(μ-Di­hydrogen pyrazine-2,3,5,6-tetra­carboxyl­ato-κ6O2,N1,O6;O3,N4,O5)bis­(di­aqua­lithium) monohydrate

Starosta, W.; Leciejewicz, J.

doi:10.1107/S1600536814007223

metal-organic compounds

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Volume 70| Part 5| May 2014| Page m172

doi:10.1107/S1600536814007223

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(μ-Dihydrogen pyrazine-2,3,5,6-tetracarboxylato-κ⁶O²,N¹,O⁶;O³,N⁴,O⁵)bis(diaqualithium) monohydrate

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 17 March 2014; accepted 1 April 2014; online 9 April 2014)

The structure of the title compound, [Li₂(C₈H₂N₂O₈)(H₂O)₄]·H₂O, is composed of dinuclear molecules in which the ligand bridges two symmetry-related Li^I ions, each coordinated also by two water O atoms, in an O,N,O′-manner. The Li and N atoms occupy special positions on twofold rotation axes, whereas a crystal water molecule is located at the intersection of three twofold rotation axes. The Li^I cation shows a distorted trigonal–bipyramidal coordination. Two carboxylate groups remain protonated and form short interligand hydrogen bonds. The molecules are held together by a network of hydrogen bonds in which the coordinating and solvation water molecules act as donors and carboxylate O atoms as acceptors, forming a three-dimensional architecture.

CCDC reference: 994866

Related literature

For the structure of a lithium complex with pyrazine-2,3,5,6-tetracarboxylate and water ligands, see: Starosta & Leciejewicz (2010 ). The structure of pyrazine-2,3,5,6-tetracarboxylic acid dihydrate was reported by Vishweshwar et al. (2001 ).

Experimental

Crystal data

[Li₂(C₈H₂N₂O₈)(H₂O)₄]·H₂O
M_r = 358.08
Orthorhombic, I b a m
a = 6.3807 (4) Å
b = 9.8331 (6) Å
c = 22.1717 (16) Å
V = 1391.10 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.16 mm⁻¹
T = 293 K
0.12 × 0.10 × 0.06 mm

Data collection

Agilent SuperNova (Dual, Cu at zero, Eos) diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.979, T_max = 0.993
3622 measured reflections
917 independent reflections
769 reflections with I > 2σ(I)
R_int = 0.061

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.100
S = 1.06
917 reflections
78 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Selected bond lengths (Å)

Li1—N1	2.053 (4)
Li1—O1	2.1581 (17)
Li1—O3	1.969 (3)
Li1—O3ⁱ	1.969 (3)
Li1—O1ⁱ	2.1580 (17)
Symmetry code: (i) -x+2, -y, z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H1⋯O2ⁱⁱ	1.20 (1)	1.20 (1)	2.402 (3)	177 (8)
O3—H32⋯O3ⁱⁱⁱ	0.87 (2)	2.00 (2)	2.839 (3)	163 (4)
O3—H31⋯O1^iv	0.86 (2)	2.03 (2)	2.8825 (19)	177 (2)
O3—H33⋯O4^v	0.86 (2)	2.10 (2)	2.9454 (17)	169 (6)
Symmetry codes: (ii) x, y, -z; (iii) $[-x+2, y, -z+{\script{1\over 2}}]$ ; (iv) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ ; (v) $[-x+{\script{3\over 2}}, -y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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: 994866

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536814007223/kp2468sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814007223/kp2468Isup2.hkl

checkCIF report

Comment top

The structure of the title compound reveals a dimeric unit of 2/m crystallographic symmetry in which two symmetry related doubly aqua-coordinated Li(I) ions are bridged by a ligand molecule via its both N,O,O bonding sites (Fig.1). The Li(I) cation is in distorted trigonal bipyramidal coordination. Its equatorial plane is formed by N1, O3, O3⁽ⁱ⁾ and the Li1 atoms; the O1 and O1⁽ⁱ⁾ atoms are at the apices. The O1—Li—O1⁽ⁱ⁾ angle is 151.7 (3)° and Li—O and Li—N bond distances are listed in Table 1. The pyrazine ring is planar. Two carboxylate groups remain protonated to maintain charge balance. Bond distances and bond angles within the hetero-ring do not differ from those reperted in the structure of the parent acid (Vishweshwar et al., 2001). Short, symmetric hydrogen bond is formed in which the carboxylate O2 atom is as a donor and the O1⁽ⁱⁱ⁾ is as an acceptor (Table 2). A dihedral angle formed with the pyrazine ring by the carboxylic group C1/O1/O2 is 4.7 (1)°. Fourier maps show a clear disorder in hydrogen positions at the solvation and coordinated water molecules with position occupancy of aproximately 0.5. The title molecules are held together by a network of hydrogen bonds (Table 2) in which coordinated water molecules act as donors and carboxylate O atoms as acceptors forming molecular layers propagating in the crystal a direction (Fig.2). A view of a single layer is displayed in Fig. 2. The layers are linked by weak hydrogen bonds in which solvation water molecules are involved. Another Li(I) complex with the title ligand is known (Starosta & Leciejewicz, 2010). Its polarized dinuclear structural unit is built of a doubly protonated ligand molecule chelated by its N,O,O bonding moiety to an Li(I) ion and an Li(I) ion coordinated by four aqua O atoms. Two of the latter bridge the Li ions to form a catenated polymeric structure propagating in the crystal a direction.

