Issue contents
Download PDF of article
Download CIF
3D view
Navigation
Highlighting
Dictionary of Crystallography reference
IUPAC Gold Book reference
more ...
Download citation
FormatBIBTeX
EndNote
RefMan
Refer
Medline
CIF
SGML
Plain Text
share
Previous article
Next article
Previous article
Issue contents
Download PDF of article
Download CIF
3D view
Navigation
Highlighting
Dictionary of Crystallography reference
IUPAC Gold Book reference
more ...
Download citation
FormatBIBTeX
EndNote
RefMan
Refer
Medline
CIF
SGML
Plain Text
share
Next article

metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 68| Part 4| April 2012| Pages m496-m497
doi:10.1107/S1600536812012743

Poly[hydrazin-1-ium [di­aqua­bis­­(μ4-pyridazine-3,6-di­carboxyl­ato)trilithate] monohydrate]

Wojciech Starostaa and Janusz Leciejewicza*

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

(Received 5 March 2012; accepted 23 March 2012; online 31 March 2012)

The structure of the title compound, {(N2H5)[Li3(C6H2N2O4)2(H2O)2]·H2O}n, is composed of mol­ecular dimers, each built up of two symmetry-related LiI ions with distorted trigonal–bipyramidal coordinations bridged by two deprotonated ligand mol­ecules via their N,O-bonding sites. Doubly solvated LiI ions with a distorted tetra­hedral geometry link adjacent dimers, forming a polymer generated by bridging bidentate carboxyl­ato O atoms to LiI ions in adjacent dimers, forming anionic layers parallel to the ac plane with monoprotonated hydrazinium cations and crystal water mol­ecules positioned between them. The layers are held together by an extended system of hydrogen bonds in which the hydrazinium cations and coordinated and crystal water mol­ecules act as donors and carboxyl­ate O atoms act as acceptors.

Related literature

For the crystal structures of LiI complexes with pyridazine-3,6-dicarboxyl­ate ligands, see: Starosta & Leciejewicz (2010[Starosta, W. & Leciejewicz, J. (2010). Acta Cryst. E66, m1362-m1363.], 2011[Starosta, W. & Leciejewicz, J. (2011). Acta Cryst. E67, m1455-m1456.], 2012[Starosta, W. & Leciejewicz, J. (2012). Acta Cryst. E68, m324-m325.]). The structure of a hydrazine adduct of pyridazine-3,6-dicarb­oxy­lic acid was also reported by Starosta & Leciejewicz (2008[Starosta, W. & Leciejewicz, J. (2008). Acta Cryst. E64, o461.]).

[Scheme 1]

Experimental

Crystal data

  • (N2H5)[Li3(C6H2N2O4)2(H2O)2]·H2O

  • Mr = 440.12

  • Triclinic, [P \overline 1]

  • a = 5.215 (1) Å

  • b = 7.3356 (15) Å

  • c = 24.001 (5) Å

  • α = 97.62 (3)°

  • β = 90.62 (3)°

  • γ = 95.77 (3)°

  • V = 905.2 (3) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.14 mm−1

  • T = 293 K

  • 0.40 × 0.14 × 0.06 mm
Data collection

  • Kuma KM-4 four-cricle diffractometer

  • Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008[Oxford Diffraction (2008). CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]) Tmin = 0.982, Tmax = 0.992

  • 5141 measured reflections

  • 4676 independent reflections

  • 2660 reflections with I > 2σ(I)

  • Rint = 0.051

  • 3 standard reflections every 200 reflections intensity decay: 1.4%
Refinement

  • R[F2 > 2σ(F2)] = 0.057

  • wR(F2) = 0.243

  • S = 1.06

  • 4676 reflections

  • 329 parameters

  • 10 restraints

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

  • Δρmax = 0.56 e Å−3

  • Δρmin = −0.48 e Å−3

Table 1
Selected bond lengths (Å)

