The first oxazoline adduct of Zn(acac)2: bis­(acetyl­acetonato-κ2O,O′)(2-phenyl-2-oxazoline-κN)zinc(II)

Río, I. del; Gossage, R.A.

doi:10.1107/S1600536808042712

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 1| January 2009| Pages m103-m104

doi:10.1107/S1600536808042712

Open

access

The first oxazoline adduct of Zn(acac)₂: bis(acetylacetonato-κ²O,O′)(2-phenyl-2-oxazoline-κN)zinc(II)

Ignacio del Río ^a and Robert A. Gossage ^b ^*

^aDepartamento de Química Orgánica e Inorgánica, Facultad de Química, Universidad de Oviedo, Avda. Julián Clavería, 8, 33006 Oviedo, Spain, and ^bDepartment of Chemistry & Biology, Ryerson University, 350 Victoria Street, Toronto, ON M5B 2K3, Canada
^*Correspondence e-mail: gossage@ryerson.ca

(Received 3 October 2008; accepted 15 December 2008; online 20 December 2008)

The title material, [Zn(C₅H₇O₂)₂(C₉H₉NO)], was synthesized by the treatment of bis(acetylacetonato)zinc(II) monohydrate with 2-phenyl-2-oxazoline. The Zn atom is coordinated by two chelating acetylacetonate groups and one oxazoline ligand in the apical position of a slightly distorted square-pyramidal metal–ligand geometry.

Related literature

For general background, see: Addison et al. (1984 ); Itoh et al. (1989 ); Kaeriyama (1974 ); Williams (1989 ). For related structures, see: Barclay et al. (2003 ); Brahma et al. (2008 ); Decken et al. (2006 ); Fronczek et al. (1990 ); Gossage & Jenkins (2008 ); Gossage et al. (2009 ); Hamid et al. (2005 ); Qian et al. (2006 ).

Experimental

Crystal data

[Zn(C₅H₇O₂)₂(C₉H₉NO)]
M_r = 410.77
Orthorhombic, P 2₁ 2₁ 2₁
a = 9.5009 (3) Å
b = 14.1674 (4) Å
c = 14.2407 (5) Å
V = 1916.84 (11) Å³
Z = 4
Cu Kα radiation
μ = 2.03 mm⁻¹
T = 200 (2) K
0.28 × 0.15 × 0.08 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: refined from ΔF (Parkin et al., 1995 ) T_min = 0.542, T_max = 0.859
8596 measured reflections
3600 independent reflections
3466 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.080
S = 1.05
3600 reflections
236 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Selected bond lengths (Å)

N1—Zn1	2.0844 (19)
O2—Zn1	2.0253 (19)
O3—Zn1	2.0136 (17)
O4—Zn1	2.0359 (19)
O5—Zn1	2.0169 (18)

Data collection: COLLECT (Nonius, 1998 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: DIRDIF96 (Beurskens et al., 1996 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: EUCLID (Spek, 1982 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808042712/kj2105sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808042712/kj2105Isup2.hkl

checkCIF report

Comment top

In recent years, zinc acetylacetonate (ZAA) complexes have found significant applications in CVD technology (Itoh et al., 1989; Kaeriyama, 1974; Williams, 1989), as Lewis acids in coordination chemistry (Brahma et al., 2008; Fronczek et al., 1990; Hamid et al., 2005) and are used for the formation of inorganic polymers (Qian et al., 2006). In many cases, the ZAA species are paired with N-donor ligands to modify and tune their physical and spectroscopic properties. We recently disclosed the syntheses and structural characterization of a number of Zn coordination compounds containing monodentate 2-oxazoline ligands (Barclay et al., 2003; Decken et al., 2006; Gossage & Jenkins, 2008; Gossage et al., 2009). These materials represent a number of structural motifs around the Zn²⁺coordination sphere which includes the observation of pseudo-tetrahedral and distorted trigonal bipyramidal geometries. The nature of these coordination motifs are obviously influenced by both the nature of the oxazoline ligand(s) and the structure and donor properties of the various formal anions appending the Zn atom. In this report, we expand these investigations to include ZAA precursors and describe our first results in the coupling of oxazolines to a ZAA unit.

