Bis(hydrazin-1-ium) bis­(μ2-pyridazine-3,6-dicarboxyl­ato)bis­(aqua­lithiate) octa­aqua­bis­(μ3-pyridazine-3,6-dicarboxyl­ato)tetra­lithium

Starosta, W.; Leciejewicz, J.

doi:10.1107/S1600536812007192

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Pages m324-m325

doi:10.1107/S1600536812007192

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Bis(hydrazin-1-ium) bis(μ₂-pyridazine-3,6-dicarboxylato)bis(aqualithiate) octaaquabis(μ₃-pyridazine-3,6-dicarboxylato)tetralithium

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 24 January 2012; accepted 17 February 2012; online 24 February 2012)

The unit cell of the title compound, (N₂H₅)₂[Li₂(C₆H₂N₂O₄)₂(H₂O)₂]·[Li₄(C₆H₂N₂O₄)₂(H₂O)₈], comprises two centrosymmetric complexes, one double negatively charged and one neutral, and two mono-protonated hydrazine cations. The anionic complex molecule is a dimer, built of a pair of symmetry-related pyridazine-3,6-dicarboxylate ligands and a pair of Li^I ions, each coordinated by two N,O-chelating sites donated by a ligand molecule and an aqua O atom at the apical position. The pentacoordination around the Li^I ions is partway between a trigonal–bipyramidal and a square-pyramidal arrangement. The two carboxylic acid groups of the ligand are deprotonated and one carboxylate O atom of each group is not involved in the coordination, and this applies to both the anionic and the neutral complex. The neutral complex molecule is also composed of a pair of Li^I ions and a pair of ligand molecules related by a centre of symmetry. They form a dimeric core in which the pentacoordination of the Li^I ions includes two N,O-bonding groups donated by two ligands and an aqua O atom. The pentacoordination is described as partway between a trigonal–bipyramidal and a square-pyramidal arrangement. The coordinated carboxylate group is bidentate–bridging, forming with an Li(H₂O)₃ unit a neutral tetrameric molecule. The coordination of the tetracoordinated Li^I ion shows a slightly distorted tetrahedral geometry. An extended system of O—H⋯O and N—H⋯O hydrogen bonds contributes to the stability of the crystal structure.

Related literature

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

Experimental

Crystal data

(N₂H₅)₂[Li₂(C₆H₂N₂O₄)₂(H₂O)₂]·[Li₄(C₆H₂N₂O₄)₂(H₂O)₈]
M_r = 952.30
Triclinic, $[P \overline 1]$
a = 7.0999 (14) Å
b = 7.2390 (14) Å
c = 22.608 (5) Å
α = 86.40 (3)°
β = 87.68 (3)°
γ = 61.49 (3)°
V = 1018.9 (3) Å³
Z = 1
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 293 K
0.72 × 0.35 × 0.11 mm

Data collection

Kuma KM-4 four-circle diffractometer
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis RED. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ) T_min = 0.970, T_max = 0.985
5515 measured reflections
5058 independent reflections
3362 reflections with I > 2σ(I)
R_int = 0.090
3 standard reflections every 200 reflections intensity decay: 5.8%

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.204
S = 1.05
5058 reflections
383 parameters
All H -atom parameters refined
Δρ_max = 0.63 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Table 1
Selected bond lengths (Å)

