catena-Poly[[lithium-μ2-(di­hydrogen pyrazine-2,3,5,6-tetra­carboxyl­ato)-κ6O2,N1,O6;O3,N4,O5-lithium-di-μ-aqua-κ4O:O] 2.5-hydrate]

Starosta, W.; Leciejewicz, J.

doi:10.1107/S160053681401174X

metal-organic compounds

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ISSN: 2056-9890

Volume 70| Part 6| June 2014| Pages m234-m235

doi:10.1107/S160053681401174X

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catena-Poly[[lithium-μ₂-(dihydrogen pyrazine-2,3,5,6-tetracarboxylato)-κ⁶O²,N¹,O⁶;O³,N⁴,O⁵-lithium-di-μ-aqua-κ⁴O:O] 2.5-hydrate]

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 29 April 2014; accepted 21 May 2014; online 24 May 2014)

The title coordination polymer, {[Li₂(C₈H₂N₂O₈)(H₂O)₂]·2.5H₂O}_n, is built up from molecular ribbons propagating in the c-axis direction of the orthorhombic unit cell; the ligand bridges two Li⁺ ions using both its N,O,O′-bonding sites and adjacent Li⁺ ions are bridged by pairs of water molecules. The coordination geometry of the metal ion is distorted trigonal bipyramidal, with the ligand O atoms in the axial sites. Two of the carboxylate groups of the ligand remain protonated and form short symmetric O—H⋯O hydrogen bonds. In the crystal, the ribbons interact via a network of O—H⋯O hydrogen bonds in which coordinating water molecules act as donors and carboxylate O atoms within adjacent ribbons act as acceptors, giving rise to a three-dimensional framework. O—H⋯N interactions are also observed. The asymmetric unit contains quarter of the ligand and the complete ligand has 2/m symmetry; the Li⁺ ion lies on a special position with m.. site symmetry. Both bridging water molecules have m2m site symmetry and both lattice water molecules have m.. site symmetry; one of the latter was modelled with a site occupancy of 0.25.

CCDC reference: 1004410

Related literature

For the structures of related lithium complexes with pyrazine-2,3,5,6-tetracarboxylate and water ligands, see: Starosta & Leciejewicz (2010 , 2014 ).

Experimental

Crystal data

[Li₂(C₈H₂N₂O₈)(H₂O)₂]·2.5H₂O
M_r = 174.53
Orthorhombic, C m c m
a = 12.0554 (3) Å
b = 6.39040 (17) Å
c = 19.3383 (4) Å
V = 1489.80 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.15 mm⁻¹
T = 567 K
0.24 × 0.20 × 0.05 mm

Data collection

Agilent SuperNova (Dual, Cu at zero, Eos) diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.701, T_max = 1.000
7496 measured reflections
1151 independent reflections
997 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.122
S = 1.07
1151 reflections
85 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Selected bond lengths (Å)

Li1—O1	2.1538 (13)
Li1—O3	1.982 (4)
Li1—O4	1.976 (4)
Li1—N1	2.116 (3)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O6—H62⋯N1	0.87 (2)	2.28 (11)	2.886 (12)	127 (12)
O5—H5⋯O1ⁱ	0.85 (2)	1.95 (2)	2.7711 (13)	163 (2)
O3—H3⋯O5ⁱⁱ	0.82 (4)	1.92 (4)	2.730 (2)	173 (4)
O4—H4⋯O5ⁱⁱⁱ	0.90 (3)	1.83 (3)	2.726 (2)	179 (3)
O2—H2⋯O2^iv	1.21 (1)	1.21 (1)	2.409 (3)	175 (1)
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) x, -y+1, -z+1; (iii) -x+1, -y, -z+1; (iv) x, -y, -z+1.

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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

CCDC reference: 1004410

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S160053681401174X/hb7224sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681401174X/hb7224Isup2.hkl

