Bis(μ-2-methyl­quinolin-8-olato)-κ³ N,O:O;κ³ O:N,O-bis­[(acetato-κO)(methanol-κO)zinc(II)]

Abstract

The reaction of zinc acetate and 2-methyl-8-hydroxy­quinoline in methanol yielded the centrosymmetric dinuclear title compound, [Zn₂(C₁₀H₈NO)₂(CH₃CO₂)₂(CH₃OH)₂], which has the Zn atom within a distorted NO₄ trigonal–bipyramidal coordination geometry. Methanol–acetate O—H⋯O hydrogen bonds link the dinculear units into a linear supra­molecular chain extending parallel to [100].

Related literature

Unlike 8-hydroxy­quinoline, which yields a large number of metal derivatives, 2-methyl-8-hydroxy­quinoline forms only a small number of metal chelates. Besides a related chloride salt (Sattarzadeh et al., 2009 ▶), there is only one crystal structure report of another zinc derivative; for aqua­bis(2-methyl­quinolin-8-ato)zinc, see: da Silva et al. (2007 ▶).

Experimental

Crystal data

• [Zn₂(C₁₀H₈NO)₂(C₂H₃O₂)₂(CH₄O)₂]

• M _r = 629.26

• Triclinic,

• a = 6.9496 (1) Å

• b = 9.6262 (2) Å

• c = 9.8232 (2) Å

• α = 75.241 (1)°

• β = 89.688 (1)°

• γ = 86.596 (1)°

• V = 634.32 (2) ų

• Z = 1

• Mo Kα radiation

• μ = 1.95 mm⁻¹

• T = 100 K

• 0.38 × 0.28 × 0.18 mm

Data collection

• Bruker SMART APEX diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.525, T _max = 0.721

• 5601 measured reflections

• 2855 independent reflections

• 2534 reflections with I > 2σ(I)

• R _int = 0.042

Refinement

• R[F ² > 2σ(F ²)] = 0.076

• wR(F ²) = 0.230

• S = 1.13

• 2855 reflections

• 175 parameters

• H-atom parameters constrained

• Δρ_max = 3.72 e Å⁻³

• Δρ_min = −1.85 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2009 ▶).

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4⋯O3i	0.84	1.88	2.602 (6)	143

Symmetry code: (i) .

supplementary crystallographic information

Experimental

Zinc acetate (0.17 g, 0.75 mmol) and 2-methyl-8-hydroxyquinoline (0.24 g, 1.5 mmol) were loaded into a convection tube; the tube was filled with dry methanol and kept at 333 K. Crystals were collected from the side arm after several days. Although well formed, all specimens had a slightly blemished interior.

Refinement

The crystal used in the study was a multiply twinned crystal. The diffraction intensities were separated with the RLATT routine of the data collection software, and that component that diffracted to the highest 2θ limit was selected for integration. Although the specimen diffracted strongly, with a high proportion of 'observeds', there was serious overlapping between the main component and the minor components, particularly at low angles.

Carbon-bound H-atoms were placed in calculated positions (C—H 0.95 to 0.98 Å; O–H 0.84 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2 to 1.5U(C, O).

The final difference Fourier map had a large peak/deep hole in the vicinity of the Zn1 atom. These could not be reduced even with the 2θ maximum was lowered to 50 °.

Figures

Fig. 1.

Thermal ellipsoid plot (Barbour, 2001) of dinuclear [Zn(C10H8NO)(CH3OH)(CH3CO2)]2; ellipsoids are drawn at the 70% probability level and H atoms of arbitrary radius. The unlabelled atoms are related by a centre of inversion.

Crystal data

[Zn2(C10H8NO)2(C2H3O2)2(CH4O)2]	Z = 1
Mr = 629.26	F(000) = 324
Triclinic, P1	Dx = 1.647 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.9496 (1) Å	Cell parameters from 3551 reflections
b = 9.6262 (2) Å	θ = 2.2–28.3°
c = 9.8232 (2) Å	µ = 1.95 mm−1
α = 75.241 (1)°	T = 100 K
β = 89.688 (1)°	Block, yellow
γ = 86.596 (1)°	0.38 × 0.28 × 0.18 mm
V = 634.32 (2) Å3

Data collection

Bruker SMART APEX diffractometer	2855 independent reflections
Radiation source: fine-focus sealed tube	2534 reflections with I > 2σ(I)
graphite	Rint = 0.042
ω scans	θmax = 27.5°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.525, Tmax = 0.721	k = −12→12
5601 measured reflections	l = −12→12

