supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers buy article online

Acta Cryst. (2007). E63, m2940    [ doi:10.1107/S1600536807054852 ]

Di-[mu]2-acetato-1:2[kappa]3O,O':O;2:3[kappa]3O:O,O'-tetrakis([mu]2-2-hydroxybenzoato)-1:2[kappa]4O:O';2:3[kappa]4O:O'-bis(1,10-phenanthroline)-1[kappa]2N,N';3[kappa]2N,N'-trizinc(II)

J.-H. Cai, Y.-H. Xu and S. W. Ng

Abstract top

The centrosymmetric trinuclear title compound, [Zn3(C2H3O2)2(C7H5O3)4(C12H8N2)2], has six carboxylate groups each bridging two metal centers. The Zn atom on a center of inversion is coordinated by six O atoms in an octahedral environment. The other Zn atoms are each chelated by the N-heterocycle, and their coordination number is also six as the acetate group also functions as a chelating group. The hydroxy group of one of the two symmetry-independent salicylate groups is disordered over two positions in a 2:1 ratio.

Comment top

The 2,2'-bipyridine adduct of zinc disalicylate exists in two form, a monomeric form (Lemoine et al., 2004) and a cyclotetrameric form (Wang et al., 2004). The attempt to synthesize the 1,10-phenanthroline analog gave the trinuclear compound in which part of the acetate entity that was present as the counterion is incorporated. The centrosymmetric trinuclear compound has six carboxylate groups each bridging two metal centers. The zinc atom on a center-of-inversion is coordinated to six oxygen atoms in an octahedral environment. The other zinc atoms are each chelated by the N-heterocycle, but their coordination number is six as the acetate group that is engaged in bridging also functions as a chelating group (Fig. 1).

Related literature top

For the structure of the diaquazinc derivative of salicylic acid, see Klug et al. (1958). The monomeric 2,2'-bipyridine adduct is reported by Lemoine et al. (2004) and the cyclic tetramer by Wang et al. (2004)

Experimental top

A solution of salicylic acid (1.0 mmol, 0.138 g) and sodium hydroxde (1.0 mmol, 0.040 g) in methanol (8 ml) was added to a solution of zinc acetate (1.0 mmol, 0.183 g) in methanol (8 ml). 1,10-Phenanthroline (1.0 mmol, 0.180 g), dissolved in methanol (5 ml), was then added. The mixture was placed in a 25-ml Teflon-lined stainless-steel Parr bomb. The bomb was heated at 363 K for five days. Colorless prismatic crystals were collected manually from the cool solution.

Refinement top

The hydroxy group of one of the two salicylate groups is disordered over two positions. The phenylene ring was refined as a rigid hexagon of 1.39 Å sides, and the hydroxy group was placed on both ortho-positions, subject to the two C–O distances being within 0.01 Å of each other. These were restrained to be nearly coplanar with the ring.

Carbon-hydrogen atoms were placed in calculated positions (C—H 0.93 Å), and were included in the refinement in the riding model approximation, with their temperature factors set to 1.2 times the Ueq of the parent atoms.

