Crystal structure of dicesium hydrogen citrate from laboratory single-crystal and powder X-ray diffraction data and DFT comparison

Rammohan, A.; Sarjeant, A.A.; Kaduk, J.A.

doi:10.1107/S2056989017000792

research communications

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ISSN: 2056-9890

Volume 73| Part 2| February 2017| Pages 231-234

https://doi.org/10.1107/S2056989017000792

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Crystal structure of dicesium hydrogen citrate from laboratory single-crystal and powder X-ray diffraction data and DFT comparison

Alagappa Rammohan,^a ‡ Amy A. Sarjeant ^b and James A. Kaduk ^c ^*

^aAtlantic International University, Honolulu HI , USA, ^bDepartment of Chemistry, Northwestern University, Evanston IL , USA, and ^cIllinois Institute of Technology, Department of Chemistry, 3101 S. Dearborn St., Chicago IL 60616, USA
^*Correspondence e-mail: kaduk@polycrystallography.com

Edited by M. Weil, Vienna University of Technology, Austria (Received 4 January 2017; accepted 16 January 2017; online 20 January 2017)

The crystal structure of dicesium hydrogen citrate, 2Cs⁺·C₆H₆O₇²⁻, has been solved using laboratory X-ray single-crystal diffraction data, refined using laboratory powder X-ray data, and optimized using density functional techniques. The Cs⁺ cation is nine-coordinate, with a bond-valence sum of 0.92 valence units. The CsO₉ coordination polyhedra share edges and corners to form a three-dimensional framework. The citrate anion is located on a mirror plane. Its central hydroxy/carboxylate O—H⋯O hydrogen bond is short, and (unusually) intermolecular. The centrosymmetric end-end carboxylate hydrogen bond is exceptionally short (O⋯O = 2.416 Å) and strong. These hydrogen bonds contribute 16.5 and 21.7 kcal mol⁻¹, respectively, to the crystal energy. The hydrophobic methylene groups occupy pockets in the framework.

Keywords: crystal structure; powder diffraction; density functional theory; citrate; cesium.

CCDC references: 1527789; 1527790; 1527791; 1527792

1. Chemical context

In the course of a systematic study of the crystal structures of group 1 (alkali metal) citrate salts to understand the anion's conformational flexibility, ionization, coordination tendencies, and hydrogen bonding, we have determined several new crystal structures. Most of the new structures were solved using X-ray powder diffraction data (laboratory and/or synchrotron), but single crystals were used where available. The general trends and conclusions about the sixteen new compounds and twelve previously determined structures are being reported separately (Rammohan & Kaduk, 2017a ). Eleven of the new structures – NaKHC₆H₅O₇, NaK₂C₆H₅O₇, Na₃C₆H₅O₇, NaH₂C₆H₅O₇, Na₂HC₆H₅O₇, K₃C₆H₅O₇, Rb₂HC₆H₅O₇, Rb₃C₆H₅O₇(H₂O), Rb₃C₆H₅O₇, Na₅H(C₆H₅O₇)₂, and CsH₂C₆H₅O₇ – have been published recently (Rammohan & Kaduk, 2016a ,b ,c ,d ,e , 2017b ,c ,d ,e ,f , Rammohan et al., 2016 ), and two additional structures – KH₂C₆H₅O₇ and KH₂C₆H₅O₇(H₂O)₂ – have been communicated to the Cambridge Structural Database (CSD) (Kaduk & Stern, 2016a ,b ). We report here synthesis and crystal structure of another alkali metal citrate salt, 2Cs⁺·HC₆H₅O₇²⁻.

2. Structural commentary

The asymmetric unit of the title compound is shown in Fig. 1. The root-mean-square deviation of the non-hydrogen atoms in the experimentally determined and in the DFT-optimized structures is 0.098 Å (Fig. 2). The largest differences are 0.13 Å, at Cs19 and O11. This good agreement provides strong evidence that the experimentally determined structure is correct (van de Streek & Neumann, 2014 ). The following discussion uses the DFT-optimized structure.

Figure 1
The asymmetric unit of the title compound, with the atom numbering. The atoms are represented by 50% probability spheroids.

Figure 2
Comparison of the refined and optimized structures of dicesium hydrogen citrate. The refined structure is in red, and the DFT-optimized structure is in blue.