checkCIF report

Comment top

The structure of the title compound is composed of molecular ribbons propagating in the crystal [001] direction. The structural unit of a ribbon is built of a centro-symmetric ligand molecule which bridges two Li ions using its both N,O,O bonding sites. Two water molecules chelated simultaneously to Li ions belonging to adjacent structural units, bridge them into a molecular ribbon [Fig.1]. The coordination environment of a Li ion is distorted trigonal bipyramidal. Its equatorial plane is composed of coplanar Li1, N1,O3,O4 atoms; O1 and O1ⁱ are at the apices. The Li—O and Li—N bond distances are usual (Table 2). Within a ligand two carboxylate groups remain protonated to maintain charge balance and form short, intramolecular symmetric hydrogen bonds of 2.409 (1) Å (Table 3). The ligand ring is almost planar (r.m.s. is 0.0003 (1) Å; the carboxylate C17/O1/O12 group makes with it a dihedral angle of 2.6 (1)°. Bond distances and bond angles within the hetero-ring do not differ from those reported in the structures of two other Li complexes with the title ligand (Starosta & Leciejewicz, 2010, 2014). The Fourier map shows two solvation water molecules (O5 and O6), both at special positions. The refinemt reveals a disorder of the O6 aqua molecule with 0.25 positional occupancy i.e. two molecules at random in a unit cell. This molecule locates coplanarly with the N1, O3, O4 and Li1 atoms at a distance of 2.538 (2) Å from the latter. The ribbons are held together by a system of hydrogen bonds in which coordinated and solvation water molecules act as donors and carboxylate O atoms as acceptors giving rise to a three-dimensional framework. The structures of two other Li complexes with the title ligand have been recently reported. The structural unit of the title polymer is closely related to that one observed in the structure of the first compound which cosists of discrete dimeric molecules built of two aqua-coordinated Li ions bridged by the ligand molecule via both its N,O,O bonding sites (Starosta & Leciejewicz, 2014). The structure of the second complex is built of anions each consisting of an aqua coordinated Li ion cheleted to a doubly deprotonated ligand molecule and of aqua coordinated Li cations (Starosta & Leciejewicz, 2010).

Related literature top

For the structures of related lithium complexes with pyrazine-2,3,5,6-tetracarboxylate and water ligands, see: Starosta & Leciejewicz (2010, 2014).

Experimental top

An aqueous solution containing 2 mmol of lithium nitrate and a small excess over 1 mmol of pyrazine-2,3,5,6-tetracarboxylic acid dihydrate was heated under reflux with stirring at ca 330 K for 10 h. After cooling to room temperature the solution was left to evaporate. Three days later well formed colorless blocks of the title compound were found, which were washed with cold methanol and dried in the air.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); 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 fragment of a [001] chain in the title compound with 50% probability displacement ellipsoids. Symmetry code: ⁱ x, y, -z + 1; ⁱⁱ -x + 1, y, z; ⁱⁱⁱ x, -y, -z + 1.
	Fig. 2. The alignment of the ribbons viewed along the crystal a direction.

catena-Poly[[lithium-µ₂-(dihydrogen pyrazine-2,3,5,6-tetracarboxylato)-κ⁶O²,N¹,O⁶;O³,N⁴,O⁵-lithium-di-µ-aqua-κ⁴O:O] 2.5-hydrate] top

Crystal data top

[Li(C₈H₂N₂O₈)(H₂O)₂]·2.5H₂O	F(000) = 716
M_r = 349.06	D_x = 1.556 Mg m⁻³
Orthorhombic, Cmcm	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2c 2	Cell parameters from 3296 reflections
a = 12.0554 (3) Å	θ = 3.8–31.9°
b = 6.39040 (17) Å	µ = 0.15 mm⁻¹
c = 19.3383 (4) Å	T = 293 K
V = 1489.80 (6) Å³	Block, colourless
Z = 4	0.24 × 0.20 × 0.05 mm

Data collection top

Agilent SuperNova (Dual, Cu at zero, Eos) diffractometer	1151 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	997 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.029
Detector resolution: 16.0131 pixels mm^-1	θ_max = 30.0°, θ_min = 3.4°
ω scans	h = −16→16
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −8→8
T_min = 0.701, T_max = 1.000	l = −27→27
7496 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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0592P)² + 0.9014P] where P = (F_o² + 2F_c²)/3
1151 reflections	(Δ/σ)_max < 0.001
85 parameters	Δρ_max = 0.25 e Å⁻³
3 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

[Li(C₈H₂N₂O₈)(H₂O)₂]·2.5H₂O	V = 1489.80 (6) Å³
M_r = 349.06	Z = 4
Orthorhombic, Cmcm	Mo Kα radiation
a = 12.0554 (3) Å	µ = 0.15 mm⁻¹
b = 6.39040 (17) Å	T = 293 K
c = 19.3383 (4) Å	0.24 × 0.20 × 0.05 mm

