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Acta Cryst. (2007). E63, m1437    [ doi:10.1107/S1600536807018399 ]

[meso-Tetrakis(4-pentyloxyphenyl)porphyrinato]silver(II)

Y.-J. Xu, X.-X. Yang, H. Cao and H.-B. Zhao

Abstract top

In the title compound, [Ag(C64H68N4O4)], the planar 24-membered porphyrin ring is located across on an inversion center; the four-coordinate AgII ion is located at the inversion center, with Ag-N distances of 2.0930 (13) and 2.1037 (13) Å. The 4-pentyloxyphenyl groups are twisted with respect to the porphyrin mean plane, the dihedral angles being 65.73 (9) and 58.42 (8)°.

Comment top

Porphyrins and their metal complexes are used as catalysts (Ostovic & Bruice, 1989), photosensitizers (Milgrom, 1984; Davila & Harriman, 1990) or useful synthetic precursors to mono-oxygenase and allosteric enzyme model systems (Tabushi & Kugimiya, 1986). In this paper, the structure of silver(II) meso-tetrakis[p-(pentyloxy)phenyl]porphyrinate is reported.

The title complex, (I), (Fig. 1) crystallizes in the centrosymmetric space group P 21/c. The porphyrin moiety is essentially planar, the macrocyclic core 24-menbered ring is planar with the mean deviation of 0.0428 Å. The four-coordinate AgII ion is located at its center with Ag—N distances of 2.0918 (18)–2.1024 (18) Å, from the surrounding pyrrole N atoms, which agrees with that found in a related compound (Scheidt et al., 1986).

The p-pentyloxyphenyl groups are rotated at angles of 65.73 (9)ånd 58.42 (8)° with respect to the porphyrin mean plane, due to steric hindrance with the pyrrole-H atoms of the macrocycle.

Related literature top

The corresponding silver(II) tetraphenylporphyrinate (Scheidt et al., 1986) crystallizes in the triclinic system with Ag—N distances of 2.082 (3) and 2.101 (3) Å, respectively.

For related literature, see: Davila & Harriman (1990); Milgrom (1984); Ostovic & Bruice (1989); Tabushi & Kugimiya (1986).

Experimental top

Single crystals were recrystallization from a chloroform solution at room temperature.

