catena-Poly[[(diaqua­calcium)-bis­(μ-2-fluorobenzoato)-1′:1κ3O:O,O′;1:1′′κ3O,O′:O] 2,2′-bipyridine hemi­solvate]

Zhang, B.-S.; Lin, J.-L.; Jin, X.-F.; Huang, R.; Luo, L.-L.

doi:10.1107/S1600536811053311

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 1| January 2012| Pages m55-m56

doi:10.1107/S1600536811053311

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catena-Poly[[(diaquacalcium)-bis(μ-2-fluorobenzoato)-1′:1κ³O:O,O′;1:1′′κ³O,O′:O] 2,2′-bipyridine hemisolvate]

Bi-Song Zhang,^a ^* Jian-Li Lin,^b Xiu-Fang Jin,^a Rong Huang ^a and Ling-Ling Luo ^a

^aCollege of Material Science and Chemical Engineering, Jinhua College of Profession and Technology, Jinhua, Zhejiang 321017, People's Republic of China, and ^bState Key Laboratory Base of Novel Functional Materials and Preparation, Science Center of Applied Solid State Chemistry Research, Ningbo University, Ningbo, Zhejiang 315211, People's Republic of China
^*Correspondence e-mail: zbs_jy@163.com

(Received 7 October 2011; accepted 11 December 2011; online 17 December 2011)

In the title compound, {[Ca(C₇H₄FO₂)₂(H₂O)₂]·0.5C₁₀H₈N₂}_n, the Ca^II atom is coordinated by eigth O atoms from four 2-fluorobenzoate ligands and two water molecules, resulting in a distorted CaO₈ square-antiprismatic coordination environment. The 2-fluorobenzoate ligand bridges two symmetry-related Ca^II atoms, giving rise to a chain structure extending along [100]. The distances between the Ca atom and its two symmetry-related counterparts are 4.054 (2) and 4.106 (2) Å. The polymeric chains are connected by classical O—H⋯N hydrogen bonds into a layer structure parallel to (010). The layers are connected by non-classical C—H⋯F hydrogen bonds into a three-dimensional supramolecular structure. O—H⋯O and C—H⋯O interactions also occur. The uncoordinated 2,2′-bipyridine molecule is located on a centre of symmetry at the mid-point of the bond between the two heterocycles. One of the two benzene rings is disordered over two sites with occupancy factors of 0.60 and 0.40.

Related literature

For other metal complexes with the 2-fluorobenzoato ligand, see: Zhang et al. (2005a ,b ); Zhang (2006 , 2008); Jin (2011 ). For related structures, see: Zhang (2009 ); Karipides et al. (1988 ).

Experimental

Crystal data

[Ca(C₇H₄FO₂)₂(H₂O)₂]·0.5C₁₀H₈N₂
M_r = 432.41
Triclinic, $[P \overline 1]$
a = 7.9063 (16) Å
b = 10.212 (2) Å
c = 12.147 (2) Å
α = 94.68 (3)°
β = 104.33 (3)°
γ = 92.98 (3)°
V = 944.4 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.39 mm⁻¹
T = 295 K
0.34 × 0.19 × 0.16 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.914, T_max = 0.939
7478 measured reflections
3306 independent reflections
2136 reflections with I > 2σ(I)
R_int = 0.053

Refinement

R[F² > 2σ(F²)] = 0.061
wR(F²) = 0.214
S = 1.17
3306 reflections
271 parameters
H-atom parameters constrained
Δρ_max = 0.64 e Å⁻³
Δρ_min = −0.73 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯N1	0.82	2.21	2.835 (5)	133
O1—H1B⋯O5ⁱ	0.82	2.02	2.782 (5)	154
O2—H2A⋯O4ⁱⁱ	0.82	2.12	2.741 (5)	132
O2—H2B⋯F1ⁱⁱⁱ	0.82	2.62	3.363 (5)	151
C7—H7⋯O2ⁱ	0.93	2.60	3.189 (7)	122
C10—H10⋯F2^iv	0.93	2.54	3.281 (2)	136
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) -x, -y+2, -z+1; (iii) x, y-1, z; (iv) -x, -y+3, -z+1.