Computing details top

Data collection: SMART (Bruker, 2003); 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: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures top
[Figure 1] Fig. 1. Thermal displacement ellipsoid plot (50% probability) showing the numbering scheme. Hydrogen atoms are drawn as spheres of arbitrary radii; the minor disorder component is not shown.
Di-µ2-acetato-1:2κ3O,O':O;2:3κ3O:O,O'-tetrakis(µ2-2- hydroxybenzoato)-1:2κ4O:O';2:3κ4O:O'-bis(1,10-phenanthroline)- 1κ2N,N';3κ2N,N'-trizinc(II) top
Crystal data top
[Zn3(C2H3O2)2(C7H5O3)4(C12H8N2)2]F(000) = 1248
Mr = 1223.05Dx = 1.608 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 873 reflections
a = 10.534 (3) Åθ = 2.6–27.3°
b = 11.682 (3) ŵ = 1.49 mm−1
c = 20.533 (5) ÅT = 293 K
β = 91.847 (3)°Prism, colorless
V = 2526 (1) Å30.20 × 0.16 × 0.15 mm
Z = 2
Data collection top
Bruker SMART
diffractometer		5515 independent reflections
Radiation source: fine-focus sealed tube4428 reflections with I > 2σ(I)
graphiteRint = 0.027
φ and ω scansθmax = 27.1°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −9→13
Tmin = 0.524, Tmax = 0.807k = −13→15
14442 measured reflectionsl = −22→26
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)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109H-atom parameters constrained
S = 0.87 w = 1/[σ2(Fo2) + (0.0711P)2 + 2.1051P]
where P = (Fo2 + 2Fc2)/3
5515 reflections(Δ/σ)max = 0.001
369 parametersΔρmax = 0.65 e Å−3
6 restraintsΔρmin = −0.66 e Å−3
Crystal data top
[Zn3(C2H3O2)2(C7H5O3)4(C12H8N2)2]V = 2526 (1) Å3
Mr = 1223.05Z = 2
Monoclinic, P21/nMo Kα radiation
a = 10.534 (3) ŵ = 1.49 mm−1
b = 11.682 (3) ÅT = 293 K
c = 20.533 (5) Å0.20 × 0.16 × 0.15 mm
β = 91.847 (3)°
Data collection top
Bruker SMART
diffractometer		5515 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		4428 reflections with I > 2σ(I)
Tmin = 0.524, Tmax = 0.807Rint = 0.027
14442 measured reflectionsθmax = 27.1°
Refinement top
R[F2 > 2σ(F2)] = 0.038H-atom parameters constrained
wR(F2) = 0.109Δρmax = 0.65 e Å−3
S = 0.87Δρmin = −0.66 e Å−3
5515 reflectionsAbsolute structure: ?
369 parametersFlack parameter: ?
6 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Zn10.50000.50000.50000.03664 (12)
Zn20.66125 (3)0.24138 (2)0.481223 (14)0.03545 (10)
O10.4523 (2)0.42396 (19)0.41149 (10)0.0558 (5)
O20.52731 (19)0.24531 (17)0.40656 (10)0.0469 (5)
O30.4709 (3)0.1262 (3)0.30547 (17)0.0597 (11)0.678 (6)
