Different ZnII cation coordination geometries in di-μ-acetato-bis{2-chloro-6-[(pyridine-2-ylmethylimino)methyl]phenol} dizinc(II) chloroform monosolvate

Article abstract of DOI:10.1107/S0108270113027212

In the title compound, di-μ-acetato-κ² O:O;κ² O:O′-bis[(6-chloro-2-{(E)-[(pyridin-2-yl) methylimino]methyl}phenolato-κ³ N,N′,O)zinc(II)], [Zn₂(C₁₃H₁₀ClN₂O)₂(C ₂H₃O₂)₂]·CHCl₃, the Zn^II cation adopts a five-coordinate geometry and is coordinated by two N atoms and one O atom of a tridentate 6-chloro-2-{(E)-[(pyridin-2-yl) methylimino]methyl}phenolate ligand and two O atoms of two bridging acetate groups, but their coordination geometries differ. One Zn^II cation adopts a distorted trigonal bipyramidal geometry and the other a square-pyramidal geometry. The two acetate ligands bridge two Zn^II cations with mono-and bidentate coordination modes. The title compound exhibits a strong emission at 460 nm upon excitation at 325 nm with a quantum yield of 23.1%.

Full text of DOI:10.1107/S0108270113027212

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
2012). Here, we have designed a new Schiff base ligand,
namely 6-chloro-2-{(E)-[(pyridin-2-yl)methylimino]methyl}-
phenol (L1), containing a 2-picolyl group, and synthesized a
ZnII complex incorporating this ligand, viz [Zn2(L1)2-
(CH3COO)2]ꢀCHCl3, (I). The structural and luminescence
properties of (I) were examined to establish its potential as a
fluorescence emitter in electroluminescent devices.
ISSN 0108-2701
Different ZnII cation coordination
geometries in di-l-acetato-bis{2-
chloro-6-[(pyridine-2-ylmethylimino)-
methyl]phenol}dizinc(II) chloroform
monosolvate
Young-Inn Kim,a Jin Young Lee,a Young-Kwang Songa and
Sung Kwon Kangb*
aDepartment of Chemistry Education and Department of Chemical Materials,
Graduate School, Pusan National University, Busan 609-735, Republic of Korea, and
bDepartment of Chemistry, Chungnam National University, Daejeon 305-764,
Republic of Korea
Correspondence e-mail: skkang@cnu.ac.kr
2. Experimental
Received 17 August 2013
Accepted 3 October 2013
2.1. Synthesis and crystallization
In the title compound, di-ꢀ-acetato-ꢁ2O:O;ꢁ2O:O0-bis[(6-
chloro-2-{(E)-[(pyridin-2-yl)methylimino]methyl}phenolato-
ꢁ3N,N0,O)zinc(II)], [Zn2(C13H10ClN2O)2(C2H3O2)2]ꢀCHCl3,
the ZnII cation adopts a five-coordinate geometry and is
coordinated by two N atoms and one O atom of a tridentate
6-chloro-2-{(E)-[(pyridin-2-yl)methylimino]methyl}phenolate
ligand and two O atoms of two bridging acetate groups, but
their coordination geometries differ. One ZnII cation adopts a
distorted trigonal bipyramidal geometry and the other a
square-pyramidal geometry. The two acetate ligands bridge
two ZnII cations with mono- and bidentate coordination
modes. The title compound exhibits a strong emission at
460 nm upon excitation at 325 nm with a quantum yield of
23.1%.
For the preparation of ligand L1, 2-picolylamine (0.54 g,
5 mmol) was added to a solution of 3-chloro-2-hydroxy-
benzaldehyde (0.785 g, 5 mmol) in methanol (30 ml) and the
resulting solution stirred at 303 K for 3 h. A brown oil was
obtained after evaporation. The pure ligand was obtained as a
yellow powder by recrystallization from a solution in chloro-
form–hexane (1:6 v/v) (yield 1.16 g, 94%).
For the preparation of the title compound, (I), a methanol
solution (30 ml) of the Schiff base ligand L1 (1.23 g, 5 mmol)
was added to a methanol solution (10 ml) of zinc acetate
(1.095 g, 5 mmol) and the resulting solution stirred at 303 K
for 3 h. The yellow powder which formed was filtered off and
washed with hexane (yield 0.88 g, 24%). Yellow crystals of (I)
were obtained by recrystallization from a solution in chloro-
form–hexane (1:1 v/v) at room temperature. Analysis calcu-
lated for C30H26Cl2N4O6Zn2: C 48.67, H 3.54, N 7.57,
O 12.97%; found: C 48.65, H 3.56, N 7.36, O 12.75%.
Keywords: crystal structure; zinc(II) complexes; dinuclear
complexes.
2.2. Refinement
1. Introduction
Crystal data, data collection and structure refinement
details are summarized in Table 1. All H atoms were posi-
tioned geometrically and refined using a riding model, with
Schiff base ligands have been studied extensively in coordi-
nation chemistry due to their facile syntheses, easily tunable
steric and electronic properties, and good solubility in
˚
C—H = 0.93–0.98 A, and with Uiso(H) = 1.5Ueq(C) for methyl
H atoms or 1.2Ueq(C) otherwise. The maximum and minimum
¨
¨
¨
common solvents (Gumrukc¸u et al., 2012; Tong et al., 2013).