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ); 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811053311/rk2307sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811053311/rk2307Isup2.hkl

checkCIF report

Comment top

A metal ions with 2-fluorobenzoato ligands can form, among others, mononuclear, dinuclear, one-dimensional chain complexes (Zhang et al., 2005a, b; Zhang, 2006, 2008; Jin, 2011). Only a few reports of one-dimensional chain structure complexes includinng uncoordinated 2,2'-bipyridine molecules have been published.

In this paper we would like to report the synthesis, molecular and crystal structures of an one-dimensional chain complex including 2-fluorobenzoato, 2,2'-bipyridine and calcium(II). The crystal structure of title compound is similar to previously published structures (Zhang, 2009; Karipides et al., 1988). Within the title compound, each Ca^II ion is coordinated by eight O atoms from two water molecules and four carboxyl groups of 2-fluorobenzoic acid anions in a distorted square-antiprismayic geometry. Two µ₃-carboxyl group of the 2-fluorobenzoic anions bridges two symmetry related calcium(II) atoms giving rise to an one-dimensional chain structure extending along the [1 0 0] direction, with Ca–O bond lengths in the range of 2.381 (4)Å to 2.726 (4)Å. Separation between Ca1 and Ca1ⁱ, Ca1 and Ca1ⁱⁱ [symmetry codes: (i) -x, 2-y, 1-z; (ii) 1-x, 2-y, 1-z] are 4.054 (2)Å and 4.106 (2)Å (Fig. 1). The polymeric chains are connected via O1–H1A···N1 hydrogen bonds interactions between the coordinates water and 2,2'-bipyridine molecules in to a two dimensional layer structure parallel to (0 1 0) (Fig.2). The middle of bond C5–C5ⁱⁱⁱ [symmetry code: (iii) -x, 2-y, -z] of non-coordinated 2,2'-bipyridine molecule is located in center of symmetry position. The layers are connected by C10–H10···F2^v [symmetry code: (v) -x, 3-y, 1-z] weak hydrogen bonds interactions in to a three-dimensional supramolecular structure (Fig. 2). The O1–H1A···N1 and C10–H10···F2^v bond lengths are 2.835 (5)Å and 3.281 (2)Å, the O1–H1A···N1 and C10–H10···F2^v bond angles are 133° and 136°.

Related literature top

For other metal complexes with the 2-fluorobenzoato ligand, see: Zhang et al. (2005a,b); Zhang (2006, 2008); Jin (2011). For related structures, see: Zhang (2009); Karipides et al. (1988).

Experimental top

CaCO₃ (0.1005 g, 1.00 mmol), 2-fluorobenzoic acid (0.0625 g, 0.45 mmol), 2,2'-bipyridine (0.0512 g, 0.33 mmol), CH₃OH/H₂O (v/v = 1:2, 15 ml) were mixed and stirred for 2.0 h. Subsequently, the resulting cream suspension was heated in a 23 ml Teflon-lined stainless steel autoclave at 433 K for 5800 minutes. After the autoclave was cooled to room temperature according to the procedure at 2600 minutes. The solid was filtered off. The resulting filtrate was allowed to stand at room temperature, and slow evaporation for 2 months afforded colorless block single crystals.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The structure unit of the title compound, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. Symmetry codes: (i) -x, 2-y, 1-z; (ii) 1-x, 2-y, 1-z); (iii) -x, 2-y, -z.
	Fig. 2. A packing diagram of the title complex, viewed along the a axis. The O1–H1A···N1 and C10–H10···F2^v hydrogen bonds (dashed lines) in the title compound. Symmetry code: (v) -x, 3-y, 1-z.

catena-Poly[[(diaquacalcium)-bis(µ-2-fluorobenzoato)-1':1κ³O:O,O';1:1''κ³O,O':O] 2,2'-bipyridine hemisolvate] top