The crystal structure determination of the title compound reveals that the central Zn atom is coordinated by four O-atoms of two chelating (i.e.,κ²O,O') acetylacetonato (acac) fragments in addition to the attachment of the oxazoline ligand via the N-atom. Th Zn–N bond length is similar to that of the distorted tetrahedral (at Zn) complexes (Barclay et al., 2003) [ZnX₂(Phox-κ¹N)₂] (Zn–N = 2.026 (2) and 2.050 (2) Å for X = Cl; Zn–N = 2.025 (3) and 2.053 (3) Å for X = Br; Phox = 2-phenyl-2-oxazoline) and the related (Decken et al., 2006) five-coordinate species [Zn(S₂CNEt₂-κ²S,S')₂(Phox-κ¹N)] (Zn–N = 2.082 (4) Å). The Zn–O bond lengths of the formally anionic acac ligands of the title material are all inequivalent but fall within a narrow range (2.01–2.04 Å).

The Zn-phox complex reported by Decken et al. (2006) possesses a coordination motif around Zn that is best described (Addison et al., 1984) as highly distorted trigonal bipyramidal (τ = 0.65) whereas the title complex is strongly disposed towards a structure of idealized square pyramidal (τ = 0.04). The τ parameter is a numerical descriptor defined as unity for pure trigonal bipyramidal structures and zero for true square pyramidal ones (Addison et al., 1984).

This coordination geometry places the N-bound oxazoline in the formal apical position of such a square pyramid. ZAA complexes containing N-donor lignads are often found to be octahedral in nature with an "O₄N₂" donor atom set (Brahma et al., 2008; Fronczek et al., 1990; Hamid et al., 2005; Qian et al., 2006). The title material therefore represents the more rare "O₄N"-type compound.

Our structural studies have so far observed both four- and five-coordinate ZnX₂(X = halide, S₂CNRR', acac) oxazoline systems (Barclay et al., 2003; Decken et al., 2006; Gossage & Jenkins, 2008; Gossage et al., 2009). Intriguingly, an octahedral Zn-oxazoline complex has yet to be observed; this suggests that perhaps the use of weakly coordinating anions (e.g., NO₃^-, ClO₄^-,etc.) and/or sterically smaller oxazolines may assist us in discovering this structural class of Zn materials. Our future work will involve such investigations.

Related literature top

For general background, see: Addison et al. (1984); Itoh et al. (1989); Kaeriyama (1974); Williams (1989). For related structures, see: Barclay et al. (2003); Brahma et al. (2008); Decken et al. (2006); Fronczek et al. (1990); Gossage & Jenkins (2008); Gossage et al. (2009); Hamid et al. (2005); Qian et al. (2006).

Experimental top

The treatment of a benzene solution of commercially available bis(acetylacetonato-κ²O,O')zinc(II) (in the form of the monohydrate) with an excess of Phox leads to the formation of a clear and colourless solution. The removal of volatile components (vacuo) followed by re-crystallization (CH₂Cl₂/Et₂O) of the resulting off white oily solid leads to the isolation of colourless crystals of the product (65%).

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: DIRDIF96 (Beurskens et al., 1996); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: EUCLID (Spek, 1982); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. View of the title compound. Ellipsoids are drawn at the 30% probability level.

bis(acetylacetonato-κ²O,O')(2-phenyl-2-oxazoline- κN)zinc(II) top

Crystal data top

[Zn(C₅H₇O₂)₂(C₉H₉NO)]	F(000) = 856
M_r = 410.77	D_x = 1.430 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1999 reflections
a = 9.5009 (3) Å	θ = 4.4–69.6°
b = 14.1674 (4) Å	µ = 2.03 mm⁻¹
c = 14.2407 (5) Å	T = 200 K
V = 1916.84 (11) Å³	Blocks, white
Z = 4	0.28 × 0.15 × 0.08 mm

