Redetermination of cis-diaqua­diglycolato­zinc(II)

Kennedy, P.; Francis, N.; Rovnyak, D.; Kastner, M.E.

doi:10.1107/S1600536808039585

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page m1635

doi:10.1107/S1600536808039585

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Redetermination of cis-diaquadiglycolatozinc(II)

Paul Kennedy,^a Neferterneken Francis,^a David Rovnyak ^a and Margaret E. Kastner ^a ^*

^aDepartment of Chemistry, Bucknell University, Lewisburg, PA 17837, USA
^*Correspondence e-mail: kastner@bucknell.edu

(Received 5 November 2008; accepted 24 November 2008; online 29 November 2008)

The title complex, [Zn(C₂H₃O₃)₂(H₂O)₂], was prepared and the crystal structure determined as part of a ⁶⁷Zn solid state nuclear magnetic resonance study. In the title complex, the Zn atom has a disorted octahedral coordination comprising two bidentate glycolate ligands and two water molecules. The water molecules are cis to each other; one is trans to a carboxylate O atom and the other trans to an alcohol O atom. The crystal structure has an extensive O—H⋯O hydrogen-bond network.

Related literature

The crystal structure of the title complex was first reported by Fischinger & Webb (1969 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

[Zn(C₂H₃O₃)₂(H₂O)₂]
M_r = 251.49
Monoclinic, P 2₁ /c
a = 11.391 (2) Å
b = 5.857 (1) Å
c = 12.511 (2) Å
β = 91.198 (9)°
V = 834.5 (2) Å³
Z = 4
Mo Kα radiation
μ = 2.96 mm⁻¹
T = 273 (2) K
0.3 × 0.3 × 0.1 mm

Data collection

Bruker P4 diffractometer
Absorption correction: ψ scan (SADABS; Bruker, 2000 ) T_min = 0.425, T_max = 0.744
2102 measured reflections
2102 independent reflections
1751 reflections with I > 2σ(I)
3 standard reflections every 97 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.072
S = 0.99
2102 reflections
119 parameters
H-atom parameters constrained
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H8⋯O4ⁱ	0.90	1.93	2.821 (3)	167
O1—H7⋯O8ⁱⁱ	0.88	1.84	2.716 (3)	174
O2—H6⋯O5ⁱ	0.91	1.82	2.697 (3)	161
O2—H5⋯O5ⁱⁱⁱ	0.85	1.88	2.688 (3)	158
O6—H4⋯O8^iv	0.84	1.82	2.665 (2)	177
O3—H3⋯O7^iv	0.83	1.97	2.761 (3)	160
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) -x+2, -y, -z+1; (iv) x, y-1, z.

Data collection: XSCANS (Bruker, 2000); cell refinement: XSCANS; data reduction: XSCANS; 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/S1600536808039585/su2079sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808039585/su2079Isup2.hkl

checkCIF report

Comment top

As part of a Zinc-67 solid state nuclear magnetic resonance study the title complex, (I), was prepared and the crystal structure determined. The structure of this complex was first report by Fischinger & Webb (1969) but no fractional crystal coordinates were reported.

The molecular structure of (I) is illustrated in Fig. 1. The zinc atom has a distorted octahedral coordination sphere composed of two bidentate gylcolato ligands and two water molecules. The water molecules are cis to each other; one (O1) is trans to a carboxylate O-atom (O4), and the other, (O2), is trans to an alcohol O-atom (O6). The bond distances and angles are normal for zinc(II) complexes (Allen et al., 1987)

In the crystal structure of (I) there in an extensive O—H···O hydrogen bonding network (Table 1). The two water molecules (O1 and O2) bond to the two oxygens (O4 and O5) of a carboxylate group related by the c-glide. The two alcohol groups (O3 and O6) form hydrogen bonds with the other carboxylate group (atoms O7 and O8) translated by one unit cell along the b axis. The carbonyl oxygen O8 of this ligand also makes a two dimensional hydrogen bonded network with one of the waters (O1) around the inversion center. The other water molecule, (O2), forms an H-bond with a carbonyl oxygen (O5) related by the 2-fold screw axis.

Related literature top

The crystal structure of the title complex was first reported by Fischinger & Webb (1969). For bond-length data, see: Allen et al. (1987).

