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

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).

Key indicators

• Single-crystal X-ray study
• T = 200 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.064
• wR factor = 0.165
• Data-to-parameter ratio = 19.0

checkCIF/PLATON results

No syntax errors found



Alert level C
RINTA01_ALERT_3_C  The value of Rint is greater than 0.12
            Rint given   0.143
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low ....         46 Perc.
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      2.621

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF          ?
PLAT007_ALERT_5_G Note: Number of Unrefined D-H Atoms ............          2
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ          ?
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          4

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   3 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   4 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

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S1. Comment

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

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).

S2. Experimental

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).

S3. Refinement

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 U_iso(H) = 1.2 U_eq(C) or 1.5 U_eq(C) for methyl groups. The O-bound H atoms of methanol were located in a difference Fourier map and refined isotropically.

Computing details

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

	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

Crystal data

[Ca(C19H11F2O2)2(CH4O)4]·4CH4O	F(000) = 1928
Mr = 914.97	Dx = 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) Å^3	Block, colorless
Z = 4	0.32 × 0.23 × 0.14 mm

Data collection

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

Refinement

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

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Ca1—O1^i	2.2692 (19)	C9—C10	1.375 (4)
Ca1—O1	2.2693 (19)	C9—H9	0.9500
Ca1—O4^i	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—O3^i	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
O1^i—Ca1—O1	180.00 (8)	C12—C13—H13	119.1
O1^i—Ca1—O4^i	95.07 (8)	C8—C13—H13	119.1
O1—Ca1—O4^i	84.93 (8)	C14—C19—C18	121.2 (3)
O1^i—Ca1—O4	84.93 (8)	C14—C19—H19	119.4
O1—Ca1—O4	95.07 (8)	C18—C19—H19	119.4
O4^i—Ca1—O4	180.0	C9—C10—C11	117.9 (3)
O1^i—Ca1—O3	90.78 (8)	C9—C10—H10	121.0
O1—Ca1—O3	89.22 (8)	C11—C10—H10	121.0
O4^i—Ca1—O3	89.48 (8)	C5—C4—C3	121.5 (3)
O4—Ca1—O3	90.52 (8)	C5—C4—H4	119.2
O1^i—Ca1—O3^i	89.22 (8)	C3—C4—H4	119.2
O1—Ca1—O3^i	90.78 (8)	F2—C11—C12	119.4 (3)
O4^i—Ca1—O3^i	90.52 (8)	F2—C11—C10	118.1 (3)
O4—Ca1—O3^i	89.48 (8)	C12—C11—C10	122.5 (3)
O3—Ca1—O3^i	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)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H1···O6^ii	0.89 (4)	1.78 (4)	2.636 (3)	162 (4)
O4—H2···O5^iii	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.