Monoclinic polymorph of poly[aqua(μ₄-hydrogen tartrato)sodium]

Abstract

A monoclinic polymorph of the title compound, [Na(C₄H₅O₆)(H₂O)]_n, is reported and complements an ortho­rhom­bic form [Kubozono, Hirano, Nagasawa, Maeda & Kashino (1993 ▶). Bull. Chem. Soc. Jpn, 66, 2166–2173]. The asymmetric unit contains a hydrogen tartrate anion, an Na⁺ cation and a water mol­ecule. The Na⁺ ion is surrounded by seven O atoms derived from one independent and three symmetry-related hydrogen tartrate anions, and a water mol­ecule, forming a distorted penta­gonal–bipyramidal geometry. Independent units are linked via a pair of inter­molecular bifurcated O—H⋯O acceptor bonds, generating an R ₂ ¹(6) ring motif to form polymeric two-dimensional arrays parallel to the (100) plane. In the crystal packing, the arrays are linked by adjacent ring motifs, together with additional inter­molecular O—H⋯O inter­actions, into a three-dimensional network.

Related literature

For the optical activity of tartaric acid, see: Synoradzki et al. (2008 ▶). For Na—O distances, see: Wong et al. (2009 ▶). For the ortho­rhom­bic polymorph of C₄H₅O₆Na·H₂O, see: Kubozono et al. (1993 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

• [Na(C₄H₅O₆)(H₂O)]

• M _r = 190.09

• Monoclinic,

• a = 8.9723 (2) Å

• b = 7.1457 (1) Å

• c = 12.0186 (2) Å

• β = 119.571 (1)°

• V = 670.18 (2) ų

• Z = 4

• Mo Kα radiation

• μ = 0.24 mm⁻¹

• T = 100 K

• 0.40 × 0.09 × 0.05 mm

Data collection

• Bruker SMART APEXII CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.895, T _max = 0.979

• 6649 measured reflections

• 1947 independent reflections

• 1532 reflections with I > 2σ(I)

• R _int = 0.034

Refinement

• R[F ² > 2σ(F ²)] = 0.037

• wR(F ²) = 0.092

• S = 1.03

• 1947 reflections

• 109 parameters

• H-atom parameters constrained

• Δρ_max = 0.51 e Å⁻³

• Δρ_min = −0.29 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O1⋯O6i	0.86	1.69	2.5496 (13)	175
O1W—H1W1⋯O5ii	0.83	1.94	2.7585 (14)	167
O1W—H2W1⋯O6iii	0.90	1.94	2.8006 (15)	161
O3—H1O3⋯O5ii	0.78	2.14	2.7575 (19)	137
O4—H1O4⋯O1Wiv	0.79	1.90	2.6784 (14)	170

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

supplementary crystallographic information

Comment

Tartaric acid is found free throughout nature, especially in many fruits and in wine, and as salts with Ca²⁺, K⁺, and Na⁺. It has many applications such as in making silver mirrors, in the manufacture of soft drinks, to provide tartness to foods, in tanning leather, and in making blueprints. Tartaric acid has optical activity (Synoradzki et al., 2008).

Kubozono et al. (1993) reported the structure of the title compound, in the orthorhombic space group P2₁2₁2₁. Herein, a new polymorph of the title compound is reported which crystallizes in the monoclinic space group P2₁/c. The asymmetric unit contains a hydrogen tartrate anion, a Na cation and a water molecule (Fig. 1). The independent unit forms polymeric two-dimensional networks parallel to the plane (100) (Fig. 2). Each Na⁺ ion is surrounded by seven O atoms (Fig. 3) derived from a independent and three symmetry related hydrogen tartrate anions; and a water molecule, forming a distorted pentagonal bipyramidal geometry with Na—O distances ranging from 2.3331 (12) to 2.6740 (12) Å which are comparable to those reported in (Wong et al., 2009), whereas the angles around the Na⁺ ion range from 62.55 (4) to 151.93 (4)°. Bond lengths and angles are within normal ranges and comparable to the orthorhombic polymorph of C₄H₅O₆Na.H₂O (Kubozono et al., 1993).

