Crystals of the title compound, [Zn(C
45H
28N
4O
2)(H
2O)]·2C
6H
5NO
2, consist of multiporphyrin supramolecular assemblies sustained by intermolecular COOH
COOH and Zn(H
2O)
COOH hydrogen bonds. One of the two nitrobenzene solvent molecules hydrogen bonds peripherally to these arrays.
Supporting information
CCDC reference: 628504
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.
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.
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.
aqua[20-(4-carboxyphenyl)-5,10,15-triphenylporphyrinato]zinc(II) nitrobenzene disolvate
top
Crystal data top
[Zn(C45H28N4O2)(H2O)]·2C6H5NO2 | Z = 2 |
Mr = 986.32 | F(000) = 1020 |
Triclinic, P1 | Dx = 1.458 Mg m−3 |
a = 12.3796 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 13.4467 (2) Å | Cell parameters from 8452 reflections |
c = 15.5757 (3) Å | θ = 1.9–28.2° |
α = 78.1094 (5)° | µ = 0.61 mm−1 |
β = 69.5983 (6)° | T = 110 K |
γ = 68.0862 (6)° | Plate, pink |
V = 2245.96 (7) Å3 | 0.40 × 0.20 × 0.10 mm |
Data collection top
Nonius KappaCCD diffractometer | 7911 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.048 |
Graphite monochromator | θmax = 28.2°, θmin = 1.9° |
Detector resolution: 12.8 pixels mm-1 | h = −16→16 |
1 ° ϕ and ω scans | k = −16→17 |
28770 measured reflections | l = −18→20 |
10851 independent reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.063 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.182 | H-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 parameters | Δρmax = 1.68 e Å−3 |
0 restraints | Δρmin = −0.85 e Å−3 |
Crystal data top
[Zn(C45H28N4O2)(H2O)]·2C6H5NO2 | γ = 68.0862 (6)° |
Mr = 986.32 | V = 2245.96 (7) Å3 |
Triclinic, P1 | Z = 2 |
a = 12.3796 (2) Å | Mo Kα radiation |
b = 13.4467 (2) Å | µ = 0.61 mm−1 |
c = 15.5757 (3) Å | T = 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 reflections | Rint = 0.048 |
10851 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.063 | 0 restraints |
wR(F2) = 0.182 | H-atom parameters constrained |
S = 1.04 | Δρmax = 1.68 e Å−3 |
10851 reflections | Δρmin = −0.85 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
Zn1 | 0.85736 (3) | 0.32326 (2) | 0.25011 (2) | 0.02061 (12) | |
C1 | 1.0776 (3) | 0.2743 (2) | 0.31838 (19) | 0.0184 (6) | |
C2 | 1.1711 (3) | 0.1868 (2) | 0.3485 (2) | 0.0217 (6) | |
H2 | 1.2332 | 0.1926 | 0.3677 | 0.026* | |
C3 | 1.1533 (3) | 0.0940 (2) | 0.3443 (2) | 0.0210 (6) | |
H3 | 1.2000 | 0.0230 | 0.3609 | 0.025* | |
C4 | 1.0505 (3) | 0.1238 (2) | 0.30975 (19) | 0.0183 (6) | |
C5 | 1.0078 (3) | 0.0510 (2) | 0.28898 (19) | 0.0179 (6) | |
C6 | 0.9173 (3) | 0.0792 (2) | 0.2456 (2) | 0.0194 (6) | |
C7 | 0.8783 (3) | 0.0036 (2) | 0.2195 (2) | 0.0216 (6) | |
H7 | 0.9084 | −0.0727 | 0.2291 | 0.026* | |
C8 | 0.7908 (3) | 0.0622 (2) | 0.1787 (2) | 0.0227 (6) | |
H8 | 0.7482 | 0.0348 | 0.1542 | 0.027* | |
C9 | 0.7744 (3) | 0.1741 (2) | 0.1796 (2) | 0.0198 (6) | |
C10 | 0.6887 (3) | 0.2605 (2) | 0.1450 (2) | 0.0205 (6) | |
