Poly[hydrazin-1-ium [diaqua-bis-(μ(4)-pyridazine-3,6-dicarboxyl-ato)trilithate] monohydrate].

The structure of the title compound, {(N(2)H(5))[Li(3)(C(6)H(2)N(2)O(4))(2)(H(2)O)(2)]·H(2)O}(n), is composed of mol-ecular dimers, each built up of two symmetry-related Li(I) ions with distorted trigonal-bipyramidal coordinations bridged by two deprotonated ligand mol-ecules via their N,O-bonding sites. Doubly solvated Li(I) ions with a distorted tetra-hedral geometry link adjacent dimers, forming a polymer generated by bridging bidentate carboxyl-ato O atoms to Li(I) ions in adjacent dimers, forming anionic layers parallel to the ac plane with monoprotonated hydrazinium cations and crystal water mol-ecules 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 mol-ecules act as donors and carboxyl-ate O atoms act as acceptors.

Related literature

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

Crystal data

(N2H5)[Li3(C6H2N2O4)2(H2O)2]·H2O

M = 440.12

Triclinic,

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 ▶) T min = 0.982, T max = 0.992

5141 measured reflections

4676 independent reflections

2660 reflections with I > 2σ(I)

R int = 0.051

3 standard reflections every 200 reflections intensity decay: 1.4%

Refinement

R[F 2 > 2σ(F 2)] = 0.057

wR(F 2) = 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

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, global. DOI: 10.1107/S1600536812012743/kp2395sup1.cif

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

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

(N2H5)[Li3(C6H2N2O4)2(H2O)2]·H2O	Z = 2
Mr = 440.12	F(000) = 452
Triclinic, P1	Dx = 1.615 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.215 (1) Å	Cell parameters from 25 reflections
b = 7.3356 (15) Å	θ = 6–15°
c = 24.001 (5) Å	µ = 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

Kuma KM-4 four-cricle diffractometer	2660 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.051
Graphite monochromator	θmax = 30.1°, θmin = 1.7°
profile data from ω/2θ scans	h = −7→0
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008)	k = −9→10
Tmin = 0.982, Tmax = 0.992	l = −31→33
5141 measured reflections	3 standard reflections every 200 reflections
4676 independent reflections	intensity decay: 1.4%

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.243	H 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 parameters	Δρmax = 0.56 e Å−3
10 restraints	Δρmin = −0.48 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
O21	0.5659 (4)	0.6958 (3)	−0.10200 (9)	0.0309 (5)
O12	0.1688 (4)	0.6942 (3)	0.56969 (10)	0.0294 (5)
N21	0.7101 (4)	0.8483 (3)	0.00022 (10)	0.0205 (5)
O11	0.5736 (4)	0.7887 (3)	0.60076 (9)	0.0306 (5)
N11	0.7993 (5)	0.8737 (3)	0.44798 (10)	0.0227 (5)
O23	0.6818 (5)	0.9204 (3)	0.19576 (9)	0.0301 (5)
O22	0.1624 (4)	0.6266 (3)	−0.07499 (10)	0.0307 (5)
N12	0.7115 (5)	0.8489 (3)	0.49847 (10)	0.0219 (5)
O24	0.9860 (5)	1.0790 (3)	0.15156 (9)	0.0335 (5)
C23	0.6641 (5)	0.8841 (4)	0.09640 (12)	0.0215 (6)
C17	0.4028 (5)	0.7428 (4)	0.56305 (12)	0.0218 (5)
N22	0.7999 (5)	0.9209 (3)	0.05164 (10)	0.0225 (5)
C28	0.7876 (6)	0.9699 (4)	0.15267 (13)	0.0255 (6)
C18	0.7881 (6)	0.8250 (4)	0.34710 (12)	0.0258 (6)
O13	0.9742 (5)	0.9479 (3)	0.34981 (10)	0.0368 (6)
C16	0.6660 (6)	0.7916 (4)	0.40213 (12)	0.0219 (6)
C27	0.3945 (5)	0.6834 (4)	−0.06642 (12)	0.0225 (6)
C14	0.3368 (6)	0.6633 (4)	0.45630 (12)	0.0244 (6)
H14	0.1787	0.5962	0.4605	0.029*
C24	0.4272 (6)	0.7763 (4)	0.09217 (13)	0.0261 (6)
H24	0.3370	0.7524	0.1241	0.031*
C26	0.4807 (5)	0.7464 (4)	−0.00552 (12)	0.0199 (5)
C25	0.3319 (5)	0.7071 (4)	0.03952 (13)	0.0259 (6)
H25	0.1732	0.6362	0.0342	0.031*
C13	0.4859 (5)	0.7499 (4)	0.50274 (12)	0.0198 (5)
C15	0.4332 (6)	0.6814 (4)	0.40447 (13)	0.0275 (6)
H15	0.3468	0.6225	0.3719	0.033*
Li1	1.0824 (10)	1.0999 (8)	0.4223 (2)	0.0296 (11)
Li2	0.9101 (9)	0.8297 (8)	−0.0796 (2)	0.0283 (11)
Li3	0.7103 (10)	0.6895 (7)	0.2248 (2)	0.0278 (11)
N1	0.4289 (6)	0.1897 (5)	0.27436 (13)	0.0376 (7)
N2	0.1607 (6)	0.1293 (5)	0.26487 (13)	0.0404 (7)
O1	0.4489 (5)	0.4788 (4)	0.20777 (11)	0.0344 (6)
H11	0.449 (10)	0.404 (7)	0.230 (2)	0.052*
H12	0.449 (9)	0.426 (7)	0.170 (2)	0.052*
O3	0.9495 (6)	0.4090 (4)	0.32720 (12)	0.0462 (7)
H31	0.912 (10)	0.399 (8)	0.3605 (11)	0.069*
H32	0.852 (9)	0.474 (7)	0.3144 (19)	0.069*
O2	0.9871 (5)	0.5947 (4)	0.18013 (13)	0.0465 (7)
O14	0.6997 (5)	0.7239 (4)	0.30427 (10)	0.0383 (6)
H22	0.977 (14)	0.524 (8)	0.1501 (17)	0.10 (2)*
H21	1.112 (9)	0.559 (8)	0.195 (3)	0.08 (2)*
H1	0.451 (11)	0.188 (7)	0.3107 (9)	0.064 (16)*
H4	0.138 (13)	0.029 (6)	0.283 (2)	0.081 (18)*
H2	0.497 (9)	0.104 (5)	0.2505 (18)	0.058 (14)*
H5	0.066 (12)	0.221 (7)	0.280 (3)	0.11 (3)*
H3	0.124 (12)	0.102 (8)	0.2283 (10)	0.082 (19)*

