catena-Poly[[bis­(μ-3-amino­pyrazine-2-carboxyl­ato)-κ3N1,O:O;κ3O:N1,O)dilithium]-di-μ-aqua]

Starosta, W.; Leciejewicz, J.

doi:10.1107/S1600536810020647

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Pages m744-m745

doi:10.1107/S1600536810020647

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catena-Poly[[bis(μ-3-aminopyrazine-2-carboxylato)-κ³N¹,O:O;κ³O:N¹,O)dilithium]-di-μ-aqua]

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 21 May 2010; accepted 31 May 2010; online 5 June 2010)

The title compound, [Li(C₅H₄N₃O₂)(H₂O)]_n, is composed of centrosymmetric dinuclear units, in which the Li^I ions are bridged by two carboxylate O atoms donated by two ligands. The dinuclear unit is nearly planar [r.m.s. deviation = 0.0125 (2) Å]. The Li^I ion is coordinated by an N,O-chelating ligand, a bridging carboxylate O atom from another ligand and two bridging water O atoms in a distorted trigonal-bipyramidal geometry. The water O atoms bridge the dinuclear units into a polymeric molecular column along [010]. The columns are held together by O—H⋯O and N—H⋯N hydrogen bonds. An intramolecular N—H⋯O interaction also occurs.

Related literature

For the structures of metal (M) complexes with the 3-aminopyrazine-2-carboxylate ligand, see: Leciejewicz et al. (1997 [M = Ca(II)], 1998 [M = Sr(II)]); Ptasiewicz-Bąk & Leciejewicz (1997 [M = Mg(II)], 1999 [M = Ni(II)]); Tayebee et al. (2008 ) [M = Na(I)]. For the structure of an Li(I) complex with pyrazine-2,3-dicarboxylate and aqua ligands, see: Tombul et al. (2008 ).

Experimental

Crystal data

[Li(C₅H₄N₃O₂)(H₂O)]
M_r = 163.07
Monoclinic, P 2₁ /c
a = 14.279 (3) Å
b = 3.6000 (7) Å
c = 13.300 (3) Å
β = 106.43 (3)°
V = 655.7 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 293 K
0.26 × 0.21 × 0.04 mm

Data collection

Kuma KM-4 four-circle diffractometer
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ) T_min = 0.980, T_max = 0.994
1997 measured reflections
1913 independent reflections
1297 reflections with I > 2σ(I)
R_int = 0.017
3 standard reflections every 200 reflections intensity decay: 7.3%

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.147
S = 1.04
1913 reflections
115 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Selected bond lengths (Å)

Li1—N1	2.118 (3)
Li1—O1	1.999 (3)
Li1—O1ⁱ	1.995 (3)
Li1—O3	2.065 (3)
Li1—O3ⁱⁱ	2.201 (3)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x, y-1, z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H31⋯O2ⁱⁱⁱ	0.88 (1)	1.83 (1)	2.7028 (16)	175 (2)
O3—H32⋯O1^iv	0.84 (2)	2.54 (2)	2.9083 (17)	108 (2)
N3—H1⋯O2	0.86	2.08	2.7229 (17)	131
N3—H2⋯N2^v	0.86	2.30	3.1278 (19)	162
Symmetry codes: (iii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iv) -x+1, -y+2, -z+1; (v) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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, global. DOI: 10.1107/S1600536810020647/hy2312sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810020647/hy2312Isup2.hkl

checkCIF report

Comment top

Structural studies of divalent metal ion complexes with 3-aminopyrazine-2-carboxylate ligand have shown that the structures of Mg(II) and Ni(II) complexes consist of ML₂(H₂O)₂ monomers. In the Mg(II) comoplex, the ligand adopts a cis configuration (Ptasiewicz-Bąk & Leciejewicz, 1997), while in the Ni(II) complex, a trans configuration (Ptasiewicz-Bąk & Leciejewicz, 1999). Catenated polymeric molecular patterns have been reported in the structures of a Ca(II) complex (Leciejewicz et al., 1997) and a Sr(II) complex (Leciejewicz et al., 1998), in which metal ions are bridged by ligand carboxylate groups acting as bidentate. On the other hand, the structure of a Na(I) complex with the title ligand (Tayebee et al.,2008) is three-dimensional polymeric with Na(I) ions linked by an extended bridging system formed mainly by coordinated water O atoms.

