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Acta Crystallogr Sect E Struct Rep Online. 2008 December 1; 64(Pt 12): m1507–m1508.
Published online 2008 November 8. doi:  10.1107/S1600536808033709
PMCID: PMC2960028

(Croconato-κ2 O,O′)bis­(1,10-phenanthroline-κ2 N,N′)zinc(II)

Abstract

In the title compound, [Zn(C5O5)(C12H8N2)2], the Zn atom is in a slightly distorted octa­hedral environment. The mol­ecule lies across a twofold rotation axis, around which two 1,10-phenanthroline ligands are arranged. There are short contacts between the 1,10-phenanthroline groups and the O atoms of the croconate ligand, which probably stabilize the crystal structure via weak C—H(...)O interactions.

Related literature

For related literature, see: Braga et al. (2002 [triangle]); Carranza et al. (2004 [triangle]); Castro et al. (1992 [triangle], 2002 [triangle]); Chen et al. (2005 [triangle], 2007 [triangle], 2008 [triangle]); Faus et al. (1994 [triangle]); Maji et al. (2003 [triangle]); Seitz & Imming (1992 [triangle]); Sletten et al. (1998 [triangle]); Wang et al. (2002 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-m1507-scheme1.jpg

Experimental

Crystal data

  • [Zn(C5O5)(C12H8N2)2]
  • M r = 565.83
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-m1507-efi3.jpg
  • a = 12.2605 (4) Å
  • b = 11.0133 (3) Å
  • c = 17.2745 (5) Å
  • V = 2332.55 (12) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 1.11 mm−1
  • T = 293 (2) K
  • 0.28 × 0.23 × 0.15 mm

Data collection

  • Bruker APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (APEX2; Bruker, 2005 [triangle]) T min = 0.743, T max = 0.782 (expected range = 0.805–0.847)
  • 9769 measured reflections
  • 2627 independent reflections
  • 2164 reflections with I > 2σ(I)
  • R int = 0.019

Refinement

  • R[F 2 > 2σ(F 2)] = 0.029
  • wR(F 2) = 0.096
  • S = 1.28
  • 2627 reflections
  • 179 parameters
  • H-atom parameters constrained
  • Δρmax = 0.29 e Å−3
  • Δρmin = −0.32 e Å−3

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SIR97 (Altomare et al., 1999 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Table 1
Selected bond lengths (Å)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808033709/sg2254sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808033709/sg2254Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was supported by the National Natural Science Foundation of China (grant No. 50673054).

supplementary crystallographic information

Comment

The dianion of croconic acid(4,5-dihydroxycyclopent-4-ene-1,2,3-trione), (C5O5)2-, is one of the cyclic aromatic oxocarbons (CO)n2- characterized by extensive delocalization of the π electrons all over the ring (Seitz & Imming, 1992). Previous reports reveal that croconate is a polydent ligand(Chen et al., 2005, Maji et al., 2003, Wang et al., 2002, Sletten et al., 1998). According to the concept of 'molecular self-organization' and 'molecular engineering', transition metal croconates associated with another ligand such as terpyridine (Castro et al. 2002), bis((bis(2-pyridylcarbonyl) amido (Maji et al., 2003), 2,2'-bipyridine (Castro et al., 1992) or the tetrakis(2-pyridyl)pyrazine (Carranza et al. 2004) show interesting properties in magnetism, biochemistry, catalyst et al.

1,10-Phenanthroline(phen) is a well known neutral bidentate ligand. There have been considerable interests in the synthesis of open-framework phen-based metal complexes because of their interesting structure chemistry and potential applications(Faus et al. 1994). Recently, many research activities have focused on the synthesis of hybrid framework by incorporate organic ligand in the structure of phen-based complexes. Among the family of cyclic oxocarbons of the formula (CO)n2- [n=2–6 for oxalate, deltate, squarate, croconate and rhodizonate anions, respectively], the croconate moiety, (C5O5)2-, was found to be a good candidate and has been successfully incorporated into phen-based frameworks in our previous work, [M(phen)2(C5O5)] (M= Cu, Ni, Co, Mn) (Chen et al., 2005, 2007, 2008). Here, we report a new member of this family: [Zn(phen)2(C5O5)].

In the title structure, asymmetry unit contains a phen moiety and half a coroconte group coordinated with a zinc ion. The title compound lies across twofold rotation axes which passes through the Zn atom and bisects the croconate ligand, around which two phen ligand are arranged in a chiral propeller manner. A unit cell contains four [Zn(phen)2(C5O5)] molecules.