C11 | 0.6695 (3) | 0.3694 (2) | 0.14675 (19) | 0.0203 (6) | |
C12 | 0.5823 (3) | 0.4573 (2) | 0.1099 (2) | 0.0225 (6) | |
H12 | 0.5311 | 0.4514 | 0.0792 | 0.027* | |
C13 | 0.5874 (3) | 0.5497 (2) | 0.1276 (2) | 0.0224 (6) | |
H13 | 0.5401 | 0.6207 | 0.1117 | 0.027* | |
C14 | 0.6787 (3) | 0.5199 (2) | 0.17531 (19) | 0.0190 (6) | |
C15 | 0.7132 (3) | 0.5932 (2) | 0.20340 (19) | 0.0187 (6) | |
C16 | 0.8167 (3) | 0.5653 (2) | 0.23345 (19) | 0.0185 (6) | |
C17 | 0.8595 (3) | 0.6408 (2) | 0.2552 (2) | 0.0202 (6) | |
H17 | 0.8238 | 0.7169 | 0.2512 | 0.024* | |
C18 | 0.9599 (3) | 0.5829 (2) | 0.2824 (2) | 0.0205 (6) | |
H18 | 1.0091 | 0.6105 | 0.2995 | 0.025* | |
C19 | 0.9773 (3) | 0.4706 (2) | 0.28014 (19) | 0.0188 (6) | |
C20 | 1.0651 (3) | 0.3838 (2) | 0.31220 (19) | 0.0187 (6) | |
N21 | 1.0052 (2) | 0.23414 (18) | 0.29563 (16) | 0.0174 (5) | |
N22 | 0.8516 (2) | 0.18250 (18) | 0.22092 (17) | 0.0198 (5) | |
N23 | 0.7277 (2) | 0.41009 (18) | 0.18452 (16) | 0.0186 (5) | |
N24 | 0.8912 (2) | 0.46265 (18) | 0.24840 (16) | 0.0189 (5) | |
C25 | 1.0634 (3) | −0.0664 (2) | 0.3153 (2) | 0.0206 (6) | |
C26 | 1.1286 (3) | −0.1407 (2) | 0.2490 (2) | 0.0248 (6) | |
H26 | 1.1415 | −0.1167 | 0.1855 | 0.030* | |
C27 | 1.1743 (3) | −0.2497 (2) | 0.2760 (3) | 0.0319 (7) | |
H27 | 1.2179 | −0.3000 | 0.2309 | 0.038* | |
C28 | 1.1566 (3) | −0.2850 (3) | 0.3680 (3) | 0.0376 (8) | |
H28 | 1.1873 | −0.3596 | 0.3859 | 0.045* | |
C29 | 1.0943 (3) | −0.2123 (3) | 0.4341 (2) | 0.0327 (8) | |
H29 | 1.0834 | −0.2365 | 0.4973 | 0.039* | |
C30 | 1.0475 (3) | −0.1032 (2) | 0.4074 (2) | 0.0255 (6) | |
H30 | 1.0039 | −0.0534 | 0.4529 | 0.031* | |
C31 | 0.6105 (3) | 0.2313 (2) | 0.1060 (2) | 0.0209 (6) | |
C32 | 0.6521 (3) | 0.2020 (3) | 0.0170 (2) | 0.0277 (7) | |
H32 | 0.7313 | 0.2012 | −0.0210 | 0.033* | |
C33 | 0.5782 (3) | 0.1736 (3) | −0.0172 (2) | 0.0305 (7) | |
H33 | 0.6075 | 0.1532 | −0.0782 | 0.037* | |
C34 | 0.4619 (3) | 0.1751 (3) | 0.0377 (2) | 0.0300 (7) | |
H34 | 0.4116 | 0.1556 | 0.0146 | 0.036* | |
C35 | 0.4202 (3) | 0.2053 (3) | 0.1262 (2) | 0.0298 (7) | |
H35 | 0.3404 | 0.2075 | 0.1637 | 0.036* | |
C36 | 0.4942 (3) | 0.2324 (2) | 0.1608 (2) | 0.0270 (7) | |
H36 | 0.4651 | 0.2518 | 0.2221 | 0.032* | |
C37 | 0.6297 (3) | 0.7077 (2) | 0.2040 (2) | 0.0189 (6) | |
C38 | 0.6683 (3) | 0.7928 (2) | 0.1517 (2) | 0.0219 (6) | |
H38 | 0.7512 | 0.7797 | 0.1158 | 0.026* | |
C39 | 0.5847 (3) | 0.8975 (2) | 0.1524 (2) | 0.0257 (7) | |
H39 | 0.6112 | 0.9550 | 0.1162 | 0.031* | |
C40 | 0.4641 (3) | 0.9180 (2) | 0.2052 (2) | 0.0267 (7) | |
H40 | 0.4076 | 0.9890 | 0.2048 | 0.032* | |
C41 | 0.4263 (3) | 0.8335 (2) | 0.2591 (2) | 0.0258 (6) | |
H41 | 0.3440 | 0.8471 | 0.2966 | 0.031* | |
C42 | 0.5086 (3) | 0.7298 (2) | 0.2579 (2) | 0.0225 (6) | |
H42 | 0.4818 | 0.6727 | 0.2947 | 0.027* | |
C43 | 1.1503 (3) | 0.4079 (2) | 0.3472 (2) | 0.0183 (6) | |
C44 | 1.2512 (3) | 0.4360 (2) | 0.2871 (2) | 0.0221 (6) | |
H44 | 1.2630 | 0.4454 | 0.2227 | 0.027* | |
C45 | 1.3333 (3) | 0.4498 (2) | 0.3211 (2) | 0.0227 (6) | |
