(Acetato-κO)(acetato-κ²O,O')[2-(3,5-di-methyl-1H-pyrazol-1-yl-κN²)quinoline-κN]zinc(II).

The Zn(II) atom in the title compound, [Zn(C₂H₃O₂)₂(C₁₄H₁₃N₃)], is coordinated by an N₂O₃ donor set defined by the quinolinyl- and pyrazolyl-N atoms of the chelating heterocyclic ligand, and three carboxyl-ate-O atoms derived from the monodentate and bidentate carboxyl-ate ligands. Distortions from the ideal square-pyramidal coordination geometry relate to the restricted bite angle of the chelating ligands, i.e. O-Zn-O = 59.65 (5) and N-Zn-N = 76.50 (6)°, and the close approach of the non-coordinating carbonyl atom [Zn⋯O = 2.858 (2) Å]. In the crystal, mol-ecules are consolidated into a three-dimensional architecture by C-H⋯O inter-actions.

Related literature

For background to luminescent coordination complexes, see: Bai et al. (2011 ▶, 2012 ▶); Chou et al. (2011 ▶); Wang (2001 ▶). For the synthesis, see: Savel’eva et al. (2009 ▶); Scott et al. (1952 ▶). For the structure of the dichlorido analogue, see: Najib et al. (2012 ▶). For additional geometric analysis, see: Addison et al. (1984 ▶).

Experimental

Crystal data

[Zn(C2H3O2)2(C14H13N3)]

M = 406.73

Triclinic,

a = 7.6586 (4) Å

b = 10.7334 (6) Å

c = 11.5772 (4) Å

α = 69.437 (4)°

β = 81.546 (3)°

γ = 72.736 (4)°

V = 849.93 (7) Å3

Z = 2

Cu Kα radiation

μ = 2.27 mm−1

T = 100 K

0.25 × 0.15 × 0.05 mm

Data collection

Agilent SuperNova Dual diffractometer with Atlas detector

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ▶) T min = 0.617, T max = 1.000

6205 measured reflections

3498 independent reflections

3322 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.081

S = 1.03

3498 reflections

239 parameters

H-atom parameters constrained

Δρmax = 0.67 e Å−3

Δρmin = −0.45 e Å−3

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812025664/hb6839sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812025664/hb6839Isup2.hkl

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

[Zn(C2H3O2)2(C14H13N3)]	Z = 2
Mr = 406.73	F(000) = 420
Triclinic, P1	Dx = 1.589 Mg m−3
Hall symbol: -P 1	Cu Kα radiation, λ = 1.54184 Å
a = 7.6586 (4) Å	Cell parameters from 3775 reflections
b = 10.7334 (6) Å	θ = 4.6–76.3°
c = 11.5772 (4) Å	µ = 2.27 mm−1
α = 69.437 (4)°	T = 100 K
β = 81.546 (3)°	Prism, light-brown
γ = 72.736 (4)°	0.25 × 0.15 × 0.05 mm
V = 849.93 (7) Å3

Agilent SuperNova Dual diffractometer with Atlas detector	3498 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	3322 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.021
Detector resolution: 10.4041 pixels mm-1	θmax = 76.5°, θmin = 4.6°
ω scan	h = −9→9
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −12→13
Tmin = 0.617, Tmax = 1.000	l = −11→14
6205 measured reflections

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) = 0.081	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0448P)2 + 0.5376P] where P = (Fo2 + 2Fc2)/3
3498 reflections	(Δ/σ)max = 0.001
239 parameters	Δρmax = 0.67 e Å−3
0 restraints	Δρmin = −0.45 e Å−3

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.