Crystal data top

[Ca(C₇H₄FO₂)₂(H₂O)₂]·0.5C₁₀H₈N₂	Z = 2
M_r = 432.41	F(000) = 446
Triclinic, P1	D_x = 1.521 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.9063 (16) Å	Cell parameters from 5423 reflections
b = 10.212 (2) Å	θ = 3.2–25.0°
c = 12.147 (2) Å	µ = 0.39 mm⁻¹
α = 94.68 (3)°	T = 295 K
β = 104.33 (3)°	Block, colourless
γ = 92.98 (3)°	0.34 × 0.19 × 0.16 mm
V = 944.4 (3) Å³

Data collection top

Rigaku R-AXIS RAPID diffractometer	3306 independent reflections
Radiation source: fine-focus sealed tube	2136 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
ω scans	θ_max = 25.0°, θ_min = 3.2°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −9→9
T_min = 0.914, T_max = 0.939	k = −12→12
7478 measured reflections	l = −14→14

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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.214	H-atom parameters constrained
S = 1.17	w = 1/[σ²(F_o²) + (0.071P)² + 2.358P] where P = (F_o² + 2F_c²)/3
3306 reflections	(Δ/σ)_max < 0.001
271 parameters	Δρ_max = 0.64 e Å⁻³
0 restraints	Δρ_min = −0.73 e Å⁻³