Data collection top

Nonius KappaCCD diffractometer	3600 independent reflections
Radiation source: fine-focus sealed tube	3466 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	R_int = 0.035
Detector resolution: 9 pixels mm^-1	θ_max = 69.6°, θ_min = 4.4°
ϕ and ω scans	h = −11→11
Absorption correction: part of the refinement model (ΔF) (Parkin et al., 1995)	k = −17→17
T_min = 0.542, T_max = 0.859	l = −17→17
8596 measured reflections

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.080	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0434P)² + 0.5913P] where P = (F_o² + 2F_c²)/3
3600 reflections	(Δ/σ)_max < 0.001
236 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³
0 constraints

Crystal data top

[Zn(C₅H₇O₂)₂(C₉H₉NO)]	V = 1916.84 (11) Å³
M_r = 410.77	Z = 4
Orthorhombic, P2₁2₁2₁	Cu Kα radiation
a = 9.5009 (3) Å	µ = 2.03 mm⁻¹
b = 14.1674 (4) Å	T = 200 K
c = 14.2407 (5) Å	0.28 × 0.15 × 0.08 mm

Data collection top

Nonius KappaCCD diffractometer	3600 independent reflections
Absorption correction: part of the refinement model (ΔF) (Parkin et al., 1995)	3466 reflections with I > 2σ(I)
T_min = 0.542, T_max = 0.859	R_int = 0.035
8596 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.080	H-atom parameters constrained
S = 1.05	Δρ_max = 0.24 e Å⁻³
3600 reflections	Δρ_min = −0.29 e Å⁻³
236 parameters

Special details top

Experimental. Absorption correction: Parkin et al., 1995. Cubic fit to sin(θ)/λ; 24 parameters ¹H NMR [300 MHz: CDCl₃]: δ_H (vs. TMS) = 1.87 [s, 12H, –CH₃], 4.03 [t, J = 11.7 Hz, 2H, –CH₂N], 4.48 [t, 2H, –CH₂O], 5.26 [s, 2H, –CH], 7.38 [m, 4H, ArH], 7.85 [d, J = 8.8 Hz,1H, ArH]; ¹³C{¹H}NMR (75 MHz; CDCl₃): δ_C (vs. TMS) = 28.1, 53.7, 68.2, 99.9, 125.9, 128.2, 129.0, 132.0, 165.0(w), 193.1).

