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Crystals of the title compound, [Zn(C45H28N4O2)(H2O)]·2C6H5NO2, consist of multiporphyrin supra­molecular assemblies sustained by inter­molecular COOH...COOH and Zn(H2O)...COOH hydrogen bonds. One of the two nitro­benzene solvent mol­ecules hydrogen bonds peripherally to these arrays.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106038996/sf3019sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106038996/sf3019Isup2.hkl
Contains datablock I

CCDC reference: 628504

Comment top

Following our earlier studies on the designed construction of framework solids from symmetrically functionalized porphyrin building blocks of square-planar D4h symmetry (Goldberg, 2005, and references therein), the supramolecular chemistry of porphyrin derivatives of reduced symmetry has also deserved considerable attention (Vinodu & Goldberg, 2003; George & Goldberg, 2006; George et al., 2006). Within this context, porphyrin cores substituted with four, three or two carboxylic acid functions of complementary hydrogen-bonding capacity have been investigated (Diskin-Posner & Goldberg, 1999; Vinodu & Goldberg, 2003; Vinodu & Goldberg, 2004a). In most cases, the predominant propensity of these groups to associate via the cyclic dimeric (COOH)2 hydrogen-bonding synthon has been demonstrated. In related structures based on five- or six-coordinate metalloporphyrins, wherein the core-metal ion is coordinated axially to oxo- (as methanol or water) or pyridine-type ligands, hydrogen-bond formation was observed also between the lateral carboxylic acid function of one unit and the axial ligand of a neighboring porphyrin entity (George & Goldberg, 2006; Vinodu & Goldberg, 2004b). We report here on the self-assembly features of the title compound, (I), which bears two different substituents capable of forming O—H···O hydrogen bonds. The COOH and H2O groups on the porphyrin can act both as H-atom donors and as acceptors, while molecules of nitrobenzene may reveal the latter functionality only. Fig. 1 shows the molecular structure of (I). The metalloporphyrin entity exhibits a slightly domed conformation typical of five-coordinate zinc–porphyrin complexes, with the central zinc ion deviating 0.199 (1) Å from the plane of the four pyrrole N atoms towards the water ligand (e.g. Lipstman & Goldberg, 2006; Allen, 2002). The porphyrin core itself adopts a saddle conformation, with the pyrrole N atoms deviating alternately ±0.043 (1) Å from this plane. The bond lengths and bond angles in (I) (Table 1) show standard values (Cambridge Structural Database; Version 5.27; Allen, 2002), in particular for the Zn—N(pyrrole) distances (Shmilovits et al., 2004).

Fig. 2 illustrates the main hydrogen-bonding motif in (I). The porphyrin groups organize in pairs around inversion at (1/2,1/2,1/2), with head-to-head orientation of their carboxylic acid functions. Association within these dimers is effected by the common strong (COOH)2 centrosymmetric synthon of self-complementary hydrogen-bonding. It is characterized by an OH···O distance of 2.677 (3) Å. Additional weak hydrogen bonding then occurs between such adjacent porphyrin dimers displaced by ±a with respect to the central pair. This interaction is between the axial water ligand of one species and the carboxylic CO acceptor sites of a neighboring unit, with an OH···O distance of 2.952 (4) Å. Thus, every porphyrin molecule is involved in four hydrogen bonds, which results in the formation of one-dimensional hydrogen-bonded assemblies of inter-connected porphyrin dimers (Table 2). The periphery of these chains is lined with the lipophilic phenyl substituents. In addition, however, the axial water ligands form another hydrogen bond, via their second H atom, to the nitro group of one of the nitrobenzene solvent molecules- - C53 through O61 – with an OH···O distance of 2.767 (4) Å (Table 2 and Fig. 3).

Fig. 3 shows that the remaining molecules of nitrobenzene, C62 through O70, reside in channel voids centered at (0, y, 0), which are created between the hydrogen-bonded arrays. This imparts to this structure the characteristics of a channel clathrate (Byrn et al., 1993). There are no specific interactions (other than dispersion) between these solvent species and the surrounding porphyrin units.

Experimental top

The free-base porphyrin moiety was synthesized by a standard literature procedure (Adler et al., 1970). Condensation of a 3:1 mixture of benzaldehyde and 4-carbomethoxybenzealdehyde with distilled pyrrole in hot propionic acid, followed by separation on a silica-gel column, led to the isolation of 5,10,15-triphenyl-20-(4-carbomethoxyphenyl)porphyrin. The latter was then converted to the corresponding carboxyphenyl porphyrin by alkaline hydrolysis, and subsequently metalated with zinc. The final as well as the intermediate products were fully characterized by 1H NMR, UV–vis and MS spectral techniques. Crystallization of the title porphyrin was carried out by evaporation of a nitrobenzene solution in air.

