8-Hydr­oxy-2-methyl­quinolinium dichlorido(2-methyl­quinolin-8-olato-κ² N,O)zincate(II) methanol solvate

Abstract

The reaction of zinc chloride and 2-methyl-8-hydroxy­quinoline in methanol yielded the title monosolvated salt, (C₁₀H₁₀NO)[ZnCl₂(C₁₀H₈NO)]·CH₃OH, which has the Zn atom within a distorted Cl₂NO tetra­hedral coordination geometry. Supra­molecular chains feature in the crystal structure, comprising all components of the structure stabilized by a combination of O—H⋯O, N—H⋯O and O—H⋯Cl hydrogen bonding.

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 acetate 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

• (C₁₀H₁₀NO)[ZnCl₂(C₁₀H₈NO)]·CH₄O

• M _r = 486.68

• Monoclinic,

• a = 10.0717 (2) Å

• b = 13.7886 (3) Å

• c = 15.4828 (3) Å

• β = 105.48 (1)°

• V = 2072.15 (7) ų

• Z = 4

• Mo Kα radiation

• μ = 1.47 mm⁻¹

• T = 100 K

• 0.32 × 0.12 × 0.08 mm

Data collection

• Bruker SMART APEX diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.651, T _max = 0.892

• 18982 measured reflections

• 4753 independent reflections

• 3600 reflections with I > 2σ(I)

• R _int = 0.036

Refinement

• R[F ² > 2σ(F ²)] = 0.039

• wR(F ²) = 0.108

• S = 1.02

• 4753 reflections

• 277 parameters

• 3 restraints

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 1.08 e Å⁻³

• Δρ_min = −1.00 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
O2—H2O⋯O1	0.84 (1)	1.70 (1)	2.534 (3)	177 (4)
O3—H3O⋯Cl1i	0.84 (1)	2.47 (3)	3.239 (4)	153 (5)
N2—H2N⋯O3	0.88 (1)	1.87 (2)	2.727 (4)	163 (3)

Symmetry code: (i) .

supplementary crystallographic information

Experimental

Zinc chloride (0.10 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.

Refinement

Carbon-bound H-atoms were placed in calculated positions (C—H 0.95 to 0.98 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2 to 1.5U(C). The O–H and N–H hydrogen atoms were located in a difference Fourier map, and were refined with distance restraints of O–H 0.84±0.01 Å and N–H 0.88±01 Å; their temperature factors were freely refined.

The final difference Fourier map had a large peak/deep hole in the vicinity of the O3 atom.

Figures

Fig. 1.

Thermal ellipsoid plot (Barbour, 2001) of [C10H10NO][Zn(C10H8NO)Cl2].CH3OH; ellipsoids are drawn at the 70% probability level and H atoms of arbitrary radius.

Crystal data

(C10H10NO)[ZnCl2(C10H8NO)]·CH4O	F(000) = 1000
Mr = 486.68	Dx = 1.560 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4908 reflections
a = 10.0717 (2) Å	θ = 2.6–27.1°
b = 13.7886 (3) Å	µ = 1.47 mm−1
c = 15.4828 (3) Å	T = 100 K
β = 105.48 (1)°	Block, yellow
V = 2072.15 (7) Å3	0.32 × 0.12 × 0.08 mm
Z = 4

Data collection

Bruker SMART APEX diffractometer	4753 independent reflections
Radiation source: fine-focus sealed tube	3600 reflections with I > 2σ(I)
graphite	Rint = 0.036
ω scans	θmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
Tmin = 0.651, Tmax = 0.892	k = −17→17
18982 measured reflections	l = −20→20

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0493P)2 + 2.8684P] where P = (Fo2 + 2Fc2)/3
4753 reflections	(Δ/σ)max = 0.001
277 parameters	Δρmax = 1.08 e Å−3
3 restraints	Δρmin = −1.00 e Å−3

