metal-organic compounds
Poly[μ5-{hydrogen bis[(E)-cinnamato]}-caesium]
aScience and Engineering Faculty, Queensland University of Technology, GPO Box 2434, Brisbane, Queensland 4001, Australia
*Correspondence e-mail: g.smith@qut.edu.au
In the structure of the title polymeric complex, [Cs(C9H7O2)(C9H8O2)]n, a caesium salt of trans-cinnamic acid, the Cs+ ions of the two individual irregular CsO8 coordination polyhedra lie on twofold rotation axes and are linked by four bridging carboxyl O-atom donors from two cinnamate ligand species. These two ligand components are interlinked through a delocalized H atom within a short O⋯H⋯O hydrogen bond. Structure extension gives a two-dimensional coordination polymer which lies parallel to (001). The structure was determined from a crystal twinned by non-merohedry, with a twin component ratio of approximately 1:1.
CCDC reference: 981265
Related literature
For the structures of the ammonium salts of hydrogen bis(3-chlorocinnamate) and hydrogen bis(3-bromocinnamate), see: Chowdhury & Kariuki (2006). For structures of alkali metal salts of ring-substituted trans-cinnamic acid, see: Kariuki et al. (1994, 1995); Crowther et al. (2008); Smith & Wermuth (2009, 2011). For the structure of trans-cinnamic acid, see: Wierda et al. (1989); Abdelmoty et al. (2005).
Experimental
Crystal data
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Data collection: CrysAlis PRO (Agilent, 2013); cell CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 2012); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON.
Supporting information
CCDC reference: 981265
10.1107/S1600536814000804/wm2798sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814000804/wm2798Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814000804/wm2798Isup3.cml
The title compound was synthesized by heating together for 10 minutes, 148 mg (1.0 mmol) of trans-cinnamic acid and 75 mg (0.5 mmol) of CsOH in 15 ml of an 1:9 (vol/vol) ethanol–water mixture. Partial room temperature evaporation of the solution gave colourless elongated crystals of the title complex from which a specimen was cleaved for the X-ray analysis. These crystals were invariably twinned, a feature identified in the later structure solution and
routines.Hydrogen atoms were placed in calculated positions [C—H = 0.95 Å] and allowed to ride in the 1 0 0, 0 1 0, 1.5 0 1) reducing the conventional R-factor from 0.23 to 0.072, with a final BASF factor (HKLF 5 format) of 0.4836. Maximum and minimum residual electron densities were 1.26 eÅ-3 (1.00 Å from Cs1) and -2.19 eÅ-3 (1.94 Å from H14B), respectively.
with Uiso(H) = 1.2Ueq(C). The carboxylic acid H-atom was found to be delocalized in a site approximating to midway between two carboxyl O-atoms of the dimeric acid–anion unit and was subsequently allowed to ride at that site, with Uiso(H) = 1.5Ueq(O). The presence of a non-merohedral twin was identified using TwinRotMat within PLATON (Spek, 2009) (twin law:The
of trans-cinnamic acid was reported by Wierda et al. (1989) and Abdelmoty et al. (2005). The alkali metal salts of trans-cinnamic acid are unknown in the crystallographic literature although a limited number of examples of salts of ring-substituted cinnamates have been reported, e.g. the sodium salts of 2-nitrocinnamate [a dihydrate (Smith & Wermuth, 2009)], of 2-chlorocinnamate [a dihydrate (Kariuki et al., 1995)], of 3-chlorocinnamate [anhydrous (Crowther et al., 2008), of 4-chlorocinnamate [a dihydrate (Kariuki et al., 1994); potassium salts of 3-chloro- and 3-bromocinnamate [both anhydrous (Crowther et al., 2008)]; and a rubidium salt of 2-nitrocinnamate [a monohydrate (Smith & Wermuth, 2011)].The reaction of trans-cinnamic acid with caesium hydroxide in aqueous ethanol afforded crystals of the title complex, [Cs(C9H7O2)(C9H8O2)]n, (I), the structure of which is reported herein.
In the structure of (I) the π–π interactions are present in the structure [minimun ring centroid separation = 4.826 (8) Å].