Li1—O11ⁱ	2.011 (4)
Li1—N11ⁱ	2.185 (4)
Li1—N12	2.209 (4)
Li1—O13	1.999 (4)
Li1—O15	1.961 (5)
Li2—O21	1.998 (4)
Li2—N22	2.175 (5)
Li2—O25	1.974 (4)
Li2—O24ⁱⁱ	2.023 (5)
Li2—N21ⁱⁱ	2.170 (4)
Li3—O21	1.951 (5)
Li3—O3	2.019 (5)
Li3—O2	1.926 (4)
Li3—O1	1.954 (4)
Symmetry codes: (i) -x, -y+2, -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
O25—H252⋯O22ⁱⁱⁱ	0.90 (4)	1.87 (4)	2.752 (3)	168 (3)
O1—H11⋯O23^iv	0.74 (4)	2.10 (4)	2.832 (3)	173 (4)
N1—H1⋯O3	1.01 (4)	1.99 (4)	2.972 (3)	164 (3)
O2—H21⋯O23^v	0.83 (3)	2.07 (3)	2.889 (3)	171 (3)
O2—H22⋯O11^vi	0.81 (4)	1.88 (4)	2.691 (3)	172 (4)
N1—H2⋯O22ⁱⁱⁱ	0.91 (3)	1.97 (4)	2.826 (3)	156 (3)
O3—H32⋯O24ⁱⁱ	0.94 (3)	1.71 (3)	2.635 (2)	165 (3)
N1—H3⋯O13	0.89 (4)	1.84 (4)	2.720 (3)	174 (3)
O15—H152⋯O12^vii	0.86 (5)	1.92 (5)	2.755 (3)	162 (5)
O15—H151⋯O14^viii	0.79 (4)	2.04 (4)	2.790 (3)	160 (4)
O3—H31⋯O14^ix	0.71 (4)	2.14 (4)	2.833 (3)	165 (4)
O1—H12⋯O12^x	0.83 (4)	2.06 (4)	2.839 (3)	155 (3)
Symmetry codes: (ii) -x, -y+1, -z; (iii) x, y+1, z; (iv) -x+1, -y, -z; (v) -x, -y, -z; (vi) -x, -y+1, -z+1; (vii) -x+1, -y+2, -z+1; (viii) x-1, y+1, z; (ix) x-1, y, z; (x) -x+1, -y+1, -z+1.

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/S1600536812007192/kp2385sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812007192/kp2385Isup2.hkl

checkCIF report

Comment top

The structure of the original Li^I complex with pyridazine-3,6-dicarboxylate and water ligands was reported to consist of molecular ribbons in which Li^I ions are octahedrally coordinated by two fully deprotonated ligand molecules and two aqua O atoms are bridged by protons located in a centre of symmetry (Starosta & Leciejewicz, 2010). Removal of these protons by adding a few drops of hydrazine resulted in a two-dimensional catenated polymeric structure (Starosta & Leciejewicz, 2011). When few more drops of hydrazine were added to the aqueous solution of the original complex, crystals of a new compound with a triclinic centrosymmetric structure were identified. This structure is built of two mono protonated hydrazine cations, a centrosymmetric dimeric anion and a neutral centrosymmetric tetrameric molecule. The dimeric anion consists of pairs of symmetry related: Li^I ions, fully deprotonated ligand molecules and water O15 atom (Fig. 1). The Li1 ion, coordinated by two N,O bonding groups donated by two ligands and the aqua O15 atom shows transition from a distorted trigonal–bipyramidal geometry [with an equatorial plane composed of O13, N11ⁱⁱ and O15 atoms with r.m.s. of 0.0059 (1) Å, the Li1 ion is 0.0119 (1) Å out of this plane, N12 and O11ⁱⁱ atoms are at axial positions; symmetry code: ⁱ -x, -y + 1, -z; ⁱⁱ -x, -y + 2, -z + 1] to a square-pyramidal geometry [where the aqua O15 is at the apical position]. The pyridazine ring is planar (r.m.s. of 0.0017 (1) Å); carboxylate groups C17/O11/O12 and C18/O13/O14 make with it dihedral angles of 1.4 (1)° and 1.7 (1)°, respectively. An anionic dimer constitutes the core of the other complex molecule. The coordination of the Li2 ion can be described by transition from trigonal–bipyramidal arrrangement [N22, O24ⁱ and O25 atoms form the equatorial plane, r.m.s. 0.0044 (1) Å, the Li2 ion is 0.0088 (1) Å out of the equatorial plane; O21 and N21ⁱ are at the apices] to the square-pyramdidal one [with the water O25 at the apical position]. The pyridazine ring is planar [r.m.s. 0.0009 (1) Å]; the carboxylate C27/O21/O22 and C28/O23/O24 groups make with it dihedral angles of 5.9 (1)° and 0.7 (1)°, respectively. In contrast to the anion complex, the carboxylato O21 atom in the neutral complex molecule acts as bidentate bridging to a Li(H₂O)₃ group completing a tetranuclear molecule. The coordination environment of the Li3 ion formed by the O1, O2, O3 and O21 atoms is distorted tetrahedral. Pyridazine ring planes of the anion and the tetrameric molecule are inclined by an angle of 65.7 (1)° each to the other (Fig. 2). The observed Li—O and Li—N bond distances (Table 1) are close to those reported in two other Li^I complexes with the title ligand (Starosta & Leciejewicz, 2010, 2011). Bond distances in the protonated hydrazine cations are almost the same as those reported in the structure of an hydrazine adduct of the pyridazine-3,6-dicarboxylate acid (Starosta & Leciejewicz, 2008). An extended hydrogen bond system in which coordinated water molecules act as donors, carboxylate O atoms are as acceptors contributes to the stability of the structure (Table 2).