Most of the bond lengths, bond angles, and torsion angles fall within the normal ranges indicated by a Mercury Mogul geometry check (Macrae et al., 2008 ). The C1—C2—C3 angle of 114.1° is flagged as unusual (average = 104.0 (32), Z-score = 3.1). The Cs⁺ cation is 9-coordinate, with a bond-valence sum of 0.92 valence units. The location of the citrate anion on a mirror plane and the coordination of all seven oxygen atoms to Cs⁺ cations presumably are the source of the slight distortion. The citrate anion occurs in the trans,trans conformation, which is one of the two low-energy conformations of an isolated citrate moiety. The citrate anion triply chelates to two Cs⁺ cations through O12, O17, and O15. The citrate also chelates through O12/O16, O15/O17, and O15/O16. The Mulliken overlap populations and atomic charges indicate that the metal-oxygen bonding is ionic. The Bravais–Friedel–Donnay–Harker (Bravais, 1866 ; Friedel, 1907 ; Donnay & Harker, 1937 ) morphology is blocky, with {020} as major faces. A 4th-order spherical harmonic model was included in the refinement. The texture index was 1.016, indicating that preferred orientation was slight in the rotated flat-plate specimen.

3. Supramolecular features

The CsO₉ coordination polyhedra share edges and corners to form a three-dimensional framework (Fig. 3). The central hydroxy/carboxylate O—H⋯O hydrogen O17—H18⋯O16 is short, and (unusually) intermolecular. The centrosymmetric end-end O12—H20—O12 hydrogen bond (with H20 situated on an inversion center) is exceptionally short and strong (Table 1). By the correlation of Rammohan & Kaduk (2017a), these hydrogen bonds contribute 16.5 and 21.7 kcal mol⁻¹ to the crystal energy. The hydrophobic methylene groups occupy pockets in the framework (Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O12—H20⋯O12ⁱ	1.208	1.208	2.416	180.0
O17—H18⋯O16ⁱⁱ	0.999	1.634	2.632	178.2
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 3
Crystal structure of Cs₂HC₆H₅O₇, viewed down the a-axis. CsO₉ polyhedra are green.

4. Database survey

Details of the comprehensive literature search for citrate structures are presented in Rammohan & Kaduk (2017a). A reduced cell search of the cell of dicesium hydrogen citrate in the Cambridge Structural Database (Groom et al., 2016 ) (increasing the default tolerance from 1.5 to 2.0%) yielded 100 hits, but combining the cell search with the elements C, H, Cs, and O only yielded no hits.

5. Synthesis and crystallization

Citric acid monohydrate, H₃C₆H₅O₇(H₂O), (2.0796 g, 10.0 mmol) was dissolved in 20 ml deionized water. Cs₂CO₃ (3.2582 g, 10.0 mmol, Sigma–Aldrich) was added to the citric acid solution slowly with stirring. The resulting clear colourless solution was evaporated to dryness in a 333 K oven. Single crystals were isolated from the colourless solid.

6. Refinement

A single crystal was mounted in inert oil and transferred to the cold gas stream of a Bruker Kappa APEX CCD area detector system equipped with a Cu Kα sealed tube with MX optics. Despite suggestions from multiple programs that the space group was Pnma, all attempts to refine the structure in this space group yielded unreasonable disorder and non-positive-definite displacement coefficients. Presumably the poor crystal quality and/or twinning were the source of the problems. The best refinement using single crystal data was obtained using space group P2₁2₁2₁.

A portion of the sample was ground in a mortar and pestle, and blended with NIST SRM 640b silicon internal standard. The powder pattern indicated that the sample contained about 24 wt% CsHC₆H₅O₇ (Rammohan & Kaduk, 2017f), which was included as phase 2 in the refinement. The Si internal standard was included as phase 3.

Initial Rietveld refinements used the single crystal P2₁2₁2₁ model, but were unstable. The ADDSYM module of PLATON (Spek, 2009 ) suggested the presence of an additional center of symmetry, and that the correct space group was Pnma (with a transformation of axes). Refinement in the higher-symmetry space group was uneventful. Pseudo-Voigt profile coefficients were as parameterized in Thompson et al. (1987 ) with profile coefficients for Simpson's rule integration of the pseudo-Voigt function according to Howard (1982 ). The asymmetry correction of Finger et al. (1994 ) was applied, and microstrain broadening by Stephens (1999 ). The structure was refined by the Rietveld method using GSAS/EXPGUI (Larson & Von Dreele, 2004 ; Toby, 2001 ). All C—C and C—O bond lengths were restrained, as were all bond angles. The hydrogen atoms were included at fixed positions, which were recalculated during the course of the refinement using Materials Studio (Dassault Systemes, 2014 ). The limited resolution of the powder data precluded refining displacement coefficients, which were fixed at typical values for alkali metal citrates. Diffraction data are displayed in Fig. 4. Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

	Phase 1	Phase 2
Crystal data
Chemical formula	2Cs⁺·C₆H₆O₇²⁻	C₆H₇CsO₇
M_r	455.92	324.02
Crystal system, space group	Orthorhombic, Pnma	Orthorhombic, Pna2₁
Temperature (K)	300	300
a, b, c (Å)	9.8466 (3), 15.8872 (5), 6.5959 (2)	8.7362, 20.5351, 5.1682
V (Å³)	1031.82 (6)	927.17
Z	4	4
Radiation type	Kα₁, Kα₂, λ = 1.540629, 1.544451 Å	Kα₁, Kα₂, λ = 1.540629, 1.544451 Å
Specimen shape, size (mm)	Flat sheet, 24 × 24	Flat sheet, 24 × 24