(Fig. 1) comprises two independent irregular CsO8 coordination polyhedra [Cs1—O, 3.060 (8)–3.183 (9) Å; Cs2—O, 3.063 (9)–3.377 (9) Å: Table 1], in which the Cs+ ions lie on a twofold rotation axis and are linked by four bridging carboxyl O-donors from the two trans-cinnamate ligand species. These two ligand species are inter-linked through a delocalized H atom on an approximately central intermediate site within a short O14A···H14B··· O14B hydrogen bond [2.462 (10) Å] (Table 2). Although this phenomenon involving coordinating dimeric carboxylate species is not known among the alkali metal substituted-cinnamate structures, it is found in both ammonium hydrogen bis(3-chlorocinnamate) and ammonium hydrogen bis(3-bromocinnamate) (Chowdhury & Kariuki, 2006), with the O···H···O values [2.554 (6) Å for the 3-Cl-analogue and 2.466 (5) Å for the 3-Br-analogue] similar to that in the structure of (I). In this complex, the two Cs+ ions are quadruply bridged giving a Cs1···Cs2 separation of 3.9318 (3) Å and generate an overall two-dimensional coordination polymer lying parallel to (001) (Figs. 2, 3). No inter-ringThe two linked cinnamate species in the title complex are close to coplanar [inter-ring dihedral angle = 3.9 (6)°], with the side chain carboxyl group of the A ligand component slightly rotated out of the plane [torsion angle C11A—C12A— C13A—O13A = 169.0 (13)°] compared to that of the B ligand component [torsion angle C11B—C12B— C13B—O14B = -179.2 (11)°]. With the analogous ammonium hydrogen salts of the 3-chloro- and 3-bromocinnamates (Chowdhury & Kariuki, 2006), the two cinnamate components are related either by crystallographic inversion symmetry (3-Cl) with the two benzene rings essentially planar, or by twofold rotational symmetry (3-Br) with the two rings significantly rotated out of the least-squares plane [inter-ring dihedral angle = 29.8 (2)°].
For the structures of the ammonium salts of hydrogen bis(3-chlorocinnamate) and hydrogen bis(3-bromocinnamate), see: Chowdhury & Kariuki (2006). For structures of alkali metal salts of ring-substituted trans-cinnamic acid, see: Kariuki et al. (1994, 1995); Crowther et al. (2008); Smith & Wermuth (2009, 2011). For the structure of trans-cinnamic acid, see: Wierda et al. (1989); Abdelmoty et al. (2005).
Data collection: CrysAlis PRO (Agilent, 2013); cell
CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 2012); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).Fig. 1. The atom-numbering scheme and the molecular configuration of the two ligands and the two CsO8 coordination polyhedra of the title complex, with non-H atoms drawn with displacement ellipsoids at the 40% probability level. The two Cs+ cations lie on twofold rotation axes. The O14A···O14B hydrogen bond with the delocalized H atom (H14B) is shown as a dashed link. [For symmetry codes: see Table 1]. | |
Fig. 2. A view of the partially expanded polymeric extension of the structure viewed along the approximate a-cell direction. C-bound H atoms are omitted. A and B denote the two different ligand components. | |