	U11	U22	U33	U12	U13	U23
O21	0.0201 (10)	0.0448 (13)	0.0251 (11)	−0.0021 (9)	0.0015 (8)	−0.0012 (9)
O12	0.0152 (10)	0.0384 (12)	0.0354 (12)	0.0010 (8)	0.0057 (8)	0.0091 (9)
N21	0.0150 (11)	0.0246 (11)	0.0215 (12)	0.0002 (8)	0.0003 (8)	0.0029 (9)
O11	0.0194 (10)	0.0481 (13)	0.0235 (11)	−0.0024 (9)	0.0014 (8)	0.0065 (9)
N11	0.0177 (11)	0.0273 (12)	0.0236 (12)	−0.0010 (9)	0.0000 (9)	0.0071 (9)
O23	0.0348 (12)	0.0328 (11)	0.0240 (11)	0.0046 (9)	0.0060 (9)	0.0071 (8)
O22	0.0164 (10)	0.0389 (12)	0.0344 (12)	−0.0016 (8)	−0.0022 (8)	−0.0004 (9)
N12	0.0168 (11)	0.0272 (12)	0.0220 (12)	0.0019 (9)	0.0019 (9)	0.0039 (9)
O24	0.0317 (13)	0.0422 (13)	0.0237 (11)	−0.0107 (10)	−0.0029 (9)	0.0048 (9)
C23	0.0184 (13)	0.0228 (13)	0.0240 (13)	0.0029 (10)	0.0022 (10)	0.0046 (10)
C17	0.0192 (13)	0.0234 (13)	0.0236 (13)	0.0044 (10)	0.0031 (10)	0.0041 (10)
N22	0.0165 (11)	0.0266 (12)	0.0239 (12)	0.0008 (9)	0.0005 (9)	0.0026 (9)
C28	0.0259 (15)	0.0251 (13)	0.0262 (15)	0.0050 (11)	0.0014 (11)	0.0036 (11)
C18	0.0274 (15)	0.0281 (14)	0.0225 (14)	0.0027 (11)	0.0033 (11)	0.0061 (11)
O13	0.0379 (13)	0.0428 (13)	0.0266 (12)	−0.0125 (10)	0.0073 (10)	0.0053 (9)
C16	0.0213 (13)	0.0231 (13)	0.0209 (13)	0.0013 (10)	0.0003 (10)	0.0029 (10)
C27	0.0181 (13)	0.0237 (13)	0.0257 (14)	0.0037 (10)	−0.0019 (10)	0.0016 (10)
C14	0.0182 (13)	0.0282 (14)	0.0262 (14)	−0.0020 (10)	−0.0003 (10)	0.0047 (11)
C24	0.0195 (14)	0.0326 (15)	0.0269 (15)	−0.0001 (11)	0.0056 (11)	0.0083 (11)
C26	0.0130 (12)	0.0209 (12)	0.0262 (14)	0.0049 (9)	0.0010 (10)	0.0030 (10)
C25	0.0148 (13)	0.0294 (14)	0.0329 (16)	−0.0023 (10)	0.0021 (11)	0.0060 (12)
C13	0.0146 (12)	0.0234 (12)	0.0226 (13)	0.0047 (9)	0.0030 (9)	0.0054 (9)
C15	0.0225 (14)	0.0310 (15)	0.0263 (15)	−0.0040 (11)	−0.0045 (11)	0.0000 (11)
Li1	0.017 (2)	0.037 (3)	0.034 (3)	−0.002 (2)	0.000 (2)	0.004 (2)
Li2	0.017 (2)	0.038 (3)	0.029 (3)	0.001 (2)	0.0007 (19)	0.002 (2)
Li3	0.030 (3)	0.034 (3)	0.018 (2)	−0.002 (2)	0.0002 (19)	0.0032 (19)
N1	0.0311 (15)	0.0461 (17)	0.0335 (16)	−0.0010 (12)	−0.0028 (12)	0.0021 (13)
N2	0.0354 (17)	0.054 (2)	0.0300 (16)	−0.0107 (14)	−0.0003 (12)	0.0093 (14)
O1	0.0334 (13)	0.0375 (13)	0.0298 (13)	−0.0042 (10)	0.0006 (10)	0.0012 (10)
O3	0.0443 (16)	0.0570 (17)	0.0426 (15)	0.0141 (13)	0.0074 (12)	0.0186 (13)
O2	0.0270 (14)	0.0605 (18)	0.0490 (17)	0.0069 (12)	0.0068 (12)	−0.0063 (14)
O14	0.0470 (15)	0.0435 (14)	0.0210 (11)	−0.0076 (11)	−0.0008 (10)	0.0006 (9)

