catena-Poly[[μ(2)-aqua-diaqua-bis-(μ(4)-pyridazine-3,6-dicarboxyl-ato)tetra-lithium] monohydrate].

In the polymeric structure of the title compound {[Li(2)(C(6)H(2)N(2)O(4))(2)Li(H(2)O)(2)Li(H(2)O)]·H(2)O}(n), the coordination of two independent Li(I) ions is distorted trigonal-bipyramidal and that of the other two independent Li(I) ions is distorted tetra-hedral. The former two Li(I) ions are bridged by hetero-ring N atoms of two independent pyridazine-3,6-dicarboxyl-ate ligands, making a dimeric moiety. The carboxyl-ato-O atoms of both bidentate ligands bridge the dimers to adjacent independent aqua-coordinated Li(I) ions, forming mol-ecular ribbons. The latter are bridged by ligand carboxyl-ato and aqua O atoms, forming mol-ecular layers parallel to (100) which are held together by an extended system of O-H⋯O hydrogen bonds.

Related literature

For the crystal structure of a LiI complex with water and pyridazine-3,6-dicarboxyl­ate ligands, see: Starosta & Leciejewicz (2010 ▶).

Experimental

Crystal data

[Li4(C6H2N2O4)2(H2O)3]·H2O

M = 432.02

Triclinic,

a = 7.1460 (14) Å

b = 10.553 (2) Å

c = 11.849 (2) Å

α = 74.76 (3)°

β = 88.84 (3)°

γ = 82.66 (3)°

V = 855.0 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.15 mm−1

T = 293 K

0.63 × 0.11 × 0.10 mm

Data collection

Kuma KM4 four-circle diffractometer

Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008 ▶) T min = 0.984, T max = 0.987

5238 measured reflections

4991 independent reflections

3628 reflections with I > 2σ(I)

R int = 0.040

3 standard reflections every 200 reflections intensity decay: 2.3%

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.142

S = 1.07

4991 reflections

321 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.52 e Å−3

Δρmin = −0.40 e Å−3

Data collection: KM-4 Software (Kuma, 1996 ▶); cell refinement: KM-4 Software; 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.

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536811038992/vm2123sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811038992/vm2123Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Li4(C6H2N2O4)2(H2O)3]·H2O	Z = 2
Mr = 432.02	F(000) = 440
Triclinic, P1	Dx = 1.678 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.1460 (14) Å	Cell parameters from 25 reflections
b = 10.553 (2) Å	θ = 6–15°
c = 11.849 (2) Å	µ = 0.15 mm−1
α = 74.76 (3)°	T = 293 K
β = 88.84 (3)°	Columns, colourless
γ = 82.66 (3)°	0.63 × 0.11 × 0.10 mm
V = 855.0 (3) Å3

Kuma KM4 four-circle diffractometer	3628 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.040
graphite	θmax = 30.1°, θmin = 1.8°
profile data from ω/2θ scans	h = −10→9
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008)	k = −14→0
Tmin = 0.984, Tmax = 0.987	l = −16→16
5238 measured reflections	3 standard reflections every 200 reflections
4991 independent reflections	intensity decay: 2.3%

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.142	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ2(Fo2) + (0.0933P)2 + 0.1387P] where P = (Fo2 + 2Fc2)/3
4991 reflections	(Δ/σ)max = 0.001
321 parameters	Δρmax = 0.52 e Å−3
0 restraints	Δρmin = −0.40 e Å−3

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.