Fig. 3. The packing of the layered structure of compound (I) viewed along b. |
[Cs(C9H7O2)(C9H8O2)] | F(000) = 840 |
Mr = 428.21 | Dx = 1.655 Mg m−3 |
Monoclinic, P2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yc | Cell parameters from 1674 reflections |
a = 7.8608 (6) Å | θ = 3.6–28.2° |
b = 5.6985 (7) Å | µ = 2.17 mm−1 |
c = 38.817 (3) Å | T = 200 K |
β = 98.733 (6)° | Plate, colourless |
V = 1718.6 (3) Å3 | 0.35 × 0.35 × 0.06 mm |
Z = 4 |
Oxford Diffraction Gemini-S CCD-detector diffractometer | 3353 independent reflections |
Radiation source: Enhance (Mo) X-ray source | 2552 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
Detector resolution: 16.077 pixels mm-1 | θmax = 26.0°, θmin = 3.2° |
ω scans | h = −9→9 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013) | k = −7→7 |
Tmin = 0.711, Tmax = 0.980 | l = −11→47 |
6675 measured reflections |
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)] = 0.071 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.144 | H-atom parameters constrained |
S = 1.19 | w = 1/[σ2(Fo2) + (0.020P)2 + 18.34P] where P = (Fo2 + 2Fc2)/3 |
3353 reflections | (Δ/σ)max = 0.001 |
210 parameters | Δρmax = 1.26 e Å−3 |
0 restraints | Δρmin = −2.19 e Å−3 |
[Cs(C9H7O2)(C9H8O2)] | V = 1718.6 (3) Å3 |
Mr = 428.21 | Z = 4 |
Monoclinic, P2/c | Mo Kα radiation |
a = 7.8608 (6) Å | µ = 2.17 mm−1 |
b = 5.6985 (7) Å | T = 200 K |
c = 38.817 (3) Å | 0.35 × 0.35 × 0.06 mm |
β = 98.733 (6)° |
Oxford Diffraction Gemini-S CCD-detector diffractometer | 3353 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013) | 2552 reflections with I > 2σ(I) |
Tmin = 0.711, Tmax = 0.980 | Rint = 0.046 |
6675 measured reflections |
R[F2 > 2σ(F2)] = 0.071 | 0 restraints |
wR(F2) = 0.144 | H-atom parameters constrained |
S = 1.19 | w = 1/[σ2(Fo2) + (0.020P)2 + 18.34P] where P = (Fo2 + 2Fc2)/3 |
3353 reflections | Δρmax = 1.26 e Å−3 |
210 parameters | Δρmin = −2.19 e Å−3 |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
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 | ||
Cs1 | 0.50000 | 0.6438 (2) | 0.25000 | 0.0261 (3) | |
Cs2 | 0.00000 | 0.6257 (2) | 0.25000 | 0.0300 (3) | |
O13A | 0.2828 (13) | −0.1322 (15) | 0.3028 (2) | 0.037 (3) | |
O13B | 0.2180 (12) | 0.3903 (14) | 0.20079 (19) | 0.030 (3) | |
O14A | 0.3036 (12) | 0.2355 (14) | 0.28374 (18) | 0.029 (3) | |
O14B | 0.2197 (13) | 0.0396 (14) | 0.22718 (18) | 0.033 (3) | |
C1A | 0.5037 (15) | 0.4316 (19) | 0.3905 (3) | 0.025 (3) | |
C1B | 0.0000 (15) | 0.079 (2) | 0.1031 (3) | 0.025 (3) | |
C2A | 0.5963 (19) | 0.636 (2) | 0.3964 (3) | 0.035 (4) | |
C2B | 0.0132 (16) | 0.208 (2) | 0.0728 (3) | 0.028 (3) | |
C3A | 0.6620 (19) | 0.707 (2) | 0.4301 (4) | 0.042 (5) | |
C3B | −0.0664 (16) | 0.128 (3) | 0.0403 (3) | 0.040 (4) | |
C4A | 0.6346 (18) | 0.574 (3) | 0.4585 (3) | 0.042 (5) | |
C4B | −0.1524 (18) | −0.082 (2) | 0.0373 (3) | 0.041 (4) | |
C5A | 0.5426 (19) | 0.373 (3) | 0.4529 (3) | 0.039 (4) | |
C5B | −0.1628 (16) | −0.210 (2) | 0.0668 (3) | 0.035 (4) | |
C6A | 0.4764 (15) | 0.299 (2) | 0.4191 (3) | 0.029 (4) | |