Li1—N11 2.260 (6)
Li1—O13 1.982 (6)
Li1—O11i 2.010 (5)
Li1—O12ii 2.088 (6)
Li1—N12i 2.144 (6)
Li2—O21 1.990 (6)
Li2—N21 2.186 (6)
Li2—O24iii 1.995 (6)
Li2—O22iv 2.097 (6)
Li2—N22iii 2.276 (6)
Li3—O14 1.893 (5)
Li3—O2 1.938 (6)
Li3—O1 1.952 (6)
Li3—O23 1.934 (6)
Symmetry codes: (i) -x+2, -y+2, -z+1; (ii) -x+1, -y+2, -z+1; (iii) -x+2, -y+2, -z; (iv) x+1, y, z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N2—H3⋯O24v 0.89 (2) 1.95 (2) 2.824 (4) 168 (6)
N2—H5⋯O3vi 0.92 (2) 1.82 (3) 2.709 (5) 162 (7)
N1—H2⋯O23vii 0.90 (2) 2.07 (2) 2.965 (4) 175 (5)
N2—H4⋯O13v 0.90 (2) 1.96 (5) 2.716 (4) 140 (6)
N1—H1⋯O11viii 0.88 (2) 2.12 (2) 2.981 (4) 167 (5)
O2—H21⋯O1iv 0.82 (2) 1.94 (3) 2.737 (4) 163 (7)
O2—H22⋯O22ix 0.83 (2) 2.07 (3) 2.868 (4) 162 (7)
O3—H31⋯O12viii 0.84 (2) 1.93 (2) 2.741 (4) 164 (5)
O3—H32⋯O14 0.81 (2) 2.11 (3) 2.875 (4) 156 (5)
O1—H12⋯O21ix 0.93 (5) 1.76 (5) 2.684 (3) 174 (4)
O1—H11⋯N1 0.82 (5) 2.00 (5) 2.814 (4) 171 (5)
Symmetry codes: (iv) x+1, y, z; (v) x-1, y-1, z; (vi) x-1, y, z; (vii) x, y-1, z; (viii) -x+1, -y+1, -z+1; (ix) -x+1, -y+1, -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[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812012743/kp2395sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812012743/kp2395Isup2.hkl

checkCIF report


Comment top

It has been reported (Starosta & Leciejewicz, 2010), that the structure of a LiI complex with pyridazine-3,6-dicarbaxylate and water ligands is built of centrosymmtric monomers bridged by strong, centrosymmetric hydrogen bonds. Deprotonization by an addition of a small amount of hydrazine resulted in a compound with a polymeric structure composed of centrosymmetric tetramers in which two LiI ions, bridged by two fully deprotonated pyridazine-3,6-dicarboxylate ligands are linked to two triply solvated LiI ions. The latter bridge the tetramer via two aqua O atoms to adjacent tetramers (Starosta & Leciejewicz, 2011). An addition of few more drops of hydrazine gave rise to a compound with a structure built of centrosymmetric anions in which two LiI ions, are bridged by two fully deprotonated pyridazine-3,6-dicarboxylato ligands with the charge compensated by two mono protonated hydrazine cations and neutral centrosymmetric tetrameric molecules as in previous compound. While studying the reaction products of LiNO3 with the title ligand we have obtained a new compound. Its structure is reported below. The structure of the title compound is polymeric. Its unit cell contains two symmetry independent dinuclear moieties (dimers) related by a centre of symmetry each built of two Li ions and two fully deprotonated pyridazine-3,6-dicarboxylate ligands (Fig. 1). The dimers are bridged by a doubly solvated symmetry independent Li3 ion. In each dimer, ligand carboxylato groups act as bidentate. Apart from participation in the N,O-bonding groups chelating the intra-dimer Li ions, they use the second O atoms to bridge the dimers to doubly solvated Li3 ions forming an anionic ribbon propagating in the unit cell c direction (Symmetry code:i-x + 1, -y + 2, -z + 1; ii -x + 2, -y + 2, -z + 1; iv -x + 2, -y + 2,-z; v x + 1, y, z)(Fig. 1). A second bridging pathway with a direction normal to the ribbons links them into a polymeric two-dimensional framework (Fig. 2). The two dimers and two doubly solvated Li3 ions carry a charge of (2-) which is compensated by two inversion symmetry related mono-protonated hydrazinium cations positioned between adjacent dimers. In the asymmetric unit there is a crystal water molecule. The coordination polyhedron around the Li1 ion, a distorted trigonal-bipyramid, is composed of O13, O12i, N12ii atoms which make an equatorial plane, the Li1 ion is 0.0863 (2) Å out of it, N11 and O11ii atoms are at apical positions. The strongly distorted trigonal-bipyramidal coordination of the Li2 ion consists of N21, O22v and O24iv atoms which constitute its equatorial plane with the Li2 ion 0.0893 (2) Å out of it; O21 and N22iv atoms are at the apices. The penta-coordination mode of Li1 and Li2 ions can be also visualized as a transition from distorted trigonal-bipyramid to a deformed square-pyramid, the latter with O12i and O24iv atoms at apical positions in case of Li1 and Li2 ions, respectively. Li—O and Li—N bond distances (Table 1) fall in the same range as those observed in the LiI complexes with title and water ligands (Starosta & Leciejewicz, 2010, 2011, 2012). The ligand 1 and 2 pyridazine rings are planar with r.m.s. of 0.0123 (2) Å and 0.0077 (1) Å, respectively. The carboxylato groups C17/O11/12 and C18/O13/O14 make dihedral angles with the ligand ring 1 of 17.8 (2)° and 13.3 (2)°, respectively; the respective angles between C27//O21/O22 and C28/O23/24 groups and the ligand ring 2 are 15.9 (2)° and 8.4 (2)°. Li3 ion shows a distorted tetrahedral coordination geometry with a pair of bridging carboxylato O13 and O23 atoms and a pair of coordinated water O1, O2 atoms in trans arrangement. Li3 ion is neither coplanar with the dimer 1 nor the dimer 2 as indicated by the O14—Li3—O23 angle of 110.6 (3)°; its position in respect to adjacent dimers makes a half-open cavity which is occupied by the hydrazinium cation. The layers are held together by an extended system of hydrogen bonds in which hydrazinium cation, coordinated, and crystal water molecules act as donors to carboxylato O atoms (Table 2).