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

	x	y	z	Uiso*/Ueq
Zn1	0.50382 (3)	0.63261 (3)	0.23689 (2)	0.02655 (11)
Cl1	0.48941 (8)	0.76378 (6)	0.31836 (5)	0.03149 (18)
Cl2	0.39683 (8)	0.50528 (6)	0.27699 (5)	0.03503 (19)
O1	0.6980 (2)	0.60686 (17)	0.23887 (13)	0.0318 (5)
O2	0.9135 (2)	0.63848 (15)	0.36428 (13)	0.0258 (4)
H2O	0.843 (3)	0.626 (3)	0.3225 (19)	0.054 (13)*
O3	1.1916 (3)	0.6985 (4)	0.3410 (2)	0.1114 (18)
H3O	1.2770 (14)	0.706 (5)	0.353 (4)	0.11 (2)*
N1	0.4760 (2)	0.63643 (17)	0.10133 (15)	0.0232 (5)
N2	1.1439 (2)	0.64419 (17)	0.49938 (16)	0.0239 (5)
H2N	1.143 (4)	0.657 (3)	0.4435 (10)	0.040 (10)*
C1	0.7143 (3)	0.6004 (2)	0.15652 (19)	0.0257 (6)
C2	0.8383 (3)	0.5781 (2)	0.1389 (2)	0.0345 (7)
H2	0.9178	0.5676	0.1872	0.041*
C3	0.8481 (3)	0.5708 (2)	0.0502 (2)	0.0363 (8)
H3	0.9347	0.5557	0.0401	0.044*
C4	0.7372 (4)	0.5847 (2)	−0.0217 (2)	0.0344 (7)
H4	0.7466	0.5793	−0.0810	0.041*
C5	0.6079 (3)	0.6075 (2)	−0.00683 (19)	0.0280 (6)
C6	0.5975 (3)	0.6156 (2)	0.08206 (18)	0.0238 (6)
C7	0.4857 (4)	0.6220 (2)	−0.0757 (2)	0.0324 (7)
H7	0.4873	0.6172	−0.1366	0.039*
C8	0.3656 (3)	0.6428 (2)	−0.05527 (19)	0.0303 (7)
H8	0.2839	0.6530	−0.1020	0.036*
C9	0.3619 (3)	0.6491 (2)	0.03512 (19)	0.0259 (6)
C10	0.2318 (3)	0.6695 (2)	0.0599 (2)	0.0322 (7)
H10A	0.2445	0.7264	0.0992	0.048*
H10B	0.2074	0.6134	0.0914	0.048*
H10C	0.1577	0.6823	0.0056	0.048*
C11	0.8990 (3)	0.61926 (19)	0.44627 (18)	0.0211 (5)
C12	0.7783 (3)	0.5956 (2)	0.46570 (19)	0.0254 (6)
H12	0.6953	0.5926	0.4189	0.031*
C13	0.7759 (3)	0.5758 (2)	0.5544 (2)	0.0267 (6)
H13	0.6909	0.5594	0.5664	0.032*
C14	0.8927 (3)	0.5795 (2)	0.62372 (19)	0.0279 (6)
H14	0.8887	0.5657	0.6831	0.033*
C15	1.0188 (3)	0.6040 (2)	0.60665 (18)	0.0241 (6)
C16	1.0214 (3)	0.62310 (19)	0.51737 (18)	0.0218 (6)
C17	1.1463 (3)	0.6076 (2)	0.6733 (2)	0.0300 (7)
H17	1.1488	0.5961	0.7342	0.036*
C18	1.2650 (3)	0.6276 (2)	0.6509 (2)	0.0309 (7)
H18	1.3496	0.6293	0.6964	0.037*
C19	1.2646 (3)	0.6457 (2)	0.5617 (2)	0.0284 (6)
C20	1.3919 (3)	0.6644 (3)	0.5335 (2)	0.0381 (8)
H20A	1.3932	0.6227	0.4825	0.057*
H20B	1.4726	0.6504	0.5834	0.057*
H20C	1.3940	0.7326	0.5158	0.057*
C21	1.1182 (4)	0.7302 (3)	0.2615 (2)	0.0478 (9)
H21C	1.1577	0.7911	0.2471	0.072*
H21B	1.0228	0.7413	0.2632	0.072*
