.1°, θ_min = 2.2°
profile data from ω/2θ scan	h = 0→7
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008)	k = −11→11
T_min = 0.951, T_max = 0.966	l = −13→13
2414 measured reflections	3 standard reflections every 200 reflections
2185 independent reflections	intensity decay: 3.7%

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.151	All H-atom parameters refined
S = 1.04	w = 1/[σ²(F_o²) + (0.121P)²] where P = (F_o² + 2F_c²)/3
2185 reflections	(Δ/σ)_max < 0.001
151 parameters	Δρ_max = 0.62 e Å⁻³
0 restraints	Δρ_min = −0.43 e Å⁻³

Crystal data top

[Li₂(C₄H₂N₃O₄)₂(H₂O)₄]	γ = 85.16 (3)°
M_r = 398.12	V = 376.12 (13) Å³
Triclinic, P1	Z = 1
a = 5.1264 (10) Å	Mo Kα radiation
b = 8.0350 (16) Å	µ = 0.16 mm⁻¹
c = 10.040 (2) Å	T = 293 K
α = 68.60 (3)°	0.45 × 0.26 × 0.22 mm
β = 77.64 (3)°

Data collection top

Kuma KM-4 four-circle diffractometer	1695 reflections with I > 2σ(I)
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008)	R_int = 0.110
T_min = 0.951, T_max = 0.966	3 standard reflections every 200 reflections
2414 measured reflections	intensity decay: 3.7%
2185 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.151	All H-atom parameters refined
S = 1.04	Δρ_max = 0.62 e Å⁻³
2185 reflections	Δρ_min = −0.43 e Å⁻³
151 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
O1	0.21219 (19)	0.40701 (15)	0.33815 (11)	0.0281 (2)
N3	0.6270 (2)	0.17626 (16)	0.33674 (12)	0.0254 (3)
C5	0.6283 (2)	0.17546 (15)	0.11571 (12)	0.0194 (2)
C4	0.5041 (2)	0.24296 (16)	0.22126 (12)	0.0195 (3)
N1	0.8213 (2)	0.07012 (16)	0.17492 (12)	0.0245 (3)
C6	0.2768 (2)	0.36533 (16)	0.22992 (13)	0.0205 (3)
N2	0.8203 (2)	0.07056 (17)	0.30842 (13)	0.0295 (3)
O3	0.38723 (19)	0.29832 (14)	−0.07107 (10)	0.0269 (2)
O4	0.7499 (2)	0.13549 (15)	−0.10818 (11)	0.0301 (3)
O5	0.71001 (19)	0.56809 (15)	0.36456 (11)	0.0280 (2)
O6	0.7261 (3)	0.19431 (19)	0.60872 (13)	0.0419 (3)
Li1	0.4924 (5)	0.3334 (4)	0.4828 (3)	0.0317 (5)
H52	0.871 (4)	0.527 (3)	0.358 (2)	0.032 (5)*
H51	0.682 (4)	0.618 (3)	0.272 (3)	0.042 (6)*
O2	0.15267 (19)	0.42563 (14)	0.12078 (11)	0.0266 (2)
C7	0.5863 (2)	0.20502 (16)	−0.03313 (12)	0.0207 (3)
H61	0.848 (8)	0.120 (5)	0.600 (4)	0.094 (12)*
H62	0.735 (8)	0.181 (6)	0.701 (5)	0.117 (14)*
H2	0.214 (8)	0.380 (6)	0.047 (5)	0.099 (12)*
H1	0.944 (4)	0.012 (3)	0.136 (2)	0.036 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0267 (4)	0.0409 (6)	0.0228 (5)	0.0088 (4)	−0.0017 (3)	−0.0222 (4)
N3	0.0307 (5)	0.0320 (6)	0.0160 (5)	0.0076 (4)	−0.0041 (4)	−0.0134 (4)
C5	0.0236 (5)	0.0229 (5)	0.0130 (5)	0.0028 (4)	−0.0005 (4)	−0.0104 (4)
C4	0.0236 (5)	0.0232 (5)	0.0131 (5)	0.0020 (4)	0.0000 (4)	−0.0106 (4)
N1	0.0300 (5)	0.0298 (5)	0.0163 (5)	0.0098 (4)	−0.0044 (4)	−0.0135 (4)
C6	0.0205 (5)	0.0248 (6)	0.0170 (5)	0.0014 (4)	0.0014 (4)	−0.0117 (4)
N2	0.0367 (6)	0.0372 (6)	0.0188 (5)	0.0135 (5)	−0.0091 (4)	−0.0159 (5)
O3	0.0302 (5)	0.0359 (5)	0.0171 (4)	0.0086 (4)	−0.0051 (3)	−0.0138 (4)
O4	0.0360 (5)	0.0401 (6)	0.0175 (4)	0.0134 (4)	−0.0031 (4)	−0.0184 (4)
O5	0.0258 (5)	0.0406 (6)	0.0181 (4)	0.0071 (4)	−0.0011 (3)	−0.0144 (4)
O6	0.0534 (7)	0.0546 (7)	0.0232 (5)	0.0265 (5)	−0.0144 (5)	−0.0224 (5)
Li1	0.0375 (12)	0.0382 (13)	0.0210 (11)	0.0030 (10)	−0.0014 (9)	−0.0158 (10)
O2	0.0275 (4)	0.0341 (5)	0.0215 (5)	0.0086 (3)	−0.0050 (3)	−0.0155 (4)
C7	0.0259 (5)	0.0241 (5)	0.0132 (5)	0.0016 (4)	−0.0006 (4)	−0.0102 (4)