The title compound is composed of centrosymmetric dinuclear units, in which each of the two Li^I ions is cheletated by a ligand via an N,O-bonding group. Its O atom acts as bidentate and bridges the other Li^I ion (Fig. 1). The dinuclear unit is nearly planar with r.m.s. of 0.0125 (2) Å. The Li^I ion is also coordinated by two water O atoms, which bridge the dinuclear units into molecular columns along two bridging pathways propagating in the b-axis direction (Fig. 2). The coordination geometry of the Li^I ion is trigonal bipyramidal, with the equatorial plane formed by O1, O3, O3ⁱⁱ and with N1 and O1ⁱ at the axial positions [symmetry codes: (i) 1-x, 1-y, 1-z; (ii) x, y-1, z]. The Li—O and Li—N bond distances (Table 1) and bond angles are typical for Li(I) complexes with carboxylate ligands (see, for example, Tombul et al., 2008). The columns are linked by a network of hydrogen bonds, in which water O atoms are donors and the non-bonded carboxylate O atoms in adjacent columns act as acceptors. A weak hydrogen bond links an amino N atom with a hetero-ring N atom in the adjacent column. An intramolecular hydrogen bond which operates between the amino N3 atom and the non-bonding carboxylate O2 atom is also observed (Table 2).

Related literature top

For the structures of metal (M) complexes with the 3-aminopyrazine-2-carboxylate ligand, see: Leciejewicz et al. (1997 [M = Ca(II)], 1998 [M = Sr(II)]); Ptasiewicz-Bąk & Leciejewicz (1997 [M = Mg(II)], 1999 [M = Ni(II)]); Tayebee et al. (2008) [M = Na(I)]. For the structure of an Li(I) complex with pyrazine-2,3-dicarboxylate and aqua ligands, see: Tombul et al. (2008).

Experimental top

The title compound was synthesized by reacting 50 ml of boiling aqueous solutions, one containing 1 mmol of 3-aminopyrazine-2-carboxylic acid (Aldrich), the other containing 1 mmol of lithium hydroxide (Aldrich). The mixture was boiled under reflux for 3 h and after cooling to room temperature, filtered and left to crystallize. A few days later, colourless single crystals in the form of flat needles were found after evaporation to dryness. They were extracted, washed with cold ethanol and dried in air. A crystal used for X-ray data collection was cut to adopt the shape of a flat plate.

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. The dinuclear unit of the title compound. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) 1-x, 1-y, 1-z; (ii) x, -1+y, z; (iii) 1-x, 2-y, 1-z.]
	Fig. 2. Packing diagram of the title compound.

catena-Poly[[bis(µ-3-aminopyrazine-2-carboxylato)- κ³N¹,O:O;κ³O: N¹,O)dilithium]-di-µ-aqua] top

Crystal data top

[Li(C₅H₄N₃O₂)(H₂O)]	F(000) = 336
M_r = 163.07	D_x = 1.652 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 14.279 (3) Å	θ = 6–15°
b = 3.6000 (7) Å	µ = 0.13 mm⁻¹
c = 13.300 (3) Å	T = 293 K
β = 106.43 (3)°	Plate, colourless
V = 655.7 (2) Å³	0.26 × 0.21 × 0.04 mm
Z = 4

Data collection top

Kuma KM-4 four-circle diffractometer	1297 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.017
Graphite monochromator	θ_max = 30.1°, θ_min = 1.5°
profile data from ω–2θ scans	h = −19→19
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2006)	k = −5→0
T_min = 0.980, T_max = 0.994	l = 0→18
1997 measured reflections	3 standard reflections every 200 reflections
1913 independent reflections	intensity decay: 7.3%

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.147	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.1051P)² + 0.022P] where P = (F_o² + 2F_c²)/3
1913 reflections	(Δ/σ)_max < 0.001
115 parameters	Δρ_max = 0.51 e Å⁻³
3 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

[Li(C₅H₄N₃O₂)(H₂O)]	V = 655.7 (2) Å³
M_r = 163.07	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.279 (3) Å	µ = 0.13 mm⁻¹
b = 3.6000 (7) Å	T = 293 K
c = 13.300 (3) Å	0.26 × 0.21 × 0.04 mm
β = 106.43 (3)°