Data collection
Diffractometer	Bruker D2 Phaser	Bruker D2 Phaser
Specimen mounting	Standard PMMA holder	Standard PMMA holder
Data collection mode	Reflection	Reflection
Scan method	Step	Step
2θ values (°)	2θ_min = 5.042 2θ_max = 70.050 2θ_step = 0.020	2θ_min = 5.042 2θ_max = 70.050 2θ_step = 0.020

Refinement
R factors and goodness of fit	R_p = 0.050, R_wp = 0.062, R_exp = 0.030, R(F²) = 0.081, χ² = 4.494	R_p = 0.050, R_wp = 0.062, R_exp = 0.030, R(F²) = 0.081, χ² = 4.494
No. of parameters	57	57
No. of restraints	18	18
The same symmetry and lattice parameters were used for the DFT calculation. Computer programs: DIFFRAC.Measurement (Bruker, 2009 ), SHELXT (Sheldrick, 2015 ), GSAS (Larson & Von Dreele, 2004), DIAMOND (Crystal Impact, 2015 ), publCIF (Westrip, 2010 ).

Figure 4
Rietveld plot for the refinement of Cs₂HC₆H₅O₇. The red crosses represent the observed data points, and the green line is the calculated pattern. The magenta curve is the difference pattern, plotted at the same scale as the other patterns. The row of black tick marks indicates the reflection positions, the row of red tick marks indicates the positions of the CsH₂C₆H₅O₇ impurity peaks, and the blue tick marks indicate the Si internal standard peaks.

7. DFT calculations

After the Rietveld refinement, a density functional geometry optimization (fixed experimental unit cell) was carried out using CRYSTAL14 (Dovesi et al., 2014 ). The basis sets for the C, H, and O atoms were those of Peintinger et al. (2012 ), and the basis set for Cs was that of Sophia et al. (2014 ). The calculation was run on eight 2.1 GHz Xeon cores (each with 6 Gb RAM) of a 304-core Dell Linux cluster at IIT, used 8 k-points and the B3LYP functional, and took about 13 h. The U_iso values from the Rietveld refinement were assigned to the optimized fractional coordinates.

Supporting information

CCDC references: 1527789; 1527790; 1527791; 1527792

Crystal structure: contains datablocks RAMM016C_publ, ramm016c_DFT, RAMM016C_overall, RAMM016C_phase_1, RAMM016C_phase_2, RAMM016C_phase_3, RAMM016C_p_01. DOI: https://doi.org/10.1107/S2056989017000792/wm5358sup1.cif

Supporting information file. DOI: https://doi.org/10.1107/S2056989017000792/wm5358RAMM016C_phase_3sup2.cml

checkCIF report

Computing details top

Data collection: DIFFRAC.Measurement (Bruker, 2009) for RAMM016C_phase_2. Program(s) used to solve structure: SHELXT (Sheldrick, 2015) for RAMM016C_phase_1, RAMM016C_phase_2. Molecular graphics: DIAMOND (Crystal Impact, 2015) for RAMM016C_phase_2. Software used to prepare material for publication: publCIF (Westrip, 2010) for RAMM016C_phase_2.

(RAMM016C_phase_1) Dicesium hydrogen citrate top

Crystal data top

2Cs⁺·C₆H₆O₇²⁻	c = 6.5959 (2) Å
M_r = 455.92	V = 1031.82 (6) Å³
Orthorhombic, Pnma	Z = 4
Hall symbol: -P 2ac 2n	D_x = 2.935 Mg m⁻³
a = 9.8466 (3) Å	T = 300 K
b = 15.8872 (5) Å

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.485 (3)	0.4027 (17)	0.728 (4)	0.03*
C2	0.536 (3)	0.3251 (14)	0.837 (3)	0.03*
C3	0.503 (4)	0.25	0.697 (5)	0.03*
C6	0.595 (3)	0.25	0.507 (4)	0.03*
H7	0.4982	0.8239	0.0123	0.039*
H8	0.3388	0.8299	0.1638	0.039*
O11	0.389 (2)	0.4449 (13)	0.807 (4)	0.03*
O12	0.549 (3)	0.4350 (14)	0.580 (3)	0.03*
O15	0.529 (3)	0.25	0.340 (4)	0.03*
O16	0.724 (3)	0.25	0.524 (4)	0.03*
O17	0.367 (4)	0.25	0.627 (4)	0.03*
H18	0.3147	0.25	0.748	0.039*
Cs19	0.28419 (18)	0.39202 (15)	0.2547 (10)	0.02*
H20	0.5	0.5	0.5	0.039*