	x	y	z	Uiso*/Ueq
O12	0.66029 (14)	0.62545 (9)	1.13840 (8)	0.0237 (2)
N12	0.89610 (15)	0.37798 (10)	0.88294 (9)	0.0187 (2)
O13	1.03460 (14)	0.36050 (9)	0.67631 (8)	0.0239 (2)
O42	0.76213 (16)	0.82985 (10)	0.46053 (10)	0.0275 (2)
O11	0.76083 (16)	0.40826 (9)	1.20181 (8)	0.0280 (2)
N21	1.11362 (15)	0.11238 (10)	1.10459 (9)	0.0192 (2)
O23	1.25615 (16)	0.09387 (9)	0.78141 (8)	0.0264 (2)
O14	0.79238 (14)	0.50339 (10)	0.58467 (8)	0.0261 (2)
O24	1.33640 (15)	−0.12661 (9)	0.84009 (9)	0.0272 (2)
N11	0.85009 (15)	0.39281 (10)	0.98916 (9)	0.0183 (2)
N22	1.16009 (15)	0.10114 (10)	0.99701 (9)	0.0184 (2)
C26	1.17284 (17)	0.01344 (11)	1.19732 (10)	0.0179 (2)
C17	0.71991 (17)	0.51348 (11)	1.12415 (10)	0.0176 (2)
C16	0.74862 (16)	0.50523 (11)	0.99854 (10)	0.0162 (2)
C15	0.67929 (18)	0.60722 (12)	0.90249 (11)	0.0216 (2)
H15	0.6104	0.6847	0.9118	0.026*
C28	1.28781 (17)	−0.01463 (12)	0.85721 (11)	0.0183 (2)
C23	1.25859 (16)	−0.01031 (11)	0.98389 (10)	0.0168 (2)
C18	0.89136 (17)	0.44348 (11)	0.67313 (10)	0.0182 (2)
C13	0.83030 (17)	0.47216 (11)	0.78829 (10)	0.0172 (2)
C14	0.71722 (19)	0.58842 (12)	0.79303 (11)	0.0221 (3)
H14	0.6695	0.6505	0.7255	0.027*
Li3	0.9854 (4)	0.1617 (2)	1.4735 (2)	0.0260 (5)
Li2	1.1410 (4)	0.2530 (2)	0.8362 (2)	0.0252 (5)
Li1	0.8796 (4)	0.2444 (2)	1.1597 (2)	0.0264 (5)
O41	0.55920 (17)	0.61557 (13)	0.36637 (10)	0.0346 (3)
O1	0.4656 (2)	0.86090 (18)	0.60889 (14)	0.0508 (4)
Li4	0.7754 (4)	0.6481 (2)	0.4458 (2)	0.0276 (5)
H441	0.580 (3)	0.615 (2)	0.296 (2)	0.051 (7)*
H442	0.468 (3)	0.573 (2)	0.391 (2)	0.051 (7)*
C24	1.32555 (18)	−0.11597 (11)	1.07838 (11)	0.0211 (2)
H24	1.3954	−0.1921	1.0670	0.025*
C25	1.28368 (19)	−0.10253 (12)	1.18890 (11)	0.0217 (2)
H25	1.3275	−0.1681	1.2553	0.026*
C27	1.10638 (18)	0.03368 (12)	1.31489 (11)	0.0206 (2)
O21	1.00788 (16)	0.14240 (10)	1.31261 (9)	0.0292 (2)
O22	1.15259 (16)	−0.05770 (10)	1.40266 (9)	0.0310 (2)
O31	0.8353 (3)	0.32916 (12)	1.43507 (11)	0.0528 (4)
H311	0.799 (3)	0.366 (2)	1.368 (2)	0.053 (7)*
H11	0.425 (4)	0.870 (3)	0.680 (2)	0.058 (7)*
H422	0.750 (3)	0.874 (3)	0.389 (2)	0.052 (7)*
H421	0.664 (4)	0.847 (3)	0.494 (3)	0.076 (9)*
H312	0.812 (4)	0.374 (3)	1.474 (2)	0.068 (8)*
H12	0.391 (6)	0.835 (4)	0.577 (4)	0.135 (17)*