Data collection top

Kuma KM-4 four-circle diffractometer	1297 reflections with I > 2σ(I)
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2006)	R_int = 0.017
T_min = 0.980, T_max = 0.994	3 standard reflections every 200 reflections
1997 measured reflections	intensity decay: 7.3%
1913 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	3 restraints
wR(F²) = 0.147	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.51 e Å⁻³
1913 reflections	Δρ_min = −0.39 e Å⁻³
115 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C2	0.25443 (8)	0.4711 (3)	0.39664 (9)	0.0184 (3)
O2	0.32090 (8)	0.2294 (4)	0.26435 (8)	0.0336 (3)
N1	0.27984 (8)	0.6065 (3)	0.49343 (8)	0.0216 (3)
N2	0.08397 (8)	0.5364 (4)	0.38343 (10)	0.0285 (3)
N3	0.12597 (9)	0.2931 (4)	0.24154 (10)	0.0320 (3)
H2	0.0649	0.2745	0.2090	0.038*
H1	0.1690	0.2235	0.2115	0.038*
O1	0.42229 (7)	0.4275 (4)	0.41421 (8)	0.0352 (3)
C7	0.33887 (9)	0.3657 (4)	0.35429 (10)	0.0218 (3)
C3	0.15415 (9)	0.4307 (4)	0.33936 (10)	0.0217 (3)
C6	0.20958 (10)	0.7070 (4)	0.53653 (11)	0.0254 (3)
H6	0.2262	0.8010	0.6044	0.030*
C5	0.11268 (10)	0.6720 (4)	0.48077 (12)	0.0284 (3)
H5	0.0653	0.7459	0.5123	0.034*
Li1	0.43334 (19)	0.6091 (9)	0.5591 (2)	0.0370 (6)
O3	0.44058 (8)	1.0866 (3)	0.64699 (9)	0.0338 (3)
H32	0.4986 (11)	1.117 (6)	0.6825 (15)	0.041*
H31	0.4047 (13)	1.146 (6)	0.6882 (14)	0.041*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C2	0.0170 (5)	0.0153 (5)	0.0223 (6)	−0.0007 (4)	0.0048 (4)	0.0018 (4)
O2	0.0301 (5)	0.0450 (7)	0.0277 (5)	−0.0089 (5)	0.0114 (4)	−0.0120 (5)
N1	0.0209 (5)	0.0192 (5)	0.0242 (5)	0.0012 (4)	0.0057 (4)	−0.0006 (4)
N2	0.0194 (5)	0.0264 (6)	0.0390 (6)	0.0012 (4)	0.0071 (4)	0.0025 (5)
N3	0.0227 (5)	0.0401 (7)	0.0290 (6)	−0.0056 (5)	0.0002 (4)	−0.0052 (5)
O1	0.0183 (5)	0.0522 (7)	0.0338 (5)	0.0004 (5)	0.0052 (4)	−0.0142 (5)
C7	0.0202 (6)	0.0209 (6)	0.0242 (5)	−0.0021 (4)	0.0064 (4)	−0.0015 (5)
C3	0.0199 (5)	0.0171 (5)	0.0262 (6)	−0.0019 (4)	0.0033 (4)	0.0034 (5)
C6	0.0282 (6)	0.0225 (7)	0.0273 (6)	0.0020 (5)	0.0108 (5)	−0.0020 (5)
C5	0.0238 (6)	0.0237 (7)	0.0408 (8)	0.0031 (5)	0.0140 (5)	0.0006 (6)
Li1	0.0256 (12)	0.0484 (17)	0.0355 (13)	0.0016 (11)	0.0060 (10)	−0.0120 (12)
O3	0.0256 (5)	0.0411 (7)	0.0352 (6)	−0.0012 (5)	0.0092 (4)	−0.0069 (5)

Geometric parameters (Å, º) top

C2—N1	1.3274 (16)	C6—C5	1.378 (2)
C2—C3	1.4263 (17)	C6—H6	0.9300
C2—C7	1.5164 (17)	C5—H5	0.9300
O2—C7	1.2505 (17)	Li1—N1	2.118 (3)
N1—C6	1.3385 (17)	Li1—O1	1.999 (3)
N2—C5	1.335 (2)	Li1—O1ⁱ	1.995 (3)
N2—C3	1.3510 (18)	Li1—O3	2.065 (3)
N3—C3	1.3431 (18)	Li1—O3ⁱⁱ	2.201 (3)
N3—H2	0.8600	Li1—Li1ⁱ	2.900 (5)
N3—H1	0.8600	O3—H32	0.837 (15)
O1—C7	1.2515 (17)	O3—H31	0.875 (14)