Geometric parameters (Å, º) top

C1—C2	1.510 (2)	O12—H20	1.25 (2)
C1—O11	1.270 (2)	O15—C6	1.275 (6)
C1—O12	1.273 (6)	O15—Cs19	3.35 (2)
C2—C1	1.510 (2)	O15—Cs19ⁱⁱ	3.35 (2)
C2—C3	1.540 (2)	O15—Cs19^viii	3.43 (2)
C2—H7ⁱ	1.05 (3)	O15—Cs19^vii	3.43 (2)
C2—H8ⁱ	1.23 (3)	O16—C6	1.273 (6)
C3—C2	1.540 (2)	O16—Cs19^viii	2.971 (18)
C3—C2ⁱⁱ	1.540 (2)	O16—Cs19^vii	2.971 (18)
C3—C6	1.550 (2)	O17—C3	1.421 (6)
C3—O17	1.421 (6)	O17—H18	0.95 (3)
C6—C3	1.550 (2)	O17—Cs19	3.43 (2)
C6—O15	1.275 (6)	O17—Cs19ⁱⁱ	3.43 (2)
C6—O16	1.273 (6)	H18—O17	0.95 (3)
H7—C2ⁱⁱⁱ	1.05 (3)	Cs19—O11^ix	3.24 (2)
H8—C2ⁱⁱⁱ	1.23 (3)	Cs19—O11	3.88 (2)
O11—C1	1.270 (2)	Cs19—O11^x	3.12 (2)
O11—Cs19	3.88 (2)	Cs19—O12	3.44 (3)
O11—Cs19^iv	3.24 (2)	Cs19—O12^vi	3.38 (3)
O11—Cs19^v	3.12 (2)	Cs19—O12^xi	3.27 (2)
O12—C1	1.273 (6)	Cs19—O15	3.35 (2)
O12—Cs19	3.44 (3)	Cs19—O15^xii	3.43 (2)
O12—Cs19^vi	3.38 (3)	Cs19—O16^xii	2.971 (18)
O12—Cs19^vii	3.27 (2)	Cs19—O17	3.43 (2)

C2—C1—O11	119 (2)	Cs19—O17—Cs19ⁱⁱ	82.2 (6)
C2—C1—O12	122 (2)	O11^ix—Cs19—O11^x	93.4 (5)
O11—C1—O12	118 (3)	O11^ix—Cs19—O12	106.0 (6)
C1—C2—C3	106.4 (17)	O11^ix—Cs19—O12^vi	85.9 (5)
C1—C2—H7ⁱⁱⁱ	111 (2)	O11^ix—Cs19—O12^xv	63.7 (6)
C1—C2—H8ⁱⁱⁱ	106 (2)	O11^ix—Cs19—O15	95.7 (6)
C3—C2—H7ⁱⁱⁱ	119 (3)	O11^ix—Cs19—O15^xvi	103.7 (6)
C3—C2—H8ⁱⁱⁱ	105 (2)	O11^ix—Cs19—O16^xvi	72.3 (6)
H7ⁱⁱⁱ—C2—H8ⁱⁱⁱ	108.8 (18)	O11^ix—Cs19—O17	138.4 (6)
C2—C3—C2ⁱⁱ	102 (3)	O11^x—Cs19—O12	100.4 (6)
C2—C3—C6	111.1 (18)	O11^x—Cs19—O12^vi	63.6 (6)
C2—C3—O17	113 (2)	O11^x—Cs19—O12^xv	60.9 (6)
C2ⁱⁱ—C3—C6	111.1 (18)	O11^x—Cs19—O15	159.0 (5)
C2ⁱⁱ—C3—O17	113 (2)	O11^x—Cs19—O15^xvi	99.6 (5)
C6—C3—O17	107 (2)	O11^x—Cs19—O16^xvi	126.1 (6)
C3—C6—O15	114 (3)	O11^x—Cs19—O17	126.6 (6)
C3—C6—O16	121 (3)	O12—Cs19—O12^vi	43.1 (7)
C1—O11—Cs19^iv	118.2 (17)	O12—Cs19—O12^xv	156.1 (7)
C1—O11—Cs19^v	143.2 (19)	O12—Cs19—O15	58.9 (5)
Cs19^iv—O11—Cs19^v	98.2 (7)	O12—Cs19—O15^xvi	142.9 (5)
C1—O12—Cs19	92 (3)	O12—Cs19—O16^xvi	133.4 (7)
C1—O12—Cs19^vi	109 (2)	O12—Cs19—O17	60.4 (5)
C1—O12—Cs19^xiii	141.7 (17)	O12^vi—Cs19—O12^xv	113.1 (5)
Cs19—O12—Cs19^vi	136.9 (7)	O12^vi—Cs19—O15	98.2 (5)
Cs19—O12—Cs19^xiii	94.3 (6)	O12^vi—Cs19—O15^xvi	161.4 (5)
C6—O15—Cs19	120.8 (14)	O12^vi—Cs19—O16^xvi	156.0 (7)
C6—O15—Cs19ⁱⁱ	120.8 (14)	O12^vi—Cs19—O17	100.8 (6)
C6—O15—Cs19^xiv	77.5 (15)	O12^xv—Cs19—O15	139.8 (6)
C6—O15—Cs19^xiii	77.5 (15)	O12^xv—Cs19—O15^xvi	59.7 (6)
Cs19—O15—Cs19ⁱⁱ	84.7 (7)	O12^xv—Cs19—O16^xvi	66.4 (6)
Cs19—O15—Cs19^xiv	159.7 (9)	O12^xv—Cs19—O17	141.9 (7)
Cs19—O15—Cs19^xiii	93.05 (18)	O15—Cs19—O15^xvi	96.59 (14)
Cs19ⁱⁱ—O15—Cs19^xiv	93.05 (18)	O15—Cs19—O16^xvi	74.7 (5)
Cs19ⁱⁱ—O15—Cs19^xiii	159.7 (9)	O15—Cs19—O17	42.8 (7)
Cs19^xiv—O15—Cs19^xiii	82.1 (6)	O15^xvi—Cs19—O16^xvi	40.7 (6)
C6—O16—Cs19^xiv	98.2 (15)	O15^xvi—Cs19—O17	82.6 (7)
C6—O16—Cs19^xiii	98.2 (15)	O16^xvi—Cs19—O17	89.5 (5)
Cs19^xiv—O16—Cs19^xiii	98.8 (8)	O12—H20—O12^vi	180.0