Related literature top

For the structure of a lithium complex with pyrazine-2,3,5,6-tetracarboxylate and water ligands, see: Starosta & Leciejewicz (2010). The structure of pyrazine-2,3,5,6-tetracarboxylic acid dihydrate was reported by Vishweshwar et al. (2001).

Experimental top

Hot aqueous solutions, one containing 1 mmol of pyrazine-2,3,5,6-tetracarboxylic acid dihydrate, the other 4 mmol s of lithium nitrate (Aldrich) were mixed and boiled under reflux with constant stirring for 6 h. After cooling to room temperature the solution was left to evaporate. A couple of days latter, single-crystal blocks deposited on the bottom of a crystallization pot. They were washed with cold ethanol and dried in 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. The molecule of the title compound with atom labelling scheme and 50% probability displacement ellipsoids. Symmetry code: ⁱ -x, -y, z; ⁱⁱ x, y, -z; ⁱⁱⁱ -x, -y, -z.
	Fig. 2. A single molecular layer composed of the dimers linked by a hydrogen bond network as viewed along the crystal c direction.

(µ-Dihydrogen pyrazine-2,3,5,6-tetracarboxylato-κ⁶O²,N¹,O⁶;O³,N⁴,O⁵)bis(diaqualithium) monohydrate top

Crystal data top

[Li₂(C₈H₂N₂O₈)(H₂O)₄]·H₂O	Z = 4
M_r = 358.08	F(000) = 736
Orthorhombic, Ibam	D_x = 1.710 Mg m⁻³
Hall symbol: -I 2 2c	Mo Kα radiation, λ = 0.71073 Å
a = 6.3807 (4) Å	µ = 0.16 mm⁻¹
b = 9.8331 (6) Å	T = 293 K
c = 22.1717 (16) Å	Plate, colourless
V = 1391.10 (16) Å³	0.12 × 0.10 × 0.06 mm

Data collection top

Agilent SuperNova (Dual, Cu at zero, Eos) diffractometer	917 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	769 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.061
Detector resolution: 16.0131 pixels mm^-1	θ_max = 29.3°, θ_min = 3.7°
ω scans	h = −8→8
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −12→13
T_min = 0.979, T_max = 0.993	l = −29→29
3622 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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.024P)² + 2.020P] where P = (F_o² + 2F_c²)/3
917 reflections	(Δ/σ)_max < 0.001
78 parameters	Δρ_max = 0.25 e Å⁻³
4 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

[Li₂(C₈H₂N₂O₈)(H₂O)₄]·H₂O	V = 1391.10 (16) Å³
M_r = 358.08	Z = 4
Orthorhombic, Ibam	Mo Kα radiation
a = 6.3807 (4) Å	µ = 0.16 mm⁻¹
b = 9.8331 (6) Å	T = 293 K
c = 22.1717 (16) Å	0.12 × 0.10 × 0.06 mm

Data collection top

Agilent SuperNova (Dual, Cu at zero, Eos) diffractometer	917 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	769 reflections with I > 2σ(I)
T_min = 0.979, T_max = 0.993	R_int = 0.061
3622 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	4 restraints
wR(F²) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.25 e Å⁻³
917 reflections	Δρ_min = −0.22 e Å⁻³
78 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)
N1	1.0000	0.0000	0.06097 (8)	0.0207 (4)
O1	0.7218 (2)	0.11263 (14)	0.12977 (5)	0.0328 (3)
O3	1.1372 (3)	0.14626 (15)	0.19959 (7)	0.0376 (4)
O2	0.5112 (3)	0.16787 (13)	0.05418 (6)	0.0356 (4)
C2	0.8398 (3)	0.05696 (15)	0.03197 (7)	0.0203 (3)
C7	0.6800 (3)	0.11721 (16)	0.07586 (8)	0.0251 (4)
Li1	1.0000	0.0000	0.15359 (19)	0.0360 (10)
O4	0.0000	0.5000	0.2500	0.0595 (9)
H31	1.158 (4)	0.219 (2)	0.1789 (10)	0.056 (8)*
H1	0.506 (12)	0.168 (4)	0.0000	0.097 (15)*
H32	1.068 (6)	0.161 (4)	0.2328 (13)	0.037 (13)*	0.50
H41	0.043 (12)	0.459 (6)	0.2190 (17)	0.10 (3)*	0.50
H33	1.254 (6)	0.111 (6)	0.211 (2)	0.08 (2)*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0218 (8)	0.0189 (8)	0.0214 (9)	0.0016 (8)	0.000	0.000
O1	0.0355 (7)	0.0383 (7)	0.0244 (6)	0.0065 (6)	0.0072 (6)	−0.0025 (5)
O3	0.0474 (9)	0.0347 (8)	0.0308 (8)	−0.0074 (7)	−0.0008 (7)	0.0004 (6)
O2	0.0293 (7)	0.0400 (7)	0.0376 (7)	0.0154 (6)	0.0050 (7)	0.0002 (6)
C2	0.0198 (8)	0.0174 (7)	0.0239 (8)	0.0002 (6)	0.0008 (6)	−0.0009 (6)
C7	0.0258 (8)	0.0203 (7)	0.0293 (9)	0.0019 (6)	0.0047 (7)	−0.0008 (6)
Li1	0.046 (2)	0.039 (2)	0.024 (2)	−0.005 (2)	0.000	0.000
O4	0.076 (3)	0.065 (2)	0.0372 (19)	0.000	0.000	0.000