As a good π-conjugation system, the croconate dianion('free' ligand) in its simple salt has a plannar D5 h conformation with five almost identical C?O bonds and five almost identical C?C bonds, such as in Rb2C5O5 and Cs2C5O5 crystals (Braga et al., 2002). However, the coordinated ligand in title complex obvioulsy deviates from D5 h symmetry. The C?O bond involving coordinated O atoms is longer than that involving the uncoordinated O atoms. In the title complex, the C?O bond lengths are 1.229 (3) Å and 1.228 (4) Å for the uncoordinated O atoms and 1.277 (2) Å for the coordinated O atoms.

The molecuar conformation of [Zn(phen)2(C5O5)] is close to [Co(phen)2(C5O5)] and [Ni(phen)2(C5O5)] while different from [Cu(phen)2(C5O5)] and [Mn(phen)2(C5O5)]. The dihedral angle between the two phen planes for the title compound is 85.3 (1)° and the croconate and phen planes are also effectively perpendicular, with a dihedral angle of 87.7 (1)°. Compared with our previous reported result(Chen et al. 2005, 2007, 2008), the crystal growth method not only influence crystal packing motif, but also have effect on the moleular configuration. The crystal of [Zn(phen)2(C5O5)], [Co(phen)2(C5O5)] and [Ni(phen)2(C5O5)] are grown by hydrothermal method while the cyrstal of [Cu(phen)2(C5O5)] and [Mn(phen)2(C5O5)] are obtained by solvent evaporation under room temperature. Correspondingly, the crystal packing motif for crystal of Ni, Co, and Zn complexes are Pbcn, while it is C2/c for Cu and Mn complexes. As for the molecular configuration, the dihendral angles between the two phen planes for the complexes of Zn, Co, Ni are 87.7 (1)°, 85.7 (1)°, 86.0 (1)° which are almost perpendicular to each other, but they are 46.5 (1)° and 40.7 (1)° for Cu and Mn complexes.

According to the Jahn-teller effect theotry (if a d-orbital of a transiton metal ion is empty or full-filled and the other equivalent orbital is half full-filled, the coordinate enviorment of the transition metal ion will be distorted to form a more stable configuration), Cu2+ and Mn2+ have a strong tendency to Jahn-teller distortion while Zn2+ and Ni2+ are not. So, the local polyhedral MN4O2(M=Zn, Co, Ni) in their complexes are close to the octahedral while MN4O2(M=Mn, Cui) in their complexes are severely distorted from the octahedral. In the tiltle comound, the values of the angles subtended by the bidentate at zinc atom [77.37 (6)°] deviate significantly from the ideal vaue of 90° due to the small bite size of the five-memberbered plannar chelate rings.

As shown in Fig.2, the dipole moments of [Zn(phen)2(C5O5)] are arranged alternatively along +b and-b directions. There are short contacts between the phen groups and the O atoms of the croconate [e.g. C(6)—H(6)···O(1) (x, -y, -1/2 + z) and C(11)—H(11)···O(3)(-1/2 + x, -1/2 + y, 3/2 - z), which probably stablize the crystal structure.

Experimental

[K2(C5O5)](0.10 g) and Zn(CH3COO)2.2H2O (0.10 g) were dissolved in solvent of water 15 ml. The mixture was heated to 340–350 K under continuous stirring for 20 min. To the resulting yellow solution, an ethanol solution (10 ml) of 1,10-phenanthroline (0.1 mol/L) was added to cause an immediate precipation of yellow microcrystal. After the solutions were left to stand at room temperature for 30 minutes, they were collected by filter suction, washed with water. Then the obtained precipation and 15 ml water was placed in the teflon liner of an autoclave, which was sealed and heated to 433 K for 48 h, cooled at speed of 10 K/min, whereupon yellow block of [Zn(phen)2(C5O5)] were obtained.

Refinement

All H atoms were geometrically fixed and allowed to ride on their attached atoms, which C—H = 0.93 Å and Uiso(H)= 1.2 Ueq(C).

Figures

Fig. 1.
Molecular structure with thermal ellipsoids at 30% probability levels. [symmetry code: -x + 1/2, y, -z + 3/2]
Fig. 2.
A packing diagram of the title compound.

