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Acta Cryst. (2013). E69, m122-m123    [ doi:10.1107/S1600536813000044 ]

Bis(4,4''-difluoro-1,1':3',1''-terphenyl-2'-carboxylato-[kappa]O)tetrakis(methanol-[kappa]O)calcium methanol tetrasolvate

N. Kim, H. Noh, S. Yoon and C. R. Park

Abstract top

In the title compound, [Ca(C19H11F2O2)2(CH3OH)4]·4CH3OH, the Ca2+ ion is located on an inversion centre and is hexacoordinated by two O atoms of two 4,4''-difluoro-1,1':3',1''-terphenyl-2'-carboxylate ligands and four O atoms of four methanol ligands, forming a CaO6 polyhedron with a slightly distorted octahedral coordination geometry. The Ca-O-C angle between the carboxylate group and the calcium ion is 171.8 (2)°. Two types of intermolecular hydrogen-bond interactions (C=O...H and O-H...O) between the carboxylate ligand, the methanol solvent molecules and the coordinating methanol ligands generate a two-dimensional network parallel to (001).

Comment top

Octahedral mononuclear transition metal complexes with ligated carboxylates are well known structure for basic of inorganic chemistry (Chavez et al., 2001; Kannan et al., 2011). Few mononuclear calcium complexes with carboxylate ligands (Perrin et al., 2009; Godino Salido et al., 2004; Huang et al., 2010) are reported possible due to easy polymerization behavior (Murugavel et al., 2003; Jisha et al., 2010; Yang et al., 2004). Here, we report the structure of an octahedrally coordinated Ca2+ complex which crystallizes in the orthorhombic space group Pbca with one half molecule in the asymmetric unit. The selected bond distances and angles of [Ca(C19H11O2F2)2(CH4O)4] are given in Table 1 with the structure of the molecule shown, in Fig 1, and its crystal packing involving strong intermolecular C=O···H, O—H···O interactions are detailed in Fig 2 and Table 2.

Related literature top

For background to metal complexes with 4,4''-difluoro-1,1':3',1''-terphenyl-2'-carboxylate ligands, see: Kannan et al. (2011); Chavez et al. (2001). For mononuclear calcium complexes with carboxylate ligands, see: Perrin et al. (2009); Godino Salido et al. (2004); Huang et al. (2010). For their polymerization behavior, see: Jisha et al. (2010); Murugavel & Banerjee (2003); Yang et al. (2004).

Experimental top

To a solution of sodium 4,4''-difluoro-1,1':3',1''-terphenyl-2'-carboxylate (0.200 g, 0.602 mmol) in 15 ml of methanol, Ca(CF3SO3)2 (0.204 g, 0.602 mmol) was added at room temperature. After stirring for 30 min, colorless block type crystals were collected from slow evaporization. Yield = 51%, (0.281 g).

Refinement top

H atoms were placed at calculated positions and refined as riding with C–H(aromatic) = 0.95 Å, C–H(CH3) = 0.98 Å, and with Uiso(H) = 1.2 Ueq(C) or 1.5 Ueq(C) for methyl groups. The O-bound H atoms of methanol were located in a difference Fourier map and refined isotropically.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick,2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing the atom-numbering and with displacement ellipsoids drawn at the 50% probability level.
[Figure 2] Fig. 2. A crystal packing diagram of the title compound, showing the hydrogen bonds and with displacement ellipsoids drawn at the 50% probability level.
Bis(4,4''-difluoro-1,1':3',1''-terphenyl-2'-carboxylato- κO)tetrakis(methanol-κO)calcium methanol tetrasolvate top
Crystal data top
[Ca(C19H11F2O2)2(CH4O)4]·4CH4OF(000) = 1928
Mr = 914.97Dx = 1.321 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -p 2ac 2abCell parameters from 2898 reflections
a = 15.4611 (19) Åθ = 2.2–22.0°
b = 14.2436 (18) ŵ = 0.21 mm1
c = 20.886 (3) ÅT = 200 K
V = 4599.5 (10) Å3Block, colorless
Z = 40.32 × 0.23 × 0.14 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
5709 independent reflections
Radiation source: fine-focus sealed tube2624 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.143
phi and ω scansθmax = 28.3°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 1420
Tmin = 0.521, Tmax = 1.00k = 1818
32627 measured reflectionsl = 2327
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)] = 0.064Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.165H atoms treated by a mixture of independent and constrained refinement
S = 0.98 w = 1/[σ2(Fo2) + (0.0644P)2]
where P = (Fo2 + 2Fc2)/3
5709 reflections(Δ/σ)max < 0.001
300 parametersΔρmax = 0.43 e Å3
0 restraintsΔρmin = 0.45 e Å3
Crystal data top
[Ca(C19H11F2O2)2(CH4O)4]·4CH4OV = 4599.5 (10) Å3
Mr = 914.97Z = 4
Orthorhombic, PbcaMo Kα radiation
a = 15.4611 (19) ŵ = 0.21 mm1
b = 14.2436 (18) ÅT = 200 K
c = 20.886 (3) Å0.32 × 0.23 × 0.14 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
5709 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
2624 reflections with I > 2σ(I)
Tmin = 0.521, Tmax = 1.00Rint = 0.143
32627 measured reflectionsθmax = 28.3°
Refinement top
R[F2 > 2σ(F2)] = 0.064H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.165Δρmax = 0.43 e Å3
S = 0.98Δρmin = 0.45 e Å3
5709 reflectionsAbsolute structure: ?
300 parametersFlack parameter: ?
0 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
Ca11.00000.00000.50000.0296 (2)
O20.79691 (12)0.20766 (14)0.46541 (10)0.0359 (5)
O10.92097 (13)0.12979 (14)0.47660 (10)0.0382 (6)
O30.94225 (15)0.07389 (16)0.40917 (11)0.0416 (6)
O41.12075 (14)0.04631 (15)0.44165 (11)0.0436 (6)
F21.02858 (13)0.35764 (16)0.71251 (10)0.0657 (6)
F10.68180 (14)0.03347 (16)0.22211 (11)0.0698 (7)
C150.7834 (2)0.2459 (2)0.27894 (15)0.0414 (8)
H150.77660.31200.27540.050*
C10.87736 (19)0.1973 (2)0.45564 (14)0.0293 (7)
C80.99166 (19)0.3377 (2)0.51732 (15)0.0349 (8)
C20.92369 (18)0.27084 (19)0.41636 (15)0.0297 (7)
C60.9544 (2)0.3437 (2)0.31427 (17)0.0439 (9)
H60.94600.34760.26930.053*
C140.8506 (2)0.2098 (2)0.31613 (15)0.0353 (8)
C30.97877 (18)0.3349 (2)0.44720 (16)0.0327 (8)
C70.91018 (19)0.2756 (2)0.35003 (15)0.0344 (8)
C51.0100 (2)0.4050 (2)0.34434 (17)0.0455 (9)
H51.04070.45010.31970.055*
C90.9219 (2)0.3391 (2)0.56012 (16)0.0368 (8)
H90.86470.33510.54360.044*
C131.0747 (2)0.3425 (2)0.54382 (17)0.0400 (8)
H131.12350.34140.51610.048*
C190.8596 (2)0.1135 (2)0.31971 (16)0.0451 (9)
H190.90490.08760.34480.054*
C100.9335 (2)0.3462 (2)0.62520 (16)0.0428 (8)
H100.88550.34790.65350.051*
C41.0216 (2)0.4017 (2)0.40898 (18)0.0426 (9)
H41.05950.44550.42870.051*
C111.0168 (2)0.3508 (2)0.64801 (17)0.0454 (9)
C121.0876 (2)0.3486 (2)0.60847 (17)0.0439 (9)
H121.14440.35120.62560.053*
C170.7379 (2)0.0923 (3)0.25238 (17)0.0479 (9)
C211.1492 (2)0.1374 (2)0.42276 (18)0.0514 (10)
H21A1.10190.17030.40110.077*
H21B1.19840.13140.39340.077*
H21C1.16690.17300.46070.077*
C200.9850 (2)0.1026 (3)0.35239 (19)0.0562 (10)
H20A1.01030.04770.33120.084*
H20B0.94330.13270.32360.084*
H20C1.03090.14740.36320.084*
C180.8036 (2)0.0540 (2)0.28735 (17)0.0503 (10)
H180.81080.01220.28950.060*
C160.7266 (2)0.1872 (3)0.24715 (16)0.0472 (9)
H160.68080.21230.22220.057*
O50.24558 (14)0.91787 (15)0.43929 (12)0.0451 (6)
H5A0.23730.88280.47110.068*
O60.78040 (14)0.86827 (15)0.41295 (12)0.0483 (6)
H6A0.75760.81920.42750.073*
C230.7269 (2)0.9463 (2)0.42684 (19)0.0504 (10)
H23A0.70590.94170.47100.076*
H23B0.67750.94680.39740.076*
H23C0.76011.00440.42170.076*
C220.2469 (2)0.8631 (3)0.38278 (18)0.0554 (10)
H22A0.25030.90450.34540.083*
H22B0.19400.82540.38030.083*
H22C0.29740.82150.38350.083*
H21.163 (2)0.003 (3)0.4370 (19)0.078 (13)*
H10.892 (3)0.104 (3)0.4134 (19)0.084 (15)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ca10.0215 (4)0.0302 (4)0.0370 (5)0.0015 (4)0.0028 (4)0.0044 (4)
O20.0218 (12)0.0384 (12)0.0474 (15)0.0003 (9)0.0029 (9)0.0063 (11)
O10.0323 (13)0.0324 (12)0.0498 (15)0.0075 (10)0.0001 (10)0.0092 (11)
O30.0317 (14)0.0506 (15)0.0424 (15)0.0045 (12)0.0031 (10)0.0080 (11)
O40.0311 (13)0.0363 (13)0.0635 (17)0.0029 (11)0.0164 (11)0.0084 (12)
F20.0575 (14)0.0938 (17)0.0456 (15)0.0085 (12)0.0073 (10)0.0017 (12)
F10.0726 (16)0.0703 (15)0.0663 (16)0.0189 (12)0.0069 (12)0.0205 (12)
C150.049 (2)0.0419 (19)0.034 (2)0.0009 (17)0.0049 (16)0.0006 (16)
C10.0267 (18)0.0323 (16)0.0289 (18)0.0018 (14)0.0024 (13)0.0011 (14)
C80.0302 (18)0.0283 (16)0.046 (2)0.0047 (14)0.0023 (15)0.0028 (14)
C20.0221 (16)0.0286 (16)0.039 (2)0.0030 (13)0.0053 (13)0.0005 (14)
C60.046 (2)0.048 (2)0.038 (2)0.0018 (17)0.0053 (16)0.0051 (17)
C140.038 (2)0.0380 (18)0.0298 (19)0.0003 (15)0.0071 (14)0.0016 (15)
C30.0244 (17)0.0344 (17)0.039 (2)0.0024 (14)0.0027 (14)0.0016 (15)
C70.0326 (19)0.0334 (17)0.037 (2)0.0036 (14)0.0092 (14)0.0017 (15)
C50.050 (2)0.0404 (19)0.046 (2)0.0122 (17)0.0131 (17)0.0055 (17)
C90.0301 (19)0.0355 (18)0.045 (2)0.0006 (14)0.0005 (15)0.0024 (15)
C130.0250 (18)0.0425 (19)0.052 (2)0.0040 (15)0.0025 (15)0.0006 (17)
C190.055 (2)0.0374 (19)0.043 (2)0.0013 (17)0.0025 (17)0.0010 (16)
C100.036 (2)0.047 (2)0.045 (2)0.0004 (15)0.0014 (16)0.0009 (17)
C40.035 (2)0.0391 (19)0.053 (2)0.0065 (15)0.0053 (16)0.0005 (17)
C110.050 (2)0.049 (2)0.038 (2)0.0034 (17)0.0063 (17)0.0002 (17)
C120.032 (2)0.051 (2)0.049 (2)0.0045 (16)0.0059 (16)0.0017 (18)
C170.049 (2)0.056 (2)0.039 (2)0.0108 (19)0.0065 (17)0.015 (2)
C210.051 (2)0.044 (2)0.060 (3)0.0037 (18)0.0096 (18)0.0131 (18)
C200.053 (2)0.053 (2)0.062 (3)0.0039 (19)0.0097 (19)0.011 (2)
C180.065 (3)0.037 (2)0.049 (2)0.0060 (19)0.0053 (19)0.0065 (18)
C160.047 (2)0.059 (2)0.036 (2)0.0054 (18)0.0005 (17)0.0051 (18)
O50.0352 (13)0.0449 (14)0.0553 (17)0.0028 (11)0.0104 (12)0.0055 (12)
O60.0331 (14)0.0410 (13)0.0710 (18)0.0088 (11)0.0044 (11)0.0040 (13)
C230.045 (2)0.039 (2)0.067 (3)0.0086 (17)0.0080 (18)0.0013 (18)
C220.054 (2)0.060 (2)0.052 (3)0.006 (2)0.0038 (18)0.001 (2)
Geometric parameters (Å, º) top
Ca1—O1i2.2692 (19)C9—C101.375 (4)
Ca1—O12.2693 (19)C9—H90.9500
Ca1—O4i2.325 (2)C13—C121.368 (4)
Ca1—O42.325 (2)C13—H130.9500
Ca1—O32.346 (2)C19—C181.388 (4)
Ca1—O3i2.346 (2)C19—H190.9500
O2—C11.269 (3)C10—C111.375 (5)
O1—C11.253 (3)C10—H100.9500
O3—C201.418 (4)C4—H40.9500
O3—H10.89 (4)C11—C121.371 (5)
O4—C211.425 (4)C12—H120.9500
O4—H20.91 (4)C17—C181.364 (5)
F2—C111.363 (4)C17—C161.367 (5)
F1—C171.362 (4)C21—H21A0.9800
C15—C161.382 (5)C21—H21B0.9800
C15—C141.395 (4)C21—H21C0.9800
C15—H150.9500C20—H20A0.9800
C1—C21.511 (4)C20—H20B0.9800
C8—C131.400 (4)C20—H20C0.9800
C8—C91.401 (4)C18—H180.9500
C8—C31.479 (4)C16—H160.9500
C2—C71.403 (4)O5—C221.415 (4)
C2—C31.404 (4)O5—H5A0.8400
C6—C51.377 (5)O6—C231.416 (4)
C6—C71.403 (4)O6—H6A0.8400
C6—H60.9500C23—H23A0.9800
C14—C191.380 (4)C23—H23B0.9800
C14—C71.492 (4)C23—H23C0.9800
C3—C41.408 (4)C22—H22A0.9800
C5—C41.363 (5)C22—H22B0.9800
C5—H50.9500C22—H22C0.9800
O1i—Ca1—O1180.00 (8)C12—C13—H13119.1
O1i—Ca1—O4i95.07 (8)C8—C13—H13119.1
O1—Ca1—O4i84.93 (8)C14—C19—C18121.2 (3)
O1i—Ca1—O484.93 (8)C14—C19—H19119.4
O1—Ca1—O495.07 (8)C18—C19—H19119.4
O4i—Ca1—O4180.0C9—C10—C11117.9 (3)
O1i—Ca1—O390.78 (8)C9—C10—H10121.0
O1—Ca1—O389.22 (8)C11—C10—H10121.0
O4i—Ca1—O389.48 (8)C5—C4—C3121.5 (3)
O4—Ca1—O390.52 (8)C5—C4—H4119.2
O1i—Ca1—O3i89.22 (8)C3—C4—H4119.2
O1—Ca1—O3i90.78 (8)F2—C11—C12119.4 (3)
O4i—Ca1—O3i90.52 (8)F2—C11—C10118.1 (3)
O4—Ca1—O3i89.48 (8)C12—C11—C10122.5 (3)
O3—Ca1—O3i180.0C13—C12—C11118.7 (3)
C1—O1—Ca1171.8 (2)C13—C12—H12120.6
C20—O3—Ca1128.9 (2)C11—C12—H12120.6
C20—O3—H1110 (3)F1—C17—C18118.4 (3)
Ca1—O3—H1118 (3)F1—C17—C16119.3 (3)
C21—O4—Ca1130.6 (2)C18—C17—C16122.2 (3)
C21—O4—H2112 (2)O4—C21—H21A109.5
Ca1—O4—H2116 (2)O4—C21—H21B109.5
C16—C15—C14121.2 (3)H21A—C21—H21B109.5
C16—C15—H15119.4O4—C21—H21C109.5
C14—C15—H15119.4H21A—C21—H21C109.5
O1—C1—O2124.1 (3)H21B—C21—H21C109.5
O1—C1—C2117.8 (3)O3—C20—H20A109.5
O2—C1—C2118.1 (3)O3—C20—H20B109.5
C13—C8—C9117.0 (3)H20A—C20—H20B109.5
C13—C8—C3121.1 (3)O3—C20—H20C109.5
C9—C8—C3121.9 (3)H20A—C20—H20C109.5
C7—C2—C3120.8 (3)H20B—C20—H20C109.5
C7—C2—C1119.9 (3)C17—C18—C19118.7 (3)
C3—C2—C1119.3 (3)C17—C18—H18120.6
C5—C6—C7120.0 (3)C19—C18—H18120.6
C5—C6—H6120.0C17—C16—C15118.6 (3)
C7—C6—H6120.0C17—C16—H16120.7
C19—C14—C15118.1 (3)C15—C16—H16120.7
C19—C14—C7122.4 (3)C22—O5—H5A109.5
C15—C14—C7119.5 (3)C23—O6—H6A109.5
C2—C3—C4117.7 (3)O6—C23—H23A109.5
C2—C3—C8123.6 (3)O6—C23—H23B109.5
C4—C3—C8118.7 (3)H23A—C23—H23B109.5
C6—C7—C2119.1 (3)O6—C23—H23C109.5
C6—C7—C14118.9 (3)H23A—C23—H23C109.5
C2—C7—C14122.0 (3)H23B—C23—H23C109.5
C4—C5—C6120.8 (3)O5—C22—H22A109.5
C4—C5—H5119.6O5—C22—H22B109.5
C6—C5—H5119.6H22A—C22—H22B109.5
C10—C9—C8122.1 (3)O5—C22—H22C109.5
C10—C9—H9119.0H22A—C22—H22C109.5
C8—C9—H9119.0H22B—C22—H22C109.5
C12—C13—C8121.8 (3)
Symmetry code: (i) x+2, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H1···O6ii0.89 (4)1.78 (4)2.636 (3)162 (4)
O4—H2···O5iii0.91 (4)1.76 (4)2.660 (3)172 (4)
O6—H6A···O2iv0.841.962.804 (3)177
O5—H5A···O2v0.841.922.755 (3)170
Symmetry codes: (ii) x, y1, z; (iii) x+1, y1, z; (iv) x+3/2, y+1/2, z; (v) x+1, y+1, z+1.
Selected bond lengths (Å) top
Ca1—O1i2.2692 (19)Ca1—O42.325 (2)
Ca1—O12.2693 (19)Ca1—O32.346 (2)
Ca1—O4i2.325 (2)Ca1—O3i2.346 (2)
Symmetry code: (i) x+2, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H1···O6ii0.89 (4)1.78 (4)2.636 (3)162 (4)
O4—H2···O5iii0.91 (4)1.76 (4)2.660 (3)172 (4)
O6—H6A···O2iv0.841.962.804 (3)177.3
O5—H5A···O2v0.841.922.755 (3)169.9
Symmetry codes: (ii) x, y1, z; (iii) x+1, y1, z; (iv) x+3/2, y+1/2, z; (v) x+1, y+1, z+1.
Acknowledgements top

This work was supported by the International Collaborative R&D Program of the Korea Institute of Energy Technology Evaluation and Planning (KETEP) grant funded by Korea Government Ministry of Knowledge Economy (20118520010020).

references
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