N1—C2—C3	120.87 (11)	N2—C5—H5	118.6
N1—C2—C7	115.10 (11)	C6—C5—H5	118.6
C3—C2—C7	124.03 (11)	O1ⁱ—Li1—O1	86.88 (11)
C2—N1—C6	118.83 (11)	O1ⁱ—Li1—O3	94.05 (12)
C2—N1—Li1	111.64 (11)	O1—Li1—O3	142.73 (18)
C6—N1—Li1	129.48 (11)	O1ⁱ—Li1—N1	165.94 (15)
C5—N2—C3	117.50 (11)	O1—Li1—N1	79.08 (10)
C3—N3—H2	120.0	O3—Li1—N1	96.74 (12)
C3—N3—H1	120.0	O1ⁱ—Li1—O3ⁱⁱ	87.61 (12)
H2—N3—H1	120.0	O1—Li1—O3ⁱⁱ	102.21 (14)
C7—O1—Li1ⁱ	148.32 (12)	O3—Li1—O3ⁱⁱ	115.07 (14)
C7—O1—Li1	118.26 (11)	N1—Li1—O3ⁱⁱ	95.90 (13)
Li1ⁱ—O1—Li1	93.13 (11)	O1ⁱ—Li1—Li1ⁱ	43.49 (8)
O2—C7—O1	125.43 (12)	O1—Li1—Li1ⁱ	43.38 (8)
O2—C7—C2	118.94 (12)	O3—Li1—Li1ⁱ	126.66 (18)
O1—C7—C2	115.63 (11)	N1—Li1—Li1ⁱ	122.46 (16)
N3—C3—N2	117.93 (12)	O3ⁱⁱ—Li1—Li1ⁱ	96.72 (16)
N3—C3—C2	122.37 (12)	Li1—O3—Li1ⁱⁱⁱ	115.07 (14)
N2—C3—C2	119.69 (12)	Li1—O3—H32	108.2 (15)
N1—C6—C5	120.32 (12)	Li1ⁱⁱⁱ—O3—H32	94.4 (16)
N1—C6—H6	119.8	Li1—O3—H31	127.7 (15)
C5—C6—H6	119.8	Li1ⁱⁱⁱ—O3—H31	100.2 (15)
N2—C5—C6	122.78 (13)	H32—O3—H31	106.0 (15)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H31···O2^iv	0.88 (1)	1.83 (1)	2.7028 (16)	175 (2)
O3—H32···O1^v	0.84 (2)	2.54 (2)	2.9083 (17)	108 (2)
N3—H1···O2	0.86	2.08	2.7229 (17)	131
N3—H2···N2^vi	0.86	2.30	3.1278 (19)	162

Symmetry codes: (iv) x, −y+3/2, z+1/2; (v) −x+1, −y+2, −z+1; (vi) −x, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Li(C₅H₄N₃O₂)(H₂O)]
M_r	163.07
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	14.279 (3), 3.6000 (7), 13.300 (3)
β (°)	106.43 (3)
V (Å³)	655.7 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.26 × 0.21 × 0.04

Data collection
Diffractometer	Kuma KM-4 four-circle diffractometer
Absorption correction	Analytical (CrysAlis RED; Oxford Diffraction, 2006)
T_min, T_max	0.980, 0.994
No. of measured, independent and observed [I > 2σ(I)] reflections	1997, 1913, 1297
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.705

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.147, 1.04
No. of reflections	1913
No. of parameters	115
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)	0.51, −0.39

Computer programs: KM-4 Software (Kuma, 1996), DATAPROC (Kuma, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Li1—N1	2.118 (3)	Li1—O3	2.065 (3)
Li1—O1	1.999 (3)	Li1—O3ⁱⁱ	2.201 (3)
Li1—O1ⁱ	1.995 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H31···O2ⁱⁱⁱ	0.875 (14)	1.830 (14)	2.7028 (16)	175.1 (19)
O3—H32···O1^iv	0.837 (15)	2.54 (2)	2.9083 (17)	108.1 (16)
N3—H1···O2	0.86	2.08	2.7229 (17)	131
N3—H2···N2^v	0.86	2.30	3.1278 (19)	162

Symmetry codes: (iii) x, −y+3/2, z+1/2; (iv) −x+1, −y+2, −z+1; (v) −x, y−1/2, −z+1/2.

References

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Ptasiewicz-Bąk, H. & Leciejewicz, J. (1997). Pol. J. Chem. 71, 1350–1358. Google Scholar
Ptasiewicz-Bąk, H. & Leciejewicz, J. (1999). Pol. J. Chem. 73, 717–725. Google Scholar
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