Related literature top

For the crystal structures of LiI complexes with pyridazine-3,6-dicarboxylate ligands, see: Starosta & Leciejewicz (2010, 2011, 2012). The structure of a hydrazine adduct of pyridazine-3,6-dicarboxylic acid was also reported by Starosta & Leciejewicz (2008).

Experimental top

A reaction of 1 mmol of pyridazine-3,6-dicarboxylic acid with 2 mmol s of lithium nitrate both dissolved in 50 ml of hot water and then boiled under reflux with stirring for 6 h yielded a compound which was identified by its lattice parameters as that one reported earlier (Starosta & Leciejewicz, 2010). After an addition of few drops of hydrazine, its warm aqueous solution was stirred for two h without heating. Left to crystallize at room temperature, single-crystal plates of the title compound were found after a couple of days. They were washed with cold ethanol and dried in air.

Refinement top

Coordinated water, hydrazine hydrogen atoms and crystal water molecule were located in a difference map and refined isotropically, while H atoms attached to pyridazine-ring C atoms were located at calculated positions and treated as riding on the parent atoms with C—H=0.93 Å and Uiso(H)=1.2Ueq(C).

Structure description top

It has been reported (Starosta & Leciejewicz, 2010), that the structure of a LiI complex with pyridazine-3,6-dicarbaxylate and water ligands is built of centrosymmtric monomers bridged by strong, centrosymmetric hydrogen bonds. Deprotonization by an addition of a small amount of hydrazine resulted in a compound with a polymeric structure composed of centrosymmetric tetramers in which two LiI ions, bridged by two fully deprotonated pyridazine-3,6-dicarboxylate ligands are linked to two triply solvated LiI ions. The latter bridge the tetramer via two aqua O atoms to adjacent tetramers (Starosta & Leciejewicz, 2011). An addition of few more drops of hydrazine gave rise to a compound with a structure built of centrosymmetric anions in which two LiI ions, are bridged by two fully deprotonated pyridazine-3,6-dicarboxylato ligands with the charge compensated by two mono protonated hydrazine cations and neutral centrosymmetric tetrameric molecules as in previous compound. While studying the reaction products of LiNO3 with the title ligand we have obtained a new compound. Its structure is reported below. The structure of the title compound is polymeric. Its unit cell contains two symmetry independent dinuclear moieties (dimers) related by a centre of symmetry each built of two Li ions and two fully deprotonated pyridazine-3,6-dicarboxylate ligands (Fig. 1). The dimers are bridged by a doubly solvated symmetry independent Li3 ion. In each dimer, ligand carboxylato groups act as bidentate. Apart from participation in the N,O-bonding groups chelating the intra-dimer Li ions, they use the second O atoms to bridge the dimers to doubly solvated Li3 ions forming an anionic ribbon propagating in the unit cell c direction (Symmetry code:i-x + 1, -y + 2, -z + 1; ii -x + 2, -y + 2, -z + 1; iv -x + 2, -y + 2,-z; v x + 1, y, z)(Fig. 1). A second bridging pathway with a direction normal to the ribbons links them into a polymeric two-dimensional framework (Fig. 2). The two dimers and two doubly solvated Li3 ions carry a charge of (2-) which is compensated by two inversion symmetry related mono-protonated hydrazinium cations positioned between adjacent dimers. In the asymmetric unit there is a crystal water molecule. The coordination polyhedron around the Li1 ion, a distorted trigonal-bipyramid, is composed of O13, O12i, N12ii atoms which make an equatorial plane, the Li1 ion is 0.0863 (2) Å out of it, N11 and O11ii atoms are at apical positions. The strongly distorted trigonal-bipyramidal coordination of the Li2 ion consists of N21, O22v and O24iv atoms which constitute its equatorial plane with the Li2 ion 0.0893 (2) Å out of it; O21 and N22iv atoms are at the apices. The penta-coordination mode of Li1 and Li2 ions can be also visualized as a transition from distorted trigonal-bipyramid to a deformed square-pyramid, the latter with O12i and O24iv atoms at apical positions in case of Li1 and Li2 ions, respectively. Li—O and Li—N bond distances (Table 1) fall in the same range as those observed in the LiI complexes with title and water ligands (Starosta & Leciejewicz, 2010, 2011, 2012). The ligand 1 and 2 pyridazine rings are planar with r.m.s. of 0.0123 (2) Å and 0.0077 (1) Å, respectively. The carboxylato groups C17/O11/12 and C18/O13/O14 make dihedral angles with the ligand ring 1 of 17.8 (2)° and 13.3 (2)°, respectively; the respective angles between C27//O21/O22 and C28/O23/24 groups and the ligand ring 2 are 15.9 (2)° and 8.4 (2)°. Li3 ion shows a distorted tetrahedral coordination geometry with a pair of bridging carboxylato O13 and O23 atoms and a pair of coordinated water O1, O2 atoms in trans arrangement. Li3 ion is neither coplanar with the dimer 1 nor the dimer 2 as indicated by the O14—Li3—O23 angle of 110.6 (3)°; its position in respect to adjacent dimers makes a half-open cavity which is occupied by the hydrazinium cation. The layers are held together by an extended system of hydrogen bonds in which hydrazinium cation, coordinated, and crystal water molecules act as donors to carboxylato O atoms (Table 2).