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
C1	0.3061 (3)	−0.0086 (3)	−0.06798 (17)	0.0483 (7)
H1A	0.2514	0.0460	−0.0870	0.058*
H1B	0.2575	−0.0654	−0.0879	0.058*
C2	0.4526 (3)	−0.0046 (2)	−0.10858 (16)	0.0433 (6)
H2A	0.4650	−0.0522	−0.1569	0.052*
H2B	0.4720	0.0570	−0.1352	0.052*
C3	0.4621 (2)	−0.01785 (18)	0.04907 (15)	0.0316 (5)
C4	0.5407 (3)	−0.02065 (17)	0.13820 (16)	0.0319 (5)
C5	0.6862 (3)	−0.01280 (19)	0.13607 (17)	0.0374 (5)
H5	0.7331	−0.0086	0.0789	0.045*
C6	0.7613 (3)	−0.0112 (2)	0.21951 (18)	0.0430 (6)
H6	0.8589	−0.0061	0.2181	0.052*
C7	0.6925 (3)	−0.0173 (2)	0.30468 (18)	0.0406 (6)
H7	0.7435	−0.0149	0.3604	0.049*
C8	0.5487 (3)	−0.0269 (2)	0.30720 (18)	0.0418 (6)
H8	0.5027	−0.0317	0.3646	0.050*
C9	0.4715 (3)	−0.02941 (19)	0.22414 (18)	0.0378 (6)
H9	0.3743	−0.0369	0.2260	0.045*
C10	−0.1142 (4)	−0.2000 (3)	−0.0308 (2)	0.0620 (9)
H10A	−0.1390	−0.1528	−0.0763	0.093*
H10B	−0.1980	−0.2232	−0.0010	0.093*
H10C	−0.0667	−0.2512	−0.0616	0.093*
C11	−0.0186 (3)	−0.1573 (2)	0.0420 (2)	0.0426 (6)
C12	0.0308 (3)	−0.21237 (19)	0.1148 (2)	0.0485 (7)
H12	0.0107	−0.2766	0.1119	0.058*
C13	0.1077 (3)	−0.18128 (18)	0.1921 (2)	0.0409 (6)
C14	0.1554 (4)	−0.2508 (2)	0.2652 (2)	0.0602 (8)
H14A	0.2077	−0.2183	0.3129	0.090*
H14B	0.2141	−0.2977	0.2364	0.090*
H14C	0.0748	−0.2807	0.2929	0.090*
C15	0.0715 (4)	0.2718 (2)	−0.0305 (2)	0.0611 (9)
H15A	0.0125	0.2405	−0.0756	0.092*
H15B	0.1545	0.2951	−0.0612	0.092*
H15C	0.0210	0.3235	−0.0030	0.092*
C16	0.1131 (3)	0.20281 (19)	0.0454 (2)	0.0430 (7)
C17	0.1982 (3)	0.23396 (18)	0.1187 (2)	0.0466 (7)
H17	0.2349	0.2946	0.1139	0.056*
C18	0.2333 (3)	0.18219 (18)	0.19881 (19)	0.0407 (6)
C19	0.3242 (4)	0.2251 (2)	0.2731 (2)	0.0591 (9)
H19A	0.3384	0.1802	0.3228	0.089*
H19B	0.2791	0.2804	0.2978	0.089*
H19C	0.4135	0.2421	0.2466	0.089*
N1	0.32955 (19)	−0.00883 (16)	0.03537 (13)	0.0343 (4)
O1	0.54378 (17)	−0.02335 (15)	−0.02807 (12)	0.0415 (4)
O2	0.0063 (2)	−0.06991 (14)	0.03232 (13)	0.0445 (5)
O3	0.1428 (2)	−0.09589 (12)	0.20636 (12)	0.0397 (4)
O4	0.0640 (2)	0.12044 (14)	0.03780 (13)	0.0454 (5)
O5	0.1921 (2)	0.09787 (12)	0.21440 (13)	0.0402 (4)
Zn1	0.14228 (3)	0.00792 (2)	0.10978 (2)	0.03289 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0386 (13)	0.078 (2)	0.0279 (12)	−0.0026 (15)	−0.0031 (10)	0.0011 (15)
C2	0.0376 (12)	0.0633 (17)	0.0291 (11)	0.0052 (13)	−0.0037 (9)	0.0008 (15)
C3	0.0341 (12)	0.0299 (13)	0.0307 (11)	−0.0014 (10)	0.0023 (9)	−0.0004 (10)
C4	0.0354 (12)	0.0272 (12)	0.0331 (11)	0.0032 (10)	−0.0031 (9)	−0.0007 (9)
C5	0.0336 (12)	0.0412 (14)	0.0374 (12)	0.0001 (11)	0.0012 (9)	0.0030 (11)
C6	0.0332 (12)	0.0524 (17)	0.0435 (14)	−0.0003 (13)	−0.0040 (10)	0.0027 (14)
C7	0.0400 (13)	0.0421 (14)	0.0398 (13)	0.0048 (12)	−0.0103 (10)	−0.0032 (12)
C8	0.0427 (14)	0.0507 (17)	0.0321 (12)	0.0070 (12)	−0.0009 (10)	0.0006 (11)
C9	0.0313 (12)	0.0457 (16)	0.0365 (13)	0.0020 (11)	0.0007 (10)	−0.0022 (11)
C10	0.068 (2)	0.0600 (19)	0.0585 (19)	−0.0184 (17)	−0.0087 (16)	−0.0061 (16)
C11	0.0338 (14)	0.0421 (15)	0.0519 (16)	−0.0045 (12)	0.0040 (12)	−0.0090 (12)
C12	0.0532 (17)	0.0314 (13)	0.0610 (18)	−0.0033 (12)	−0.0049 (15)	−0.0036 (14)
C13	0.0409 (15)	0.0313 (13)	0.0505 (15)	0.0014 (11)	0.0046 (12)	0.0035 (11)
C14	0.067 (2)	0.0442 (16)	0.069 (2)	0.0031 (16)	−0.0091 (18)	0.0123 (15)
C15	0.080 (2)	0.049 (2)	0.0546 (19)	0.0087 (17)	−0.0094 (18)	0.0076 (15)
C16	0.0487 (17)	0.0333 (14)	0.0471 (16)	0.0081 (12)	0.0045 (13)	0.0025 (11)
C17	0.0545 (16)	0.0306 (13)	0.0548 (18)	−0.0056 (12)	0.0001 (14)	0.0031 (13)
C18	0.0430 (15)	0.0346 (14)	0.0446 (15)	−0.0032 (12)	0.0031 (12)	−0.0030 (11)
C19	0.073 (2)	0.0449 (17)	0.0589 (19)	−0.0137 (16)	−0.0123 (16)	−0.0033 (14)
N1	0.0333 (10)	0.0416 (11)	0.0281 (9)	−0.0003 (10)	−0.0020 (7)	−0.0012 (9)
O1	0.0335 (8)	0.0607 (13)	0.0303 (8)	0.0036 (9)	0.0014 (7)	0.0009 (8)
O2	0.0448 (11)	0.0447 (12)	0.0439 (10)	−0.0115 (9)	−0.0053 (8)	0.0031 (9)
O3	0.0431 (10)	0.0378 (9)	0.0384 (9)	−0.0065 (9)	0.0006 (9)	0.0031 (7)
O4	0.0506 (12)	0.0378 (10)	0.0478 (11)	0.0042 (9)	−0.0092 (9)	0.0004 (8)
O5	0.0517 (12)	0.0340 (9)	0.0350 (10)	−0.0027 (8)	0.0014 (8)	−0.0017 (7)
Zn1	0.03214 (17)	0.03310 (17)	0.03342 (17)	−0.00265 (14)	0.00149 (12)	0.00024 (14)

