Bis(4,4′′-difluoro-1,1′:3′,1′′-terphenyl-2′-carboxyl­ato-κO)tetra­kis­(methanol-κO)calcium methanol tetra­solvate

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

doi:10.1107/S1600536813000044

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 2| February 2013| Pages m122-m123

doi:10.1107/S1600536813000044

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Bis(4,4′′-difluoro-1,1′:3′,1′′-terphenyl-2′-carboxylato-κO)tetrakis(methanol-κO)calcium methanol tetrasolvate

Namseok Kim,^a Heeso Noh,^b Sungho Yoon ^a ^* and Chan Ryang Park ^a ^*

^aDepartment of Bio & Nano Chemistry, College of Natural Sciences, Kookmin University, 861-1 Jeongneung-dong, Seongbuk-gu, Seoul 136-702, Republic of Korea, and ^bDepartment of Physics, College of Natural Sciences, Kookmin University, 861-1 Jeongneung-dong, Seongbuk-gu, Seoul 136-702, Republic of Korea.
^*Correspondence e-mail: yoona@kookmin.ac.kr, crpark@kookmin.ac.kr

(Received 21 November 2012; accepted 2 January 2013; online 23 January 2013)

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).

Related literature

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

Crystal data

[Ca(C₁₉H₁₁F₂O₂)₂(CH₄O)₄]·4CH₄O
M_r = 914.97
Orthorhombic, P b c a
a = 15.4611 (19) Å
b = 14.2436 (18) Å
c = 20.886 (3) Å
V = 4599.5 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 200 K
0.32 × 0.23 × 0.14 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.521, T_max = 1.00
32627 measured reflections
5709 independent reflections
2624 reflections with I > 2σ(I)
R_int = 0.143

Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.165
S = 0.98
5709 reflections
300 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Selected bond lengths (Å)

Ca1—O1	2.2693 (19)
Ca1—O4	2.325 (2)
Ca1—O3	2.346 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H1⋯O6ⁱⁱ	0.89 (4)	1.78 (4)	2.636 (3)	162 (4)
O4—H2⋯O5ⁱⁱⁱ	0.91 (4)	1.76 (4)	2.660 (3)	172 (4)
O6—H6A⋯O2^iv	0.84	1.96	2.804 (3)	177
O5—H5A⋯O2^v	0.84	1.92	2.755 (3)	170
Symmetry codes: (ii) x, y-1, z; (iii) x+1, y-1, z; (iv) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z]$ ; (v) -x+1, -y+1, -z+1.

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813000044/ru2047sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813000044/ru2047Isup2.hkl

checkCIF report

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).

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

	Fig. 1. The molecular structure of the title compound, showing the atom-numbering and with displacement ellipsoids drawn at the 50% probability level.
	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]·4CH₄O	F(000) = 1928
M_r = 914.97	D_x = 1.321 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -p 2ac 2ab	Cell parameters from 2898 reflections
a = 15.4611 (19) Å	θ = 2.2–22.0°
b = 14.2436 (18) Å	µ = 0.21 mm⁻¹
c = 20.886 (3) Å	T = 200 K
V = 4599.5 (10) Å³	Block, colorless
Z = 4	0.32 × 0.23 × 0.14 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	5709 independent reflections
Radiation source: fine-focus sealed tube	2624 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.143
phi and ω scans	θ_max = 28.3°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −14→20
T_min = 0.521, T_max = 1.00	k = −18→18
32627 measured reflections	l = −23→27

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.165	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	w = 1/[σ²(F_o²) + (0.0644P)²] where P = (F_o² + 2F_c²)/3
5709 reflections	(Δ/σ)_max < 0.001
300 parameters	Δρ_max = 0.43 e Å⁻³
0 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

[Ca(C₁₉H₁₁F₂O₂)₂(CH₄O)₄]·4CH₄O	V = 4599.5 (10) Å³
M_r = 914.97	Z = 4
Orthorhombic, Pbca	Mo Kα radiation
a = 15.4611 (19) Å	µ = 0.21 mm⁻¹
b = 14.2436 (18) Å	T = 200 K
c = 20.886 (3) Å	0.32 × 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)
T_min = 0.521, T_max = 1.00	R_int = 0.143
32627 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	0 restraints
wR(F²) = 0.165	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	Δρ_max = 0.43 e Å⁻³
5709 reflections	Δρ_min = −0.45 e Å⁻³
300 parameters

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

	x	y	z	U_iso*/U_eq
Ca1	1.0000	0.0000	0.5000	0.0296 (2)
O2	0.79691 (12)	0.20766 (14)	0.46541 (10)	0.0359 (5)
O1	0.92097 (13)	0.12979 (14)	0.47660 (10)	0.0382 (6)
O3	0.94225 (15)	−0.07389 (16)	0.40917 (11)	0.0416 (6)
O4	1.12075 (14)	0.04631 (15)	0.44165 (11)	0.0436 (6)
F2	1.02858 (13)	0.35764 (16)	0.71251 (10)	0.0657 (6)
F1	0.68180 (14)	0.03347 (16)	0.22211 (11)	0.0698 (7)
C15	0.7834 (2)	0.2459 (2)	0.27894 (15)	0.0414 (8)
H15	0.7766	0.3120	0.2754	0.050*
C1	0.87736 (19)	0.1973 (2)	0.45564 (14)	0.0293 (7)
C8	0.99166 (19)	0.3377 (2)	0.51732 (15)	0.0349 (8)
C2	0.92369 (18)	0.27084 (19)	0.41636 (15)	0.0297 (7)
C6	0.9544 (2)	0.3437 (2)	0.31427 (17)	0.0439 (9)
H6	0.9460	0.3476	0.2693	0.053*
C14	0.8506 (2)	0.2098 (2)	0.31613 (15)	0.0353 (8)
C3	0.97877 (18)	0.3349 (2)	0.44720 (16)	0.0327 (8)
C7	0.91018 (19)	0.2756 (2)	0.35003 (15)	0.0344 (8)
C5	1.0100 (2)	0.4050 (2)	0.34434 (17)	0.0455 (9)
H5	1.0407	0.4501	0.3197	0.055*
C9	0.9219 (2)	0.3391 (2)	0.56012 (16)	0.0368 (8)
H9	0.8647	0.3351	0.5436	0.044*
C13	1.0747 (2)	0.3425 (2)	0.54382 (17)	0.0400 (8)
H13	1.1235	0.3414	0.5161	0.048*
C19	0.8596 (2)	0.1135 (2)	0.31971 (16)	0.0451 (9)
H19	0.9049	0.0876	0.3448	0.054*
C10	0.9335 (2)	0.3462 (2)	0.62520 (16)	0.0428 (8)
H10	0.8855	0.3479	0.6535	0.051*
C4	1.0216 (2)	0.4017 (2)	0.40898 (18)	0.0426 (9)
H4	1.0595	0.4455	0.4287	0.051*
C11	1.0168 (2)	0.3508 (2)	0.64801 (17)	0.0454 (9)
C12	1.0876 (2)	0.3486 (2)	0.60847 (17)	0.0439 (9)
H12	1.1444	0.3512	0.6256	0.053*
C17	0.7379 (2)	0.0923 (3)	0.25238 (17)	0.0479 (9)
C21	1.1492 (2)	0.1374 (2)	0.42276 (18)	0.0514 (10)
H21A	1.1019	0.1703	0.4011	0.077*
H21B	1.1984	0.1314	0.3934	0.077*
H21C	1.1669	0.1730	0.4607	0.077*
C20	0.9850 (2)	−0.1026 (3)	0.35239 (19)	0.0562 (10)
H20A	1.0103	−0.0477	0.3312	0.084*
H20B	0.9433	−0.1327	0.3236	0.084*
H20C	1.0309	−0.1474	0.3632	0.084*
C18	0.8036 (2)	0.0540 (2)	0.28735 (17)	0.0503 (10)
H18	0.8108	−0.0122	0.2895	0.060*
C16	0.7266 (2)	0.1872 (3)	0.24715 (16)	0.0472 (9)
H16	0.6808	0.2123	0.2222	0.057*
O5	0.24558 (14)	0.91787 (15)	0.43929 (12)	0.0451 (6)
H5A	0.2373	0.8828	0.4711	0.068*
O6	0.78040 (14)	0.86827 (15)	0.41295 (12)	0.0483 (6)
H6A	0.7576	0.8192	0.4275	0.073*
C23	0.7269 (2)	0.9463 (2)	0.42684 (19)	0.0504 (10)
H23A	0.7059	0.9417	0.4710	0.076*
H23B	0.6775	0.9468	0.3974	0.076*
H23C	0.7601	1.0044	0.4217	0.076*
C22	0.2469 (2)	0.8631 (3)	0.38278 (18)	0.0554 (10)
H22A	0.2503	0.9045	0.3454	0.083*
H22B	0.1940	0.8254	0.3803	0.083*
H22C	0.2974	0.8215	0.3835	0.083*
H2	1.163 (2)	0.003 (3)	0.4370 (19)	0.078 (13)*
H1	0.892 (3)	−0.104 (3)	0.4134 (19)	0.084 (15)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ca1	0.0215 (4)	0.0302 (4)	0.0370 (5)	0.0015 (4)	0.0028 (4)	0.0044 (4)
O2	0.0218 (12)	0.0384 (12)	0.0474 (15)	0.0003 (9)	0.0029 (9)	0.0063 (11)
O1	0.0323 (13)	0.0324 (12)	0.0498 (15)	0.0075 (10)	−0.0001 (10)	0.0092 (11)
O3	0.0317 (14)	0.0506 (15)	0.0424 (15)	−0.0045 (12)	0.0031 (10)	−0.0080 (11)
O4	0.0311 (13)	0.0363 (13)	0.0635 (17)	0.0029 (11)	0.0164 (11)	0.0084 (12)
F2	0.0575 (14)	0.0938 (17)	0.0456 (15)	−0.0085 (12)	−0.0073 (10)	−0.0017 (12)
F1	0.0726 (16)	0.0703 (15)	0.0663 (16)	−0.0189 (12)	−0.0069 (12)	−0.0205 (12)
C15	0.049 (2)	0.0419 (19)	0.034 (2)	−0.0009 (17)	0.0049 (16)	0.0006 (16)
C1	0.0267 (18)	0.0323 (16)	0.0289 (18)	−0.0018 (14)	−0.0024 (13)	−0.0011 (14)
C8	0.0302 (18)	0.0283 (16)	0.046 (2)	−0.0047 (14)	0.0023 (15)	−0.0028 (14)
C2	0.0221 (16)	0.0286 (16)	0.039 (2)	0.0030 (13)	0.0053 (13)	0.0005 (14)
C6	0.046 (2)	0.048 (2)	0.038 (2)	−0.0018 (17)	0.0053 (16)	0.0051 (17)
C14	0.038 (2)	0.0380 (18)	0.0298 (19)	0.0003 (15)	0.0071 (14)	0.0016 (15)
C3	0.0244 (17)	0.0344 (17)	0.039 (2)	0.0024 (14)	0.0027 (14)	0.0016 (15)
C7	0.0326 (19)	0.0334 (17)	0.037 (2)	0.0036 (14)	0.0092 (14)	0.0017 (15)
C5	0.050 (2)	0.0404 (19)	0.046 (2)	−0.0122 (17)	0.0131 (17)	0.0055 (17)
C9	0.0301 (19)	0.0355 (18)	0.045 (2)	0.0006 (14)	0.0005 (15)	−0.0024 (15)
C13	0.0250 (18)	0.0425 (19)	0.052 (2)	−0.0040 (15)	0.0025 (15)	−0.0006 (17)
C19	0.055 (2)	0.0374 (19)	0.043 (2)	0.0013 (17)	−0.0025 (17)	0.0010 (16)
C10	0.036 (2)	0.047 (2)	0.045 (2)	0.0004 (15)	0.0014 (16)	−0.0009 (17)
C4	0.035 (2)	0.0391 (19)	0.053 (2)	−0.0065 (15)	0.0053 (16)	−0.0005 (17)
C11	0.050 (2)	0.049 (2)	0.038 (2)	−0.0034 (17)	−0.0063 (17)	−0.0002 (17)
C12	0.032 (2)	0.051 (2)	0.049 (2)	−0.0045 (16)	−0.0059 (16)	−0.0017 (18)
C17	0.049 (2)	0.056 (2)	0.039 (2)	−0.0108 (19)	0.0065 (17)	−0.015 (2)
C21	0.051 (2)	0.044 (2)	0.060 (3)	−0.0037 (18)	0.0096 (18)	0.0131 (18)
C20	0.053 (2)	0.053 (2)	0.062 (3)	0.0039 (19)	0.0097 (19)	−0.011 (2)
C18	0.065 (3)	0.037 (2)	0.049 (2)	−0.0060 (19)	0.0053 (19)	−0.0065 (18)
C16	0.047 (2)	0.059 (2)	0.036 (2)	0.0054 (18)	−0.0005 (17)	−0.0051 (18)
O5	0.0352 (13)	0.0449 (14)	0.0553 (17)	0.0028 (11)	0.0104 (12)	0.0055 (12)
O6	0.0331 (14)	0.0410 (13)	0.0710 (18)	−0.0088 (11)	0.0044 (11)	0.0040 (13)
C23	0.045 (2)	0.039 (2)	0.067 (3)	−0.0086 (17)	0.0080 (18)	0.0013 (18)
C22	0.054 (2)	0.060 (2)	0.052 (3)	0.006 (2)	0.0038 (18)	0.001 (2)

Geometric parameters (Å, º) top

Ca1—O1ⁱ	2.2692 (19)	C9—C10	1.375 (4)
Ca1—O1	2.2693 (19)	C9—H9	0.9500
Ca1—O4ⁱ	2.325 (2)	C13—C12	1.368 (4)
Ca1—O4	2.325 (2)	C13—H13	0.9500
Ca1—O3	2.346 (2)	C19—C18	1.388 (4)
Ca1—O3ⁱ	2.346 (2)	C19—H19	0.9500
O2—C1	1.269 (3)	C10—C11	1.375 (5)
O1—C1	1.253 (3)	C10—H10	0.9500
O3—C20	1.418 (4)	C4—H4	0.9500
O3—H1	0.89 (4)	C11—C12	1.371 (5)
O4—C21	1.425 (4)	C12—H12	0.9500
O4—H2	0.91 (4)	C17—C18	1.364 (5)
F2—C11	1.363 (4)	C17—C16	1.367 (5)
F1—C17	1.362 (4)	C21—H21A	0.9800
C15—C16	1.382 (5)	C21—H21B	0.9800
C15—C14	1.395 (4)	C21—H21C	0.9800
C15—H15	0.9500	C20—H20A	0.9800
C1—C2	1.511 (4)	C20—H20B	0.9800
C8—C13	1.400 (4)	C20—H20C	0.9800
C8—C9	1.401 (4)	C18—H18	0.9500
C8—C3	1.479 (4)	C16—H16	0.9500
C2—C7	1.403 (4)	O5—C22	1.415 (4)
C2—C3	1.404 (4)	O5—H5A	0.8400
C6—C5	1.377 (5)	O6—C23	1.416 (4)
C6—C7	1.403 (4)	O6—H6A	0.8400
C6—H6	0.9500	C23—H23A	0.9800
C14—C19	1.380 (4)	C23—H23B	0.9800
C14—C7	1.492 (4)	C23—H23C	0.9800
C3—C4	1.408 (4)	C22—H22A	0.9800
C5—C4	1.363 (5)	C22—H22B	0.9800
C5—H5	0.9500	C22—H22C	0.9800