Refinement top

H atoms were located in calculated positions, and were constrained to ride on their parent atoms, with C—H distances of 0.95 Å, O—H distances of 0.96–0.97 Å, and with Uiso(H) = 1.2Ueq(C) and 1.5Ueq(O). Least certain are those of the water ligand, as its actual orientation could not be reliably determined. The final residual electron-density maps contained three relatively high peaks within 1.0–1.7 e/Å3 in the vicinity of the C53/O61 nitrobenzene solvent molecule, which appears to be partly disordered. This disorder and the appearance of the above-mentioned peaks could not be accounted for reliably by discrete atoms.

Computing details top

Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing the atom labeling scheme. Displacement ellipsoids are shown at the 50% probability level at ca 110 K. H atoms have been omitted, except for those involved in hydrogen bonding.
[Figure 2] Fig. 2. A stereoview of the hydrogen-bonding interaction scheme in (I). H atoms have been omitted, except for those involved in the hydrogen bonds. The Zn, N and O atoms are marked by darkened spheres. For clarity molecules of the nitrobenzene solvent are excluded. Note the chain connectivity of the (COOH)2 hydrogen bonded porphyrin dimers (centered at 1/2,1/2,1/2) along the vertical direction.
[Figure 3] Fig. 3. A stereoview of the crystal packing down the b axis. Half of the nitrobenzene solvate species are hydrogen bonded to the axial water ligands of (I), while the other half reside in interporphyrin chanel voids centered at (0, y, 0). The Zn, N and O atoms are marked by darkened spheres.
aqua[20-(4-carboxyphenyl)-5,10,15-triphenylporphyrinato]zinc(II) nitrobenzene disolvate top
Crystal data top
[Zn(C45H28N4O2)(H2O)]·2C6H5NO2Z = 2
Mr = 986.32F(000) = 1020
Triclinic, P1Dx = 1.458 Mg m3
a = 12.3796 (2) ÅMo Kα radiation, λ = 0.71073 Å
b = 13.4467 (2) ÅCell parameters from 8452 reflections
c = 15.5757 (3) Åθ = 1.9–28.2°
α = 78.1094 (5)°µ = 0.61 mm1
β = 69.5983 (6)°T = 110 K
γ = 68.0862 (6)°Plate, pink
V = 2245.96 (7) Å30.40 × 0.20 × 0.10 mm
Data collection top
Nonius KappaCCD
diffractometer
7911 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.048
Graphite monochromatorθmax = 28.2°, θmin = 1.9°
Detector resolution: 12.8 pixels mm-1h = 1616
1 ° ϕ and ω scansk = 1617
28770 measured reflectionsl = 1820
10851 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.063Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.182H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.1008P)2 + 2.0583P]
where P = (Fo2 + 2Fc2)/3
10851 reflections(Δ/σ)max = 0.001
642 parametersΔρmax = 1.68 e Å3
0 restraintsΔρmin = 0.85 e Å3
Crystal data top
[Zn(C45H28N4O2)(H2O)]·2C6H5NO2γ = 68.0862 (6)°
Mr = 986.32V = 2245.96 (7) Å3
Triclinic, P1Z = 2
a = 12.3796 (2) ÅMo Kα radiation
b = 13.4467 (2) ŵ = 0.61 mm1
c = 15.5757 (3) ÅT = 110 K
α = 78.1094 (5)°0.40 × 0.20 × 0.10 mm
β = 69.5983 (6)°
Data collection top
Nonius KappaCCD
diffractometer
7911 reflections with I > 2σ(I)
28770 measured reflectionsRint = 0.048
10851 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0630 restraints
wR(F2) = 0.182H-atom parameters constrained
S = 1.04Δρmax = 1.68 e Å3
10851 reflectionsΔρmin = 0.85 e Å3
642 parameters
Special details top

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.

