Poly[di-μ2-aqua-μ2-(5-methyl­pyrazine-2-carboxyl­ato)-(5-methyl­pyrazine-2-carboxyl­ato)-μ3-nitrato-trilithium]

Starosta, W.; Leciejewicz, J.

doi:10.1107/S1600536811024548

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Pages m1000-m1001

doi:10.1107/S1600536811024548

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Poly[di-μ₂-aqua-μ₂-(5-methylpyrazine-2-carboxylato)-(5-methylpyrazine-2-carboxylato)-μ₃-nitrato-trilithium]

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 10 June 2011; accepted 22 June 2011; online 30 June 2011)

The asymmetric unit of the title compound, [Li₃(C₆H₅N₂O₂)₂(NO₃)(H₂O)₂]_n contains three Li^I ions, two ligand anions, two water molecules and a nitrate anion. Related by a centre of inversion, they form a centrosymmetric molecular cluster in which one of the Li^I ions shows trigonal–bipyramidal and the other two distorted tetrahedral coordination. Li^I ions are bridged by water O atoms and carboxylate O atoms donated by one of the ligands. The clusters, bridged by two nitrato O atoms, form molecular columns along [010], which are held together by O—H⋯O and O—H⋯N hydrogen bonds and π–π interactions [centroid–centroid distances = 3.694 (1) and 3.796 (1) Å].

Related literature

For the structure of a lithium complex with 3-aminopyrazine-2-carboxylate and aqua ligands, see: Starosta & Leciejewicz (2010 ). The structures of two complexes with pyridazine carboxylate ligands have been also determined, see: Starosta & Leciejewicz (2011a ,b ). For the structure of a Li^I complex with pyrimidine carboxylate and nitrate ligands, see: Starosta & Leciejewicz (2011c ).

Experimental

Crystal data

[Li₃(C₆H₅N₂O₂)₂(NO₃)(H₂O)₂]
M_r = 393.10
Monoclinic, P 2₁ /c
a = 13.0222 (1) Å
b = 7.2288 (1) Å
c = 18.5819 (2) Å
β = 100.760 (1)°
V = 1718.45 (3) Å³
Z = 4
Cu Kα radiation
μ = 1.10 mm⁻¹
T = 293 K
0.23 × 0.20 × 0.07 mm

Data collection

Oxford Diffraction Xcalibur Ruby diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.672, T_max = 1.000
15696 measured reflections
3215 independent reflections
2787 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.122
S = 1.07
3215 reflections
277 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Selected bond lengths (Å)

Li1—O11ⁱ	2.029 (3)
Li1—O11	2.039 (3)
Li1—O1	2.085 (3)
Li1—O4	2.114 (3)
Li1—N11	2.293 (3)
Li2—O12ⁱ	1.958 (3)
Li2—O4	1.965 (3)
Li2—O5	1.970 (3)
Li2—O2ⁱⁱ	2.163 (3)
Li3—O31	1.978 (3)
Li3—O5	2.025 (4)
Li3—O1	2.039 (3)
Li3—N31	2.117 (3)
Symmetry codes: (i) -x+2, -y, -z+2; (ii) x, y-1, z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H41⋯O32ⁱⁱⁱ	0.85 (2)	1.92 (2)	2.7449 (15)	165.3 (19)
O4—H42⋯N12^iv	0.85 (2)	2.03 (2)	2.8414 (17)	159.0 (19)
O5—H52⋯N32^v	0.84 (2)	2.05 (2)	2.8550 (17)	162 (2)
O5—H51⋯O31ⁱⁱⁱ	0.86 (2)	1.85 (2)	2.7055 (15)	172 (2)
Symmetry codes: (iii) -x+1, -y, -z+2; (iv) $[-x+2, y-{\script{1\over 2}}, -z+{\script{5\over 2}}]$ ; (v) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); 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

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811024548/kp2334sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811024548/kp2334Isup2.hkl