	x	y	z	Uiso*/Ueq
Zn	0.81157 (3)	0.72065 (2)	0.729830 (19)	0.01539 (9)
O1	0.54802 (18)	0.81205 (15)	0.67857 (12)	0.0237 (3)
O2	0.7235 (2)	0.72283 (17)	0.54526 (14)	0.0333 (3)
O3	0.97606 (19)	0.83912 (14)	0.66803 (13)	0.0251 (3)
O4	0.8163 (2)	0.95459 (18)	0.79237 (13)	0.0346 (4)
N1	0.9903 (2)	0.53183 (15)	0.73964 (13)	0.0157 (3)
N2	0.9663 (2)	0.42401 (15)	0.84284 (13)	0.0148 (3)
N3	0.76154 (19)	0.59226 (15)	0.91411 (13)	0.0147 (3)
C1	0.5715 (3)	0.78835 (18)	0.57607 (17)	0.0191 (3)
C2	0.4136 (3)	0.8434 (2)	0.49227 (18)	0.0247 (4)
H2A	0.4333	0.7891	0.4366	0.037*
H2B	0.4053	0.9401	0.4436	0.037*
H2C	0.2996	0.8367	0.5421	0.037*
C3	0.9376 (3)	0.93922 (19)	0.71118 (16)	0.0203 (4)
C4	1.0519 (3)	1.0407 (2)	0.65732 (18)	0.0238 (4)
H4A	1.0008	1.1202	0.6865	0.036*
H4B	1.0515	1.0719	0.5670	0.036*
H4C	1.1778	0.9961	0.6834	0.036*
C5	1.1702 (3)	0.56456 (19)	0.54237 (16)	0.0216 (4)
H5A	1.1823	0.5196	0.4800	0.032*
H5B	1.2888	0.5773	0.5503	0.032*
H5C	1.0801	0.6546	0.5171	0.032*
C6	1.1083 (2)	0.47655 (18)	0.66347 (16)	0.0169 (3)
C7	1.1602 (2)	0.33201 (18)	0.71639 (16)	0.0172 (3)
H7	1.2427	0.2686	0.6804	0.021*
C8	1.0696 (2)	0.29988 (18)	0.82920 (16)	0.0162 (3)
C9	1.0774 (3)	0.15864 (18)	0.91825 (16)	0.0197 (3)
H9A	1.1598	0.0897	0.8838	0.029*
H9B	0.9545	0.1441	0.9330	0.029*
H9C	1.1231	0.1494	0.9964	0.029*
C10	0.8445 (2)	0.45914 (18)	0.93770 (15)	0.0146 (3)
C11	0.8173 (2)	0.35645 (18)	1.04951 (16)	0.0175 (3)
H11	0.8819	0.2624	1.0634	0.021*
C12	0.6956 (2)	0.39558 (19)	1.13728 (16)	0.0186 (3)
H12	0.6735	0.3279	1.2127	0.022*
C13	0.6026 (2)	0.53597 (18)	1.11662 (16)	0.0165 (3)
C14	0.4758 (2)	0.5825 (2)	1.20508 (16)	0.0197 (4)
H14	0.4464	0.5176	1.2803	0.024*
C15	0.3960 (2)	0.7202 (2)	1.18233 (17)	0.0212 (4)
H15	0.3129	0.7509	1.2423	0.025*
C16	0.4366 (2)	0.81699 (19)	1.06979 (17)	0.0204 (4)
H16	0.3813	0.9126	1.0554	0.025*
C17	0.5549 (2)	0.77526 (18)	0.98073 (16)	0.0183 (3)
H17	0.5788	0.8414	0.9047	0.022*
C18	0.6406 (2)	0.63361 (18)	1.00311 (15)	0.0157 (3)