Group 12 metal complexes containing Schiff base ligands
attract research interest due to their potential applications,
including as emitting materials for organic light-emitting
diodes, light-harvesting materials for photocatalysis and
fluorescent sensors for organic or inorganic analytes (Chavan
& Bharate, 2013; Kuai et al., 2013). Recently, we synthesized
Zn and Hg complexes with Schiff base ligands and reported
their structural properties (Kim & Kang, 2010; Kim et al., 2011,
˚
residual electron-density peaks were located 0.93 and 0.72 A,
respectively, from atom Cl46.
3. Results and discussion
The photoluminescence (PL) spectra of the Schiff base ligand
L1 and its ZnII complex, (I), were investigated at room
temperature. Complex (I) exhibits a strong emission at 460 nm
1348 # 2013 International Union of Crystallography
doi:10.1107/S0108270113027212
Acta Cryst. (2013). C69, 1348–1350

metal-organic compounds
Table 2
Selected geometric parameters (A, ).
Table 1
Experimental details.
ꢂ
˚
Zn1—O16
Zn1—O18
Zn1—O22
Zn1—N8
Zn1—N1
2.0055 (15)
2.0240 (15)
2.0624 (14)
2.0815 (17)
2.1622 (18)
O20—Zn2
O22—Zn2
Zn2—O41
Zn2—N33
Zn2—N26
1.9929 (16)
2.0707 (14)
1.9936 (15)
2.0877 (17)
2.1388 (18)
Crystal data
Chemical formula
[Zn2(C13H10ClN2O)2(C2H3O2)2]ꢀ-
CHCl3
859.55
Triclinic, P1
Mr
Crystal system, space group
Temperature (K)
173
9.3167 (3), 10.1345 (3), 19.4988 (6)
88.344 (1), 88.179 (1), 67.092 (5)
1694.75 (11)
˚
O18—Zn1—O22
O18—Zn1—N8
O22—Zn1—N8
O16—Zn1—N1
O20—Zn2—O41
97.46 (6)
124.88 (7)
136.30 (7)
164.71 (6)
107.08 (7)
O20—Zn2—O22
O20—Zn2—N33
O22—Zn2—N33
O20—Zn2—N26
O41—Zn2—N26
98.42 (6)
103.57 (7)
157.27 (7)
103.02 (7)
148.73 (7)
a, b, c (A)
ꢄ, ꢅ, ꢆ (ꢂ)
3
˚
V (A )
Z
Radiation type
2
Mo Kꢄ
1.86
0.11 ꢄ 0.09 ꢄ 0.08
ꢀ (mmꢃ1
Crystal size (mm)
)
emissions from metal-centred or MLCT/LMCT (metal-to-
ligand charge transfer/ligand-to-metal charge transfer) excited
states are expected (Chen et al., 2006). It is worth noting that
the quantum yield of complex (I) was greatly enhanced (up to
23.1%) compared with that of the ligand (<1%). This result
could be explained by the fact that the chelation of the ligand
to the ZnII cation increases the rigidity of the ligand and thus
reduces the loss of energy by thermal vibrational decay (Das et
al., 2006).
Data collection
Diffractometer
Bruker SMART CCD area-detector
diffractometer
Multi-scan (SADABS; Bruker, 2002)
0.81, 0.858
33219, 8444, 6461
Absorption correction
Tmin, Tmax
No. of measured, independent and
observed [I > 2ꢇ(I)] reflections
Rint
0.042
0.667
ꢃ1
˚
(sin ꢈ/ꢉ)max (A
)
Refinement
R[F2 > 2ꢇ(F2)], wR(F2), S
No. of reflections
No. of parameters
0.033, 0.075, 1.02
8444
435
H-atom parameters constrained
The structural analysis of (I) (Fig. 1 and Table 2) shows that
the ZnII cations are each coordinated in a tridentate fashion
by L1 and bridged by a pair of acetate ligands; one acetate is
O:O0-bridging through both O atoms and the other is O:O-
bridging through one O atom. The coordination geometry
around atom Zn1 is distorted trigonal bipyramidal, with the
equatorial plane defined by Schiff base ligand atom N8,
acetate atom O18 and bridging acetate atom O22, and with
atoms N1 and O16 occupying axial positions (Fig. 2). The
calculated trigonality index, ꢃ = 0.47, indicates that atom Zn1
has a distorted trigonal bipyramidal geometry (ꢃ = 1 for a
perfect trigonal bipyramidal geometry and ꢃ = 0 for a perfect
square-pyramidal geometry; Addison et al., 1984). However,
the calculated ꢃ value around atom Zn2 was 0.14, indicating a
nearly square-pyramidal geometry. The basal positions are
occupied by atoms N26, N33 and O41 of a tridentate Schiff
base ligand and bridging acetate atom O22, and acetate atom
O20 occupies the apical position. The deviation from the ideal
geometries may be due to the restricted bite angle of the
tridentate Schiff base ligand. The relatively short Zn1ꢀ ꢀ ꢀO24
H-atom treatment
˚
ꢃ3
Áꢊmax, Áꢊmin (e A
)
0.57, ꢃ0.52
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS2013
(Sheldrick, 2008), SHELXL2013 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia,
2012) and WinGX (Farrugia, 2012).
upon excitation at 325 nm with a quantum yield of 23.1%,
whereas the ligand shows a broad emission (full width at half-
maximum 135 nm) with a maximum peak at 435 nm with less
than 1% quantum yield, both in dimethylformamide solution.