H45 | 1.4022 | 0.4673 | 0.2798 | 0.027* | |
C46 | 1.3160 (3) | 0.4384 (2) | 0.4153 (2) | 0.0203 (6) | |
C47 | 1.2135 (3) | 0.4140 (3) | 0.4761 (2) | 0.0262 (7) | |
H47 | 1.1998 | 0.4077 | 0.5406 | 0.031* | |
C48 | 1.1322 (3) | 0.3989 (3) | 0.4416 (2) | 0.0256 (6) | |
H48 | 1.0628 | 0.3822 | 0.4830 | 0.031* | |
C49 | 1.4031 (3) | 0.4564 (2) | 0.4509 (2) | 0.0243 (6) | |
O50 | 1.3933 (3) | 0.4223 (2) | 0.53772 (17) | 0.0418 (6) | |
H50 | 1.4347 | 0.4545 | 0.5602 | 0.063* | |
O51 | 1.4789 (2) | 0.49886 (17) | 0.40274 (15) | 0.0266 (5) | |
O52 | 0.7285 (3) | 0.3504 (2) | 0.39054 (19) | 0.0443 (7) | |
H52A | 0.6563 | 0.4137 | 0.3967 | 0.066* | |
H52B | 0.6978 | 0.2908 | 0.4132 | 0.066* | |
C53 | 0.6396 (4) | 0.0447 (3) | 0.4218 (3) | 0.0465 (10) | |
C54 | 0.5553 (4) | 0.0300 (4) | 0.3812 (3) | 0.0627 (14) | |
H54 | 0.4943 | 0.0871 | 0.3602 | 0.075* | |
C55 | 0.5772 (6) | −0.0782 (5) | 0.3780 (3) | 0.0634 (14) | |
H55 | 0.5261 | −0.0936 | 0.3527 | 0.076* | |
C56 | 0.6593 (7) | −0.1630 (5) | 0.4051 (4) | 0.083 (2) | |
H56 | 0.6628 | −0.2346 | 0.4041 | 0.099* | |
C57 | 0.7352 (6) | −0.1413 (5) | 0.4336 (4) | 0.0768 (18) | |
H57 | 0.8005 | −0.2003 | 0.4475 | 0.092* | |
C58 | 0.7284 (4) | −0.0404 (3) | 0.4449 (3) | 0.0397 (9) | |
H58 | 0.7848 | −0.0308 | 0.4684 | 0.048* | |
N59 | 0.6288 (5) | 0.1471 (4) | 0.4340 (3) | 0.0697 (13) | |
O60 | 0.6960 (5) | 0.1570 (3) | 0.4747 (3) | 0.0902 (15) | |
O61 | 0.5565 (4) | 0.2264 (3) | 0.4010 (4) | 0.1039 (17) | |
C62 | 0.0210 (3) | 0.7031 (3) | 0.0145 (2) | 0.0306 (7) | |
C63 | −0.0311 (3) | 0.6661 (3) | −0.0328 (2) | 0.0312 (7) | |
H63 | −0.0096 | 0.5913 | −0.0369 | 0.037* | |
C64 | −0.1154 (3) | 0.7408 (3) | −0.0741 (2) | 0.0360 (8) | |
H64 | −0.1532 | 0.7175 | −0.1061 | 0.043* | |
C65 | −0.1441 (4) | 0.8503 (3) | −0.0681 (2) | 0.0422 (9) | |
H65 | −0.2010 | 0.9015 | −0.0969 | 0.051* | |
C66 | −0.0914 (4) | 0.8851 (3) | −0.0211 (3) | 0.0402 (9) | |
H66 | −0.1120 | 0.9600 | −0.0178 | 0.048* | |
C67 | −0.0082 (3) | 0.8116 (3) | 0.0219 (2) | 0.0369 (8) | |
H67 | 0.0276 | 0.8351 | 0.0553 | 0.044* | |
N68 | 0.1097 (3) | 0.6233 (3) | 0.0587 (2) | 0.0358 (7) | |
O69 | 0.1599 (3) | 0.6565 (3) | 0.09608 (19) | 0.0496 (7) | |
O70 | 0.1282 (3) | 0.5273 (2) | 0.05631 (19) | 0.0449 (7) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn1 | 0.02007 (19) | 0.01476 (18) | 0.0304 (2) | −0.00570 (13) | −0.01307 (15) | 0.00047 (12) |
C1 | 0.0186 (14) | 0.0166 (13) | 0.0210 (14) | −0.0048 (11) | −0.0076 (11) | −0.0033 (10) |
C2 | 0.0196 (14) | 0.0214 (14) | 0.0262 (15) | −0.0036 (11) | −0.0107 (12) | −0.0058 (11) |
C3 | 0.0211 (14) | 0.0148 (13) | 0.0269 (15) | −0.0018 (11) | −0.0097 (12) | −0.0047 (10) |
C4 | 0.0188 (14) | 0.0152 (13) | 0.0197 (14) | −0.0029 (11) | −0.0067 (11) | −0.0027 (10) |
C5 | 0.0178 (13) | 0.0141 (13) | 0.0209 (14) | −0.0039 (10) | −0.0056 (11) | −0.0027 (10) |
C6 | 0.0211 (14) | 0.0157 (13) | 0.0222 (14) | −0.0065 (11) | −0.0069 (12) | −0.0015 (10) |
