trans-Diaqua­(pyridazine-3-carboxyl­ato-κ2N2,O)lithium

Starosta, W.; Leciejewicz, J.

doi:10.1107/S1600536811000493

metal-organic compounds

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Volume 67| Part 2| February 2011| Page m202

doi:10.1107/S1600536811000493

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trans-Diaqua(pyridazine-3-carboxylato-κ²N²,O)lithium

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 4 January 2011; accepted 5 January 2011; online 15 January 2011)

The structure of the title complex, [Li(C₅H₃N₂O₂)(H₂O)₂], is built of monomeric molecules. In each, an Li⁺ ion is N,O-chelated by the pyridazine-3-carboxylate ligand and two water O atoms. The coordination geometry of the metal ion is distorted tetrahedral. The monomers are linked by a system of hydrogen bonds in which water molecules act as donors and carboxylate O atoms act as acceptors. O—H⋯N hydrogen bonding is also present.

Related literature

For the structures of 3d transition metal complexes with the title ligand, see: Ardiwinata et al. (1989 ); Gryz et al. (2003 , 2004 ). The structures of complexes with: Mg²⁺ (Gryz et al., 2006 ); Ca²⁺ (Starosta & Leciejewicz, 2007 ); UO₂²⁺ (Leciejewicz & Starosta, 2009 ) and Pb²⁺ (Starosta & Leciejewicz, 2010 ) have been also reported. For the structure of pyridazine-3-carboxylic acid hydrochloride, see: Gryz et al. (2003).

Experimental

Crystal data

[Li(C₅H₃N₂O₂)(H₂O)₂]
M_r = 166.07
Monoclinic, P 2₁ /c
a = 7.4620 (15) Å
b = 13.738 (3) Å
c = 8.0330 (16) Å
β = 112.27 (3)°
V = 762.1 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 293 K
0.41 × 0.13 × 0.11 mm

Data collection

Kuma KM-4 four-circle diffractometer
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008) $[Oxford Diffraction (2008). CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ T_min = 0.972, T_max = 0.989
1681 measured reflections
1579 independent reflections
878 reflections with I > 2σ(I)
R_int = 0.044
3 standard reflections every 200 reflections intensity decay: 0.1%

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.150
S = 0.99
1579 reflections
137 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Selected bond lengths (Å)

O1—Li1	1.950 (5)
O3—Li1	1.896 (5)
N2—Li1	2.095 (4)
Li1—O4	1.907 (5)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H41⋯O2ⁱ	0.85 (4)	1.90 (4)	2.720 (3)	164 (3)
O4—H42⋯O2ⁱⁱ	0.84 (4)	2.07 (4)	2.823 (3)	150 (4)
O3—H32⋯O1ⁱⁱⁱ	0.99 (4)	1.77 (4)	2.741 (3)	167 (3)
O3—H31⋯N1^iv	0.77 (5)	2.10 (5)	2.840 (3)	160 (5)
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) -x+1, -y+1, -z+2; (iii) -x+1, -y+1, -z+1; (iv) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

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/S1600536811000493/kp2302sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811000493/kp2302Isup2.hkl

checkCIF report

Comment top

Metal ion complexes with pyridazine-3-carboxylate ligand show a veriaty of coordination modes and molecular patterns. Monomeric molecules with octahedral coordination geometry have been reported in the structures of a Mn complex (Ardiwinata et al. 1989), two Zn complexes (Gryz et al., 2003, 2004) and a Mg complex (Gryz et al., 2006). On the other hand, the structure of a Ca complex is built of binuclear molecules (Starosta & Leciejewicz, 2007). The structure of an uranyl complex is also composed of binuclear molecules but with a different system of internal bridging as compared to that one observed in the crystals of the Ca compound (Leciejewicz & Starosta, 2009). The structure of a Pb complex is catenated polymeric (Starosta & Leciejewicz, 2010). The crystal structure of the title compound contains discrete mononuclear molecules. In each, a Li¹⁺ ion is chelated by one pyridazine-3-carboxylate ligand molecule which uses its N,O- bonding site and two water O atoms arranged in trans mode. The coordination environment of the metal ion is slightly distorted tetrahedral. The relevant Li—O and Li—N bond distances and bond angles are in fair agreement with those reported for Li¹⁺ complexes with carboxylate ligands. The pyridazine ring is almost planar [r.m.s. deviation is 0.0099 (1) Å]. The C7/O1/O2 carboxylic group makes with the ring a dihedral angle of 2.0 (1)°. Bond lengths and bond angles within the ligand molecule are close to those reported for the pyridazine-3-carboxylic acid hydrochloride (Gryz et al. 2003) and other metal complexes with the title ligand. Coordinated water molecules and carboxylate O atoms participate in a network of hydrogen bonds. An O—H···N of 2.840 (3)%A is also observed. This network is responsible for the stability of the crystal structure.