Symmetry codes: (i) −x+1, y−1/2, −z+1; (ii) x, −y+1/2, z; (iii) −x+1, y+1/2, −z+1; (iv) x, y, z+1; (v) −x+1/2, −y+1, z+1/2; (vi) −x+1, −y+1, −z+1; (vii) x+1/2, y, −z+1/2; (viii) x+1/2, −y+1/2, −z+1/2; (ix) x, y, z−1; (x) −x+1/2, −y+1, z−1/2; (xi) x−1/2, y, −z+1/2; (xii) x−1/2, −y+1/2, −z+1/2; (xiii) x+3/2, y, −z+3/2; (xiv) x+3/2, −y+3/2, −z+3/2; (xv) x+1/2, y, −z+3/2; (xvi) x+1/2, −y+3/2, −z+3/2.

(RAMM016C_phase_2) cesium dihydrogen citrate top

Crystal data top

C₆H₇CsO₇	c = 5.1682 Å
M_r = 324.02	V = 927.17 Å³
Orthorhombic, Pna2₁	Z = 4
Hall symbol: P 2c -2n	D_x = 2.321 Mg m⁻³
a = 8.7362 Å	T = 300 K
b = 20.5351 Å

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.1877	0.0459	0.281	0.065*
C2	0.3465	0.0446	0.166	0.009*
C3	0.4423	0.0965	0.304	0.009*
C4	0.6089	0.0896	0.212	0.009*
C5	0.7062	0.1464	0.317	0.065*
C6	0.3805	0.1664	0.241	0.065*
O7	0.1302	−0.0065	0.333	0.065*
O8	0.1066	0.0875	0.223	0.065*
O9	0.371	0.1861	0.009	0.065*
O10	0.351	0.2038	0.417	0.065*
O11	0.7164	0.1977	0.185	0.065*
O12	0.7293	0.1503	0.553	0.065*
O13	0.4359	0.0847	0.577	0.065*
H14	0.4007	−0.0062	0.1958	0.012*
H15	0.3339	0.0538	−0.0498	0.012*
H16	0.4251	0.132	0.7041	0.085*
H17	0.6502	0.0404	0.2549	0.012*
H18	0.6012	0.0942	−0.0229	0.012*
Cs19	0.04535	0.20017	0.7594	0.0503*
H20	0.0694	−0.0507	0.5686	0.039*
H21	0.67528	0.243	0.2524	0.039*