checkCIF report

Comment top

The asymmetric unit of the title compound contains three Li^I ions, two 5-methylpyrazine-2-carboxylate anions, two water molecules and a nitrate anion (Fig. 1). The coordination environment of the Li1 ion is composed of N11, O11ⁱ, O1, O4 and O11 atoms. The latter three form a base of a distorted trigonal bipyramid, N11,O11ⁱ atoms are at its apices. Li1 ion is 0.0097 (2)Å out of the basal plane. The Li2 ion is coordinated by water O4, O5, carboxylate O12ⁱ and nitrate O2ⁱⁱⁱ atoms which form a distorted tetrahedral coordination environment. The same distorted tetrahedral coordination geometry shows the Li3 ion sorrounded by N31, O31, O1 and O5 atoms. The observed Li—O and Li—N bond distances (Table 1) are typical of Li complexes with azine carboxylate ligands. Both methylpyrazine rings are planar with r.m.s. of 0.0074 (1)Å for ring 1 and 0.0069 (1)Å for ring 3; carboxylate groups C17/O11/O12 and C37/O31/O32 make with relevant rings dihedral angles of 11.2 (1)°, and 11,0(1)°, respectively. The nitrate anion is planar [r.m.s. 0.0002 (1) Å]. Its O1 atom acts as bidentate and bridges Li1 and Li3 ions, while the O2 atom chelates the Li2 ion. Nitrato O3 atom is not coordinated at all. Li1 and Li1ⁱ ions bridged by bidentate carboxylate O11 and O11ⁱ form a core of a centrosymmetric cluster composed of Li1 and Li3 ions bridged by bidentate nitrato O1 atom, Li1 and Li2 bridged by the aqua O4 atom, Li2 and Li3 bridged by the aqua O5 atom. The clusters bridged via nitrato O1 and O2 atoms, form molecular columns along the direction [010] and they are held together by a network of hydrogen bonds in which aqua O4 and O5 molecules are as donors and carboxylate O31 and O32 atoms are acceptors. π-π interactions between methylpyrazine rings of adjacent columns are defined: the centres of gravity of the ring (N11, C12, C13, N12, C15, C16) and its symmetry generated hetrerocyclic rings [2-x, -1/2+y,5/2-z; 2-x,1/2+y,5/2-z] both are separated by 3.694 (1) Å, and the ring (N31, C32, C33, N32, C35, C36) operated by symmetry [1-x, -1/2+y, 3/2-z; 1-x, 1/2+y, 3/2-z] generates two equal stacking contacts of 3.796 (1) Å (Fig. 2). However, their shifts are about 3.5 Å. Molecular columns composed of centrosymmetric dimers have been also observed in the structure of a Li^I complex with 3-aminopyrazine-2-carboxylate and water ligands (Starosta & Leciejewicz, 2010). Molecular layers built of centrosymmetric dimers have been reported in the structure of a complex with pyridazine-4-carboxylate and water ligands (Starosta & Leciejewicz, 2011a) while centrosymmetric molecular ribbons bridged by nitrate ions form double-layers in the structure of a complex with pyrimidine-2-carboxylate and nitrate ligands (Starosta & Leciejewicz, 2011b). On the other hand, monomeric molecules, in which a Li^I ion is chelated by ligand N,O bonding group and two aqua O atoms constitute the structure of a complex with pyridazine-3-carboxylate and water ligands (Starosta & Leciejewicz, 2011a).

Related literature top

For the structure of a lithium(I) complex with 3-aminopyrazine-2-carboxylate and aqua ligands, see: Starosta & Leciejewicz (2010). The structures of two complexes with pyridazine carboxylate ligands have been also determined, see: Starosta & Leciejewicz (2011a,b). For the structure of a Li^I complex with pyrimidine carboxylate and nitrate ligands, see: Starosta & Leciejewicz (2011c).

Experimental top

Hot aqueous solutions, one containig 1 mmol of 5-methylpyrazine-2-carboxylic acid (Aldrich), the other 1 mmol of lithium (I) nitrate were mixed and boiled under reflux with constant stirring for 5 h. Left for evaporation at room temperature. After a couple of days yellow single-crystal plates of the title complex deposited on the bottom of a crystallization pot. Crystals were washed with cold ethanol and dried in air.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); 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 dimeric structural unit of the title compound with atom labelling scheme and 50% probability displacement ellipsoids. Symmetry code: (i) -x + 2, -y, -z + 2; (ii) x, y - 1, z; (iii) x, y + 1, z.
	Fig. 2. The alignment of the polyhedra columns in the unit cell.

Poly[di-µ₂-aqua-µ₂-(5-methylpyrazine-2-carboxylato)- (5-methylpyrazine-2-carboxylato)-µ₃-nitrato-trilithium] top

Crystal data top

[Li₃(C₆H₅N₂O₂)₂(NO₃)(H₂O)₂]	Z = 4
M_r = 393.10	F(000) = 808
Monoclinic, P2₁/c	D_x = 1.519 Mg m⁻³
Hall symbol: -P 2ybc	Cu Kα radiation, λ = 1.54184 Å
a = 13.0222 (1) Å	µ = 1.10 mm⁻¹
b = 7.2288 (1) Å	T = 293 K
c = 18.5819 (2) Å	Plate, yellow
β = 100.760 (1)°	0.23 × 0.20 × 0.07 mm
V = 1718.45 (3) Å³

Data collection top

Oxford Diffraction Xcalibur Ruby diffractometer	3215 independent reflections
Radiation source: Enhance (Cu) X-ray Source	2787 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
Detector resolution: 10.4922 pixels mm^-1	θ_max = 70.1°, θ_min = 3.5°
ω scans	h = −15→15
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −8→7
T_min = 0.672, T_max = 1.000	l = −22→22
15696 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)] = 0.040	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) + (0.0709P)² + 0.484P] where P = (F_o² + 2F_c²)/3
3215 reflections	(Δ/σ)_max = 0.001
277 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