Geometric parameters (Å, º) top

N1—C2ⁱ	1.3313 (18)	O2—C7	1.280 (2)
N1—C2	1.3313 (18)	O2—H1	1.202 (3)
Li1—N1	2.053 (4)	C2—C2ⁱⁱ	1.418 (3)
O1—C7	1.226 (2)	C2—C7	1.529 (2)
Li1—O1	2.1581 (17)	Li1—O3ⁱ	1.969 (3)
Li1—O3	1.969 (3)	Li1—O1ⁱ	2.1580 (17)
O3—H31	0.858 (16)	Li1—H33	2.33 (5)
O3—H32	0.870 (19)	O4—H41	0.84 (2)
O3—H33	0.86 (2)

C2ⁱ—N1—C2	122.24 (19)	O2—C7—C2	118.22 (15)
C2ⁱ—N1—Li1	118.88 (10)	O3ⁱ—Li1—O3	117.6 (2)
C2—N1—Li1	118.88 (10)	O3ⁱ—Li1—N1	121.21 (11)
C7—O1—Li1	115.89 (16)	O3—Li1—N1	121.21 (11)
Li1—O3—H31	113.4 (17)	O3ⁱ—Li1—O1ⁱ	96.76 (7)
Li1—O3—H32	110 (3)	O3—Li1—O1ⁱ	97.81 (7)
H31—O3—H32	113 (3)	N1—Li1—O1ⁱ	75.84 (11)
Li1—O3—H33	104 (4)	O3ⁱ—Li1—O1	97.81 (7)
H31—O3—H33	111 (4)	O3—Li1—O1	96.76 (7)
H32—O3—H33	105 (4)	N1—Li1—O1	75.84 (11)
C7—O2—H1	113 (4)	O1ⁱ—Li1—O1	151.7 (2)
N1—C2—C2ⁱⁱ	118.88 (10)	O3ⁱ—Li1—H33	111.5 (14)
N1—C2—C7	111.58 (14)	O3—Li1—H33	20.9 (10)
C2ⁱⁱ—C2—C7	129.53 (9)	N1—Li1—H33	123.2 (14)
O1—C7—O2	124.31 (16)	O1ⁱ—Li1—H33	78.6 (10)
O1—C7—C2	117.47 (16)	O1—Li1—H33	117.7 (10)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1···O2ⁱⁱ	1.20 (1)	1.20 (1)	2.402 (3)	177 (8)
O3—H32···O3ⁱⁱⁱ	0.87 (2)	2.00 (2)	2.839 (3)	163 (4)
O3—H31···O1^iv	0.86 (2)	2.03 (2)	2.8825 (19)	177 (2)
O3—H33···O4^v	0.86 (2)	2.10 (2)	2.9454 (17)	169 (6)

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

Selected bond lengths (Å) top

Li1—N1	2.053 (4)	Li1—O3ⁱ	1.969 (3)
Li1—O1	2.1581 (17)	Li1—O1ⁱ	2.1580 (17)
Li1—O3	1.969 (3)

Symmetry code: (i) −x+2, −y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1···O2ⁱⁱ	1.202 (3)	1.202 (3)	2.402 (3)	177 (8)
O3—H32···O3ⁱⁱⁱ	0.870 (19)	2.00 (2)	2.839 (3)	163 (4)
O3—H31···O1^iv	0.858 (16)	2.026 (17)	2.8825 (19)	177 (2)
O3—H33···O4^v	0.86 (2)	2.10 (2)	2.9454 (17)	169 (6)

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

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
Vishweshwar, P., Nangia, A. & Lynch, V. M. (2001). Chem. Commun. pp. 179–180. Web of Science CSD CrossRef Google Scholar

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