	U11	U22	U33	U12	U13	U23
O12	0.0342 (5)	0.0132 (4)	0.0244 (4)	0.0040 (3)	0.0013 (4)	−0.0094 (3)
N12	0.0258 (5)	0.0115 (4)	0.0171 (5)	0.0034 (4)	0.0014 (4)	−0.0036 (4)
O13	0.0291 (5)	0.0205 (4)	0.0199 (4)	0.0073 (4)	0.0015 (3)	−0.0063 (3)
O42	0.0341 (5)	0.0226 (5)	0.0253 (5)	0.0030 (4)	−0.0001 (4)	−0.0086 (4)
O11	0.0496 (6)	0.0141 (4)	0.0175 (4)	0.0058 (4)	−0.0002 (4)	−0.0037 (3)
N21	0.0270 (5)	0.0116 (4)	0.0172 (5)	0.0029 (4)	0.0023 (4)	−0.0035 (4)
O23	0.0423 (6)	0.0151 (4)	0.0196 (4)	0.0039 (4)	0.0012 (4)	−0.0040 (3)
O14	0.0323 (5)	0.0243 (5)	0.0183 (4)	0.0049 (4)	−0.0022 (4)	−0.0036 (3)
O24	0.0394 (6)	0.0148 (4)	0.0290 (5)	0.0023 (4)	0.0047 (4)	−0.0116 (4)
N11	0.0259 (5)	0.0113 (4)	0.0167 (5)	0.0027 (4)	0.0015 (4)	−0.0044 (3)
N22	0.0257 (5)	0.0107 (4)	0.0172 (4)	0.0029 (4)	0.0021 (4)	−0.0034 (3)
C26	0.0236 (5)	0.0107 (5)	0.0185 (5)	0.0007 (4)	0.0017 (4)	−0.0036 (4)
C17	0.0228 (5)	0.0128 (5)	0.0180 (5)	0.0010 (4)	−0.0001 (4)	−0.0067 (4)
C16	0.0211 (5)	0.0095 (5)	0.0179 (5)	0.0011 (4)	0.0006 (4)	−0.0048 (4)
C15	0.0279 (6)	0.0128 (5)	0.0221 (6)	0.0057 (4)	0.0005 (5)	−0.0053 (4)
C28	0.0218 (5)	0.0137 (5)	0.0202 (5)	0.0008 (4)	0.0012 (4)	−0.0074 (4)
C23	0.0206 (5)	0.0106 (5)	0.0188 (5)	0.0002 (4)	0.0010 (4)	−0.0045 (4)
C18	0.0238 (5)	0.0130 (5)	0.0173 (5)	−0.0006 (4)	0.0020 (4)	−0.0039 (4)
C13	0.0210 (5)	0.0129 (5)	0.0167 (5)	0.0013 (4)	0.0005 (4)	−0.0041 (4)
C14	0.0301 (6)	0.0139 (5)	0.0185 (5)	0.0069 (4)	−0.0016 (4)	−0.0018 (4)
Li3	0.0390 (13)	0.0175 (10)	0.0202 (10)	−0.0006 (9)	0.0014 (9)	−0.0039 (8)
Li2	0.0346 (12)	0.0147 (10)	0.0235 (10)	0.0050 (9)	0.0004 (9)	−0.0043 (8)
Li1	0.0370 (12)	0.0139 (10)	0.0266 (11)	0.0059 (9)	−0.0005 (9)	−0.0066 (8)
O41	0.0340 (6)	0.0450 (7)	0.0264 (5)	−0.0075 (5)	0.0030 (4)	−0.0113 (5)
O1	0.0392 (7)	0.0700 (10)	0.0429 (8)	−0.0024 (7)	0.0095 (6)	−0.0170 (7)
Li4	0.0376 (13)	0.0201 (11)	0.0239 (11)	−0.0003 (9)	0.0035 (9)	−0.0052 (9)
C24	0.0267 (6)	0.0108 (5)	0.0237 (6)	0.0055 (4)	0.0005 (5)	−0.0047 (4)
C25	0.0295 (6)	0.0119 (5)	0.0202 (5)	0.0047 (4)	−0.0006 (4)	−0.0013 (4)
C27	0.0262 (6)	0.0169 (5)	0.0186 (5)	−0.0005 (4)	0.0014 (4)	−0.0058 (4)
O21	0.0442 (6)	0.0206 (5)	0.0209 (4)	0.0102 (4)	−0.0001 (4)	−0.0091 (4)
O22	0.0451 (6)	0.0225 (5)	0.0198 (4)	0.0022 (4)	0.0040 (4)	0.0010 (4)
O31	0.1059 (13)	0.0231 (5)	0.0228 (5)	0.0250 (7)	−0.0087 (6)	−0.0090 (5)