The quantum yields were calculated using 9,10-diphenyl-
anthracene (0.91) as a reference. The emission of the ZnII
1
complex should probably be assigned to (ꢂ–ꢂ*) intraligand
fluorescence, since the ZnII cation is difficult to oxidize or
reduce due to its stable d10 configuration. Therefore, no
˚
distance of 2.6480 (17) A is a weak but significant interaction
Figure 1
The molecular structure of the title compound, (I), showing the atom-
numbering scheme. Displacement ellipsoids are drawn at the 50%
probability level.
Figure 2
The coordination environments around atoms Zn1 and Zn2.
ꢁ
Acta Cryst. (2013). C69, 1348–1350
Kim et al.
[Zn2(C13H10ClN2O)2(C2H3O2)2]ꢀCHCl3 1349

metal-organic compounds
that influences the geometry about Zn1 and thus inhibits the
adoption of a square-pyramidal geometry very significantly.
The acetate ligand containing atom O24 is thus not entirely
square pyramidal. The complex exhibits a strong emission and
high quantum yield in its photoluminescence spectra.
˚
This work was supported by the Basic Science Research
Program through the National Research Foundation of Korea
(NRF), funded by the Ministry of Education, Science and
Technology (grant No. 20110003799).
monodentate. The Zn1ꢀ ꢀ ꢀO24 distance is 1.12 A shorter than
the sum of the van der Waals radii (Bondi, 1964). It is inter-
esting that two different coordination environments have been
adopted about the ZnII cations in (I). Such compounds are
relatively rare among dinuclear compounds compared with
those exhibiting similar geometries. For example, dinuclear Zn
compounds based on quinolin-8-ol (Yuan et al., 2012) or di-
thiocarbamate (Onwudiwe & Ajibade, 2010) revealed that
each ZnII cation is five-coordinate, with a distorted trigonal
bipyramidal geometry around both of the ZnII cations. In the
structure of (I), the close contact between the CHCl3 solvent
molecule and the monodentate bridging acetate ligand
[C43ꢀ ꢀ ꢀO24 = 3.071 (2) A] is due to a simple electrostatic
The two acetate ligands bridge the two ZnII cations with
both mono- and bidentate coordination modes, as confirmed
by IR data. The asymmetric and symmetric stretching vibra-
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: OV3038). Services for accessing these data are
described at the back of the journal.
References
Addison, A. W., Rao, T. N., Reedjik, J., van Rijin, T. & Verschoor, G. C. (1984).
J. Chem. Soc. Dalton Trans. pp. 1349–1356.
Bondi, A. (1964). J. Phys. Chem. 68, 441–452.
Bruker (2002). SADABS, SAINT and SMART. Bruker AXS Inc., Madison,
Wisconsin, USA.
Chavan, S. S. & Bharate, B. G. (2013). Inorg. Chim. Acta, 394, 598–604.
Chen, W.-T., Zeng, X.-R., Fang, X.-N., Li, X.-F. & Kuang, H.-M. (2006). Acta
Cryst. C62, m571–m573.
Das, D., Chand, B. G., Sarker, K. K., Dinda, J. & Sinha, C. (2006). Polyhedron,
25, 2333–2340.
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.
˚
interaction.
tions of the acetate groups appear at 1575 and 1436 cmꢃ1
respectively. The difference between asym(COO) and
sym(COO) (Áꢋ = 139 cmꢃ1), which is smaller than the value
,
ꢋ
¨
¨
¨
¨
Gumrukc¸u, G., Karaoglan, G. K., Erdogmus, A., Gul, A. & Avciata, U. (2012).
ꢋ
Dyes Pigm. 95, 280–289.
of 164 cmꢃ1 observed in ionic acetate, reflects the bidentate
bridging coordination mode (Tarafder et al., 2001). The
asymmetric and symmetric stretching vibrations of the
monodentate bridging acetate group appear at 1609 and
1348 cmꢃ1, respectively. In the tridentate Schiff base ligands,
the 2-picolyl rings (N1–C7 and N26–C32) are twisted by
13.45 (10) and 13.06 (11)ꢂ from the mean plane of the imino-
methylphenol groups (N8–O16 and N33–O41, respectively).
In summary, the two ZnII cations in (I) adopt different five-
coordinate geometries, viz. distorted trigonal bipyramidal and
Kim, Y.-I. & Kang, S. K. (2010). Acta Cryst. E66, m1251.
Kim, Y.-I., Song, Y.-K., Yun, S.-J., Kim, I.-C. & Kang, S. K. (2011). Acta Cryst.
E67, m52–m53.
Kim, Y.-I., Yun, S.-J., Hwang, I.-H., Kim, D.-Y. & Kang, S. K. (2012). Acta
Cryst. E68, m504–m505.
Kuai, H.-W., Cheng, X.-C. & Zhu, X.-H. (2013). Polyhedron, 50, 390–397.
Onwudiwe, D. C. & Ajibade, P. A. (2010). Polyhedron, 29, 1431–1436.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Tarafder, M. T. H., Kasbollah, A., Crouse, K. A., Ali, A. M., Yamin, B. M. &
Fun, H.-K. (2001). Polyhedron, 20, 2363–2370.