H21A	1.1200	0.6817	0.2156	0.072*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Zn1	0.02484 (18)	0.0370 (2)	0.01749 (17)	−0.00010 (14)	0.00511 (13)	0.00387 (14)
Cl1	0.0333 (4)	0.0367 (4)	0.0238 (3)	−0.0047 (3)	0.0066 (3)	−0.0003 (3)
Cl2	0.0401 (4)	0.0349 (4)	0.0342 (4)	−0.0009 (3)	0.0170 (3)	0.0076 (3)
O1	0.0251 (11)	0.0528 (14)	0.0170 (10)	−0.0012 (10)	0.0047 (8)	0.0001 (9)
O2	0.0260 (10)	0.0327 (11)	0.0173 (10)	−0.0003 (9)	0.0032 (8)	0.0002 (8)
O3	0.0368 (18)	0.240 (5)	0.063 (2)	0.040 (2)	0.0233 (16)	0.091 (3)
N1	0.0269 (12)	0.0231 (12)	0.0180 (11)	−0.0054 (10)	0.0029 (9)	0.0023 (9)
N2	0.0252 (12)	0.0233 (12)	0.0219 (12)	0.0037 (10)	0.0037 (10)	0.0026 (10)
C1	0.0268 (15)	0.0291 (15)	0.0212 (14)	−0.0070 (12)	0.0063 (11)	−0.0022 (11)
C2	0.0294 (16)	0.0411 (19)	0.0340 (17)	−0.0086 (14)	0.0100 (13)	−0.0070 (14)
C3	0.0348 (18)	0.0404 (19)	0.0404 (19)	−0.0108 (14)	0.0216 (15)	−0.0121 (15)
C4	0.048 (2)	0.0317 (17)	0.0290 (16)	−0.0104 (15)	0.0197 (15)	−0.0057 (13)
C5	0.0413 (17)	0.0217 (14)	0.0222 (14)	−0.0087 (12)	0.0108 (13)	0.0003 (11)
C6	0.0286 (15)	0.0237 (14)	0.0189 (13)	−0.0073 (11)	0.0062 (11)	−0.0001 (10)
C7	0.053 (2)	0.0247 (15)	0.0175 (14)	−0.0061 (14)	0.0055 (13)	−0.0002 (11)
C8	0.0424 (18)	0.0250 (15)	0.0162 (13)	−0.0023 (13)	−0.0050 (12)	0.0019 (11)
C9	0.0306 (15)	0.0206 (14)	0.0230 (14)	−0.0036 (11)	0.0009 (12)	0.0017 (11)
C10	0.0299 (16)	0.0333 (16)	0.0288 (16)	0.0019 (13)	−0.0001 (13)	0.0029 (13)
C11	0.0276 (14)	0.0176 (13)	0.0170 (12)	0.0024 (11)	0.0041 (11)	0.0006 (10)
C12	0.0271 (15)	0.0254 (14)	0.0227 (14)	0.0006 (11)	0.0048 (12)	−0.0022 (11)
C13	0.0295 (15)	0.0253 (15)	0.0281 (15)	0.0009 (12)	0.0123 (12)	0.0011 (12)
C14	0.0379 (17)	0.0252 (15)	0.0210 (14)	0.0042 (13)	0.0086 (12)	0.0017 (11)
C15	0.0306 (15)	0.0196 (13)	0.0209 (14)	0.0044 (11)	0.0049 (11)	−0.0026 (11)
C16	0.0266 (14)	0.0181 (13)	0.0199 (13)	0.0033 (11)	0.0047 (11)	−0.0005 (10)
C17	0.0380 (17)	0.0286 (16)	0.0198 (14)	0.0054 (13)	0.0016 (12)	−0.0013 (12)
C18	0.0282 (15)	0.0321 (16)	0.0260 (15)	0.0031 (13)	−0.0040 (12)	−0.0026 (12)
C19	0.0274 (15)	0.0230 (15)	0.0307 (16)	0.0033 (12)	0.0005 (12)	0.0000 (12)
C20	0.0264 (16)	0.0411 (19)	0.043 (2)	−0.0007 (14)	0.0029 (14)	0.0084 (15)
C21	0.048 (2)	0.057 (2)	0.040 (2)	−0.0010 (18)	0.0137 (17)	0.0023 (18)