C7 | 0.0237 (15) | 0.0163 (13) | 0.0275 (16) | −0.0076 (11) | −0.0098 (12) | −0.0020 (10) |
C8 | 0.0249 (15) | 0.0199 (14) | 0.0279 (16) | −0.0107 (12) | −0.0082 (12) | −0.0046 (11) |
C9 | 0.0207 (14) | 0.0193 (14) | 0.0228 (15) | −0.0075 (11) | −0.0089 (12) | −0.0025 (10) |
C10 | 0.0170 (14) | 0.0228 (14) | 0.0228 (15) | −0.0074 (11) | −0.0058 (11) | −0.0031 (10) |
C11 | 0.0192 (14) | 0.0224 (14) | 0.0193 (14) | −0.0057 (11) | −0.0066 (11) | −0.0021 (10) |
C12 | 0.0222 (15) | 0.0240 (15) | 0.0249 (15) | −0.0072 (12) | −0.0120 (12) | −0.0014 (11) |
C13 | 0.0225 (15) | 0.0185 (14) | 0.0267 (16) | −0.0047 (11) | −0.0117 (12) | 0.0010 (11) |
C14 | 0.0177 (14) | 0.0183 (13) | 0.0198 (14) | −0.0045 (11) | −0.0061 (11) | −0.0007 (10) |
C15 | 0.0194 (14) | 0.0166 (13) | 0.0185 (14) | −0.0052 (11) | −0.0059 (11) | 0.0008 (10) |
C16 | 0.0209 (14) | 0.0158 (13) | 0.0182 (14) | −0.0064 (11) | −0.0056 (11) | 0.0000 (10) |
C17 | 0.0226 (15) | 0.0159 (13) | 0.0218 (14) | −0.0064 (11) | −0.0068 (12) | −0.0012 (10) |
C18 | 0.0224 (15) | 0.0186 (14) | 0.0232 (15) | −0.0076 (11) | −0.0085 (12) | −0.0028 (10) |
C19 | 0.0187 (14) | 0.0193 (13) | 0.0198 (14) | −0.0074 (11) | −0.0065 (11) | −0.0016 (10) |
C20 | 0.0185 (14) | 0.0196 (14) | 0.0202 (14) | −0.0068 (11) | −0.0064 (11) | −0.0042 (10) |
N21 | 0.0182 (12) | 0.0155 (11) | 0.0208 (12) | −0.0058 (9) | −0.0078 (10) | −0.0026 (8) |
N22 | 0.0189 (12) | 0.0158 (11) | 0.0277 (13) | −0.0047 (9) | −0.0116 (10) | −0.0018 (9) |
N23 | 0.0183 (12) | 0.0163 (11) | 0.0229 (12) | −0.0049 (9) | −0.0091 (10) | −0.0016 (9) |
N24 | 0.0188 (12) | 0.0164 (11) | 0.0222 (12) | −0.0052 (9) | −0.0079 (10) | −0.0009 (9) |
C25 | 0.0183 (14) | 0.0174 (14) | 0.0272 (15) | −0.0054 (11) | −0.0093 (12) | −0.0007 (11) |
C26 | 0.0238 (16) | 0.0226 (15) | 0.0284 (16) | −0.0043 (12) | −0.0092 (13) | −0.0072 (11) |
C27 | 0.0281 (17) | 0.0190 (15) | 0.047 (2) | −0.0017 (13) | −0.0107 (15) | −0.0116 (13) |
C28 | 0.0352 (19) | 0.0164 (15) | 0.059 (2) | −0.0026 (14) | −0.0187 (17) | −0.0006 (14) |
C29 | 0.0349 (19) | 0.0270 (17) | 0.0340 (18) | −0.0081 (14) | −0.0150 (15) | 0.0066 (13) |
C30 | 0.0256 (16) | 0.0211 (15) | 0.0290 (17) | −0.0061 (12) | −0.0089 (13) | −0.0024 (11) |
C31 | 0.0221 (15) | 0.0166 (13) | 0.0279 (16) | −0.0063 (11) | −0.0149 (12) | 0.0023 (10) |
C32 | 0.0271 (16) | 0.0347 (17) | 0.0243 (16) | −0.0151 (14) | −0.0073 (13) | −0.0005 (12) |
C33 | 0.0353 (19) | 0.0367 (18) | 0.0264 (17) | −0.0156 (15) | −0.0143 (14) | −0.0009 (13) |
C34 | 0.0345 (18) | 0.0302 (17) | 0.0370 (19) | −0.0158 (14) | −0.0224 (15) | 0.0031 (13) |
C35 | 0.0229 (16) | 0.0303 (17) | 0.0381 (19) | −0.0108 (13) | −0.0094 (14) | −0.0025 (13) |
C36 | 0.0245 (16) | 0.0286 (16) | 0.0308 (17) | −0.0081 (13) | −0.0109 (13) | −0.0054 (12) |
C37 | 0.0197 (14) | 0.0154 (13) | 0.0231 (14) | −0.0041 (11) | −0.0106 (12) | −0.0007 (10) |
C38 | 0.0238 (15) | 0.0209 (14) | 0.0220 (15) | −0.0080 (12) | −0.0085 (12) | 0.0003 (10) |
C39 | 0.0329 (17) | 0.0194 (14) | 0.0287 (16) | −0.0094 (13) | −0.0152 (14) | 0.0023 (11) |