Tong, W.-L., Yiu, S.-M. & Chan, M. C. W. (2013). Inorg. Chem. 52, 7114–7124.
Yuan, G.-Z., Huo, Y.-P., Nie, X.-L., Fang, X.-M. & Zhu, S.-Z. (2012).
Tetrahedron, 68, 8018–8023.
ꢁ
1350 Kim et al. [Zn2(C13H10ClN2O)2(C2H3O2)2]ꢀCHCl3
Acta Cryst. (2013). C69, 1348–1350

supplementary materials
supplementary materials
Acta Cryst. (2013). C69, 1348-1350 [doi:10.1107/S0108270113027212]
Different ZnII cation coordination geometries in di-µ-acetato-bis{2-
chloro-6-[(pyridine-2-ylmethylimino)methyl]phenol}dizinc(II) chloroform
monosolvate
Young-Inn Kim, Jin Young Lee, Young-Kwang Song and Sung Kwon Kang
Computing details
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002);
program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013
(Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for
publication: WinGX (Farrugia, 2012).
Di-µ-acetato-κ2O:O;κ2O:O′-bis[(6-chloro-2-{(E)-[(pyridin-2-yl)methylimino]methyl}phenolato-
κ3N,N′,O)dizinc(II)]
Crystal data
[Zn2(C13H10ClN2O)2(C2H3O2)2]·CHCl3
Mr = 859.55
Triclinic, P1
Hall symbol: -P 1
a = 9.3167 (3) Å
b = 10.1345 (3) Å
c = 19.4988 (6) Å
α = 88.344 (1)°
Z = 2
F(000) = 868
Dx = 1.684 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 7509 reflections
θ = 2.4–27.8°
µ = 1.86 mm−1
T = 173 K
β = 88.179 (1)°
Block, yellow
γ = 67.092 (5)°
V = 1694.75 (11) Å3
0.11 × 0.09 × 0.08 mm
Data collection
Bruker SMART CCD area-detector
diffractometer
Radiation source: fine-focus sealed tube
φ and ω scans
8444 independent reflections
6461 reflections with I > 2σ(I)
Rint = 0.042
θ
max = 28.3°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
h = −12→12
k = −13→13
l = −25→25
T
min = 0.81, Tmax = 0.858
33219 measured reflections
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.033
wR(F2) = 0.075
8444 reflections
435 parameters
0 restraints
Hydrogen site location: inferred from
neighbouring sites
S = 1.02
Acta Cryst. (2013). C69, 1348-1350
sup-1

supplementary materials
H-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0285P)2 + 0.6869P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.002
Δρmax = 0.57 e Å−3
Δρmin = −0.52 e Å−3
Special details
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.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
Zn1
N1
0.12351 (3)
0.0622 (2)
−0.0514 (3)
−0.1136
−0.00600 (3)
0.20735 (19)
0.2715 (2)
0.2238
0.73243 (2)
0.68922 (9)
0.64376 (11)
0.6311
0.02239 (7)
0.0228 (4)
0.0276 (5)
0.033*
C2
H2
C3
−0.0787 (3)
−0.1573
0.4043 (2)
0.445
0.61552 (12)
0.5839
0.0294 (5)
0.035*
H3
C4
0.0122 (3)
−0.0046
0.4775 (3)
0.568
0.63459 (12)
0.6163
0.0291 (5)
0.035*
H4
C5
0.1278 (3)
0.1903
0.4127 (2)
0.4591
0.68135 (11)
0.6952
0.0278 (5)
0.033*
H5
C6
0.1500 (2)
0.2759 (3)
0.3757
0.2778 (2)
0.2038 (2)
0.196
0.70744 (11)
0.75827 (12)
0.7385
0.0231 (4)
0.0296 (5)
0.036*
C7
H7A
H7B
N8
0.2563
0.2611
0.7991
0.036*
0.2829 (2)
0.3633 (2)
0.4077
0.06100 (19)
0.0006 (2)
0.0539
0.77723 (9)
0.83020 (11)
0.8532
0.0247 (4)
0.0268 (5)
0.032*
C9
H9
C10
C11
C12
C13
H13
C14
H14
C15
H15
O16
Cl17
O18
C19
O20
C21
H21A
H21B
H21C
O22
C23
0.3919 (2)
0.3293 (2)
0.3836 (2)
0.4820 (3)
0.5128
−0.1401 (2)
−0.2333 (2)
−0.3736 (2)
−0.4175 (3)
−0.5107
0.85753 (11)
0.82810 (11)
0.85734 (12)
0.91201 (12)
0.9292
0.0252 (5)
0.0243 (5)
0.0278 (5)
0.0320 (5)
0.038*
0.5353 (3)
0.5993
−0.3216 (3)
−0.3491
0.94154 (13)
0.9794
0.0370 (6)
0.044*
0.4918 (3)
0.5294
−0.1870 (3)
−0.1238
0.91384 (12)
0.9327
0.0339 (6)
0.041*
0.23312 (17)
0.32355 (8)
0.14669 (18)
0.0722 (3)
−0.05985 (18)
0.1470 (3)
0.0886
−0.19773 (16)
−0.49756 (6)
−0.08622 (17)
−0.1353 (2)
−0.13743 (18)
−0.1967 (3)
−0.2451
0.77802 (8)
0.82101 (4)
0.63698 (8)
0.60040 (11)
0.61439 (8)
0.53258 (13)
0.5125
0.0306 (4)
0.04292 (17)
0.0307 (4)
0.0252 (5)
0.0314 (4)
0.0438 (7)
0.066*
0.2519
−0.2634
0.5397
0.066*
0.148
−0.1206
0.5023
0.066*
−0.10557 (16)
−0.1521 (2)
0.02143 (15)
0.1061 (2)
0.75060 (7)
0.80257 (11)
0.0217 (3)
0.0238 (5)
Acta Cryst. (2013). C69, 1348-1350
sup-2

supplementary materials
O24
C25
H25A
H25B
H25C
Zn2
−0.06025 (19)
−0.3211 (3)
−0.3502
0.14191 (18)
0.1581 (3)
0.0776
0.83339 (8)
0.82280 (14)
0.8301
0.0337 (4)
0.0437 (7)
0.066*
−0.3825
0.2188
0.7869
0.066*
−0.3391
0.2112
0.8644
0.066*
−0.22632 (3)
−0.1962 (2)
−0.0938 (3)
−0.0342
−0.05543 (3)
−0.23525 (19)
−0.2822 (2)
−0.2302
0.68600 (2)
0.75259 (9)
0.80403 (12)
0.8141
0.02211 (7)
0.0254 (4)
0.0316 (5)
0.038*
N26
C27
H27
C28
H28
C29
H29
C30
H30
C31
C32
H32A
H32B
N33
C34
H34
C35
C36
H36
C37
H37
C38
H38
C39
C40
O41
Cl42
C43
H43
Cl44
Cl45
Cl46
−0.0745 (3)
−0.0045
−0.4034 (3)
−0.4317
0.84194 (13)
0.8777
0.0357 (6)
0.043*
−0.1598 (3)
−0.1469
−0.4839 (3)
−0.5675
0.82664 (13)
0.8513
0.0354 (6)
0.043*
−0.2644 (3)
−0.323
−0.4370 (2)
−0.489
0.77396 (12)
0.7624
0.0310 (5)
0.037*
−0.2809 (2)
−0.3930 (3)
−0.358
−0.3120 (2)
−0.2580 (2)
−0.325
0.73864 (11)
0.68012 (12)
0.6427
0.0245 (5)
0.0286 (5)
0.034*
−0.4954
−0.2521
0.6954
0.034*
−0.4032 (2)
−0.5139 (2)
−0.5781
−0.11798 (19)
−0.0489 (2)
−0.0943
0.65592 (9)
0.61506 (11)
0.6021
0.0241 (4)
0.0260 (5)
0.031*
−0.5471 (2)
−0.6663 (3)
−0.715
0.0929 (2)
0.1453 (3)
0.0861
0.58758 (11)
0.53886 (12)
0.5253
0.0236 (5)
0.0300 (5)
0.036*
−0.7121 (3)
−0.7867
0.2803 (3)
0.3108
0.51113 (12)
0.4773
0.0342 (6)
0.041*
−0.6452 (3)
−0.6774
0.3714 (3)
0.4647
0.53440 (12)
0.5171
0.0327 (5)
0.039*
−0.5315 (3)
−0.4715 (2)
−0.35985 (17)
−0.46209 (7)
0.0534 (3)
0.0363
0.3236 (2)
0.1818 (2)
0.14223 (16)
0.44486 (7)
0.1866 (3)
0.1409
0.58299 (12)
0.61046 (11)
0.65452 (8)
0.61578 (4)
0.97360 (12)
0.9328
0.0274 (5)
0.0242 (5)
0.0297 (4)
0.04275 (16)
0.0351 (6)
0.042*
0.15883 (9)
−0.12729 (9)
0.16266 (10)
0.29191 (8)
0.29218 (10)
0.05223 (9)
0.94888 (4)
1.00975 (5)
1.03176 (4)
0.05178 (19)
0.0640 (2)
0.0635 (2)
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
Zn1
N1
C2
C3
C4
C5
C6
C7
0.01941 (12)
0.0234 (9)
0.02432 (14)
0.0252 (10)
0.0301 (12)
0.0303 (12)
0.0283 (12)
0.0305 (12)
0.0293 (12)
0.0343 (13)
0.02604 (14)
−0.01093 (10)
−0.0121 (8)
−0.0146 (10)
−0.0110 (10)
−0.0148 (10)
−0.0196 (10)
−0.0146 (9)
−0.0238 (11)
−0.00397 (10)
−0.0013 (7)
−0.0048 (9)
−0.0054 (10)
0.0011 (10)
−0.0012 (10)
0.0028 (8)
−0.00252 (10)
−0.0031 (8)
−0.0013 (10)
0.0005 (10)
0.0013 (10)
−0.0026 (10)
−0.0044 (9)
0.0036 (10)
0.0224 (9)
0.0298 (12)
0.0291 (12)
0.0277 (12)
0.0284 (12)
0.0207 (11)
0.0292 (12)
0.0265 (11)
0.0286 (12)
0.0338 (12)
0.0316 (12)
0.0233 (10)
0.0350 (12)
−0.0074 (10)
Acta Cryst. (2013). C69, 1348-1350
sup-3

supplementary materials
N8
0.0233 (9)
0.0235 (11)
0.0212 (10)
0.0183 (10)
0.0220 (11)
0.0300 (12)
0.0379 (14)
0.0353 (13)
0.0279 (8)
0.0443 (4)
0.0299 (8)
0.0295 (11)
0.0278 (8)
0.0444 (15)
0.0212 (7)
0.0248 (11)
0.0372 (9)
0.0239 (12)
0.02110 (12)
0.0278 (10)
0.0344 (13)
0.0412 (14)
0.0449 (14)
0.0377 (13)
0.0275 (11)
0.0319 (12)
0.0243 (9)
0.0216 (10)
0.0197 (10)
0.0272 (12)
0.0322 (13)
0.0315 (12)
0.0249 (11)
0.0194 (10)
0.0290 (8)
0.0418 (3)
0.0406 (14)
0.0581 (4)
0.0475 (4)
0.0813 (6)
0.0264 (10)
0.0316 (12)
0.0300 (12)
0.0263 (11)
0.0275 (12)
0.0306 (13)
0.0424 (15)
0.0393 (14)
0.0249 (8)
0.0253 (3)
0.0374 (9)
0.0222 (11)
0.0404 (10)
0.0579 (18)
0.0220 (8)
0.0227 (11)
0.0456 (10)
0.0594 (18)
0.02209 (13)
0.0229 (10)
0.0287 (12)
0.0336 (14)
0.0301 (13)
0.0273 (12)
0.0230 (11)
0.0252 (12)
0.0239 (9)
0.0306 (12)
0.0265 (11)
0.0342 (13)
0.0398 (14)
0.0315 (13)
0.0268 (12)
0.0268 (12)
0.0244 (8)
0.0294 (3)
0.0400 (14)
0.0574 (5)
0.0737 (6)
0.0555 (5)
0.0278 (10)
0.0295 (12)
0.0266 (12)
0.0281 (12)
0.0355 (13)
0.0347 (13)
0.0327 (14)
0.0327 (13)
0.0400 (9)
0.0606 (4)
0.0300 (9)
0.0253 (11)
0.0325 (9)
0.0369 (15)
0.0245 (8)
0.0241 (11)
0.0264 (9)
0.0413 (15)
0.02625 (14)
0.0288 (10)
0.0362 (13)
0.0333 (13)
0.0337 (14)
0.0337 (13)
0.0257 (12)
0.0350 (13)
0.0277 (10)
0.0304 (12)
0.0238 (11)
0.0282 (12)
0.0265 (12)
0.0304 (13)
0.0326 (13)
0.0256 (11)
0.0399 (9)
0.0634 (4)
0.0286 (13)
0.0520 (4)
0.0693 (5)
0.0603 (5)
−0.0132 (8)
−0.0149 (9)
−0.0120 (9)
−0.0082 (9)
−0.0111 (9)
−0.0112 (10)
−0.0173 (12)
−0.0199 (11)
−0.0102 (7)
−0.0137 (3)
−0.0183 (7)
−0.0114 (9)
−0.0199 (7)
−0.0279 (14)
−0.0109 (6)
−0.0096 (9)
−0.0242 (8)
−0.0085 (12)
−0.01157 (10)
−0.0135 (8)
−0.0171 (10)
−0.0156 (11)
−0.0180 (11)
−0.0193 (10)
−0.0129 (9)
−0.0179 (10)
−0.0132 (8)
−0.0147 (9)
−0.0078 (9)
−0.0110 (10)
−0.0090 (11)
−0.0075 (10)
−0.0122 (9)
−0.0083 (9)
−0.0142 (7)
−0.0202 (3)
−0.0194 (12)
−0.0359 (4)
−0.0212 (4)
−0.0333 (4)
−0.0031 (8)
−0.0009 (9)
−0.0018 (9)
−0.0006 (8)
−0.0011 (9)
−0.0032 (10)
−0.0132 (11)
−0.0088 (11)
−0.0143 (7)
−0.0202 (3)
0.0015 (7)
−0.0018 (8)
−0.0054 (10)
−0.0029 (9)
−0.0046 (9)
−0.0037 (10)
0.0043 (11)
0.0051 (12)
−0.0015 (11)
−0.0006 (7)
−0.0006 (3)
−0.0103 (7)
−0.0008 (9)
−0.0110 (8)
−0.0208 (13)
−0.0030 (6)
0.0034 (9)
C9
C10
C11
C12
C13
C14
C15
O16
Cl17
O18
C19
O20
C21
O22
C23
O24
C25
Zn2
N26
C27
C28
C29
C30
C31
C32
N33
C34
C35
C36
C37
C38
C39
C40
O41
Cl42
C43
Cl44
Cl45
Cl46
−0.0024 (9)
0.0041 (7)
0.0101 (12)
−0.0012 (6)
−0.0033 (9)
−0.0029 (7)
0.0036 (11)
−0.00336 (10)
−0.0016 (8)
−0.0074 (10)
−0.0078 (11)
0.0028 (11)
0.0052 (10)
0.0068 (9)
−0.0069 (8)
−0.0149 (13)
−0.00028 (10)
0.0012 (8)
0.0028 (10)
0.0049 (11)
0.0068 (11)
−0.0023 (10)
−0.0052 (9)
0.0002 (10)
−0.0018 (8)
−0.0076 (10)
−0.0042 (9)
−0.0067 (10)
0.0019 (11)
0.0072 (10)
0.0013 (10)
−0.0010 (9)
0.0044 (7)
−0.0028 (10)
0.0001 (8)
0.0005 (9)
−0.0007 (8)
−0.0039 (9)
−0.0085 (10)
−0.0023 (10)
−0.0021 (9)
0.0001 (8)
−0.0143 (7)
−0.0174 (3)
−0.0040 (11)
−0.0089 (3)
0.0131 (4)
0.0092 (3)
−0.0022 (11)
0.0103 (4)
−0.0262 (4)
0.0220 (4)
−0.0277 (4)
Geometric parameters (Å, º)
Zn1—O16
Zn1—O18
Zn1—O22
Zn1—N8
Zn1—N1
Zn1—Zn2
N1—C6
2.0055 (15)
O22—Zn2
2.0707 (14)
2.0240 (15)
2.0624 (14)
2.0815 (17)
2.1622 (18)
3.6301 (3)
1.339 (3)
C23—O24
C23—C25
C25—H25A
C25—H25B
C25—H25C
Zn2—O41
1.230 (2)
1.497 (3)
0.96
0.96
0.96
1.9936 (15)
Acta Cryst. (2013). C69, 1348-1350
sup-4

supplementary materials
N1—C2
1.349 (3)
1.371 (3)
0.93
Zn2—N33
Zn2—N26
N26—C31
N26—C27
C27—C28
C27—H27
C28—C29
C28—H28
C29—C30
C29—H29
C30—C31
C30—H30
C31—C32
C32—N33
C32—H32A
C32—H32B
N33—C34
C34—C35
C34—H34
C35—C36
C35—C40
C36—C37
C36—H36
C37—C38
C37—H37
C38—C39
C38—H38
C39—C40
C39—Cl42
C40—O41
C43—Cl45
C43—Cl46
C43—Cl44
C43—H43
2.0877 (17)
2.1388 (18)
1.343 (3)
1.350 (3)
1.368 (3)
0.93
C2—C3
C2—H2
C3—C4
1.390 (3)
0.93
C3—H3
C4—C5
1.378 (3)
0.93
C4—H4
1.385 (3)
0.93
C5—C6
1.384 (3)
0.93
C5—H5
1.380 (3)
0.93
C6—C7
1.506 (3)
1.460 (3)
0.97
C7—N8
1.381 (3)
0.93
C7—H7A
C7—H7B
N8—C9
0.97
1.512 (3)
1.451 (3)
0.97
1.288 (3)
1.434 (3)
0.93
C9—C10
C9—H9
0.97
C10—C15
C10—C11
C11—O16
C11—C12
C12—C13
C12—Cl17
C13—C14
C13—H13
C14—C15
C14—H14
C15—H15
O18—C19
C19—O20
C19—C21
O20—Zn2
C21—H21A
C21—H21B
C21—H21C
O22—C23
1.410 (3)
1.429 (3)
1.292 (2)
1.419 (3)
1.375 (3)
1.737 (2)
1.396 (3)
0.93
1.283 (3)
1.437 (3)
0.93
1.413 (3)
1.430 (3)
1.365 (3)
0.93
1.392 (3)
0.93
1.364 (3)
0.93
1.375 (3)
0.93
0.93
1.249 (2)
1.259 (3)
1.508 (3)
1.9929 (16)
0.96
1.419 (3)
1.740 (2)
1.301 (2)
1.744 (3)
1.755 (2)
1.758 (3)
0.98
0.96
0.96
1.297 (3)
O16—Zn1—O18
O16—Zn1—O22
O18—Zn1—O22
O16—Zn1—N8
O18—Zn1—N8
O22—Zn1—N8
O16—Zn1—N1
O18—Zn1—N1
O22—Zn1—N1
N8—Zn1—N1
94.40 (7)
100.33 (6)
97.46 (6)
87.81 (7)
124.88 (7)
136.30 (7)
164.71 (6)
90.25 (7)
93.48 (6)
77.61 (7)
97.72 (4)
69.18 (4)
28.62 (4)
O24—C23—C25
O22—C23—C25
C23—C25—H25A
C23—C25—H25B
121.9 (2)
117.23 (19)
109.5
109.5
H25A—C25—H25B
C23—C25—H25C
H25A—C25—H25C
H25B—C25—H25C
O20—Zn2—O41
O20—Zn2—O22
O41—Zn2—O22
O20—Zn2—N33
O41—Zn2—N33
109.5
109.5
109.5
109.5
107.08 (7)
98.42 (6)
91.73 (6)
103.57 (7)
87.31 (6)
O16—Zn1—Zn2
O18—Zn1—Zn2
O22—Zn1—Zn2
Acta Cryst. (2013). C69, 1348-1350
sup-5

supplementary materials
N8—Zn1—Zn2
N1—Zn1—Zn2
C6—N1—C2
164.66 (5)
97.55 (4)
118.08 (19)
116.33 (14)
125.52 (14)
122.5 (2)
118.7
O22—Zn2—N33
O20—Zn2—N26
O41—Zn2—N26
O22—Zn2—N26
N33—Zn2—N26
O20—Zn2—Zn1
O41—Zn2—Zn1
O22—Zn2—Zn1
N33—Zn2—Zn1
N26—Zn2—Zn1
C31—N26—C27
C31—N26—Zn2
C27—N26—Zn2
N26—C27—C28
N26—C27—H27
C28—C27—H27
C27—C28—C29
C27—C28—H28
C29—C28—H28
C30—C29—C28
C30—C29—H29
C28—C29—H29
C29—C30—C31
C29—C30—H30
C31—C30—H30
N26—C31—C30
N26—C31—C32
C30—C31—C32
N33—C32—C31
N33—C32—H32A
C31—C32—H32A
N33—C32—H32B
C31—C32—H32B
157.27 (7)
103.02 (7)
148.73 (7)
92.09 (6)
77.51 (7)
69.95 (4)
100.86 (4)
28.50 (4)
170.70 (5)
97.16 (5)
117.97 (19)
116.18 (14)
125.72 (15)
122.4 (2)
118.8
C6—N1—Zn1
C2—N1—Zn1
N1—C2—C3
N1—C2—H2
C3—C2—H2
118.7
C2—C3—C4
119.3 (2)
120.3
C2—C3—H3
C4—C3—H3
120.3
C5—C4—C3
118.3 (2)
120.9
C5—C4—H4
C3—C4—H4
120.9
C4—C5—C6
119.4 (2)
120.3
C4—C5—H5
118.8
C6—C5—H5
120.3
119.5 (2)
120.2
N1—C6—C5
122.36 (19)
117.00 (19)
120.64 (19)
111.75 (17)
109.3
N1—C6—C7
120.3
C5—C6—C7
118.5 (2)
120.8
N8—C7—C6
N8—C7—H7A
C6—C7—H7A
N8—C7—H7B
C6—C7—H7B
H7A—C7—H7B
C9—N8—C7
120.8
109.3
119.2 (2)
120.4
109.3
109.3
120.4
107.9
122.4 (2)
116.80 (19)
120.7 (2)
110.88 (17)
109.5
116.57 (18)
124.47 (15)
117.25 (13)
127.1 (2)
116.5
C9—N8—Zn1
C7—N8—Zn1
N8—C9—C10
N8—C9—H9
109.5
C10—C9—H9
C15—C10—C11
C15—C10—C9
C11—C10—C9
O16—C11—C12
O16—C11—C10
C12—C11—C10
C13—C12—C11
C13—C12—Cl17
C11—C12—Cl17
C12—C13—C14
C12—C13—H13
C14—C13—H13
C15—C14—C13
C15—C14—H14
C13—C14—H14
C14—C15—C10
C14—C15—H15
116.5
109.5
120.4 (2)
116.9 (2)
122.65 (19)
120.92 (19)
124.4 (2)
114.63 (19)
124.0 (2)
118.22 (18)
117.75 (16)
119.8 (2)
120.1
109.5
H32A—C32—H32B
C34—N33—C32
C34—N33—Zn2
C32—N33—Zn2
N33—C34—C35
N33—C34—H34
C35—C34—H34
C36—C35—C40
C36—C35—C34
C40—C35—C34
C37—C36—C35
C37—C36—H36
C35—C36—H36
C36—C37—C38
C36—C37—H37
C38—C37—H37
108.1
117.12 (18)
126.44 (15)
116.29 (13)
125.6 (2)
117.2
117.2
120.5 (2)
116.7 (2)
122.71 (18)
122.0 (2)
119
120.1
118.8 (2)
120.6
119
120.6
118.9 (2)
120.6
122.3 (2)
118.8
120.6
Acta Cryst. (2013). C69, 1348-1350
sup-6

supplementary materials
C10—C15—H15
C11—O16—Zn1
C19—O18—Zn1
O18—C19—O20
O18—C19—C21
O20—C19—C21
C19—O20—Zn2
C19—C21—H21A
C19—C21—H21B
H21A—C21—H21B
C19—C21—H21C
H21A—C21—H21C
H21B—C21—H21C
C23—O22—Zn1
C23—O22—Zn2
Zn1—O22—Zn2
O24—C23—O22
118.8
C39—C38—C37
C39—C38—H38
C37—C38—H38
C38—C39—C40
C38—C39—Cl42
C40—C39—Cl42
O41—C40—C39
O41—C40—C35
C39—C40—C35
C40—O41—Zn2
Cl45—C43—Cl46
Cl45—C43—Cl44
Cl46—C43—Cl44
Cl45—C43—H43
Cl46—C43—H43
Cl44—C43—H43
120.0 (2)
120
129.72 (14)
136.70 (15)
126.4 (2)
116.7 (2)
116.9 (2)
136.59 (15)
109.5
120
123.8 (2)
118.59 (18)
117.53 (16)
120.6 (2)
124.8 (2)
114.61 (18)
128.56 (14)
110.76 (14)
110.76 (14)
109.39 (13)
108.6
109.5
109.5
109.5
109.5
109.5
105.30 (12)
131.33 (13)
122.88 (7)
120.9 (2)
108.6
108.6
Acta Cryst. (2013). C69, 1348-1350
sup-7

Copyright of Acta Crystallographica: Section C (International Union of Crystallography -
IUCr) is the property of International Union of Crystallography - IUCr and its content may
not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's
express written permission. However, users may print, download, or email articles for
individual use.