Experimental top

Glycolic acid (100 mg, 3 mmol), purchased from Sigma-Aldrich (99%), was dissolved in 5 ml of deionized water. Basic zinc carbonate (80 mg, 2 mmol) was added and the mixture stirred for 10 minutes while heating to ca. 60°C. The resulting mixture was filtered, and the filtrate left to stand at room temperature until large needle-like crystals grew by slow evaporation of the water.

Computing details top

Data collection: XSCANS (Bruker, 2000); cell refinement: XSCANS (Bruker, 2000); data reduction: XSCANS (Bruker, 2000); 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 view of the molecular structure of compound (I), showing the atom numbering scheme and dispacement ellipsods drawn at the 50% probability level.

cis-diaquadiglycolatozinc(II) top

Crystal data top

[Zn(C₂H₃O₃)₂(H₂O)₂]	F(000) = 512
M_r = 251.49	D_x = 2.002 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 20 reflections
a = 11.391 (2) Å	θ = 9.6–17.4°
b = 5.857 (1) Å	µ = 2.96 mm⁻¹
c = 12.511 (2) Å	T = 273 K
β = 91.198 (9)°	Needle, colorless
V = 834.5 (2) Å³	0.3 × 0.3 × 0.1 mm
Z = 4

Data collection top

Bruker P4 diffractometer	1751 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.000
Graphite monochromator	θ_max = 28.5°, θ_min = 3.3°
2θ/ω scans	h = −15→15
Absorption correction: ψ scan (SADABS; Bruker, 2000)	k = 0→7
T_min = 0.425, T_max = 0.744	l = 0→16
2102 measured reflections	3 standard reflections every 97 reflections
2102 independent reflections	intensity decay: none

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.030	H-atom parameters constrained
wR(F²) = 0.072	w = 1/[σ²(F_o²) + (0.0337P)² + 0.5879P] where P = (F_o² + 2F_c²)/3
S = 0.99	(Δ/σ)_max = 0.030
2102 reflections	Δρ_max = 0.45 e Å⁻³
119 parameters	Δρ_min = −0.51 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0094 (8)

Crystal data top

[Zn(C₂H₃O₃)₂(H₂O)₂]	V = 834.5 (2) Å³
M_r = 251.49	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.391 (2) Å	µ = 2.96 mm⁻¹
b = 5.857 (1) Å	T = 273 K
c = 12.511 (2) Å	0.3 × 0.3 × 0.1 mm
β = 91.198 (9)°

