The title compound, [ZnCl2(C18H14N4O)], crystallizes with two molecules in the asymmetric unit, which differ in the tautomeric (neutral and zwitterionic) forms of the coordinating organic ligand. In both molecules, the ZnII atom adopts a distorted square-pyramidal geometry by two N and one O atoms of the Schiff base ligand and two Cl atoms acting as monodentate chloride anions. The crystal packing is stabilized by N-HN and N-HCl hydrogen bonds, forming a two-dimensional network parallel to the ac plane.
The title compound crystallizes with two different molecules in the asymmetric
unit (Fig. 1), which differ from two tautomeric forms of the Schiff base. The
ligand molecules coordinate respectively to one of the zinc(II) atom in a
tridentate manner in his hydrazide form and to the other zinc(II) center in
the tautomeric form where the nitrogen atom of the uncoordinated pyridine ring
is protonated by the proton atom from the nitrogen of the hydrazide moiety. In
both cases the coordination manner creates two five-membered chelate metalla
rings. The two molecules in the asymmetric unit interact via hydrogen
bond N—H···N between the two uncoordinated pyridine rings. The bond between
Zn center and the pyridine nitrogen are slightly (2.200 (3) and 2.131 (3) Å)
different to the two other Zn–N bonds (2.078 (3) and 2.136 (3)). These
distances are comparable to those found in the complex [Zn(H2BzpClPh)Cl2]
(H2BzpClPh is 2-benzoylpyridine-para-chloro-phenylhydrazone)
(Despaigne et al., 2009). In the complex, significant variations
observed for the C—O and Zn—O bond distances in the two hydrazone
moieties. The C1—O1 bond distance of 1.252 (4) Å is in accordance with a
higher single bond character while the C19—O2 bond distance of 1.217 (4) Å
is in accordance with a double bond character. The Zn2—O2 bond distance is
2.248 (2) Å while the Zn1—O1 length is 2.127 Å. The decreasing of the
length is in accordance with the presence of a negative charge at the oxygen
atom O1, which increases the strength of the Zn1—O1 bond. The largest angles
around the Zn(II) centers (&>: N3—Zn1—O1 = 148.50 (11) ° and &>
N7—Zn2—O2 = 114.79 (11) °) are slightly larger than the second-largest
ones (&>: N2—Zn1—Cl2 = 128.30 (10)and &>: N6—Zn2—Cl3 = 133.10 (10)
°). Since the distortion ( = (-)/60) value of the coordination
polyhedron, &> = 0.337 for Zn1 and &> = 0.191 for Zn2 which can be
compared with the ideal value for 1 for trigonal-bipyramidal and 0 for
square-pyramidal (Addison et al., 1984), the environment of the
center can be determinate. Each zinc center has a square pyramidal geometry
with appreciable distortions as shown by the Addison &> parameter. The basal
plane for earch ZnII center is respectively constructed by the coordination
of two nitrogen atoms and one oxygen atom from the organic ligand molecule and
one chloride atom acting as monodentate anion to zinc. The fifth coordination
site is completed by a monodentate chloride anion.
For related structures: see: Addison et al. (1984); Despaigne et
al. (2009).
In a 50 ml round bottom flask introduce isonicotinic hydrazide (1 g, 0.0073 mol)
dissolved in methanol (10 ml). Benzoylpyridine (1.35 g, 0.0073 mol) in
methanol (10 ml) and two drops of galcial acetic acid, were added. The mixture
was refluxed for six hours to yield a quantitative precipitate. The white
precipitate formed, was separated by filtration, washed with ether and dried
under vacuum (yield: 75.2%); m.p.=206 °C. 1H NMR in C2D6SO,
(p.p.m.): 7.44&# (m, 13H, HAr),, 8.82 (s, 1H, –NH). 13C NMR in
(p.p.m.): 121&# (CAr), 152 (C=N), 162 (C=O). IR (cm-1)
, , , , . Anal. Calc. for
C18H14N4O (%): C, 71.51; H, 4.67; N, 18.53. Found: C, 71.53; H, 4.68; N,
18.57. Into an ethanolic solution (10 ml) of zinc chloride (0.067 g, 0.005 mmol) was added an ethanolic solution (10 ml) of the ligand prepared above
(0.15 g, 0.005 mmol). The resulting yellow mixture is heated at 60°C for two
hours. The yellow precipitate was discarded and the resulting filtrate was
then allowed to evaporate slowly in an open atmosphere. After two days, yellow
crystals suitable for X-ray analysis were obtained. The crystals were
separated and dried (yield: 73%); Anal. Calc. for C18H14ZnCl2N4O (%):
C, 49.29; H, 3.22; N, 12.77. Found: C, 49.32; H, 3.20; N, 12.75. Selected IR
data (cm-1, KBr pellet): , , , 700.