Data collection top

Agilent SuperNova (Dual, Cu at zero, Eos) diffractometer	1151 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	997 reflections with I > 2σ(I)
T_min = 0.701, T_max = 1.000	R_int = 0.029
7496 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	3 restraints
wR(F²) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.25 e Å⁻³
1151 reflections	Δρ_min = −0.29 e Å⁻³
85 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	Occ. (<1)
O1	0.67161 (8)	0.07053 (19)	0.35355 (5)	0.0435 (3)
O4	0.5000	−0.1345 (3)	0.2500	0.0388 (4)
O2	0.79263 (8)	0.04117 (18)	0.43921 (5)	0.0413 (3)
O5	0.33035 (11)	0.4166 (2)	0.7500	0.0379 (3)
O3	0.5000	0.3004 (4)	0.2500	0.0533 (6)
N1	0.5000	0.0321 (2)	0.43101 (7)	0.0270 (3)
C2	0.59630 (8)	0.01679 (18)	0.46407 (6)	0.0259 (3)
C7	0.69421 (10)	0.0441 (2)	0.41465 (6)	0.0310 (3)
Li1	0.5000	0.0823 (7)	0.32284 (17)	0.0463 (8)
H4	0.555 (2)	−0.229 (5)	0.2500	0.070 (9)*
H3	0.445 (3)	0.377 (7)	0.2500	0.097 (13)*
H5	0.2920 (19)	0.432 (3)	0.7135 (10)	0.068 (7)*
H2	0.797 (3)	0.0000	0.5000	0.097 (12)*
O6	0.5000	0.4486 (17)	0.3733 (5)	0.077 (2)	0.25
H61	0.5000	0.578 (7)	0.386 (7)	0.115*	0.25
H62	0.5000	0.39 (2)	0.413 (4)	0.115*	0.25

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0302 (5)	0.0732 (8)	0.0270 (5)	−0.0022 (4)	0.0051 (3)	0.0037 (4)
O4	0.0299 (9)	0.0406 (10)	0.0459 (11)	0.000	0.000	0.000
O2	0.0207 (4)	0.0659 (7)	0.0374 (5)	−0.0024 (4)	0.0029 (3)	0.0018 (4)
O5	0.0240 (6)	0.0562 (9)	0.0334 (7)	0.0024 (6)	0.000	0.000
O3	0.0336 (11)	0.0356 (11)	0.0908 (18)	0.000	0.000	0.000
N1	0.0207 (6)	0.0370 (7)	0.0232 (6)	0.000	0.000	−0.0010 (5)
C2	0.0198 (5)	0.0335 (6)	0.0244 (5)	−0.0005 (4)	0.0010 (4)	−0.0025 (4)
C7	0.0226 (5)	0.0410 (7)	0.0295 (6)	−0.0015 (4)	0.0048 (4)	−0.0021 (5)
Li1	0.0421 (18)	0.070 (2)	0.0271 (15)	0.000	0.000	0.0075 (15)
O6	0.049 (4)	0.101 (7)	0.081 (5)	0.000	0.000	−0.020 (5)

Geometric parameters (Å, º) top

O1—C7	1.2242 (16)	O3—Li1ⁱⁱ	1.982 (4)
Li1—O1	2.1538 (13)	O3—H3	0.82 (4)
Li1—O1ⁱ	2.1538 (13)	N1—C2	1.3289 (12)
Li1—O3	1.982 (4)	N1—C2ⁱ	1.3289 (12)
Li1—O4	1.976 (4)	C2—C2ⁱⁱⁱ	1.406 (2)
Li1—N1	2.116 (3)	C2—C7	1.5287 (15)
O4—Li1ⁱⁱ	1.976 (4)	Li1—O6	2.536 (11)
O4—H4	0.90 (3)	Li1—Li1ⁱⁱ	2.817 (7)
O2—C7	1.2780 (15)	O6—H61	0.86 (2)
O2—H2	1.2057 (19)	O6—H62	0.87 (2)
O5—H5	0.85 (2)

C7—O1—Li1	119.00 (12)	O3—Li1—O1	102.74 (10)
Li1ⁱⁱ—O4—Li1	91.0 (2)	N1—Li1—O1	73.87 (9)
Li1ⁱⁱ—O4—H4	118.2 (11)	O4—Li1—O1ⁱ	99.91 (12)
Li1—O4—H4	118.2 (11)	O3—Li1—O1ⁱ	102.74 (10)
C7—O2—H2	113.8 (18)	N1—Li1—O1ⁱ	73.87 (9)
Li1—O3—Li1ⁱⁱ	90.6 (3)	O1—Li1—O1ⁱ	147.72 (17)
Li1—O3—H3	114.8 (18)	O4—Li1—O6	157.2 (3)
Li1ⁱⁱ—O3—H3	114.8 (18)	O3—Li1—O6	67.9 (3)
C2—N1—C2ⁱ	121.76 (13)	N1—Li1—O6	76.1 (3)
C2—N1—Li1	119.12 (7)	O1—Li1—O6	85.76 (13)
C2ⁱ—N1—Li1	119.12 (7)	O1ⁱ—Li1—O6	85.76 (13)
N1—C2—C2ⁱⁱⁱ	119.12 (7)	O4—Li1—Li1ⁱⁱ	44.52 (11)
N1—C2—C7	111.44 (10)	O3—Li1—Li1ⁱⁱ	44.70 (13)
C2ⁱⁱⁱ—C2—C7	129.43 (6)	N1—Li1—Li1ⁱⁱ	171.28 (12)
O1—C7—O2	124.56 (11)	O1—Li1—Li1ⁱⁱ	106.01 (9)
O1—C7—C2	116.56 (11)	O1ⁱ—Li1—Li1ⁱⁱ	106.01 (9)
O2—C7—C2	118.87 (11)	O6—Li1—Li1ⁱⁱ	112.6 (3)
O4—Li1—O3	89.22 (15)	Li1—O6—H61	174 (10)
O4—Li1—N1	126.8 (2)	Li1—O6—H62	85 (10)
O3—Li1—N1	144.0 (2)	H61—O6—H62	101 (3)
O4—Li1—O1	99.91 (12)