Data collection top

Bruker P4 diffractometer	1751 reflections with I > 2σ(I)
Absorption correction: ψ scan (SADABS; Bruker, 2000)	R_int = 0.000
T_min = 0.425, T_max = 0.744	3 standard reflections every 97 reflections
2102 measured reflections	intensity decay: none
2102 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.072	H-atom parameters constrained
S = 0.99	Δρ_max = 0.45 e Å⁻³
2102 reflections	Δρ_min = −0.51 e Å⁻³
119 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
Zn	0.76227 (2)	0.14144 (5)	0.65837 (2)	0.02431 (11)
O1	0.73409 (15)	0.0926 (3)	0.82160 (13)	0.0323 (4)
O2	0.91409 (16)	0.3091 (3)	0.69490 (15)	0.0349 (4)
O3	0.82248 (17)	−0.1945 (3)	0.64048 (13)	0.0307 (4)
O4	0.80776 (17)	0.1349 (3)	0.49645 (13)	0.0310 (4)
O5	0.90455 (17)	−0.0608 (4)	0.37503 (13)	0.0367 (4)
O6	0.58388 (16)	0.0302 (3)	0.63177 (15)	0.0339 (4)
O7	0.66840 (15)	0.4419 (3)	0.64627 (14)	0.0299 (4)
O8	0.49499 (15)	0.6096 (3)	0.62300 (13)	0.0275 (4)
C1	0.8665 (2)	−0.2479 (4)	0.53732 (19)	0.0297 (5)
H1A	0.8215	−0.3727	0.5062	0.036*
H1B	0.9477	−0.2968	0.5444	0.036*
C2	0.8588 (2)	−0.0423 (4)	0.46432 (18)	0.0242 (5)
C3	0.4989 (2)	0.2052 (4)	0.62244 (18)	0.0242 (5)
H2A	0.4422	0.1896	0.6787	0.029*
H2B	0.4575	0.1927	0.5542	0.029*
C4	0.5587 (2)	0.4364 (4)	0.63092 (16)	0.0218 (4)
H3	0.7697	−0.2865	0.6547	0.050*
H4	0.5587	−0.1048	0.6293	0.050*
H5	0.9803	0.2654	0.6719	0.050*
H6	0.9284	0.3898	0.7563	0.050*
H7	0.6612	0.0892	0.8427	0.050*
H8	0.7688	0.1759	0.8742	0.050*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn	0.02730 (16)	0.01890 (15)	0.02686 (15)	0.00221 (12)	0.00378 (10)	−0.00151 (11)
O1	0.0314 (9)	0.0381 (10)	0.0275 (8)	−0.0050 (8)	0.0044 (7)	−0.0032 (7)
O2	0.0280 (9)	0.0360 (10)	0.0408 (10)	−0.0002 (8)	0.0038 (7)	−0.0114 (8)
O3	0.0452 (10)	0.0204 (8)	0.0269 (8)	0.0026 (8)	0.0121 (7)	0.0011 (7)
O4	0.0404 (10)	0.0270 (9)	0.0260 (8)	0.0094 (8)	0.0063 (7)	0.0037 (7)
O5	0.0435 (11)	0.0390 (11)	0.0280 (9)	0.0100 (9)	0.0116 (8)	0.0036 (8)
O6	0.0327 (10)	0.0161 (8)	0.0527 (11)	0.0002 (8)	−0.0013 (8)	−0.0041 (8)
O7	0.0268 (9)	0.0174 (8)	0.0457 (10)	0.0012 (7)	0.0026 (7)	−0.0014 (8)
O8	0.0294 (9)	0.0198 (8)	0.0333 (9)	0.0036 (7)	0.0046 (7)	0.0029 (7)
C1	0.0414 (14)	0.0203 (11)	0.0277 (12)	0.0026 (11)	0.0100 (10)	−0.0006 (10)
C2	0.0216 (11)	0.0255 (12)	0.0257 (11)	−0.0017 (10)	0.0017 (8)	0.0014 (9)
C3	0.0294 (12)	0.0196 (10)	0.0238 (10)	−0.0008 (10)	−0.0008 (9)	−0.0002 (9)
C4	0.0284 (11)	0.0185 (10)	0.0188 (9)	−0.0011 (9)	0.0049 (8)	0.0010 (8)

Geometric parameters (Å, º) top

Zn—O2	2.0325 (19)	O4—C2	1.259 (3)
Zn—O7	2.0630 (17)	O5—C2	1.247 (3)
Zn—O1	2.0935 (17)	O6—C3	1.412 (3)
Zn—O3	2.0974 (18)	O6—H4	0.8417
Zn—O4	2.1019 (17)	O7—C4	1.261 (3)
Zn—O6	2.1531 (19)	O8—C4	1.250 (3)
O1—H7	0.8768	C1—C2	1.513 (3)
O1—H8	0.9037	C1—H1A	0.9700
O2—H5	0.8522	C1—H1B	0.9700
O2—H6	0.9135	C3—C4	1.518 (3)
O3—C1	1.429 (3)	C3—H2A	0.9700
O3—H3	0.8293	C3—H2B	0.9700

O2—Zn—O7	92.38 (7)	C2—O4—Zn	116.58 (15)
O2—Zn—O1	89.65 (7)	C3—O6—Zn	115.85 (14)
O7—Zn—O1	95.65 (7)	C3—O6—H4	116.5
O2—Zn—O3	101.47 (8)	Zn—O6—H4	127.6
O7—Zn—O3	164.27 (7)	C4—O7—Zn	120.00 (16)
O1—Zn—O3	91.89 (7)	O3—C1—C2	110.72 (19)
O2—Zn—O4	89.99 (7)	O3—C1—H1A	109.5
O7—Zn—O4	94.74 (7)	C2—C1—H1A	109.5
O1—Zn—O4	169.61 (7)	O3—C1—H1B	109.5
O3—Zn—O4	78.01 (7)	C2—C1—H1B	109.5
O2—Zn—O6	167.62 (7)	H1A—C1—H1B	108.1
O7—Zn—O6	76.15 (7)	O5—C2—O4	124.2 (2)
O1—Zn—O6	86.90 (7)	O5—C2—C1	116.8 (2)
O3—Zn—O6	90.53 (7)	O4—C2—C1	119.00 (19)
O4—Zn—O6	95.53 (7)	O6—C3—C4	109.64 (19)
Zn—O1—H7	117.5	O6—C3—H2A	109.7
Zn—O1—H8	124.3	C4—C3—H2A	109.7
H7—O1—H8	101.3	O6—C3—H2B	109.7
Zn—O2—H5	122.2	C4—C3—H2B	109.7
Zn—O2—H6	125.1	H2A—C3—H2B	108.2
H5—O2—H6	107.2	O8—C4—O7	124.3 (2)
C1—O3—Zn	115.05 (14)	O8—C4—C3	117.4 (2)
C1—O3—H3	108.8	O7—C4—C3	118.3 (2)
Zn—O3—H3	110.3