The H-atoms were located in calculated positions. Least certain are those of the water ligand, as its actual orientation could not be reliably determined.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Zn10.85736 (3)0.32326 (2)0.25011 (2)0.02061 (12)
C11.0776 (3)0.2743 (2)0.31838 (19)0.0184 (6)
C21.1711 (3)0.1868 (2)0.3485 (2)0.0217 (6)
H21.23320.19260.36770.026*
C31.1533 (3)0.0940 (2)0.3443 (2)0.0210 (6)
H31.20000.02300.36090.025*
C41.0505 (3)0.1238 (2)0.30975 (19)0.0183 (6)
C51.0078 (3)0.0510 (2)0.28898 (19)0.0179 (6)
C60.9173 (3)0.0792 (2)0.2456 (2)0.0194 (6)
C70.8783 (3)0.0036 (2)0.2195 (2)0.0216 (6)
H70.90840.07270.22910.026*
C80.7908 (3)0.0622 (2)0.1787 (2)0.0227 (6)
H80.74820.03480.15420.027*
C90.7744 (3)0.1741 (2)0.1796 (2)0.0198 (6)
C100.6887 (3)0.2605 (2)0.1450 (2)0.0205 (6)
C110.6695 (3)0.3694 (2)0.14675 (19)0.0203 (6)
C120.5823 (3)0.4573 (2)0.1099 (2)0.0225 (6)
H120.53110.45140.07920.027*
C130.5874 (3)0.5497 (2)0.1276 (2)0.0224 (6)
H130.54010.62070.11170.027*
C140.6787 (3)0.5199 (2)0.17531 (19)0.0190 (6)
C150.7132 (3)0.5932 (2)0.20340 (19)0.0187 (6)
C160.8167 (3)0.5653 (2)0.23345 (19)0.0185 (6)
C170.8595 (3)0.6408 (2)0.2552 (2)0.0202 (6)
H170.82380.71690.25120.024*
C180.9599 (3)0.5829 (2)0.2824 (2)0.0205 (6)
H181.00910.61050.29950.025*
C190.9773 (3)0.4706 (2)0.28014 (19)0.0188 (6)
C201.0651 (3)0.3838 (2)0.31220 (19)0.0187 (6)
N211.0052 (2)0.23414 (18)0.29563 (16)0.0174 (5)
N220.8516 (2)0.18250 (18)0.22092 (17)0.0198 (5)
N230.7277 (2)0.41009 (18)0.18452 (16)0.0186 (5)
N240.8912 (2)0.46265 (18)0.24840 (16)0.0189 (5)
C251.0634 (3)0.0664 (2)0.3153 (2)0.0206 (6)
C261.1286 (3)0.1407 (2)0.2490 (2)0.0248 (6)
H261.14150.11670.18550.030*
C271.1743 (3)0.2497 (2)0.2760 (3)0.0319 (7)
H271.21790.30000.23090.038*
C281.1566 (3)0.2850 (3)0.3680 (3)0.0376 (8)
H281.18730.35960.38590.045*
C291.0943 (3)0.2123 (3)0.4341 (2)0.0327 (8)
H291.08340.23650.49730.039*
C301.0475 (3)0.1032 (2)0.4074 (2)0.0255 (6)
H301.00390.05340.45290.031*
C310.6105 (3)0.2313 (2)0.1060 (2)0.0209 (6)
C320.6521 (3)0.2020 (3)0.0170 (2)0.0277 (7)
H320.73130.20120.02100.033*
C330.5782 (3)0.1736 (3)0.0172 (2)0.0305 (7)
H330.60750.15320.07820.037*
C340.4619 (3)0.1751 (3)0.0377 (2)0.0300 (7)
H340.41160.15560.01460.036*
C350.4202 (3)0.2053 (3)0.1262 (2)0.0298 (7)
H350.34040.20750.16370.036*
C360.4942 (3)0.2324 (2)0.1608 (2)0.0270 (7)
H360.46510.25180.22210.032*
C370.6297 (3)0.7077 (2)0.2040 (2)0.0189 (6)
C380.6683 (3)0.7928 (2)0.1517 (2)0.0219 (6)
H380.75120.77970.11580.026*
C390.5847 (3)0.8975 (2)0.1524 (2)0.0257 (7)
H390.61120.95500.11620.031*
C400.4641 (3)0.9180 (2)0.2052 (2)0.0267 (7)
H400.40760.98900.20480.032*
C410.4263 (3)0.8335 (2)0.2591 (2)0.0258 (6)
H410.34400.84710.29660.031*
C420.5086 (3)0.7298 (2)0.2579 (2)0.0225 (6)
H420.48180.67270.29470.027*
C431.1503 (3)0.4079 (2)0.3472 (2)0.0183 (6)
C441.2512 (3)0.4360 (2)0.2871 (2)0.0221 (6)
H441.26300.44540.22270.027*
C451.3333 (3)0.4498 (2)0.3211 (2)0.0227 (6)
H451.40220.46730.27980.027*
C461.3160 (3)0.4384 (2)0.4153 (2)0.0203 (6)
C471.2135 (3)0.4140 (3)0.4761 (2)0.0262 (7)