The molecular structure is linked via intermolecular bifurcated O1W—H1W1···O5 and O3—H1O3···O5 acceptor bonds, generating R¹₂(6) ring motif (Bernstein et al., 1995). In the crystal packing (Fig. 4), the polymeric two-dimensional arrays are linked by adjacent ring motifs, together with intermolecular O1—H1O1···O6, O1W—H2W1···O6 and O4—H1O4···O1W interactions, into a three-dimensional network.

Experimental

Anhydrous tartaric acid (1.5 g, 0.1 mmol) was dissolved in water in a flat bottom flask with magnetic stirrer. In a separating funnel, sodium bicarbonate (0.85g, 0.1 mmol) was dissolved in water. The sodium bicarbonate solution was added in small portions to the flask of tartaric acid with stirring. The reaction mixture was refluxed for 1 h. After cooling the reaction mixture to room temperature, it was left for overnight stirring. The colourless crystals that subsequently formed were filtered and washed with methanol and dried at 353 K.

Refinement

All H atoms were located in a difference Fourier map and fixed at these positions [C—H = 0.92–1.00 Å; O—H = 0.77–0.90 Å] and U_iso(H) = 1.2 U_eq(C) and 1.5 U_eq(O).

Figures

Fig. 1.

The asymmetric unit of the title compound, showing 50% probability displacement ellipsoids for non-H atoms and the atom-numbering scheme.

Fig. 2.

The polymeric structure of the title compound, viewed down the a axis, showing 2-dimensional array parallel to the (100) plane. All H atoms have been omitted for clarity.

Fig. 3.

Part of a 2-dimensional array, highlighting the coordination environment for Na+. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity. Symmetry codes: (%) -x, 1/2 + y, 3/2 - z; (#) -x, -1/2 + y, 1/2 - z; ($) x, 3/2 - y, -1/2 + z.

Fig. 4.

The crystal packing of the title compound, viewed down the b axis. Hydrogen bonds are shown as dashed lines. C-bound H atoms have been omitted for clarity.

Crystal data

[Na(C4H5O6)(H2O)]	F(000) = 392
Mr = 190.09	Dx = 1.884 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1671 reflections
a = 8.9723 (2) Å	θ = 2.6–29.9°
b = 7.1457 (1) Å	µ = 0.24 mm−1
c = 12.0186 (2) Å	T = 100 K
β = 119.571 (1)°	Needle, colourless
V = 670.18 (2) Å3	0.40 × 0.09 × 0.05 mm
Z = 4

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	1947 independent reflections
Radiation source: fine-focus sealed tube	1532 reflections with I > 2σ(I)
graphite	Rint = 0.034
φ and ω scans	θmax = 30.0°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −12→12
Tmin = 0.895, Tmax = 0.979	k = −10→10
6649 measured reflections	l = −13→16

Refinement

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.092	All H-atom parameters refined
S = 1.03	w = 1/[σ2(Fo2) + (0.0406P)2 + 0.2259P] where P = (Fo2 + 2Fc2)/3
1947 reflections	(Δ/σ)max < 0.001
109 parameters	Δρmax = 0.51 e Å−3
0 restraints	Δρmin = −0.29 e Å−3

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 (Ų)