Refinement top

H atoms were placed in calculated positions with C—H = 0.95, 0.98 or 0.99 Å, and refined in riding mode, with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. A view of (I), with the atom-labeling scheme and 30% probability displacement ellipsoids.
meso-Tetrakis(4-pentyloxyphenyl)porphyrinato]silver(II) top
Crystal data top
[Ag(C64H68N4O4)]F(000) = 1118
Mr = 1065.09Dx = 1.293 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5101 reflections
a = 13.678 (2) Åθ = 2.3–26.0°
b = 16.164 (3) ŵ = 0.42 mm−1
c = 12.396 (2) ÅT = 187 K
β = 93.788 (2)°Block, purple
V = 2734.7 (8) Å30.36 × 0.30 × 0.12 mm
Z = 2
Data collection top
Bruker SMART APEX CCD
diffractometer		5226 independent reflections
Radiation source: fine-focus sealed tube4753 reflections with I > 2σ(I)
graphiteRint = 0.015
φ and ω' scansθmax = 25.9°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2002)		h = −16→16
Tmin = 0.864, Tmax = 0.952k = −17→19
14680 measured reflectionsl = −15→14
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)] = 0.027Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.075H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0429P)2 + 1.2689P]
where P = (Fo2 + 2Fc2)/3
5226 reflections(Δ/σ)max < 0.001
333 parametersΔρmax = 0.63 e Å−3
8 restraintsΔρmin = −0.34 e Å−3
Crystal data top
[Ag(C64H68N4O4)]V = 2734.7 (8) Å3
Mr = 1065.09Z = 2
Monoclinic, P21/cMo Kα radiation
a = 13.678 (2) ŵ = 0.42 mm−1
b = 16.164 (3) ÅT = 187 K
c = 12.396 (2) Å0.36 × 0.30 × 0.12 mm
β = 93.788 (2)°
Data collection top
Bruker SMART APEX CCD
diffractometer		5226 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2002)		4753 reflections with I > 2σ(I)
Tmin = 0.864, Tmax = 0.952Rint = 0.015
14680 measured reflectionsθmax = 25.9°
Refinement top
R[F2 > 2σ(F2)] = 0.027H-atom parameters constrained
wR(F2) = 0.075Δρmax = 0.63 e Å−3
S = 1.05Δρmin = −0.34 e Å−3
5226 reflectionsAbsolute structure: ?
333 parametersFlack parameter: ?
8 restraintsRogers parameter: ?
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ag0.00000.00000.50000.02183 (7)
N10.06302 (10)0.11126 (8)0.45039 (11)0.0244 (3)
N2−0.09288 (10)0.06840 (8)0.59370 (11)0.0254 (3)
O10.47339 (9)0.12144 (10)0.03853 (11)0.0449 (3)
O2−0.11905 (11)0.55140 (8)0.62631 (11)0.0423 (3)
C10.04189 (12)0.18952 (10)0.48553 (13)0.0249 (3)
C20.11104 (12)0.24725 (10)0.44355 (13)0.0281 (3)
H20.11350.30520.45590.034*
C30.17160 (12)0.20282 (10)0.38324 (14)0.0282 (3)
H30.22430.22430.34550.034*
C40.14163 (12)0.11674 (10)0.38650 (13)0.0253 (3)
C50.18590 (12)0.05000 (10)0.33525 (13)0.0255 (3)
C6−0.03328 (12)0.21064 (10)0.55457 (13)0.0249 (3)
C7−0.09475 (12)0.15377 (10)0.60421 (13)0.0253 (3)
C8−0.17030 (13)0.17448 (11)0.67589 (14)0.0307 (4)
H8−0.18860.22870.69640.037*
C9−0.21041 (13)0.10282 (11)0.70860 (14)0.0314 (4)
H9−0.26070.09770.75750.038*
C10−0.16286 (12)0.03542 (11)0.65556 (13)0.0258 (3)
