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Acta Cryst. (2007). E63, m2388    [ doi:10.1107/S1600536807040123 ]

Bis{N-[(1Z,3Z)-1,3-bis(4-fluorophenyl)-3-(phenylimino)prop-1-enyl]aniline(1-)}zinc(II)

Y.-L. Peng, M.-L. Hsueh and C.-C. Lin

Abstract top

In the title complex, [Zn(C27H19F2N2)2], a twofold rotation axis passes through the Zn atom, which is tetrahedrally coordinated by four N atoms from two diketiminate ligands. There are no intermolecular interactions of note in the crystal structure.

Comment top

Biodegradable polymers have been attracting considerable attention recently due to their potential applications in the environmental protection as well as in the medical field. Among biodegradable polymers, the aliphatic polyesters, such as poly(ε-caprolactone) (PCL), (Endo et al., 1987) poly(lactide) (PLA) (Chamberlain et al., 1999), and their copolymers are especially interested for their applications in the medical field as biodegradable surgical sutures or as a delivery medium for controlled release of drugs (Ni & Yu, 1997). Therefore, there has been increasing interest in the development of efficient catalytic systems for the preparation of PLA and PCL (Wu et al., 2006). The major polymerization method used to synthesize these polymers has been the ring-opening polymerization (ROP) of lactones/lactides and functionally related compounds. For examples, aluminium alkoxides (Duda et al., 1990), stannous (Sawhney et al., 1993), yttrium (Stevels et al., 1996) as well as trivalent lanthanide derivatives (Simic et al., 1997), lithium (Ko & Lin, 2001), magnesium (Shueh et al., 2004; Chamberlain et al., 2001), calcium (Chisholm et al., 2003) and zinc (Chamberlain et al., 2001; Rieth et al., 2002) have been reported to be effective initiators that initiate ROP of lactones/lactides, yielding polymers with both high molecular weights and high yields. Among them, zinc diketiminato-based catalytic systems are especially attracted and well suited as initiators for the ROP of lactones and lactides due to their high Lewis acidity. Recently, we have reported that Zn complexes of diketiminato-based ligands are very active catalysts for ROP of lactide (Chen et al., 2005). Herein, we report the crystal structure of a potentially useful Zn complex with bulky diketiminato ligands.

In the title mononuclear ZnII compound, the Zn atom is tetracoordinated with four N atoms from two diketiminato ligands (Fig. 1). The Zn atom lies on a C2 rotation symmetry. By comparison with the Zn complexes reported in the literature, we notice that the Zn—N coordinated bond distances (1.989 (2) and 1.994 (2) Å)(Table 1) of the title compound are consistent with that reported for [(BDI-2)Zn(µ–OiPr)]2 (1.990 (8) and 2.021 (7) Å) (Chamberlain et al., 2001).

Related literature top

For related literature, see: Chamberlain et al. (1999, 2001); Chen et al. (2005); Chisholm et al. (2003); Duda et al. (1990); Endo et al. (1987); Ko & Lin (2001); Rieth et al. (2002); Sawhney et al. (1993); Shueh et al. (2004); Simic et al. (1997); Stevels et al. (1996); Wu et al. (2006).

For related literature, see: Ni & Yu (1997 or??? 1998).

Experimental top

The title compound was prepared by the reaction of N-((1Z,3Z)-1,3-bis(4-fluorophenyl)-3-(phenylimino)prop-1- enyl)benzenamine (0.82 g, 2.0 mmol) with ZnEt2 (1.1 ml, 1.0 M in hexane, 1.1 mmol) in hexane (20 ml). The mixture was stirred at 25°C for 6 h and was then evaporated to dryness under vacuum. The residue was extracted with hot hexane (30 ml), and the resulting hexane solution was then concentrated to ca 15 ml. Yellow crystals were obtained at room temperature after 16 h. Yield: 0.61 g (69%).

Refinement top

All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with C—H distances of 0.93 Å and Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL (Bruker, 1999).

Figures top
[Figure 1] Fig. 1. A view of the molecular structure of (I) with displacement ellipsoids shown at the 20% probability level. All the H atoms are omitted for clarity.
Bis{N-[(1Z,3Z)-1,3-bis(4-fluorophenyl)-3- (phenylimino)prop-1-enyl]aniline(1-)}zinc(II) top
Crystal data top
[Zn(C27H19F2N2)2]F000 = 1824
Mr = 884.26Dx = 1.358 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 3748 reflections
a = 21.967 (2) Åθ = 2.5–25.5º
b = 10.6232 (10) ŵ = 0.63 mm−1
c = 19.2852 (19) ÅT = 298 (2) K
β = 106.102 (2)ºParallelpiped, yellow
V = 4323.8 (7) Å30.50 × 0.25 × 0.14 mm
Z = 4
Data collection top
Bruker SMART 1000 CCD
diffractometer		4272 independent reflections
Radiation source: fine-focus sealed tube3043 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.048
T = 298(2) Kθmax = 26.1º
φ and ω scansθmin = 1.9º
Absorption correction: multi-scan
(SADABS, Sheldrick, 1996)		h = −27→24
Tmin = 0.524, Tmax = 1.000k = −13→11
12028 measured reflectionsl = −23→23
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.105  w = 1/[σ2(Fo2) + (0.059P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.95(Δ/σ)max = 0.001
4272 reflectionsΔρmax = 0.36 e Å−3
285 parametersΔρmin = −0.30 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Zn(C27H19F2N2)2]V = 4323.8 (7) Å3
Mr = 884.26Z = 4
Monoclinic, C2/cMo Kα
a = 21.967 (2) ŵ = 0.63 mm−1
b = 10.6232 (10) ÅT = 298 (2) K
c = 19.2852 (19) Å0.50 × 0.25 × 0.14 mm
β = 106.102 (2)º
Data collection top
Bruker SMART 1000 CCD
diffractometer		4272 independent reflections
Absorption correction: multi-scan
(SADABS, Sheldrick, 1996)		3043 reflections with I > 2σ(I)
Tmin = 0.524, Tmax = 1.000Rint = 0.048
12028 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.040285 parameters
wR(F2) = 0.105H-atom parameters constrained
S = 0.95Δρmax = 0.36 e Å−3
4272 reflectionsΔρmin = −0.30 e Å−3
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 > 2sigma(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
Zn0.50000.15528 (4)1.25000.03975 (14)
F10.72953 (9)0.0113 (2)0.97921 (11)0.0977 (7)
F20.33272 (10)0.65322 (18)0.92235 (10)0.0936 (6)
N10.54684 (9)0.06780 (18)1.18950 (9)0.0403 (5)
N20.44306 (9)0.25386 (19)1.16987 (9)0.0424 (5)
C10.55117 (11)0.1220 (2)1.12847 (11)0.0391 (5)
C20.51558 (11)0.2276 (2)1.09706 (11)0.0428 (6)
H2A0.52920.26691.06090.051*
C30.46282 (11)0.2823 (2)1.11195 (11)0.0412 (5)
C40.57425 (12)−0.0522 (2)1.21246 (12)0.0429 (6)
C50.62314 (13)−0.0624 (3)1.27565 (13)0.0550 (7)
H5A0.64060.00971.30080.066*
C60.64604 (16)−0.1804 (3)1.30144 (15)0.0682 (9)
H6A0.6791−0.18691.34360.082*
C70.62031 (17)−0.2870 (3)1.26521 (18)0.0714 (9)
H7A0.6355−0.36581.28280.086*
C80.57228 (17)−0.2772 (3)1.20321 (18)0.0709 (9)
H8A0.5551−0.34971.17840.085*
C90.54883 (15)−0.1610 (3)1.17676 (15)0.0587 (7)
H9A0.5157−0.15591.13460.070*
C100.59870 (11)0.0783 (2)1.09063 (12)0.0401 (5)
C110.66212 (12)0.0696 (2)1.12655 (13)0.0495 (6)
H11A0.67530.07901.17640.059*
C120.70666 (13)0.0471 (3)1.08923 (16)0.0581 (7)
H12A0.74950.04191.11350.070*
C130.68610 (14)0.0326 (3)1.01600 (16)0.0596 (7)