C40 | 0.0276 (16) | 0.0186 (14) | 0.0376 (18) | −0.0023 (12) | −0.0197 (14) | −0.0030 (12) |
C41 | 0.0196 (15) | 0.0252 (15) | 0.0326 (17) | −0.0040 (12) | −0.0102 (13) | −0.0049 (12) |
C42 | 0.0218 (15) | 0.0216 (14) | 0.0265 (16) | −0.0086 (12) | −0.0100 (12) | 0.0005 (11) |
C43 | 0.0183 (14) | 0.0147 (13) | 0.0238 (15) | −0.0043 (10) | −0.0097 (11) | −0.0017 (10) |
C44 | 0.0245 (15) | 0.0239 (14) | 0.0200 (15) | −0.0096 (12) | −0.0070 (12) | −0.0023 (11) |
C45 | 0.0202 (15) | 0.0226 (14) | 0.0263 (16) | −0.0089 (12) | −0.0050 (12) | −0.0042 (11) |
C46 | 0.0233 (15) | 0.0176 (13) | 0.0227 (15) | −0.0075 (11) | −0.0102 (12) | −0.0002 (10) |
C47 | 0.0295 (17) | 0.0330 (17) | 0.0221 (15) | −0.0156 (13) | −0.0103 (13) | 0.0000 (12) |
C48 | 0.0234 (15) | 0.0347 (17) | 0.0216 (15) | −0.0145 (13) | −0.0048 (12) | −0.0023 (12) |
C49 | 0.0249 (16) | 0.0221 (14) | 0.0283 (16) | −0.0079 (12) | −0.0108 (13) | −0.0016 (11) |
O50 | 0.0529 (17) | 0.0652 (18) | 0.0286 (13) | −0.0417 (14) | −0.0222 (12) | 0.0113 (11) |
O51 | 0.0259 (12) | 0.0303 (12) | 0.0300 (12) | −0.0152 (9) | −0.0119 (9) | 0.0013 (9) |
O52 | 0.0428 (16) | 0.0393 (14) | 0.0454 (16) | −0.0127 (12) | −0.0081 (13) | −0.0033 (11) |
C53 | 0.038 (2) | 0.052 (2) | 0.032 (2) | 0.0000 (18) | −0.0065 (17) | −0.0024 (16) |
C54 | 0.033 (2) | 0.081 (4) | 0.057 (3) | −0.018 (2) | 0.000 (2) | 0.007 (2) |
C55 | 0.096 (4) | 0.081 (4) | 0.027 (2) | −0.045 (3) | −0.019 (2) | −0.003 (2) |
C56 | 0.106 (5) | 0.070 (4) | 0.058 (3) | −0.040 (4) | 0.012 (3) | −0.022 (3) |
C57 | 0.074 (4) | 0.071 (3) | 0.083 (4) | −0.047 (3) | 0.017 (3) | −0.029 (3) |
C58 | 0.0322 (19) | 0.047 (2) | 0.037 (2) | −0.0137 (16) | −0.0081 (16) | −0.0012 (15) |
N59 | 0.072 (3) | 0.055 (3) | 0.067 (3) | −0.028 (2) | −0.004 (2) | 0.006 (2) |
O60 | 0.147 (4) | 0.060 (2) | 0.077 (3) | −0.065 (3) | −0.013 (3) | −0.0106 (19) |
O61 | 0.069 (3) | 0.053 (2) | 0.151 (4) | −0.005 (2) | −0.019 (3) | 0.020 (2) |
C62 | 0.0285 (17) | 0.0410 (19) | 0.0225 (16) | −0.0172 (15) | −0.0013 (13) | −0.0029 (13) |
C63 | 0.0322 (18) | 0.0390 (18) | 0.0244 (17) | −0.0165 (15) | −0.0026 (14) | −0.0082 (13) |
C64 | 0.0303 (18) | 0.055 (2) | 0.0247 (17) | −0.0191 (16) | −0.0049 (14) | −0.0044 (14) |
C65 | 0.033 (2) | 0.051 (2) | 0.0277 (19) | −0.0106 (17) | 0.0010 (15) | 0.0053 (15) |
C66 | 0.042 (2) | 0.0334 (19) | 0.035 (2) | −0.0158 (16) | 0.0044 (16) | −0.0029 (14) |
C67 | 0.038 (2) | 0.046 (2) | 0.0290 (18) | −0.0263 (17) | 0.0028 (15) | −0.0083 (15) |
N68 | 0.0330 (16) | 0.054 (2) | 0.0255 (15) | −0.0231 (14) | −0.0074 (13) | 0.0013 (12) |
O69 | 0.0513 (18) | 0.078 (2) | 0.0367 (15) | −0.0406 (16) | −0.0192 (13) | 0.0074 (13) |
O70 | 0.0431 (16) | 0.0408 (16) | 0.0459 (16) | −0.0103 (12) | −0.0133 (13) | −0.0004 (11) |
Geometric parameters (Å, º) top
Zn1—N21 | 2.051 (2) | C33—H33 | 0.9500 |
Zn1—N23 | 2.058 (2) | C34—C35 | 1.382 (5) |
Zn1—N24 | 2.061 (2) | C34—H34 | 0.9500 |
Zn1—N22 | 2.067 (2) | C35—C36 | 1.392 (5) |