O1ⁱ—Ca1—O1	180.00 (8)	C12—C13—H13	119.1
O1ⁱ—Ca1—O4ⁱ	95.07 (8)	C8—C13—H13	119.1
O1—Ca1—O4ⁱ	84.93 (8)	C14—C19—C18	121.2 (3)
O1ⁱ—Ca1—O4	84.93 (8)	C14—C19—H19	119.4
O1—Ca1—O4	95.07 (8)	C18—C19—H19	119.4
O4ⁱ—Ca1—O4	180.0	C9—C10—C11	117.9 (3)
O1ⁱ—Ca1—O3	90.78 (8)	C9—C10—H10	121.0
O1—Ca1—O3	89.22 (8)	C11—C10—H10	121.0
O4ⁱ—Ca1—O3	89.48 (8)	C5—C4—C3	121.5 (3)
O4—Ca1—O3	90.52 (8)	C5—C4—H4	119.2
O1ⁱ—Ca1—O3ⁱ	89.22 (8)	C3—C4—H4	119.2
O1—Ca1—O3ⁱ	90.78 (8)	F2—C11—C12	119.4 (3)
O4ⁱ—Ca1—O3ⁱ	90.52 (8)	F2—C11—C10	118.1 (3)
O4—Ca1—O3ⁱ	89.48 (8)	C12—C11—C10	122.5 (3)
O3—Ca1—O3ⁱ	180.0	C13—C12—C11	118.7 (3)
C1—O1—Ca1	171.8 (2)	C13—C12—H12	120.6
C20—O3—Ca1	128.9 (2)	C11—C12—H12	120.6
C20—O3—H1	110 (3)	F1—C17—C18	118.4 (3)
Ca1—O3—H1	118 (3)	F1—C17—C16	119.3 (3)
C21—O4—Ca1	130.6 (2)	C18—C17—C16	122.2 (3)
C21—O4—H2	112 (2)	O4—C21—H21A	109.5
Ca1—O4—H2	116 (2)	O4—C21—H21B	109.5
C16—C15—C14	121.2 (3)	H21A—C21—H21B	109.5
C16—C15—H15	119.4	O4—C21—H21C	109.5
C14—C15—H15	119.4	H21A—C21—H21C	109.5
O1—C1—O2	124.1 (3)	H21B—C21—H21C	109.5
O1—C1—C2	117.8 (3)	O3—C20—H20A	109.5
O2—C1—C2	118.1 (3)	O3—C20—H20B	109.5
C13—C8—C9	117.0 (3)	H20A—C20—H20B	109.5
C13—C8—C3	121.1 (3)	O3—C20—H20C	109.5
C9—C8—C3	121.9 (3)	H20A—C20—H20C	109.5
C7—C2—C3	120.8 (3)	H20B—C20—H20C	109.5
C7—C2—C1	119.9 (3)	C17—C18—C19	118.7 (3)
C3—C2—C1	119.3 (3)	C17—C18—H18	120.6
C5—C6—C7	120.0 (3)	C19—C18—H18	120.6
C5—C6—H6	120.0	C17—C16—C15	118.6 (3)
C7—C6—H6	120.0	C17—C16—H16	120.7
C19—C14—C15	118.1 (3)	C15—C16—H16	120.7
C19—C14—C7	122.4 (3)	C22—O5—H5A	109.5
C15—C14—C7	119.5 (3)	C23—O6—H6A	109.5
C2—C3—C4	117.7 (3)	O6—C23—H23A	109.5
C2—C3—C8	123.6 (3)	O6—C23—H23B	109.5
C4—C3—C8	118.7 (3)	H23A—C23—H23B	109.5
C6—C7—C2	119.1 (3)	O6—C23—H23C	109.5
C6—C7—C14	118.9 (3)	H23A—C23—H23C	109.5
C2—C7—C14	122.0 (3)	H23B—C23—H23C	109.5
C4—C5—C6	120.8 (3)	O5—C22—H22A	109.5
C4—C5—H5	119.6	O5—C22—H22B	109.5
C6—C5—H5	119.6	H22A—C22—H22B	109.5
C10—C9—C8	122.1 (3)	O5—C22—H22C	109.5
C10—C9—H9	119.0	H22A—C22—H22C	109.5
C8—C9—H9	119.0	H22B—C22—H22C	109.5
C12—C13—C8	121.8 (3)

Symmetry code: (i) −x+2, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H1···O6ⁱⁱ	0.89 (4)	1.78 (4)	2.636 (3)	162 (4)
O4—H2···O5ⁱⁱⁱ	0.91 (4)	1.76 (4)	2.660 (3)	172 (4)
O6—H6A···O2^iv	0.84	1.96	2.804 (3)	177
O5—H5A···O2^v	0.84	1.92	2.755 (3)	170

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

Experimental details

Crystal data
Chemical formula	[Ca(C₁₉H₁₁F₂O₂)₂(CH₄O)₄]·4CH₄O
M_r	914.97
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	200
a, b, c (Å)	15.4611 (19), 14.2436 (18), 20.886 (3)
V (Å³)	4599.5 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.21
Crystal size (mm)	0.32 × 0.23 × 0.14

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.521, 1.00
No. of measured, independent and observed [I > 2σ(I)] reflections	32627, 5709, 2624
R_int	0.143
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.165, 0.98
No. of reflections	5709
No. of parameters	300
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.45

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick,2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Ca1—O1ⁱ	2.2692 (19)	Ca1—O4	2.325 (2)
Ca1—O1	2.2693 (19)	Ca1—O3	2.346 (2)
Ca1—O4ⁱ	2.325 (2)	Ca1—O3ⁱ	2.346 (2)

Symmetry code: (i) −x+2, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H1···O6ⁱⁱ	0.89 (4)	1.78 (4)	2.636 (3)	162 (4)
O4—H2···O5ⁱⁱⁱ	0.91 (4)	1.76 (4)	2.660 (3)	172 (4)
O6—H6A···O2^iv	0.84	1.96	2.804 (3)	177.3
O5—H5A···O2^v	0.84	1.92	2.755 (3)	169.9

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

Acknowledgements

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

Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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Volume 69| Part 2| February 2013| Pages m122-m123

doi:10.1107/S1600536813000044

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Bis(4,4′′-di­fluoro-1,1′:3′,1′′-terphenyl-2′-carboxyl­ato-κO)tetra­kis­(methanol-κO)calcium methanol tetra­solvate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

Bis(4,4′′-difluoro-1,1′:3′,1′′-terphenyl-2′-carboxylato-κO)tetrakis(methanol-κO)calcium methanol tetrasolvate