O2—Zn—O3—C1	−84.29 (19)	O2—Zn—O7—C4	−174.79 (18)
O7—Zn—O3—C1	67.0 (3)	O1—Zn—O7—C4	−84.91 (18)
O1—Zn—O3—C1	−174.31 (18)	O3—Zn—O7—C4	33.4 (4)
O4—Zn—O3—C1	3.24 (18)	O4—Zn—O7—C4	95.01 (18)
O6—Zn—O3—C1	98.77 (18)	O6—Zn—O7—C4	0.47 (17)
O2—Zn—O4—C2	94.74 (19)	Zn—O3—C1—C2	0.1 (3)
O7—Zn—O4—C2	−172.86 (19)	Zn—O4—C2—O5	−170.4 (2)
O1—Zn—O4—C2	6.7 (5)	Zn—O4—C2—C1	9.4 (3)
O3—Zn—O4—C2	−6.98 (18)	O3—C1—C2—O5	173.5 (2)
O6—Zn—O4—C2	−96.36 (19)	O3—C1—C2—O4	−6.3 (3)
O2—Zn—O6—C3	21.4 (5)	Zn—O6—C3—C4	1.6 (2)
O7—Zn—O6—C3	−1.22 (16)	Zn—O7—C4—O8	179.73 (17)
O1—Zn—O6—C3	95.41 (17)	Zn—O7—C4—C3	0.3 (3)
O3—Zn—O6—C3	−172.75 (16)	O6—C3—C4—O8	179.2 (2)
O4—Zn—O6—C3	−94.73 (17)	O6—C3—C4—O7	−1.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H8···O4ⁱ	0.90	1.93	2.821 (3)	167
O1—H7···O8ⁱⁱ	0.88	1.84	2.716 (3)	174
O2—H6···O5ⁱ	0.91	1.82	2.697 (3)	161
O2—H5···O5ⁱⁱⁱ	0.85	1.88	2.688 (3)	158
O6—H4···O8^iv	0.84	1.82	2.665 (2)	177
O3—H3···O7^iv	0.83	1.97	2.761 (3)	160

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

Experimental details

Crystal data
Chemical formula	[Zn(C₂H₃O₃)₂(H₂O)₂]
M_r	251.49
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	273
a, b, c (Å)	11.391 (2), 5.857 (1), 12.511 (2)
β (°)	91.198 (9)
V (Å³)	834.5 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.96
Crystal size (mm)	0.3 × 0.3 × 0.1

Data collection
Diffractometer	Bruker P4 diffractometer
Absorption correction	ψ scan (SADABS; Bruker, 2000)
T_min, T_max	0.425, 0.744
No. of measured, independent and observed [I > 2σ(I)] reflections	2102, 2102, 1751
R_int	0.000
(sin θ/λ)_max (Å⁻¹)	0.671

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.072, 0.99
No. of reflections	2102
No. of parameters	119
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.51

Computer programs: XSCANS (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H8···O4ⁱ	0.90	1.93	2.821 (3)	167
O1—H7···O8ⁱⁱ	0.88	1.84	2.716 (3)	174
O2—H6···O5ⁱ	0.91	1.82	2.697 (3)	161
O2—H5···O5ⁱⁱⁱ	0.85	1.88	2.688 (3)	158
O6—H4···O8^iv	0.84	1.82	2.665 (2)	177
O3—H3···O7^iv	0.83	1.97	2.761 (3)	160

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

Acknowledgements

The authors thank the Research Corporation (CC6447) for financial support and the National Science Foundation for grant No. ILI8951058.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
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Fischinger, A. J. & Webb, L. E. (1969). Chem. Commun. pp. 407–408. CSD CrossRef Google Scholar
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