Related literature top

For the structures of 3d transition metal complexes with the title ligand, see: Ardiwinata et al. (1989), Gryz et al. (2003), and Gryz, et al. (2004). The structures of complexes with: Mg²⁺ (Gryz et al., 2006); Ca²⁺ (Starosta & Leciejewicz, 2007); UO₂²⁺ (Leciejewicz & Starosta, 2009) and Pb²⁺ (Starosta & Leciejewicz, 2010) have been also reported. For the structure of pyridazine-3-carboxylic acid hydrochloride, see: Gryz et al. (2003).

Experimental top

30 mL of an aqueous solution containing 1 mmol of LiOH (Aldrich) was titrated with 0.1 N HCl until pH of ca 6 was reached. Then, a solution of 1 mmol of pyridazine-3-carboxylic acid in 30 mL of hot water was added, the mixture heated at 323 K with stirring for 3 h on a water bath and then left to crystallise at the ambient temperature. After evaporating to dryness well formed single crystals were found on the bottom of the reaction pot. They were washed with 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. A molecule of the title compound with atom labelling scheme and 50% probability displacement ellipsoids.
	Fig. 2. A packing diagram.

trans-Diaqua(pyridazine-3-carboxylato- κ²N²,O)lithium top

Crystal data top

[Li(C₅H₃N₂O₂)(H₂O)₂]	F(000) = 344
M_r = 166.07	D_x = 1.447 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.4620 (15) Å	Cell parameters from 3 reflections
b = 13.738 (3) Å	θ = 6–15°
c = 8.0330 (16) Å	µ = 0.12 mm⁻¹
β = 112.27 (3)°	T = 293 K
V = 762.1 (3) Å³	Blocks, colourless
Z = 4	0.41 × 0.13 × 0.11 mm

Data collection top

Kuma KM-4 four-circle diffractometer	878 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.044
Graphite monochromator	θ_max = 27.1°, θ_min = 3.0°
profile data from ω/2θ scans	h = 0→9
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008)	k = 0→17
T_min = 0.972, T_max = 0.989	l = −10→8
1681 measured reflections	3 standard reflections every 200 reflections
1579 independent reflections	intensity decay: 0.1%

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.150	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ²(F_o²) + (0.1002P)²] where P = (F_o² + 2F_c²)/3
1579 reflections	(Δ/σ)_max < 0.001
137 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

[Li(C₅H₃N₂O₂)(H₂O)₂]	V = 762.1 (3) Å³
M_r = 166.07	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.4620 (15) Å	µ = 0.12 mm⁻¹
b = 13.738 (3) Å	T = 293 K
c = 8.0330 (16) Å	0.41 × 0.13 × 0.11 mm
β = 112.27 (3)°