[Li₃(C₆H₅N₂O₂)₂(NO₃)(H₂O)₂]	V = 1718.45 (3) Å³
M_r = 393.10	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 13.0222 (1) Å	µ = 1.10 mm⁻¹
b = 7.2288 (1) Å	T = 293 K
c = 18.5819 (2) Å	0.23 × 0.20 × 0.07 mm
β = 100.760 (1)°

Data collection top

Oxford Diffraction Xcalibur Ruby diffractometer	3215 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	2787 reflections with I > 2σ(I)
T_min = 0.672, T_max = 1.000	R_int = 0.026
15696 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.35 e Å⁻³
3215 reflections	Δρ_min = −0.31 e Å⁻³
277 parameters

Special details top

Experimental. (CrysAlis PRO; Oxford Diffraction Ltd., Version 1.171.33.66 (release 28-04-2010 CrysAlis171 .NET) (compiled Apr 28 2010,14:27:37) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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
Li1	0.90455 (19)	0.0331 (4)	1.03878 (13)	0.0379 (6)
Li2	0.7564 (2)	−0.2877 (4)	0.97211 (14)	0.0373 (6)
Li3	0.6256 (2)	0.0936 (5)	0.92945 (15)	0.0486 (7)
O31	0.47521 (9)	0.15187 (19)	0.91969 (6)	0.0482 (3)
O32	0.32570 (9)	0.1336 (2)	0.83857 (6)	0.0519 (4)
N31	0.58804 (10)	0.1142 (2)	0.81387 (7)	0.0371 (3)
C32	0.48413 (11)	0.1347 (2)	0.79451 (8)	0.0324 (3)
C33	0.43759 (12)	0.1538 (2)	0.72158 (8)	0.0392 (4)
H33	0.3653	0.1662	0.7095	0.047*
N32	0.49310 (11)	0.1548 (2)	0.66817 (7)	0.0419 (3)
C35	0.59618 (13)	0.1305 (2)	0.68670 (9)	0.0378 (4)
C36	0.64232 (12)	0.1096 (2)	0.76008 (9)	0.0407 (4)
H36	0.7142	0.0918	0.7720	0.049*
C37	0.42190 (12)	0.1403 (2)	0.85605 (8)	0.0357 (4)
C38	0.65821 (16)	0.1281 (3)	0.62641 (10)	0.0541 (5)
H38A	0.7279	0.0859	0.6454	0.081*
H38B	0.6609	0.2506	0.6070	0.081*
H38C	0.6256	0.0461	0.5882	0.081*
O12	1.20280 (8)	0.20920 (18)	1.11942 (6)	0.0430 (3)
O11	1.05909 (8)	0.09788 (18)	1.04975 (6)	0.0440 (3)
N11	0.95349 (10)	0.11349 (19)	1.15973 (7)	0.0353 (3)
N1	0.77531 (11)	0.3393 (2)	0.98615 (7)	0.0428 (4)
O1	0.76826 (9)	0.16678 (16)	0.98797 (6)	0.0457 (3)
O2	0.70264 (13)	0.4302 (2)	0.95323 (9)	0.0748 (5)
O3	0.85484 (14)	0.4171 (3)	1.01733 (9)	0.0840 (6)
O5	0.61725 (8)	−0.17265 (17)	0.96171 (6)	0.0378 (3)
H51	0.5869 (17)	−0.177 (3)	0.9989 (13)	0.057*
H52	0.5778 (18)	−0.236 (3)	0.9301 (13)	0.057*
O4	0.81382 (9)	−0.18568 (16)	1.06931 (5)	0.0335 (3)
C15	0.95823 (13)	0.1348 (2)	1.28881 (8)	0.0373 (4)
C12	1.05656 (11)	0.1468 (2)	1.17399 (7)	0.0295 (3)
C16	0.90570 (12)	0.1100 (2)	1.21690 (9)	0.0401 (4)
H16	0.8339	0.0900	1.2086	0.048*
C13	1.10941 (12)	0.1720 (2)	1.24494 (8)	0.0360 (4)
H13	1.1809	0.1954	1.2531	0.043*