Li1—O21	2.018 (3)	N11—C16	1.3386 (14)
Li1—O24i	2.101 (3)	N22—C23	1.3352 (15)
N11—Li1	2.202 (3)	C26—C25	1.3959 (16)
O11—Li1	2.005 (2)	C26—C27	1.5217 (17)
N21—Li1	2.237 (3)	C17—C16	1.5219 (16)
Li2—O12ii	2.107 (3)	C16—C15	1.3936 (17)
O13—Li2	2.040 (3)	C15—C14	1.3792 (17)
N12—Li2	2.206 (3)	C15—H15	0.9300
N22—Li2	2.137 (3)	C28—C23	1.5231 (16)
O23—Li2	2.029 (2)	C23—C24	1.3982 (17)
Li3—O31	1.896 (3)	C18—C13	1.5176 (16)
Li3—O22iii	1.924 (3)	C13—C14	1.3937 (16)
Li3—O21	1.971 (3)	C14—H14	0.9300
Li3—O42ii	2.002 (3)	Li3—Li4ii	3.133 (4)
O42—Li3ii	2.002 (3)	Li3—Li3iii	3.283 (5)
Li2—Li4iv	3.295 (4)	O41—Li4	1.938 (3)
O12—C17	1.2569 (14)	O41—H441	0.84 (3)
O12—Li2ii	2.107 (3)	O41—H442	0.84 (2)
N12—C13	1.3352 (16)	O1—H11	0.91 (3)
N12—N11	1.3380 (14)	O1—H12	0.77 (4)
O13—C18	1.2535 (15)	Li4—O13iv	1.976 (3)
O13—Li4iv	1.976 (3)	Li4—Li3ii	3.133 (4)
O42—Li4	1.961 (3)	Li4—Li2iv	3.295 (4)
O42—H422	0.86 (3)	Li4—H422	2.28 (3)
O42—H421	0.82 (3)	C24—C25	1.3768 (18)
O11—C17	1.2474 (15)	C24—H24	0.9300
N21—C26	1.3339 (16)	C25—H25	0.9300
N21—N22	1.3423 (14)	C27—O22	1.2353 (16)
O23—C28	1.2531 (16)	C27—O21	1.2612 (16)
O14—C18	1.2515 (16)	O22—Li3iii	1.924 (3)
O14—Li4	1.922 (3)	O31—H311	0.81 (3)
O24—C28	1.2556 (14)	O31—H312	0.75 (3)
O24—Li1i	2.101 (3)
C17—O12—Li2ii	118.39 (11)	Li4ii—Li3—Li3iii	133.53 (13)
C13—N12—N11	119.30 (10)	O23—Li2—O13	95.51 (11)
C13—N12—Li2	109.89 (10)	O23—Li2—O12ii	113.67 (12)
N11—N12—Li2	127.57 (10)	O13—Li2—O12ii	99.66 (11)
C18—O13—Li4iv	128.88 (11)	O23—Li2—N22	78.96 (9)
C18—O13—Li2	118.04 (11)	O13—Li2—N22	157.39 (15)
Li4iv—O13—Li2	110.25 (11)	O12ii—Li2—N22	102.64 (11)
Li4—O42—Li3ii	104.46 (12)	O23—Li2—N12	151.64 (14)
Li4—O42—H422	100.8 (17)	O13—Li2—N12	77.64 (9)
Li3ii—O42—H422	111.7 (16)	O12ii—Li2—N12	94.65 (10)
Li4—O42—H421	109 (2)	N22—Li2—N12	96.76 (11)
Li3ii—O42—H421	121 (2)	O23—Li2—Li4iv	71.49 (9)
H422—O42—H421	108 (2)	O13—Li2—Li4iv	34.23 (7)
C17—O11—Li1	120.35 (11)	O12ii—Li2—Li4iv	87.26 (10)
C26—N21—N22	119.26 (10)	N22—Li2—Li4iv	150.33 (11)
C26—N21—Li1	108.68 (10)	N12—Li2—Li4iv	110.40 (10)
N22—N21—Li1	129.45 (10)	O11—Li1—O21	100.76 (12)
C28—O23—Li2	117.34 (10)	O11—Li1—O24i	106.87 (12)
C18—O14—Li4	144.59 (13)	O21—Li1—O24i	98.88 (12)
C28—O24—Li1i	116.63 (11)	O11—Li1—N11	77.16 (9)
N12—N11—C16	119.33 (10)	O21—Li1—N11	155.87 (15)
N12—N11—Li1	129.04 (10)	O24i—Li1—N11	104.75 (12)
C16—N11—Li1	110.95 (10)	O11—Li1—N21	155.62 (15)
C23—N22—N21	119.79 (10)	O21—Li1—N21	76.83 (9)
C23—N22—Li2	111.01 (10)	O24i—Li1—N21	97.44 (10)
N21—N22—Li2	128.28 (10)	N11—Li1—N21	95.10 (11)
N21—C26—C25	123.30 (11)	Li4—O41—H441	113.3 (16)
N21—C26—C27	115.14 (10)	Li4—O41—H442	132.4 (15)
C25—C26—C27	121.54 (11)	H441—O41—H442	109 (2)
O11—C17—O12	127.16 (11)	H11—O1—H12	112 (3)
O11—C17—C16	116.17 (10)	O14—Li4—O41	101.46 (13)
O12—C17—C16	116.66 (11)	O14—Li4—O42	119.36 (13)
N11—C16—C15	123.40 (11)	O41—Li4—O42	113.99 (14)
N11—C16—C17	113.81 (10)	O14—Li4—O13iv	117.61 (13)
C15—C16—C17	122.76 (10)	O41—Li4—O13iv	98.62 (12)
C14—C15—C16	117.16 (11)	O42—Li4—O13iv	104.16 (13)
C14—C15—H15	121.4	O14—Li4—Li3ii	99.97 (11)
C16—C15—H15	121.4	O41—Li4—Li3ii	151.72 (13)
O23—C28—O24	127.23 (12)	O42—Li4—Li3ii	38.23 (8)
O23—C28—C23	116.20 (10)	O13iv—Li4—Li3ii	87.47 (11)
O24—C28—C23	116.54 (11)	O14—Li4—Li2iv	147.07 (12)
N22—C23—C24	122.97 (11)	O41—Li4—Li2iv	73.92 (10)
N22—C23—C28	114.46 (10)	O42—Li4—Li2iv	91.18 (10)
C24—C23—C28	122.55 (10)	O13iv—Li4—Li2iv	35.52 (7)
O14—C18—O13	126.36 (12)	Li3ii—Li4—Li2iv	97.25 (9)
O14—C18—C13	116.92 (11)	O14—Li4—H422	140.9 (7)
O13—C18—C13	116.71 (11)	O41—Li4—H422	101.3 (6)
N12—C13—C14	123.64 (11)	O42—Li4—H422	21.6 (6)
N12—C13—C18	114.30 (10)	O13iv—Li4—H422	89.7 (7)
C14—C13—C18	122.05 (11)	Li3ii—Li4—H422	50.9 (6)
C15—C14—C13	116.97 (11)	Li2iv—Li4—H422	70.4 (7)
C15—C14—H14	121.5	C25—C24—C23	117.20 (11)
C13—C14—H14	121.5	C25—C24—H24	121.4
O31—Li3—O22iii	103.19 (14)	C23—C24—H24	121.4
O31—Li3—O21	96.46 (12)	C24—C25—C26	117.37 (11)
O22iii—Li3—O21	125.74 (14)	C24—C25—H25	121.3
O31—Li3—O42ii	111.96 (14)	C26—C25—H25	121.3
O22iii—Li3—O42ii	107.33 (12)	O22—C27—O21	126.48 (12)
O21—Li3—O42ii	111.05 (13)	O22—C27—C26	117.17 (11)
O31—Li3—Li4ii	74.81 (11)	O21—C27—C26	116.35 (11)
O22iii—Li3—Li4ii	113.96 (11)	C27—O21—Li3	108.76 (11)
O21—Li3—Li4ii	119.92 (12)	C27—O21—Li1	117.39 (11)
O42ii—Li3—Li4ii	37.31 (7)	Li3—O21—Li1	133.16 (11)
O31—Li3—Li3iii	149.11 (18)	C27—O22—Li3iii	134.00 (13)
O22iii—Li3—Li3iii	57.89 (8)	Li3—O31—H311	122.0 (18)
O21—Li3—Li3iii	79.98 (11)	Li3—O31—H312	127 (2)
O42ii—Li3—Li3iii	97.71 (12)	H311—O31—H312	110 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O31—H312···O14v	0.75 (3)	2.11 (3)	2.8572 (17)	171 (3)
O42—H421···O1	0.82 (3)	1.97 (3)	2.768 (2)	165 (3)
O42—H422···O23iv	0.86 (3)	1.95 (3)	2.7676 (16)	158 (2)
O1—H11···O24vi	0.91 (3)	2.00 (3)	2.9036 (19)	175 (2)
O31—H311···O11	0.81 (3)	1.92 (3)	2.7117 (17)	163 (2)
O41—H442···O14vii	0.84 (2)	2.10 (2)	2.9306 (18)	167 (2)
O41—H441···O12viii	0.84 (3)	1.92 (3)	2.7607 (16)	172 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O31—H312⋯O14i	0.75 (3)	2.11 (3)	2.8572 (17)	171 (3)
O42—H421⋯O1	0.82 (3)	1.97 (3)	2.768 (2)	165 (3)
O42—H422⋯O23ii	0.86 (3)	1.95 (3)	2.7676 (16)	158 (2)
O1—H11⋯O24iii	0.91 (3)	2.00 (3)	2.9036 (19)	175 (2)
O31—H311⋯O11	0.81 (3)	1.92 (3)	2.7117 (17)	163 (2)
O41—H442⋯O14iv	0.84 (2)	2.10 (2)	2.9306 (18)	167 (2)
O41—H441⋯O12v	0.84 (3)	1.92 (3)	2.7607 (16)	172 (2)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .