Dichloridobis(1-ethyl-2,6-dimethyl-pyridinium-4-olate-κO)zinc(II).

In the title compound, [ZnCl(2)(C(9)H(13)NO)(2)], the Zn(II) ion is coordinated by two Cl(-) anions and two O atoms of two zwitterionic organic ligands in a distorted tetra-hedral arrangement. In the crystal, mol-ecules are linked into sheets parallel to the bc plane by C-H⋯Cl and C-H⋯O hydrogen bonds and weak π-π inter-actions [centroid-centroid distance = 3.669 (1) Å].

Related literature

For general background to pyridinium compounds, see: Anwar et al. (1997 ▶, 1999 ▶); Damiano et al. (2007 ▶); Darensbourg et al. (2003 ▶); Mootz & Wusson (1981 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the preparation of 1-ethyl-2,6-dimethyl-4(1H)-pyridinone trihydrate, see: Garratt (1963 ▶).

Experimental

Crystal data

[ZnCl2(C9H13NO)2]

M = 438.68

Monoclinic,

a = 30.365 (2) Å

b = 8.5366 (6) Å

c = 15.7982 (12) Å

β = 94.281 (4)°

V = 4083.7 (5) Å3

Z = 8

Mo Kα radiation

μ = 1.48 mm−1

T = 293 K

0.25 × 0.25 × 0.23 mm

Data collection

Bruker SMART APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS, Bruker, 2008 ▶) T min = 0.709, T max = 0.727

19140 measured reflections

5069 independent reflections

4248 reflections with I > 2σ(I)

R int = 0.042

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.084

S = 0.99

5069 reflections

233 parameters

H-atom parameters constrained

Δρmax = 0.61 e Å−3

Δρmin = −0.56 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: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681004119X/ci5172sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681004119X/ci5172Isup2.hkl

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

[ZnCl2(C9H13NO)2]	F(000) = 1824
Mr = 438.68	Dx = 1.427 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5069 reflections
a = 30.365 (2) Å	θ = 1.3–28.3°
b = 8.5366 (6) Å	µ = 1.48 mm−1
c = 15.7982 (12) Å	T = 293 K
β = 94.281 (4)°	Block, yellow
V = 4083.7 (5) Å3	0.25 × 0.25 × 0.23 mm
Z = 8

Bruker SMART APEXII area-detector diffractometer	5069 independent reflections
Radiation source: fine-focus sealed tube	4248 reflections with I > 2σ(I)
graphite	Rint = 0.042
ω and φ scans	θmax = 28.3°, θmin = 1.3°
Absorption correction: multi-scan (SADABS, Bruker, 2008)	h = −40→40
Tmin = 0.709, Tmax = 0.727	k = −11→10
19140 measured reflections	l = −21→20

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)] = 0.031	H-atom parameters constrained
wR(F2) = 0.084	w = 1/[σ2(Fo2) + (0.0343P)2 + 3.3394P] where P = (Fo2 + 2Fc2)/3
S = 0.99	(Δ/σ)max = 0.001
5069 reflections	Δρmax = 0.61 e Å−3
233 parameters	Δρmin = −0.56 e Å−3
0 restraints	Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00082 (11)

