ISSN 10637745, Crystallography Reports, 2015, Vol. 60, No. 1, pp. 72–74. © Pleiades Publishing, Inc., 2015. Original Russian Text © E.K. Titaeva, N.V. Somov, V.N. Portnov, D.N. Titaev, 2015, published in Kristallografiya, 2015, Vol. 60, No. 1, pp. 78–81.
STRUCTURE OF ORGANIC COMPOUNDS
Crystal Structure of Monobasic Sodium Tartrate Monohydrate E. K. Titaeva, N. V. Somov, V. N. Portnov, and D. N. Titaev University of Nizhni Novgorod, pr. Gagarina 23, Nizhni Novgorod, 603950 Russia email:
[email protected] Received May 7, 2014
Abstract—Crystals of a new polymorphic modification of monobasic sodium tartrate monohydrate NaHC4H4O6 ⋅ H2O have been grown in a metasilicate gel. Their atomic structure is solved by Xray diffrac tion. DOI: 10.1134/S1063774515010265
The initial fragment of crystal I structure was found by direct methods within the SHELX97 software [9]. Other atoms of the structure, including hydrogen atoms, were found from difference electron density maps. The parameters of atomic structure I were refined by the fullmatrix leastsquares method on F2
INTRODUCTION Crystals of tartrates (salts of tartaric acid) are promising materials in the food industry, medicine, laser technique, and electronics. Sodium tartrate in the pure state is most frequently used in the food industry to control the acidity of food products. The pharmacologic properties of sodium tartrate, as well as sodium and bismuth tartrates, were described in [1, 2]. Tartrate crystals, which possess nonlinear optical properties, are promising materials for laser technol ogy [3, 4]. The ferroelectric properties of some tartrate crystals allow their use in electronics [5]. In this study we grew for the first time single crystals of monobasic sodium tartrate monohydrate NaHC4H4O6 · H2O (I) from a metasilicate gel and analyzed them by Xray diffraction. The structural data are deposited into the Cambridge Structural Database (CCDC no. 992955).
Table 1. Crystallographic characteristics, experimental de tails, and parameters of the structure refinement I Chemical formula M T, K Sp. gr., Z a, b, с, Å α, β, γ, deg V, Å3 ρ, g/cm3; μ, mm–1 F(000) Crystal size, mm Duffractometer/radiation; λ, Å/monochromator
EXPERIMENTAL Crystals I were grown using a gel prepared based on sodium metasilicate and tartaric acid [6]. The gel was obtained by mixing solutions of sodium metasilicate (GOST (state standard) 423977) and ltartaric acid with concentrations of 1 mol/kg distilled water; the volume ratio of the solutions was 1 : 3. Gel ripening occurred at a temperature of 22(1)°С; the gel density was 1.06(2) g/cm3 and pH was 5.0(5). Approximately after 24h, crystals with linear sizes of 0.5–2 mm pre cipitated in the gel volume. An Xray diffraction analysis was carried out on a fourcircle automatic Oxford Diffraction Gemini S diffractometer with a Sapphire III CCD detector. The experimental details are listed in Table 1. The data collection and processing were performed with the aid of the CrysAlisPro program [7]; absorp tion was taken into account empirically by the algo rithm of [8].
Scan mode θmin; θmax, deg Limits of h, k, l Number of measured reflec tions: total/unique/with I > 2σ(I)/Rint Number of refined parameters GOF R1/wR1 on F 2 > 2σ(F2 ) R1/wR1 on all reflections Δρmin /Δρmax, e/Å3 Programs
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NaHC4H4O6 ⋅ H2O 190.09 293(2) P 1, 2 6.5005(3), 7.0897(3), 8.0213(3) 91.748(3), 101.600(4), 110.238(4) 337.75(3) 1.869; 0.233 196 0.484 × 0.237 × 0.165 Xcalibur, Sapphire3, Gemini/MoKα; 0.71073/graphite ω 3.429; 30.501 –9 ≤ h ≤ 9, –10 ≤ k ≤ 10, –11 ≤ l ≤ 11 6024/2051/1950/0.0153 135 1.084 0.0297/0.0825 0.0312/0.0836 –0.203/0.527 SHELX’97 [9], CrysAl isPro [7], WinGX [10]
CRYSTAL STRUCTURE OF MONOBASIC SODIUM TARTRATE MONOHYDRATE
73
O C a
0
Na
c
Fig. 1. Polyhedral image of the crystal structure of monobasic tartrate sodium monohydrate I.