Refinement

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)] = 0.076	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.230	H-atom parameters constrained
S = 1.13	w = 1/[σ2(Fo2) + (0.1574P)2 + 1.7954P] where P = (Fo2 + 2Fc2)/3
2855 reflections	(Δ/σ)max = 0.001
175 parameters	Δρmax = 3.72 e Å−3
0 restraints	Δρmin = −1.85 e Å−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Zn1	0.57254 (8)	0.63131 (6)	0.87572 (5)	0.0148 (3)
O1	0.5349 (5)	0.4205 (4)	0.9193 (4)	0.0174 (8)
O2	0.4331 (6)	0.8211 (4)	0.8160 (4)	0.0201 (8)
O3	0.1619 (6)	0.7137 (5)	0.8017 (4)	0.0236 (9)
O4	0.8356 (6)	0.6830 (5)	0.9340 (4)	0.0233 (9)
H4	0.9089	0.7231	0.8695	0.028*
N1	0.6717 (6)	0.5859 (5)	0.6847 (5)	0.0165 (9)
C1	0.5872 (7)	0.3551 (6)	0.8200 (5)	0.0169 (10)
C2	0.5764 (8)	0.2097 (6)	0.8320 (6)	0.0184 (10)
H2	0.5313	0.1493	0.9168	0.022*
C3	0.6315 (9)	0.1497 (6)	0.7196 (6)	0.0229 (11)
H3	0.6238	0.0492	0.7303	0.028*
C4	0.6955 (8)	0.2334 (6)	0.5956 (6)	0.0232 (11)
H4A	0.7301	0.1912	0.5207	0.028*
C5	0.7104 (8)	0.3827 (6)	0.5786 (6)	0.0191 (10)
C6	0.6596 (7)	0.4431 (6)	0.6917 (5)	0.0150 (9)
C7	0.7707 (8)	0.4776 (6)	0.4547 (6)	0.0196 (11)
H7	0.8029	0.4427	0.3748	0.023*
C8	0.7834 (8)	0.6205 (6)	0.4485 (5)	0.0208 (11)
H8	0.8248	0.6846	0.3646	0.025*
C9	0.7341 (8)	0.6730 (6)	0.5687 (5)	0.0178 (10)
C10	0.7542 (9)	0.8281 (6)	0.5643 (6)	0.0227 (11)
H10A	0.7336	0.8427	0.6586	0.034*
H10B	0.6582	0.8879	0.4988	0.034*
H10C	0.8838	0.8552	0.5326	0.034*
C11	0.2496 (8)	0.8207 (6)	0.8104 (5)	0.0179 (10)
C12	0.1384 (9)	0.9585 (7)	0.8161 (7)	0.0297 (13)
H12A	0.2244	1.0381	0.7939	0.045*
H12B	0.0864	0.9488	0.9108	0.045*
H12C	0.0322	0.9780	0.7474	0.045*
C13	0.9045 (8)	0.6565 (7)	1.0750 (6)	0.0233 (11)
H13A	1.0426	0.6285	1.0786	0.035*
H13B	0.8350	0.5787	1.1356	0.035*
H13C	0.8832	0.7441	1.1079	0.035*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Zn1	0.0190 (4)	0.0192 (4)	0.0083 (4)	−0.0030 (2)	0.0016 (2)	−0.0068 (2)
O1	0.027 (2)	0.0212 (18)	0.0063 (16)	−0.0035 (15)	0.0078 (14)	−0.0071 (14)
O2	0.025 (2)	0.0206 (19)	0.0146 (17)	−0.0033 (15)	0.0021 (15)	−0.0033 (14)
O3	0.023 (2)	0.032 (2)	0.020 (2)	−0.0040 (16)	0.0045 (16)	−0.0146 (17)
O4	0.0186 (19)	0.041 (2)	0.0123 (18)	−0.0090 (16)	0.0026 (14)	−0.0094 (16)
N1	0.018 (2)	0.024 (2)	0.0098 (19)	−0.0017 (16)	−0.0004 (15)	−0.0079 (16)
C1	0.018 (2)	0.024 (3)	0.012 (2)	−0.0030 (19)	0.0016 (18)	−0.0084 (19)
C2	0.023 (3)	0.019 (2)	0.015 (2)	−0.0026 (19)	0.0028 (19)	−0.0058 (19)
C3	0.030 (3)	0.021 (3)	0.021 (3)	0.001 (2)	−0.002 (2)	−0.012 (2)
C4	0.025 (3)	0.029 (3)	0.020 (3)	−0.001 (2)	0.000 (2)	−0.015 (2)
C5	0.017 (2)	0.027 (3)	0.016 (2)	0.000 (2)	−0.0011 (19)	−0.012 (2)
C6	0.017 (2)	0.021 (2)	0.008 (2)	0.0006 (18)	0.0004 (17)	−0.0055 (18)
C7	0.018 (2)	0.032 (3)	0.012 (2)	0.002 (2)	0.0005 (19)	−0.012 (2)
C8	0.020 (3)	0.033 (3)	0.010 (2)	−0.001 (2)	−0.0003 (19)	−0.008 (2)
C9	0.018 (2)	0.027 (3)	0.009 (2)	−0.003 (2)	0.0009 (18)	−0.0058 (19)
C10	0.035 (3)	0.023 (3)	0.012 (2)	−0.006 (2)	0.003 (2)	−0.006 (2)
C11	0.020 (2)	0.024 (3)	0.010 (2)	0.0004 (19)	0.0012 (18)	−0.0057 (19)
C12	0.027 (3)	0.027 (3)	0.034 (3)	0.002 (2)	0.002 (2)	−0.006 (2)
C13	0.023 (3)	0.035 (3)	0.013 (2)	−0.004 (2)	0.001 (2)	−0.009 (2)