C140.62417 (15)0.0373 (3)0.97884 (14)0.0583 (7)
H14A0.61150.02410.92920.070*
C150.57990 (12)0.0620 (3)1.01597 (12)0.0486 (6)
H15A0.53720.06780.99090.058*
C160.42858 (11)0.3809 (2)1.06036 (12)0.0411 (6)
C170.41609 (13)0.4975 (2)1.08620 (14)0.0534 (7)
H17A0.42910.51321.13560.064*
C180.38494 (15)0.5900 (3)1.04009 (16)0.0625 (8)
H18A0.37710.66821.05760.075*
C190.36572 (14)0.5641 (3)0.96792 (16)0.0629 (8)
C200.37753 (14)0.4522 (3)0.93986 (14)0.0633 (8)
H20A0.36410.43770.89040.076*
C210.40987 (13)0.3606 (3)0.98648 (13)0.0540 (7)
H21A0.41920.28440.96810.065*
C220.37975 (12)0.2775 (2)1.17125 (12)0.0434 (6)
C230.36800 (14)0.3224 (3)1.23379 (14)0.0563 (7)
H23A0.40140.34781.27250.068*
C240.30590 (17)0.3294 (3)1.23820 (17)0.0731 (10)
H24A0.29820.36011.28010.088*
C250.25627 (16)0.2920 (3)1.1824 (2)0.0775 (10)
H25A0.21510.29581.18660.093*
C260.26751 (14)0.2485 (3)1.11993 (17)0.0688 (8)
H26A0.23380.22391.08130.083*
C270.32846 (12)0.2416 (2)1.11452 (14)0.0513 (6)
H27A0.33550.21231.07200.062*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn0.0429 (2)0.0499 (3)0.0307 (2)0.0000.01727 (16)0.000
F10.0807 (14)0.1299 (18)0.1090 (14)0.0018 (12)0.0703 (12)−0.0228 (13)
F20.1059 (16)0.0791 (13)0.0928 (13)0.0291 (11)0.0227 (12)0.0447 (11)
N10.0457 (12)0.0467 (11)0.0319 (9)0.0068 (9)0.0167 (8)0.0036 (9)
N20.0427 (12)0.0517 (12)0.0372 (10)0.0062 (9)0.0182 (9)0.0043 (9)
C10.0383 (13)0.0491 (14)0.0323 (11)0.0012 (10)0.0138 (10)0.0006 (10)
C20.0458 (15)0.0536 (15)0.0345 (11)0.0054 (11)0.0202 (10)0.0083 (11)
C30.0437 (14)0.0472 (14)0.0349 (11)0.0016 (11)0.0144 (10)0.0003 (11)
C40.0498 (15)0.0502 (15)0.0354 (11)0.0061 (12)0.0231 (11)0.0050 (11)
C50.0649 (19)0.0583 (17)0.0425 (13)0.0105 (14)0.0163 (13)0.0038 (12)
C60.082 (2)0.074 (2)0.0500 (16)0.0247 (17)0.0200 (15)0.0170 (15)
C70.097 (3)0.0561 (19)0.074 (2)0.0246 (18)0.0461 (19)0.0225 (17)
C80.094 (3)0.0479 (18)0.081 (2)−0.0023 (16)0.041 (2)−0.0005 (16)
C90.0685 (19)0.0552 (17)0.0527 (15)−0.0006 (15)0.0174 (13)−0.0014 (14)
C100.0419 (14)0.0427 (13)0.0406 (12)0.0028 (10)0.0196 (11)0.0040 (10)
C110.0504 (17)0.0556 (16)0.0461 (13)0.0068 (12)0.0195 (12)0.0024 (12)
C120.0415 (16)0.0621 (18)0.0756 (18)0.0077 (13)0.0247 (14)0.0039 (15)
C130.0573 (19)0.0666 (19)0.0701 (18)0.0022 (14)0.0431 (15)−0.0042 (15)
C140.071 (2)0.0680 (18)0.0461 (14)−0.0005 (15)0.0338 (14)−0.0049 (13)
C150.0453 (15)0.0631 (17)0.0417 (12)−0.0008 (12)0.0190 (11)−0.0033 (12)
C160.0411 (14)0.0450 (14)0.0416 (12)0.0035 (10)0.0186 (11)0.0039 (10)
C170.0628 (18)0.0510 (17)0.0505 (14)0.0008 (13)0.0226 (13)0.0026 (12)
C180.077 (2)0.0423 (16)0.0741 (19)0.0078 (14)0.0312 (16)0.0065 (15)
C190.0630 (19)0.0569 (18)0.0716 (19)0.0122 (14)0.0232 (15)0.0256 (15)
C200.070 (2)0.075 (2)0.0444 (14)0.0102 (16)0.0153 (13)0.0124 (14)
C210.0635 (18)0.0565 (16)0.0446 (13)0.0094 (13)0.0191 (12)0.0041 (12)
C220.0463 (15)0.0452 (14)0.0443 (13)0.0088 (11)0.0219 (11)0.0082 (11)
C230.0637 (18)0.0658 (19)0.0468 (14)0.0173 (14)0.0274 (13)0.0049 (13)
C240.084 (2)0.087 (2)0.0666 (19)0.0328 (19)0.0501 (18)0.0177 (17)