H3O0.51320.13180.33950.072*0.678 (6)
O3'0.3022 (7)0.4892 (6)0.3252 (4)0.129 (6)0.322 (6)
H3'0.34240.49920.35960.155*0.322 (6)
O40.4271 (2)0.36795 (18)0.55363 (12)0.0564 (6)
O50.54382 (19)0.20916 (17)0.55701 (10)0.0449 (5)
O60.2546 (3)0.4024 (2)0.63370 (17)0.0939 (11)
H6O0.19610.43940.64860.113*
O70.68027 (17)0.41700 (17)0.49590 (10)0.0436 (4)
O80.8313 (2)0.3264 (2)0.54866 (12)0.0654 (6)
N10.8123 (2)0.23767 (18)0.41080 (11)0.0383 (5)
N20.7265 (2)0.06882 (19)0.48697 (11)0.0387 (5)
C10.4616 (2)0.3288 (2)0.38461 (13)0.0402 (6)
C20.3911 (2)0.3120 (3)0.32077 (13)0.0410 (6)
C30.3126 (3)0.3986 (3)0.29541 (15)0.0538 (8)
H30.30660.46740.31790.065*0.322 (6)
C40.2437 (3)0.3843 (4)0.23748 (17)0.0643 (9)
H40.18950.44180.22220.077*
C50.2556 (3)0.2851 (4)0.20281 (17)0.0654 (10)
H50.21050.27590.16350.078*
C60.3336 (4)0.1993 (4)0.22567 (17)0.0666 (10)
H60.34300.13310.20110.080*
C70.3996 (3)0.2101 (3)0.28591 (16)0.0519 (7)
H70.44860.14990.30240.062*0.678 (6)
C80.4555 (3)0.2705 (2)0.57659 (13)0.0382 (6)
C90.3734 (3)0.2265 (2)0.62912 (13)0.0415 (6)
C100.2767 (3)0.2940 (3)0.65424 (17)0.0570 (8)
C110.1974 (4)0.2487 (4)0.7010 (2)0.0700 (10)
H110.13360.29360.71800.084*
C120.2137 (4)0.1386 (4)0.72163 (18)0.0705 (11)
H120.16000.10900.75250.085*
C130.3079 (4)0.0706 (3)0.69766 (17)0.0648 (9)
H130.3177−0.00460.71180.078*
C140.3882 (3)0.1158 (3)0.65202 (15)0.0504 (7)
H140.45340.07080.63650.060*
C150.7842 (3)0.4174 (3)0.53085 (14)0.0437 (6)
C160.8460 (3)0.5300 (3)0.5450 (2)0.0737 (11)
H16A0.91480.51960.57620.110*
H16B0.78490.58180.56230.110*
H16C0.87820.56120.50550.110*
C170.8725 (2)0.1351 (2)0.40841 (13)0.0381 (6)
C180.8542 (3)0.3217 (3)0.37389 (15)0.0494 (7)
H180.81330.39210.37500.059*
C190.9572 (3)0.3090 (3)0.33339 (16)0.0584 (8)
H190.98470.37050.30880.070*
C201.0167 (3)0.2069 (3)0.33018 (17)0.0587 (8)
H201.08470.19740.30290.070*
C210.9755 (3)0.1147 (3)0.36844 (15)0.0468 (7)
C221.0342 (3)0.0040 (3)0.36999 (18)0.0603 (9)
H221.1030−0.00970.34380.072*
C230.9925 (3)−0.0803 (3)0.40818 (18)0.0567 (8)
H231.0324−0.15130.40780.068*
C240.8880 (3)−0.0626 (2)0.44929 (15)0.0466 (7)
C250.8397 (3)−0.1471 (3)0.49062 (18)0.0560 (8)
H250.8769−0.21920.49250.067*
C260.7391 (3)−0.1231 (3)0.52754 (19)0.0581 (8)
H260.7064−0.17900.55460.070*
C270.6841 (3)−0.0141 (3)0.52503 (16)0.0492 (7)
H270.61530.00100.55100.059*
C280.8269 (2)0.0453 (2)0.44954 (13)0.0380 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0366 (2)0.0344 (2)0.0390 (2)0.00356 (17)0.00383 (17)−0.00187 (16)