Zn1—O52 | 2.219 (3) | C35—H35 | 0.9500 |
C1—N21 | 1.372 (4) | C36—H36 | 0.9500 |
C1—C20 | 1.408 (4) | C37—C42 | 1.391 (4) |
C1—C2 | 1.441 (4) | C37—C38 | 1.398 (4) |
C2—C3 | 1.363 (4) | C38—C39 | 1.402 (4) |
C2—H2 | 0.9500 | C38—H38 | 0.9500 |
C3—C4 | 1.441 (4) | C39—C40 | 1.383 (5) |
C3—H3 | 0.9500 | C39—H39 | 0.9500 |
C4—N21 | 1.376 (3) | C40—C41 | 1.395 (4) |
C4—C5 | 1.407 (4) | C40—H40 | 0.9500 |
C5—C6 | 1.400 (4) | C41—C42 | 1.386 (4) |
C5—C25 | 1.500 (4) | C41—H41 | 0.9500 |
C6—N22 | 1.376 (4) | C42—H42 | 0.9500 |
C6—C7 | 1.452 (4) | C43—C48 | 1.394 (4) |
C7—C8 | 1.354 (4) | C43—C44 | 1.403 (4) |
C7—H7 | 0.9500 | C44—C45 | 1.381 (4) |
C8—C9 | 1.445 (4) | C44—H44 | 0.9500 |
C8—H8 | 0.9500 | C45—C46 | 1.391 (4) |
C9—N22 | 1.371 (4) | C45—H45 | 0.9500 |
C9—C10 | 1.410 (4) | C46—C47 | 1.401 (4) |
C10—C11 | 1.398 (4) | C46—C49 | 1.481 (4) |
C10—C31 | 1.501 (4) | C47—C48 | 1.384 (5) |
C11—N23 | 1.374 (4) | C47—H47 | 0.9500 |
C11—C12 | 1.447 (4) | C48—H48 | 0.9500 |
C12—C13 | 1.354 (4) | C49—O51 | 1.226 (4) |
C12—H12 | 0.9500 | C49—O50 | 1.314 (4) |
C13—C14 | 1.455 (4) | O50—H50 | 0.9632 |
C13—H13 | 0.9500 | O52—H52A | 0.9687 |
C14—N23 | 1.369 (4) | O52—H52B | 0.9644 |
C14—C15 | 1.404 (4) | C53—C58 | 1.347 (5) |
C15—C16 | 1.410 (4) | C53—N59 | 1.379 (6) |
C15—C37 | 1.500 (4) | C53—C54 | 1.482 (7) |
C16—N24 | 1.370 (4) | C54—C55 | 1.384 (7) |
C16—C17 | 1.448 (4) | C54—H54 | 0.9500 |
C17—C18 | 1.355 (4) | C55—C56 | 1.322 (9) |
C17—H17 | 0.9500 | C55—H55 | 0.9500 |
C18—C19 | 1.450 (4) | C56—C57 | 1.310 (9) |
C18—H18 | 0.9500 | C56—H56 | 0.9500 |
C19—N24 | 1.366 (4) | C57—C58 | 1.372 (6) |
C19—C20 | 1.409 (4) | C57—H57 | 0.9500 |
C20—C43 | 1.498 (4) | C58—H58 | 0.9500 |
C25—C30 | 1.387 (4) | N59—O61 | 1.260 (6) |
C25—C26 | 1.400 (4) | N59—O60 | 1.264 (7) |
C26—C27 | 1.392 (4) | C62—C67 | 1.385 (5) |
C26—H26 | 0.9500 | C62—C63 | 1.388 (5) |
C27—C28 | 1.380 (5) | C62—N68 | 1.475 (5) |
C27—H27 | 0.9500 | C63—C64 | 1.389 (5) |
C28—C29 | 1.382 (5) | C63—H63 | 0.9500 |
C28—H28 | 0.9500 | C64—C65 | 1.395 (6) |
C29—C30 | 1.394 (4) | C64—H64 | 0.9500 |
C29—H29 | 0.9500 | C65—C66 | 1.372 (6) |
C30—H30 | 0.9500 | C65—H65 | 0.9500 |
C31—C32 | 1.384 (4) | C66—C67 | 1.390 (6) |
C31—C36 | 1.391 (4) | C66—H66 | 0.9500 |
C32—C33 | 1.396 (5) | C67—H67 | 0.9500 |
C32—H32 | 0.9500 | N68—O69 | 1.221 (4) |
C33—C34 | 1.389 (5) | N68—O70 | 1.230 (4) |
| | | |
N21—Zn1—N23 | 171.21 (9) | C36—C31—C10 | 119.3 (3) |
N21—Zn1—N24 | 90.53 (9) | C31—C32—C33 | 120.4 (3) |
N23—Zn1—N24 | 89.08 (9) | C31—C32—H32 | 119.8 |
N21—Zn1—N22 | 88.87 (9) | C33—C32—H32 | 119.8 |
N23—Zn1—N22 | 89.47 (9) | C34—C33—C32 | 120.3 (3) |
N24—Zn1—N22 | 166.50 (10) | C34—C33—H33 | 119.9 |
N21—Zn1—O52 | 94.14 (10) | C32—C33—H33 | 119.9 |
N23—Zn1—O52 | 94.63 (10) | C35—C34—C33 | 119.2 (3) |
N24—Zn1—O52 | 89.03 (10) | C35—C34—H34 | 120.4 |
N22—Zn1—O52 | 104.46 (10) | C33—C34—H34 | 120.4 |
N21—C1—C20 | 125.8 (3) | C34—C35—C36 | 120.6 (3) |
N21—C1—C2 | 109.6 (2) | C34—C35—H35 | 119.7 |
C20—C1—C2 | 124.6 (3) | C36—C35—H35 | 119.7 |