Crystal data top

[Ca(C₇H₄FO₂)₂(H₂O)₂]·0.5C₁₀H₈N₂	γ = 92.98 (3)°
M_r = 432.41	V = 944.4 (3) Å³
Triclinic, P1	Z = 2
a = 7.9063 (16) Å	Mo Kα radiation
b = 10.212 (2) Å	µ = 0.39 mm⁻¹
c = 12.147 (2) Å	T = 295 K
α = 94.68 (3)°	0.34 × 0.19 × 0.16 mm
β = 104.33 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	3306 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2136 reflections with I > 2σ(I)
T_min = 0.914, T_max = 0.939	R_int = 0.053
7478 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.061	0 restraints
wR(F²) = 0.214	H-atom parameters constrained
S = 1.17	Δρ_max = 0.64 e Å⁻³
3306 reflections	Δρ_min = −0.73 e Å⁻³
271 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	Occ. (<1)
Ca1	0.23787 (12)	0.95355 (10)	0.48080 (8)	0.0330 (3)
N1	0.1493 (6)	0.8835 (5)	0.0638 (4)	0.0459 (12)
F1	0.1676 (5)	1.4460 (3)	0.4314 (4)	0.0647 (11)
O1	0.2997 (5)	0.8935 (4)	0.3020 (3)	0.0428 (9)
H1B	0.3916	0.9137	0.2857	0.064*
H1A	0.2274	0.8545	0.2473	0.064*
O2	0.1035 (5)	0.7532 (4)	0.5270 (4)	0.0517 (11)
H2B	0.1394	0.6793	0.5299	0.078*
H2A	0.0534	0.7759	0.5762	0.078*
O3	0.4861 (4)	1.1408 (4)	0.4636 (3)	0.0380 (9)
O4	0.2084 (4)	1.1781 (4)	0.4336 (3)	0.0436 (10)
O5	0.3472 (5)	1.0424 (4)	0.6789 (3)	0.0507 (11)
O6	0.0613 (4)	1.0541 (4)	0.6240 (3)	0.0375 (9)
C1	0.2246 (8)	0.7775 (7)	0.0316 (5)	0.0537 (15)
H1	0.3002	0.7371	0.0879	0.064*
C2	0.1969 (9)	0.7248 (7)	−0.0800 (6)	0.0586 (17)
H2	0.2531	0.6515	−0.0983	0.070*
C3	0.0851 (9)	0.7826 (7)	−0.1626 (5)	0.0593 (17)
H3	0.0631	0.7486	−0.2386	0.071*
C4	0.0047 (9)	0.8916 (6)	−0.1334 (5)	0.0529 (15)
H4	−0.0718	0.9320	−0.1893	0.063*
C5	0.0395 (7)	0.9410 (5)	−0.0186 (4)	0.0392 (12)
C6	0.3995 (6)	1.3357 (5)	0.3811 (4)	0.0336 (11)
C7	0.5394 (7)	1.3466 (6)	0.3307 (5)	0.0419 (13)
H7	0.6040	1.2740	0.3246	0.050*
C8	0.5851 (8)	1.4617 (7)	0.2894 (6)	0.0552 (16)
H8	0.6800	1.4661	0.2570	0.066*
C9	0.4894 (8)	1.5710 (7)	0.2961 (5)	0.0552 (16)
H9	0.5214	1.6488	0.2692	0.066*
C10	0.3478 (8)	1.5643 (6)	0.3423 (5)	0.0533 (16)
H10	0.2817	1.6364	0.3461	0.064*
C11	0.3055 (7)	1.4467 (5)	0.3833 (5)	0.0400 (12)
C12	0.3609 (6)	1.2121 (5)	0.4293 (4)	0.0357 (12)
C13	0.2199 (18)	1.1634 (13)	0.7949 (10)	0.0336 (19)	0.60
C14	0.1266 (13)	1.2791 (9)	0.7976 (9)	0.0575 (19)	0.60
F2	0.0396 (13)	1.3184 (9)	0.7157 (9)	0.106 (3)	0.60
C15	0.145 (3)	1.358 (2)	0.898 (2)	0.086 (4)	0.60
H15	0.0837	1.4337	0.8966	0.103*	0.60
C16	0.245 (4)	1.331 (3)	0.996 (2)	0.098 (5)	0.60
H16	0.2534	1.3858	1.0627	0.117*	0.60
C17	0.339 (4)	1.220 (3)	0.9984 (15)	0.077 (4)	0.60
H17	0.4103	1.2005	1.0676	0.093*	0.60
C18	0.3310 (17)	1.1353 (13)	0.8991 (9)	0.046 (2)	0.60
H18	0.3973	1.0624	0.9022	0.056*	0.60
C13'	0.210 (2)	1.1874 (17)	0.8095 (12)	0.0336 (19)	0.40
C14'	0.103 (3)	1.292 (2)	0.7984 (19)	0.0575 (19)	0.40
H14A	0.0297	1.3032	0.7277	0.069*	0.40
C15'	0.105 (4)	1.379 (2)	0.893 (2)	0.086 (4)	0.40