C6B | −0.0870 (15) | −0.133 (2) | 0.0997 (3) | 0.031 (4) | |
C11A | 0.4356 (17) | 0.359 (2) | 0.3541 (3) | 0.032 (4) | |
C11B | 0.0831 (14) | 0.173 (2) | 0.1369 (3) | 0.025 (3) | |
C12A | 0.3722 (13) | 0.155 (2) | 0.3444 (3) | 0.023 (3) | |
C12B | 0.1178 (15) | 0.054 (2) | 0.1672 (3) | 0.026 (3) | |
C13A | 0.3148 (16) | 0.076 (2) | 0.3078 (3) | 0.028 (4) | |
C13B | 0.1901 (15) | 0.176 (2) | 0.1998 (3) | 0.027 (4) | |
H2A | 0.61560 | 0.73090 | 0.37720 | 0.0410* | |
H2B | 0.07640 | 0.35110 | 0.07440 | 0.0340* | |
H3A | 0.72650 | 0.84820 | 0.43360 | 0.0510* | |
H3B | −0.06090 | 0.21990 | 0.02000 | 0.0480* | |
H4A | 0.67930 | 0.62310 | 0.48150 | 0.0500* | |
H4B | −0.20410 | −0.13800 | 0.01520 | 0.0490* | |
H5A | 0.52280 | 0.28000 | 0.47230 | 0.0470* | |
H5B | −0.22320 | −0.35490 | 0.06480 | 0.0410* | |
H6A | 0.41240 | 0.15700 | 0.41580 | 0.0350* | |
H6B | −0.09500 | −0.22560 | 0.11970 | 0.0370* | |
H11A | 0.43910 | 0.47280 | 0.33640 | 0.0380* | |
H11B | 0.11540 | 0.33430 | 0.13740 | 0.0290* | |
H12A | 0.36110 | 0.04540 | 0.36230 | 0.0280* | |
H12B | 0.09570 | −0.10990 | 0.16760 | 0.0320* | |
H14B | 0.26080 | 0.13620 | 0.25500 | 0.0500* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cs1 | 0.0221 (5) | 0.0212 (5) | 0.0350 (5) | 0.0000 | 0.0041 (5) | 0.0000 |
Cs2 | 0.0232 (5) | 0.0238 (6) | 0.0438 (6) | 0.0000 | 0.0075 (6) | 0.0000 |
O13A | 0.056 (5) | 0.027 (5) | 0.028 (4) | −0.001 (6) | 0.003 (4) | −0.006 (4) |
O13B | 0.047 (5) | 0.026 (4) | 0.016 (4) | −0.004 (5) | 0.000 (4) | 0.000 (3) |
O14A | 0.046 (6) | 0.033 (5) | 0.006 (3) | −0.003 (4) | −0.006 (3) | −0.005 (3) |
O14B | 0.055 (5) | 0.025 (4) | 0.013 (4) | −0.004 (5) | −0.015 (4) | −0.005 (3) |
C1A | 0.022 (6) | 0.022 (6) | 0.030 (6) | 0.003 (5) | 0.006 (5) | −0.009 (5) |
C1B | 0.020 (5) | 0.034 (6) | 0.022 (5) | 0.004 (6) | 0.005 (5) | −0.007 (5) |
C2A | 0.038 (7) | 0.027 (6) | 0.039 (6) | −0.004 (7) | 0.007 (6) | 0.003 (6) |
C2B | 0.027 (6) | 0.028 (6) | 0.027 (6) | 0.007 (6) | 0.000 (5) | −0.003 (5) |
C3A | 0.044 (9) | 0.021 (7) | 0.059 (9) | 0.012 (6) | −0.002 (7) | −0.024 (6) |
C3B | 0.043 (8) | 0.050 (8) | 0.027 (6) | 0.026 (8) | 0.005 (5) | 0.000 (7) |
C4A | 0.031 (7) | 0.059 (10) | 0.033 (7) | 0.006 (8) | −0.001 (6) | −0.022 (7) |
C4B | 0.037 (7) | 0.053 (8) | 0.030 (7) | −0.011 (8) | −0.003 (6) | −0.012 (6) |
C5A | 0.035 (7) | 0.048 (7) | 0.035 (6) | −0.003 (8) | 0.005 (6) | 0.012 (7) |
C5B | 0.029 (7) | 0.021 (6) | 0.054 (8) | −0.005 (6) | 0.006 (6) | −0.004 (6) |
C6A | 0.031 (7) | 0.027 (7) | 0.030 (6) | −0.007 (6) | 0.005 (5) | 0.004 (5) |
C6B | 0.032 (7) | 0.027 (6) | 0.032 (6) | −0.002 (6) | 0.002 (5) | −0.002 (6) |
C11A | 0.035 (7) | 0.029 (6) | 0.032 (6) | −0.002 (7) | 0.006 (6) | 0.002 (6) |
C11B | 0.030 (6) | 0.021 (6) | 0.021 (5) | −0.004 (5) | −0.001 (4) | 0.001 (5) |
C12A | 0.036 (6) | 0.017 (6) | 0.016 (5) | −0.008 (5) | 0.002 (4) | −0.008 (5) |
C12B | 0.038 (7) | 0.013 (5) | 0.027 (6) | −0.009 (5) | 0.001 (5) | 0.006 (5) |
C13A | 0.021 (6) | 0.036 (8) | 0.027 (6) | −0.002 (6) | 0.003 (5) | 0.002 (5) |