Data collection top

Kuma KM-4 four-circle diffractometer	878 reflections with I > 2σ(I)
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008)	R_int = 0.044
T_min = 0.972, T_max = 0.989	3 standard reflections every 200 reflections
1681 measured reflections	intensity decay: 0.1%
1579 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.150	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	Δρ_max = 0.25 e Å⁻³
1579 reflections	Δρ_min = −0.30 e Å⁻³
137 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
O1	0.5660 (2)	0.46534 (12)	0.7782 (2)	0.0433 (5)
O2	0.7322 (3)	0.35353 (12)	0.9796 (2)	0.0453 (5)
O3	0.6476 (3)	0.62905 (16)	0.5350 (3)	0.0504 (5)
N2	0.7489 (3)	0.60891 (13)	0.9918 (2)	0.0341 (5)
C3	0.7981 (3)	0.51905 (15)	1.0537 (3)	0.0297 (5)
N1	0.8297 (3)	0.68561 (14)	1.0952 (3)	0.0436 (5)
C4	0.9386 (3)	0.5005 (2)	1.2220 (3)	0.0380 (6)
C6	0.9614 (4)	0.6700 (2)	1.2587 (3)	0.0447 (6)
C7	0.6887 (3)	0.43841 (16)	0.9250 (3)	0.0331 (5)
C5	1.0237 (4)	0.5780 (2)	1.3266 (3)	0.0430 (6)
Li1	0.5577 (6)	0.6038 (3)	0.7221 (5)	0.0411 (9)
H3	0.974 (4)	0.440 (2)	1.258 (3)	0.043 (7)*
H6	1.006 (4)	0.728 (2)	1.330 (3)	0.042 (7)*
H41	0.332 (5)	0.741 (3)	0.668 (4)	0.063 (9)*
O4	0.3421 (3)	0.68308 (15)	0.7066 (3)	0.0480 (5)
H42	0.344 (6)	0.691 (3)	0.811 (6)	0.089 (13)*
H32	0.573 (5)	0.604 (2)	0.413 (5)	0.086 (11)*
H31	0.678 (6)	0.682 (4)	0.527 (6)	0.108 (17)*
H5	1.112 (5)	0.571 (2)	1.441 (4)	0.064 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0484 (10)	0.0356 (9)	0.0360 (9)	−0.0082 (8)	0.0048 (8)	−0.0012 (7)
O2	0.0622 (12)	0.0271 (9)	0.0441 (10)	0.0006 (8)	0.0173 (9)	−0.0001 (7)
O3	0.0643 (13)	0.0424 (11)	0.0410 (10)	−0.0133 (10)	0.0161 (10)	−0.0018 (8)
N2	0.0328 (11)	0.0277 (10)	0.0367 (10)	0.0018 (8)	0.0076 (9)	−0.0019 (8)
C3	0.0279 (10)	0.0301 (11)	0.0335 (10)	0.0011 (9)	0.0143 (9)	−0.0013 (9)
N1	0.0438 (12)	0.0338 (11)	0.0462 (12)	−0.0015 (9)	0.0094 (10)	−0.0071 (9)
C4	0.0373 (12)	0.0388 (13)	0.0369 (12)	0.0033 (11)	0.0129 (10)	0.0047 (11)
C6	0.0440 (15)	0.0427 (14)	0.0429 (14)	−0.0128 (12)	0.0114 (12)	−0.0120 (11)
C7	0.0372 (12)	0.0318 (12)	0.0347 (12)	−0.0018 (10)	0.0184 (11)	−0.0014 (9)
C5	0.0333 (13)	0.0566 (15)	0.0328 (13)	−0.0066 (12)	0.0052 (11)	0.0002 (11)
Li1	0.035 (2)	0.043 (2)	0.038 (2)	−0.0004 (18)	0.0061 (18)	0.0022 (17)
O4	0.0532 (12)	0.0418 (11)	0.0478 (12)	0.0100 (9)	0.0177 (9)	0.0099 (9)

Geometric parameters (Å, º) top

O1—C7	1.244 (3)	N1—C6	1.326 (3)
O1—Li1	1.950 (5)	C4—C5	1.357 (4)
O2—C7	1.245 (3)	C4—H3	0.89 (3)
O3—Li1	1.896 (5)	C6—C5	1.386 (4)
O3—H32	0.99 (4)	C6—H6	0.96 (3)
O3—H31	0.77 (5)	C5—H5	0.91 (3)
N2—C3	1.329 (3)	Li1—O4	1.907 (5)
N2—N1	1.336 (3)	Li1—H42	2.31 (4)
N2—Li1	2.095 (4)	O4—H41	0.85 (4)
C3—C4	1.385 (3)	O4—H42	0.84 (4)
C3—C7	1.524 (3)