C17	1.11144 (11)	0.1522 (2)	1.10905 (7)	0.0302 (3)
N12	1.06118 (11)	0.1639 (2)	1.30230 (7)	0.0402 (3)
C18	0.90366 (16)	0.1308 (3)	1.35290 (10)	0.0538 (5)
H18A	0.9461	0.0659	1.3928	0.081*
H18B	0.8377	0.0688	1.3393	0.081*
H18C	0.8922	0.2551	1.3678	0.081*
H42	0.8562 (17)	−0.250 (3)	1.0999 (12)	0.050 (5)*
H41	0.7640 (17)	−0.161 (3)	1.0912 (11)	0.048 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Li1	0.0343 (12)	0.0511 (16)	0.0284 (11)	−0.0012 (11)	0.0061 (9)	−0.0045 (11)
Li2	0.0387 (13)	0.0443 (15)	0.0308 (12)	−0.0021 (11)	0.0115 (10)	−0.0018 (11)
Li3	0.0405 (14)	0.073 (2)	0.0317 (13)	0.0052 (14)	0.0061 (11)	0.0076 (13)
O31	0.0377 (6)	0.0820 (9)	0.0270 (5)	0.0121 (6)	0.0111 (4)	0.0055 (5)
O32	0.0318 (6)	0.0881 (10)	0.0383 (6)	0.0059 (6)	0.0127 (5)	0.0048 (6)
N31	0.0315 (6)	0.0520 (8)	0.0286 (6)	0.0081 (6)	0.0075 (5)	0.0056 (5)
C32	0.0307 (7)	0.0395 (8)	0.0280 (7)	0.0055 (6)	0.0078 (6)	0.0043 (6)
C33	0.0318 (8)	0.0559 (10)	0.0300 (7)	0.0047 (7)	0.0061 (6)	0.0059 (7)
N32	0.0425 (8)	0.0568 (9)	0.0271 (6)	0.0027 (6)	0.0081 (5)	0.0045 (6)
C35	0.0411 (8)	0.0423 (9)	0.0327 (7)	0.0025 (7)	0.0143 (6)	0.0017 (6)
C36	0.0311 (7)	0.0565 (10)	0.0366 (8)	0.0083 (7)	0.0120 (6)	0.0049 (7)
C37	0.0332 (8)	0.0464 (9)	0.0292 (7)	0.0086 (6)	0.0102 (6)	0.0063 (6)
C38	0.0568 (11)	0.0709 (13)	0.0409 (9)	0.0036 (9)	0.0256 (8)	0.0030 (9)
O12	0.0359 (6)	0.0620 (8)	0.0335 (5)	−0.0121 (5)	0.0123 (4)	−0.0051 (5)
O11	0.0376 (6)	0.0699 (8)	0.0255 (5)	−0.0032 (5)	0.0082 (4)	−0.0126 (5)
N11	0.0322 (6)	0.0450 (8)	0.0292 (6)	−0.0065 (5)	0.0065 (5)	−0.0037 (5)
N1	0.0540 (9)	0.0426 (8)	0.0383 (7)	0.0039 (7)	0.0255 (7)	0.0003 (6)
O1	0.0556 (7)	0.0316 (6)	0.0503 (7)	0.0030 (5)	0.0106 (6)	0.0020 (5)
O2	0.0892 (11)	0.0701 (10)	0.0720 (10)	0.0418 (9)	0.0327 (8)	0.0276 (8)
O3	0.0938 (12)	0.0904 (12)	0.0750 (11)	−0.0459 (10)	0.0344 (9)	−0.0309 (9)
O5	0.0318 (5)	0.0577 (7)	0.0245 (5)	0.0002 (5)	0.0069 (4)	−0.0042 (5)
O4	0.0312 (5)	0.0455 (6)	0.0240 (5)	0.0041 (5)	0.0054 (4)	0.0039 (4)
C15	0.0459 (9)	0.0362 (8)	0.0336 (8)	−0.0085 (7)	0.0173 (7)	−0.0046 (6)
C12	0.0309 (7)	0.0318 (7)	0.0262 (7)	−0.0033 (6)	0.0067 (6)	−0.0024 (5)
C16	0.0328 (8)	0.0505 (10)	0.0389 (8)	−0.0080 (7)	0.0121 (6)	−0.0050 (7)
C13	0.0337 (8)	0.0477 (9)	0.0271 (7)	−0.0078 (7)	0.0071 (6)	−0.0064 (6)
C17	0.0322 (7)	0.0344 (8)	0.0246 (6)	0.0009 (6)	0.0065 (5)	−0.0014 (5)
N12	0.0458 (8)	0.0499 (8)	0.0257 (6)	−0.0101 (6)	0.0090 (5)	−0.0059 (5)
C18	0.0676 (12)	0.0582 (11)	0.0439 (9)	−0.0142 (9)	0.0322 (9)	−0.0076 (8)

Geometric parameters (Å, º) top

Li1—O11ⁱ	2.029 (3)	C38—H38A	0.9600
Li1—O11	2.039 (3)	C38—H38B	0.9600
Li1—O1	2.085 (3)	C38—H38C	0.9600
Li1—O4	2.114 (3)	O12—C17	1.2397 (18)
Li1—N11	2.293 (3)	O12—Li2ⁱ	1.958 (3)
Li1—Li1ⁱ	3.134 (5)	O11—C17	1.2460 (18)
Li2—O12ⁱ	1.958 (3)	O11—Li1ⁱ	2.029 (3)
Li2—O4	1.965 (3)	N11—C16	1.328 (2)
Li2—O5	1.970 (3)	N11—C12	1.3404 (19)
Li2—O2ⁱⁱ	2.163 (3)	N1—O2	1.219 (2)
Li2—O3ⁱⁱ	2.550 (4)	N1—O3	1.225 (2)
Li2—C17ⁱ	2.677 (3)	N1—O1	1.2516 (19)
Li2—N1ⁱⁱ	2.715 (3)	N1—Li2ⁱⁱⁱ	2.715 (3)
Li2—H52	2.34 (2)	O2—Li2ⁱⁱⁱ	2.163 (3)
Li3—O31	1.978 (3)	O3—Li2ⁱⁱⁱ	2.550 (4)
Li3—O5	2.025 (4)	O5—H51	0.86 (2)
Li3—O1	2.039 (3)	O5—H52	0.84 (2)
Li3—N31	2.117 (3)	O4—H42	0.85 (2)
Li3—O2	2.637 (4)	O4—H41	0.85 (2)
O31—C37	1.2573 (19)	C15—N12	1.334 (2)
O32—C37	1.2351 (19)	C15—C16	1.394 (2)
N31—C36	1.328 (2)	C15—C18	1.497 (2)
N31—C32	1.3419 (19)	C12—C13	1.381 (2)
C32—C33	1.384 (2)	C12—C17	1.5134 (18)
C32—C37	1.5205 (19)	C16—H16	0.9300
C33—N32	1.332 (2)	C13—N12	1.336 (2)
C33—H33	0.9300	C13—H13	0.9300
N32—C35	1.334 (2)	C17—Li2ⁱ	2.677 (3)
C35—C36	1.392 (2)	C18—H18A	0.9600
C35—C38	1.498 (2)	C18—H18B	0.9600
C36—H36	0.9300	C18—H18C	0.9600

O11ⁱ—Li1—O11	79.21 (10)	N31—C36—H36	118.6
O11ⁱ—Li1—O1	99.02 (11)	C35—C36—H36	118.6
O11—Li1—O1	132.82 (15)	O32—C37—O31	127.21 (13)
O11ⁱ—Li1—O4	95.45 (12)	O32—C37—C32	117.25 (13)
O11—Li1—O4	137.34 (15)	O31—C37—C32	115.53 (13)
O1—Li1—O4	89.83 (11)	C35—C38—H38A	109.5
O11ⁱ—Li1—N11	148.03 (14)	C35—C38—H38B	109.5
O11—Li1—N11	75.84 (9)	H38A—C38—H38B	109.5
O1—Li1—N11	112.56 (12)	C35—C38—H38C	109.5
O4—Li1—N11	89.63 (10)	H38A—C38—H38C	109.5
O11ⁱ—Li1—Li1ⁱ	39.72 (7)	H38B—C38—H38C	109.5
O11—Li1—Li1ⁱ	39.50 (7)	C17—O12—Li2ⁱ	111.69 (12)
O1—Li1—Li1ⁱ	122.93 (15)	C17—O11—Li1ⁱ	133.79 (12)
O4—Li1—Li1ⁱ	122.68 (16)	C17—O11—Li1	121.84 (11)
N11—Li1—Li1ⁱ	112.96 (13)	Li1ⁱ—O11—Li1	100.79 (10)
O12ⁱ—Li2—O4	124.82 (15)	C16—N11—C12	116.54 (13)
O12ⁱ—Li2—O5	100.73 (13)	C16—N11—Li1	133.87 (12)
O4—Li2—O5	96.72 (12)	C12—N11—Li1	108.90 (11)
O12ⁱ—Li2—O2ⁱⁱ	105.34 (13)	O2—N1—O3	119.92 (19)
O4—Li2—O2ⁱⁱ	123.98 (14)	O2—N1—O1	119.79 (17)
O5—Li2—O2ⁱⁱ	96.79 (12)	O3—N1—O1	120.29 (17)
O12ⁱ—Li2—O3ⁱⁱ	109.12 (12)	O2—N1—Li2ⁱⁱⁱ	50.83 (12)
O4—Li2—O3ⁱⁱ	85.96 (11)	O3—N1—Li2ⁱⁱⁱ	69.11 (13)
O5—Li2—O3ⁱⁱ	141.47 (14)	O1—N1—Li2ⁱⁱⁱ	170.49 (13)
O2ⁱⁱ—Li2—O3ⁱⁱ	52.56 (8)	N1—O1—Li3	107.95 (14)
O12ⁱ—Li2—C17ⁱ	25.49 (5)	N1—O1—Li1	114.41 (13)
O4—Li2—C17ⁱ	101.89 (11)	Li3—O1—Li1	137.29 (14)
O5—Li2—C17ⁱ	117.81 (13)	N1—O2—Li2ⁱⁱⁱ	103.26 (16)
O2ⁱⁱ—Li2—C17ⁱ	118.44 (11)	N1—O2—Li3	79.75 (13)
O3ⁱⁱ—Li2—C17ⁱ	98.94 (10)	Li2ⁱⁱⁱ—O2—Li3	176.60 (12)
O12ⁱ—Li2—N1ⁱⁱ	109.68 (12)	N1—O3—Li2ⁱⁱⁱ	84.22 (14)
O4—Li2—N1ⁱⁱ	105.79 (12)	Li2—O5—Li3	109.33 (13)
O5—Li2—N1ⁱⁱ	119.60 (13)	Li2—O5—H51	117.3 (14)
O2ⁱⁱ—Li2—N1ⁱⁱ	25.90 (6)	Li3—O5—H51	109.4 (14)
O3ⁱⁱ—Li2—N1ⁱⁱ	26.66 (5)	Li2—O5—H52	105.8 (15)
C17ⁱ—Li2—N1ⁱⁱ	111.17 (10)	Li3—O5—H52	111.6 (15)
O12ⁱ—Li2—H52	94.5 (6)	H51—O5—H52	103 (2)
O4—Li2—H52	115.4 (6)	Li2—O4—Li1	99.79 (11)
O5—Li2—H52	20.1 (6)	Li2—O4—H42	119.7 (14)
O2ⁱⁱ—Li2—H52	80.0 (6)	Li1—O4—H42	105.3 (14)
O3ⁱⁱ—Li2—H52	130.7 (6)	Li2—O4—H41	109.1 (14)
C17ⁱ—Li2—H52	117.2 (6)	Li1—O4—H41	119.0 (14)
N1ⁱⁱ—Li2—H52	105.0 (6)	H42—O4—H41	104.7 (19)
O31—Li3—O5	97.02 (14)	N12—C15—C16	119.77 (13)
O31—Li3—O1	141.39 (18)	N12—C15—C18	117.61 (15)
O5—Li3—O1	100.53 (13)	C16—C15—C18	122.62 (15)
O31—Li3—N31	81.64 (11)	N11—C12—C13	120.98 (13)
O5—Li3—N31	110.61 (16)	N11—C12—C17	116.84 (12)
O1—Li3—N31	122.54 (15)	C13—C12—C17	122.18 (13)
O31—Li3—O2	99.10 (14)	N11—C16—C15	123.00 (14)
O5—Li3—O2	150.13 (14)	N11—C16—H16	118.5
O1—Li3—O2	52.51 (9)	C15—C16—H16	118.5
N31—Li3—O2	96.54 (13)	N12—C13—C12	122.10 (14)
C37—O31—Li3	115.81 (12)	N12—C13—H13	119.0
C36—N31—C32	116.92 (13)	C12—C13—H13	119.0
C36—N31—Li3	135.00 (13)	O12—C17—O11	126.37 (13)
C32—N31—Li3	108.08 (12)	O12—C17—C12	117.84 (12)
N31—C32—C33	120.58 (13)	O11—C17—C12	115.79 (13)
N31—C32—C37	116.98 (12)	O12—C17—Li2ⁱ	42.82 (9)
C33—C32—C37	122.43 (13)	O11—C17—Li2ⁱ	85.43 (10)
N32—C33—C32	122.04 (14)	C12—C17—Li2ⁱ	155.18 (12)
N32—C33—H33	119.0	C15—N12—C13	117.58 (13)
C32—C33—H33	119.0	C15—C18—H18A	109.5
C33—N32—C35	117.83 (13)	C15—C18—H18B	109.5
N32—C35—C36	119.78 (14)	H18A—C18—H18B	109.5
N32—C35—C38	117.75 (15)	C15—C18—H18C	109.5
C36—C35—C38	122.47 (15)	H18A—C18—H18C	109.5
N31—C36—C35	122.80 (14)	H18B—C18—H18C	109.5