H471.19980.40770.54060.031*
C481.1322 (3)0.3989 (3)0.4416 (2)0.0256 (6)
H481.06280.38220.48300.031*
C491.4031 (3)0.4564 (2)0.4509 (2)0.0243 (6)
O501.3933 (3)0.4223 (2)0.53772 (17)0.0418 (6)
H501.43470.45450.56020.063*
O511.4789 (2)0.49886 (17)0.40274 (15)0.0266 (5)
O520.7285 (3)0.3504 (2)0.39054 (19)0.0443 (7)
H52A0.65630.41370.39670.066*
H52B0.69780.29080.41320.066*
C530.6396 (4)0.0447 (3)0.4218 (3)0.0465 (10)
C540.5553 (4)0.0300 (4)0.3812 (3)0.0627 (14)
H540.49430.08710.36020.075*
C550.5772 (6)0.0782 (5)0.3780 (3)0.0634 (14)
H550.52610.09360.35270.076*
C560.6593 (7)0.1630 (5)0.4051 (4)0.083 (2)
H560.66280.23460.40410.099*
C570.7352 (6)0.1413 (5)0.4336 (4)0.0768 (18)
H570.80050.20030.44750.092*
C580.7284 (4)0.0404 (3)0.4449 (3)0.0397 (9)
H580.78480.03080.46840.048*
N590.6288 (5)0.1471 (4)0.4340 (3)0.0697 (13)
O600.6960 (5)0.1570 (3)0.4747 (3)0.0902 (15)
O610.5565 (4)0.2264 (3)0.4010 (4)0.1039 (17)
C620.0210 (3)0.7031 (3)0.0145 (2)0.0306 (7)
C630.0311 (3)0.6661 (3)0.0328 (2)0.0312 (7)
H630.00960.59130.03690.037*
C640.1154 (3)0.7408 (3)0.0741 (2)0.0360 (8)
H640.15320.71750.10610.043*
C650.1441 (4)0.8503 (3)0.0681 (2)0.0422 (9)
H650.20100.90150.09690.051*
C660.0914 (4)0.8851 (3)0.0211 (3)0.0402 (9)
H660.11200.96000.01780.048*
C670.0082 (3)0.8116 (3)0.0219 (2)0.0369 (8)
H670.02760.83510.05530.044*
N680.1097 (3)0.6233 (3)0.0587 (2)0.0358 (7)
O690.1599 (3)0.6565 (3)0.09608 (19)0.0496 (7)
O700.1282 (3)0.5273 (2)0.05631 (19)0.0449 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.02007 (19)0.01476 (18)0.0304 (2)0.00570 (13)0.01307 (15)0.00047 (12)
C10.0186 (14)0.0166 (13)0.0210 (14)0.0048 (11)0.0076 (11)0.0033 (10)
C20.0196 (14)0.0214 (14)0.0262 (15)0.0036 (11)0.0107 (12)0.0058 (11)
C30.0211 (14)0.0148 (13)0.0269 (15)0.0018 (11)0.0097 (12)0.0047 (10)
C40.0188 (14)0.0152 (13)0.0197 (14)0.0029 (11)0.0067 (11)0.0027 (10)
C50.0178 (13)0.0141 (13)0.0209 (14)0.0039 (10)0.0056 (11)0.0027 (10)
C60.0211 (14)0.0157 (13)0.0222 (14)0.0065 (11)0.0069 (12)0.0015 (10)
C70.0237 (15)0.0163 (13)0.0275 (16)0.0076 (11)0.0098 (12)0.0020 (10)
C80.0249 (15)0.0199 (14)0.0279 (16)0.0107 (12)0.0082 (12)0.0046 (11)
C90.0207 (14)0.0193 (14)0.0228 (15)0.0075 (11)0.0089 (12)0.0025 (10)
C100.0170 (14)0.0228 (14)0.0228 (15)0.0074 (11)0.0058 (11)0.0031 (10)
C110.0192 (14)0.0224 (14)0.0193 (14)0.0057 (11)0.0066 (11)0.0021 (10)
C120.0222 (15)0.0240 (15)0.0249 (15)0.0072 (12)0.0120 (12)0.0014 (11)
C130.0225 (15)0.0185 (14)0.0267 (16)0.0047 (11)0.0117 (12)0.0010 (11)
C140.0177 (14)0.0183 (13)0.0198 (14)0.0045 (11)0.0061 (11)0.0007 (10)
C150.0194 (14)0.0166 (13)0.0185 (14)0.0052 (11)0.0059 (11)0.0008 (10)
C160.0209 (14)0.0158 (13)0.0182 (14)0.0064 (11)0.0056 (11)0.0000 (10)
C170.0226 (15)0.0159 (13)0.0218 (14)0.0064 (11)0.0068 (12)0.0012 (10)
C180.0224 (15)0.0186 (14)0.0232 (15)0.0076 (11)0.0085 (12)0.0028 (10)
C190.0187 (14)0.0193 (13)0.0198 (14)0.0074 (11)0.0065 (11)0.0016 (10)
C200.0185 (14)0.0196 (14)0.0202 (14)0.0068 (11)0.0064 (11)0.0042 (10)
N210.0182 (12)0.0155 (11)0.0208 (12)0.0058 (9)0.0078 (10)0.0026 (8)
N220.0189 (12)0.0158 (11)0.0277 (13)0.0047 (9)0.0116 (10)0.0018 (9)