Crystal data

[Zn(C5O5)(C12H8N2)2]F000 = 1152
Mr = 565.83Dx = 1.611 Mg m3
Orthorhombic, PbcnMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2n 2abCell parameters from 3967 reflections
a = 12.2605 (4) Åθ = 2.8–27.5º
b = 11.0133 (3) ŵ = 1.11 mm1
c = 17.2745 (5) ÅT = 293 (2) K
V = 2332.55 (12) Å3Prism, yellow
Z = 40.28 × 0.23 × 0.15 mm

Data collection

Bruker APEXII CCD area-detector diffractometer2627 independent reflections
Radiation source: fine-focus sealed tube2164 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.019
Detector resolution: 10.0 pixels mm-1θmax = 27.6º
T = 295(2) Kθmin = 2.4º
[var phi] and ω scansh = −15→14
Absorption correction: multi-scan(APEX2; Bruker, 2005)k = −14→13
Tmin = 0.743, Tmax = 0.782l = −21→21
9769 measured reflections

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.029  w = 1/[σ2(Fo2) + (0.0414P)2 + 0.6435P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.096(Δ/σ)max < 0.001
S = 1.28Δρmax = 0.29 e Å3
2627 reflectionsΔρmin = −0.32 e Å3
179 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0037 (5)
Secondary atom site location: difference Fourier map

Special details

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)

xyzUiso*/Ueq
C11.14583 (16)−0.08987 (18)0.66696 (12)0.0370 (4)
H11.1977−0.07250.70470.044*
C21.17077 (19)−0.1768 (2)0.61125 (13)0.0442 (5)
H21.2374−0.21710.61230.053*
C31.09642 (18)−0.20164 (18)0.55543 (12)0.0411 (5)
H31.1121−0.25980.51800.049*
C40.99594 (16)−0.14043 (18)0.55356 (12)0.0346 (4)
C50.97663 (15)−0.05585 (16)0.61341 (10)0.0284 (4)
C60.91524 (18)−0.15647 (19)0.49514 (12)0.0406 (5)
H60.9282−0.21100.45510.049*
C70.82034 (19)−0.09419 (19)0.49667 (13)0.0434 (5)
H70.7700−0.10510.45700.052*
C80.79598 (16)−0.01181 (19)0.55831 (11)0.0371 (4)
C90.87469 (15)0.00774 (16)0.61615 (11)0.0305 (4)
C100.69824 (18)0.0534 (2)0.56380 (14)0.0503 (6)
H100.64430.04380.52640.060*
C110.68264 (19)0.1309 (2)0.62399 (15)0.0535 (6)
H110.61770.17400.62810.064*
C120.76426 (18)0.1457 (2)0.67964 (13)0.0460 (5)
H120.75220.19850.72080.055*
C130.96697 (16)0.35065 (18)0.78378 (11)0.0334 (4)
C140.94811 (17)0.47521 (18)0.80990 (13)0.0409 (5)
C151.00000.5549 (3)0.75000.0419 (7)
N11.05186 (12)−0.03074 (13)0.66885 (9)0.0290 (3)
N20.85892 (13)0.08653 (15)0.67547 (9)0.0352 (4)
O10.93325 (12)0.25245 (13)0.81491 (8)0.0415 (3)
O20.89952 (16)0.50881 (16)0.86832 (11)0.0659 (5)
O31.00000.6664 (2)0.75000.0560 (7)
Zn11.00000.10546 (3)0.75000.03197 (13)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0350 (10)0.0405 (11)0.0355 (11)0.0036 (8)−0.0035 (8)0.0000 (8)
C20.0441 (11)0.0421 (11)0.0465 (13)0.0118 (9)0.0055 (10)−0.0014 (9)
C30.0551 (13)0.0326 (10)0.0356 (11)0.0030 (9)0.0093 (9)−0.0061 (9)
C40.0457 (11)0.0278 (8)0.0302 (10)−0.0086 (8)0.0057 (8)−0.0008 (8)
C50.0348 (9)0.0270 (9)0.0235 (9)−0.0044 (7)−0.0003 (7)0.0029 (7)
C60.0579 (13)0.0387 (11)0.0253 (10)−0.0166 (10)−0.0015 (9)−0.0029 (8)
C70.0504 (12)0.0458 (12)0.0340 (12)−0.0204 (10)−0.0078 (9)0.0041 (9)
C80.0347 (9)0.0427 (11)0.0340 (11)−0.0090 (8)−0.0040 (8)0.0107 (8)
C90.0325 (9)0.0317 (9)0.0275 (10)−0.0034 (7)0.0032 (7)0.0062 (7)
C100.0369 (11)0.0632 (15)0.0507 (14)−0.0041 (10)−0.0093 (10)0.0208 (12)
C110.0378 (11)0.0656 (15)0.0572 (15)0.0163 (11)0.0031 (10)0.0239 (13)
C120.0486 (12)0.0514 (13)0.0380 (12)0.0166 (10)0.0035 (9)0.0067 (10)
C130.0377 (9)0.0342 (10)0.0283 (10)−0.0010 (8)0.0009 (8)−0.0019 (8)
C140.0403 (11)0.0357 (10)0.0468 (13)0.0004 (9)0.0011 (9)−0.0078 (9)
C150.0364 (14)0.0334 (15)0.056 (2)0.000−0.0102 (13)0.000
N10.0323 (8)0.0298 (8)0.0250 (8)0.0014 (6)0.0021 (6)0.0004 (6)
N20.0361 (8)0.0388 (9)0.0307 (9)0.0075 (7)0.0039 (7)0.0040 (7)
O10.0567 (9)0.0360 (7)0.0320 (8)−0.0025 (6)0.0138 (6)0.0001 (6)
O20.0795 (12)0.0528 (10)0.0653 (12)−0.0019 (9)0.0307 (10)−0.0207 (9)
O30.0662 (16)0.0286 (11)0.0731 (18)0.000−0.0109 (12)0.000
Zn10.0409 (2)0.03008 (19)0.0249 (2)0.0000.00062 (12)0.000