Related literature top

For the crystal structures of Li^I complexes with pyridazine-3,6-dicarboxylate and water ligands, see: Starosta & Leciejewicz (2010); Starosta & Leciejewicz (2011). The structure of a hydrazine adduct of pyridazine-3,6-dicarboxylic acid was reported by Starosta & Leciejewicz (2008).

Experimental top

Single crystals of the compound obtained earlier (Starosta & Leciejewicz, 2010) were dissolved in warm water. Few drops of hydrazine were then added and the solution was stirred for 3 h without heating. Left to crystallize at room temperature, single-crystal blocks of the title compound were found after three days. They were washed with cold ethanol and dried in 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. Structural units of the title compound with atom labelling scheme and 50% probability displacement ellipsoids. Symmetry code: ⁱ -x, -y + 1, -z; ⁱⁱ -x, -y + 2, -z + 1.
	Fig. 2. Crystal packing of the title compound.

Bis(hydrazin-1-ium) bis(µ₂-pyridazine-3,6-dicarboxylato)bis(aqualithiate) octaaquabis(µ₃-pyridazine-3,6-dicarboxylato)tetralithium top

Crystal data top

(N₂H₅)₂[Li₂(C₆H₂N₂O₄)₂(H₂O)₂]·[Li₄(C₆H₂N₂O₄)₂(H₂O)₈]	Z = 1
M_r = 952.30	F(000) = 492
Triclinic, P1	D_x = 1.552 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.0999 (14) Å	Cell parameters from 25 reflections
b = 7.2390 (14) Å	θ = 6–15°
c = 22.608 (5) Å	µ = 0.14 mm⁻¹
α = 86.40 (3)°	T = 293 K
β = 87.68 (3)°	Block, colourless
γ = 61.49 (3)°	0.72 × 0.35 × 0.11 mm
V = 1018.9 (3) Å³

Data collection top

Kuma KM-4 four-circle diffractometer	3362 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.090
Graphite monochromator	θ_max = 30.1°, θ_min = 1.8°
profile data from ω/2θ scans	h = −10→9
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008)	k = −9→10
T_min = 0.970, T_max = 0.985	l = −31→0
5515 measured reflections	3 standard reflections every 200 reflections
5058 independent reflections	intensity decay: 5.8%

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.204	All H-atom parameters refined
S = 1.05	w = 1/[σ²(F_o²) + (0.1491P)² + 0.1309P] where P = (F_o² + 2F_c²)/3
5058 reflections	(Δ/σ)_max < 0.001
383 parameters	Δρ_max = 0.63 e Å⁻³
0 restraints	Δρ_min = −0.41 e Å⁻³

Crystal data top

(N₂H₅)₂[Li₂(C₆H₂N₂O₄)₂(H₂O)₂]·[Li₄(C₆H₂N₂O₄)₂(H₂O)₈]	γ = 61.49 (3)°
M_r = 952.30	V = 1018.9 (3) Å³
Triclinic, P1	Z = 1
a = 7.0999 (14) Å	Mo Kα radiation
b = 7.2390 (14) Å	µ = 0.14 mm⁻¹
c = 22.608 (5) Å	T = 293 K
α = 86.40 (3)°	0.72 × 0.35 × 0.11 mm
β = 87.68 (3)°