H15A	0.0335	1.4483	0.8857	0.103*	0.40
C16'	0.215 (7)	1.361 (4)	0.999 (2)	0.098 (5)	0.40
H16A	0.2165	1.4195	1.0621	0.117*	0.40
C17'	0.322 (5)	1.257 (3)	1.0098 (16)	0.077 (4)	0.40
H17A	0.3957	1.2456	1.0805	0.093*	0.40
C18'	0.3201 (18)	1.1702 (12)	0.9152 (10)	0.046 (2)	0.40
F2'	0.4186 (11)	1.0508 (9)	0.9175 (6)	0.053 (2)	0.40
C19	0.2072 (6)	1.0851 (5)	0.6954 (4)	0.0365 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ca1	0.0245 (5)	0.0387 (6)	0.0370 (6)	0.0046 (4)	0.0087 (4)	0.0071 (4)
N1	0.042 (3)	0.055 (3)	0.040 (3)	0.005 (2)	0.009 (2)	0.006 (2)
F1	0.055 (2)	0.047 (2)	0.110 (3)	0.0161 (16)	0.048 (2)	0.019 (2)
O1	0.0347 (19)	0.059 (3)	0.0338 (19)	0.0002 (17)	0.0097 (16)	−0.0018 (17)
O2	0.039 (2)	0.043 (2)	0.085 (3)	0.0101 (17)	0.031 (2)	0.023 (2)
O3	0.0280 (17)	0.044 (2)	0.045 (2)	0.0104 (16)	0.0109 (16)	0.0129 (17)
O4	0.0304 (18)	0.036 (2)	0.071 (3)	0.0020 (15)	0.0215 (18)	0.0185 (19)
O5	0.0291 (18)	0.078 (3)	0.046 (2)	0.0059 (19)	0.0136 (17)	−0.005 (2)
O6	0.0214 (16)	0.048 (2)	0.041 (2)	0.0007 (15)	0.0059 (15)	0.0017 (16)
C1	0.050 (3)	0.063 (4)	0.050 (3)	0.012 (3)	0.012 (3)	0.011 (3)
C2	0.063 (4)	0.061 (4)	0.056 (4)	0.014 (3)	0.021 (3)	0.002 (3)
C3	0.074 (4)	0.060 (4)	0.043 (3)	0.007 (3)	0.015 (3)	−0.005 (3)
C4	0.071 (4)	0.048 (4)	0.038 (3)	0.002 (3)	0.012 (3)	0.002 (3)
C5	0.036 (3)	0.045 (3)	0.035 (3)	−0.002 (2)	0.009 (2)	0.002 (2)
C6	0.030 (2)	0.032 (3)	0.039 (3)	0.001 (2)	0.008 (2)	0.008 (2)
C7	0.038 (3)	0.042 (3)	0.050 (3)	0.006 (2)	0.015 (3)	0.014 (3)
C8	0.052 (3)	0.062 (4)	0.059 (4)	0.001 (3)	0.025 (3)	0.019 (3)
C9	0.060 (4)	0.057 (4)	0.055 (4)	0.000 (3)	0.023 (3)	0.018 (3)
C10	0.056 (4)	0.036 (3)	0.065 (4)	0.009 (3)	0.007 (3)	0.017 (3)
C11	0.035 (3)	0.042 (3)	0.049 (3)	0.004 (2)	0.017 (2)	0.009 (2)
C12	0.024 (2)	0.047 (3)	0.034 (3)	0.002 (2)	0.003 (2)	0.005 (2)
C13	0.033 (3)	0.026 (5)	0.044 (4)	0.004 (3)	0.022 (3)	−0.018 (4)
C14	0.049 (4)	0.057 (5)	0.078 (5)	0.003 (4)	0.037 (4)	0.008 (4)
F2	0.101 (6)	0.097 (7)	0.122 (7)	0.025 (5)	0.026 (6)	0.016 (6)
C15	0.073 (11)	0.059 (7)	0.141 (9)	−0.013 (5)	0.078 (8)	−0.042 (7)
C16	0.088 (14)	0.095 (14)	0.114 (8)	−0.034 (8)	0.068 (8)	−0.075 (8)
C17	0.066 (8)	0.110 (17)	0.048 (5)	−0.032 (8)	0.023 (5)	−0.044 (6)
C18	0.050 (4)	0.060 (7)	0.025 (4)	−0.017 (5)	0.014 (3)	−0.027 (4)
C13'	0.033 (3)	0.026 (5)	0.044 (4)	0.004 (3)	0.022 (3)	−0.018 (4)
C14'	0.049 (4)	0.057 (5)	0.078 (5)	0.003 (4)	0.037 (4)	0.008 (4)
C15'	0.073 (11)	0.059 (7)	0.141 (9)	−0.013 (5)	0.078 (8)	−0.042 (7)
C16'	0.088 (14)	0.095 (14)	0.114 (8)	−0.034 (8)	0.068 (8)	−0.075 (8)
C17'	0.066 (8)	0.110 (17)	0.048 (5)	−0.032 (8)	0.023 (5)	−0.044 (6)
C18'	0.050 (4)	0.060 (7)	0.025 (4)	−0.017 (5)	0.014 (3)	−0.027 (4)
F2'	0.050 (5)	0.070 (6)	0.035 (4)	0.017 (4)	0.001 (4)	0.016 (4)
C19	0.032 (3)	0.039 (3)	0.040 (3)	0.002 (2)	0.011 (2)	0.007 (2)