Geometric parameters (Å, º) top

C1—N1	1.489 (3)	C11—C12	1.379 (4)
C1—C2	1.508 (3)	C12—C13	1.393 (4)
C1—H1A	0.9700	C12—H12	0.9300
C1—H1B	0.9700	C13—O3	1.271 (3)
C2—O1	1.461 (3)	C13—C14	1.503 (4)
C2—H2A	0.9700	C14—H14A	0.9600
C2—H2B	0.9700	C14—H14B	0.9600
C3—N1	1.281 (3)	C14—H14C	0.9600
C3—O1	1.347 (3)	C15—C16	1.510 (4)
C3—C4	1.473 (3)	C15—H15A	0.9600
C4—C5	1.387 (4)	C15—H15B	0.9600
C4—C9	1.395 (4)	C15—H15C	0.9600
C5—C6	1.387 (3)	C16—O4	1.261 (4)
C5—H5	0.9300	C16—C17	1.393 (4)
C6—C7	1.381 (4)	C17—C18	1.397 (4)
C6—H6	0.9300	C17—H17	0.9300
C7—C8	1.373 (4)	C18—O5	1.277 (3)
C7—H7	0.9300	C18—C19	1.495 (4)
C8—C9	1.392 (4)	C19—H19A	0.9600
C8—H8	0.9300	C19—H19B	0.9600
C9—H9	0.9300	C19—H19C	0.9600
C10—C11	1.506 (4)	N1—Zn1	2.0844 (19)
C10—H10A	0.9600	O2—Zn1	2.0253 (19)
C10—H10B	0.9600	O3—Zn1	2.0136 (17)
C10—H10C	0.9600	O4—Zn1	2.0359 (19)
C11—O2	1.268 (4)	O5—Zn1	2.0169 (18)