C250.059 (2)0.092 (2)0.096 (2)0.0266 (18)0.047 (2)0.029 (2)
C260.0512 (19)0.075 (2)0.081 (2)0.0045 (15)0.0209 (16)0.0123 (17)
C270.0484 (16)0.0565 (16)0.0531 (15)0.0051 (13)0.0207 (13)0.0034 (13)
Geometric parameters (Å, °) top
Zn—N1i1.9875 (18)C11—H11A0.9300
Zn—N11.9875 (18)C12—C131.367 (4)
Zn—N2i1.9942 (19)C12—H12A0.9300
Zn—N21.9942 (19)C13—C141.351 (4)
F1—C131.356 (3)C14—C151.383 (3)
F2—C191.356 (3)C14—H14A0.9300
N1—C11.337 (3)C15—H15A0.9300
N1—C41.427 (3)C16—C211.386 (3)
N2—C31.340 (3)C16—C171.391 (3)
N2—C221.421 (3)C17—C181.374 (4)
C1—C21.405 (3)C17—H17A0.9300
C1—C101.503 (3)C18—C191.366 (4)
C2—C31.396 (3)C18—H18A0.9300
C2—H2A0.9300C19—C201.361 (4)
C3—C161.496 (3)C20—C211.380 (4)
C4—C91.382 (4)C20—H20A0.9300
C4—C51.387 (3)C21—H21A0.9300
C5—C61.390 (4)C22—C271.389 (4)
C5—H5A0.9300C22—C231.386 (3)
C6—C71.368 (4)C23—C241.392 (4)
C6—H6A0.9300C23—H23A0.9300
C7—C81.362 (4)C24—C251.361 (5)
C7—H7A0.9300C24—H24A0.9300
C8—C91.379 (4)C25—C261.376 (4)
C8—H8A0.9300C25—H25A0.9300
C9—H9A0.9300C26—C271.374 (4)
C10—C111.376 (3)C26—H26A0.9300
C10—C151.394 (3)C27—H27A0.9300
C11—C121.387 (3)
N1i—Zn—N1124.24 (11)C11—C12—H12A120.7
N1i—Zn—N2i96.10 (7)C14—C13—F1118.6 (3)
N1—Zn—N2i112.64 (8)C14—C13—C12122.6 (2)
N1i—Zn—N2112.64 (8)F1—C13—C12118.7 (3)
N1—Zn—N296.10 (7)C13—C14—C15118.8 (2)
N2i—Zn—N2116.65 (12)C13—C14—H14A120.6
C1—N1—C4122.07 (19)C15—C14—H14A120.6
C1—N1—Zn119.36 (16)C14—C15—C10120.6 (2)
C4—N1—Zn118.57 (13)C14—C15—H15A119.7
C3—N2—C22121.39 (19)C10—C15—H15A119.7
C3—N2—Zn119.06 (16)C21—C16—C17118.4 (2)
C22—N2—Zn119.01 (14)C21—C16—C3121.7 (2)
N1—C1—C2123.8 (2)C17—C16—C3119.9 (2)
N1—C1—C10121.5 (2)C18—C17—C16121.2 (2)
C2—C1—C10114.56 (19)C18—C17—H17A119.4
C3—C2—C1129.7 (2)C16—C17—H17A119.4
C3—C2—H2A115.2C19—C18—C17118.3 (3)
C1—C2—H2A115.2C19—C18—H18A120.9
N2—C3—C2123.8 (2)C17—C18—H18A120.9
N2—C3—C16119.5 (2)F2—C19—C20118.6 (3)
C2—C3—C16116.61 (19)F2—C19—C18118.6 (3)
C9—C4—C5118.7 (2)C20—C19—C18122.8 (3)
C9—C4—N1121.0 (2)C19—C20—C21118.5 (3)
C5—C4—N1120.0 (2)C19—C20—H20A120.7
C4—C5—C6120.0 (3)C21—C20—H20A120.7
C4—C5—H5A120.0C20—C21—C16120.8 (3)
C6—C5—H5A120.0C20—C21—H21A119.6
C7—C6—C5120.4 (3)C16—C21—H21A119.6
C7—C6—H6A119.8C27—C22—C23118.3 (2)
C5—C6—H6A119.8C27—C22—N2121.4 (2)
C8—C7—C6119.6 (3)C23—C22—N2119.8 (2)
C8—C7—H7A120.2C22—C23—C24119.6 (3)
C6—C7—H7A120.2C22—C23—H23A120.2
C7—C8—C9120.8 (3)C24—C23—H23A120.2
C7—C8—H8A119.6C25—C24—C23121.4 (3)
C9—C8—H8A119.6C25—C24—H24A119.3
C8—C9—C4120.4 (3)C23—C24—H24A119.3
C8—C9—H9A119.8C24—C25—C26119.4 (3)
C4—C9—H9A119.8C24—C25—H25A120.3
C11—C10—C15118.7 (2)C26—C25—H25A120.3
C11—C10—C1121.2 (2)C27—C26—C25120.0 (3)
C15—C10—C1119.5 (2)C27—C26—H26A120.0
C10—C11—C12120.8 (2)C25—C26—H26A120.0
C10—C11—H11A119.6C26—C27—C22121.4 (3)
C12—C11—H11A119.6C26—C27—H27A119.3
C13—C12—C11118.5 (3)C22—C27—H27A119.3
C13—C12—H12A120.7
Symmetry codes: (i) −x+1, y, −z+5/2.
Acknowledgements top

Financial support from the National Science Council of the Republic of China is gratefully appreciated.

references
References top

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