	U11	U22	U33	U12	U13	U23
Zn	0.01744 (13)	0.01236 (13)	0.01501 (13)	−0.00462 (9)	−0.00080 (9)	−0.00227 (9)
O1	0.0225 (7)	0.0315 (7)	0.0164 (6)	−0.0077 (6)	−0.0021 (5)	−0.0058 (5)
O2	0.0279 (8)	0.0360 (8)	0.0346 (8)	0.0037 (6)	−0.0070 (6)	−0.0178 (7)
O3	0.0254 (7)	0.0173 (6)	0.0335 (7)	−0.0087 (5)	−0.0018 (6)	−0.0067 (5)
O4	0.0350 (8)	0.0474 (9)	0.0219 (7)	−0.0177 (7)	0.0070 (6)	−0.0096 (6)
N1	0.0193 (7)	0.0134 (7)	0.0132 (6)	−0.0059 (6)	−0.0005 (5)	−0.0015 (5)
N2	0.0172 (7)	0.0121 (6)	0.0133 (6)	−0.0044 (5)	−0.0012 (5)	−0.0012 (5)
N3	0.0159 (7)	0.0141 (7)	0.0139 (6)	−0.0045 (5)	−0.0019 (5)	−0.0034 (5)
C1	0.0218 (9)	0.0131 (8)	0.0210 (8)	−0.0073 (7)	−0.0013 (7)	−0.0013 (6)
C2	0.0265 (10)	0.0261 (10)	0.0220 (9)	−0.0074 (8)	−0.0060 (7)	−0.0062 (7)
C3	0.0231 (9)	0.0210 (9)	0.0125 (7)	−0.0048 (7)	−0.0062 (6)	0.0009 (6)
C4	0.0294 (10)	0.0212 (9)	0.0253 (9)	−0.0116 (8)	0.0022 (7)	−0.0103 (7)
C5	0.0258 (9)	0.0205 (9)	0.0179 (8)	−0.0085 (7)	0.0030 (7)	−0.0053 (7)
C6	0.0178 (8)	0.0186 (8)	0.0159 (8)	−0.0062 (7)	−0.0010 (6)	−0.0063 (7)
C7	0.0180 (8)	0.0163 (8)	0.0188 (8)	−0.0048 (6)	−0.0019 (6)	−0.0070 (7)
C8	0.0173 (8)	0.0139 (8)	0.0184 (8)	−0.0037 (6)	−0.0040 (6)	−0.0055 (6)
C9	0.0232 (9)	0.0134 (8)	0.0201 (8)	−0.0032 (7)	−0.0030 (7)	−0.0034 (7)
C10	0.0153 (8)	0.0150 (8)	0.0139 (7)	−0.0056 (6)	−0.0022 (6)	−0.0031 (6)
C11	0.0204 (8)	0.0145 (8)	0.0167 (8)	−0.0056 (6)	−0.0020 (6)	−0.0026 (6)
C12	0.0205 (8)	0.0183 (8)	0.0148 (8)	−0.0075 (7)	−0.0015 (6)	−0.0007 (6)
C13	0.0151 (8)	0.0196 (8)	0.0161 (8)	−0.0071 (7)	−0.0018 (6)	−0.0049 (7)
C14	0.0187 (8)	0.0255 (9)	0.0152 (8)	−0.0078 (7)	0.0001 (6)	−0.0058 (7)
C15	0.0166 (8)	0.0288 (10)	0.0206 (8)	−0.0053 (7)	0.0002 (6)	−0.0118 (7)
C16	0.0171 (8)	0.0205 (9)	0.0246 (9)	−0.0034 (7)	−0.0029 (7)	−0.0089 (7)
C17	0.0177 (8)	0.0168 (8)	0.0203 (8)	−0.0049 (7)	−0.0027 (6)	−0.0049 (7)
C18	0.0151 (8)	0.0178 (8)	0.0150 (8)	−0.0059 (6)	−0.0024 (6)	−0.0041 (6)