Geometric parameters (Å, º) top

Ca1—O1	2.381 (4)	C6—C11	1.390 (7)
Ca1—O6ⁱ	2.386 (3)	C6—C7	1.394 (7)
Ca1—O3ⁱⁱ	2.396 (3)	C6—C12	1.483 (7)
Ca1—O4	2.418 (4)	C7—C8	1.380 (8)
Ca1—O2	2.426 (4)	C7—H7	0.9300
Ca1—O5	2.427 (4)	C8—C9	1.388 (9)
Ca1—O6	2.662 (4)	C8—H8	0.9300
Ca1—O3	2.726 (4)	C9—C10	1.372 (9)
Ca1—C19	2.904 (5)	C9—H9	0.9300
Ca1—C12	2.935 (6)	C10—C11	1.393 (8)
Ca1—Ca1ⁱ	4.054 (2)	C10—H10	0.9300
Ca1—Ca1ⁱⁱ	4.106 (2)	C13—C19	1.373 (13)
Ca1—H2A	2.7683	C13—C18	1.411 (14)
N1—C1	1.338 (8)	C13—C14	1.428 (11)
N1—C5	1.349 (7)	C14—F2	1.1740
F1—C11	1.358 (6)	C14—C15	1.380 (18)
O1—H1B	0.8200	C15—C16	1.32 (2)
O1—H1A	0.8200	C15—H15	0.9300
O2—H2B	0.8200	C16—C17	1.39 (2)
O2—H2A	0.8200	C16—H16	0.9300
O3—C12	1.267 (6)	C17—C18	1.410 (15)
O3—Ca1ⁱⁱ	2.396 (3)	C17—H17	0.9300
O4—C12	1.253 (6)	C18—H18	0.9300
O5—C19	1.266 (6)	C13'—C14'	1.3900
O6—C19	1.266 (6)	C13'—C18'	1.3900
O6—Ca1ⁱ	2.386 (3)	C13'—C19	1.660 (17)
C1—C2	1.376 (9)	C14'—C15'	1.3900
C1—H1	0.9300	C14'—H14A	0.9300
C2—C3	1.360 (9)	C15'—C16'	1.3900
C2—H2	0.9300	C15'—H15A	0.9300
C3—C4	1.374 (9)	C16'—C17'	1.3900
C3—H3	0.9300	C16'—H16A	0.9300
C4—C5	1.399 (8)	C17'—C18'	1.3900
C4—H4	0.9300	C17'—H17A	0.9300
C5—C5ⁱⁱⁱ	1.474 (11)	C18'—F2'	1.4796