For the crystal structures of LiI complexes with pyridazine-3,6-dicarboxylate ligands, see: Starosta & Leciejewicz (2010, 2011, 2012). The structure of a hydrazine adduct of pyridazine-3,6-dicarboxylic acid was also reported by Starosta & Leciejewicz (2008).

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
[Figure 1] Fig. 1. A molecule of the title compound with atom labelling scheme and 50% probability displacement ellipsoids. For clarity, hydrogen atoms are not labelled. Symmetry code: i-x + 1, -y + 2, -z + 1; ii -x + 2, -y + 2, -z + 1; iv -x + 2, -y + 2,-z; v x + 1, y, z.
[Figure 2] Fig. 2. Packing diagram of the structure viewed along the a axis.
Poly[hydrazin-1-ium [diaquabis(µ4-pyridazine-3,6-dicarboxylato)trilithate] monohydrate] top
Crystal data top
(N2H5)[Li3(C6H2N2O4)2(H2O)2]·H2OZ = 2
Mr = 440.12F(000) = 452
Triclinic, P1Dx = 1.615 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.215 (1) ÅCell parameters from 25 reflections
b = 7.3356 (15) Åθ = 6–15°
c = 24.001 (5) ŵ = 0.14 mm−1
α = 97.62 (3)°T = 293 K
β = 90.62 (3)°Plate, colourless
γ = 95.77 (3)°0.40 × 0.14 × 0.06 mm
V = 905.2 (3) Å3
Data collection top
Kuma KM-4 four-cricle
diffractometer		2660 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.051
Graphite monochromatorθmax = 30.1°, θmin = 1.7°
profile data from ω/2θ scansh = −7→0
Absorption correction: analytical
(CrysAlis RED; Oxford Diffraction, 2008)		k = −9→10
Tmin = 0.982, Tmax = 0.992l = −31→33
5141 measured reflections3 standard reflections every 200 reflections
4676 independent reflections intensity decay: 1.4%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.057Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.243H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.1704P)2 + 0.0007P]
where P = (Fo2 + 2Fc2)/3
4676 reflections(Δ/σ)max < 0.001
329 parametersΔρmax = 0.56 e Å−3
10 restraintsΔρmin = −0.48 e Å−3
Crystal data top
(N2H5)[Li3(C6H2N2O4)2(H2O)2]·H2Oγ = 95.77 (3)°
Mr = 440.12V = 905.2 (3) Å3
Triclinic, P1Z = 2
a = 5.215 (1) ÅMo Kα radiation
b = 7.3356 (15) ŵ = 0.14 mm−1
c = 24.001 (5) ÅT = 293 K
α = 97.62 (3)°0.40 × 0.14 × 0.06 mm
β = 90.62 (3)°
Data collection top
Kuma KM-4 four-cricle
diffractometer		2660 reflections with I > 2σ(I)
Absorption correction: analytical
(CrysAlis RED; Oxford Diffraction, 2008)		Rint = 0.051
Tmin = 0.982, Tmax = 0.9923 standard reflections every 200 reflections
5141 measured reflections intensity decay: 1.4%
4676 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.05710 restraints
wR(F2) = 0.243H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.56 e Å−3
4676 reflectionsΔρmin = −0.48 e Å−3
329 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
xyzUiso*/Ueq
O210.5659 (4)0.6958 (3)−0.10200 (9)0.0309 (5)
O120.1688 (4)0.6942 (3)0.56969 (10)0.0294 (5)
N210.7101 (4)0.8483 (3)0.00022 (10)0.0205 (5)
O110.5736 (4)0.7887 (3)0.60076 (9)0.0306 (5)
N110.7993 (5)0.8737 (3)0.44798 (10)0.0227 (5)
O230.6818 (5)0.9204 (3)0.19576 (9)0.0301 (5)
O220.1624 (4)0.6266 (3)−0.07499 (10)0.0307 (5)
N120.7115 (5)0.8489 (3)0.49847 (10)0.0219 (5)
O240.9860 (5)1.0790 (3)0.15156 (9)0.0335 (5)
C230.6641 (5)0.8841 (4)0.09640 (12)0.0215 (6)
C170.4028 (5)0.7428 (4)0.56305 (12)0.0218 (5)
N220.7999 (5)0.9209 (3)0.05164 (10)0.0225 (5)
C280.7876 (6)0.9699 (4)0.15267 (13)0.0255 (6)
C180.7881 (6)0.8250 (4)0.34710 (12)0.0258 (6)
O130.9742 (5)0.9479 (3)0.34981 (10)0.0368 (6)
C160.6660 (6)0.7916 (4)0.40213 (12)0.0219 (6)
C270.3945 (5)0.6834 (4)−0.06642 (12)0.0225 (6)
C140.3368 (6)0.6633 (4)0.45630 (12)0.0244 (6)
H140.17870.59620.46050.029*
C240.4272 (6)0.7763 (4)0.09217 (13)0.0261 (6)
H240.33700.75240.12410.031*
C260.4807 (5)0.7464 (4)−0.00552 (12)0.0199 (5)
C250.3319 (5)0.7071 (4)0.03952 (13)0.0259 (6)
H250.17320.63620.03420.031*
C130.4859 (5)0.7499 (4)0.50274 (12)0.0198 (5)
C150.4332 (6)0.6814 (4)0.40447 (13)0.0275 (6)