N230.0183 (12)0.0163 (11)0.0229 (12)0.0049 (9)0.0091 (10)0.0016 (9)
N240.0188 (12)0.0164 (11)0.0222 (12)0.0052 (9)0.0079 (10)0.0009 (9)
C250.0183 (14)0.0174 (14)0.0272 (15)0.0054 (11)0.0093 (12)0.0007 (11)
C260.0238 (16)0.0226 (15)0.0284 (16)0.0043 (12)0.0092 (13)0.0072 (11)
C270.0281 (17)0.0190 (15)0.047 (2)0.0017 (13)0.0107 (15)0.0116 (13)
C280.0352 (19)0.0164 (15)0.059 (2)0.0026 (14)0.0187 (17)0.0006 (14)
C290.0349 (19)0.0270 (17)0.0340 (18)0.0081 (14)0.0150 (15)0.0066 (13)
C300.0256 (16)0.0211 (15)0.0290 (17)0.0061 (12)0.0089 (13)0.0024 (11)
C310.0221 (15)0.0166 (13)0.0279 (16)0.0063 (11)0.0149 (12)0.0023 (10)
C320.0271 (16)0.0347 (17)0.0243 (16)0.0151 (14)0.0073 (13)0.0005 (12)
C330.0353 (19)0.0367 (18)0.0264 (17)0.0156 (15)0.0143 (14)0.0009 (13)
C340.0345 (18)0.0302 (17)0.0370 (19)0.0158 (14)0.0224 (15)0.0031 (13)
C350.0229 (16)0.0303 (17)0.0381 (19)0.0108 (13)0.0094 (14)0.0025 (13)
C360.0245 (16)0.0286 (16)0.0308 (17)0.0081 (13)0.0109 (13)0.0054 (12)
C370.0197 (14)0.0154 (13)0.0231 (14)0.0041 (11)0.0106 (12)0.0007 (10)
C380.0238 (15)0.0209 (14)0.0220 (15)0.0080 (12)0.0085 (12)0.0003 (10)
C390.0329 (17)0.0194 (14)0.0287 (16)0.0094 (13)0.0152 (14)0.0023 (11)
C400.0276 (16)0.0186 (14)0.0376 (18)0.0023 (12)0.0197 (14)0.0030 (12)
C410.0196 (15)0.0252 (15)0.0326 (17)0.0040 (12)0.0102 (13)0.0049 (12)
C420.0218 (15)0.0216 (14)0.0265 (16)0.0086 (12)0.0100 (12)0.0005 (11)
C430.0183 (14)0.0147 (13)0.0238 (15)0.0043 (10)0.0097 (11)0.0017 (10)
C440.0245 (15)0.0239 (14)0.0200 (15)0.0096 (12)0.0070 (12)0.0023 (11)
C450.0202 (15)0.0226 (14)0.0263 (16)0.0089 (12)0.0050 (12)0.0042 (11)
C460.0233 (15)0.0176 (13)0.0227 (15)0.0075 (11)0.0102 (12)0.0002 (10)
C470.0295 (17)0.0330 (17)0.0221 (15)0.0156 (13)0.0103 (13)0.0000 (12)
C480.0234 (15)0.0347 (17)0.0216 (15)0.0145 (13)0.0048 (12)0.0023 (12)
C490.0249 (16)0.0221 (14)0.0283 (16)0.0079 (12)0.0108 (13)0.0016 (11)
O500.0529 (17)0.0652 (18)0.0286 (13)0.0417 (14)0.0222 (12)0.0113 (11)
O510.0259 (12)0.0303 (12)0.0300 (12)0.0152 (9)0.0119 (9)0.0013 (9)
O520.0428 (16)0.0393 (14)0.0454 (16)0.0127 (12)0.0081 (13)0.0033 (11)
C530.038 (2)0.052 (2)0.032 (2)0.0000 (18)0.0065 (17)0.0024 (16)
C540.033 (2)0.081 (4)0.057 (3)0.018 (2)0.000 (2)0.007 (2)
C550.096 (4)0.081 (4)0.027 (2)0.045 (3)0.019 (2)0.003 (2)
C560.106 (5)0.070 (4)0.058 (3)0.040 (4)0.012 (3)0.022 (3)
C570.074 (4)0.071 (3)0.083 (4)0.047 (3)0.017 (3)0.029 (3)
C580.0322 (19)0.047 (2)0.037 (2)0.0137 (16)0.0081 (16)0.0012 (15)
N590.072 (3)0.055 (3)0.067 (3)0.028 (2)0.004 (2)0.006 (2)
O600.147 (4)0.060 (2)0.077 (3)0.065 (3)0.013 (3)0.0106 (19)
O610.069 (3)0.053 (2)0.151 (4)0.005 (2)0.019 (3)0.020 (2)
C620.0285 (17)0.0410 (19)0.0225 (16)0.0172 (15)0.0013 (13)0.0029 (13)
C630.0322 (18)0.0390 (18)0.0244 (17)0.0165 (15)0.0026 (14)0.0082 (13)
C640.0303 (18)0.055 (2)0.0247 (17)0.0191 (16)0.0049 (14)0.0044 (14)
C650.033 (2)0.051 (2)0.0277 (19)0.0106 (17)0.0010 (15)0.0053 (15)
C660.042 (2)0.0334 (19)0.035 (2)0.0158 (16)0.0044 (16)0.0029 (14)
C670.038 (2)0.046 (2)0.0290 (18)0.0263 (17)0.0028 (15)0.0083 (15)