O1—Ca1—O6ⁱ	86.09 (12)	C19—O5—Ca1	98.8 (3)
O1—Ca1—O3ⁱⁱ	77.46 (13)	C19—O6—Ca1ⁱ	163.8 (3)
O6ⁱ—Ca1—O3ⁱⁱ	152.43 (14)	C19—O6—Ca1	87.8 (3)
O1—Ca1—O4	90.21 (14)	Ca1ⁱ—O6—Ca1	106.69 (13)
O6ⁱ—Ca1—O4	77.91 (13)	N1—C1—C2	123.9 (6)
O3ⁱⁱ—Ca1—O4	123.52 (13)	N1—C1—H1	118.0
O1—Ca1—O2	104.41 (15)	C2—C1—H1	118.0
O6ⁱ—Ca1—O2	75.11 (13)	C3—C2—C1	118.3 (6)
O3ⁱⁱ—Ca1—O2	87.62 (13)	C3—C2—H2	120.8
O4—Ca1—O2	148.15 (13)	C1—C2—H2	120.8
O1—Ca1—O5	147.97 (13)	C2—C3—C4	119.8 (6)
O6ⁱ—Ca1—O5	124.39 (13)	C2—C3—H3	120.1
O3ⁱⁱ—Ca1—O5	77.36 (13)	C4—C3—H3	120.1
O4—Ca1—O5	87.44 (15)	C3—C4—C5	119.1 (6)
O2—Ca1—O5	93.99 (15)	C3—C4—H4	120.4
O1—Ca1—O6	157.37 (12)	C5—C4—H4	120.4
O6ⁱ—Ca1—O6	73.31 (13)	N1—C5—C4	121.3 (5)
O3ⁱⁱ—Ca1—O6	125.15 (12)	N1—C5—C5ⁱⁱⁱ	116.6 (6)
O4—Ca1—O6	76.64 (12)	C4—C5—C5ⁱⁱⁱ	122.1 (6)
O2—Ca1—O6	79.65 (13)	C11—C6—C7	115.6 (5)
O5—Ca1—O6	51.10 (11)	C11—C6—C12	124.3 (5)
O1—Ca1—O3	75.15 (12)	C7—C6—C12	120.2 (5)
O6ⁱ—Ca1—O3	123.49 (12)	C8—C7—C6	122.1 (5)
O3ⁱⁱ—Ca1—O3	73.59 (13)	C8—C7—H7	118.9
O4—Ca1—O3	50.07 (11)	C6—C7—H7	118.9
O2—Ca1—O3	160.92 (12)	C7—C8—C9	120.0 (6)
O5—Ca1—O3	78.98 (13)	C7—C8—H8	120.0
O6—Ca1—O3	108.30 (12)	C9—C8—H8	120.0
O1—Ca1—C19	166.43 (14)	C10—C9—C8	120.1 (6)
O6ⁱ—Ca1—C19	98.95 (14)	C10—C9—H9	119.9
O3ⁱⁱ—Ca1—C19	102.15 (14)	C8—C9—H9	119.9
O4—Ca1—C19	78.65 (14)	C9—C10—C11	118.4 (6)
O2—Ca1—C19	89.09 (15)	C9—C10—H10	120.8
O5—Ca1—C19	25.52 (13)	C11—C10—H10	120.8
O6—Ca1—C19	25.84 (12)	F1—C11—C6	120.0 (5)
O3—Ca1—C19	91.65 (13)	F1—C11—C10	116.3 (5)
O1—Ca1—C12	80.01 (14)	C6—C11—C10	123.7 (5)
O6ⁱ—Ca1—C12	99.63 (13)	O4—C12—O3	121.1 (5)
O3ⁱⁱ—Ca1—C12	99.11 (13)	O4—C12—C6	120.9 (4)
O4—Ca1—C12	24.73 (12)	O3—C12—C6	118.0 (4)
O2—Ca1—C12	172.69 (14)	O4—C12—Ca1	53.8 (3)
O5—Ca1—C12	84.77 (15)	O3—C12—Ca1	68.0 (3)
O6—Ca1—C12	94.05 (13)	C6—C12—Ca1	168.8 (3)
O3—Ca1—C12	25.52 (11)	C19—C13—C18	121.3 (9)
C19—Ca1—C12	86.70 (15)	C19—C13—C14	121.9 (9)
O1—Ca1—Ca1ⁱ	124.48 (10)	C18—C13—C14	116.8 (9)
O6ⁱ—Ca1—Ca1ⁱ	38.98 (9)	F2—C14—C15	115.4 (10)
O3ⁱⁱ—Ca1—Ca1ⁱ	154.16 (10)	F2—C14—C13	123.5 (5)
O4—Ca1—Ca1ⁱ	74.03 (9)	C15—C14—C13	120.9 (12)
O2—Ca1—Ca1ⁱ	74.38 (9)	C16—C15—C14	122.7 (14)
O5—Ca1—Ca1ⁱ	85.42 (9)	C16—C15—H15	118.7
O6—Ca1—Ca1ⁱ	34.33 (7)	C14—C15—H15	118.7
O3—Ca1—Ca1ⁱ	122.07 (9)	C15—C16—C17	118.8 (13)
C19—Ca1—Ca1ⁱ	60.03 (10)	C15—C16—H16	120.6
C12—Ca1—Ca1ⁱ	98.33 (11)	C17—C16—H16	120.6
O1—Ca1—Ca1ⁱⁱ	72.73 (9)	C16—C17—C18	122.1 (15)
O6ⁱ—Ca1—Ca1ⁱⁱ	152.07 (10)	C16—C17—H17	118.9
O3ⁱⁱ—Ca1—Ca1ⁱⁱ	39.55 (9)	C18—C17—H17	118.9
O4—Ca1—Ca1ⁱⁱ	84.04 (9)	C17—C18—C13	118.6 (12)
O2—Ca1—Ca1ⁱⁱ	127.10 (10)	C17—C18—H18	120.7
O5—Ca1—Ca1ⁱⁱ	75.25 (9)	C13—C18—H18	120.7
O6—Ca1—Ca1ⁱⁱ	122.98 (9)	C14'—C13'—C18'	120.0
O3—Ca1—Ca1ⁱⁱ	34.04 (7)	C14'—C13'—C19	119.4 (5)
C19—Ca1—Ca1ⁱⁱ	98.16 (11)	C18'—C13'—C19	120.6 (5)
C12—Ca1—Ca1ⁱⁱ	59.56 (10)	C13'—C14'—C15'	120.0
Ca1ⁱ—Ca1—Ca1ⁱⁱ	151.36 (6)	C13'—C14'—H14A	120.0
O1—Ca1—H2A	120.1	C15'—C14'—H14A	120.0
O6ⁱ—Ca1—H2A	73.1	C16'—C15'—C14'	120.0
O3ⁱⁱ—Ca1—H2A	96.2	C16'—C15'—H15A	120.0
O4—Ca1—H2A	135.5	C14'—C15'—H15A	120.0
O2—Ca1—H2A	16.5	C17'—C16'—C15'	120.0
O5—Ca1—H2A	82.1	C17'—C16'—H16A	120.0
O6—Ca1—H2A	63.2	C15'—C16'—H16A	120.0
O3—Ca1—H2A	160.0	C16'—C17'—C18'	120.0
C19—Ca1—H2A	73.5	C16'—C17'—H17A	120.0
C12—Ca1—H2A	157.2	C18'—C17'—H17A	120.0
Ca1ⁱ—Ca1—H2A	62.1	C17'—C18'—C13'	120.0
Ca1ⁱⁱ—Ca1—H2A	133.4	C17'—C18'—F2'	125.0
C1—N1—C5	117.5 (5)	C13'—C18'—F2'	114.8
Ca1—O1—H1B	124.9	O5—C19—O6	121.1 (5)
Ca1—O1—H1A	123.3	O5—C19—C13	117.2 (7)
H1B—O1—H1A	111.6	O6—C19—C13	121.7 (7)
Ca1—O2—H2B	129.3	O5—C19—C13'	120.8 (7)
Ca1—O2—H2A	106.1	O6—C19—C13'	118.0 (7)
H2B—O2—H2A	115.3	C13—C19—C13'	4.8 (6)
C12—O3—Ca1ⁱⁱ	167.0 (3)	O5—C19—Ca1	55.7 (3)
C12—O3—Ca1	86.5 (3)	O6—C19—Ca1	66.4 (3)
Ca1ⁱⁱ—O3—Ca1	106.41 (13)	C13—C19—Ca1	168.7 (8)
C12—O4—Ca1	101.4 (3)	C13'—C19—Ca1	167.9 (8)