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C2	−0.01906 (5)	1.0155 (2)	0.10794 (11)	0.0359 (4)
C3	0.01997 (6)	0.9693 (2)	0.14837 (11)	0.0374 (4)
H3	0.0255	0.8629	0.1558	0.045*
C4	0.05235 (5)	1.0787 (2)	0.17944 (11)	0.0364 (4)
C5	0.04059 (5)	1.2375 (2)	0.16743 (12)	0.0383 (4)
H5	0.0603	1.3145	0.1880	0.046*
C6	0.00144 (6)	1.2821 (2)	0.12668 (11)	0.0377 (4)
C7	−0.07005 (6)	1.2200 (3)	0.04757 (12)	0.0466 (4)
H7A	−0.0797	1.1375	0.0082	0.056*
H7B	−0.0646	1.3131	0.0147	0.056*
C8	−0.10658 (6)	1.2540 (3)	0.10526 (14)	0.0568 (5)
H8A	−0.1111	1.1639	0.1399	0.085*
H8B	−0.1334	1.2777	0.0715	0.085*
H8C	−0.0984	1.3419	0.1409	0.085*
C9	−0.05273 (7)	0.8962 (3)	0.07675 (14)	0.0507 (5)
H9A	−0.0810	0.9241	0.0956	0.076*
H9B	−0.0442	0.7949	0.0988	0.076*
H9C	−0.0545	0.8931	0.0159	0.076*
C10	−0.00998 (7)	1.4522 (2)	0.11818 (15)	0.0554 (5)
H10A	−0.0341	1.4755	0.1520	0.083*
H10B	−0.0183	1.4759	0.0598	0.083*
H10C	0.0152	1.5142	0.1374	0.083*
C12	0.26273 (6)	0.9691 (2)	0.45067 (12)	0.0416 (4)
C13	0.21875 (6)	0.9588 (2)	0.42739 (12)	0.0419 (4)
H13	0.1987	0.9930	0.4650	0.050*
C14	0.20270 (6)	0.8981 (2)	0.34832 (11)	0.0391 (4)
C15	0.23516 (6)	0.8424 (2)	0.29655 (13)	0.0459 (4)
H15	0.2263	0.7964	0.2447	0.055*
C16	0.27915 (6)	0.8540 (2)	0.32029 (13)	0.0434 (4)
C17	0.34104 (6)	0.9425 (2)	0.41988 (14)	0.0468 (4)
H17A	0.3451	1.0363	0.4542	0.056*
H17B	0.3561	0.9581	0.3686	0.056*
C18	0.36164 (8)	0.8059 (3)	0.46811 (18)	0.0676 (7)
H18A	0.3477	0.7925	0.5202	0.101*
H18B	0.3926	0.8254	0.4805	0.101*
H18C	0.3578	0.7127	0.4344	0.101*
C19	0.27833 (7)	1.0377 (3)	0.53495 (15)	0.0652 (7)
H19A	0.2934	1.1346	0.5264	0.098*
H19B	0.2981	0.9657	0.5649	0.098*
H19C	0.2534	1.0567	0.5676	0.098*
C20	0.31287 (8)	0.7970 (4)	0.26254 (16)	0.0698 (7)
H20A	0.2981	0.7509	0.2127	0.105*
H20B	0.3315	0.7201	0.2916	0.105*
H20C	0.3306	0.8836	0.2463	0.105*
Cl1	0.08868 (2)	0.63005 (6)	0.23807 (5)	0.06526 (17)
Cl2	0.163428 (18)	0.86170 (7)	0.10513 (3)	0.05362 (14)
N1	−0.02813 (5)	1.17136 (17)	0.09508 (9)	0.0364 (3)
N11	0.29302 (5)	0.92018 (19)	0.39652 (10)	0.0401 (3)
O1	0.08947 (4)	1.04133 (16)	0.21754 (10)	0.0509 (3)
O2	0.16095 (4)	0.89431 (19)	0.32761 (9)	0.0514 (3)
Zn1	0.126091 (6)	0.85132 (2)	0.221676 (13)	0.03522 (8)