C3—C2—C1 | 107.0 (3) | C35—C36—C31 | 120.3 (3) |
C3—C2—H2 | 126.5 | C35—C36—H36 | 119.9 |
C1—C2—H2 | 126.5 | C31—C36—H36 | 119.9 |
C2—C3—C4 | 107.1 (2) | C42—C37—C38 | 118.8 (3) |
C2—C3—H3 | 126.4 | C42—C37—C15 | 118.6 (3) |
C4—C3—H3 | 126.4 | C38—C37—C15 | 122.7 (3) |
N21—C4—C5 | 125.5 (3) | C37—C38—C39 | 120.0 (3) |
N21—C4—C3 | 109.4 (2) | C37—C38—H38 | 120.0 |
C5—C4—C3 | 125.0 (3) | C39—C38—H38 | 120.0 |
C6—C5—C4 | 125.2 (3) | C40—C39—C38 | 120.6 (3) |
C6—C5—C25 | 117.2 (2) | C40—C39—H39 | 119.7 |
C4—C5—C25 | 117.6 (3) | C38—C39—H39 | 119.7 |
N22—C6—C5 | 125.5 (3) | C39—C40—C41 | 119.4 (3) |
N22—C6—C7 | 109.3 (3) | C39—C40—H40 | 120.3 |
C5—C6—C7 | 125.1 (3) | C41—C40—H40 | 120.3 |
C8—C7—C6 | 107.1 (2) | C42—C41—C40 | 120.1 (3) |
C8—C7—H7 | 126.5 | C42—C41—H41 | 120.0 |
C6—C7—H7 | 126.5 | C40—C41—H41 | 120.0 |
C7—C8—C9 | 107.1 (3) | C41—C42—C37 | 121.2 (3) |
C7—C8—H8 | 126.5 | C41—C42—H42 | 119.4 |
C9—C8—H8 | 126.5 | C37—C42—H42 | 119.4 |
N22—C9—C10 | 126.1 (3) | C48—C43—C44 | 118.7 (3) |
N22—C9—C8 | 109.8 (2) | C48—C43—C20 | 119.7 (3) |
C10—C9—C8 | 124.0 (3) | C44—C43—C20 | 121.6 (3) |
C11—C10—C9 | 125.1 (3) | C45—C44—C43 | 120.3 (3) |
C11—C10—C31 | 118.5 (3) | C45—C44—H44 | 119.9 |
C9—C10—C31 | 116.4 (2) | C43—C44—H44 | 119.9 |
N23—C11—C10 | 126.1 (3) | C44—C45—C46 | 120.6 (3) |
N23—C11—C12 | 109.3 (2) | C44—C45—H45 | 119.7 |
C10—C11—C12 | 124.6 (3) | C46—C45—H45 | 119.7 |
C13—C12—C11 | 107.1 (3) | C45—C46—C47 | 119.6 (3) |
C13—C12—H12 | 126.5 | C45—C46—C49 | 120.0 (3) |
C11—C12—H12 | 126.5 | C47—C46—C49 | 120.4 (3) |
C12—C13—C14 | 107.3 (3) | C48—C47—C46 | 119.6 (3) |
C12—C13—H13 | 126.4 | C48—C47—H47 | 120.2 |
C14—C13—H13 | 126.4 | C46—C47—H47 | 120.2 |
N23—C14—C15 | 126.3 (3) | C47—C48—C43 | 121.1 (3) |
N23—C14—C13 | 108.9 (2) | C47—C48—H48 | 119.4 |
C15—C14—C13 | 124.7 (3) | C43—C48—H48 | 119.4 |
C14—C15—C16 | 124.5 (3) | O51—C49—O50 | 122.8 (3) |
C14—C15—C37 | 116.2 (3) | O51—C49—C46 | 122.6 (3) |
C16—C15—C37 | 119.3 (3) | O50—C49—C46 | 114.7 (3) |
N24—C16—C15 | 125.6 (3) | C49—O50—H50 | 109.4 |
N24—C16—C17 | 109.2 (3) | Zn1—O52—H52A | 116.9 |
C15—C16—C17 | 125.2 (3) | Zn1—O52—H52B | 108.8 |
C18—C17—C16 | 107.4 (2) | H52A—O52—H52B | 104.7 |
C18—C17—H17 | 126.3 | C58—C53—N59 | 119.6 (5) |
C16—C17—H17 | 126.3 | C58—C53—C54 | 120.8 (4) |
C17—C18—C19 | 106.4 (3) | N59—C53—C54 | 119.5 (4) |
C17—C18—H18 | 126.8 | C55—C54—C53 | 111.0 (4) |
C19—C18—H18 | 126.8 | C55—C54—H54 | 124.5 |
N24—C19—C20 | 125.8 (3) | C53—C54—H54 | 124.5 |
N24—C19—C18 | 109.8 (2) | C56—C55—C54 | 129.1 (6) |
C20—C19—C18 | 124.3 (3) | C56—C55—H55 | 115.5 |
C1—C20—C19 | 125.7 (3) | C54—C55—H55 | 115.5 |
C1—C20—C43 | 115.7 (2) | C57—C56—C55 | 115.2 (6) |
C19—C20—C43 | 118.5 (2) | C57—C56—H56 | 122.4 |
C1—N21—C4 | 106.9 (2) | C55—C56—H56 | 122.4 |
C1—N21—Zn1 | 125.95 (18) | C56—C57—C58 | 125.5 (7) |
C4—N21—Zn1 | 127.15 (19) | C56—C57—H57 | 117.3 |
C9—N22—C6 | 106.7 (2) | C58—C57—H57 | 117.3 |
C9—N22—Zn1 | 126.37 (18) | C53—C58—C57 | 118.2 (5) |