N1—C1—C2	103.94 (19)	C12—C13—C14	119.9 (3)
N1—C1—H1A	111.0	C13—C14—H14A	109.5
C2—C1—H1A	111.0	C13—C14—H14B	109.5
N1—C1—H1B	111.0	H14A—C14—H14B	109.5
C2—C1—H1B	111.0	C13—C14—H14C	109.5
H1A—C1—H1B	109.0	H14A—C14—H14C	109.5
O1—C2—C1	103.86 (18)	H14B—C14—H14C	109.5
O1—C2—H2A	111.0	C16—C15—H15A	109.5
C1—C2—H2A	111.0	C16—C15—H15B	109.5
O1—C2—H2B	111.0	H15A—C15—H15B	109.5
C1—C2—H2B	111.0	C16—C15—H15C	109.5
H2A—C2—H2B	109.0	H15A—C15—H15C	109.5
N1—C3—O1	116.6 (2)	H15B—C15—H15C	109.5
N1—C3—C4	129.2 (2)	O4—C16—C17	124.9 (3)
O1—C3—C4	114.17 (19)	O4—C16—C15	116.2 (3)
C5—C4—C9	119.7 (2)	C17—C16—C15	118.9 (3)
C5—C4—C3	118.9 (2)	C16—C17—C18	125.8 (2)
C9—C4—C3	121.3 (2)	C16—C17—H17	117.1
C6—C5—C4	119.7 (2)	C18—C17—H17	117.1
C6—C5—H5	120.1	O5—C18—C17	124.1 (3)
C4—C5—H5	120.1	O5—C18—C19	115.8 (3)
C7—C6—C5	120.5 (2)	C17—C18—C19	120.2 (3)
C7—C6—H6	119.7	C18—C19—H19A	109.5
C5—C6—H6	119.7	C18—C19—H19B	109.5
C8—C7—C6	120.0 (2)	H19A—C19—H19B	109.5
C8—C7—H7	120.0	C18—C19—H19C	109.5
C6—C7—H7	120.0	H19A—C19—H19C	109.5
C7—C8—C9	120.3 (2)	H19B—C19—H19C	109.5
C7—C8—H8	119.9	C3—N1—C1	107.34 (19)
C9—C8—H8	119.9	C3—N1—Zn1	140.65 (16)
C8—C9—C4	119.7 (2)	C1—N1—Zn1	112.00 (14)
C8—C9—H9	120.2	C3—O1—C2	106.74 (17)
C4—C9—H9	120.2	C11—O2—Zn1	126.22 (19)
C11—C10—H10A	109.5	C13—O3—Zn1	125.81 (17)
C11—C10—H10B	109.5	C16—O4—Zn1	123.14 (18)
H10A—C10—H10B	109.5	C18—O5—Zn1	122.33 (18)
C11—C10—H10C	109.5	O3—Zn1—O5	87.50 (7)
H10A—C10—H10C	109.5	O3—Zn1—O2	88.62 (8)
H10B—C10—H10C	109.5	O5—Zn1—O2	153.64 (8)
O2—C11—C12	124.8 (3)	O3—Zn1—O4	156.45 (8)
O2—C11—C10	115.4 (3)	O5—Zn1—O4	87.87 (8)
C12—C11—C10	119.7 (3)	O2—Zn1—O4	85.36 (8)
C11—C12—C13	126.4 (3)	O3—Zn1—N1	105.19 (8)
C11—C12—H12	116.8	O5—Zn1—N1	104.31 (8)
C13—C12—H12	116.8	O2—Zn1—N1	101.87 (8)
O3—C13—C12	124.4 (3)	O4—Zn1—N1	98.33 (8)
O3—C13—C14	115.7 (3)