C13B | 0.023 (6) | 0.043 (8) | 0.015 (5) | 0.000 (6) | −0.001 (5) | −0.010 (6) |
Cs1—O13B | 3.060 (8) | C2A—C3A | 1.392 (19) |
Cs1—O14A | 3.182 (8) | C2B—C3B | 1.397 (17) |
Cs1—O13Ai | 3.132 (9) | C3A—C4A | 1.38 (2) |
Cs1—O14Bi | 3.183 (9) | C3B—C4B | 1.37 (2) |
Cs1—O13Bii | 3.060 (8) | C4A—C5A | 1.35 (2) |
Cs1—O14Aii | 3.182 (8) | C4B—C5B | 1.371 (16) |
Cs1—O13Aiii | 3.132 (9) | C5A—C6A | 1.401 (17) |
Cs1—O14Biii | 3.183 (9) | C5B—C6B | 1.396 (16) |
Cs2—O13B | 3.063 (8) | C11A—C12A | 1.298 (16) |
Cs2—O14A | 3.377 (9) | C11B—C12B | 1.349 (16) |
Cs2—O13Ai | 3.108 (9) | C12A—C13A | 1.493 (16) |
Cs2—O14Bi | 3.130 (9) | C12B—C13B | 1.480 (16) |
Cs2—O13Biv | 3.063 (8) | C2A—H2A | 0.9500 |
Cs2—O14Aiv | 3.377 (9) | C2B—H2B | 0.9500 |
Cs2—O13Av | 3.108 (9) | C3A—H3A | 0.9500 |
Cs2—O14Bv | 3.130 (9) | C3B—H3B | 0.9500 |
O13A—C13A | 1.222 (14) | C4A—H4A | 0.9500 |
O13B—C13B | 1.240 (14) | C4B—H4B | 0.9500 |
O14A—C13A | 1.297 (14) | C5A—H5A | 0.9500 |
O14B—C13B | 1.309 (14) | C5B—H5B | 0.9500 |
O14B—H14B | 1.2100 | C6A—H6A | 0.9500 |
C1A—C11A | 1.492 (16) | C6B—H6B | 0.9500 |
C1A—C2A | 1.374 (17) | C11A—H11A | 0.9500 |
C1A—C6A | 1.386 (16) | C11B—H11B | 0.9500 |
C1B—C11B | 1.475 (16) | C12A—H12A | 0.9500 |
C1B—C6B | 1.385 (16) | C12B—H12B | 0.9500 |
C1B—C2B | 1.404 (16) | ||
O13B—Cs1—O14A | 64.0 (2) | Cs2—O14A—C13A | 135.0 (8) |
O13Ai—Cs1—O13B | 100.7 (2) | Cs1vi—O14B—C13B | 132.6 (7) |
O13B—Cs1—O14Bi | 75.9 (2) | Cs2vi—O14B—C13B | 129.8 (7) |
O13B—Cs1—O13Bii | 123.7 (2) | Cs1vi—O14B—Cs2vi | 77.04 (18) |
O13B—Cs1—O14Aii | 75.4 (2) | Cs1—O14A—H14B | 93.00 |
O13Aiii—Cs1—O13B | 101.5 (2) | Cs2—O14A—H14B | 83.00 |
O13B—Cs1—O14Biii | 155.98 (19) | Cs2vi—O14B—H14B | 100.00 |
O13Ai—Cs1—O14A | 71.5 (2) | Cs1vi—O14B—H14B | 90.00 |
O14A—Cs1—O14Bi | 105.9 (2) | C13B—O14B—H14B | 116.00 |
O13Bii—Cs1—O14A | 75.4 (2) | C6A—C1A—C11A | 122.0 (10) |
O14A—Cs1—O14Aii | 86.0 (2) | C2A—C1A—C6A | 118.1 (11) |
O13Aiii—Cs1—O14A | 156.1 (2) | C2A—C1A—C11A | 119.9 (10) |
O14A—Cs1—O14Biii | 139.65 (18) | C2B—C1B—C6B | 118.4 (11) |
O13Ai—Cs1—O14Bi | 58.0 (2) | C2B—C1B—C11B | 118.4 (10) |
O13Ai—Cs1—O13Bii | 101.5 (2) | C6B—C1B—C11B | 123.2 (10) |
O13Ai—Cs1—O14Aii | 156.1 (2) | C1A—C2A—C3A | 121.0 (11) |
O13Ai—Cs1—O13Aiii | 131.9 (2) | C1B—C2B—C3B | 120.4 (12) |
O13Ai—Cs1—O14Biii | 87.3 (2) | C2A—C3A—C4A | 120.7 (12) |
O13Bii—Cs1—O14Bi | 155.98 (19) | C2B—C3B—C4B | 120.6 (12) |
O14Aii—Cs1—O14Bi | 139.65 (18) | C3A—C4A—C5A | 118.7 (12) |
O13Aiii—Cs1—O14Bi | 87.3 (2) | C3B—C4B—C5B | 119.0 (11) |
O14Bi—Cs1—O14Biii | 89.8 (2) | C4A—C5A—C6A | 121.2 (12) |
O13Bii—Cs1—O14Aii | 64.0 (2) | C4B—C5B—C6B | 121.7 (11) |
O13Aiii—Cs1—O13Bii | 100.7 (2) | C1A—C6A—C5A | 120.4 (11) |
O13Bii—Cs1—O14Biii | 75.9 (2) | C1B—C6B—C5B | 119.8 (11) |
O13Aiii—Cs1—O14Aii | 71.5 (2) | C1A—C11A—C12A | 126.2 (11) |
O14Aii—Cs1—O14Biii | 105.9 (2) | C1B—C11B—C12B | 126.6 (11) |
O13Aiii—Cs1—O14Biii | 58.0 (2) | C11A—C12A—C13A | 126.4 (11) |
O13B—Cs2—O14A | 61.58 (19) | C11B—C12B—C13B | 120.7 (10) |
O13Ai—Cs2—O13B | 101.2 (2) | O13A—C13A—C12A | 118.0 (10) |
O13B—Cs2—O14Bi | 76.6 (2) | O13A—C13A—O14A | 125.2 (11) |