H150.34680.62250.37190.033*
Li11.0824 (10)1.0999 (8)0.4223 (2)0.0296 (11)
Li20.9101 (9)0.8297 (8)−0.0796 (2)0.0283 (11)
Li30.7103 (10)0.6895 (7)0.2248 (2)0.0278 (11)
N10.4289 (6)0.1897 (5)0.27436 (13)0.0376 (7)
N20.1607 (6)0.1293 (5)0.26487 (13)0.0404 (7)
O10.4489 (5)0.4788 (4)0.20777 (11)0.0344 (6)
H110.449 (10)0.404 (7)0.230 (2)0.052*
H120.449 (9)0.426 (7)0.170 (2)0.052*
O30.9495 (6)0.4090 (4)0.32720 (12)0.0462 (7)
H310.912 (10)0.399 (8)0.3605 (11)0.069*
H320.852 (9)0.474 (7)0.3144 (19)0.069*
O20.9871 (5)0.5947 (4)0.18013 (13)0.0465 (7)
O140.6997 (5)0.7239 (4)0.30427 (10)0.0383 (6)
H220.977 (14)0.524 (8)0.1501 (17)0.10 (2)*
H211.112 (9)0.559 (8)0.195 (3)0.08 (2)*
H10.451 (11)0.188 (7)0.3107 (9)0.064 (16)*
H40.138 (13)0.029 (6)0.283 (2)0.081 (18)*
H20.497 (9)0.104 (5)0.2505 (18)0.058 (14)*
H50.066 (12)0.221 (7)0.280 (3)0.11 (3)*
H30.124 (12)0.102 (8)0.2283 (10)0.082 (19)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O210.0201 (10)0.0448 (13)0.0251 (11)−0.0021 (9)0.0015 (8)−0.0012 (9)
O120.0152 (10)0.0384 (12)0.0354 (12)0.0010 (8)0.0057 (8)0.0091 (9)
N210.0150 (11)0.0246 (11)0.0215 (12)0.0002 (8)0.0003 (8)0.0029 (9)
O110.0194 (10)0.0481 (13)0.0235 (11)−0.0024 (9)0.0014 (8)0.0065 (9)
N110.0177 (11)0.0273 (12)0.0236 (12)−0.0010 (9)0.0000 (9)0.0071 (9)
O230.0348 (12)0.0328 (11)0.0240 (11)0.0046 (9)0.0060 (9)0.0071 (8)
O220.0164 (10)0.0389 (12)0.0344 (12)−0.0016 (8)−0.0022 (8)−0.0004 (9)
N120.0168 (11)0.0272 (12)0.0220 (12)0.0019 (9)0.0019 (9)0.0039 (9)
O240.0317 (13)0.0422 (13)0.0237 (11)−0.0107 (10)−0.0029 (9)0.0048 (9)
C230.0184 (13)0.0228 (13)0.0240 (13)0.0029 (10)0.0022 (10)0.0046 (10)
C170.0192 (13)0.0234 (13)0.0236 (13)0.0044 (10)0.0031 (10)0.0041 (10)
N220.0165 (11)0.0266 (12)0.0239 (12)0.0008 (9)0.0005 (9)0.0026 (9)
C280.0259 (15)0.0251 (13)0.0262 (15)0.0050 (11)0.0014 (11)0.0036 (11)
C180.0274 (15)0.0281 (14)0.0225 (14)0.0027 (11)0.0033 (11)0.0061 (11)
O130.0379 (13)0.0428 (13)0.0266 (12)−0.0125 (10)0.0073 (10)0.0053 (9)
C160.0213 (13)0.0231 (13)0.0209 (13)0.0013 (10)0.0003 (10)0.0029 (10)
C270.0181 (13)0.0237 (13)0.0257 (14)0.0037 (10)−0.0019 (10)0.0016 (10)
C140.0182 (13)0.0282 (14)0.0262 (14)−0.0020 (10)−0.0003 (10)0.0047 (11)
C240.0195 (14)0.0326 (15)0.0269 (15)−0.0001 (11)0.0056 (11)0.0083 (11)
C260.0130 (12)0.0209 (12)0.0262 (14)0.0049 (9)0.0010 (10)0.0030 (10)
C250.0148 (13)0.0294 (14)0.0329 (16)−0.0023 (10)0.0021 (11)0.0060 (12)
C130.0146 (12)0.0234 (12)0.0226 (13)0.0047 (9)0.0030 (9)0.0054 (9)
C150.0225 (14)0.0310 (15)0.0263 (15)−0.0040 (11)−0.0045 (11)0.0000 (11)
Li10.017 (2)0.037 (3)0.034 (3)−0.002 (2)0.000 (2)0.004 (2)
Li20.017 (2)0.038 (3)0.029 (3)0.001 (2)0.0007 (19)0.002 (2)
Li30.030 (3)0.034 (3)0.018 (2)−0.002 (2)0.0002 (19)0.0032 (19)
N10.0311 (15)0.0461 (17)0.0335 (16)−0.0010 (12)−0.0028 (12)0.0021 (13)
N20.0354 (17)0.054 (2)0.0300 (16)−0.0107 (14)−0.0003 (12)0.0093 (14)
O10.0334 (13)0.0375 (13)0.0298 (13)−0.0042 (10)0.0006 (10)0.0012 (10)
O30.0443 (16)0.0570 (17)0.0426 (15)0.0141 (13)0.0074 (12)0.0186 (13)
O20.0270 (14)0.0605 (18)0.0490 (17)0.0069 (12)0.0068 (12)−0.0063 (14)
O140.0470 (15)0.0435 (14)0.0210 (11)−0.0076 (11)−0.0008 (10)0.0006 (9)
Geometric parameters (Å, º) top
O21—C271.248 (4)C24—H240.9300
O12—C171.254 (3)C26—C251.382 (4)
O12—Li1i2.088 (6)C25—H250.9300
N21—N221.337 (3)C15—H150.9300
N21—C261.341 (3)Li1—N112.260 (6)
O11—C171.252 (4)Li1—O131.982 (6)
O11—Li1ii2.010 (6)Li1—O11ii2.010 (5)
N11—N121.329 (3)Li1—O12i2.088 (6)
N11—C161.334 (4)Li1—N12ii2.144 (6)
O23—C281.256 (4)Li2—O211.990 (6)
O22—C271.246 (4)Li2—N212.186 (6)
O22—Li2iii2.097 (6)Li2—O24iv1.995 (6)
N12—C131.331 (4)Li2—O22v2.097 (6)
N12—Li1ii2.144 (6)Li2—N22iv2.276 (6)
O24—C281.245 (4)Li3—O141.893 (5)
O24—Li2iv1.995 (6)Li3—O21.938 (6)
C23—N221.335 (4)Li3—O11.952 (6)
C23—C241.393 (4)Li3—O231.934 (6)
C23—C281.520 (4)N1—N21.430 (4)
C17—C131.521 (4)N1—H10.88 (2)