N1—C1—C2—O1	11.7 (3)	C10—C11—O2—Zn1	−174.4 (2)
N1—C3—C4—C5	−167.8 (3)	C12—C13—O3—Zn1	−16.7 (4)
O1—C3—C4—C5	10.4 (4)	C14—C13—O3—Zn1	163.0 (2)
N1—C3—C4—C9	11.2 (5)	C17—C16—O4—Zn1	−17.8 (4)
O1—C3—C4—C9	−170.6 (2)	C15—C16—O4—Zn1	163.8 (2)
C9—C4—C5—C6	−1.7 (4)	C17—C18—O5—Zn1	26.4 (4)
C3—C4—C5—C6	177.3 (2)	C19—C18—O5—Zn1	−153.8 (2)
C4—C5—C6—C7	−0.1 (5)	C13—O3—Zn1—O5	174.6 (2)
C5—C6—C7—C8	1.3 (5)	C13—O3—Zn1—O2	20.7 (2)
C6—C7—C8—C9	−0.7 (5)	C13—O3—Zn1—O4	95.8 (3)
C7—C8—C9—C4	−1.0 (4)	C13—O3—Zn1—N1	−81.2 (2)
C5—C4—C9—C8	2.2 (4)	C18—O5—Zn1—O3	167.7 (2)
C3—C4—C9—C8	−176.7 (2)	C18—O5—Zn1—O2	−110.5 (2)
O2—C11—C12—C13	4.3 (5)	C18—O5—Zn1—O4	−35.4 (2)
C10—C11—C12—C13	−173.1 (3)	C18—O5—Zn1—N1	62.7 (2)
C11—C12—C13—O3	0.4 (5)	C11—O2—Zn1—O3	−16.6 (2)
C11—C12—C13—C14	−179.3 (3)	C11—O2—Zn1—O5	−98.1 (3)
O4—C16—C17—C18	−5.6 (5)	C11—O2—Zn1—O4	−173.8 (2)
C15—C16—C17—C18	172.8 (3)	C11—O2—Zn1—N1	88.7 (2)
C16—C17—C18—O5	0.8 (5)	C16—O4—Zn1—O3	110.2 (3)
C16—C17—C18—C19	−179.0 (3)	C16—O4—Zn1—O5	31.4 (2)
O1—C3—N1—C1	0.8 (4)	C16—O4—Zn1—O2	−174.1 (2)
C4—C3—N1—C1	178.9 (3)	C16—O4—Zn1—N1	−72.7 (2)
O1—C3—N1—Zn1	−177.5 (2)	C3—N1—Zn1—O3	−51.4 (3)
C4—C3—N1—Zn1	0.6 (5)	C1—N1—Zn1—O3	130.4 (2)
C2—C1—N1—C3	−8.1 (4)	C3—N1—Zn1—O5	39.9 (3)
C2—C1—N1—Zn1	170.75 (19)	C1—N1—Zn1—O5	−138.3 (2)
N1—C3—O1—C2	7.2 (3)	C3—N1—Zn1—O2	−143.2 (3)
C4—C3—O1—C2	−171.2 (2)	C1—N1—Zn1—O2	38.5 (2)
C1—C2—O1—C3	−11.5 (3)	C3—N1—Zn1—O4	129.8 (3)
C12—C11—O2—Zn1	8.1 (4)	C1—N1—Zn1—O4	−48.4 (2)

Experimental details

Crystal data
Chemical formula	[Zn(C₅H₇O₂)₂(C₉H₉NO)]
M_r	410.77
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	200
a, b, c (Å)	9.5009 (3), 14.1674 (4), 14.2407 (5)
V (Å³)	1916.84 (11)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	2.03
Crystal size (mm)	0.28 × 0.15 × 0.08