Zn—O1	2.0388 (14)	C5—H5B	0.9800
Zn—O2	2.3240 (15)	C5—H5C	0.9800
Zn—O3	1.9397 (13)	C6—C7	1.406 (2)
Zn—N1	2.0570 (15)	C7—C8	1.366 (2)
Zn—N3	2.1460 (14)	C7—H7	0.9500
O1—C1	1.276 (2)	C8—C9	1.494 (2)
O2—C1	1.243 (2)	C9—H9A	0.9800
O3—C3	1.279 (2)	C9—H9B	0.9800
O4—C3	1.239 (2)	C9—H9C	0.9800
N1—C6	1.327 (2)	C10—C11	1.410 (2)
N1—N2	1.3752 (19)	C11—C12	1.366 (3)
N2—C8	1.383 (2)	C11—H11	0.9500
N2—C10	1.414 (2)	C12—C13	1.412 (3)
N3—C10	1.326 (2)	C12—H12	0.9500
N3—C18	1.383 (2)	C13—C18	1.418 (2)
C1—C2	1.507 (3)	C13—C14	1.422 (2)
C2—H2A	0.9800	C14—C15	1.365 (3)
C2—H2B	0.9800	C14—H14	0.9500
C2—H2C	0.9800	C15—C16	1.413 (3)
C3—C4	1.507 (3)	C15—H15	0.9500
C4—H4A	0.9800	C16—C17	1.376 (3)
C4—H4B	0.9800	C16—H16	0.9500
C4—H4C	0.9800	C17—C18	1.411 (2)
C5—C6	1.491 (2)	C17—H17	0.9500
C5—H5A	0.9800
O3—Zn—O1	115.05 (6)	H5A—C5—H5C	109.5
O3—Zn—N1	100.66 (6)	H5B—C5—H5C	109.5
O1—Zn—N1	133.70 (6)	N1—C6—C7	109.92 (15)
O3—Zn—N3	130.20 (6)	N1—C6—C5	121.23 (16)
O1—Zn—N3	99.32 (5)	C7—C6—C5	128.84 (16)
N1—Zn—N3	76.50 (6)	C8—C7—C6	107.15 (16)
O3—Zn—O2	100.51 (6)	C8—C7—H7	126.4
O1—Zn—O2	59.65 (5)	C6—C7—H7	126.4
N1—Zn—O2	86.61 (6)	C7—C8—N2	106.19 (15)
N3—Zn—O2	128.42 (6)	C7—C8—C9	126.73 (16)
C1—O1—Zn	96.11 (11)	N2—C8—C9	127.07 (15)
C1—O2—Zn	83.96 (12)	C8—C9—H9A	109.5
C3—O3—Zn	113.89 (12)	C8—C9—H9B	109.5
C6—N1—N2	106.53 (14)	H9A—C9—H9B	109.5
C6—N1—Zn	137.00 (12)	C8—C9—H9C	109.5
N2—N1—Zn	115.34 (10)	H9A—C9—H9C	109.5
N1—N2—C8	110.21 (13)	H9B—C9—H9C	109.5
N1—N2—C10	116.43 (14)	N3—C10—N2	115.77 (14)
C8—N2—C10	133.36 (14)	N3—C10—C11	123.55 (16)
C10—N3—C18	118.69 (14)	N2—C10—C11	120.68 (15)
C10—N3—Zn	114.76 (11)	C12—C11—C10	118.35 (16)
C18—N3—Zn	126.25 (11)	C12—C11—H11	120.8
O2—C1—O1	120.25 (17)	C10—C11—H11	120.8
O2—C1—C2	120.74 (17)	C11—C12—C13	120.42 (16)
O1—C1—C2	119.00 (17)	C11—C12—H12	119.8
C1—C2—H2A	109.5	C13—C12—H12	119.8
C1—C2—H2B	109.5	C12—C13—C18	117.95 (16)
H2A—C2—H2B	109.5	C12—C13—C14	122.76 (16)
C1—C2—H2C	109.5	C18—C13—C14	119.28 (16)
H2A—C2—H2C	109.5	C15—C14—C13	120.20 (16)
H2B—C2—H2C	109.5	C15—C14—H14	119.9
O4—C3—O3	123.91 (18)	C13—C14—H14	119.9
O4—C3—C4	120.51 (18)	C14—C15—C16	120.16 (17)
O3—C3—C4	115.58 (16)	C14—C15—H15	119.9
C3—C4—H4A	109.5	C16—C15—H15	119.9
C3—C4—H4B	109.5	C17—C16—C15	121.15 (17)
H4A—C4—H4B	109.5	C17—C16—H16	119.4
C3—C4—H4C	109.5	C15—C16—H16	119.4
H4A—C4—H4C	109.5	C16—C17—C18	119.54 (16)
H4B—C4—H4C	109.5	C16—C17—H17	120.2
C6—C5—H5A	109.5	C18—C17—H17	120.2
C6—C5—H5B	109.5	N3—C18—C17	119.36 (15)
H5A—C5—H5B	109.5	N3—C18—C13	121.01 (16)
C6—C5—H5C	109.5	C17—C18—C13	119.63 (16)