O13B—Cs2—O13Biv | 128.1 (2) | O14A—C13A—C12A | 116.9 (10) |
O13B—Cs2—O14Aiv | 84.2 (2) | O14B—C13B—C12B | 114.4 (10) |
O13Av—Cs2—O13B | 101.3 (2) | O13B—C13B—O14B | 123.4 (10) |
O13B—Cs2—O14Bv | 153.1 (2) | O13B—C13B—C12B | 122.2 (10) |
O13Ai—Cs2—O14A | 69.2 (2) | C1A—C2A—H2A | 120.00 |
O14A—Cs2—O14Bi | 102.6 (2) | C3A—C2A—H2A | 119.00 |
O13Biv—Cs2—O14A | 84.2 (2) | C1B—C2B—H2B | 120.00 |
O14A—Cs2—O14Aiv | 97.7 (2) | C3B—C2B—H2B | 120.00 |
O13Av—Cs2—O14A | 160.1 (2) | C2A—C3A—H3A | 120.00 |
O14A—Cs2—O14Bv | 140.74 (18) | C4A—C3A—H3A | 120.00 |
O13Ai—Cs2—O14Bi | 58.8 (2) | C2B—C3B—H3B | 120.00 |
O13Ai—Cs2—O13Biv | 101.3 (2) | C4B—C3B—H3B | 120.00 |
O13Ai—Cs2—O14Aiv | 160.1 (2) | C3A—C4A—H4A | 121.00 |
O13Ai—Cs2—O13Av | 127.3 (2) | C5A—C4A—H4A | 121.00 |
O13Ai—Cs2—O14Bv | 81.3 (2) | C3B—C4B—H4B | 121.00 |
O13Biv—Cs2—O14Bi | 153.1 (2) | C5B—C4B—H4B | 120.00 |
O14Aiv—Cs2—O14Bi | 140.74 (18) | C4A—C5A—H5A | 119.00 |
O13Av—Cs2—O14Bi | 81.3 (2) | C6A—C5A—H5A | 119.00 |
O14Bi—Cs2—O14Bv | 82.2 (2) | C4B—C5B—H5B | 119.00 |
O13Biv—Cs2—O14Aiv | 61.58 (19) | C6B—C5B—H5B | 119.00 |
O13Av—Cs2—O13Biv | 101.2 (2) | C1A—C6A—H6A | 120.00 |
O13Biv—Cs2—O14Bv | 76.6 (2) | C5A—C6A—H6A | 120.00 |
O13Av—Cs2—O14Aiv | 69.2 (2) | C1B—C6B—H6B | 120.00 |
O14Aiv—Cs2—O14Bv | 102.6 (2) | C5B—C6B—H6B | 120.00 |
O13Av—Cs2—O14Bv | 58.8 (2) | C1A—C11A—H11A | 117.00 |
Cs1vi—O13A—C13A | 112.3 (8) | C12A—C11A—H11A | 117.00 |
Cs2vi—O13A—C13A | 130.2 (8) | C1B—C11B—H11B | 117.00 |
Cs1vi—O13A—Cs2vi | 78.11 (18) | C12B—C11B—H11B | 117.00 |
Cs1—O13B—Cs2 | 79.91 (18) | C11A—C12A—H12A | 117.00 |
Cs1—O13B—C13B | 126.3 (7) | C13A—C12A—H12A | 117.00 |
Cs2—O13B—C13B | 109.7 (7) | C11B—C12B—H12B | 120.00 |
Cs1—O14A—Cs2 | 73.59 (16) | C13B—C12B—H12B | 120.00 |
Cs1—O14A—C13A | 145.6 (8) | ||
O14A—Cs1—O13B—Cs2 | 65.6 (2) | O13Biv—Cs2—O14A—Cs1 | −160.72 (18) |
O14A—Cs1—O13B—C13B | −41.6 (9) | O13Biv—Cs2—O14A—C13A | −3.5 (9) |
O13Ai—Cs1—O13B—Cs2 | 2.5 (2) | O14Aiv—Cs2—O14A—Cs1 | 139.03 (16) |
O13Ai—Cs1—O13B—C13B | −104.7 (9) | O14Aiv—Cs2—O14A—C13A | −63.8 (10) |
O14Bi—Cs1—O13B—Cs2 | −50.38 (19) | O14Bv—Cs2—O14A—Cs1 | −100.2 (3) |
O14Bi—Cs1—O13B—C13B | −157.5 (9) | O14Bv—Cs2—O14A—C13A | 57.0 (11) |
O13Bii—Cs1—O13B—Cs2 | 114.2 (2) | O13B—Cs2—O13Ai—Cs1 | 2.5 (2) |
O13Bii—Cs1—O13B—C13B | 7.0 (10) | O14A—Cs2—O13Ai—Cs1 | 56.01 (18) |
O14Aii—Cs1—O13B—Cs2 | 158.3 (2) | O13B—Cs2—O14Bi—Cs1 | −49.32 (18) |
O14Aii—Cs1—O13B—C13B | 51.2 (9) | O14A—Cs2—O14Bi—Cs1 | 7.01 (18) |
O13Aiii—Cs1—O13B—Cs2 | −134.6 (2) | Cs1vi—O13A—C13A—O14A | 56.2 (15) |
O13Aiii—Cs1—O13B—C13B | 118.3 (9) | Cs1vi—O13A—C13A—C12A | −123.5 (9) |
O14Biii—Cs1—O13B—Cs2 | −105.2 (5) | Cs2vi—O13A—C13A—O14A | −37.0 (18) |
O14Biii—Cs1—O13B—C13B | 147.6 (9) | Cs2vi—O13A—C13A—C12A | 143.3 (8) |
O13B—Cs1—O14A—Cs2 | −57.9 (2) | Cs1—O13B—C13B—O14B | 31.2 (16) |
O13B—Cs1—O14A—C13A | 151.0 (13) | Cs1—O13B—C13B—C12B | −149.6 (8) |
O13Ai—Cs1—O14A—Cs2 | 54.52 (19) | Cs2—O13B—C13B—O14B | −60.7 (13) |
O13Ai—Cs1—O14A—C13A | −96.5 (12) | Cs2—O13B—C13B—C12B | 118.6 (10) |
O14Bi—Cs1—O14A—Cs2 | 7.10 (18) | Cs1—O14A—C13A—O13A | −125.8 (12) |