Six low-resolution reflections affected by the beamstop were omitted from the
refinement using the OMIT instruction in SHELXL97 (Sheldrick,
2008). All H atoms were initially located in difference Fourier maps,
the final refinements, all benzene-bound H atoms were positioned with
idealized geometry and included in the calculations as riding on their parent
atoms, with C—H = 0.97 Å and Uiso(H) = 1.2Ueq(C). The
positions of the H atoms borne by nitrogen atoms were refined freely, giving
restraints on N—H distances in the range 0.87 (2) Å with Uiso(H)
= 1.2Ueq(N).
Data collection: CrystalClear-SM Expert (Rigaku, 2009); cell refinement: CrystalClear-SM Expert (Rigaku, 2009); data reduction: CrystalClear-SM Expert (Rigaku, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and CRYSTALBUILDER (Welter, 2006); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
An ORTEP view of the title compound, showing the atom-numbering
scheme. Displacement ellipsoids are plotted at the 50% probability level.
[ZnCl2(C18H14N4O)]Z = 4Mr = 438.6F(000) = 888Triclinic, P1Dx = 1.569 Mg m3Hall symbol:
-P 1Mo K radiation,
= 0.71070 Åa = 11.517 (3) ÅCell parameters from 5145 reflectionsb = 13.248 (2) Å = 0.4&#°c = 13.459 (1) ŵ = 1.63 mm1 = 91.130 (5)°T = 293 K = 104.708 (4)°Prism, yellow = 109.798 (4)°0.45 × 0.22 × 0.18 mmV = )
Nonius KappaCCD diffractometer6674 independent reflectionsRadiation source: fine-focus sealed tube, Nonius KappaCCD4122 reflections with I > 2(I)Graphite monochromatorRint = 0.040Detector resolution: 9 pixels mm-1max = 25.3°, min = 1.6°phi and
scansh = 1313Absorption correction: multi-scan (ABSCOR; Rigaku, 2009)k = 1515Tmin = 0.379, Tmax = 0.745l = 161615524 measured reflections
Refinement on F2Secondary atom site location: difference Fourier mapLeast-squares matrix: fullHydrogen site location: difference Fourier mapR[F2 > 2(F2)] = 0.042H atoms treated by a mixture of independent and constrained refinementwR(F2) = 0.102
w = 1/[2(Fo2) + (0.0372P)2]
where P = (Fo2 + 2Fc2)/3S = 0.97(Δ/)max = 0.0016668 reflectionsΔmax = 0.32 e Å3476 parametersΔmin = 0.42 e Å31 restraintExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc23/sin(2)]-1/4Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0013 (3)
[ZnCl2(C18H14N4O)] = 109.798 (4)°Mr = 438.6V = )
Å3Triclinic, P1Z = 4a = 11.517 (3) ÅMo K radiationb = 13.248 (2) ŵ = 1.63 mm1c = 13.459 (1) ÅT = 293 K = 91.130 (5)°0.45 × 0.22 × 0.18 mm = 104.708 (4)°
Nonius KappaCCD diffractometer6674 independent reflectionsAbsorption correction: multi-scan (ABSCOR; Rigaku, 2009)4122 reflections with I > 2(I)Tmin = 0.379, Tmax = 0.745Rint = 0.04015524 measured reflectionsmax = 25.3°
R[F2 > 2(F2)] = 0.042H atoms treated by a mixture of independent and constrained refinementwR(F2) = 0.102Δmax = 0.32 e Å3S = 0.97Δmin = 0.42 e Å36668 reflectionsAbsolute structure:
?476 parametersFlack parameter: ?1 restraintRogers parameter: ?
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
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.
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 >
(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. Six low-resolution reflections were rejected due to beamstop
shading using the OMIT instruction from SHELX97-L.
xyzUiso*/UeqZn10.17339 (4)0.03172 (4)0.30977 (3)0.04231 (15)Cl10.13436 (11)0.14621 (9)0.29370 (9)0.0661 (3)Cl20.00008 (9)0.07571 (9)0.31555 (8)0.0552 (3)O10.1627 (3)0.0699 (3)0.15571 (19)0.0685 (10)N10.3803 (3)0.1689 (3)0.2234 (2)0.0429 (8)N20.3573 (3)0.1346 (2)0.3148 (2)0.0404 (8)N30.2819 (3)0.0655 (2)0.4742 (2)0.0393 (8)N40.2859 (3)0.2290 (3)0.1453 (2)0.0488 (9)H4N0.288 (3)0.247 (3)0.215 (3)0.059*C10.2704 (4)0.1297 (3)0.1489 (3)0.0416 (10)C20.4498 (3)0.1642 (3)0.4008 (3)0.0369 (9)C30.4088 (3)0.1201 (3)0.4924 (2)0.0356 (9)C40.4913 (4)0.1357 (3)0.5905 (3)0.0479 (11)H40.57850.17500.60260.058*C50.4432 (4)0.0924 (3)0.6705 (3)0.0540 (12)H50.49820.10010.73640.065*C60.3148 (4)0.0384 (3)0.6523 (3)0.0548 (12)H60.28050.01010.70560.066*C70.2368 (4)0.0265 (3)0.5531 (3)0.0482 (11)H70.14900.01030.54060.058*C80.2787 (3)0.1648 (3)0.0446 (2)0.0378 (9)C90.1685 (4)0.1343 (3)0.0369 (3)0.0510 (11)H90.09030.09110.02780.061*C100.1756 (4)0.1681 (3)0.1311 (3)0.0529 (12)H100.10140.14790.18610.064*C110.3953 (4)0.2585 (3)0.0685 (3)0.0514 (11)H110.47250.30010.08050.062*C120.3932 (4)0.2275 (3)0.0277 (3)0.0437 (10)H120.46880.24850.08140.052*C130.5813 (3)0.2388 (3)0.4099 (2)0.0361 (9)C140.6004 (4)0.3387 (3)0.3735 (3)0.0447 (10)H140.52980.35680.34080.054*C150.7222 (4)0.4112 (4)0.3850 (3)0.0566 (12)H150.73440.47850.36140.068*C160.8262 (4)0.3831 (5)0.4321 (3)0.0732 (16)H160.90900.43120.43920.088*C170.8084 (4)0.2860 (5)0.4682 (4)0.0765 (16)H170.87930.26810.50030.092*C180.6868 (4)0.2134 (4)0.4579 (3)0.0539 (11)H180.67590.14710.48340.065*Zn20.31778 (4)0.47927 (4)0.17144 (3)0.04310 (16)Cl30.50465 (9)0.47545 (9)0.15904 (7)0.0536 (3)Cl40.32363 (11)0.64860 (9)0.19446 (9)0.0688 (4)O20.3419 (2)0.4448 (2)0.33683 (18)0.0530 (8)N50.1412 (3)0.3230 (3)0.2757 (2)0.0439 (8)H5N0.085 (3)0.265 (2)0.283 (3)0.053*N60.1446 (3)0.3573 (2)0.1811 (2)0.0414 (8)N70.1966 (3)0.4295 (3)0.0172 (2)0.0460 (9)N80.2668 (3)0.2860 (3)0.6574 (2)0.0478 (9)C190.2514 (3)0.3738 (3)0.3533 (3)0.0406 (10)C200.0454 (3)0.3233 (3)0.1017 (3)0.0375 (9)C210.0725 (3)0.3694 (3)0.0067 (2)0.0365 (9)C220.0200 (4)0.3560 (3)0.0847 (3)0.0468 (11)H220.10590.31760.08990.056*C230.0162 (4)0.4007 (4)0.1695 (3)0.0605 (13)H230.04510.39140.23250.073*C240.1421 (4)0.4581 (4)0.1598 (3)0.0611 (13)H240.16850.48730.21610.073*C250.2298 (4)0.4721 (4)0.0645 (3)0.0581 (12)H250.31560.51300.05710.070*C260.2530 (3)0.3413 (3)0.4580 (2)0.0360 (9)C270.3693 (3)0.3604 (3)0.5289 (3)0.0395 (9)H270.44540.39240.51110.047*C280.3718 (4)0.3316 (3)0.6264 (3)0.0451 (10)H280.45130.34460.67360.054*C290.1532 (4)0.2681 (3)0.5884 (3)0.0477 (11)H290.07860.23620.60850.057*C300.1422 (3)0.2949 (3)0.4894 (3)0.0433 (10)H300.06170.28220.44380.052*C310.0845 (3)0.2501 (3)0.1009 (3)0.0396 (9)C320.1420 (4)0.2719 (3)0.1729 (3)0.0484 (11)H320.09640.33070.22330.058*C330.2659 (4)0.2085 (4)0.1718 (4)0.0658 (13)H330.30400.22470.22020.079*C340.3308 (4)0.1214 (4)0.0979 (4)0.0699 (14)H340.41400.07780.09620.084*C350.2754 (4)0.0976 (4)0.0266 (4)0.0708 (14)H350.32130.03810.02310.085*C360.1524 (4)0.1606 (3)0.0274 (3)0.0572 (12)H360.11500.14340.02100.069*
U11U22U33U12U13U23Zn10.0348 (3)0.0483 (3)0.0352 (2)0.0049 (2)0.00822 (19)0.0085 (2)Cl10.0643 (7)0.0521 (7)0.0679 (7)0.0167 (6)0.0003 (6)0.0003 (6)Cl20.0417 (6)0.0625 (7)0.0589 (6)0.0144 (5)0.0150 (5)0.0116 (5)O10.0372 (16)0.108 (3)0.0367 (15)0.0019 (17)0.0071 (12)0.0231 (16)N10.0378 (18)0.055 (2)0.0263 (15)0.0062 (16)0.0066 (13)0.0109 (14)N20.0388 (18)0.0483 (19)0.0290 (15)0.0085 (15)0.0098 (14)0.0108 (14)N30.0416 (19)0.0428 (19)0.0333 (16)0.0112 (15)0.0146 (14)0.0098 (14)N40.055 (2)0.055 (2)0.0299 (17)0.0147 (19)0.0083 (16)0.0119 (16)C10.043 (2)0.048 (2)0.0304 (19)0.012 (2)0.0078 (18)0.0131 (17)C20.039 (2)0.036 (2)0.0320 (19)0.0091 (18)0.0088 (17)0.0089 (16)C30.035 (2)0.036 (2)0.0319 (19)0.0088 (18)0.0090 (16)0.0079 (16)C40.041 (2)0.054 (3)0.036 (2)0.005 (2)0.0056 (18)0.0066 (19)C50.058 (3)0.067 (3)0.032 (2)0.018 (2)0.0091 (19)0.017 (2)C60.064 (3)0.065 (3)0.036 (2)0.020 (2)0.019 (2)0.014 (2)C70.045 (2)0.052 (3)0.043 (2)0.008 (2)0.0153 (19)0.016 (2)C80.037 (2)0.041 (2)0.0318 (19)0.0103 (18)0.0076 (16)0.0081 (17)C90.041 (2)0.064 (3)0.037 (2)0.008 (2)0.0048 (18)0.015 (2)C100.052 (3)0.063 (3)0.033 (2)0.015 (2)0.0000 (19)0.010 (2)C110.048 (2)0.057 (3)0.040 (2)0.005 (2)0.0127 (19)0.013 (2)C120.042 (2)0.053 (3)0.0266 (18)0.010 (2)0.0039 (16)0.0089 (18)C130.032 (2)0.044 (2)0.0294 (18)0.0130 (18)0.0059 (16)0.0037 (17)C140.041 (2)0.052 (3)0.040 (2)0.014 (2)0.0113 (18)0.0108 (19)C150.053 (3)0.054 (3)0.054 (2)0.003 (2)0.021 (2)0.007 (2)C160.039 (3)0.091 (4)0.061 (3)0.011 (3)0.011 (2)0.009 (3)C170.031 (2)0.127 (5)0.071 (3)0.027 (3)0.012 (2)0.028 (3)C180.051 (3)0.070 (3)0.052 (2)0.030 (2)0.019 (2)0.027 (2)Zn20.0313 (2)0.0511 (3)0.0382 (3)0.0049 (2)0.00794 (19)0.0067 (2)Cl30.0450 (6)0.0684 (7)0.0499 (6)0.0215 (5)0.0158 (5)0.0086 (5)Cl40.0511 (7)0.0624 (7)0.0814 (8)0.0248 (6)0.0065 (6)0.0050 (6)O20.0337 (15)0.0702 (19)0.0363 (14)0.0019 (14)0.0052 (12)0.0095 (13)N50.0336 (18)0.056 (2)0.0309 (16)0.0033 (16)0.0063 (14)0.0119 (16)N60.0359 (17)0.053 (2)0.0280 (15)0.0086 (16)0.0051 (13)0.0090 (14)N70.0383 (18)0.053 (2)0.0368 (17)0.0035 (16)0.0111 (14)0.0088 (15)N80.049 (2)0.054 (2)0.0324 (16)0.0127 (17)0.0038 (16)0.0106 (15)C190.031 (2)0.056 (3)0.0318 (19)0.013 (2)0.0073 (16)0.0049 (18)C200.031 (2)0.043 (2)0.0341 (19)0.0083 (18)0.0078 (16)0.0036 (17)C210.037 (2)0.037 (2)0.0344 (19)0.0115 (18)0.0089 (17)0.0053 (17)C220.041 (2)0.057 (3)0.036 (2)0.014 (2)0.0030 (18)0.0120 (19)C230.064 (3)0.070 (3)0.038 (2)0.020 (3)0.003 (2)0.010 (2)C240.077 (3)0.073 (3)0.034 (2)0.024 (3)0.021 (2)0.022 (2)C250.052 (3)0.072 (3)0.045 (2)0.012 (2)0.020 (2)0.013 (2)C260.034 (2)0.042 (2)0.0296 (18)0.0112 (17)0.0073 (16)0.0049 (16)C270.031 (2)0.048 (2)0.0334 (19)0.0101 (18)0.0045 (16)0.0069 (17)C280.041 (2)0.054 (3)0.031 (2)0.015 (2)0.0027 (18)0.0009 (18)C290.044 (2)0.061 (3)0.035 (2)0.012 (2)0.0147 (18)0.0110 (19)C300.030 (2)0.057 (3)0.036 (2)0.0110 (19)0.0046 (17)0.0082 (19)C310.030 (2)0.045 (2)0.037 (2)0.0095 (18)0.0037 (17)0.0095 (18)C320.042 (2)0.055 (3)0.042 (2)0.012 (2)0.0095 (19)0.0108 (19)C330.042 (3)0.088 (4)0.069 (3)0.019 (3)0.022 (2)0.017 (3)C340.035 (2)0.066 (3)0.094 (4)0.002 (2)0.014 (3)0.014 (3)C350.048 (3)0.052 (3)0.095 (4)0.005 (2)0.007 (3)0.006 (3)C360.041 (2)0.050 (3)0.068 (3)0.010 (2)0.004 (2)0.009 (2)