C2ⁱ—N1—C2—C2ⁱⁱⁱ	0.1 (3)	Li1ⁱⁱ—O3—Li1—O6	180.000 (2)
Li1—N1—C2—C2ⁱⁱⁱ	−179.94 (18)	C2—N1—Li1—O4	90.02 (13)
C2ⁱ—N1—C2—C7	−178.85 (10)	C2ⁱ—N1—Li1—O4	−90.02 (13)
Li1—N1—C2—C7	1.1 (2)	C2—N1—Li1—O3	−89.98 (13)
Li1—O1—C7—O2	−177.66 (16)	C2ⁱ—N1—Li1—O3	89.98 (13)
Li1—O1—C7—C2	1.3 (2)	C2—N1—Li1—O1	−0.42 (18)
N1—C2—C7—O1	−1.57 (17)	C2ⁱ—N1—Li1—O1	179.54 (12)
C2ⁱⁱⁱ—C2—C7—O1	179.61 (16)	C2—N1—Li1—O1ⁱ	−179.55 (12)
N1—C2—C7—O2	177.46 (12)	C2ⁱ—N1—Li1—O1ⁱ	0.42 (18)
C2ⁱⁱⁱ—C2—C7—O2	−1.4 (2)	C2—N1—Li1—O6	−89.98 (13)
Li1ⁱⁱ—O4—Li1—O3	0.0	C2ⁱ—N1—Li1—O6	89.98 (13)
Li1ⁱⁱ—O4—Li1—N1	180.0	C2—N1—Li1—Li1ⁱⁱ	90.02 (13)
Li1ⁱⁱ—O4—Li1—O1	−102.80 (12)	C2ⁱ—N1—Li1—Li1ⁱⁱ	−90.02 (13)
Li1ⁱⁱ—O4—Li1—O1ⁱ	102.80 (12)	C7—O1—Li1—O4	−126.14 (15)
Li1ⁱⁱ—O4—Li1—O6	0.000 (4)	C7—O1—Li1—O3	142.40 (14)
Li1ⁱⁱ—O3—Li1—O4	0.0	C7—O1—Li1—N1	−0.56 (19)
Li1ⁱⁱ—O3—Li1—N1	180.0	C7—O1—Li1—O1ⁱ	1.0 (5)
Li1ⁱⁱ—O3—Li1—O1	99.99 (14)	C7—O1—Li1—O6	76.2 (3)
Li1ⁱⁱ—O3—Li1—O1ⁱ	−99.99 (14)	C7—O1—Li1—Li1ⁱⁱ	−171.48 (10)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O6—H62···N1	0.87 (2)	2.28 (11)	2.886 (12)	127 (12)
O5—H5···O1^iv	0.85 (2)	1.95 (2)	2.7711 (13)	163 (2)
O3—H3···O5^v	0.82 (4)	1.92 (4)	2.730 (2)	173 (4)
O4—H4···O5^vi	0.90 (3)	1.83 (3)	2.726 (2)	179 (3)
O2—H2···O2ⁱⁱⁱ	1.21 (1)	1.21 (1)	2.409 (3)	175 (1)

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

Selected bond lengths (Å) top

Li1—O1	2.1538 (13)	Li1—O4	1.976 (4)
Li1—O3	1.982 (4)	Li1—N1	2.116 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O6—H62···N1	0.87 (2)	2.28 (11)	2.886 (12)	127 (12)
O5—H5···O1ⁱ	0.85 (2)	1.95 (2)	2.7711 (13)	163 (2)
O3—H3···O5ⁱⁱ	0.82 (4)	1.92 (4)	2.730 (2)	173 (4)
O4—H4···O5ⁱⁱⁱ	0.90 (3)	1.83 (3)	2.726 (2)	179 (3)
O2—H2···O2^iv	1.206 (3)	1.206 (3)	2.409 (3)	175.3 (5)

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

References

Agilent (2011). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Starosta, W. & Leciejewicz, J. (2010). Acta Cryst. E66, m1561–m1562. Web of Science CrossRef CAS IUCr Journals Google Scholar
Starosta, W. & Leciejewicz, J. (2014). Acta Cryst. E70, m172. CSD CrossRef IUCr Journals Google Scholar

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