	x	y	z	Uiso*/Ueq
Na1	−0.01684 (8)	0.60710 (8)	0.68653 (6)	0.01242 (15)
O1	0.40344 (13)	0.43067 (13)	1.07635 (10)	0.0119 (2)
H1O1	0.4044	0.3103	1.0786	0.018*
C1	0.26779 (18)	0.50448 (18)	0.97844 (15)	0.0099 (3)
O1W	−0.25610 (13)	0.58582 (13)	0.72347 (11)	0.0129 (2)
H1W1	−0.2558	0.6856	0.7595	0.019*
H2W1	−0.3646	0.5522	0.6686	0.019*
O2	0.15291 (13)	0.41821 (13)	0.89112 (11)	0.0130 (2)
C2	0.26731 (18)	0.71881 (18)	0.98483 (14)	0.0088 (3)
H2A	0.3650	0.7643	0.9739	0.011*
O3	0.10842 (13)	0.79014 (13)	0.88733 (10)	0.0106 (2)
H1O3	0.0405	0.7814	0.9094	0.016*
C3	0.29897 (18)	0.78670 (18)	1.11559 (14)	0.0094 (3)
H3A	0.4058	0.7442	1.1778	0.011*
O4	0.16227 (13)	0.72503 (13)	1.13335 (11)	0.0128 (2)
H1O4	0.1864	0.6265	1.1677	0.019*
C4	0.30326 (18)	1.00147 (18)	1.11769 (14)	0.0100 (3)
O5	0.19847 (14)	1.08865 (13)	1.13774 (11)	0.0148 (2)
O6	0.41681 (13)	1.07517 (13)	1.09721 (11)	0.0122 (2)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Na1	0.0142 (3)	0.0111 (3)	0.0123 (3)	−0.0020 (2)	0.0068 (3)	−0.0009 (2)
O1	0.0127 (5)	0.0075 (4)	0.0133 (6)	0.0015 (4)	0.0046 (5)	0.0013 (4)
C1	0.0125 (7)	0.0096 (6)	0.0112 (7)	0.0011 (5)	0.0087 (6)	0.0002 (5)
O1W	0.0130 (5)	0.0103 (5)	0.0156 (6)	−0.0014 (4)	0.0071 (5)	−0.0022 (4)
O2	0.0135 (5)	0.0099 (4)	0.0130 (6)	−0.0008 (4)	0.0045 (5)	−0.0016 (4)
C2	0.0092 (6)	0.0080 (6)	0.0085 (7)	0.0009 (5)	0.0040 (6)	0.0009 (5)
O3	0.0098 (5)	0.0119 (5)	0.0097 (5)	0.0016 (4)	0.0044 (4)	0.0012 (4)
C3	0.0107 (7)	0.0075 (6)	0.0100 (7)	0.0001 (5)	0.0050 (6)	0.0003 (5)
O4	0.0164 (5)	0.0093 (4)	0.0172 (6)	0.0014 (4)	0.0118 (5)	0.0030 (4)
C4	0.0107 (7)	0.0087 (6)	0.0071 (7)	−0.0006 (5)	0.0016 (6)	−0.0012 (5)
O5	0.0133 (5)	0.0108 (5)	0.0212 (6)	0.0009 (4)	0.0092 (5)	−0.0033 (4)
O6	0.0137 (5)	0.0092 (4)	0.0145 (6)	0.0000 (4)	0.0076 (5)	0.0006 (4)

Geometric parameters (Å, °)