in the SHELX97 software [9] using the WinGX inter active medium [10]. RESULTS AND DISCUSSION There are data in the literature on two polymor phous modifications of monobasic sodium tartrate monohydrate crystals: monoclinic (a = 8 .9723(2) Å, b = 7.1457 (1) Å, c = 12.0186 (2) Å, β = 119.571(1)°, sp. gr. P21/с) (II) [11] and orthorhombic (a = 7.2425(6) Å, b = 8.676 (1) Å, c = 10.592(1) Å, sp. gr. P212121) (III) [12]. Some of thermodynamic, optical, electrical, and mechanical properties of crystal III were described in [13]. Crystals of modification III were obtained by evap orating an aqueous solution. The atomic structure is a threedimensional framework composed of Na+ cat ions and ltartrate anions. The coordination environ ment of sodium ion in structure III includes eight oxy gen ions: one atom of water molecule, three atoms of hydroxyl groups, and four atoms of carboxyl groups.
Crystals of modification II were obtained by the temperaturedrop method from an aqueous solution. In contrast to crystals of modification III, they have a layered structure formed by Na+ cations and tartrate anions of spatial configurations l and d. The layers in structure II are oriented parallel to the (100) plane. The coordination polyhedron of sodium ion is a dis torted pentagonal bipyramid, the vertices of which contain seven oxygen atoms: one atom of water mole cule, three atoms of hydroxyl groups, and three atoms of carboxyl groups. The atomic structure of crystal I obtained in this study is described by the triclinic sym metry group P 1 ; the unit cell contains two formula units (Table 1). Crystal I has a layered structure. The layers oriented parallel to the (001) plane (Fig. 1) are twodimensional polymer networks composed of Na+ cations and l and dtartrate anions of two spatial con figurations. The coordination polyhedron of sodium ion in structure I is a distorted pentagonal bipyramid similar
Table 2. Interatomic distances and bond angles in crystal I Bond Na1–O6 Na1–O5 Na1–O7 Na1–O4 Na1ii–O7 Na1i–O4 Na1–O1
d, Å 2.3804(9) 2.4359(9) 2.4445(8) 2.4900(8) 2.4999(9) 2.5489(8) 2.6162(10)
ω, deg
Angle O6–Na–O5 O6–Na1–O7 O5–Na1–O7 O6–Na1–O4 O5–Na1–O4 O7–Na1–O4 O6–Na1–O7ii
148.95(3) 73.61(3) 75.63(3) 123.28(3) 80.51(3) 129.62(3) 82.69(3)
Angle ii
O5–Na1–O7 O7–Na1–O7ii O4–Na1–O7ii O6–Na1–O4i O5–Na1–O4i O7–Na1–O4i O4–Na1–O4i
Symmetrically equivalent positions are (i) –x – 1, –y, –z and (ii) –x – 1, –y – 1, –z. CRYSTALLOGRAPHY REPORTS
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ω, deg
Angle
ω, deg
90.68(3) 85.17(3) 139.16(3) 124.13(3) 78.36(3) 139.13(3) 75.06(3)
O7ii–Na1–O4i
64.10(2) 62.77(3) 146.97(3) 131.73(3) 67.57(3) 107.67(3) 85.20(3)
O6–Na1–O1 O5–Na1–O1 O7–Na1–O1 O4–Na1–O1 O7ii–Na1–O1 O4i–Na1–O1
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Table 3. Geometric parameters of hydrogen bonds in crystal I D–H⋅⋅⋅A
d(D–H), Å
d(H⋅⋅⋅A), Å
D–H⋅⋅⋅A, deg
d(D⋅⋅⋅A), Å
O4–H6⋅⋅⋅O1 O4–H6⋅⋅⋅O6i O6–H5⋅⋅⋅O5ii O2–H3⋅⋅⋅O3iii O3–H4⋅⋅⋅O2iv O5–H7⋅⋅⋅O1v O5–H8⋅⋅⋅O3vi
0.832(18) 0.832(18) 0.82(2) 0.90(4) 0.76(4) 0.8668(7) 0.8278(8)
2.290(1) 2.305(1) 1.883(1) 1.579(1) 1.717(1) 1.899(1) 2.062(1)
124(1) 116(1) 174(1) 177(1) 173(1) 161(1) 170(1)
2.841(1) 2.770(1) 2.703(1) 2.475(1) 2.475(1) 2.733(1) 2.881(1)
Symmetrically equivalent positions are: (i) –x, –y, –z, (ii) –x – 1, –y – 1, –z, (iii) x, y + 1, z, (iv) x, y – 1, z, and (v) –x – 1, –y, –z; (vi) x – 1, y, z – 1.