Zn20.03094 (17)0.03523 (17)0.04044 (18)0.00558 (11)0.00519 (12)−0.00037 (12)
O10.0630 (14)0.0581 (13)0.0454 (11)0.0113 (11)−0.0103 (10)−0.0113 (10)
O20.0380 (10)0.0533 (12)0.0489 (11)0.0051 (9)−0.0029 (9)−0.0045 (9)
O30.070 (2)0.0418 (18)0.066 (2)0.0129 (15)−0.0090 (17)−0.0103 (15)
O3'0.197 (14)0.058 (6)0.126 (10)0.027 (7)−0.093 (9)−0.004 (5)
O40.0528 (13)0.0425 (11)0.0755 (15)0.0102 (9)0.0252 (11)0.0150 (10)
O50.0420 (11)0.0445 (10)0.0490 (11)0.0098 (9)0.0151 (9)0.0066 (9)
O60.091 (2)0.0586 (16)0.136 (3)0.0258 (15)0.064 (2)0.0017 (16)
O70.0328 (9)0.0445 (10)0.0535 (11)0.0034 (8)0.0017 (8)−0.0069 (9)
O80.0687 (16)0.0620 (15)0.0647 (15)0.0163 (12)−0.0107 (12)0.0029 (12)
N10.0340 (11)0.0385 (11)0.0425 (12)0.0029 (9)0.0054 (9)−0.0004 (9)
N20.0295 (11)0.0382 (11)0.0485 (13)0.0000 (9)0.0031 (9)−0.0008 (10)
C10.0317 (13)0.0522 (16)0.0368 (13)−0.0007 (11)0.0050 (10)0.0010 (12)
C20.0333 (13)0.0541 (16)0.0360 (13)−0.0066 (12)0.0057 (11)−0.0014 (12)
C30.0505 (18)0.066 (2)0.0440 (16)−0.0023 (15)−0.0028 (14)0.0100 (15)
C40.0525 (19)0.091 (3)0.0493 (18)−0.0137 (18)−0.0038 (15)0.0202 (18)
C50.052 (2)0.099 (3)0.0448 (17)−0.023 (2)0.0001 (15)0.0067 (18)
C60.064 (2)0.080 (2)0.056 (2)−0.021 (2)0.0080 (17)−0.0212 (18)
C70.0437 (16)0.0589 (18)0.0535 (18)−0.0064 (14)0.0071 (14)−0.0056 (14)
C80.0337 (13)0.0402 (14)0.0409 (14)0.0000 (11)0.0046 (11)−0.0002 (11)
C90.0377 (14)0.0491 (15)0.0379 (14)−0.0026 (12)0.0056 (11)−0.0011 (11)
C100.0523 (19)0.0594 (19)0.0605 (19)0.0004 (15)0.0206 (15)−0.0074 (16)
C110.057 (2)0.088 (3)0.067 (2)−0.0026 (18)0.0285 (18)−0.0063 (19)
C120.059 (2)0.102 (3)0.051 (2)−0.019 (2)0.0160 (16)0.0064 (19)
C130.064 (2)0.073 (2)0.058 (2)−0.0118 (18)0.0048 (17)0.0216 (17)
C140.0454 (16)0.0560 (18)0.0499 (17)0.0018 (14)0.0045 (13)0.0088 (14)
C150.0356 (14)0.0475 (16)0.0483 (16)0.0001 (12)0.0071 (12)−0.0066 (12)
C160.051 (2)0.066 (2)0.105 (3)−0.0151 (17)0.009 (2)−0.028 (2)
C170.0296 (12)0.0433 (14)0.0415 (14)0.0036 (10)0.0022 (10)−0.0070 (11)
C180.0488 (17)0.0483 (16)0.0514 (17)0.0019 (13)0.0065 (13)0.0045 (13)
C190.0503 (18)0.069 (2)0.0561 (19)−0.0085 (16)0.0112 (15)0.0123 (16)
C200.0429 (17)0.078 (2)0.0565 (19)0.0025 (16)0.0166 (14)−0.0009 (17)
C210.0332 (14)0.0600 (18)0.0475 (16)0.0049 (12)0.0073 (12)−0.0122 (13)
C220.0428 (17)0.070 (2)0.069 (2)0.0168 (15)0.0123 (15)−0.0173 (17)
C230.0453 (17)0.0496 (17)0.075 (2)0.0146 (14)0.0012 (15)−0.0216 (16)
C240.0371 (14)0.0393 (14)0.0628 (18)0.0056 (11)−0.0061 (13)−0.0117 (13)
C250.0543 (19)0.0330 (14)0.080 (2)0.0044 (13)−0.0091 (16)−0.0025 (14)
C260.0549 (19)0.0410 (16)0.078 (2)−0.0074 (14)0.0013 (17)0.0116 (15)
C270.0370 (15)0.0475 (16)0.0635 (19)−0.0033 (12)0.0082 (13)0.0048 (14)
C280.0293 (12)0.0387 (13)0.0457 (14)0.0031 (10)−0.0012 (11)−0.0063 (11)
Geometric parameters (Å, °) top
Zn1—O42.058 (2)C6—H60.9300
Zn1—O4i2.058 (2)C7—H70.9300
Zn1—O1i2.070 (2)C8—C91.496 (4)
Zn1—O12.070 (2)C9—C141.382 (4)
Zn1—O7i2.1362 (19)C9—C101.400 (4)
Zn1—O72.1362 (19)C10—C111.396 (5)
Zn2—O22.050 (2)C11—C121.363 (6)
Zn2—O52.0537 (19)C11—H110.9300
Zn2—O72.082 (2)C12—C131.375 (6)
Zn2—N22.132 (2)C12—H120.9300
Zn2—N12.185 (2)C13—C141.387 (4)
Zn2—O82.440 (3)C13—H130.9300
O1—C11.246 (3)C14—H140.9300
O2—C11.270 (3)C15—C161.492 (4)
O3—C71.291 (4)C16—H16A0.9600
O3—H3O0.8200C16—H16B0.9600
O3'—C31.228 (8)C16—H16C0.9600
O3'—H3'0.8200C17—C211.401 (4)
O4—C81.265 (3)C17—C281.439 (4)
O5—C81.250 (3)C18—C191.396 (4)
O6—C101.353 (4)C18—H180.9300
O6—H6O0.8200C19—C201.350 (5)
O7—C151.290 (3)C19—H190.9300
O8—C151.224 (4)C20—C211.410 (5)
N1—C181.324 (4)C20—H200.9300
N1—C171.357 (3)C21—C221.433 (4)
N2—C271.331 (4)C22—C231.342 (5)
N2—C281.356 (3)C22—H220.9300
C1—C21.499 (4)C23—C241.424 (4)
C2—C71.393 (4)C23—H230.9300
C2—C31.397 (4)C24—C251.407 (5)
C3—C41.384 (5)C24—C281.415 (4)
C3—H30.9300C25—C261.352 (5)
C4—C51.368 (6)C25—H250.9300
C4—H40.9300C26—C271.399 (4)
C5—C61.370 (6)C26—H260.9300
C5—H50.9300C27—H270.9300
C6—C71.405 (5)
O4—Zn1—O4i180.00 (8)C2—C7—C6119.4 (3)
O4—Zn1—O1i86.34 (10)C2—C7—H7120.3
O4i—Zn1—O1i93.66 (10)C6—C7—H7120.3
O4—Zn1—O193.66 (10)O5—C8—O4124.4 (3)
O4i—Zn1—O186.34 (10)O5—C8—C9119.2 (2)
O1i—Zn1—O1180.0O4—C8—C9116.3 (2)
O4—Zn1—O7i88.39 (8)C14—C9—C10118.5 (3)
O4i—Zn1—O7i91.61 (8)C14—C9—C8120.4 (3)
O1i—Zn1—O7i87.79 (8)C10—C9—C8121.1 (3)
O1—Zn1—O7i92.21 (8)O6—C10—C11118.0 (3)
O4—Zn1—O791.61 (8)O6—C10—C9122.2 (3)
O4i—Zn1—O788.39 (8)C11—C10—C9119.9 (3)
O1i—Zn1—O792.21 (8)C12—C11—C10120.0 (4)
O1—Zn1—O787.79 (8)C12—C11—H11120.0
O7i—Zn1—O7180.0C10—C11—H11120.0
O2—Zn2—O598.85 (9)C11—C12—C13121.2 (3)
O2—Zn2—O798.44 (8)C11—C12—H12119.4
O5—Zn2—O797.38 (8)C13—C12—H12119.4
O2—Zn2—N2105.98 (8)C12—C13—C14119.0 (4)
O5—Zn2—N289.18 (8)C12—C13—H13120.5
O7—Zn2—N2153.43 (8)C14—C13—H13120.5
O2—Zn2—N190.23 (9)C9—C14—C13121.4 (3)
O5—Zn2—N1165.29 (8)C9—C14—H14119.3
O7—Zn2—N192.67 (8)C13—C14—H14119.3
N2—Zn2—N177.15 (8)O8—C15—O7119.4 (3)
O2—Zn2—O8152.90 (8)O8—C15—C16122.5 (3)
O5—Zn2—O895.38 (9)O7—C15—C16118.0 (3)
O7—Zn2—O856.72 (8)C15—C16—H16A109.5
N2—Zn2—O897.13 (8)C15—C16—H16B109.5
N1—Zn2—O881.17 (9)H16A—C16—H16B109.5
C1—O1—Zn1138.7 (2)C15—C16—H16C109.5
C1—O2—Zn2129.52 (18)H16A—C16—H16C109.5
C7—O3—H3O120.0H16B—C16—H16C109.5
C3—O3'—H3'120.0N1—C17—C21122.9 (3)
C8—O4—Zn1141.86 (19)N1—C17—C28117.2 (2)
C8—O5—Zn2127.65 (18)C21—C17—C28119.9 (3)
C10—O6—H6O120.0N1—C18—C19122.8 (3)
C15—O7—Zn299.21 (17)N1—C18—H18118.6
C15—O7—Zn1135.74 (18)C19—C18—H18118.6
Zn2—O7—Zn1111.80 (9)C20—C19—C18119.6 (3)
C15—O8—Zn284.32 (18)C20—C19—H19120.2
C18—N1—C17118.0 (2)C18—C19—H19120.2
C18—N1—Zn2128.86 (19)C19—C20—C21119.7 (3)
C17—N1—Zn2113.11 (17)C19—C20—H20120.1
C27—N2—C28117.9 (2)C21—C20—H20120.1
C27—N2—Zn2127.40 (19)C17—C21—C20117.0 (3)
C28—N2—Zn2114.59 (17)C17—C21—C22118.8 (3)
O1—C1—O2125.3 (3)C20—C21—C22124.1 (3)
O1—C1—C2117.4 (3)C23—C22—C21121.7 (3)
O2—C1—C2117.3 (2)C23—C22—H22119.1
C7—C2—C3118.3 (3)C21—C22—H22119.1
C7—C2—C1121.6 (3)C22—C23—C24120.9 (3)
C3—C2—C1120.1 (3)C22—C23—H23119.6
O3'—C3—C4118.6 (6)C24—C23—H23119.6
O3'—C3—C2120.0 (5)C25—C24—C28116.7 (3)
C4—C3—C2121.4 (3)C25—C24—C23123.8 (3)
C4—C3—H3119.3C28—C24—C23119.5 (3)
C2—C3—H3119.3C26—C25—C24119.9 (3)
C5—C4—C3119.7 (4)C26—C25—H25120.1
C5—C4—H4120.2C24—C25—H25120.1
C3—C4—H4120.2C25—C26—C27119.9 (3)
C4—C5—C6120.4 (3)C25—C26—H26120.0
C4—C5—H5119.8C27—C26—H26120.0
C6—C5—H5119.8N2—C27—C26122.5 (3)
C5—C6—C7120.7 (4)N2—C27—H27118.7
C5—C6—H6119.7C26—C27—H27118.7
C7—C6—H6119.7N2—C28—C24123.1 (3)
O3—C7—C2122.4 (3)N2—C28—C17117.8 (2)
O3—C7—C6118.1 (3)C24—C28—C17119.1 (2)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Acknowledgements top

We are grateful to the Ministry of Education Foundation of the Guangxi Zhuang Autonomous Region for funding this study. We thank Hechi University and the University of Malaya for supporting this study.

references
References top

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Bruker (2003). SMART (Version 5.625A) and SAINT (Version 6.02A). Bruker AXS Inc., Madison, Wisconsin, USA.

Klug, H. P., Alexander, L. E. & Sumner, G. G. (1958). Acta Cryst. 11, 41–46.

Lemoine, P., Bendada, K. & Viossat, B. (2004). Acta Cryst. C60, m489–m491.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Wang, Y., Odoko, M. & Okabe, N. (2004). Acta Cryst. C60, m479–m481.

Westrip, S. P. (2007). PublCIF. In preparation.