Data collection top

Kuma KM-4 four-circle diffractometer	3362 reflections with I > 2σ(I)
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008)	R_int = 0.090
T_min = 0.970, T_max = 0.985	3 standard reflections every 200 reflections
5515 measured reflections	intensity decay: 5.8%
5058 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.204	All H-atom parameters refined
S = 1.05	Δρ_max = 0.63 e Å⁻³
5058 reflections	Δρ_min = −0.41 e Å⁻³
383 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
O21	0.0159 (3)	0.2157 (2)	0.13963 (7)	0.0274 (4)
N22	0.1040 (3)	0.2333 (3)	0.02543 (8)	0.0215 (4)
O23	0.4250 (3)	−0.0353 (3)	−0.15562 (7)	0.0304 (4)
O3	−0.1383 (3)	0.5109 (3)	0.25070 (8)	0.0318 (4)
O25	0.2519 (3)	0.4707 (3)	0.11076 (8)	0.0336 (4)
N21	0.1517 (3)	0.2519 (3)	−0.03187 (8)	0.0220 (4)
C26	0.2698 (3)	0.0806 (3)	−0.06167 (9)	0.0203 (4)
O22	0.1593 (3)	−0.1328 (2)	0.14161 (7)	0.0349 (4)
O24	0.2395 (3)	0.3096 (3)	−0.14339 (7)	0.0375 (4)
O2	−0.1801 (3)	0.0810 (3)	0.24722 (9)	0.0345 (4)
O1	0.2959 (3)	0.0402 (3)	0.24937 (9)	0.0383 (4)
C23	0.1751 (3)	0.0428 (3)	0.05183 (9)	0.0202 (4)
C28	0.1110 (3)	0.0413 (3)	0.11678 (9)	0.0211 (4)
C27	0.3165 (3)	0.1207 (3)	−0.12582 (10)	0.0233 (4)
C25	0.3482 (4)	−0.1221 (3)	−0.03609 (10)	0.0274 (5)
C24	0.2987 (4)	−0.1410 (3)	0.02252 (10)	0.0281 (5)
Li2	−0.0167 (6)	0.4703 (6)	0.09159 (18)	0.0287 (8)
Li3	−0.0032 (6)	0.2106 (6)	0.22601 (19)	0.0316 (8)
H251	0.322 (5)	0.391 (5)	0.1328 (14)	0.037 (8)*
H252	0.240 (6)	0.591 (6)	0.1232 (16)	0.062 (11)*
O14	0.5966 (3)	0.5737 (3)	0.35267 (7)	0.0347 (4)
O11	0.2464 (3)	0.9984 (3)	0.63816 (7)	0.0324 (4)
N12	0.2675 (3)	0.8464 (3)	0.47199 (8)	0.0219 (4)
O13	0.2417 (2)	0.7613 (3)	0.36274 (7)	0.0335 (4)
O12	0.6015 (3)	0.8204 (3)	0.64806 (8)	0.0380 (5)
N11	0.2686 (3)	0.8936 (3)	0.52789 (8)	0.0225 (4)
C18	0.4299 (3)	0.6839 (3)	0.38075 (9)	0.0224 (4)
C13	0.4527 (3)	0.7290 (3)	0.44400 (9)	0.0207 (4)
O15	−0.0044 (3)	1.2454 (3)	0.38668 (10)	0.0399 (5)
C16	0.4544 (3)	0.8219 (3)	0.55577 (9)	0.0215 (4)
C17	0.4323 (3)	0.8865 (4)	0.61943 (9)	0.0243 (4)
C14	0.6502 (3)	0.6519 (4)	0.47109 (11)	0.0291 (5)
C15	0.6512 (3)	0.6996 (4)	0.52851 (11)	0.0303 (5)
Li1	−0.0007 (6)	0.9775 (6)	0.40901 (18)	0.0282 (8)
N1	0.1858 (3)	0.6592 (3)	0.25346 (9)	0.0293 (4)
N2	0.3797 (4)	0.4809 (5)	0.23783 (15)	0.0537 (8)
H11	0.361 (6)	0.048 (5)	0.2240 (16)	0.045 (10)*
H4	0.451 (8)	0.543 (8)	0.225 (2)	0.088 (17)*
H1	0.069 (7)	0.618 (6)	0.2603 (18)	0.071 (12)*
H21	−0.243 (5)	0.073 (5)	0.2182 (15)	0.036 (8)*
H22	−0.197 (6)	0.046 (6)	0.2811 (18)	0.055 (10)*
H2	0.149 (6)	0.758 (5)	0.2232 (16)	0.051 (9)*
H32	−0.197 (5)	0.591 (5)	0.2153 (15)	0.041 (8)*
H3	0.211 (6)	0.694 (5)	0.2879 (16)	0.050 (9)*
H152	0.108 (8)	1.237 (8)	0.369 (2)	0.099 (17)*
H151	−0.100 (7)	1.343 (7)	0.3705 (18)	0.067 (12)*
H31	−0.219 (7)	0.545 (6)	0.2730 (19)	0.061 (13)*
H25	0.447 (5)	−0.246 (4)	−0.0595 (12)	0.029 (7)*
H24	0.350 (4)	−0.279 (4)	0.0450 (12)	0.025 (6)*
H15	0.774 (6)	0.660 (5)	0.5505 (17)	0.063 (11)*
H14	0.775 (5)	0.573 (4)	0.4502 (13)	0.030 (7)*
H12	0.348 (6)	0.042 (5)	0.2814 (17)	0.051 (10)*
H5	0.447 (9)	0.442 (8)	0.270 (2)	0.103 (17)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O21	0.0347 (9)	0.0229 (7)	0.0225 (8)	−0.0123 (7)	0.0064 (6)	−0.0037 (6)
N22	0.0231 (8)	0.0228 (8)	0.0165 (8)	−0.0094 (7)	0.0007 (6)	−0.0012 (6)
O23	0.0292 (8)	0.0322 (8)	0.0228 (8)	−0.0088 (7)	0.0082 (6)	−0.0074 (6)
O3	0.0324 (9)	0.0361 (9)	0.0217 (9)	−0.0124 (7)	0.0042 (7)	−0.0010 (7)
O25	0.0336 (9)	0.0267 (8)	0.0353 (10)	−0.0098 (7)	−0.0041 (8)	−0.0022 (7)
N21	0.0215 (8)	0.0230 (8)	0.0177 (8)	−0.0078 (7)	0.0030 (6)	−0.0012 (6)
C26	0.0178 (9)	0.0235 (9)	0.0179 (9)	−0.0083 (7)	0.0010 (7)	−0.0026 (7)
O22	0.0538 (11)	0.0249 (8)	0.0243 (8)	−0.0179 (8)	0.0047 (8)	0.0002 (6)
O24	0.0456 (10)	0.0296 (8)	0.0219 (8)	−0.0065 (7)	0.0096 (7)	0.0020 (6)
O2	0.0310 (9)	0.0528 (11)	0.0251 (9)	−0.0248 (8)	0.0013 (7)	0.0000 (8)
O1	0.0292 (9)	0.0622 (12)	0.0263 (10)	−0.0241 (9)	0.0030 (8)	−0.0047 (9)
C23	0.0193 (9)	0.0228 (9)	0.0189 (9)	−0.0104 (8)	0.0011 (8)	−0.0011 (8)
C28	0.0232 (10)	0.0267 (10)	0.0153 (9)	−0.0134 (8)	0.0014 (7)	−0.0019 (8)
C27	0.0188 (9)	0.0268 (10)	0.0210 (10)	−0.0082 (8)	0.0027 (8)	−0.0032 (8)
C25	0.0287 (11)	0.0217 (10)	0.0246 (11)	−0.0061 (8)	0.0059 (9)	−0.0052 (8)
C24	0.0295 (11)	0.0228 (10)	0.0268 (11)	−0.0089 (8)	0.0038 (9)	0.0017 (8)
Li2	0.0308 (19)	0.0224 (17)	0.0280 (19)	−0.0087 (15)	0.0019 (15)	−0.0027 (15)
Li3	0.029 (2)	0.0324 (19)	0.033 (2)	−0.0146 (16)	0.0025 (16)	−0.0038 (16)
O14	0.0218 (8)	0.0426 (9)	0.0248 (9)	−0.0027 (7)	0.0027 (6)	−0.0083 (7)
O11	0.0196 (7)	0.0527 (10)	0.0222 (8)	−0.0143 (7)	0.0040 (6)	−0.0104 (7)
N12	0.0160 (8)	0.0299 (9)	0.0169 (8)	−0.0082 (7)	0.0005 (6)	−0.0048 (7)
O13	0.0183 (7)	0.0449 (10)	0.0254 (8)	−0.0040 (7)	−0.0036 (6)	−0.0120 (7)
O12	0.0205 (8)	0.0692 (13)	0.0245 (9)	−0.0206 (8)	−0.0019 (6)	−0.0093 (8)
N11	0.0157 (8)	0.0320 (9)	0.0186 (8)	−0.0103 (7)	0.0002 (6)	−0.0028 (7)
C18	0.0184 (9)	0.0268 (10)	0.0172 (9)	−0.0066 (8)	0.0004 (7)	−0.0039 (8)
C13	0.0163 (9)	0.0248 (9)	0.0196 (9)	−0.0085 (8)	0.0007 (7)	−0.0015 (7)
O15	0.0194 (8)	0.0408 (10)	0.0521 (12)	−0.0096 (7)	0.0010 (8)	0.0071 (9)
C16	0.0171 (9)	0.0310 (10)	0.0184 (9)	−0.0130 (8)	−0.0008 (7)	−0.0004 (8)
C17	0.0201 (10)	0.0371 (11)	0.0194 (10)	−0.0163 (9)	0.0010 (8)	−0.0035 (8)
C14	0.0144 (9)	0.0391 (12)	0.0269 (11)	−0.0062 (9)	0.0028 (8)	−0.0108 (9)
C15	0.0157 (10)	0.0441 (13)	0.0277 (11)	−0.0108 (9)	−0.0044 (8)	−0.0052 (10)
Li1	0.0137 (15)	0.0357 (19)	0.0287 (19)	−0.0063 (14)	0.0018 (14)	−0.0058 (15)
N1	0.0310 (10)	0.0318 (10)	0.0241 (10)	−0.0137 (8)	−0.0041 (8)	−0.0015 (8)
N2	0.0390 (14)	0.0484 (15)	0.0519 (17)	−0.0006 (12)	−0.0123 (12)	−0.0173 (12)