O21—C27	1.248 (4)	C24—H24	0.9300
O12—C17	1.254 (3)	C26—C25	1.382 (4)
O12—Li1i	2.088 (6)	C25—H25	0.9300
N21—N22	1.337 (3)	C15—H15	0.9300
N21—C26	1.341 (3)	Li1—N11	2.260 (6)
O11—C17	1.252 (4)	Li1—O13	1.982 (6)
O11—Li1ii	2.010 (6)	Li1—O11ii	2.010 (5)
N11—N12	1.329 (3)	Li1—O12i	2.088 (6)
N11—C16	1.334 (4)	Li1—N12ii	2.144 (6)
O23—C28	1.256 (4)	Li2—O21	1.990 (6)
O22—C27	1.246 (4)	Li2—N21	2.186 (6)
O22—Li2iii	2.097 (6)	Li2—O24iv	1.995 (6)
N12—C13	1.331 (4)	Li2—O22v	2.097 (6)
N12—Li1ii	2.144 (6)	Li2—N22iv	2.276 (6)
O24—C28	1.245 (4)	Li3—O14	1.893 (5)
O24—Li2iv	1.995 (6)	Li3—O2	1.938 (6)
C23—N22	1.335 (4)	Li3—O1	1.952 (6)
C23—C24	1.393 (4)	Li3—O23	1.934 (6)
C23—C28	1.520 (4)	N1—N2	1.430 (4)
C17—C13	1.521 (4)	N1—H1	0.88 (2)
N22—Li2iv	2.276 (6)	N1—H2	0.897 (19)
C18—O14	1.240 (4)	N2—H4	0.90 (2)
C18—O13	1.251 (4)	N2—H5	0.92 (2)
C18—C16	1.511 (4)	N2—H3	0.89 (2)
C16—C15	1.396 (4)	O1—H11	0.82 (5)
C27—C26	1.522 (4)	O1—H12	0.93 (5)
C14—C15	1.364 (4)	O3—H31	0.835 (19)
C14—C13	1.395 (4)	O3—H32	0.814 (19)
C14—H14	0.9300	O2—H22	0.83 (2)
C24—C25	1.367 (4)	O2—H21	0.82 (2)
C27—O21—Li2	120.1 (3)	N12—C13—C14	123.2 (2)
C17—O12—Li1i	117.5 (2)	N12—C13—C17	113.8 (2)
N22—N21—C26	119.4 (2)	C14—C13—C17	122.9 (2)
N22—N21—Li2	129.1 (2)	C14—C15—C16	117.6 (3)
C26—N21—Li2	110.7 (2)	C14—C15—H15	121.2
C17—O11—Li1ii	117.2 (2)	C16—C15—H15	121.2
N12—N11—C16	119.5 (2)	O13—Li1—O11ii	98.3 (3)
N12—N11—Li1	129.9 (2)	O13—Li1—O12i	103.8 (3)
C16—N11—Li1	108.1 (2)	O11ii—Li1—O12i	108.2 (3)
C28—O23—Li3	126.2 (3)	O13—Li1—N12ii	153.2 (3)
C27—O22—Li2iii	116.2 (2)	O11ii—Li1—N12ii	79.1 (2)
N11—N12—C13	119.7 (2)	O12i—Li1—N12ii	102.3 (2)
N11—N12—Li1ii	128.2 (2)	O13—Li1—N11	76.6 (2)
C13—N12—Li1ii	110.9 (2)	O11ii—Li1—N11	155.5 (3)
C28—O24—Li2iv	119.8 (2)	O12i—Li1—N11	96.3 (2)
N22—C23—C24	123.0 (3)	N12ii—Li1—N11	94.7 (2)
N22—C23—C28	114.7 (2)	O21—Li2—O24iv	100.7 (3)