	U11	U22	U33	U12	U13	U23
C2	0.0331 (8)	0.0397 (9)	0.0349 (9)	−0.0027 (7)	0.0028 (6)	−0.0047 (7)
C3	0.0367 (8)	0.0331 (8)	0.0420 (10)	0.0009 (7)	0.0001 (7)	−0.0038 (7)
C4	0.0311 (8)	0.0414 (9)	0.0365 (9)	0.0019 (7)	0.0006 (6)	−0.0082 (7)
C5	0.0337 (8)	0.0372 (9)	0.0442 (10)	−0.0028 (7)	0.0040 (7)	−0.0086 (7)
C6	0.0366 (8)	0.0377 (9)	0.0395 (9)	0.0019 (7)	0.0082 (7)	−0.0019 (7)
C7	0.0382 (9)	0.0612 (12)	0.0391 (10)	0.0070 (8)	−0.0048 (7)	0.0064 (9)
C8	0.0358 (10)	0.0771 (15)	0.0569 (13)	0.0145 (10)	−0.0002 (9)	0.0079 (11)
C9	0.0406 (10)	0.0522 (11)	0.0583 (13)	−0.0106 (8)	−0.0028 (9)	−0.0086 (10)
C10	0.0540 (12)	0.0411 (11)	0.0712 (15)	0.0064 (9)	0.0054 (10)	0.0025 (10)
C12	0.0338 (8)	0.0507 (10)	0.0400 (10)	−0.0015 (7)	0.0008 (7)	−0.0080 (8)
C13	0.0310 (8)	0.0549 (11)	0.0399 (10)	0.0011 (7)	0.0034 (7)	−0.0087 (8)
C14	0.0317 (8)	0.0471 (10)	0.0380 (9)	0.0013 (7)	0.0003 (7)	−0.0002 (8)
C15	0.0391 (9)	0.0613 (12)	0.0366 (10)	0.0061 (8)	−0.0023 (7)	−0.0105 (8)
C16	0.0363 (9)	0.0532 (11)	0.0408 (10)	0.0074 (7)	0.0042 (7)	−0.0036 (8)
C17	0.0316 (8)	0.0511 (11)	0.0574 (12)	−0.0015 (8)	0.0010 (8)	0.0057 (9)
C18	0.0505 (13)	0.0731 (15)	0.0773 (17)	0.0136 (11)	−0.0076 (11)	0.0157 (13)
C19	0.0414 (11)	0.0977 (19)	0.0556 (13)	−0.0049 (11)	−0.0026 (9)	−0.0305 (13)
C20	0.0456 (12)	0.106 (2)	0.0580 (14)	0.0179 (12)	0.0083 (10)	−0.0213 (14)
Cl1	0.0609 (3)	0.0442 (3)	0.0936 (5)	−0.0149 (2)	0.0257 (3)	−0.0035 (3)
Cl2	0.0553 (3)	0.0670 (3)	0.0395 (3)	−0.0098 (2)	0.0095 (2)	0.0006 (2)
N1	0.0302 (7)	0.0440 (8)	0.0349 (8)	0.0032 (6)	0.0014 (5)	−0.0004 (6)
N11	0.0280 (7)	0.0478 (9)	0.0439 (8)	0.0019 (6)	−0.0009 (6)	−0.0009 (7)
O1	0.0375 (7)	0.0462 (7)	0.0660 (9)	0.0066 (6)	−0.0154 (6)	−0.0122 (7)
O2	0.0296 (6)	0.0840 (10)	0.0399 (7)	0.0028 (6)	−0.0032 (5)	−0.0090 (7)
Zn1	0.02879 (11)	0.03822 (13)	0.03829 (13)	−0.00233 (7)	0.00007 (8)	−0.00281 (8)

