Bis(4,4''-difluoro-1,1':3',1''-terphenyl-2'-carboxyl-ato-κO)tetra-kis-(methanol-κO)calcium methanol tetra-solvate.

In the title compound, [Ca(C(19)H(11)F(2)O(2))(2)(CH(3)OH)(4)]·4CH(3)OH, the Ca(2+) ion is located on an inversion centre and is hexa-coordinated by two O atoms of two 4,4''-difluoro-1,1':3',1''-terphenyl-2'-carboxyl-ate ligands and four O atoms of four methanol ligands, forming a CaO(6) polyhedron with a slightly distorted octa-hedral coordination geometry. The Ca-O-C angle between the carboxyl-ate group and the calcium ion is 171.8 (2)°. Two types of inter-molecular hydrogen-bond inter-actions (C=O⋯H and O-H⋯O) between the carboxyl-ate ligand, the methanol solvent mol-ecules 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 = 914.97

Orthorhombic,

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[F 2 > 2σ(F 2)] = 0.064

wR(F 2) = 0.165

S = 0.98

5709 reflections

300 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.43 e Å−3

Δρmin = −0.45 e Å−3

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.

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813000044/ru2047sup1.cif

Click here for additional data file.

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

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

[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) Å3	Block, colorless
Z = 4	0.32 × 0.23 × 0.14 mm

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 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(Fo2) + (0.0644P)2] where P = (Fo2 + 2Fc2)/3
5709 reflections	(Δ/σ)max < 0.001
300 parameters	Δρmax = 0.43 e Å−3
0 restraints	Δρmin = −0.45 e Å−3

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.

	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)*

	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)

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)

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···O2iv	0.84	1.96	2.804 (3)	177
O5—H5A···O2v	0.84	1.92	2.755 (3)	170

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⋯O2iv	0.84	1.96	2.804 (3)	177
O5—H5A⋯O2v	0.84	1.92	2.755 (3)	170

Symmetry codes: (ii) ; (iii) ; (iv) ; (v) .