C24—C23—C28	122.3 (2)	O21—Li2—O22v	106.4 (3)
O11—C17—O12	126.9 (3)	O24iv—Li2—O22v	101.2 (2)
O11—C17—C13	116.8 (2)	O21—Li2—N21	77.79 (19)
O12—C17—C13	116.3 (3)	O24iv—Li2—N21	153.1 (3)
C23—N22—N21	119.3 (2)	O22v—Li2—N21	105.0 (3)
C23—N22—Li2iv	107.7 (2)	O21—Li2—N22iv	156.5 (3)
N21—N22—Li2iv	130.4 (2)	O24iv—Li2—N22iv	76.4 (2)
O24—C28—O23	126.5 (3)	O22v—Li2—N22iv	97.0 (2)
O24—C28—C23	117.1 (3)	N21—Li2—N22iv	94.3 (2)
O23—C28—C23	116.5 (3)	O14—Li3—O23	110.5 (3)
O14—C18—O13	126.7 (3)	O14—Li3—O2	126.1 (3)
O14—C18—C16	116.8 (3)	O23—Li3—O2	101.0 (3)
O13—C18—C16	116.4 (3)	O14—Li3—O1	99.9 (3)
C18—O13—Li1	120.8 (2)	O23—Li3—O1	121.7 (3)
N11—C16—C15	122.9 (3)	O2—Li3—O1	99.0 (3)
N11—C16—C18	114.9 (2)	N2—N1—H1	103 (4)
C15—C16—C18	122.2 (3)	N2—N1—H2	100 (3)
O22—C27—O21	127.7 (3)	H1—N1—H2	118 (5)
O22—C27—C26	116.6 (3)	N1—N2—H4	103 (4)
O21—C27—C26	115.8 (2)	N1—N2—H5	109 (5)
C15—C14—C13	117.0 (3)	H4—N2—H5	112 (6)
C15—C14—H14	121.5	N1—N2—H3	111 (4)
C13—C14—H14	121.5	H4—N2—H3	112 (6)
C25—C24—C23	117.7 (3)	H5—N2—H3	109 (6)
C25—C24—H24	121.2	Li3—O1—H11	114 (4)
C23—C24—H24	121.2	Li3—O1—H12	113 (3)
N21—C26—C25	123.3 (3)	H11—O1—H12	113 (5)
N21—C26—C27	113.8 (2)	H31—O3—H32	109 (3)
C25—C26—C27	122.9 (2)	Li3—O2—H22	129 (5)
C24—C25—C26	117.4 (3)	Li3—O2—H21	121 (5)
C24—C25—H25	121.3	H22—O2—H21	100 (6)
C26—C25—H25	121.3	C18—O14—Li3	143.4 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H3···O24vi	0.89 (2)	1.95 (2)	2.824 (4)	168 (6)
N2—H5···O3iii	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···O13vi	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···O1v	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)

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) ; (ii) ; (iii) ; (iv) .

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) ; (v) ; (vi) ; (vii) ; (viii) ; (ix) .