C2—C3	1.362 (2)	C12—C19	1.498 (3)
C2—N1	1.371 (2)	C13—C14	1.406 (3)
C2—C9	1.500 (2)	C13—H13	0.93
C3—C4	1.416 (2)	C14—O2	1.286 (2)
C3—H3	0.93	C14—C15	1.409 (3)
C4—O1	1.278 (2)	C15—C16	1.364 (3)
C4—C5	1.412 (3)	C15—H15	0.93
C5—C6	1.363 (2)	C16—N11	1.368 (2)
C5—H5	0.93	C16—C20	1.502 (3)
C6—N1	1.372 (2)	C17—N11	1.490 (2)
C6—C10	1.496 (3)	C17—C18	1.503 (3)
C7—N1	1.488 (2)	C17—H17A	0.97
C7—C8	1.515 (3)	C17—H17B	0.97
C7—H7A	0.97	C18—H18A	0.96
C7—H7B	0.97	C18—H18B	0.96
C8—H8A	0.96	C18—H18C	0.96
C8—H8B	0.96	C19—H19A	0.96
C8—H8C	0.96	C19—H19B	0.96
C9—H9A	0.96	C19—H19C	0.96
C9—H9B	0.96	C20—H20A	0.96
C9—H9C	0.96	C20—H20B	0.96
C10—H10A	0.96	C20—H20C	0.96
C10—H10B	0.96	Cl1—Zn1	2.2292 (5)
C10—H10C	0.96	Cl2—Zn1	2.2349 (6)
C12—C13	1.361 (2)	O1—Zn1	1.9649 (13)
C12—N11	1.367 (2)	O2—Zn1	1.9472 (13)
C3—C2—N1	120.57 (15)	O2—C14—C15	124.24 (17)
C3—C2—C9	120.36 (17)	C13—C14—C15	115.41 (16)
N1—C2—C9	119.07 (16)	C16—C15—C14	121.93 (18)
C2—C3—C4	121.94 (16)	C16—C15—H15	119.0
C2—C3—H3	119.0	C14—C15—H15	119.0
C4—C3—H3	119.0	C15—C16—N11	120.19 (17)
O1—C4—C5	120.54 (16)	C15—C16—C20	120.50 (19)
O1—C4—C3	124.33 (17)	N11—C16—C20	119.30 (17)
C5—C4—C3	115.12 (15)	N11—C17—C18	112.90 (17)
C6—C5—C4	122.31 (16)	N11—C17—H17A	109.0
C6—C5—H5	118.8	C18—C17—H17A	109.0
C4—C5—H5	118.8	N11—C17—H17B	109.0
C5—C6—N1	120.23 (16)	C18—C17—H17B	109.0
C5—C6—C10	120.08 (17)	H17A—C17—H17B	107.8
N1—C6—C10	119.67 (16)	C17—C18—H18A	109.5
N1—C7—C8	112.78 (16)	C17—C18—H18B	109.5
N1—C7—H7A	109.0	H18A—C18—H18B	109.5
C8—C7—H7A	109.0	C17—C18—H18C	109.5
N1—C7—H7B	109.0	H18A—C18—H18C	109.5
C8—C7—H7B	109.0	H18B—C18—H18C	109.5
H7A—C7—H7B	107.8	C12—C19—H19A	109.5
C7—C8—H8A	109.5	C12—C19—H19B	109.5
C7—C8—H8B	109.5	H19A—C19—H19B	109.5
H8A—C8—H8B	109.5	C12—C19—H19C	109.5
C7—C8—H8C	109.5	H19A—C19—H19C	109.5
H8A—C8—H8C	109.5	H19B—C19—H19C	109.5
H8B—C8—H8C	109.5	C16—C20—H20A	109.5
C2—C9—H9A	109.5	C16—C20—H20B	109.5
C2—C9—H9B	109.5	H20A—C20—H20B	109.5
H9A—C9—H9B	109.5	C16—C20—H20C	109.5
C2—C9—H9C	109.5	H20A—C20—H20C	109.5
H9A—C9—H9C	109.5	H20B—C20—H20C	109.5
H9B—C9—H9C	109.5	C2—N1—C6	119.74 (14)
C6—C10—H10A	109.5	C2—N1—C7	120.04 (15)
C6—C10—H10B	109.5	C6—N1—C7	120.21 (15)
H10A—C10—H10B	109.5	C12—N11—C16	119.99 (15)