C110.26491 (12)0.07098 (10)0.26084 (13)0.0269 (3)
C120.24079 (12)0.11307 (11)0.16326 (14)0.0306 (4)
H120.17530.13060.14660.037*
C130.31194 (13)0.12909 (12)0.09132 (14)0.0346 (4)
H130.29500.15770.02580.042*
C140.40901 (13)0.10309 (12)0.11521 (15)0.0338 (4)
C150.43462 (13)0.06145 (13)0.21173 (16)0.0398 (4)
H150.50020.04390.22810.048*
C160.36250 (13)0.04596 (12)0.28369 (15)0.0361 (4)
H160.37970.01790.34950.043*
C170.57623 (14)0.10189 (15)0.06331 (19)0.0498 (5)
H17A0.58610.04120.06450.060*
H17B0.59870.12450.13490.060*
C180.63274 (15)0.14100 (15)−0.02468 (19)0.0523 (6)
H18A0.60670.1198−0.09580.063*
H18B0.70230.1242−0.01450.063*
C190.62680 (16)0.23566 (15)−0.02539 (19)0.0521 (5)
H19A0.55760.2524−0.03990.062*
H19B0.64910.25660.04710.062*
C200.68808 (18)0.27573 (17)−0.1092 (2)0.0613 (6)
H20A0.75680.2568−0.09680.074*
H20B0.66370.2567−0.18200.074*
C210.6862 (2)0.36948 (19)−0.1068 (3)0.0800 (9)
H21A0.61860.3889−0.12080.120*
H21B0.72680.3912−0.16250.120*
H21C0.71180.3890−0.03560.120*
C22−0.05032 (12)0.30117 (10)0.57551 (13)0.0252 (3)
C23−0.04484 (13)0.33313 (10)0.68103 (14)0.0300 (4)
H23−0.02500.29780.73980.036*
C24−0.06782 (13)0.41569 (10)0.70177 (14)0.0320 (4)
H24−0.06380.43590.77390.038*
C25−0.07693 (12)0.35620 (10)0.49028 (13)0.0276 (3)
H25−0.07930.33660.41790.033*
C26−0.09982 (13)0.43843 (10)0.50961 (14)0.0307 (4)
H26−0.11760.47430.45080.037*
C27−0.09674 (13)0.46849 (11)0.61594 (14)0.0295 (4)
C28−0.14184 (16)0.58336 (12)0.73057 (16)0.0417 (5)
H28A−0.11820.64110.73840.050*
H28B−0.10810.54980.78860.050*
C29−0.25253 (17)0.58070 (15)0.74160 (18)0.0525 (5)
H29A−0.28640.61060.68020.063*
H29B−0.27520.52250.73900.063*
C30−0.27887 (19)0.61995 (19)0.8472 (2)0.0649 (7)
H30A−0.24280.59070.90770.078*
H30B−0.25620.67810.84840.078*
C31−0.3873 (2)0.6187 (2)0.8663 (3)0.0884 (10)
H31A−0.41000.56050.86380.106*
H31B−0.39590.63980.94000.106*
C32−0.4512 (3)0.6679 (3)0.7878 (3)0.0971 (15)
H32A−0.42800.72530.78720.100*
H32B−0.51880.66670.80950.100*
H32C−0.44880.64410.71530.100*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ag0.02553 (11)0.01700 (10)0.02370 (11)−0.00092 (6)0.00718 (7)0.00031 (5)
N10.0269 (7)0.0202 (7)0.0271 (7)−0.0011 (5)0.0084 (5)0.0004 (5)
N20.0284 (7)0.0189 (7)0.0297 (7)−0.0001 (5)0.0088 (6)0.0007 (5)
O10.0289 (7)0.0654 (10)0.0421 (7)−0.0003 (6)0.0146 (6)0.0123 (7)
O20.0686 (9)0.0216 (7)0.0375 (7)0.0085 (6)0.0104 (6)−0.0002 (5)
C10.0269 (8)0.0207 (8)0.0271 (8)−0.0010 (6)0.0029 (6)0.0000 (6)
C20.0310 (8)0.0206 (8)0.0330 (9)−0.0040 (7)0.0050 (7)0.0000 (6)
C30.0293 (8)0.0231 (8)0.0330 (9)−0.0053 (7)0.0075 (7)0.0023 (7)
C40.0269 (8)0.0232 (8)0.0261 (8)−0.0031 (6)0.0051 (6)0.0033 (6)
C50.0266 (8)0.0243 (8)0.0260 (8)−0.0007 (6)0.0053 (6)0.0023 (6)
C60.0283 (8)0.0205 (8)0.0259 (8)0.0009 (6)0.0025 (6)0.0004 (6)
C70.0287 (8)0.0206 (8)0.0269 (8)0.0018 (6)0.0049 (6)−0.0014 (6)
C80.0354 (9)0.0234 (8)0.0345 (9)0.0022 (7)0.0117 (7)−0.0032 (7)