N22—Li2iv2.276 (6)N1—H20.897 (19)
C18—O141.240 (4)N2—H40.90 (2)
C18—O131.251 (4)N2—H50.92 (2)
C18—C161.511 (4)N2—H30.89 (2)
C16—C151.396 (4)O1—H110.82 (5)
C27—C261.522 (4)O1—H120.93 (5)
C14—C151.364 (4)O3—H310.835 (19)
C14—C131.395 (4)O3—H320.814 (19)
C14—H140.9300O2—H220.83 (2)
C24—C251.367 (4)O2—H210.82 (2)
C27—O21—Li2120.1 (3)N12—C13—C14123.2 (2)
C17—O12—Li1i117.5 (2)N12—C13—C17113.8 (2)
N22—N21—C26119.4 (2)C14—C13—C17122.9 (2)
N22—N21—Li2129.1 (2)C14—C15—C16117.6 (3)
C26—N21—Li2110.7 (2)C14—C15—H15121.2
C17—O11—Li1ii117.2 (2)C16—C15—H15121.2
N12—N11—C16119.5 (2)O13—Li1—O11ii98.3 (3)
N12—N11—Li1129.9 (2)O13—Li1—O12i103.8 (3)
C16—N11—Li1108.1 (2)O11ii—Li1—O12i108.2 (3)
C28—O23—Li3126.2 (3)O13—Li1—N12ii153.2 (3)
C27—O22—Li2iii116.2 (2)O11ii—Li1—N12ii79.1 (2)
N11—N12—C13119.7 (2)O12i—Li1—N12ii102.3 (2)
N11—N12—Li1ii128.2 (2)O13—Li1—N1176.6 (2)
C13—N12—Li1ii110.9 (2)O11ii—Li1—N11155.5 (3)
C28—O24—Li2iv119.8 (2)O12i—Li1—N1196.3 (2)
N22—C23—C24123.0 (3)N12ii—Li1—N1194.7 (2)
N22—C23—C28114.7 (2)O21—Li2—O24iv100.7 (3)
C24—C23—C28122.3 (2)O21—Li2—O22v106.4 (3)
O11—C17—O12126.9 (3)O24iv—Li2—O22v101.2 (2)
O11—C17—C13116.8 (2)O21—Li2—N2177.79 (19)
O12—C17—C13116.3 (3)O24iv—Li2—N21153.1 (3)
C23—N22—N21119.3 (2)O22v—Li2—N21105.0 (3)
C23—N22—Li2iv107.7 (2)O21—Li2—N22iv156.5 (3)
N21—N22—Li2iv130.4 (2)O24iv—Li2—N22iv76.4 (2)
O24—C28—O23126.5 (3)O22v—Li2—N22iv97.0 (2)
O24—C28—C23117.1 (3)N21—Li2—N22iv94.3 (2)
O23—C28—C23116.5 (3)O14—Li3—O23110.5 (3)
O14—C18—O13126.7 (3)O14—Li3—O2126.1 (3)
O14—C18—C16116.8 (3)O23—Li3—O2101.0 (3)
O13—C18—C16116.4 (3)O14—Li3—O199.9 (3)
C18—O13—Li1120.8 (2)O23—Li3—O1121.7 (3)
N11—C16—C15122.9 (3)O2—Li3—O199.0 (3)
N11—C16—C18114.9 (2)N2—N1—H1103 (4)
C15—C16—C18122.2 (3)N2—N1—H2100 (3)
O22—C27—O21127.7 (3)H1—N1—H2118 (5)
O22—C27—C26116.6 (3)N1—N2—H4103 (4)
O21—C27—C26115.8 (2)N1—N2—H5109 (5)
C15—C14—C13117.0 (3)H4—N2—H5112 (6)
C15—C14—H14121.5N1—N2—H3111 (4)
C13—C14—H14121.5H4—N2—H3112 (6)
C25—C24—C23117.7 (3)H5—N2—H3109 (6)
C25—C24—H24121.2Li3—O1—H11114 (4)
C23—C24—H24121.2Li3—O1—H12113 (3)
N21—C26—C25123.3 (3)H11—O1—H12113 (5)
N21—C26—C27113.8 (2)H31—O3—H32109 (3)
C25—C26—C27122.9 (2)Li3—O2—H22129 (5)
C24—C25—C26117.4 (3)Li3—O2—H21121 (5)
C24—C25—H25121.3H22—O2—H21100 (6)
C26—C25—H25121.3C18—O14—Li3143.4 (3)
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+2, −y+2, −z+1; (iii) x−1, y, z; (iv) −x+2, −y+2, −z; (v) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H3···O24vi0.89 (2)1.95 (2)2.824 (4)168 (6)
N2—H5···O3iii0.92 (2)1.82 (3)2.709 (5)162 (7)
N1—H2···O23vii0.90 (2)2.07 (2)2.965 (4)175 (5)
N2—H4···O13vi0.90 (2)1.96 (5)2.716 (4)140 (6)
N1—H1···O11viii0.88 (2)2.12 (2)2.981 (4)167 (5)
O2—H21···O1v0.82 (2)1.94 (3)2.737 (4)163 (7)
O2—H22···O22ix0.83 (2)2.07 (3)2.868 (4)162 (7)
O3—H31···O12viii0.84 (2)1.93 (2)2.741 (4)164 (5)
O3—H32···O140.81 (2)2.11 (3)2.875 (4)156 (5)
O1—H12···O21ix0.93 (5)1.76 (5)2.684 (3)174 (4)
O1—H11···N10.82 (5)2.00 (5)2.814 (4)171 (5)
Symmetry codes: (iii) x−1, y, z; (v) x+1, y, z; (vi) x−1, y−1, z; (vii) x, y−1, z; (viii) −x+1, −y+1, −z+1; (ix) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula(N2H5)[Li3(C6H2N2O4)2(H2O)2]·H2O
Mr440.12
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)5.215 (1), 7.3356 (15), 24.001 (5)
α, β, γ (°)97.62 (3), 90.62 (3), 95.77 (3)
V (Å3)905.2 (3)
Z2
Radiation typeMo Kα
µ (mm−1)0.14
Crystal size (mm)0.40 × 0.14 × 0.06
Data collection
DiffractometerKuma KM-4 four-cricle
Absorption correctionAnalytical
(CrysAlis RED; Oxford Diffraction, 2008)
Tmin, Tmax0.982, 0.992
No. of measured, independent and
observed [I > 2σ(I)] reflections		5141, 4676, 2660
Rint0.051
(sin θ/λ)max (Å−1)0.705
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.057, 0.243, 1.06
No. of reflections4676
No. of parameters329
No. of restraints10
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)0.56, −0.48