C6—C10—H10C	109.5	C12—N11—C17	119.84 (15)
H10A—C10—H10C	109.5	C16—N11—C17	120.15 (16)
H10B—C10—H10C	109.5	C4—O1—Zn1	134.31 (12)
C13—C12—N11	120.20 (16)	C14—O2—Zn1	133.29 (12)
C13—C12—C19	120.27 (17)	O2—Zn1—O1	98.22 (6)
N11—C12—C19	119.51 (16)	O2—Zn1—Cl1	107.99 (5)
C12—C13—C14	122.15 (17)	O1—Zn1—Cl1	114.29 (5)
C12—C13—H13	118.9	O2—Zn1—Cl2	115.09 (4)
C14—C13—H13	118.9	O1—Zn1—Cl2	105.10 (5)
O2—C14—C13	120.34 (16)	Cl1—Zn1—Cl2	115.06 (2)
N1—C2—C3—C4	0.7 (3)	C10—C6—N1—C7	4.0 (2)
C9—C2—C3—C4	−179.34 (17)	C8—C7—N1—C2	93.7 (2)
C2—C3—C4—O1	−179.80 (18)	C8—C7—N1—C6	−85.9 (2)
C2—C3—C4—C5	1.7 (3)	C13—C12—N11—C16	−3.0 (3)
O1—C4—C5—C6	179.59 (18)	C19—C12—N11—C16	178.4 (2)
C3—C4—C5—C6	−1.8 (3)	C13—C12—N11—C17	175.60 (18)
C4—C5—C6—N1	−0.4 (3)	C19—C12—N11—C17	−3.0 (3)
C4—C5—C6—C10	178.01 (17)	C15—C16—N11—C12	2.7 (3)
N11—C12—C13—C14	0.2 (3)	C20—C16—N11—C12	−178.4 (2)
C19—C12—C13—C14	178.8 (2)	C15—C16—N11—C17	−175.92 (18)
C12—C13—C14—O2	−178.01 (19)	C20—C16—N11—C17	3.0 (3)
C12—C13—C14—C15	2.7 (3)	C18—C17—N11—C12	90.0 (2)
O2—C14—C15—C16	177.7 (2)	C18—C17—N11—C16	−91.4 (2)
C13—C14—C15—C16	−3.0 (3)	C5—C4—O1—Zn1	−160.08 (14)
C14—C15—C16—N11	0.4 (3)	C3—C4—O1—Zn1	21.5 (3)
C14—C15—C16—C20	−178.5 (2)	C13—C14—O2—Zn1	169.24 (15)
C3—C2—N1—C6	−3.1 (3)	C15—C14—O2—Zn1	−11.6 (3)
C9—C2—N1—C6	176.98 (17)	C14—O2—Zn1—O1	−127.09 (19)
C3—C2—N1—C7	177.37 (16)	C14—O2—Zn1—Cl1	113.97 (19)
C9—C2—N1—C7	−2.6 (2)	C14—O2—Zn1—Cl2	−16.1 (2)
C5—C6—N1—C2	2.9 (3)	C4—O1—Zn1—O2	−159.12 (19)
C10—C6—N1—C2	−175.51 (17)	C4—O1—Zn1—Cl1	−45.1 (2)
C5—C6—N1—C7	−177.53 (17)	C4—O1—Zn1—Cl2	82.02 (19)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···O1i	0.96	2.53	3.344 (3)	143
C10—H10A···Cl1ii	0.96	2.82	3.740 (2)	162
C10—H10C···Cl1iii	0.96	2.82	3.745 (2)	162
C13—H13···Cl2iv	0.93	2.82	3.709 (2)	161

Table 1

Selected bond lengths (Å)

Cl1—Zn1	2.2292 (5)
Cl2—Zn1	2.2349 (6)
O1—Zn1	1.9649 (13)
O2—Zn1	1.9472 (13)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8A⋯O1i	0.96	2.53	3.344 (3)	143
C10—H10A⋯Cl1ii	0.96	2.82	3.740 (2)	162
C10—H10C⋯Cl1iii	0.96	2.82	3.745 (2)	162
C13—H13⋯Cl2iv	0.93	2.82	3.709 (2)	161

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .