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Acta Crystallogr Sect E Struct Rep Online. 2010 August 1; 66(Pt 8): m899–m900.
Published online 2010 July 7. doi:  10.1107/S1600536810026127
PMCID: PMC3007540

Di-μ-chlorido-bis­{chlorido[(R)/(S)-1,5-di­phenyl-3-(2-pyridyl-κN)-2-pyrazoline-κN 2]zinc(II)}

Abstract

In the centrosymmetric binuclear title compound, [Zn2Cl4(C20H17N3)2], the coordination geometry of the ZnII ion can be described as a distorted ZnN2Cl3 trigonal bipyramid (τ = 0.89), arising from the N,N′-bidentate ligand, a terminal chloride ion and two bridging chloride ions. The N atoms occupy one axial and one equatorial site and the terminal chloride ion occupies an equatorial site. The dihedral angle between the pyridine and pyrazole rings is 12.8 (2)°. In the crystal, aromatic π–π stacking [centroid–centroid separations = 3.812 (3) and 3.848 (3) Å] and C—H(...)Cl and C—H(...)π inter­actions help to establish the packing.

Related literature

For background to the biochemistry of zinc, see: Casas et al. (2002 [triangle]). For the synthesis of the ligand, see: Barceló-Oliver et al. (2010 [triangle]). For the fluorescent properties of related ligands, see: Bissell et al. (1993 [triangle]); Silva et al. (1997 [triangle]); Wang et al. (2001a [triangle],b [triangle]). For stability constants, see: Yamasaki & Yasuda (1956 [triangle]). For geometrical analysis, see: Addison et al. (1984 [triangle]). For a description of the Cambridge Structural Database, see: Allen (2002 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0m899-scheme1.jpg

Experimental

Crystal data

  • [Zn2Cl4(C20H17N3)2]
  • M r = 871.31
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0m899-efi1.jpg
  • a = 14.600 (3) Å
  • b = 8.6200 (17) Å
  • c = 19.524 (7) Å
  • β = 129.494 (18)°
  • V = 1896.2 (10) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 1.59 mm−1
  • T = 150 K
  • 0.21 × 0.15 × 0.04 mm

Data collection

  • Enraf–Nonius KappaCCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2000 [triangle]) T min = 0.732, T max = 0.939
  • 17229 measured reflections
  • 3467 independent reflections
  • 2206 reflections with I > 2σ(I)
  • R int = 0.096

Refinement

  • R[F 2 > 2σ(F 2)] = 0.051
  • wR(F 2) = 0.095
  • S = 1.04
  • 3467 reflections
  • 235 parameters
  • H-atom parameters constrained
  • Δρmax = 0.49 e Å−3
  • Δρmin = −0.41 e Å−3

Data collection: COLLECT (Nonius, 1998 [triangle]); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997 [triangle]); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 [triangle]).

Table 1
Selected geometric parameters (Å, °)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810026127/hb5500sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810026127/hb5500Isup2.hkl

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

Acknowledgments

The authors thank the Conselleria d’Economia, Hisenda i Innovació (competitive groups grant) of the Government of Balearic Islands and the Dirección General de Investigación Científica y Técnica of the Spanish authorities and FEDER funds (project number CTQ2006–09339/BQU) for their financial support.

supplementary crystallographic information

Comment

The interest in ZnII detection is due to the importance of this cation in living systems, because is the second (following iron) most abundant transition metal ion in human body (Casas et al., 2002). The fact that the ZnII is a d10 ion, diamagnetic and lacking d-d electronic transitions precludes usual techniques as electronic spectroscopy, e.p.r. or magnetic measurements for studying its compounds. Moreover, the major naturally occurring isotopes have zero nuclear spin and thus, the ion is NMR silent. For these reasons fluorescent probes to determine the "free" or "available" zinc(II) concentrations in living systems should be useful alternatives.

Due to their inner fluorescence properties, 1,3,5-triaryl-2Δ-pyrazolines have been utilized as fluorescence probes in some elaborated chemosensors (Bissell et al., 1993 and Silva et al., 1997). On the other hand, the fluorescent 3-(2-pyridyl) analogues of triarylpyrazolines themselves can serve as N,N'-type bidentate ligands for metal ions. Wang et al. (2001) have reported that pyridylpyrazoline derivatives show specific fluorescent behaviour towards the Zn2+ ion among divalent transition metal ions, specially for the 5-(4-cyanophenyl)-1-phenyl-3-(2-pyridyl)-2Δ-pyrazoline derivative. Stability constant in acetonitrile for the ZnL2 complex was determined as 3.4 1011 with a clear selectivity to other divalent ions as copper(II) (Wang et al., 2001). Nevertheless, no references exist in the literature related to structural studies of this type of compounds and metal ions, except for the ternary complex of bis-(2,2'-bipyridyl)ruthenium(II) and a non-fluorescent pyrazoline analogue, the 1-phenyl-3-(2-pyridyl)-5-(4-nitrophenyl)-2Δ-pyrazoline (refcode XOCXIW, Wang et al., 2001) with no coordinates available at Cambridge Structural Database (CSD, Version 5.31, February 2010 update; Allen, 2002). In the present paper, a crystallographic study of the ZnII complex of the fluorescent ligand 1,5-diphenyl-3-(2-pyridyl)-2Δ-pyrazoline (Barceló-Oliver et al., 2010) is performed.

A comparison between the previously described ligand (Barceló-Oliver et al., 2010) and its ZnII complex permits to observe a conformational modification related to the pyridine-pyrazoline moiety, where the s-trans conformation found in the ligand changes to a s-cis disposition in the complex (See Fig. 1). This feature is common in 2,2'-bipyridyl ligands.

Contrarily to previously mentioned 1:2 ZnL2 complex (Wang et al., 2001) in our hands, reaction between ZnCl2 and 1,5-diphenyl-3-(2-pyridyl)-2Δ-pyrazoline only yields a dimeric 1:1 [(LZnCl)2Cl2] compound. {Zn(Cl)((R)-1,5-diphenyl-3-(2-pyridil)-2Δ-pyrazoline)}(µ-Cl)2{Zn(Cl)((S)-1,5-diphenyl-3-(2-pyridil)-2Δ-pyrazoline)}] (I) crystallizes as a dimer with an inversion center between the chloride ligands relating the two monomers. We have not isolated any ZnL2 complex, contrarily to what happen with ZnII and 1,10-phenanthroline or 2,2'-bipyridyne, which have stability constants about 1 1017 and 2 1013 respectively (Yamasaki & Yasuda, 1956).

The dimer is formed through two bridged chlorido anions linked with long (Zn1–Cl2) and short (Zn1–Cl2i) distances to the ZnII metal ions (see Fig. 2 and Table 1). Moreover, pyridine (Zn1–N32) and imino (Zn1–N2) nitrogen atoms and a monodentate chloride ligand (Zn1–Cl1) are coordinated to both metal ions. The geometry around the metallic ion is described by means a distorted trigonal bipyramid [τ = 0.89 (Addison et al., 1984)]. The bite distance between the two bonding nitrogen atoms is 2.716 (7) Å and the dihedral angle between the pyridyl and the pyrazolyl planes is 12.8°.

Within the dimeric complex unit, some hydrogen bonds are found with the chlorine atoms as acceptors: C5 from the pyrazoline ring interacts with Cl1i, C12 from the phenyl ring bonded to N1 is in contact with Cl1 and C33 from the pyridine ring interacts with Cl2 (see Table 2 for more details). More in detail, the second hydrrogen bond (C12–H12···Cl1) forces the twist of the phenyl ring respect to the pyrazoline mean plane (N1–C11 bond): the structure of the ligand (Barceló-Oliver et al., 2010) presents an angle between mean planes of 3.47° while this value is 19.63° in the ZnII complex.

On the other hand, two pyrazoline ligands of adjacent complex units form a centrosymmetric couple along the b direction of the crystal by means of two C–H···π interactions between pyridine rings, with C34 as donors, and phenyl rings bounded to C5, corresponding to two different molecules (Table 3 and Fig. 3). This interaction yields a one-dimensional chain throrugh the crystal which is also reinforced with intramolecular π–π interactions (Table 4). To complete the structure of the crystal, two-dimensional planes are formed by means of weaker interactions relating the already described one-dimensional chains among them.

This ZnII complex is soluble in chloroform and presents a distinctive fluorescence in this solvent (λexc = 384 nm and λem = 480) related to the previously described ligand [λexc = 397 nm and λem = 464 nm (Barceló-Oliver et al., 2010)]. For this reason, this ligand could be useful for ZnII determination in low dielectric constant media. No fluorescence is observed with other metal ions such as Cu(II), Ag(I) and Cd(II), which is in agreement to previous literature data (Wang et al., 2001), possibly due to a metal quenching.

Experimental

1,5-diphenyl-3-(2-pyridyl)-2Δ-pyrazoline (2 mmol) and ZnCl2 (1 mmol) were suspended in 60 ml EtOH/H2O (50:50) and refluxed for 24 h. The solution was filtered off and left to crystallize. Orange microcrystals were obtained after 2–3 days [yield: 45%]. The complex was recrystallized from acetonitrile and orange hexagonal rods of (I) were obtained. Anal. Found: C, 54.97; H, 3.96; N, 9.60. Calc. for C40H34Cl4N6Zn2: C, 55.14; H, 3.93; N, 9.64. 1H NMR (CDCl3) (p.p.m.): δ 8.70 [bd, 2H, H(33), J = 5.0 Hz], 8.04 [bd, 2H, H(36), J = 7.8 Hz], 7.60 [bt, 2H, H(36), J = 6.3 Hz], 7.38 [m, 20H, H(arom.)], 7.30 [bd, 2H, H(34)], 5.69 [dd, 2H, H(5), Jcis = 8.5, Jtrans = 12.8 Hz], 3.99 [dd, 2H, H(4a), Jtrans = 12.8, Jgem = 17.9 Hz], 3.31 [dd, 2H, H(4 b), Jcis = 8.5, Jgem = 17.9 Hz]. IR (cm-1): 411w, 452vw, 501w, 539w, 574vw, 652w, 674m, 698m, 702m, 756 s, 763m, 782 s, 872m, 898m, 1002w, 1024w, 1041w, 1082w, 1153vs, 1174 s, 1207w, 121w, 1272m, 1321m, 1333 s, 1344 s, 1401vs, 1439m, 1452m, 1491vs, 1507m, 1535 s, 1597 s, 1608 s. UV-vis.: λmax = 374 nm in EtOH.

Refinement

All H atoms were placed in geometrically calculated positions and refined using a riding model, with C—H = 0.95–1.00 Å and Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
Reaction scheme where the s-trans conformation on the ligand is depicted by a bold blue line and the s-cis conformation found after coordination to the ZnII ion is depicted also with bold red lines.
Fig. 2.
View (50% probability) of the asymmetric unit of (I). The other half of the complex is related by an inversion center, sharing the two Cl2 atoms.
Fig. 3.
Representation of the C–H···π interaction in (I): a) the interaction forms a one-dimensional chain in the b direction; b) view along the b axis.

Crystal data

[Zn2Cl4(C20H17N3)2]F(000) = 888
Mr = 871.31Dx = 1.526 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2226 reflections
a = 14.600 (3) Åθ = 3–25.5°
b = 8.6200 (17) ŵ = 1.59 mm1
c = 19.524 (7) ÅT = 150 K
β = 129.494 (18)°Hexagon, orange
V = 1896.2 (10) Å30.21 × 0.15 × 0.04 mm
Z = 2

Data collection

Enraf–Nonius KappaCCD diffractometer3467 independent reflections
Radiation source: fine-focus sealed tube2206 reflections with I > 2σ(I)
graphiteRint = 0.096
profile fitted /o scansθmax = 25.3°, θmin = 3.2°
Absorption correction: multi-scan (SADABS; Bruker, 2000)h = −16→17
Tmin = 0.732, Tmax = 0.939k = −9→10
17229 measured reflectionsl = −23→23

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.051Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.095H-atom parameters constrained
S = 1.04w = 1/[σ2(Fo2) + (0.035P)2 + 0.9808P] where P = (Fo2 + 2Fc2)/3
3467 reflections(Δ/σ)max < 0.001
235 parametersΔρmax = 0.49 e Å3
0 restraintsΔρmin = −0.40 e Å3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Zn10.47494 (4)0.89666 (6)0.40806 (3)0.02521 (17)
Cl10.36221 (10)1.02812 (12)0.28182 (6)0.0255 (3)
Cl20.36063 (9)0.99842 (13)0.46713 (7)0.0284 (3)
N10.6991 (3)0.7462 (4)0.4103 (2)0.0244 (9)
N20.5954 (3)0.7387 (4)0.3970 (2)0.0190 (8)
C30.5733 (3)0.5958 (5)0.4026 (2)0.0189 (9)
C40.6604 (3)0.4843 (5)0.4129 (3)0.0229 (10)
H4A0.62520.4280.35690.027*
H4B0.68940.40850.46090.027*
C50.7599 (3)0.5942 (5)0.4370 (3)0.0232 (10)
H50.78330.56940.39990.028*
C110.7316 (4)0.8767 (5)0.3875 (2)0.0232 (10)
C120.6547 (4)1.0030 (5)0.3432 (3)0.0243 (10)
H120.57811.00060.32710.029*
C130.6903 (4)1.1309 (5)0.3230 (3)0.0272 (11)
H130.63841.21720.2940.033*
C140.8002 (4)1.1353 (6)0.3444 (3)0.0339 (12)
H140.82391.22410.33030.041*
C150.8750 (4)1.0108 (6)0.3860 (3)0.0346 (12)
H150.95011.01330.39970.041*
C160.8428 (4)0.8811 (6)0.4085 (3)0.0307 (11)
H160.89590.7960.4380.037*
C310.4686 (4)0.5567 (5)0.3919 (2)0.0205 (10)
N320.4102 (3)0.6778 (4)0.3938 (2)0.0187 (8)
C330.3083 (4)0.6496 (5)0.3775 (3)0.0245 (11)
H330.26710.73410.37810.029*
C340.2600 (4)0.5029 (5)0.3597 (3)0.0282 (11)
H340.18620.48740.34720.034*
C350.3201 (4)0.3800 (5)0.3603 (3)0.0290 (11)
H350.28960.27750.34960.035*
C360.4260 (4)0.4078 (5)0.3769 (3)0.0253 (10)
H360.46920.32410.37790.03*
C510.8688 (3)0.5881 (5)0.5352 (3)0.0220 (10)
C520.8970 (4)0.7056 (5)0.5938 (3)0.0248 (11)
H520.85040.79730.5730.03*
C530.9939 (4)0.6892 (6)0.6834 (3)0.0320 (12)
H531.01360.77020.72370.038*
C541.0614 (4)0.5567 (6)0.7139 (3)0.0350 (12)
H541.12690.54580.77530.042*
C551.0346 (4)0.4391 (6)0.6558 (3)0.0402 (13)
H551.08130.34740.67680.048*
C560.9389 (4)0.4562 (5)0.5664 (3)0.0335 (12)
H560.92120.37640.5260.04*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Zn10.0281 (3)0.0185 (3)0.0200 (3)−0.0029 (3)0.0111 (2)0.0000 (2)
Cl10.0283 (6)0.0241 (6)0.0206 (6)0.0053 (5)0.0139 (5)0.0035 (5)
Cl20.0256 (6)0.0318 (7)0.0241 (6)−0.0041 (5)0.0141 (5)−0.0095 (5)
N10.019 (2)0.025 (2)0.027 (2)0.0054 (17)0.0136 (19)0.0062 (16)
N20.017 (2)0.021 (2)0.0155 (18)0.0000 (16)0.0085 (17)−0.0014 (15)
C30.022 (2)0.018 (2)0.013 (2)0.001 (2)0.0099 (19)0.0001 (19)
C40.024 (3)0.023 (2)0.017 (2)0.000 (2)0.010 (2)0.0014 (19)
C50.025 (2)0.023 (2)0.025 (2)0.007 (2)0.018 (2)0.006 (2)
C110.026 (3)0.025 (3)0.019 (2)−0.005 (2)0.014 (2)−0.001 (2)
C120.023 (2)0.028 (3)0.023 (2)−0.004 (2)0.015 (2)−0.007 (2)
C130.038 (3)0.025 (3)0.024 (2)−0.002 (2)0.022 (2)−0.002 (2)
C140.044 (3)0.035 (3)0.028 (3)−0.009 (3)0.025 (3)−0.002 (2)
C150.025 (3)0.048 (3)0.031 (3)−0.005 (3)0.018 (2)0.004 (2)
C160.026 (3)0.038 (3)0.026 (2)0.000 (2)0.016 (2)0.005 (2)
C310.024 (3)0.019 (2)0.015 (2)0.003 (2)0.011 (2)0.0019 (17)
N320.019 (2)0.019 (2)0.0163 (18)−0.0018 (17)0.0106 (17)0.0015 (15)
C330.025 (3)0.026 (3)0.021 (2)0.001 (2)0.014 (2)0.0025 (19)
C340.026 (3)0.029 (3)0.028 (3)−0.006 (2)0.016 (2)0.001 (2)
C350.033 (3)0.016 (3)0.032 (3)−0.002 (2)0.018 (2)0.005 (2)
C360.027 (3)0.018 (2)0.027 (2)0.004 (2)0.015 (2)0.002 (2)
C510.018 (2)0.026 (2)0.026 (2)0.006 (2)0.016 (2)0.006 (2)
C520.024 (3)0.024 (3)0.027 (3)−0.003 (2)0.017 (2)0.001 (2)
C530.029 (3)0.037 (3)0.031 (3)−0.012 (3)0.019 (3)−0.008 (2)
C540.021 (3)0.048 (3)0.026 (3)−0.006 (2)0.010 (2)0.003 (2)
C550.031 (3)0.041 (3)0.043 (3)0.010 (2)0.021 (3)0.009 (3)
C560.031 (3)0.041 (3)0.025 (3)0.003 (2)0.017 (2)−0.003 (2)

Geometric parameters (Å, °)

Zn1—N322.048 (3)C15—C161.388 (6)
Zn1—Cl12.2153 (13)C15—H150.95
Zn1—Cl2i2.2534 (13)C16—H160.95
Zn1—N22.340 (3)C31—N321.362 (5)
Zn1—Cl22.7080 (13)C31—C361.375 (6)
Cl2—Zn1i2.2534 (13)N32—C331.332 (5)
N1—N21.365 (4)C33—C341.381 (6)
N1—C111.399 (5)C33—H330.95
N1—C51.479 (5)C34—C351.371 (6)
N2—C31.295 (5)C34—H340.95
C3—C311.445 (6)C35—C361.385 (6)
C3—C41.501 (5)C35—H350.95
C4—C51.537 (6)C36—H360.95
C4—H4A0.99C51—C521.381 (5)
C4—H4B0.99C51—C561.385 (6)
C5—C511.526 (5)C52—C531.390 (6)
C5—H51C52—H520.95
C11—C121.399 (6)C53—C541.373 (6)
C11—C161.400 (6)C53—H530.95
C12—C131.379 (6)C54—C551.380 (6)
C12—H120.95C54—H540.95
C13—C141.377 (6)C55—C561.385 (6)
C13—H130.95C55—H550.95
C14—C151.370 (6)C56—H560.95
C14—H140.95
N32—Zn1—Cl1111.57 (9)C13—C14—H14120.2
N32—Zn1—Cl2i126.79 (9)C14—C15—C16121.1 (4)
Cl1—Zn1—Cl2i121.63 (5)C14—C15—H15119.5
N32—Zn1—N276.10 (13)C16—C15—H15119.5
Cl1—Zn1—N2105.40 (9)C15—C16—C11119.5 (4)
Cl2i—Zn1—N289.25 (9)C15—C16—H16120.2
N32—Zn1—Cl290.04 (10)C11—C16—H16120.2
Cl1—Zn1—Cl294.88 (5)N32—C31—C36121.0 (4)
Cl2i—Zn1—Cl286.03 (5)N32—C31—C3116.1 (4)
N2—Zn1—Cl2158.51 (9)C36—C31—C3122.8 (4)
Zn1i—Cl2—Zn193.97 (5)C33—N32—C31118.5 (4)
N2—N1—C11122.5 (3)C33—N32—Zn1123.3 (3)
N2—N1—C5111.7 (3)C31—N32—Zn1117.9 (3)
C11—N1—C5125.1 (3)N32—C33—C34122.8 (4)
C3—N2—N1109.5 (3)N32—C33—H33118.6
C3—N2—Zn1107.7 (3)C34—C33—H33118.6
N1—N2—Zn1139.7 (3)C35—C34—C33119.0 (4)
N2—C3—C31120.4 (4)C35—C34—H34120.5
N2—C3—C4112.7 (4)C33—C34—H34120.5
C31—C3—C4126.7 (4)C34—C35—C36118.8 (4)
C3—C4—C5101.7 (3)C34—C35—H35120.6
C3—C4—H4A111.4C36—C35—H35120.6
C5—C4—H4A111.4C31—C36—C35119.9 (4)
C3—C4—H4B111.4C31—C36—H36120.1
C5—C4—H4B111.4C35—C36—H36120.1
H4A—C4—H4B109.3C52—C51—C56119.3 (4)
N1—C5—C51112.7 (3)C52—C51—C5122.6 (4)
N1—C5—C4101.5 (3)C56—C51—C5118.0 (4)
C51—C5—C4113.0 (3)C51—C52—C53119.8 (4)
N1—C5—H5109.8C51—C52—H52120.1
C51—C5—H5109.8C53—C52—H52120.1
C4—C5—H5109.8C54—C53—C52120.4 (4)
N1—C11—C12121.4 (4)C54—C53—H53119.8
N1—C11—C16119.6 (4)C52—C53—H53119.8
C12—C11—C16119.0 (4)C53—C54—C55120.3 (4)
C13—C12—C11120.0 (4)C53—C54—H54119.9
C13—C12—H12120C55—C54—H54119.9
C11—C12—H12120C54—C55—C56119.3 (5)
C14—C13—C12120.9 (4)C54—C55—H55120.3
C14—C13—H13119.6C56—C55—H55120.3
C12—C13—H13119.6C55—C56—C51120.9 (4)
C15—C14—C13119.6 (4)C55—C56—H56119.6
C15—C14—H14120.2C51—C56—H56119.6
N32—Zn1—Cl2—Zn1i126.89 (9)N1—C11—C16—C15−179.9 (4)
Cl1—Zn1—Cl2—Zn1i−121.45 (5)C12—C11—C16—C150.7 (6)
Cl2i—Zn1—Cl2—Zn1i0N2—C3—C31—N32−12.6 (5)
N2—Zn1—Cl2—Zn1i77.7 (2)C4—C3—C31—N32172.9 (3)
C11—N1—N2—C3164.2 (3)N2—C3—C31—C36164.7 (4)
C5—N1—N2—C3−6.7 (4)C4—C3—C31—C36−9.8 (6)
C11—N1—N2—Zn1−39.4 (5)C36—C31—N32—C33−2.4 (5)
C5—N1—N2—Zn1149.7 (3)C3—C31—N32—C33175.0 (3)
N32—Zn1—N2—C3−10.4 (2)C36—C31—N32—Zn1−175.8 (3)
Cl1—Zn1—N2—C3−119.4 (2)C3—C31—N32—Zn11.5 (4)
Cl2i—Zn1—N2—C3117.9 (2)Cl1—Zn1—N32—C33−67.2 (3)
Cl2—Zn1—N2—C340.8 (4)Cl2i—Zn1—N32—C33113.1 (3)
N32—Zn1—N2—N1−167.1 (4)N2—Zn1—N32—C33−168.5 (3)
Cl1—Zn1—N2—N183.9 (4)Cl2—Zn1—N32—C3328.0 (3)
Cl2i—Zn1—N2—N1−38.8 (4)Cl1—Zn1—N32—C31105.9 (3)
Cl2—Zn1—N2—N1−115.9 (4)Cl2i—Zn1—N32—C31−73.7 (3)
N1—N2—C3—C31179.4 (3)N2—Zn1—N32—C314.6 (3)
Zn1—N2—C3—C3115.1 (4)Cl2—Zn1—N32—C31−158.8 (3)
N1—N2—C3—C4−5.4 (4)C31—N32—C33—C340.6 (6)
Zn1—N2—C3—C4−169.7 (2)Zn1—N32—C33—C34173.7 (3)
N2—C3—C4—C514.3 (4)N32—C33—C34—C351.3 (6)
C31—C3—C4—C5−170.8 (3)C33—C34—C35—C36−1.4 (6)
N2—N1—C5—C51−106.1 (4)N32—C31—C36—C352.2 (6)
C11—N1—C5—C5183.4 (5)C3—C31—C36—C35−174.9 (4)
N2—N1—C5—C415.0 (4)C34—C35—C36—C31−0.3 (6)
C11—N1—C5—C4−155.6 (3)N1—C5—C51—C527.7 (5)
C3—C4—C5—N1−16.2 (4)C4—C5—C51—C52−106.5 (5)
C3—C4—C5—C51104.7 (4)N1—C5—C51—C56−174.7 (4)
N2—N1—C11—C12−5.1 (6)C4—C5—C51—C5671.1 (5)
C5—N1—C11—C12164.5 (4)C56—C51—C52—C53−1.0 (6)
N2—N1—C11—C16175.6 (3)C5—C51—C52—C53176.5 (4)
C5—N1—C11—C16−14.9 (6)C51—C52—C53—C54−0.3 (6)
N1—C11—C12—C13178.9 (3)C52—C53—C54—C550.9 (7)
C16—C11—C12—C13−1.7 (6)C53—C54—C55—C56−0.1 (7)
C11—C12—C13—C141.3 (6)C54—C55—C56—C51−1.2 (7)
C12—C13—C14—C150.2 (6)C52—C51—C56—C551.8 (7)
C13—C14—C15—C16−1.2 (7)C5—C51—C56—C55−175.9 (4)
C14—C15—C16—C110.7 (7)

Symmetry codes: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C51–C56 ring.
D—H···AD—HH···AD···AD—H···A
C5—H5···Cl1ii1.002.763.474 (5)128
C12—H12···Cl10.952.693.635 (7)174
C33—H33···Cl20.952.663.315 (5)127
C34—H34···Cg1iii0.952.653.557 (7)159

Symmetry codes: (ii) −x+1, y−1/2, −z+1/2; (iii) −x+1, −y+1, −z+1.

Table 3 Centroid–centroid interactions (Å, °)

Cg2 and Cg3 are the centroids of the C311/N32/C33–C36 and C11–C16 rings, respectively. As defined in PLATON (Spek, 2009), α is the dihedral angle between planes I and J, β is the angle between the CgI->CgJ vector and the normal to the plane I, γ is the angle between the CgI->CgJ vector and the normal to the plane J, CgI-Perp is the perpendicular distance of CgI from ring J, CgJ-Perp is the perpendicular distance of CgJ from ring I, and the slippage S is the distance between CgI and the perpendicular projection of CgJ on ring I.

CgI···CgJCg···CgαβγCgI-PerpCgJ-PerpS
Cg2···Cg2ii3.848 (3)022.022.03.5675 (17)3.5676 (17)1.442
Cg2···Cg3i3.812 (3)17.1 (2)13.127.23.3884 (17)3.7126 (18)

Symmetry codes: (i) 1-x, -1/2+y, 1/2-z; (ii) 1-x, 1-y, 1-z

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5500).

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