N680.0330 (16)0.054 (2)0.0255 (15)0.0231 (14)0.0074 (13)0.0013 (12)
O690.0513 (18)0.078 (2)0.0367 (15)0.0406 (16)0.0192 (13)0.0074 (13)
O700.0431 (16)0.0408 (16)0.0459 (16)0.0103 (12)0.0133 (13)0.0004 (11)
Geometric parameters (Å, º) top
Zn1—N212.051 (2)C33—H330.9500
Zn1—N232.058 (2)C34—C351.382 (5)
Zn1—N242.061 (2)C34—H340.9500
Zn1—N222.067 (2)C35—C361.392 (5)
Zn1—O522.219 (3)C35—H350.9500
C1—N211.372 (4)C36—H360.9500
C1—C201.408 (4)C37—C421.391 (4)
C1—C21.441 (4)C37—C381.398 (4)
C2—C31.363 (4)C38—C391.402 (4)
C2—H20.9500C38—H380.9500
C3—C41.441 (4)C39—C401.383 (5)
C3—H30.9500C39—H390.9500
C4—N211.376 (3)C40—C411.395 (4)
C4—C51.407 (4)C40—H400.9500
C5—C61.400 (4)C41—C421.386 (4)
C5—C251.500 (4)C41—H410.9500
C6—N221.376 (4)C42—H420.9500
C6—C71.452 (4)C43—C481.394 (4)
C7—C81.354 (4)C43—C441.403 (4)
C7—H70.9500C44—C451.381 (4)
C8—C91.445 (4)C44—H440.9500
C8—H80.9500C45—C461.391 (4)
C9—N221.371 (4)C45—H450.9500
C9—C101.410 (4)C46—C471.401 (4)
C10—C111.398 (4)C46—C491.481 (4)
C10—C311.501 (4)C47—C481.384 (5)
C11—N231.374 (4)C47—H470.9500
C11—C121.447 (4)C48—H480.9500
C12—C131.354 (4)C49—O511.226 (4)
C12—H120.9500C49—O501.314 (4)
C13—C141.455 (4)O50—H500.9632
C13—H130.9500O52—H52A0.9687
C14—N231.369 (4)O52—H52B0.9644
C14—C151.404 (4)C53—C581.347 (5)
C15—C161.410 (4)C53—N591.379 (6)
C15—C371.500 (4)C53—C541.482 (7)
C16—N241.370 (4)C54—C551.384 (7)
C16—C171.448 (4)C54—H540.9500
C17—C181.355 (4)C55—C561.322 (9)
C17—H170.9500C55—H550.9500
C18—C191.450 (4)C56—C571.310 (9)
C18—H180.9500C56—H560.9500
C19—N241.366 (4)C57—C581.372 (6)
C19—C201.409 (4)C57—H570.9500
C20—C431.498 (4)C58—H580.9500
C25—C301.387 (4)N59—O611.260 (6)
C25—C261.400 (4)N59—O601.264 (7)
C26—C271.392 (4)C62—C671.385 (5)
C26—H260.9500C62—C631.388 (5)
C27—C281.380 (5)C62—N681.475 (5)
C27—H270.9500C63—C641.389 (5)
C28—C291.382 (5)C63—H630.9500
C28—H280.9500C64—C651.395 (6)
C29—C301.394 (4)C64—H640.9500
C29—H290.9500C65—C661.372 (6)
C30—H300.9500C65—H650.9500
C31—C321.384 (4)C66—C671.390 (6)
C31—C361.391 (4)C66—H660.9500
C32—C331.396 (5)C67—H670.9500
C32—H320.9500N68—O691.221 (4)
C33—C341.389 (5)N68—O701.230 (4)
N21—Zn1—N23171.21 (9)C36—C31—C10119.3 (3)
N21—Zn1—N2490.53 (9)C31—C32—C33120.4 (3)
N23—Zn1—N2489.08 (9)C31—C32—H32119.8
N21—Zn1—N2288.87 (9)C33—C32—H32119.8
N23—Zn1—N2289.47 (9)C34—C33—C32120.3 (3)
N24—Zn1—N22166.50 (10)C34—C33—H33119.9
N21—Zn1—O5294.14 (10)C32—C33—H33119.9
N23—Zn1—O5294.63 (10)C35—C34—C33119.2 (3)
N24—Zn1—O5289.03 (10)C35—C34—H34120.4
N22—Zn1—O52104.46 (10)C33—C34—H34120.4
N21—C1—C20125.8 (3)C34—C35—C36120.6 (3)
N21—C1—C2109.6 (2)C34—C35—H35119.7
C20—C1—C2124.6 (3)C36—C35—H35119.7
C3—C2—C1107.0 (3)C35—C36—C31120.3 (3)
C3—C2—H2126.5C35—C36—H36119.9
C1—C2—H2126.5C31—C36—H36119.9
C2—C3—C4107.1 (2)C42—C37—C38118.8 (3)
C2—C3—H3126.4C42—C37—C15118.6 (3)
C4—C3—H3126.4C38—C37—C15122.7 (3)
N21—C4—C5125.5 (3)C37—C38—C39120.0 (3)
N21—C4—C3109.4 (2)C37—C38—H38120.0
C5—C4—C3125.0 (3)C39—C38—H38120.0
C6—C5—C4125.2 (3)C40—C39—C38120.6 (3)
C6—C5—C25117.2 (2)C40—C39—H39119.7
C4—C5—C25117.6 (3)C38—C39—H39119.7