C6—N22—Zn1 | 126.8 (2) | C53—C58—H58 | 120.9 |
C14—N23—C11 | 107.4 (2) | C57—C58—H58 | 120.9 |
C14—N23—Zn1 | 125.8 (2) | O61—N59—O60 | 122.9 (5) |
C11—N23—Zn1 | 126.74 (19) | O61—N59—C53 | 118.9 (5) |
C19—N24—C16 | 107.0 (2) | O60—N59—C53 | 118.2 (4) |
C19—N24—Zn1 | 125.83 (18) | C67—C62—C63 | 122.3 (3) |
C16—N24—Zn1 | 125.9 (2) | C67—C62—N68 | 119.4 (3) |
C30—C25—C26 | 118.9 (3) | C63—C62—N68 | 118.4 (3) |
C30—C25—C5 | 119.7 (3) | C64—C63—C62 | 118.7 (3) |
C26—C25—C5 | 121.4 (3) | C64—C63—H63 | 120.7 |
C27—C26—C25 | 120.0 (3) | C62—C63—H63 | 120.7 |
C27—C26—H26 | 120.0 | C63—C64—C65 | 119.5 (4) |
C25—C26—H26 | 120.0 | C63—C64—H64 | 120.3 |
C28—C27—C26 | 120.4 (3) | C65—C64—H64 | 120.3 |
C28—C27—H27 | 119.8 | C66—C65—C64 | 120.9 (4) |
C26—C27—H27 | 119.8 | C66—C65—H65 | 119.5 |
C27—C28—C29 | 120.3 (3) | C64—C65—H65 | 119.5 |
C27—C28—H28 | 119.9 | C65—C66—C67 | 120.5 (3) |
C29—C28—H28 | 119.9 | C65—C66—H66 | 119.7 |
C28—C29—C30 | 119.5 (3) | C67—C66—H66 | 119.7 |
C28—C29—H29 | 120.2 | C62—C67—C66 | 118.1 (4) |
C30—C29—H29 | 120.2 | C62—C67—H67 | 120.9 |
C25—C30—C29 | 121.0 (3) | C66—C67—H67 | 120.9 |
C25—C30—H30 | 119.5 | O69—N68—O70 | 123.8 (3) |
C29—C30—H30 | 119.5 | O69—N68—C62 | 118.0 (3) |
C32—C31—C36 | 119.2 (3) | O70—N68—C62 | 118.2 (3) |
C32—C31—C10 | 121.5 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O50—H50···O51i | 0.96 | 1.72 | 2.677 (3) | 174 |
O52—H52A···O51ii | 0.97 | 2.04 | 2.952 (4) | 156 |
O52—H52B···O60 | 0.96 | 1.86 | 2.767 (4) | 156 |
Symmetry codes: (i) −x+3, −y+1, −z+1; (ii) x−1, y, z. |
Experimental details
Crystal data |
Chemical formula | [Zn(C45H28N4O2)(H2O)]·2C6H5NO2 |
Mr | 986.32 |
Crystal system, space group | Triclinic, 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) |
V (Å3) | 2245.96 (7) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.61 |
Crystal size (mm) | 0.40 × 0.20 × 0.10 |
|
Data collection |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 28770, 10851, 7911 |
Rint | 0.048 |
(sin θ/λ)max (Å−1) | 0.666 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.063, 0.182, 1.04 |
No. of reflections | 10851 |
No. of parameters | 642 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.68, −0.85 |
Selected geometric parameters (Å, º) topZn1—N21 | 2.051 (2) | Zn1—N22 | 2.067 (2) |
Zn1—N23 | 2.058 (2) | Zn1—O52 | 2.219 (3) |
Zn1—N24 | 2.061 (2) | | |
| | | |
N21—Zn1—N23 | 171.21 (9) | N24—Zn1—N22 | 166.50 (10) |
N21—Zn1—N24 | 90.53 (9) | N21—Zn1—O52 | 94.14 (10) |
N23—Zn1—N24 | 89.08 (9) | N23—Zn1—O52 | 94.63 (10) |
N21—Zn1—N22 | 88.87 (9) | N24—Zn1—O52 | 89.03 (10) |
N23—Zn1—N22 | 89.47 (9) | N22—Zn1—O52 | 104.46 (10) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O50—H50···O51i | 0.96 | 1.72 | 2.677 (3) | 174.4 |
O52—H52A···O51ii | 0.97 | 2.04 | 2.952 (4) | 155.9 |
O52—H52B···O60 | 0.96 | 1.86 | 2.767 (4) | 155.5 |
Symmetry codes: (i) −x+3, −y+1, −z+1; (ii) x−1, y, z. |
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 C═O 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.