C7—O1—Li1	117.15 (19)	C4—C5—C6	117.7 (2)
Li1—O3—H32	119 (2)	C4—C5—H5	122 (2)
Li1—O3—H31	117 (3)	C6—C5—H5	120 (2)
H32—O3—H31	109 (4)	O3—Li1—O4	112.8 (2)
C3—N2—N1	120.27 (18)	O3—Li1—O1	111.8 (2)
C3—N2—Li1	109.80 (18)	O4—Li1—O1	121.6 (2)
N1—N2—Li1	129.77 (18)	O3—Li1—N2	120.4 (2)
N2—C3—C4	122.4 (2)	O4—Li1—N2	106.0 (2)
N2—C3—C7	114.86 (19)	O1—Li1—N2	81.06 (16)
C4—C3—C7	122.7 (2)	O3—Li1—C7	117.9 (2)
C6—N1—N2	118.6 (2)	O4—Li1—C7	127.7 (2)
C5—C4—C3	117.6 (2)	O1—Li1—C7	23.74 (9)
C5—C4—H3	121.3 (17)	N2—Li1—C7	57.68 (11)
C3—C4—H3	121.0 (17)	O3—Li1—H42	129.8 (11)
N1—C6—C5	123.3 (2)	O4—Li1—H42	20.1 (10)
N1—C6—H6	114.9 (15)	O1—Li1—H42	113.7 (10)
C5—C6—H6	121.7 (15)	N2—Li1—H42	86.7 (10)
O1—C7—O2	127.8 (2)	C7—Li1—H42	112.3 (11)
O1—C7—C3	116.06 (19)	Li1—O4—H41	121 (2)
O2—C7—C3	116.2 (2)	Li1—O4—H42	108 (3)
O2—C7—Li1	165.72 (18)	H41—O4—H42	102 (3)
C3—C7—Li1	77.30 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H41···O2ⁱ	0.85 (4)	1.90 (4)	2.720 (3)	164 (3)
O4—H42···O2ⁱⁱ	0.84 (4)	2.07 (4)	2.823 (3)	150 (4)
O3—H32···O1ⁱⁱⁱ	0.99 (4)	1.77 (4)	2.741 (3)	167 (3)
O3—H31···N1^iv	0.77 (5)	2.10 (5)	2.840 (3)	160 (5)

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

Experimental details

Crystal data
Chemical formula	[Li(C₅H₃N₂O₂)(H₂O)₂]
M_r	166.07
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	7.4620 (15), 13.738 (3), 8.0330 (16)
β (°)	112.27 (3)
V (Å³)	762.1 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.41 × 0.13 × 0.11

Data collection
Diffractometer	Kuma KM-4 four-circle diffractometer
Absorption correction	Analytical (CrysAlis RED; Oxford Diffraction, 2008)
T_min, T_max	0.972, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	1681, 1579, 878
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.641

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.150, 0.99
No. of reflections	1579
No. of parameters	137
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.30

Computer programs: KM-4 Software (Kuma, 1996), DATAPROC (Kuma, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

O1—Li1	1.950 (5)	N2—Li1	2.095 (4)
O3—Li1	1.896 (5)	Li1—O4	1.907 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H41···O2ⁱ	0.85 (4)	1.90 (4)	2.720 (3)	164 (3)
O4—H42···O2ⁱⁱ	0.84 (4)	2.07 (4)	2.823 (3)	150 (4)
O3—H32···O1ⁱⁱⁱ	0.99 (4)	1.77 (4)	2.741 (3)	167 (3)
O3—H31···N1^iv	0.77 (5)	2.10 (5)	2.840 (3)	160 (5)

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

References

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doi:10.1107/S1600536811000493

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