Geometric parameters (Å, º) top

C1—C2	1.5095	O12—C5	1.2389
C1—O7	1.2176	O12—O11	2.1395
C1—O8	1.1496	O12—Cs19ⁱ	3.1321
C2—C1	1.5095	O12—Cs19^v	3.6262
C2—C3	1.5313	O13—C3	1.4327
C2—H14	1.1559	O13—H16	1.1764
C2—H15	1.1365	H14—C2	1.1559
C3—C2	1.5313	H14—H15	1.8627
C3—C4	1.5377	H15—C2	1.1365
C3—C6	1.5678	H15—H14	1.8627
C3—O13	1.4327	H16—O9^viii	1.9851
C4—C3	1.5377	H16—O13	1.1764
C4—C5	1.5419	H16—Cs19	3.6122
C4—H17	1.0955	H16—Cs19^v	3.6143
C4—H18	1.2195	H17—C4	1.0955
C5—C4	1.5419	H17—H18	1.8615
C5—O11	1.2582	H18—C4	1.2195
C5—O12	1.2389	H18—H17	1.8615
C5—Cs19ⁱ	3.9020	Cs19—C5^ix	3.9020
C5—H21	2.0297	Cs19—C6	4.0289
C6—C3	1.5678	Cs19—C6^viii	3.9050
C6—O9	1.2682	Cs19—C6^x	3.972
C6—O10	1.2181	Cs19—O8	3.6503
C6—Cs19ⁱⁱ	3.9050	Cs19—O8^viii	3.3735
C6—Cs19	4.0289	Cs19—O9^viii	3.1371
C6—Cs19ⁱⁱⁱ	3.972	Cs19—O9^x	3.0722
O7—C1	1.2176	Cs19—O10	3.2042
O7—O8	2.0228	Cs19—O10^vi	3.1469
O7—H20	1.6089	Cs19—O11^xi	3.6193
O8—C1	1.1496	Cs19—O11^vi	3.9299
O8—O7	2.0228	Cs19—O11^x	3.3867
O8—Cs19ⁱⁱ	3.3735	Cs19—O12^ix	3.1321
O8—Cs19	3.6503	Cs19—O12^vi	3.6262
O8—H20^iv	1.8900	Cs19—H16	3.6122
O9—C6	1.2682	Cs19—H16^vi	3.6143
O9—O10	2.1468	Cs19—Cs19ⁱⁱ	5.1682
O9—H16ⁱⁱ	1.9851	Cs19—Cs19^viii	5.1682
O9—Cs19ⁱⁱ	3.1371	Cs19—Cs19^vi	4.8238
O9—Cs19ⁱⁱⁱ	3.0722	Cs19—Cs19^v	4.8238
O10—C6	1.2181	Cs19—H20^xii	3.6027
O10—O9	2.1468	Cs19—H21^vi	3.0848
O10—Cs19	3.2042	Cs19—H21^x	3.0236
O10—Cs19^v	3.1469	H20—O7	1.6089
O10—H21^vi	2.0673	H20—O8^xii	1.8900
O11—C5	1.2582	H20—Cs19^iv	3.6027
O11—O12	2.1395	H21—C5	2.0297
O11—Cs19^vii	3.6193	H21—O10^v	2.0673
O11—Cs19ⁱⁱⁱ	3.3867	H21—O11	1.0563
O11—Cs19^v	3.9299	H21—Cs19ⁱⁱⁱ	3.0236
O11—H21	1.0563	H21—Cs19^v	3.0848