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—N112.260 (6)Li2—O24iii1.995 (6)
Li1—O131.982 (6)Li2—O22iv2.097 (6)
Li1—O11i2.010 (5)Li2—N22iii2.276 (6)
Li1—O12ii2.088 (6)Li3—O141.893 (5)
Li1—N12i2.144 (6)Li3—O21.938 (6)
Li2—O211.990 (6)Li3—O11.952 (6)
Li2—N212.186 (6)Li3—O231.934 (6)
Symmetry codes: (i) −x+2, −y+2, −z+1; (ii) −x+1, −y+2, −z+1; (iii) −x+2, −y+2, −z; (iv) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H3···O24v0.89 (2)1.95 (2)2.824 (4)168 (6)
N2—H5···O3vi0.92 (2)1.82 (3)2.709 (5)162 (7)
N1—H2···O23vii0.897 (19)2.07 (2)2.965 (4)175 (5)
N2—H4···O13v0.90 (2)1.96 (5)2.716 (4)140 (6)
N1—H1···O11viii0.88 (2)2.12 (2)2.981 (4)167 (5)
O2—H21···O1iv0.82 (2)1.94 (3)2.737 (4)163 (7)
O2—H22···O22ix0.83 (2)2.07 (3)2.868 (4)162 (7)
O3—H31···O12viii0.835 (19)1.93 (2)2.741 (4)164 (5)
O3—H32···O140.814 (19)2.11 (3)2.875 (4)156 (5)
O1—H12···O21ix0.93 (5)1.76 (5)2.684 (3)174 (4)
O1—H11···N10.82 (5)2.00 (5)2.814 (4)171 (5)
Symmetry codes: (iv) x+1, y, z; (v) x−1, y−1, z; (vi) x−1, y, z; (vii) x, y−1, z; (viii) −x+1, −y+1, −z+1; (ix) −x+1, −y+1, −z.
 