Geometric parameters (Å, º) top

Li1—O1	2.156 (3)	N1—N2	1.3405 (15)
Li1—O5	2.089 (3)	N1—H1	0.86 (2)
Li1—O5ⁱ	2.029 (3)	C6—O2	1.3035 (16)
Li1—O6	1.916 (3)	O3—C7	1.2559 (16)
Li1—N3	2.234 (3)	O4—C7	1.2415 (15)
O1—C6	1.2229 (15)	O5—Li1ⁱ	2.029 (3)
N3—N2	1.3029 (16)	O5—H52	0.86 (2)
N3—C4	1.3529 (16)	O5—H51	0.90 (2)
C5—N1	1.3386 (17)	O6—H61	0.84 (4)
C5—C4	1.3765 (16)	O6—H62	0.91 (5)
C5—C7	1.4852 (16)	Li1—Li1ⁱ	2.831 (5)
C4—C6	1.4692 (17)	O2—H2	0.93 (5)

C6—O1—Li1	115.52 (11)	Li1—O6—H61	133 (3)
N2—N3—C4	108.64 (11)	Li1—O6—H62	132 (3)
N2—N3—Li1	140.62 (11)	H61—O6—H62	95 (4)
C4—N3—Li1	108.55 (11)	O6—Li1—O5ⁱ	92.37 (11)
N1—C5—C4	103.63 (11)	O6—Li1—O5	102.05 (13)
N1—C5—C7	123.52 (11)	O5ⁱ—Li1—O5	93.17 (11)
C4—C5—C7	132.82 (11)	O6—Li1—O1	161.54 (16)
N3—C4—C5	108.86 (11)	O5ⁱ—Li1—O1	98.57 (11)
N3—C4—C6	118.02 (11)	O5—Li1—O1	92.20 (12)
C5—C4—C6	133.12 (12)	O6—Li1—N3	89.77 (11)
C5—N1—N2	111.56 (11)	O5ⁱ—Li1—N3	165.21 (15)
C5—N1—H1	128.6 (14)	O5—Li1—N3	100.70 (11)
N2—N1—H1	119.7 (14)	O1—Li1—N3	75.95 (9)
O1—C6—O2	122.70 (12)	O6—Li1—Li1ⁱ	100.59 (15)
O1—C6—C4	119.06 (12)	O5ⁱ—Li1—Li1ⁱ	47.47 (8)
O2—C6—C4	118.23 (11)	O5—Li1—Li1ⁱ	45.70 (8)
N3—N2—N1	107.31 (11)	O1—Li1—Li1ⁱ	97.76 (14)
Li1ⁱ—O5—Li1	86.83 (11)	N3—Li1—Li1ⁱ	146.10 (17)
Li1ⁱ—O5—H52	126.9 (15)	C6—O2—H2	115 (3)
Li1—O5—H52	101.1 (13)	O4—C7—O3	126.12 (12)
Li1ⁱ—O5—H51	118.6 (15)	O4—C7—C5	117.29 (12)
Li1—O5—H51	112.5 (13)	O3—C7—C5	116.59 (11)
H52—O5—H51	107 (2)

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
O5—H52···O1ⁱⁱ	0.86 (2)	1.93 (2)	2.7873 (16)	172 (2)
O6—H61···N2ⁱⁱⁱ	0.84 (4)	2.30 (4)	3.0545 (19)	150 (4)
O5—H51···O3^iv	0.90 (2)	1.98 (3)	2.8834 (16)	174 (2)
O6—H62···O4^v	0.91 (5)	1.83 (5)	2.7343 (16)	176 (4)
N1—H1···O4^vi	0.86 (2)	1.92 (2)	2.7522 (17)	162 (2)
O2—H2···O3	0.93 (5)	1.63 (5)	2.5380 (16)	167 (4)

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

Selected bond lengths (Å) top

Li1—O1	2.156 (3)	Li1—O6	1.916 (3)
Li1—O5	2.089 (3)	Li1—N3	2.234 (3)
Li1—O5ⁱ	2.029 (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
O5—H52···O1ⁱⁱ	0.86 (2)	1.93 (2)	2.7873 (16)	172 (2)
O6—H61···N2ⁱⁱⁱ	0.84 (4)	2.30 (4)	3.0545 (19)	150 (4)
O5—H51···O3^iv	0.90 (2)	1.98 (3)	2.8834 (16)	174 (2)
O6—H62···O4^v	0.91 (5)	1.83 (5)	2.7343 (16)	176 (4)
N1—H1···O4^vi	0.86 (2)	1.92 (2)	2.7522 (17)	162 (2)
O2—H2···O3	0.93 (5)	1.63 (5)	2.5380 (16)	167 (4)

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

References

Kuma (1996). KM-4 Software. Kuma Diffraction Ltd, Wrocław, Poland. Google Scholar
Kuma (2001). DATAPROC. Kuma Diffraction Ltd, Wrocław, Poland. Google Scholar
Oxford Diffraction (2008). CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tong, X.-L., Xin, J.-H., Guo, V.-H. & Zhu, X.-P. (2011). J. Coord. Chem. 64, 2984–2994. Web of Science CSD CrossRef CAS Google Scholar

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doi:10.1107/S1600536813023167

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