Na1—O4i	2.3331 (12)	C2—O3	1.4201 (17)
Na1—O1W	2.4020 (12)	C2—C3	1.531 (2)
Na1—O3ii	2.4235 (11)	C2—H2A	1.0020
Na1—O3	2.4741 (12)	O3—Na1iii	2.4235 (11)
Na1—O2iii	2.4858 (11)	O3—H1O3	0.7774
Na1—O2	2.5479 (12)	C3—O4	1.4150 (16)
Na1—O5i	2.6740 (12)	C3—C4	1.5350 (18)
O1—C1	1.3155 (18)	C3—H3A	0.9288
O1—H1O1	0.8604	O4—Na1iv	2.3332 (11)
C1—O2	1.2149 (18)	O4—H1O4	0.7905
C1—C2	1.5336 (18)	C4—O5	1.2465 (17)
O1W—H1W1	0.8339	C4—O6	1.2741 (17)
O1W—H2W1	0.8983	O5—Na1iv	2.6740 (12)
O2—Na1ii	2.4858 (11)
O4i—Na1—O1W	151.93 (4)	C1—O2—Na1ii	145.91 (10)
O4i—Na1—O3ii	122.35 (4)	C1—O2—Na1	114.40 (9)
O1W—Na1—O3ii	80.57 (4)	Na1ii—O2—Na1	99.35 (4)
O4i—Na1—O3	87.29 (4)	O3—C2—C3	109.60 (11)
O1W—Na1—O3	82.55 (4)	O3—C2—C1	110.09 (11)
O3ii—Na1—O3	139.47 (4)	C3—C2—C1	111.35 (11)
O4i—Na1—O2iii	73.41 (4)	O3—C2—H2A	111.2
O1W—Na1—O2iii	78.92 (4)	C3—C2—H2A	107.5
O3ii—Na1—O2iii	133.11 (4)	C1—C2—H2A	107.0
O3—Na1—O2iii	78.23 (4)	C2—O3—Na1iii	131.19 (8)
O4i—Na1—O2	111.86 (4)	C2—O3—Na1	113.77 (8)
O1W—Na1—O2	87.20 (4)	Na1iii—O3—Na1	103.19 (4)
O3ii—Na1—O2	77.97 (4)	C2—O3—H1O3	109.0
O3—Na1—O2	64.61 (4)	Na1iii—O3—H1O3	91.1
O2iii—Na1—O2	141.72 (4)	Na1—O3—H1O3	103.6
O4i—Na1—O5i	62.55 (4)	O4—C3—C2	108.69 (11)
O1W—Na1—O5i	144.66 (4)	O4—C3—C4	109.00 (11)
O3ii—Na1—O5i	65.28 (3)	C2—C3—C4	108.91 (12)
O3—Na1—O5i	117.44 (4)	O4—C3—H3A	113.8
O2iii—Na1—O5i	131.27 (4)	C2—C3—H3A	108.5
O2—Na1—O5i	77.41 (4)	C4—C3—H3A	107.8
C1—O1—H1O1	114.8	C3—O4—Na1iv	130.28 (8)
O2—C1—O1	125.82 (12)	C3—O4—H1O4	108.8
O2—C1—C2	121.86 (13)	Na1iv—O4—H1O4	111.3
O1—C1—C2	112.32 (12)	O5—C4—O6	125.60 (12)
Na1—O1W—H1W1	105.6	O5—C4—C3	119.18 (12)
Na1—O1W—H2W1	128.7	O6—C4—C3	115.22 (12)
H1W1—O1W—H2W1	109.5	C4—O5—Na1iv	118.45 (9)
O1—C1—O2—Na1ii	13.8 (3)	O4i—Na1—O3—C2	−82.64 (9)
C2—C1—O2—Na1ii	−165.96 (11)	O1W—Na1—O3—C2	123.57 (9)
O1—C1—O2—Na1	−157.55 (11)	O3ii—Na1—O3—C2	57.61 (8)
C2—C1—O2—Na1	22.65 (16)	O2iii—Na1—O3—C2	−156.25 (9)
O4i—Na1—O2—C1	46.35 (11)	O2—Na1—O3—C2	33.14 (8)
O1W—Na1—O2—C1	−112.44 (10)	O5i—Na1—O3—C2	−25.64 (10)
O3ii—Na1—O2—C1	166.61 (10)	O3—C2—C3—O4	58.74 (14)
O3—Na1—O2—C1	−29.37 (9)	C1—C2—C3—O4	−63.32 (14)
O2iii—Na1—O2—C1	−44.32 (10)	O3—C2—C3—C4	−59.89 (14)
O5i—Na1—O2—C1	99.59 (10)	C1—C2—C3—C4	178.05 (11)
O2—C1—C2—O3	7.77 (19)	C2—C3—O4—Na1iv	−126.79 (10)
O1—C1—C2—O3	−172.06 (11)	C4—C3—O4—Na1iv	−8.22 (17)
O2—C1—C2—C3	129.54 (15)	O4—C3—C4—O5	2.38 (19)
O1—C1—C2—C3	−50.29 (15)	C2—C3—C4—O5	120.82 (15)
C3—C2—O3—Na1iii	66.43 (14)	O4—C3—C4—O6	−177.16 (12)
C1—C2—O3—Na1iii	−170.76 (8)	C2—C3—C4—O6	−58.73 (17)
C3—C2—O3—Na1	−157.80 (8)	O6—C4—O5—Na1iv	−177.69 (12)
C1—C2—O3—Na1	−34.99 (13)	C3—C4—O5—Na1iv	2.82 (18)

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

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···O6v	0.86	1.69	2.5496 (13)	175
O1W—H1W1···O5vi	0.83	1.94	2.7585 (14)	167
O1W—H2W1···O6vii	0.90	1.94	2.8006 (15)	161
O3—H1O3···O5vi	0.78	2.14	2.7575 (19)	137
O4—H1O4···O1Wviii	0.79	1.90	2.6784 (14)	170

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