Tetra-kis(picolinato-κN,O)zirconium(IV) dihydrate.

In the title compound, [Zr(C(6)H(4)NO(2))(4)]·2H(2)O, the Zr(IV) atom is located on a crystallographic fourfold rotoinversion axis ([Formula: see text]) and is coordinated by four picolinate anions with Zr-O and Zr-N distances of 2.120 (2) and 2.393 (2) Å, respectively. An approximate square-anti-prismatic coordination polyhedron of the N,O-coordination ligand atoms is formed, with a distortion towards dodeca-hedral geometry. The crystal packing is stabilized by inter-molecular π-π inter-actions between adjacent picolinate rings [centroid-centroid distances = 3.271 (1) and 3.640 (2) Å], as well as O-H⋯O hydrogen bonds between the solvent mol-ecules and the coordinated ligands, thereby linking the mol-ecules into a supra-molecular three-dimensional network.

Related literature

For N,O- and O,O′-bidentate ligand complexes of zirconium and hafnium, see: Steyn et al. (2008 ▶); Viljoen et al. (2010 ▶). For relevant studies of N,O- and O,O′-bidentate ligands with other transition metal atoms, see: Graham et al. (1991 ▶); Mtshali et al. (2006 ▶); Roodt et al. (2011 ▶); Schutte et al. (2008 ▶); Steyn et al. (1997 ▶); Van Aswegen et al. (1991 ▶); Van der Westhuizen et al. (2010 ▶).

Experimental

Crystal data

[Zr(C6H4NO2)4]·2H2O

M = 615.66

Tetragonal,

a = 11.083 (5) Å

c = 9.548 (5) Å

V = 1172.8 (10) Å3

Z = 2

Mo Kα radiation

μ = 0.54 mm−1

T = 100 K

0.12 × 0.09 × 0.04 mm

Data collection

Bruker X8 APEXII 4K Kappa CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.942, T max = 0.977

27234 measured reflections

1477 independent reflections

1271 reflections with I > 2σ(I)

R int = 0.074

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.100

S = 1.10

1477 reflections

87 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.64 e Å−3

Δρmin = −0.92 e Å−3

Data collection: APEX2 (Bruker, 2010 ▶); cell refinement: SAIn class="Chemical">NT-Plus (Bruker, 2004 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811031710/zq2119sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811031710/zq2119Isup2.hkl

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

[Zr(C6H4NO2)4]·2H2O	Dx = 1.743 Mg m−3
Mr = 615.66	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P42/n	Cell parameters from 9933 reflections
Hall symbol: -P 4bc	θ = 2.6–28.4°
a = 11.083 (5) Å	µ = 0.54 mm−1
c = 9.548 (5) Å	T = 100 K
V = 1172.8 (10) Å3	Cuboid, colourless
Z = 2	0.12 × 0.09 × 0.04 mm
F(000) = 624

Bruker X8 APEXII 4K Kappa CCD diffractometer	1477 independent reflections
Radiation source: fine-focus sealed tube	1271 reflections with I > 2σ(I)
graphite	Rint = 0.074
ω and φ scans	θmax = 28.5°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −14→13
Tmin = 0.942, Tmax = 0.977	k = −14→14
27234 measured reflections	l = −12→12

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ2(Fo2) + (0.0415P)2 + 2.5407P] where P = (Fo2 + 2Fc2)/3
1477 reflections	(Δ/σ)max < 0.001
87 parameters	Δρmax = 0.64 e Å−3
1 restraint	Δρmin = −0.92 e Å−3

Experimental. The intensity data were collected on a Bruker X8 ApexII 4 K Kappa CCD diffractometer using an exposure time of 40 s/frame. A total of 1709 frames were collected with a frame width of 0.5° covering up to θ = 28.40° with 99.5% completeness accomplished.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
Zr1	0.25	0.25	0.75	0.01305 (15)
O1	0.41797 (14)	0.31522 (14)	0.82454 (18)	0.01305 (15)
O2	0.56146 (18)	0.33223 (18)	0.9859 (2)	0.0263 (4)
C3	0.4700 (2)	0.1154 (2)	1.1212 (3)	0.0195 (5)
H3	0.5415	0.144	1.1601	0.023*
N1	0.31289 (18)	0.13671 (18)	0.9505 (2)	0.0157 (4)
C2	0.4174 (2)	0.1737 (2)	1.0089 (3)	0.0169 (5)
C5	0.3088 (2)	−0.0267 (2)	1.1131 (3)	0.0206 (5)
H5	0.2707	−0.0959	1.1461	0.025*
C6	0.2603 (2)	0.0372 (2)	1.0016 (3)	0.0178 (5)
H6	0.1891	0.01	0.961	0.021*
C4	0.4143 (2)	0.0137 (2)	1.1748 (3)	0.0222 (5)
H4	0.4473	−0.0269	1.251	0.027*
C1	0.4728 (2)	0.2822 (2)	0.9379 (3)	0.0183 (5)
O03	0.25	0.75	0.3385 (4)	0.0472 (9)
H03A	0.274 (4)	0.815 (3)	0.396 (4)	0.068 (15)*