Geometric parameters (Å, °)

C1—N11.324 (2)C10—H100.9300
C1—C21.391 (3)C11—C121.397 (3)
C1—H10.9300C11—H110.9300
C2—C31.355 (3)C12—N21.333 (3)
C2—H20.9300C12—H120.9300
C3—C41.405 (3)C13—O11.277 (2)
C3—H30.9300C13—C13i1.420 (4)
C4—C51.412 (3)C13—C141.462 (3)
C4—C61.424 (3)C14—O21.229 (3)
C5—N11.358 (2)C14—C151.498 (3)
C5—C91.433 (3)C15—O31.229 (4)
C6—C71.351 (3)C15—C14i1.498 (3)
C6—H60.9300N1—Zn12.1493 (15)
C7—C81.430 (3)N2—Zn12.1664 (17)
C7—H70.9300O1—Zn12.1325 (14)
C8—C101.400 (3)Zn1—O1i2.1325 (14)
C8—C91.406 (3)Zn1—N1i2.1493 (15)
C9—N21.357 (2)Zn1—N2i2.1664 (17)
C10—C111.359 (4)
N1—C1—C2123.14 (19)N2—C12—H12119.0
N1—C1—H1118.4C11—C12—H12119.0
C2—C1—H1118.4O1—C13—C13i122.05 (11)
C3—C2—C1118.91 (19)O1—C13—C14127.84 (18)
C3—C2—H2120.5C13i—C13—C14110.10 (12)
C1—C2—H2120.5O2—C14—C13127.8 (2)
C2—C3—C4120.63 (19)O2—C14—C15126.6 (2)
C2—C3—H3119.7C13—C14—C15105.61 (19)
C4—C3—H3119.7O3—C15—C14i125.84 (13)
C3—C4—C5116.54 (18)O3—C15—C14125.84 (13)
C3—C4—C6124.48 (19)C14i—C15—C14108.3 (3)
C5—C4—C6118.96 (18)C1—N1—C5118.26 (17)
N1—C5—C4122.48 (17)C1—N1—Zn1128.09 (13)
N1—C5—C9118.00 (17)C5—N1—Zn1113.65 (12)
C4—C5—C9119.52 (17)C12—N2—C9118.54 (18)
C7—C6—C4121.43 (19)C12—N2—Zn1128.01 (15)
C7—C6—H6119.3C9—N2—Zn1113.37 (12)
C4—C6—H6119.3C13—O1—Zn1107.30 (12)
C6—C7—C8121.09 (19)O1—Zn1—O1i81.23 (7)
C6—C7—H7119.5O1—Zn1—N1170.49 (6)
C8—C7—H7119.5O1i—Zn1—N194.20 (5)
C10—C8—C9117.4 (2)O1—Zn1—N1i94.20 (5)
C10—C8—C7123.7 (2)O1i—Zn1—N1i170.49 (6)
C9—C8—C7118.88 (19)N1—Zn1—N1i91.48 (8)
N2—C9—C8122.48 (18)O1—Zn1—N294.54 (6)
N2—C9—C5117.50 (17)O1i—Zn1—N293.84 (6)
C8—C9—C5120.02 (18)N1—Zn1—N277.37 (6)
C11—C10—C8119.6 (2)N1i—Zn1—N294.83 (6)
C11—C10—H10120.2O1—Zn1—N2i93.84 (6)
C8—C10—H10120.2O1i—Zn1—N2i94.54 (6)
C10—C11—C12119.9 (2)N1—Zn1—N2i94.83 (6)
C10—C11—H11120.0N1i—Zn1—N2i77.37 (6)
C12—C11—H11120.0N2—Zn1—N2i168.95 (9)
N2—C12—C11121.9 (2)

Symmetry codes: (i) −x+2, y, −z+3/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C6—H6···O1ii0.932.473.295 (2)149
C11—H11···O3iii0.932.553.147 (2)122

Symmetry codes: (ii) x, −y, z−1/2; (iii) x−1/2, y−1/2, −z+3/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SG2254).

References

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