O3—Zn—O1—C1	86.61 (12)	Zn—N1—C6—C7	−165.93 (13)
N1—Zn—O1—C1	−50.21 (13)	N2—N1—C6—C5	−178.46 (15)
N3—Zn—O1—C1	−130.39 (11)	Zn—N1—C6—C5	15.0 (3)
O2—Zn—O1—C1	−1.07 (10)	N1—C6—C7—C8	−0.2 (2)
O3—Zn—O2—C1	−111.88 (12)	C5—C6—C7—C8	178.77 (18)
O1—Zn—O2—C1	1.10 (10)	C6—C7—C8—N2	−0.27 (19)
N1—Zn—O2—C1	147.89 (12)	C6—C7—C8—C9	178.33 (17)
N3—Zn—O2—C1	78.10 (13)	N1—N2—C8—C7	0.66 (19)
O1—Zn—O3—C3	65.51 (14)	C10—N2—C8—C7	179.74 (17)
N1—Zn—O3—C3	−144.72 (13)	N1—N2—C8—C9	−177.92 (16)
N3—Zn—O3—C3	−63.46 (15)	C10—N2—C8—C9	1.2 (3)
O2—Zn—O3—C3	126.78 (13)	C18—N3—C10—N2	179.97 (14)
O3—Zn—N1—C6	−55.42 (18)	Zn—N3—C10—N2	5.87 (19)
O1—Zn—N1—C6	85.47 (19)	C18—N3—C10—C11	−0.4 (3)
N3—Zn—N1—C6	175.51 (19)	Zn—N3—C10—C11	−174.50 (13)
O2—Zn—N1—C6	44.64 (18)	N1—N2—C10—N3	2.6 (2)
O3—Zn—N1—N2	138.85 (11)	C8—N2—C10—N3	−176.44 (17)
O1—Zn—N1—N2	−80.26 (13)	N1—N2—C10—C11	−177.04 (15)
N3—Zn—N1—N2	9.79 (11)	C8—N2—C10—C11	3.9 (3)
O2—Zn—N1—N2	−121.08 (12)	N3—C10—C11—C12	1.6 (3)
C6—N1—N2—C8	−0.80 (18)	N2—C10—C11—C12	−178.81 (16)
Zn—N1—N2—C8	169.09 (11)	C10—C11—C12—C13	−1.1 (3)
C6—N1—N2—C10	179.95 (14)	C11—C12—C13—C18	−0.4 (3)
Zn—N1—N2—C10	−10.16 (18)	C11—C12—C13—C14	−179.51 (17)
O3—Zn—N3—C10	−101.18 (13)	C12—C13—C14—C15	177.08 (17)
O1—Zn—N3—C10	124.36 (12)	C18—C13—C14—C15	−2.0 (3)
N1—Zn—N3—C10	−8.53 (12)	C13—C14—C15—C16	1.1 (3)
O2—Zn—N3—C10	65.92 (14)	C14—C15—C16—C17	0.7 (3)
O3—Zn—N3—C18	85.24 (15)	C15—C16—C17—C18	−1.5 (3)
O1—Zn—N3—C18	−49.22 (14)	C10—N3—C18—C17	178.31 (15)
N1—Zn—N3—C18	177.89 (15)	Zn—N3—C18—C17	−8.3 (2)
O2—Zn—N3—C18	−107.66 (14)	C10—N3—C18—C13	−1.2 (2)
Zn—O2—C1—O1	−1.76 (17)	Zn—N3—C18—C13	172.15 (12)
Zn—O2—C1—C2	177.01 (16)	C16—C17—C18—N3	−179.02 (16)
Zn—O1—C1—O2	2.01 (19)	C16—C17—C18—C13	0.5 (3)
Zn—O1—C1—C2	−176.78 (14)	C12—C13—C18—N3	1.6 (2)
Zn—O3—C3—O4	5.5 (2)	C14—C13—C18—N3	−179.25 (15)
Zn—O3—C3—C4	−174.94 (12)	C12—C13—C18—C17	−177.93 (16)
N2—N1—C6—C7	0.63 (19)	C14—C13—C18—C17	1.2 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4B···O3i	0.98	2.57	3.544 (2)	176
C5—H5A···O2ii	0.98	2.60	3.417 (3)	141
C7—H7···O2ii	0.95	2.56	3.235 (2)	128
C9—H9C···O4iii	0.98	2.36	3.274 (2)	156
C12—H12···O1iv	0.95	2.51	3.310 (2)	142

Table 1

Selected bond lengths (Å)

Zn—O1	2.0388 (14)
Zn—O2	2.3240 (15)
Zn—O3	1.9397 (13)
Zn—N1	2.0570 (15)
Zn—N3	2.1460 (14)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4B⋯O3i	0.98	2.57	3.544 (2)	176
C5—H5A⋯O2ii	0.98	2.60	3.417 (3)	141
C7—H7⋯O2ii	0.95	2.56	3.235 (2)	128
C9—H9C⋯O4iii	0.98	2.36	3.274 (2)	156
C12—H12⋯O1iv	0.95	2.51	3.310 (2)	142

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