Geometric parameters (Å, °)

Zn1—O1	1.997 (4)	C4—C5	1.414 (8)
Zn1—O2	1.968 (4)	C4—H4A	0.9500
Zn1—O1i	2.092 (3)	C5—C7	1.402 (8)
Zn1—O4	2.045 (4)	C5—C6	1.413 (7)
Zn1—N1	2.134 (4)	C7—C8	1.369 (8)
O1—C1	1.328 (6)	C7—H7	0.9500
O1—Zn1i	2.092 (3)	C8—C9	1.431 (7)
O2—C11	1.277 (7)	C8—H8	0.9500
O3—C11	1.250 (7)	C9—C10	1.497 (7)
O4—C13	1.423 (6)	C10—H10A	0.9800
O4—H4	0.8400	C10—H10B	0.9800
N1—C9	1.319 (7)	C10—H10C	0.9800
N1—C6	1.366 (7)	C11—C12	1.508 (8)
C1—C2	1.381 (7)	C12—H12A	0.9800
C1—C6	1.435 (7)	C12—H12B	0.9800
C2—C3	1.412 (7)	C12—H12C	0.9800
C2—H2	0.9500	C13—H13A	0.9800
C3—C4	1.366 (9)	C13—H13B	0.9800
C3—H3	0.9500	C13—H13C	0.9800
O1—Zn1—O1i	75.2 (2)	C6—C5—C4	119.1 (5)
O1—Zn1—O2	142.5 (2)	N1—C6—C5	122.8 (5)
O1—Zn1—O4	114.7 (2)	N1—C6—C1	116.8 (4)
O1—Zn1—N1	79.8 (2)	C5—C6—C1	120.4 (5)
O1i—Zn1—O2	95.8 (2)	C8—C7—C5	120.2 (5)
O1i—Zn1—O4	94.5 (2)	C8—C7—H7	119.9
O1i—Zn1—N1	155.0 (2)	C5—C7—H7	119.9
O2—Zn1—O4	102.1 (2)	C7—C8—C9	119.9 (5)
O2—Zn1—N1	104.7 (2)	C7—C8—H8	120.1
O4—Zn1—N1	95.0 (2)	C9—C8—H8	120.1
C1—O1—Zn1	116.2 (3)	N1—C9—C8	120.7 (5)
C1—O1—Zn1i	139.0 (3)	N1—C9—C10	119.2 (5)
Zn1—O1—Zn1i	104.81 (16)	C8—C9—C10	120.1 (5)
C11—O2—Zn1	116.0 (3)	C9—C10—H10A	109.5
C13—O4—Zn1	125.3 (3)	C9—C10—H10B	109.5
C13—O4—H4	117.3	H10A—C10—H10B	109.5
Zn1—O4—H4	117.3	C9—C10—H10C	109.5
C9—N1—C6	119.7 (4)	H10A—C10—H10C	109.5
C9—N1—Zn1	130.0 (4)	H10B—C10—H10C	109.5
C6—N1—Zn1	110.3 (3)	O3—C11—O2	123.5 (5)
O1—C1—C2	124.6 (5)	O3—C11—C12	120.0 (5)
O1—C1—C6	117.0 (5)	O2—C11—C12	116.5 (5)
C2—C1—C6	118.4 (5)	C11—C12—H12A	109.5
C1—C2—C3	120.8 (5)	C11—C12—H12B	109.5
C1—C2—H2	119.6	H12A—C12—H12B	109.5
C3—C2—H2	119.6	C11—C12—H12C	109.5
C4—C3—C2	121.2 (5)	H12A—C12—H12C	109.5