Symmetry codes: (i) −x, −y+2, −z+1; (ii) −x+1, −y+2, −z+1; (iii) −x, −y+2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N1	0.82	2.21	2.835 (5)	133
O1—H1B···O5ⁱⁱ	0.82	2.02	2.782 (5)	154
O2—H2A···O4ⁱ	0.82	2.12	2.741 (5)	132
O2—H2B···F1^iv	0.82	2.62	3.363 (5)	151
C7—H7···O2ⁱⁱ	0.93	2.60	3.189 (7)	122
C10—H10···F2^v	0.93	2.54	3.281 (2)	136

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

Experimental details

Crystal data
Chemical formula	[Ca(C₇H₄FO₂)₂(H₂O)₂]·0.5C₁₀H₈N₂
M_r	432.41
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	7.9063 (16), 10.212 (2), 12.147 (2)
α, β, γ (°)	94.68 (3), 104.33 (3), 92.98 (3)
V (Å³)	944.4 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.39
Crystal size (mm)	0.34 × 0.19 × 0.16

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.914, 0.939
No. of measured, independent and observed [I > 2σ(I)] reflections	7478, 3306, 2136
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.214, 1.17
No. of reflections	3306
No. of parameters	271
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.64, −0.73

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N1	0.820	2.209	2.835 (5)	133
O1—H1B···O5ⁱ	0.820	2.021	2.782 (5)	154
O2—H2A···O4ⁱⁱ	0.820	2.123	2.741 (5)	132
O2—H2B···F1ⁱⁱⁱ	0.820	2.624	3.363 (5)	151
C7—H7···O2ⁱ	0.930	2.600	3.189 (7)	122
C10—H10···F2^iv	0.930	2.540	3.281 (2)	136

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

Acknowledgements

The authors gratefully acknowledge the financial support of the Education Office of Zhejiang Province (grant No. 20051316).

References

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