C90.0351 (9)0.0267 (9)0.0340 (9)0.0004 (7)0.0133 (7)−0.0010 (7)
C100.0286 (8)0.0235 (8)0.0258 (8)−0.0003 (7)0.0064 (6)0.0014 (6)
C110.0290 (8)0.0231 (8)0.0295 (8)−0.0017 (6)0.0083 (7)−0.0010 (6)
C120.0256 (8)0.0331 (9)0.0337 (9)0.0014 (7)0.0068 (7)0.0029 (7)
C130.0322 (9)0.0410 (10)0.0313 (9)0.0000 (8)0.0068 (7)0.0086 (7)
C140.0286 (9)0.0383 (10)0.0357 (9)−0.0038 (7)0.0120 (7)0.0009 (8)
C150.0265 (9)0.0477 (12)0.0458 (11)0.0038 (8)0.0068 (8)0.0112 (9)
C160.0327 (9)0.0404 (11)0.0357 (9)0.0022 (8)0.0062 (7)0.0112 (8)
C170.0300 (10)0.0624 (14)0.0586 (13)0.0052 (9)0.0159 (9)0.0135 (11)
C180.0349 (10)0.0633 (15)0.0614 (14)0.0032 (10)0.0227 (10)0.0087 (11)
C190.0428 (11)0.0645 (15)0.0502 (12)−0.0031 (10)0.0126 (10)0.0013 (11)
C200.0505 (13)0.0733 (17)0.0611 (15)−0.0064 (12)0.0117 (11)0.0147 (13)
C210.088 (2)0.0692 (19)0.081 (2)−0.0140 (16)−0.0100 (16)0.0218 (16)
C220.0259 (8)0.0205 (8)0.0297 (8)−0.0024 (6)0.0053 (6)−0.0002 (6)
C230.0374 (9)0.0240 (8)0.0283 (8)0.0018 (7)0.0001 (7)0.0016 (7)
C240.0437 (10)0.0237 (8)0.0285 (9)0.0009 (7)0.0028 (7)−0.0028 (7)
C250.0323 (8)0.0254 (8)0.0257 (8)−0.0014 (7)0.0056 (6)−0.0004 (6)
C260.0382 (9)0.0238 (8)0.0303 (9)0.0025 (7)0.0043 (7)0.0052 (7)
C270.0338 (9)0.0195 (8)0.0356 (9)0.0016 (7)0.0049 (7)−0.0012 (7)
C280.0623 (13)0.0251 (9)0.0377 (10)0.0087 (9)0.0027 (9)−0.0051 (7)
C290.0605 (14)0.0525 (13)0.0444 (12)−0.0082 (11)0.0028 (10)−0.0059 (10)
C300.0603 (15)0.0806 (19)0.0541 (14)0.0028 (13)0.0062 (12)−0.0151 (13)
C310.0686 (19)0.082 (3)0.081 (2)−0.0031 (19)0.0154 (16)−0.024 (2)
C320.077 (2)0.086 (4)0.089 (3)0.028 (2)−0.012 (2)−0.056 (3)
Geometric parameters (Å, °) top
Ag—N22.0930 (13)C17—H17A0.9900
Ag—N2i2.0930 (13)C17—H17B0.9900
Ag—N12.1037 (13)C18—C191.532 (3)
Ag—N1i2.1037 (13)C18—H18A0.9900
N1—C11.375 (2)C18—H18B0.9900
N1—C41.380 (2)C19—C201.522 (3)
N2—C101.373 (2)C19—H19A0.9900
N2—C71.386 (2)C19—H19B0.9900
O1—C141.370 (2)C20—C211.516 (4)
O1—C171.455 (2)C20—H20A0.9900
O2—C271.382 (2)C20—H20B0.9900
O2—C281.445 (2)C21—H21A0.9800
C1—C61.422 (2)C21—H21B0.9800
C1—C21.450 (2)C21—H21C0.9800
C2—C31.357 (2)C22—C231.404 (2)
C2—H20.9500C22—C251.410 (2)
C3—C41.452 (2)C23—C241.399 (2)
C3—H30.9500C23—H230.9500
C4—C51.409 (2)C24—C271.400 (2)
C5—C10i1.422 (3)C24—H240.9500
C5—C111.505 (2)C25—C261.390 (2)
C6—C71.414 (2)C25—H250.9500
C6—C221.507 (2)C26—C271.403 (2)
C7—C81.446 (2)C26—H260.9500
C8—C91.355 (2)C28—C291.530 (3)
C8—H80.9500C28—H28A0.9900
C9—C101.449 (2)C28—H28B0.9900
C9—H90.9500C29—C301.519 (3)
C10—C5i1.422 (3)C29—H29A0.9900
C11—C161.406 (2)C29—H29B0.9900
C11—C121.408 (2)C30—C311.517 (4)
C12—C131.387 (2)C30—H30A0.9900
C12—H120.9500C30—H30B0.9900
C13—C141.405 (2)C31—C321.494 (5)
C13—H130.9500C31—H31A0.9900
C14—C151.397 (3)C31—H31B0.9900
C15—C161.396 (2)C32—H32A0.9800
C15—H150.9500C32—H32B0.9800
C16—H160.9500C32—H32C0.9800
C17—C181.516 (3)
N2—Ag—N2i180.0C19—C18—H18A109.0