C4—C3—H3	119.4	H12B—C12—H12C	109.5
C2—C3—H3	119.4	O4—C13—H13A	109.5
C3—C4—C5	120.1 (5)	O4—C13—H13B	109.5
C3—C4—H4A	119.9	H13A—C13—H13B	109.5
C5—C4—H4A	119.9	O4—C13—H13C	109.5
C7—C5—C6	116.7 (5)	H13A—C13—H13C	109.5
C7—C5—C4	124.2 (5)	H13B—C13—H13C	109.5
O2—Zn1—O1—C1	102.0 (4)	C6—C1—C2—C3	−1.3 (8)
O4—Zn1—O1—C1	−89.7 (4)	C1—C2—C3—C4	−0.5 (9)
O1i—Zn1—O1—C1	−177.9 (5)	C2—C3—C4—C5	0.9 (9)
N1—Zn1—O1—C1	1.1 (4)	C3—C4—C5—C7	−178.6 (6)
O2—Zn1—O1—Zn1i	−80.1 (3)	C3—C4—C5—C6	0.5 (8)
O4—Zn1—O1—Zn1i	88.17 (19)	C9—N1—C6—C5	−0.4 (8)
O1i—Zn1—O1—Zn1i	0.0	Zn1—N1—C6—C5	178.2 (4)
N1—Zn1—O1—Zn1i	179.0 (2)	C9—N1—C6—C1	−178.9 (5)
O1—Zn1—O2—C11	7.8 (5)	Zn1—N1—C6—C1	−0.3 (6)
O4—Zn1—O2—C11	−161.4 (4)	C7—C5—C6—N1	−1.5 (8)
O1i—Zn1—O2—C11	−65.4 (4)	C4—C5—C6—N1	179.3 (5)
N1—Zn1—O2—C11	100.1 (4)	C7—C5—C6—C1	176.9 (5)
O2—Zn1—O4—C13	107.2 (4)	C4—C5—C6—C1	−2.3 (8)
O1—Zn1—O4—C13	−65.5 (5)	O1—C1—C6—N1	1.2 (7)
O1i—Zn1—O4—C13	10.3 (4)	C2—C1—C6—N1	−178.8 (5)
N1—Zn1—O4—C13	−146.6 (4)	O1—C1—C6—C5	−177.3 (5)
O2—Zn1—N1—C9	36.2 (5)	C2—C1—C6—C5	2.7 (8)
O1—Zn1—N1—C9	178.0 (5)	C6—C5—C7—C8	1.8 (8)
O4—Zn1—N1—C9	−67.7 (5)	C4—C5—C7—C8	−179.1 (5)
O1i—Zn1—N1—C9	−179.6 (4)	C5—C7—C8—C9	−0.3 (8)
O2—Zn1—N1—C6	−142.2 (3)	C6—N1—C9—C8	2.1 (8)
O1—Zn1—N1—C6	−0.4 (3)	Zn1—N1—C9—C8	−176.2 (4)
O4—Zn1—N1—C6	113.9 (3)	C6—N1—C9—C10	−177.6 (5)
O1i—Zn1—N1—C6	1.9 (6)	Zn1—N1—C9—C10	4.1 (8)
Zn1—O1—C1—C2	178.4 (4)	C7—C8—C9—N1	−1.8 (8)
Zn1i—O1—C1—C2	1.5 (9)	C7—C8—C9—C10	177.9 (5)
Zn1—O1—C1—C6	−1.6 (6)	Zn1—O2—C11—O3	−20.5 (7)
Zn1i—O1—C1—C6	−178.5 (4)	Zn1—O2—C11—C12	159.0 (4)
O1—C1—C2—C3	178.7 (5)

Symmetry codes: (i) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O3ii	0.84	1.88	2.602 (6)	143

Symmetry codes: (ii) x+1, y, z.