Geometric parameters (Å, º) top

Li1—O11ⁱ	2.011 (4)	O1—H11	0.74 (4)
Li1—N11ⁱ	2.185 (4)	O1—H12	0.83 (4)
Li1—N12	2.209 (4)	C23—C24	1.389 (3)
Li1—O13	1.999 (4)	C23—C28	1.521 (3)
Li1—O15	1.961 (5)	C25—C24	1.372 (3)
N11—Li1ⁱ	2.185 (4)	C25—H25	1.00 (3)
O21—C28	1.247 (3)	C24—H24	0.99 (3)
Li2—O21	1.998 (4)	Li3—H11	2.27 (4)
Li2—N22	2.175 (5)	O14—C18	1.242 (3)
Li2—O25	1.974 (4)	O11—C17	1.247 (3)
N21—Li2ⁱⁱ	2.170 (4)	O11—Li1ⁱ	2.011 (4)
O24—Li2ⁱⁱ	2.023 (5)	N12—N11	1.331 (3)
Li2—O24ⁱⁱ	2.023 (5)	N12—C13	1.336 (3)
Li2—N21ⁱⁱ	2.170 (4)	O13—C18	1.251 (2)
Li3—O21	1.951 (5)	O12—C17	1.252 (2)
Li3—O3	2.019 (5)	N11—C16	1.334 (2)
Li3—O2	1.926 (4)	C18—C13	1.518 (3)
Li3—O1	1.954 (4)	C13—C14	1.390 (3)
N22—C23	1.330 (2)	O15—H152	0.86 (5)
N22—N21	1.340 (2)	O15—H151	0.79 (4)
O23—C27	1.243 (3)	C16—C15	1.391 (3)
O3—H32	0.94 (3)	C16—C17	1.520 (3)
O3—H31	0.71 (4)	C14—C15	1.366 (3)
O25—H251	0.73 (3)	C14—H14	0.92 (3)
O25—H252	0.90 (4)	C15—H15	0.93 (4)
N21—C26	1.327 (3)	N1—N2	1.417 (3)
C26—C25	1.392 (3)	N1—H1	1.01 (4)
C26—C27	1.516 (3)	N1—H2	0.91 (3)
O22—C28	1.239 (2)	N1—H3	0.89 (4)
O24—C27	1.250 (3)	N2—H4	0.86 (5)
O2—H21	0.83 (3)	N2—H5	0.85 (5)
O2—H22	0.81 (4)