O5—Li3—O31—C37	−97.15 (15)	O11ⁱ—Li1—O1—Li3	59.4 (2)
O1—Li3—O31—C37	146.2 (2)	O11—Li1—O1—Li3	142.98 (18)
N31—Li3—O31—C37	12.75 (18)	O4—Li1—O1—Li3	−36.13 (18)
O2—Li3—O31—C37	108.09 (15)	N11—Li1—O1—Li3	−125.66 (17)
O31—Li3—N31—C36	174.23 (18)	Li1ⁱ—Li1—O1—Li3	93.8 (2)
O5—Li3—N31—C36	−91.4 (2)	O3—N1—O2—Li2ⁱⁱⁱ	−1.90 (17)
O1—Li3—N31—C36	26.8 (3)	O1—N1—O2—Li2ⁱⁱⁱ	178.05 (12)
O2—Li3—N31—C36	75.9 (2)	O3—N1—O2—Li3	179.73 (15)
O31—Li3—N31—C32	−6.47 (16)	O1—N1—O2—Li3	−0.32 (13)
O5—Li3—N31—C32	87.93 (16)	Li2ⁱⁱⁱ—N1—O2—Li3	−178.38 (12)
O1—Li3—N31—C32	−153.94 (18)	O31—Li3—O2—N1	151.21 (13)
O2—Li3—N31—C32	−104.75 (13)	O5—Li3—O2—N1	29.4 (3)
C36—N31—C32—C33	−1.3 (2)	O1—Li3—O2—N1	0.22 (9)
Li3—N31—C32—C33	179.29 (17)	N31—Li3—O2—N1	−126.25 (13)
C36—N31—C32—C37	−179.90 (15)	O31—Li3—O2—Li2ⁱⁱⁱ	−1 (2)
Li3—N31—C32—C37	0.65 (19)	O5—Li3—O2—Li2ⁱⁱⁱ	−122.9 (18)
N31—C32—C33—N32	−0.8 (3)	O1—Li3—O2—Li2ⁱⁱⁱ	−152.1 (19)
C37—C32—C33—N32	177.77 (15)	N31—Li3—O2—Li2ⁱⁱⁱ	81.4 (19)
C32—C33—N32—C35	2.2 (3)	O2—N1—O3—Li2ⁱⁱⁱ	1.58 (14)
C33—N32—C35—C36	−1.5 (2)	O1—N1—O3—Li2ⁱⁱⁱ	−178.38 (13)
C33—N32—C35—C38	178.88 (17)	O12ⁱ—Li2—O5—Li3	−46.98 (16)
C32—N31—C36—C35	1.9 (3)	O4—Li2—O5—Li3	80.43 (14)
Li3—N31—C36—C35	−178.82 (18)	O2ⁱⁱ—Li2—O5—Li3	−154.06 (12)
N32—C35—C36—N31	−0.5 (3)	O3ⁱⁱ—Li2—O5—Li3	172.38 (19)
C38—C35—C36—N31	179.02 (17)	C17ⁱ—Li2—O5—Li3	−26.82 (17)
Li3—O31—C37—O32	164.44 (18)	N1ⁱⁱ—Li2—O5—Li3	−167.10 (12)
Li3—O31—C37—C32	−15.7 (2)	O31—Li3—O5—Li2	176.72 (12)
N31—C32—C37—O32	−170.32 (15)	O1—Li3—O5—Li2	−37.82 (15)
C33—C32—C37—O32	11.1 (2)	N31—Li3—O5—Li2	93.04 (15)
N31—C32—C37—O31	9.8 (2)	O2—Li3—O5—Li2	−61.0 (3)
C33—C32—C37—O31	−168.76 (16)	O12ⁱ—Li2—O4—Li1	7.0 (2)
O11ⁱ—Li1—O11—C17	−161.36 (16)	O5—Li2—O4—Li1	−101.06 (12)
O1—Li1—O11—C17	106.3 (2)	O2ⁱⁱ—Li2—O4—Li1	156.06 (15)
O4—Li1—O11—C17	−75.0 (2)	O3ⁱⁱ—Li2—O4—Li1	117.56 (10)
N11—Li1—O11—C17	−1.51 (16)	C17ⁱ—Li2—O4—Li1	19.27 (13)
Li1ⁱ—Li1—O11—C17	−161.36 (16)	N1ⁱⁱ—Li2—O4—Li1	135.57 (11)
O11ⁱ—Li1—O11—Li1ⁱ	0.0	O11ⁱ—Li1—O4—Li2	−32.20 (13)
O1—Li1—O11—Li1ⁱ	−92.35 (18)	O11—Li1—O4—Li2	−112.19 (19)
O4—Li1—O11—Li1ⁱ	86.3 (2)	O1—Li1—O4—Li2	66.84 (12)
N11—Li1—O11—Li1ⁱ	159.85 (14)	N11—Li1—O4—Li2	179.41 (11)
O11ⁱ—Li1—N11—C16	−134.3 (3)	Li1ⁱ—Li1—O4—Li2	−63.25 (18)
O11—Li1—N11—C16	−174.07 (17)	C16—N11—C12—C13	1.3 (2)
O1—Li1—N11—C16	55.1 (2)	Li1—N11—C12—C13	−170.60 (14)
O4—Li1—N11—C16	−34.6 (2)	C16—N11—C12—C17	−179.63 (14)
Li1ⁱ—Li1—N11—C16	−160.31 (17)	Li1—N11—C12—C17	8.50 (17)
O11ⁱ—Li1—N11—C12	35.6 (3)	C12—N11—C16—C15	−1.4 (2)
O11—Li1—N11—C12	−4.18 (14)	Li1—N11—C16—C15	167.87 (16)
O1—Li1—N11—C12	−135.04 (14)	N12—C15—C16—N11	0.1 (3)
O4—Li1—N11—C12	135.30 (12)	C18—C15—C16—N11	179.94 (16)
Li1ⁱ—Li1—N11—C12	9.6 (2)	N11—C12—C13—N12	0.3 (2)
O2—N1—O1—Li3	0.43 (18)	C17—C12—C13—N12	−178.79 (14)
O3—N1—O1—Li3	−179.62 (14)	Li2ⁱ—O12—C17—O11	19.9 (2)
Li2ⁱⁱⁱ—N1—O1—Li3	9.6 (7)	Li2ⁱ—O12—C17—C12	−160.09 (13)
O2—N1—O1—Li1	174.88 (13)	Li1ⁱ—O11—C17—O12	32.3 (3)
O3—N1—O1—Li1	−5.17 (19)	Li1—O11—C17—O12	−173.52 (16)
Li2ⁱⁱⁱ—N1—O1—Li1	−175.9 (6)	Li1ⁱ—O11—C17—C12	−147.73 (16)
O31—Li3—O1—N1	−50.3 (3)	Li1—O11—C17—C12	6.5 (2)
O5—Li3—O1—N1	−165.93 (12)	Li1ⁱ—O11—C17—Li2ⁱ	45.70 (19)
N31—Li3—O1—N1	71.2 (2)	Li1—O11—C17—Li2ⁱ	−160.08 (14)
O2—Li3—O1—N1	−0.22 (9)	N11—C12—C17—O12	169.59 (14)
O31—Li3—O1—Li1	137.1 (2)	C13—C12—C17—O12	−11.3 (2)
O5—Li3—O1—Li1	21.5 (2)	N11—C12—C17—O11	−10.4 (2)
N31—Li3—O1—Li1	−101.4 (2)	C13—C12—C17—O11	168.67 (15)
O2—Li3—O1—Li1	−172.75 (16)	N11—C12—C17—Li2ⁱ	136.1 (2)
O11ⁱ—Li1—O1—N1	−112.83 (13)	C13—C12—C17—Li2ⁱ	−44.8 (3)
O11—Li1—O1—N1	−29.2 (2)	C16—C15—N12—C13	1.5 (2)
O4—Li1—O1—N1	151.67 (11)	C18—C15—N12—C13	−178.41 (16)
N11—Li1—O1—N1	62.14 (16)	C12—C13—N12—C15	−1.7 (2)
Li1ⁱ—Li1—O1—N1	−78.4 (2)