Geometric parameters (Å, °)

Zn1—N1	2.043 (2)	C8—H8	0.9500
Zn1—O1	1.980 (2)	C9—C10	1.488 (4)
Zn1—Cl1	2.2318 (8)	C10—H10A	0.9800
Zn1—Cl2	2.2331 (8)	C10—H10B	0.9800
O1—C1	1.331 (3)	C10—H10C	0.9800
O2—C11	1.342 (3)	C11—C12	1.368 (4)
O2—H2O	0.841 (10)	C11—C16	1.418 (4)
O3—C21	1.329 (5)	C12—C13	1.407 (4)
O3—H3O	0.836 (10)	C12—H12	0.9500
N1—C9	1.332 (4)	C13—C14	1.365 (4)
N1—C6	1.365 (4)	C13—H13	0.9500
N2—C19	1.335 (4)	C14—C15	1.406 (4)
N2—C16	1.367 (4)	C14—H14	0.9500
N2—H2N	0.881 (10)	C15—C16	1.414 (4)
C1—C2	1.382 (4)	C15—C17	1.417 (4)
C1—C6	1.426 (4)	C17—C18	1.359 (5)
C2—C3	1.406 (4)	C17—H17	0.9500
C2—H2	0.9500	C18—C19	1.402 (4)
C3—C4	1.364 (5)	C18—H18	0.9500
C3—H3	0.9500	C19—C20	1.484 (4)
C4—C5	1.417 (5)	C20—H20A	0.9800
C4—H4	0.9500	C20—H20B	0.9800
C5—C7	1.411 (4)	C20—H20C	0.9800
C5—C6	1.412 (4)	C21—H21C	0.9800
C7—C8	1.360 (5)	C21—H21B	0.9800
C7—H7	0.9500	C21—H21A	0.9800
C8—C9	1.413 (4)
O1—Zn1—N1	83.36 (9)	H10A—C10—H10B	109.5
O1—Zn1—Cl1	110.46 (7)	C9—C10—H10C	109.5
N1—Zn1—Cl1	123.24 (7)	H10A—C10—H10C	109.5
O1—Zn1—Cl2	113.75 (7)	H10B—C10—H10C	109.5
N1—Zn1—Cl2	111.22 (7)	O2—C11—C12	125.6 (3)
Cl1—Zn1—Cl2	111.78 (3)	O2—C11—C16	115.8 (2)
C1—O1—Zn1	111.79 (18)	C12—C11—C16	118.5 (3)
C11—O2—H2O	114 (3)	C11—C12—C13	120.6 (3)
C21—O3—H3O	117 (4)	C11—C12—H12	119.7
C9—N1—C6	119.9 (2)	C13—C12—H12	119.7
C9—N1—Zn1	130.4 (2)	C14—C13—C12	121.6 (3)
C6—N1—Zn1	109.52 (18)	C14—C13—H13	119.2
C19—N2—C16	123.6 (3)	C12—C13—H13	119.2
C19—N2—H2N	118 (2)	C13—C14—C15	119.6 (3)
C16—N2—H2N	118 (2)	C13—C14—H14	120.2
O1—C1—C2	123.6 (3)	C15—C14—H14	120.2
O1—C1—C6	118.6 (3)	C14—C15—C16	118.8 (3)
C2—C1—C6	117.8 (3)	C14—C15—C17	124.1 (3)
C1—C2—C3	120.7 (3)	C16—C15—C17	117.0 (3)
C1—C2—H2	119.6	N2—C16—C15	119.5 (3)
C3—C2—H2	119.6	N2—C16—C11	119.7 (2)
C4—C3—C2	122.2 (3)	C15—C16—C11	120.9 (3)
C4—C3—H3	118.9	C18—C17—C15	120.7 (3)
C2—C3—H3	118.9	C18—C17—H17	119.7
C3—C4—C5	119.0 (3)	C15—C17—H17	119.7
C3—C4—H4	120.5	C17—C18—C19	121.0 (3)
C5—C4—H4	120.5	C17—C18—H18	119.5
C7—C5—C6	116.7 (3)	C19—C18—H18	119.5
C7—C5—C4	124.2 (3)	N2—C19—C18	118.1 (3)
C6—C5—C4	119.1 (3)	N2—C19—C20	118.8 (3)
N1—C6—C5	122.2 (3)	C18—C19—C20	123.0 (3)