C28—O21—Li3	116.39 (18)	O21—Li3—O3	107.8 (2)
C28—O21—Li2	118.44 (18)	O1—Li3—O3	113.9 (2)
Li3—O21—Li2	121.83 (18)	O2—Li3—H11	126.4 (9)
C23—N22—N21	119.55 (19)	O21—Li3—H11	86.0 (9)
C23—N22—Li2	109.87 (17)	O1—Li3—H11	18.2 (9)
N21—N22—Li2	129.03 (16)	O3—Li3—H11	113.5 (9)
Li3—O3—H32	103.6 (19)	C17—O11—Li1ⁱ	118.19 (19)
Li3—O3—H31	119 (3)	N11—N12—C13	119.78 (16)
H32—O3—H31	109 (4)	N11—N12—Li1	128.99 (17)
Li2—O25—H251	118 (2)	C13—N12—Li1	110.42 (16)
Li2—O25—H252	117 (2)	C18—O13—Li1	120.27 (18)
H251—O25—H252	103 (3)	N12—N11—C16	119.80 (19)
C26—N21—N22	119.84 (16)	N12—N11—Li1ⁱ	128.45 (16)
C26—N21—Li2ⁱⁱ	110.64 (17)	C16—N11—Li1ⁱ	110.42 (17)
N22—N21—Li2ⁱⁱ	128.61 (18)	O14—C18—O13	126.8 (2)
N21—C26—C25	122.8 (2)	O14—C18—C13	117.63 (18)
N21—C26—C27	115.22 (17)	O13—C18—C13	115.53 (19)
C25—C26—C27	122.0 (2)	N12—C13—C14	122.5 (2)
C27—O24—Li2ⁱⁱ	118.10 (18)	N12—C13—C18	114.71 (16)
Li3—O2—H21	112 (2)	C14—C13—C18	122.8 (2)
Li3—O2—H22	123 (3)	Li1—O15—H152	116 (3)
H21—O2—H22	124 (3)	Li1—O15—H151	125 (3)
Li3—O1—H11	106 (3)	H152—O15—H151	104 (4)
Li3—O1—H12	126 (2)	N11—C16—C15	122.6 (2)
H11—O1—H12	112 (4)	N11—C16—C17	114.32 (19)
N22—C23—C24	122.77 (19)	C15—C16—C17	123.10 (18)
N22—C23—C28	114.86 (19)	O11—C17—O12	126.4 (2)
C24—C23—C28	122.37 (17)	O11—C17—C16	116.52 (17)
O22—C28—O21	126.7 (2)	O12—C17—C16	117.0 (2)
O22—C28—C23	116.8 (2)	C15—C14—C13	117.7 (2)
O21—C28—C23	116.54 (17)	C15—C14—H14	122.2 (17)
O23—C27—O24	126.6 (2)	C13—C14—H14	120.0 (17)
O23—C27—C26	117.45 (18)	C14—C15—C16	117.62 (18)
O24—C27—C26	115.9 (2)	C14—C15—H15	125 (2)
C24—C25—C26	117.3 (2)	C16—C15—H15	117 (2)
C24—C25—H25	122.9 (15)	O15—Li1—O13	105.5 (2)
C26—C25—H25	119.6 (15)	O15—Li1—O11ⁱ	101.59 (18)
C25—C24—C23	117.70 (18)	O13—Li1—O11ⁱ	98.88 (19)
C25—C24—H24	123.4 (16)	O15—Li1—N11ⁱ	96.05 (18)
C23—C24—H24	118.9 (16)	O13—Li1—N11ⁱ	158.4 (2)
O25—Li2—O21	100.71 (18)	O11ⁱ—Li1—N11ⁱ	77.42 (14)
O25—Li2—O24ⁱⁱ	103.7 (2)	O15—Li1—N12	98.91 (18)
O21—Li2—O24ⁱⁱ	97.81 (19)	O13—Li1—N12	76.75 (14)
O25—Li2—N21ⁱⁱ	98.65 (18)	O11ⁱ—Li1—N12	159.5 (2)
O21—Li2—N21ⁱⁱ	160.6 (2)	N11ⁱ—Li1—N12	99.15 (17)
O24ⁱⁱ—Li2—N21ⁱⁱ	77.55 (14)	N2—N1—H1	110 (2)
O25—Li2—N22	99.76 (19)	N2—N1—H2	108 (2)
O21—Li2—N22	78.43 (14)	H1—N1—H2	110 (3)
O24ⁱⁱ—Li2—N22	156.5 (2)	N2—N1—H3	105 (2)
N21ⁱⁱ—Li2—N22	98.24 (17)	H1—N1—H3	107 (3)
O2—Li3—O21	105.5 (2)	H2—N1—H3	116 (3)
O2—Li3—O1	113.9 (2)	N1—N2—H4	99 (3)
O21—Li3—O1	102.8 (2)	N1—N2—H5	103 (4)
O2—Li3—O3	112.0 (2)	H4—N2—H5	93 (4)