	U11	U22	U33	U12	U13	U23
Zr1	0.01054 (17)	0.01054 (17)	0.0181 (2)	0	0	0
O1	0.01054 (17)	0.01054 (17)	0.0181 (2)	0	0	0
O2	0.0201 (9)	0.0257 (10)	0.0332 (11)	−0.0070 (8)	−0.0066 (8)	0.0008 (8)
C3	0.0170 (11)	0.0211 (12)	0.0205 (12)	0.0015 (9)	−0.0014 (9)	−0.0035 (10)
N1	0.0141 (9)	0.0136 (9)	0.0194 (10)	−0.0005 (8)	0.0000 (8)	−0.0002 (8)
C2	0.0145 (11)	0.0160 (11)	0.0203 (12)	0.0000 (9)	0.0007 (9)	−0.0030 (9)
C5	0.0221 (12)	0.0178 (12)	0.0220 (13)	0.0026 (9)	0.0043 (10)	0.0027 (10)
C6	0.0158 (11)	0.0154 (11)	0.0223 (12)	−0.0003 (9)	0.0005 (9)	0.0003 (9)
C4	0.0236 (13)	0.0240 (13)	0.0191 (13)	0.0056 (10)	0.0003 (10)	0.0020 (10)
C1	0.0148 (11)	0.0171 (11)	0.0231 (12)	−0.0001 (9)	0.0006 (9)	−0.0032 (9)
O03	0.059 (2)	0.038 (2)	0.045 (2)	−0.0011 (18)	0	0

Zr1—O1i	2.1200 (18)	C3—C4	1.384 (4)
Zr1—O1	2.1200 (18)	C3—H3	0.93
Zr1—O1ii	2.1200 (18)	N1—C6	1.340 (3)
Zr1—O1iii	2.1200 (18)	N1—C2	1.349 (3)
Zr1—N1i	2.393 (2)	C2—C1	1.511 (4)
Zr1—N1ii	2.393 (2)	C5—C4	1.384 (4)
Zr1—N1iii	2.393 (2)	C5—C6	1.386 (4)
Zr1—N1	2.393 (2)	C5—H5	0.93
O1—C1	1.294 (3)	C6—H6	0.93
O2—C1	1.218 (3)	C4—H4	0.93
C3—C2	1.381 (4)	O03—H03A	0.941 (19)
O1i—Zr1—O1	96.47 (3)	N1i—Zr1—N1	129.78 (7)
O1i—Zr1—O1ii	96.47 (3)	N1ii—Zr1—N1	73.76 (11)
O1—Zr1—O1ii	140.77 (10)	N1iii—Zr1—N1	129.78 (7)
O1i—Zr1—O1iii	140.77 (10)	C1—O1—Zr1	126.61 (15)
O1—Zr1—O1iii	96.47 (3)	C2—C3—C4	118.7 (2)
O1ii—Zr1—O1iii	96.47 (3)	C2—C3—H3	120.7
O1i—Zr1—N1i	69.79 (7)	C4—C3—H3	120.7
O1—Zr1—N1i	145.95 (7)	C6—N1—C2	118.2 (2)
O1ii—Zr1—N1i	73.05 (7)	C6—N1—Zr1	126.65 (17)
O1iii—Zr1—N1i	78.95 (7)	C2—N1—Zr1	114.94 (16)
O1i—Zr1—N1ii	145.95 (7)	N1—C2—C3	122.8 (2)
O1—Zr1—N1ii	78.95 (7)	N1—C2—C1	113.9 (2)
O1ii—Zr1—N1ii	69.79 (7)	C3—C2—C1	123.3 (2)
O1iii—Zr1—N1ii	73.05 (7)	C4—C5—C6	119.3 (2)
N1i—Zr1—N1ii	129.78 (7)	C4—C5—H5	120.4
O1i—Zr1—N1iii	78.95 (7)	C6—C5—H5	120.4
O1—Zr1—N1iii	73.05 (7)	N1—C6—C5	122.1 (2)
O1ii—Zr1—N1iii	145.95 (7)	N1—C6—H6	118.9
O1iii—Zr1—N1iii	69.79 (7)	C5—C6—H6	118.9
N1i—Zr1—N1iii	73.76 (11)	C3—C4—C5	118.9 (2)
N1ii—Zr1—N1iii	129.78 (7)	C3—C4—H4	120.6
O1i—Zr1—N1	73.05 (7)	C5—C4—H4	120.6
O1—Zr1—N1	69.79 (7)	O2—C1—O1	124.4 (2)
O1ii—Zr1—N1	78.95 (7)	O2—C1—C2	121.4 (2)
O1iii—Zr1—N1	145.95 (7)	O1—C1—C2	114.2 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O03—H03A···O2iv	0.94 (2)	1.89 (2)	2.829 (3)	175 (5)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O03—H03A⋯O2i	0.94 (2)	1.89 (2)	2.829 (3)	175 (5)

Symmetry code: (i) .