Symmetry codes: (i) −x+2, −y, −z+2; (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
O4—H41···O32^iv	0.85 (2)	1.92 (2)	2.7449 (15)	165.3 (19)
O4—H42···N12^v	0.85 (2)	2.03 (2)	2.8414 (17)	159.0 (19)
O5—H52···N32^vi	0.84 (2)	2.05 (2)	2.8550 (17)	162 (2)
O5—H51···O31^iv	0.86 (2)	1.85 (2)	2.7055 (15)	172 (2)

Symmetry codes: (iv) −x+1, −y, −z+2; (v) −x+2, y−1/2, −z+5/2; (vi) −x+1, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	[Li₃(C₆H₅N₂O₂)₂(NO₃)(H₂O)₂]
M_r	393.10
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	13.0222 (1), 7.2288 (1), 18.5819 (2)
β (°)	100.760 (1)
V (Å³)	1718.45 (3)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	1.10
Crystal size (mm)	0.23 × 0.20 × 0.07

Data collection
Diffractometer	Oxford Diffraction Xcalibur Ruby diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)
T_min, T_max	0.672, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	15696, 3215, 2787
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.610

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.122, 1.07
No. of reflections	3215
No. of parameters	277
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.31

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Li1—O11ⁱ	2.029 (3)	Li2—O5	1.970 (3)
Li1—O11	2.039 (3)	Li2—O2ⁱⁱ	2.163 (3)
Li1—O1	2.085 (3)	Li3—O31	1.978 (3)
Li1—O4	2.114 (3)	Li3—O5	2.025 (4)
Li1—N11	2.293 (3)	Li3—O1	2.039 (3)
Li2—O12ⁱ	1.958 (3)	Li3—N31	2.117 (3)
Li2—O4	1.965 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H41···O32ⁱⁱⁱ	0.85 (2)	1.92 (2)	2.7449 (15)	165.3 (19)
O4—H42···N12^iv	0.85 (2)	2.03 (2)	2.8414 (17)	159.0 (19)
O5—H52···N32^v	0.84 (2)	2.05 (2)	2.8550 (17)	162 (2)
O5—H51···O31ⁱⁱⁱ	0.86 (2)	1.85 (2)	2.7055 (15)	172 (2)

Symmetry codes: (iii) −x+1, −y, −z+2; (iv) −x+2, y−1/2, −z+5/2; (v) −x+1, y−1/2, −z+3/2.

Acknowledgements

Thanks are due to Dr J. K. Maurin for collecting the diffraction data on the instrument at the Institute of Atomic Energy, Swierk.

References

Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, 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, m744–m745. Web of Science CSD CrossRef IUCr Journals Google Scholar
Starosta, W. & Leciejewicz, J. (2011a). Acta Cryst. E67, m202. Web of Science CSD CrossRef IUCr Journals Google Scholar
Starosta, W. & Leciejewicz, J. (2011b). Acta Cryst. E67, m425–m426. Web of Science CSD CrossRef IUCr Journals Google Scholar
Starosta, W. & Leciejewicz, J. (2011c). Acta Cryst. E67, m818. Web of Science CSD CrossRef IUCr Journals Google Scholar

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