Zn1—N22.078 (3)Zn2—N72.131 (3)Zn1—O12.127 (3)Zn2—N62.136 (3)Zn1—N32.200 (3)Zn2—Cl32.2176 (13)Zn1—Cl12.2400 (13)Zn2—Cl42.2343 (13)Zn1—Cl22.2793 (13)Zn2—O22.248 (2)O1—C11.252 (4)O2—C191.217 (4)N1—C11.330 (4)N5—N61.367 (4)N1—N21.377 (4)N5—C191.369 (4)N2—C21.304 (4)N5—H5N0.849 (18)N3—C71.336 (4)N6—C201.289 (4)N3—C31.348 (4)N7—C251.329 (5)N4—C101.318 (5)N7—C211.348 (4)N4—C111.341 (5)N8—C281.332 (5)N4—H4N0.98 (4)N8—C291.340 (5)C1—C81.503 (5)C19—C261.479 (5)C2—C131.474 (5)C20—C311.479 (5)C2—C31.490 (5)C20—C211.487 (5)C3—C41.381 (4)C21—C221.370 (5)C4—C51.382 (5)C22—C231.389 (5)C4—H40.9300C22—H220.9300C5—C61.360 (5)C23—C241.360 (6)C5—H50.9300C23—H230.9300C6—C71.379 (5)C24—C251.381 (5)C6—H60.9300C24—H240.9300C7—H70.9300C25—H250.9300C8—C121.378 (5)C26—C271.372 (5)C8—C91.380 (5)C26—C301.392 (5)C9—C101.366 (5)C27—C281.370 (5)C9—H90.9300C27—H270.9300C10—H100.9300C28—H280.9300C11—C121.370 (5)C29—C301.372 (5)C11—H110.9300C29—H290.9300C12—H120.9300C30—H300.9300C13—C181.377 (5)C31—C321.379 (5)C13—C141.387 (5)C31—C361.389 (5)C14—C151.373 (5)C32—C331.385 (5)C14—H140.9300C32—H320.9300C15—C161.379 (7)C33—C341.369 (6)C15—H150.9300C33—H330.9300C16—C171.352 (7)C34—C351.364 (6)C16—H160.9300C34—H340.9300C17—C181.374 (6)C35—C361.377 (6)C17—H170.9300C35—H350.9300C18—H180.9300C36—H360.9300N2—Zn1—O174.86 (10)N7—Zn2—N673.37 (11)N2—Zn1—N374.29 (11)N7—Zn2—Cl3103.43 (10)O1—Zn1—N3148.50 (11)N6—Zn2—Cl3133.30 (10)N2—Zn1—Cl1117.50 (10)N7—Zn2—Cl4100.89 (10)O1—Zn1—Cl1102.71 (10)N6—Zn2—Cl4114.89 (10)N3—Zn1—Cl197.02 (9)Cl3—Zn2—Cl4111.46 (5)N2—Zn1—Cl2128.30 (10)N7—Zn2—O2144.79 (11)O1—Zn1—Cl293.30 (9)N6—Zn2—O271.72 (9)N3—Zn1—Cl2100.75 (9)Cl3—Zn2—O297.10 (8)Cl1—Zn1—Cl2114.20 (5)Cl4—Zn2—O297.70 (8)C1Zn1110.7 (2)C19Zn2115.5 (2)C1N2108.2 (3)N6C19114.4 (3)C2N1120.4 (3)N6H5N122 (3)C2Zn1121.7 (2)C19H5N122 (3)N1Zn1117.9 (2)C20N5121.9 (3)C7C3118.7 (3)C20Zn2120.7 (2)C7Zn1126.2 (2)N5Zn2117.3 (2)C3Zn1114.6 (2)C25C21118.9 (3)C10C11121.3 (3)C25Zn2123.1 (3)C10H4N118 (2)C21Zn2116.5 (2)C11H4N120 (2)C28C29117.3 (3)O1N1128.2 (3)O2N5121.1 (3)O1C8117.2 (3)O2C26122.0 (3)N1C8114.5 (3)N5C26116.9 (3)N2C13124.3 (3)N6C31126.2 (3)N2C3113.6 (3)N6C21112.5 (3)C13C3122.0 (3)C31C21121.3 (3)N3C4121.0 (3)N7C22121.3 (3)N3C2115.0 (3)N7C20114.8 (3)C4C2124.0 (3)C22C20123.8 (3)C3C5119.4 (4)C21C23119.1 (4)C3H4120.3C21H22120.4C5H4120.3C23H22120.4C6C4119.6 (3)C24C22119.5 (4)C6H5120.2C24H23120.3C4H5120.2C22H23120.3C5C7118.5 (4)C23C25118.5 (4)C5H6120.8C23H24120.7C7H6120.8C25H24120.7N3C6122.9 (4)N7C24122.6 (4)N3H7118.6N7H25118.7C6H7118.6C24H25118.7C12C9118.6 (3)C27C30118.1 (3)C12C1122.0 (3)C27C19118.6 (3)C9C1119.3 (3)C30C19123.3 (3)C10C8119.4 (4)C28C26119.0 (4)C10H9120.3C28H27120.5C8H9120.3C26H27120.5N4C9121.0 (4)N8C27123.7 (3)N4H10119.5N8H28118.2C9H10119.5C27H28118.2N4C12120.0 (4)N8C30122.7 (4)N4H11120.0N8H29118.6C12H11120.0C30H29118.6C11C8119.7 (3)C29C26119.1 (3)C11H12120.2C29H30120.4C8H12120.2C26H30120.4C18C14118.8 (4)C32C36118.7 (4)C18C2121.3 (4)C32C20119.8 (3)C14C2119.8 (3)C36C20121.5 (4)C15C13120.8 (4)C31C33121.7 (4)C15H14119.6C31H32119.1C13H14119.6C33H32119.1C14C16119.2 (4)C34C32118.3 (4)C14H15120.4C34H33120.8C16H15120.4C32H33120.8C17C15120.4 (4)C35C33121.0 (4)C17H16119.8C35H34119.5C15H16119.8C33H34119.5C16C18120.7 (4)C34C36120.8 (4)C16H17119.6C34H35119.6C18H17119.6C36H35119.6C17C13120.1 (4)C35C31119.5 (4)C17H18120.0C35H36120.2C13H18120.0C31H36120.2N2—Zn1C12.0 (3)N7—Zn2C195.4 (4)N3—Zn1C114.0 (5)N6—Zn2C192.3 (3)Cl1—Zn1C1113.5 (3)Cl3—Zn2C19131.1 (3)Cl2—Zn1C1130.8 (3)Cl4—Zn2C19116.0 (3)C1N2—C2178.5 (3)C19N6—C20174.8 (4)C1N2—Zn13.3 (4)C19N6—Zn20.8 (4)O1—Zn1C2178.9 (3)N7—Zn2C2010.5 (3)N3—Zn1C25.3 (3)Cl3—Zn2C20103.5 (3)Cl1—Zn1C284.5 (3)Cl4—Zn2C2084.0 (3)Cl2—Zn1C296.8 (3)O2—Zn2C20174.1 (3)O1—Zn1N12.9 (3)N7—Zn2N5173.8 (3)N3—Zn1N1176.5 (3)Cl3—Zn2N580.9 (3)Cl1—Zn1N193.7 (3)Cl4—Zn2N591.7 (3)Cl2—Zn1N185.0 (3)O2—Zn2N51.5 (3)N2—Zn1C7179.7 (4)N6—Zn2C25179.1 (4)O1—Zn1C7168.2 (3)Cl3—Zn2C2549.3 (4)Cl1—Zn1C763.1 (3)Cl4—Zn2C2566.1 (4)Cl2—Zn1C753.3 (3)O2—Zn2C25173.3 (3)N2—Zn1C38.2 (3)N6—Zn2C2113.3 (3)O1—Zn1C320.2 (4)Cl3—Zn2C21145.0 (3)Cl1—Zn1C3108.5 (3)Cl4—Zn2C2199.6 (3)Cl2—Zn1C3135.2 (3)O2—Zn2C2121.0 (4)Zn1C1—N10.9 (6)Zn2C19—N52.8 (5)Zn1C1—C8179.5 (3)Zn2C19—C26179.6 (3)N2C1—O11.5 (6)N6C19—O21.4 (6)N2C1—C8177.2 (3)N6C19—C26179.1 (3)N1C2—C133.3 (6)N5C20—C313.7 (6)Zn1C2—C13178.5 (3)Zn2C20—C31171.7 (3)N1C2—C3180.0 (3)N5C20—C21178.5 (3)Zn1C2—C31.8 (4)Zn2C20—C216.0 (4)C7C3—C40.1 (6)C25C21—C223.2 (6)Zn1C3—C4172.2 (3)Zn2C21—C22163.2 (3)C7C3—C2177.8 (3)C25C21—C20178.7 (4)Zn1C3—C210.0 (4)Zn2C21—C2014.9 (4)N2C3—N35.8 (5)N6C21—N75.9 (5)C13C3—N3171.1 (3)C31C21—N7176.2 (3)N2C3—C4176.5 (4)N6C21—C22172.1 (4)C13C3—C46.7 (6)C31C21—C225.7 (6)N3C4—C51.5 (6)N7C22—C233.4 (6)C2C4—C5179.2 (4)C20C22—C23178.6 (4)C3C5—C62.3 (7)C21C23—C241.1 (7)C4C6—C71.5 (7)C22C24—C251.4 (7)C3C7—C60.9 (6)C21C25—C240.6 (7)Zn1C7—C6170.3 (3)Zn2C25—C24164.8 (3)C5C7—N30.1 (7)C23C25—N71.7 (7)O1C8—C12177.7 (4)O2C26—C2724.1 (6)N1C8—C123.5 (6)N5C26—C27158.2 (4)O1C8—C92.7 (6)O2C26—C30154.0 (4)N1C8—C9176.1 (4)N5C26—C3023.6 (6)C12C9—C101.1 (6)C30C27—C281.1 (6)C1C9—C10178.6 (4)C19C27—C28179.3 (3)C11C10—C91.0 (6)C29C28—C270.1 (6)C8C10—N40.3 (7)C26C28—N80.4 (6)C10C11—C121.5 (6)C28C29—C300.1 (6)N4C12—C80.7 (6)N8C30—C260.9 (6)C9C12—C110.5 (6)C27C30—C291.3 (6)C1C12—C11179.1 (4)C19C30—C29179.5 (4)N2C13—C18130.1 (4)N6C31—C3250.0 (6)C3C13—C1853.5 (5)C21C31—C32127.6 (4)N2C13—C1452.6 (5)N6C31—C36131.8 (4)C3C13—C14123.9 (4)C21C31—C3650.6 (5)C18C14—C150.1 (6)C36C32—C331.5 (6)C2C14—C15177.3 (3)C20C32—C33176.8 (4)C13C15—C161.0 (6)C31C33—C340.9 (7)C14C16—C171.2 (7)C32C34—C350.2 (7)C15C17—C180.5 (8)C33C35—C360.1 (8)C16C18—C130.4 (7)C34C36—C310.7 (7)C14C18—C170.6 (6)C32C36—C351.3 (6)C2C18—C17177.9 (4)C20C36—C35177.0 (4)
D—H···AD—HH···AD···AD—H···AN5—H5N···Cl20.85 (2)2.46 (2)3.250 (3)156 (4)N4—H4N···N8i0.98 (4)1.78 (4)2.749 (4)170 (4)Symmetry code:
(i) x, y, z1.
-->Hydrogen-bond geometry (Å, º)
D—H···AD—HH···AD···AD—H···AN5—H5N···Cl20.849 (18)2.46 (2)3.250 (3)156 (4)N4—H4N···N8i0.98 (4)1.78 (4)2.749 (4)170 (4)Symmetry code:
(i) x, y, z1.
Addison, A. W., Rao, T. N., Reedijk, J., Rijn, J. & Verschoor, G. C. (1984). J. Chem. Soc. Dalton Trans. pp. ;1356.Despaigne, A. A. R., Da Silva, J. G., do Carmo, A. C. M., Piro, O. E., Castellano, E. E. & Beraldo, H. (2009). Inorg. Chim. Acta, 362, ;2122.Rigaku
(2009). CrystalClear-SM Expert. Rigaku Corporation, Tokyo, Japan.Sheldrick, G. M. (2008). Acta Cryst. A64, 112&#.Spek, A. L. (2009). Acta Cryst. D65, 148&#.Welter, R. (2006). Acta Cryst. A62, s252.}