O14Bi—Cs1—O14A—C13A | −143.9 (12) | Cs1—O14A—C13A—C12A | 54.0 (17) |
O13Bii—Cs1—O14A—Cs2 | 162.23 (19) | Cs2—O14A—C13A—O13A | 95.3 (14) |
O13Bii—Cs1—O14A—C13A | 11.2 (12) | Cs2—O14A—C13A—C12A | −85.0 (13) |
O14Aii—Cs1—O14A—Cs2 | −133.66 (17) | Cs1vi—O14B—C13B—O13B | −109.4 (12) |
O14Aii—Cs1—O14A—C13A | 75.3 (12) | Cs1vi—O14B—C13B—C12B | 71.3 (13) |
O13Aiii—Cs1—O14A—Cs2 | −114.2 (5) | Cs2vi—O14B—C13B—O13B | 138.9 (10) |
O13Aiii—Cs1—O14A—C13A | 94.7 (13) | Cs2vi—O14B—C13B—C12B | −40.4 (14) |
O14Biii—Cs1—O14A—Cs2 | 116.3 (3) | C6A—C1A—C2A—C3A | 0.5 (19) |
O14Biii—Cs1—O14A—C13A | −34.7 (14) | C11A—C1A—C2A—C3A | −179.7 (12) |
O13B—Cs1—O13Ai—Cs2 | −2.5 (2) | C2A—C1A—C6A—C5A | −0.2 (18) |
O14A—Cs1—O13Ai—Cs2 | −60.15 (19) | C11A—C1A—C6A—C5A | 179.9 (12) |
O13B—Cs1—O14Bi—Cs2 | 49.60 (18) | C2A—C1A—C11A—C12A | 167.7 (13) |
O14A—Cs1—O14Bi—Cs2 | −7.55 (19) | C6A—C1A—C11A—C12A | −13 (2) |
O14A—Cs2—O13B—Cs1 | −61.2 (2) | C6B—C1B—C2B—C3B | 2.8 (18) |
O14A—Cs2—O13B—C13B | 63.9 (7) | C11B—C1B—C2B—C3B | −178.7 (11) |
O13Ai—Cs2—O13B—Cs1 | −2.5 (2) | C2B—C1B—C6B—C5B | −1.7 (18) |
O13Ai—Cs2—O13B—C13B | 122.6 (7) | C11B—C1B—C6B—C5B | 179.8 (11) |
O14Bi—Cs2—O13B—Cs1 | 51.35 (19) | C2B—C1B—C11B—C12B | −164.0 (12) |
O14Bi—Cs2—O13B—C13B | 176.5 (8) | C6B—C1B—C11B—C12B | 14.4 (19) |
O13Biv—Cs2—O13B—Cs1 | −116.5 (2) | C1A—C2A—C3A—C4A | 0 (2) |
O13Biv—Cs2—O13B—C13B | 8.6 (8) | C1B—C2B—C3B—C4B | −3 (2) |
O14Aiv—Cs2—O13B—Cs1 | −163.16 (19) | C2A—C3A—C4A—C5A | 0 (2) |
O14Aiv—Cs2—O13B—C13B | −38.1 (7) | C2B—C3B—C4B—C5B | 2 (2) |
O13Av—Cs2—O13B—Cs1 | 129.5 (2) | C3A—C4A—C5A—C6A | 0 (2) |
O13Av—Cs2—O13B—C13B | −105.4 (7) | C3B—C4B—C5B—C6B | −1 (2) |
O14Bv—Cs2—O13B—Cs1 | 90.3 (5) | C4A—C5A—C6A—C1A | 0 (2) |
O14Bv—Cs2—O13B—C13B | −144.6 (7) | C4B—C5B—C6B—C1B | 0.7 (19) |
O13B—Cs2—O14A—Cs1 | 59.9 (2) | C1A—C11A—C12A—C13A | −175.6 (12) |
O13B—Cs2—O14A—C13A | −142.9 (10) | C1B—C11B—C12B—C13B | −175.3 (11) |
O13Ai—Cs2—O14A—Cs1 | −56.3 (2) | C11A—C12A—C13A—O13A | 169.0 (13) |
O13Ai—Cs2—O14A—C13A | 100.9 (10) | C11A—C12A—C13A—O14A | −10.7 (18) |
O14Bi—Cs2—O14A—Cs1 | −7.12 (18) | C11B—C12B—C13B—O13B | 1.6 (18) |
O14Bi—Cs2—O14A—C13A | 150.1 (9) | C11B—C12B—C13B—O14B | −179.2 (11) |
Symmetry codes: (i) x, y+1, z; (ii) −x+1, y, −z+1/2; (iii) −x+1, y+1, −z+1/2; (iv) −x, y, −z+1/2; (v) −x, y+1, −z+1/2; (vi) x, y−1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O14B—H14B···O14A | 1.21 | 1.25 | 2.462 (10) | 180 |
C11B—H11B···O13B | 0.95 | 2.49 | 2.830 (14) | 101 |
Cs1—O13B | 3.060 (8) | Cs2—O13B | 3.063 (8) |
Cs1—O14A | 3.182 (8) | Cs2—O14A | 3.377 (9) |
Cs1—O13Ai | 3.132 (9) | Cs2—O13Ai | 3.108 (9) |
Cs1—O14Bi | 3.183 (9) | Cs2—O14Bi | 3.130 (9) |
Cs1—O13Bii | 3.060 (8) | Cs2—O13Biv | 3.063 (8) |
Cs1—O14Aii | 3.182 (8) | Cs2—O14Aiv | 3.377 (9) |
Cs1—O13Aiii | 3.132 (9) | Cs2—O13Av | 3.108 (9) |
Cs1—O14Biii | 3.183 (9) | Cs2—O14Bv | 3.130 (9) |
Symmetry codes: (i) x, y+1, z; (ii) −x+1, y, −z+1/2; (iii) −x+1, y+1, −z+1/2; (iv) −x, y, −z+1/2; (v) −x, y+1, −z+1/2. |
Acknowledgements
The author acknowledges financial support from the Science and Engineering Faculty and the University Library, Queensland University of Technology.
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
The crystal structure of trans-cinnamic acid was reported by Wierda et al. (1989) and Abdelmoty et al. (2005). The alkali metal salts of trans-cinnamic acid are unknown in the crystallographic literature although a limited number of examples of salts of ring-substituted cinnamates have been reported, e.g. the sodium salts of 2-nitrocinnamate [a dihydrate (Smith & Wermuth, 2009)], of 2-chlorocinnamate [a dihydrate (Kariuki et al., 1995)], of 3-chlorocinnamate [anhydrous (Crowther et al., 2008), of 4-chlorocinnamate [a dihydrate (Kariuki et al., 1994); potassium salts of 3-chloro- and 3-bromocinnamate [both anhydrous (Crowther et al., 2008)]; and a rubidium salt of 2-nitrocinnamate [a monohydrate (Smith & Wermuth, 2011)].
The reaction of trans-cinnamic acid with caesium hydroxide in aqueous ethanol afforded crystals of the title complex, [Cs(C9H7O2)(C9H8O2)]n, (I), the structure of which is reported herein.
In the structure of (I) the asymmetric unit (Fig. 1) comprises two independent irregular CsO8 coordination polyhedra [Cs1—O, 3.060 (8)–3.183 (9) Å; Cs2—O, 3.063 (9)–3.377 (9) Å: Table 1], in which the Cs+ ions lie on a twofold rotation axis and are linked by four bridging carboxyl O-donors from the two trans-cinnamate ligand species. These two ligand species are inter-linked through a delocalized H atom on an approximately central intermediate site within a short O14A···H14B··· O14B hydrogen bond [2.462 (10) Å] (Table 2). Although this phenomenon involving coordinating dimeric carboxylate species is not known among the alkali metal substituted-cinnamate structures, it is found in both ammonium hydrogen bis(3-chlorocinnamate) and ammonium hydrogen bis(3-bromocinnamate) (Chowdhury & Kariuki, 2006), with the O···H···O values [2.554 (6) Å for the 3-Cl-analogue and 2.466 (5) Å for the 3-Br-analogue] similar to that in the structure of (I). In this complex, the two Cs+ ions are quadruply bridged giving a Cs1···Cs2 separation of 3.9318 (3) Å and generate an overall two-dimensional coordination polymer lying parallel to (001) (Figs. 2, 3). No inter-ring π–π interactions are present in the structure [minimun ring centroid separation = 4.826 (8) Å].
The two linked cinnamate species in the title complex are close to coplanar [inter-ring dihedral angle = 3.9 (6)°], with the side chain carboxyl group of the A ligand component slightly rotated out of the plane [torsion angle C11A—C12A— C13A—O13A = 169.0 (13)°] compared to that of the B ligand component [torsion angle C11B—C12B— C13B—O14B = -179.2 (11)°]. With the analogous ammonium hydrogen salts of the 3-chloro- and 3-bromocinnamates (Chowdhury & Kariuki, 2006), the two cinnamate components are related either by crystallographic inversion symmetry (3-Cl) with the two benzene rings essentially planar, or by twofold rotational symmetry (3-Br) with the two rings significantly rotated out of the least-squares plane [inter-ring dihedral angle = 29.8 (2)°].