to that in structure II. The interatomic distances in the coordination polyhedron of sodium ion in structure I are in the range of 2.3804(9)–2.6162(10) Å (Table 2). They are in agreement with the distances obtained in [11, 12]. The occupancy of crystallographic positions by hydrogen atoms H3 and H4 belonging to carboxyl groups of tartrate anions is 0.5. In other words, only one of the aforementioned positions in a real tartrate anion is occupied by a hydrogen atom. The geometric parameters of the hydrogen bonds revealed in atomic structure I are given in Table 3. It is found that both intramolecular and intermolecular hydrogen bonds are present in structure I. Similar interactions were found in atomic structure II. There is an intermolecular hydrogen bond in crystal I between two adjacent layers (Table 3). The water mol ecule Н7–О5–Н8 belonging to one layer is a donor, and the oxygen atom O3 belonging to the other layer is an acceptor (Fig. 2). The other hydrogen bonds in Table 3 are due to intramolecular interactions; they are involved in the formation of layers. H3 O2 H1
C1
O4
O1 H2
C3
O7
O3 C2
H4
H5 O6
C4
O4
Na1 Na1
O4 H6
H7
O7
O5 O7 Na1
H8
Na1
CONCLUSIONS A new polymorphic modification of monobasic sodium tartrate monohydrate NaHC4H4O6 ⋅ H2O was obtained for the first time by growth in a gel without a feeding solution; its atomic structure was solved. It was found that the crystals of this polymorphic modifica tion have a layered structure described by the space group P1. It was shown that the atomic structure layers are polymer networks interacting via hydrogen bonds. ACKNOWLEDGMENTS This study was carried out within the basic part of government order no. 2014/134 in the field of state research; project code 2312. REFERENCES 1. M. D. William Salant, JAMA LXIII (13), 1076 (1914). 2. P. J. Hanzlik, H. D. Mehrtens, D. C. Marshal, et al., Arch. Derm. Syphilol. 22 (5), 850 (1930). 3. M. L. Labutina, M. O. Marychev, V. N. Portnov, et al., Crystallogr. Rep. 56 (1), 72 (2011). 4. D. Joseph Daniel and P. Ramasamy, Mater. Res. Bull. 47 (3), 708 (2012). 5. M. H. Rahimkutty, K. Rajendra Babu, K. Sreedharan Pillai, et al., Bull. Mater. Sci. 24 (2), 249 (2001). 6. H. K. Henisch, Crystal Growth in Gels (Pennsylvania State Univ. Press, University Park, PA, 1970; Mir, Moscow, 1973). 7. CrysAlisPro, Version 1.171.36.21 (release 20012012 CrysAlis171.NET) (Agilent Technologies, 2012). 8. CrysAlisPro, Version 1.171.36.21 (release 20012012 CrysAlis171.NET) (Agilent Technologies, compiled January 23, 2012, 18:06:46) (Empirical absorption cor rection using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm). 9. G. M. Sheldrick, SHELX97. Programs for Crystal Structure Analysis (Release 972) (Univ. of Göttingen, Göttingen, 1997). 10. L. J. Farrugia, J. Appl. Crystallogr. 32, 837 (1999). 11. M. T. M. AlDajani, H. H. Abdallah, N. Mohamed, et al., Acta Crystallogr. E 66, m138 (2010). 12. R. C. Bott, D. S. Sagatys, D. E. Lynch, et al., Acta Crystallogr. С 49, 1150 (1993). 13. V. Revathi and V. Rajendran, Int. J. Recent Sci. Res. 4 (9), 1332 (2013).
Fig. 2. Fragment of the atomic structure of monobasic sodium tartrate monohydrate I.
Translated by T. Dmitrieva CRYSTALLOGRAPHY REPORTS
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