N2—Ag—N189.20 (5)C17—C18—H18B109.0
N2i—Ag—N190.80 (5)C19—C18—H18B109.0
N2—Ag—N1i90.80 (5)H18A—C18—H18B107.8
N2i—Ag—N1i89.20 (5)C20—C19—C18113.43 (19)
N1—Ag—N1i180.00 (4)C20—C19—H19A108.9
C1—N1—C4108.11 (13)C18—C19—H19A108.9
C1—N1—Ag126.53 (11)C20—C19—H19B108.9
C4—N1—Ag124.93 (11)C18—C19—H19B108.9
C10—N2—C7108.43 (13)H19A—C19—H19B107.7
C10—N2—Ag125.16 (11)C21—C20—C19113.7 (2)
C7—N2—Ag126.41 (11)C21—C20—H20A108.8
C14—O1—C17117.60 (15)C19—C20—H20A108.8
C27—O2—C28119.46 (13)C21—C20—H20B108.8
N1—C1—C6125.95 (15)C19—C20—H20B108.8
N1—C1—C2108.83 (14)H20A—C20—H20B107.7
C6—C1—C2125.19 (15)C20—C21—H21A109.5
C3—C2—C1107.07 (15)C20—C21—H21B109.5
C3—C2—H2126.5H21A—C21—H21B109.5
C1—C2—H2126.5C20—C21—H21C109.5
C2—C3—C4107.94 (14)H21A—C21—H21C109.5
C2—C3—H3126.0H21B—C21—H21C109.5
C4—C3—H3126.0C23—C22—C25117.46 (15)
N1—C4—C5125.74 (15)C23—C22—C6121.23 (15)
N1—C4—C3108.04 (14)C25—C22—C6121.24 (14)
C5—C4—C3126.21 (15)C24—C23—C22121.57 (16)
C4—C5—C10i127.09 (15)C24—C23—H23119.2
C4—C5—C11116.82 (14)C22—C23—H23119.2
C10i—C5—C11116.08 (14)C23—C24—C27119.83 (16)
C7—C6—C1125.47 (15)C23—C24—H24120.1
C7—C6—C22116.94 (14)C27—C24—H24120.1
C1—C6—C22117.58 (14)C26—C25—C22121.60 (15)
N2—C7—C6126.22 (14)C26—C25—H25119.2
N2—C7—C8107.85 (14)C22—C25—H25119.2
C6—C7—C8125.92 (15)C25—C26—C27120.00 (16)
C9—C8—C7107.81 (15)C25—C26—H26120.0
C9—C8—H8126.1C27—C26—H26120.0
C7—C8—H8126.1O2—C27—C24124.98 (15)
C8—C9—C10107.71 (15)O2—C27—C26115.47 (15)
C8—C9—H9126.1C24—C27—C26119.48 (16)
C10—C9—H9126.1O2—C28—C29110.07 (17)
N2—C10—C5i126.01 (15)O2—C28—H28A109.6
N2—C10—C9108.17 (14)C29—C28—H28A109.6
C5i—C10—C9125.82 (14)O2—C28—H28B109.6
C16—C11—C12118.54 (15)C29—C28—H28B109.6
C16—C11—C5121.50 (15)H28A—C28—H28B108.2
C12—C11—C5119.89 (15)C30—C29—C28110.96 (19)
C13—C12—C11120.53 (16)C30—C29—H29A109.4
C13—C12—H12119.7C28—C29—H29A109.4
C11—C12—H12119.7C30—C29—H29B109.4
C12—C13—C14120.13 (16)C28—C29—H29B109.4
C12—C13—H13119.9H29A—C29—H29B108.0
C14—C13—H13119.9C31—C30—C29114.8 (2)
O1—C14—C15124.20 (16)C31—C30—H30A108.6
O1—C14—C13115.51 (16)C29—C30—H30A108.6
C15—C14—C13120.30 (16)C31—C30—H30B108.6
C16—C15—C14119.07 (16)C29—C30—H30B108.6
C16—C15—H15120.5H30A—C30—H30B107.6
C14—C15—H15120.5C32—C31—C30115.3 (3)
C15—C16—C11121.44 (16)C32—C31—H31A108.5
C15—C16—H16119.3C30—C31—H31A108.5
C11—C16—H16119.3C32—C31—H31B108.5
O1—C17—C18106.82 (17)C30—C31—H31B108.5
O1—C17—H17A110.4H31A—C31—H31B107.5
C18—C17—H17A110.4C31—C32—H32A109.5
O1—C17—H17B110.4C31—C32—H32B109.5
C18—C17—H17B110.4H32A—C32—H32B109.5
H17A—C17—H17B108.6C31—C32—H32C109.5
C17—C18—C19113.03 (19)H32A—C32—H32C109.5
C17—C18—H18A109.0H32B—C32—H32C109.5
Symmetry codes: (i) −x, −y, −z+1.
Acknowledgements top

This work is supported by National Analytical Research Center of Electrochemistry and Spectroscopy, Changchun Institute of Applied Chemistry, China.

references
References top

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