Symmetry codes: (i) −x, −y+2, −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
O25—H252···O22ⁱⁱⁱ	0.90 (4)	1.87 (4)	2.752 (3)	168 (3)
O1—H11···O23^iv	0.74 (4)	2.10 (4)	2.832 (3)	173 (4)
N1—H1···O3	1.01 (4)	1.99 (4)	2.972 (3)	164 (3)
O2—H21···O23^v	0.83 (3)	2.07 (3)	2.889 (3)	171 (3)
O2—H22···O11^vi	0.81 (4)	1.88 (4)	2.691 (3)	172 (4)
N1—H2···O22ⁱⁱⁱ	0.91 (3)	1.97 (4)	2.826 (3)	156 (3)
O3—H32···O24ⁱⁱ	0.94 (3)	1.71 (3)	2.635 (2)	165 (3)
N1—H3···O13	0.89 (4)	1.84 (4)	2.720 (3)	174 (3)
O15—H152···O12^vii	0.86 (5)	1.92 (5)	2.755 (3)	162 (5)
O15—H151···O14^viii	0.79 (4)	2.04 (4)	2.790 (3)	160 (4)
O3—H31···O14^ix	0.71 (4)	2.14 (4)	2.833 (3)	165 (4)
O1—H12···O12^x	0.83 (4)	2.06 (4)	2.839 (3)	155 (3)

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

Experimental details

Crystal data
Chemical formula	(N₂H₅)₂[Li₂(C₆H₂N₂O₄)₂(H₂O)₂]·[Li₄(C₆H₂N₂O₄)₂(H₂O)₈]
M_r	952.30
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.0999 (14), 7.2390 (14), 22.608 (5)
α, β, γ (°)	86.40 (3), 87.68 (3), 61.49 (3)
V (Å³)	1018.9 (3)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.14
Crystal size (mm)	0.72 × 0.35 × 0.11

Data collection
Diffractometer	Kuma KM-4 four-circle diffractometer
Absorption correction	Analytical (CrysAlis RED; Oxford Diffraction, 2008)
T_min, T_max	0.970, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	5515, 5058, 3362
R_int	0.090
(sin θ/λ)_max (Å⁻¹)	0.705

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.204, 1.05
No. of reflections	5058
No. of parameters	383
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.63, −0.41

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—O11ⁱ	2.011 (4)	Li2—O25	1.974 (4)
Li1—N11ⁱ	2.185 (4)	Li2—O24ⁱⁱ	2.023 (5)
Li1—N12	2.209 (4)	Li2—N21ⁱⁱ	2.170 (4)
Li1—O13	1.999 (4)	Li3—O21	1.951 (5)
Li1—O15	1.961 (5)	Li3—O3	2.019 (5)
Li2—O21	1.998 (4)	Li3—O2	1.926 (4)
Li2—N22	2.175 (5)	Li3—O1	1.954 (4)

Symmetry codes: (i) −x, −y+2, −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
O25—H252···O22ⁱⁱⁱ	0.90 (4)	1.87 (4)	2.752 (3)	168 (3)
O1—H11···O23^iv	0.74 (4)	2.10 (4)	2.832 (3)	173 (4)
N1—H1···O3	1.01 (4)	1.99 (4)	2.972 (3)	164 (3)
O2—H21···O23^v	0.83 (3)	2.07 (3)	2.889 (3)	171 (3)
O2—H22···O11^vi	0.81 (4)	1.88 (4)	2.691 (3)	172 (4)
N1—H2···O22ⁱⁱⁱ	0.91 (3)	1.97 (4)	2.826 (3)	156 (3)
O3—H32···O24ⁱⁱ	0.94 (3)	1.71 (3)	2.635 (2)	165 (3)
N1—H3···O13	0.89 (4)	1.84 (4)	2.720 (3)	174 (3)
O15—H152···O12^vii	0.86 (5)	1.92 (5)	2.755 (3)	162 (5)
O15—H151···O14^viii	0.79 (4)	2.04 (4)	2.790 (3)	160 (4)
O3—H31···O14^ix	0.71 (4)	2.14 (4)	2.833 (3)	165 (4)
O1—H12···O12^x	0.83 (4)	2.06 (4)	2.839 (3)	155 (3)

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, Oxfordshire, 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. (2008). Acta Cryst. E64, o461. Web of Science CSD CrossRef IUCr Journals Google Scholar
Starosta, W. & Leciejewicz, J. (2010). Acta Cryst. E66, m1362–m1363. Web of Science CSD CrossRef IUCr Journals Google Scholar
Starosta, W. & Leciejewicz, J. (2011). Acta Cryst. E67, m1455–m1456. Web of Science CSD CrossRef IUCr Journals Google Scholar

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Pages m324-m325

doi:10.1107/S1600536812007192

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