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Part of the refinement model (ΔF) (Parkin et al., 1995)
T_min, T_max	0.542, 0.859
No. of measured, independent and observed [I > 2σ(I)] reflections	8596, 3600, 3466
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.608

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.080, 1.05
No. of reflections	3600
No. of parameters	236
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.29

Computer programs: COLLECT (Nonius, 1998), SCALEPACK (Otwinowski & Minor, 1997), SCALEPACK and DENZO (Otwinowski & Minor, 1997), DIRDIF96 (Beurskens et al., 1996), SHELXL97 (Sheldrick, 2008), EUCLID (Spek, 1982).

Selected bond lengths (Å) top

N1—Zn1	2.0844 (19)	O4—Zn1	2.0359 (19)
O2—Zn1	2.0253 (19)	O5—Zn1	2.0169 (18)
O3—Zn1	2.0136 (17)

Acknowledgements

The authors are grateful for the support of NSERC (Canada), the Atlantic Regional Magnetic Resonance Centre (ARMRC) and for the assistance of the Spanish MEC–MCyT research project BQU2002–2326.

References

Addison, A. W., Rao, T. N., Reedijk, J., van Rijn, J. & Verschoor, G. C. (1984). J. Chem. Soc. Dalton Trans, pp. 1349–1356. Google Scholar
Barclay, T. M., del Río, I., Gossage, R. A. & Jackson, S. M. (2003). Can. J. Chem. 81, 1482–1491. Web of Science CSD CrossRef CAS Google Scholar
Beurskens, P. T., Admiraal, G., Beurskens, G., Bosman, W. P., García-Granda, S., Gould, R. O., Smits, J. M. M. & Smykalla, C. (1996). The DIRDIF96 Program Sstem. Technical Report of the Crystallography Laboratory, University of Nijmegen, The Netherlands. Google Scholar
Brahma, S., Sachin, H. P., Shivashankar, S. A., Narasimhamurthy, T. & Rathore, R. S. (2008). Acta Cryst. C64, m140–m143. Web of Science CSD CrossRef IUCr Journals Google Scholar
Decken, A., Eisnor, C. R., Gossage, R. A. & Jackson, S. M. (2006). Inorg. Chim. Acta, 359, 1743–1753. Web of Science CSD CrossRef CAS Google Scholar
Fronczek, F. R., Ivie, M. L. & Maverick, A. W. (1990). Acta Cryst. C46, 2057–2062. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Gossage, R. A. & Jenkins, H. A. (2008). Anal. Sci. 24, x155–x156. CAS Google Scholar
Gossage, R. A., Yadav, P. N., MacInnis, T. D., Quail, J. W. & Decken, A. (2009). Can. J. Chem. 87, 368–379. Web of Science CSD CrossRef CAS Google Scholar
Hamid, M., Mazhar, M., Ali, A., Zeller, M. & Hunter, A. D. (2005). Acta Cryst. E61, m1539–m1541. Web of Science CSD CrossRef IUCr Journals Google Scholar
Itoh, H., Uemura, T., Yamaguchi, H. & Naka, S. (1989). J. Mater. Sci. 24, 3549–3552. CrossRef CAS Web of Science Google Scholar
Kaeriyama, K. (1974). Makromol. Chem. 175, 2285–2291. CrossRef CAS Google Scholar
Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Parkin, S., Moezzi, B. & Hope, H. (1995). J. Appl. Cryst. 28, 53–56. CrossRef CAS Web of Science IUCr Journals Google Scholar
Qian, B.-H., Ma, W.-X., Lu, L.-D., Yang, X.-J. & Wang, X. (2006). Acta Cryst. E62, m2818–m2819. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (1982). The EUCLID Package in Computational Crystallography, edited by D. Sayre, p. 528. Oxford: Clarendon Press. Google Scholar
Williams, J. O. (1989). Angew. Chem. Int. Ed. Engl. 28, 1110–1120. CrossRef Web of Science Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.