C2—C1—O7	116.7731	O9^x—Cs19—O10^vi	59.4859
C2—C1—O8	118.4826	O9^x—Cs19—O11^xi	50.343
O7—C1—O8	117.3875	O9^x—Cs19—O11^x	58.3514
C1—C2—C3	107.8548	O9^x—Cs19—O12^ix	87.3923
C1—C2—H14	109.8752	O9^x—Cs19—Cs19ⁱⁱ	114.8276
C1—C2—H15	107.1232	O9^x—Cs19—Cs19^viii	65.1724
C3—C2—H14	110.0087	O9^x—Cs19—Cs19^vi	39.5136
C3—C2—H15	113.2215	O9^x—Cs19—Cs19^v	97.2637
H14—C2—H15	108.6894	O9^x—Cs19—H21^vi	104.5664
C2—C3—C4	108.0085	O9^x—Cs19—H21^x	62.5411
C2—C3—C6	110.6267	O10—Cs19—O10^vi	97.1512
C2—C3—O13	108.6407	O10—Cs19—O11^xi	176.0673
C4—C3—C6	110.2492	O10—Cs19—O11^x	88.658
C4—C3—O13	109.0185	O10—Cs19—O12^ix	123.6515
C6—C3—O13	110.2395	O10—Cs19—Cs19ⁱⁱ	56.4773
C3—C4—C5	110.0762	O10—Cs19—Cs19^viii	123.5227
C3—C4—H17	109.5203	O10—Cs19—Cs19^vi	138.138
C3—C4—H18	104.3867	O10—Cs19—Cs19^v	40.1379
C5—C4—H17	116.414	O10—Cs19—H21^vi	38.3222
C5—C4—H18	108.7936	O10—Cs19—H21^x	98.2538
H17—C4—H18	106.9223	O10^vi—Cs19—O11^xi	85.5337
C4—C5—O11	118.7882	O10^vi—Cs19—O11^x	102.4289
C4—C5—O12	119.0252	O10^vi—Cs19—O12^ix	62.4676
O11—C5—O12	117.9141	O10^vi—Cs19—Cs19ⁱⁱ	55.783
C3—C6—O9	120.7284	O10^vi—Cs19—Cs19^viii	124.217
C3—C6—O10	119.6742	O10^vi—Cs19—Cs19^vi	41.0239
O9—C6—O10	119.4116	O10^vi—Cs19—Cs19^v	102.8686
C1—O7—H20	143.3052	O10^vi—Cs19—H21^vi	58.9237
C1—O8—Cs19ⁱⁱ	142.4291	O10^vi—Cs19—H21^x	115.7564
C6—O9—Cs19ⁱⁱ	118.5237	O11^xi—Cs19—O11^x	87.9548
C6—O9—Cs19ⁱⁱⁱ	127.377	O11^xi—Cs19—O12^ix	60.1617
Cs19ⁱⁱ—O9—Cs19ⁱⁱⁱ	101.9433	O11^xi—Cs19—Cs19ⁱⁱ	127.4261
C6—O10—Cs19	125.0345	O11^xi—Cs19—Cs19^viii	52.5739
C6—O10—Cs19^v	134.4984	O11^xi—Cs19—Cs19^vi	44.5151
Cs19—O10—Cs19^v	98.8382	O11^xi—Cs19—Cs19^v	136.4653
C5—O11—Cs19^vii	113.4209	O11^xi—Cs19—H21^vi	144.4574
C5—O11—Cs19ⁱⁱⁱ	147.075	O11^xi—Cs19—H21^x	77.9576
C5—O11—H21	122.3074	O11^x—Cs19—O12^ix	144.3543
Cs19^vii—O11—Cs19ⁱⁱⁱ	86.9593	O11^x—Cs19—Cs19ⁱⁱ	130.5024
Cs19^vii—O11—H21	117.2654	O11^x—Cs19—Cs19^viii	49.4976
Cs19ⁱⁱⁱ—O11—H21	61.2332	O11^x—Cs19—Cs19^vi	97.8643
C5—O12—Cs19ⁱ	120.0024	O11^x—Cs19—Cs19^v	48.5256
C3—O13—H16	114.4184	O11^x—Cs19—H21^vi	98.9194
O8^viii—Cs19—O9^viii	60.0614	O11^x—Cs19—H21^x	17.8322
O8^viii—Cs19—O9^x	107.5655	O12^ix—Cs19—Cs19ⁱⁱ	70.0882
O8^viii—Cs19—O10	106.0226	O12^ix—Cs19—Cs19^viii	109.9118
O8^viii—Cs19—O10^vi	156.1712	O12^ix—Cs19—Cs19^vi	48.7345
O8^viii—Cs19—O11^xi	71.6205	O12^ix—Cs19—Cs19^v	159.551
O8^viii—Cs19—O11^x	83.8832	O12^ix—Cs19—H21^vi	99.1359
O8^viii—Cs19—O12^ix	99.0601	O12^ix—Cs19—H21^x	138.084
O8^viii—Cs19—Cs19ⁱⁱ	135.2548	Cs19ⁱⁱ—Cs19—Cs19^viii	180.0
O8^viii—Cs19—Cs19^viii	44.7452	Cs19ⁱⁱ—Cs19—Cs19^vi	90.0
O8^viii—Cs19—Cs19^vi	115.7608	Cs19ⁱⁱ—Cs19—Cs19^v	90.0
O8^viii—Cs19—Cs19^v	98.4731	Cs19ⁱⁱ—Cs19—H21^vi	31.8529
O8^viii—Cs19—H21^vi	143.5507	Cs19ⁱⁱ—Cs19—H21^x	147.4235
O8^viii—Cs19—H21^x	66.8377	Cs19^viii—Cs19—Cs19^vi	90.0
O9^viii—Cs19—O9^x	110.3022	Cs19^viii—Cs19—Cs19^v	90.0
O9^viii—Cs19—O10	58.2306	Cs19^viii—Cs19—H21^vi	148.1471
O9^viii—Cs19—O10^vi	141.1001	Cs19^viii—Cs19—H21^x	32.5765
O9^viii—Cs19—O11^xi	117.9614	Cs19^vi—Cs19—Cs19^v	129.7922
O9^viii—Cs19—O11^x	52.3974	Cs19^vi—Cs19—H21^vi	99.9449
O9^viii—Cs19—O12^ix	155.4194	Cs19^vi—Cs19—H21^x	100.1484
O9^viii—Cs19—Cs19ⁱⁱ	114.2806	Cs19^v—Cs19—H21^vi	60.4158
O9^viii—Cs19—Cs19^viii	65.7194	Cs19^v—Cs19—H21^x	59.755
O9^viii—Cs19—Cs19^vi	149.3491	H21^vi—Cs19—H21^x	115.5707
O9^viii—Cs19—Cs19^v	38.5431	O11—H21—Cs19ⁱⁱⁱ	100.9346
O9^viii—Cs19—H21^vi	92.8906	O11—H21—Cs19^v	137.5968
O9^viii—Cs19—H21^x	49.3517	Cs19ⁱⁱⁱ—H21—Cs19^v	115.5707
O9^x—Cs19—O10	128.8561