Acknowledgements

Financial support obtained from the Ministry of Science and Higher Education is gratefully acknowledged.

References

First citationKuma (1996). KM-4 Software. Kuma Diffraction Ltd. Wrocław, Poland.  Google Scholar
 First citationKuma (2001). DATAPROC. Kuma Diffraction Ltd. Wrocław, Poland.  Google Scholar
 First citationOxford Diffraction (2008). CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.  Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationStarosta, W. & Leciejewicz, J. (2008). Acta Cryst. E64, o461.  Web of Science CSD CrossRef IUCr Journals Google Scholar
 First citationStarosta, W. & Leciejewicz, J. (2010). Acta Cryst. E66, m1362–m1363.  Web of Science CSD CrossRef IUCr Journals Google Scholar
 First citationStarosta, W. & Leciejewicz, J. (2011). Acta Cryst. E67, m1455–m1456.  Web of Science CSD CrossRef IUCr Journals Google Scholar
 First citationStarosta, W. & Leciejewicz, J. (2012). Acta Cryst. E68, m324–m325.  CSD CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 68| Part 4| April 2012| Pages m496-m497
doi:10.1107/S1600536812012743
Follow Acta Cryst. E
Sign up for e-alerts
E-alerts
Follow Acta Cryst. on Twitter
Twitter
Follow us on facebook
Facebook
Sign up for RSS feeds
RSS