N22—C6—C5125.5 (3)C39—C40—C41119.4 (3)
N22—C6—C7109.3 (3)C39—C40—H40120.3
C5—C6—C7125.1 (3)C41—C40—H40120.3
C8—C7—C6107.1 (2)C42—C41—C40120.1 (3)
C8—C7—H7126.5C42—C41—H41120.0
C6—C7—H7126.5C40—C41—H41120.0
C7—C8—C9107.1 (3)C41—C42—C37121.2 (3)
C7—C8—H8126.5C41—C42—H42119.4
C9—C8—H8126.5C37—C42—H42119.4
N22—C9—C10126.1 (3)C48—C43—C44118.7 (3)
N22—C9—C8109.8 (2)C48—C43—C20119.7 (3)
C10—C9—C8124.0 (3)C44—C43—C20121.6 (3)
C11—C10—C9125.1 (3)C45—C44—C43120.3 (3)
C11—C10—C31118.5 (3)C45—C44—H44119.9
C9—C10—C31116.4 (2)C43—C44—H44119.9
N23—C11—C10126.1 (3)C44—C45—C46120.6 (3)
N23—C11—C12109.3 (2)C44—C45—H45119.7
C10—C11—C12124.6 (3)C46—C45—H45119.7
C13—C12—C11107.1 (3)C45—C46—C47119.6 (3)
C13—C12—H12126.5C45—C46—C49120.0 (3)
C11—C12—H12126.5C47—C46—C49120.4 (3)
C12—C13—C14107.3 (3)C48—C47—C46119.6 (3)
C12—C13—H13126.4C48—C47—H47120.2
C14—C13—H13126.4C46—C47—H47120.2
N23—C14—C15126.3 (3)C47—C48—C43121.1 (3)
N23—C14—C13108.9 (2)C47—C48—H48119.4
C15—C14—C13124.7 (3)C43—C48—H48119.4
C14—C15—C16124.5 (3)O51—C49—O50122.8 (3)
C14—C15—C37116.2 (3)O51—C49—C46122.6 (3)
C16—C15—C37119.3 (3)O50—C49—C46114.7 (3)
N24—C16—C15125.6 (3)C49—O50—H50109.4
N24—C16—C17109.2 (3)Zn1—O52—H52A116.9
C15—C16—C17125.2 (3)Zn1—O52—H52B108.8
C18—C17—C16107.4 (2)H52A—O52—H52B104.7
C18—C17—H17126.3C58—C53—N59119.6 (5)
C16—C17—H17126.3C58—C53—C54120.8 (4)
C17—C18—C19106.4 (3)N59—C53—C54119.5 (4)
C17—C18—H18126.8C55—C54—C53111.0 (4)
C19—C18—H18126.8C55—C54—H54124.5
N24—C19—C20125.8 (3)C53—C54—H54124.5
N24—C19—C18109.8 (2)C56—C55—C54129.1 (6)
C20—C19—C18124.3 (3)C56—C55—H55115.5
C1—C20—C19125.7 (3)C54—C55—H55115.5
C1—C20—C43115.7 (2)C57—C56—C55115.2 (6)
C19—C20—C43118.5 (2)C57—C56—H56122.4
C1—N21—C4106.9 (2)C55—C56—H56122.4
C1—N21—Zn1125.95 (18)C56—C57—C58125.5 (7)
C4—N21—Zn1127.15 (19)C56—C57—H57117.3
C9—N22—C6106.7 (2)C58—C57—H57117.3
C9—N22—Zn1126.37 (18)C53—C58—C57118.2 (5)
C6—N22—Zn1126.8 (2)C53—C58—H58120.9
C14—N23—C11107.4 (2)C57—C58—H58120.9
C14—N23—Zn1125.8 (2)O61—N59—O60122.9 (5)
C11—N23—Zn1126.74 (19)O61—N59—C53118.9 (5)
C19—N24—C16107.0 (2)O60—N59—C53118.2 (4)
C19—N24—Zn1125.83 (18)C67—C62—C63122.3 (3)
C16—N24—Zn1125.9 (2)C67—C62—N68119.4 (3)
C30—C25—C26118.9 (3)C63—C62—N68118.4 (3)
C30—C25—C5119.7 (3)C64—C63—C62118.7 (3)
C26—C25—C5121.4 (3)C64—C63—H63120.7
C27—C26—C25120.0 (3)C62—C63—H63120.7
C27—C26—H26120.0C63—C64—C65119.5 (4)
C25—C26—H26120.0C63—C64—H64120.3
C28—C27—C26120.4 (3)C65—C64—H64120.3
C28—C27—H27119.8C66—C65—C64120.9 (4)
C26—C27—H27119.8C66—C65—H65119.5
C27—C28—C29120.3 (3)C64—C65—H65119.5
C27—C28—H28119.9C65—C66—C67120.5 (3)
C29—C28—H28119.9C65—C66—H66119.7
C28—C29—C30119.5 (3)C67—C66—H66119.7
C28—C29—H29120.2C62—C67—C66118.1 (4)
C30—C29—H29120.2C62—C67—H67120.9
C25—C30—C29121.0 (3)C66—C67—H67120.9
C25—C30—H30119.5O69—N68—O70123.8 (3)
C29—C30—H30119.5O69—N68—C62118.0 (3)
C32—C31—C36119.2 (3)O70—N68—C62118.2 (3)
C32—C31—C10121.5 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O50—H50···O51i0.961.722.677 (3)174
O52—H52A···O51ii0.972.042.952 (4)156
O52—H52B···O600.961.862.767 (4)156
Symmetry codes: (i) x+3, y+1, z+1; (ii) x1, y, z.

Experimental details

Crystal data
Chemical formula[Zn(C45H28N4O2)(H2O)]·2C6H5NO2
Mr986.32
Crystal system, space groupTriclinic, P1
Temperature (K)110
a, b, c (Å)12.3796 (2), 13.4467 (2), 15.5757 (3)
α, β, γ (°)78.1094 (5), 69.5983 (6), 68.0862 (6)
V3)2245.96 (7)
Z2
Radiation typeMo Kα
µ (mm1)0.61
Crystal size (mm)0.40 × 0.20 × 0.10
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
28770, 10851, 7911
Rint0.048
(sin θ/λ)max1)0.666
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.063, 0.182, 1.04
No. of reflections10851
No. of parameters642
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.68, 0.85

Computer programs: COLLECT (Nonius, 1999), DENZO (Otwinowski & Minor, 1997), DENZO, SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), SHELXL97.

Selected geometric parameters (Å, º) top
Zn1—N212.051 (2)Zn1—N222.067 (2)
Zn1—N232.058 (2)Zn1—O522.219 (3)
Zn1—N242.061 (2)
N21—Zn1—N23171.21 (9)N24—Zn1—N22166.50 (10)
N21—Zn1—N2490.53 (9)N21—Zn1—O5294.14 (10)
N23—Zn1—N2489.08 (9)N23—Zn1—O5294.63 (10)
N21—Zn1—N2288.87 (9)N24—Zn1—O5289.03 (10)
N23—Zn1—N2289.47 (9)N22—Zn1—O52104.46 (10)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O50—H50···O51i0.961.722.677 (3)174.4
O52—H52A···O51ii0.972.042.952 (4)155.9
O52—H52B···O600.961.862.767 (4)155.5
Symmetry codes: (i) x+3, y+1, z+1; (ii) x1, y, z.
 

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