N1—C6—C1	116.6 (2)	C19—C20—H20A	109.5
C5—C6—C1	121.1 (3)	C19—C20—H20B	109.5
C8—C7—C5	120.3 (3)	H20A—C20—H20B	109.5
C8—C7—H7	119.8	C19—C20—H20C	109.5
C5—C7—H7	119.8	H20A—C20—H20C	109.5
C7—C8—C9	120.2 (3)	H20B—C20—H20C	109.5
C7—C8—H8	119.9	O3—C21—H21C	109.5
C9—C8—H8	119.9	O3—C21—H21B	109.5
N1—C9—C8	120.6 (3)	H21C—C21—H21B	109.5
N1—C9—C10	117.7 (3)	O3—C21—H21A	109.5
C8—C9—C10	121.7 (3)	H21C—C21—H21A	109.5
C9—C10—H10A	109.5	H21B—C21—H21A	109.5
C9—C10—H10B	109.5
N1—Zn1—O1—C1	−2.8 (2)	C5—C7—C8—C9	−0.5 (4)
Cl1—Zn1—O1—C1	−125.81 (18)	C6—N1—C9—C8	−1.0 (4)
Cl2—Zn1—O1—C1	107.55 (19)	Zn1—N1—C9—C8	−175.8 (2)
O1—Zn1—N1—C9	178.1 (3)	C6—N1—C9—C10	178.7 (3)
Cl1—Zn1—N1—C9	−71.7 (3)	Zn1—N1—C9—C10	3.8 (4)
Cl2—Zn1—N1—C9	65.2 (3)	C7—C8—C9—N1	1.0 (4)
O1—Zn1—N1—C6	2.88 (18)	C7—C8—C9—C10	−178.6 (3)
Cl1—Zn1—N1—C6	113.03 (17)	O2—C11—C12—C13	179.2 (3)
Cl2—Zn1—N1—C6	−110.05 (17)	C16—C11—C12—C13	0.1 (4)
Zn1—O1—C1—C2	−176.7 (3)	C11—C12—C13—C14	0.1 (4)
Zn1—O1—C1—C6	2.2 (3)	C12—C13—C14—C15	0.1 (4)
O1—C1—C2—C3	178.9 (3)	C13—C14—C15—C16	−0.7 (4)
C6—C1—C2—C3	0.1 (5)	C13—C14—C15—C17	−178.4 (3)
C1—C2—C3—C4	−0.3 (5)	C19—N2—C16—C15	1.7 (4)
C2—C3—C4—C5	0.1 (5)	C19—N2—C16—C11	−177.4 (3)
C3—C4—C5—C7	−179.0 (3)	C14—C15—C16—N2	−178.1 (3)
C3—C4—C5—C6	0.3 (4)	C17—C15—C16—N2	−0.2 (4)
C9—N1—C6—C5	0.5 (4)	C14—C15—C16—C11	0.9 (4)
Zn1—N1—C6—C5	176.3 (2)	C17—C15—C16—C11	178.9 (2)
C9—N1—C6—C1	−178.4 (3)	O2—C11—C16—N2	−0.8 (4)
Zn1—N1—C6—C1	−2.6 (3)	C12—C11—C16—N2	178.4 (2)
C7—C5—C6—N1	−0.1 (4)	O2—C11—C16—C15	−179.9 (2)
C4—C5—C6—N1	−179.4 (3)	C12—C11—C16—C15	−0.7 (4)
C7—C5—C6—C1	178.8 (3)	C14—C15—C17—C18	177.0 (3)
C4—C5—C6—C1	−0.6 (4)	C16—C15—C17—C18	−0.8 (4)
O1—C1—C6—N1	0.4 (4)	C15—C17—C18—C19	0.5 (5)
C2—C1—C6—N1	179.3 (3)	C16—N2—C19—C18	−2.0 (4)
O1—C1—C6—C5	−178.6 (3)	C16—N2—C19—C20	176.8 (3)
C2—C1—C6—C5	0.4 (4)	C17—C18—C19—N2	0.9 (4)
C6—C5—C7—C8	0.1 (4)	C17—C18—C19—C20	−177.8 (3)
C4—C5—C7—C8	179.4 (3)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···O1	0.84 (1)	1.70 (1)	2.534 (3)	177 (4)
O3—H3O···Cl1i	0.84 (1)	2.47 (3)	3.239 (4)	153 (5)
N2—H2N···O3	0.88 (1)	1.87 (2)	2.727 (4)	163 (3)

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