Symmetry codes: (i) x+1, y, z; (ii) x, y, z−1; (iii) x+1/2, −y+1/2, z−1; (iv) −x, −y, z−1/2; (v) x+1/2, −y+1/2, z; (vi) x−1/2, −y+1/2, z; (vii) x+1, y, z−1; (viii) x, y, z+1; (ix) x−1, y, z; (x) x−1/2, −y+1/2, z+1; (xi) x−1, y, z+1; (xii) −x, −y, z+1/2.

(RAMM016C_phase_3) silicon top

Crystal data top

Si	V = 160.20 Å³
M_r = 28.09	Z = 8
Cubic, Fd3m	D_x = 2.329 Mg m⁻³
Hall symbol: -F 4vw 2vw	T = 300 K
a = 5.43105 Å

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Si1	0.125	0.125	0.125	0.01*

Geometric parameters (Å, º) top

Si1—Si1ⁱ	2.3517	Si1—Si1ⁱⁱⁱ	2.3517
Si1—Si1ⁱⁱ	2.3517	Si1—Si1^iv	2.3517

Si1ⁱ—Si1—Si1ⁱⁱ	109.4712	Si1ⁱⁱ—Si1—Si1ⁱⁱⁱ	109.4712
Si1ⁱ—Si1—Si1ⁱⁱⁱ	109.4712	Si1ⁱⁱ—Si1—Si1^iv	109.4712
Si1ⁱ—Si1—Si1^iv	109.4712	Si1ⁱⁱⁱ—Si1—Si1^iv	109.4712

Symmetry codes: (i) x+1/4, y+1/4, −z; (ii) −z, x+1/4, y+1/4; (iii) y+1/4, −z, x+1/4; (iv) −x, −y, −z.

(ramm016c_DFT) top

Crystal data top

C₆H₆Cs₂O₇	b = 15.8872 Å
M_r = 455.92	c = 6.5959 Å
Orthorhombic, Pnma	V = 1031.82 Å³
Hall symbol: -P 2ac 2n	Z = 4
a = 9.8466 Å	T = 300 K

Data collection top

h = →	l = →
k = →

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.48590	0.40995	0.73839	0.03000*
C2	0.53924	0.32807	0.82202	0.03000*
H7	0.49922	0.81932	0.02513	0.03900*
H8	0.35061	0.83203	0.17117	0.03900*
O11	0.39754	0.45079	0.82841	0.03000*
O12	0.54129	0.43424	0.56822	0.03000*
Cs19	0.28894	0.39193	0.26540	0.02000*
C3	0.50141	0.25000	0.69412	0.03000*
C6	0.58468	0.25000	0.49542	0.03000*
O15	0.52651	0.25000	0.32675	0.03000*
O16	0.71279	0.25000	0.52034	0.03000*
O17	0.36003	0.25000	0.64658	0.03000*
H18	0.30582	0.25000	0.77454	0.03900*
H20	0.50000	0.50000	0.50000	0.03900*

Bond lengths (Å) top

C1—C2	1.507	O12—H20	1.208
C1—O11	1.237	C3—C2ⁱⁱⁱ	1.546
C1—O12	1.306	C3—C6	1.546
C2—C3	1.546	C3—O17	1.427
C2—H7ⁱ	1.086	C6—O15	1.251
C2—H8ⁱ	1.087	C6—O16	1.272
H7—C2ⁱⁱ	1.086	O17—H18	0.999
H8—C2ⁱⁱ	1.087	H20—O12^iv	1.208

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O12—H20···O12^iv	1.208	1.208	2.416	180.0
O17—H18···O16^v	0.999	1.634	2.632	178.2

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

Footnotes

‡Present address: CCDC, 174 Frelinghuysen Rd., Piscataway NJ 00854 USA.

Acknowledgements

We thank Andrey Rogachev for the use of computing resources at IIT.

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structure of dicesium hydrogen citrate from laboratory single-crystal and powder X-ray diffraction data and DFT comparison

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

7. DFT calculations

Supporting information

Footnotes

Acknowledgements

References

research communications

3. Supramolecular features