(2R,3R)-1,4-Dioxa­spiro­[4.4]nonane-2,3-di­carb­oxy­lic and (2R,3R)-1,4-dioxa­spiro­[4.5]decane-2,3-di­carb­oxy­lic acids

Minyaev, M.E.; Roitershtein, D.M.; Vinogradov, A.A.; Ananyev, I.V.; Nifant'ev, I.E.

doi:10.1107/S2056989018009593

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Volume 74| Part 8| August 2018| Pages 1058-1062

https://doi.org/10.1107/S2056989018009593

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(2R,3R)-1,4-Dioxaspiro[4.4]nonane-2,3-dicarboxylic and (2R,3R)-1,4-dioxaspiro[4.5]decane-2,3-dicarboxylic acids

Mikhail E. Minyaev,^a ^* Dmitrii M. Roitershtein,^a,^b Alexey A. Vinogradov,^a Ivan V. Ananyev ^c and Ilya E. Nifant'ev ^a,^d

^aA.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 29 Leninsky Prospect, 119991, Moscow, Russian Federation, ^bN.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Prospect, Moscow, 119991, Russian Federation, ^cA.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilova Str., Moscow, 119991, Russian Federation, and ^dChemistry Department, M.V. Lomonosov Moscow State University, 1 Leninskie Gory Str., Building 3, Moscow, 119991, Russian Federation
^*Correspondence e-mail: mminyaev@mail.ru

Edited by E. V. Boldyreva, Russian Academy of Sciences, Russia (Received 11 June 2018; accepted 4 July 2018; online 6 July 2018)

The title compounds, C₉H₁₂O₆ and C₁₀H₁₄O₆, were formed by careful hydrolysis of the corresponding diethyl esters. Their single crystals were grown from an ethyl acetate/hexane mixture. Crystals of both compounds have monoclinic (P2₁) symmetry with a single molecule in the asymmetric unit. Both crystal structures are very similar and display four –CO—OH⋯O=C(OH)– hydrogen bonds, forming a two-dimensional double-layered framework.

Keywords: tartric acid; 1,3-dioxolane; ketals; NMR; hydrogen bonding; crystal structure.

CCDC references: 1853435; 1853434

1. Chemical context

Transition-metal catalysis has developed as a powerful tool to create a variety of carbon–carbon and carbon–heteroatom bonds. Enantioselective versions of these reactions are especially interesting in the light of the possible pharmaceutical applications. The general route to such processes supposes the use of transition metal complexes with chiral ligands (Yang et al., 2017 ). Therefore, easily accessible ligands of this type are of great importance for homogenous catalysis. Chiral phosphine ligands and amino acids are the most popular in this respect (Crassous, 2009 ). Examples of chiral carboxylate ligands are also known (Saget et al., 2012 ), which can be useful in the synthesis of chiral coordination compounds and materials derived from them (Lam et al., 2011 ). Various tartaric acid derivatives, which are also used in organic synthesis as chiral auxiliary agents to create chiral building blocks (Kassai et al., 2000 ; Seebach et al., 2001 ), might be particularly useful in solving the stated problem. Herein we report the synthesis and structures of two tartaric acid derivatives that may potentially be used as synthetic precursors of chiral transition-metal catalysts.

Condensation of cyclopentanone or cyclohexanone with (2R,3R) diethyl tartrate led to the formation of the corresponding ketals, careful hydrolysis of which allowed us to prepare the title acids (Fig. 1).

Figure 1
The synthesis of the title compounds (I)

and (II)

2. Structural commentary

The structures of tartaric acid derivatives (I) and (II) were found as anticipated (Figs. 2 and 3, respectively), having a single molecule in the asymmetric unit. The 1,3-dioxolane, cyclopentane [in (I)] and cyclohexane [in (II)] fragments have the usual conformations. The C—C, C—O and C=O bond lengths are within regular distances (Tables 1 and 2). A detailed structural and conformational analysis for the crystal structures of some related acetals R′C₃H₃O₂(COR)₂ (R = NH₂, OAlkyl, OH; substituent R′ is at the 2-position of the 1,3-dioxolane ring) was given by Eissmann et al. (2012 ). Although the absolute structures of (I) and (II) cannot be unambiguously determined using the Flack parameter (Flack, 1983 ; Parsons, et al., 2013 ) with the SHELXL program (Sheldrick, 2015 ), the chirality at carbon atoms C2, C3 (2R,3R) is initially known from their synthetic precursor (diethyl L-tartrate), and has been also confirmed for (2R,3R)-diethyl 1,4-dioxaspiro[4.5]decane-2,3-dicarboxylate, and for (II) by optical rotation measurements (see the experimental section). The molecules of (I) and (II) have very similar positions in the unit cells, making the structures nearly isomorphous, but the c axis in (II) is elongated by almost 1.5 Å compared with that in (I) (see Table 5 below) because of the presence of an additional –(CH₂)– unit in the cycloalkane fragment in (II) (see Fig. 4 for the alignment of the cycloalkane fragments in the unit cell).

Table 1
Selected bond lengths (Å) for (I)

O1—C1	1.325 (3)	C1—C2	1.521 (4)
O2—C1	1.208 (3)	C2—C3	1.541 (4)
O3—C4	1.222 (3)	C3—C4	1.519 (4)
O4—C4	1.314 (3)	C5—C9	1.529 (4)
O5—C2	1.409 (3)	C5—C6	1.539 (4)
O5—C5	1.443 (3)	C6—C7	1.533 (4)
O6—C3	1.409 (3)	C7—C8	1.529 (4)
O6—C5	1.439 (3)	C8—C9	1.522 (4)

Table 2
Selected bond lengths (Å) for (II)

O1—C1	1.322 (2)	C2—C3	1.541 (2)
O2—C1	1.208 (2)	C3—C4	1.532 (2)
O3—C4	1.2229 (19)	C5—C6	1.519 (2)
O4—C4	1.3135 (18)	C5—C10	1.525 (2)
O5—C2	1.4107 (18)	C6—C7	1.533 (2)
O5—C5	1.4398 (18)	C7—C8	1.526 (3)
O6—C3	1.4135 (17)	C8—C9	1.532 (2)
O6—C5	1.441 (2)	C9—C10	1.538 (2)
C1—C2	1.529 (2)

Table 5
Experimental details

	(I)	(II)
Crystal data
Chemical formula	C₉H₁₂O₆	C₁₀H₁₄O₆
M_r	216.19	230.21
Crystal system, space group	Monoclinic, P2₁	Monoclinic, P2₁
Temperature (K)	100	100
a, b, c (Å)	6.2930 (8), 5.3712 (7), 14.0916 (17)	6.4272 (8), 5.2976 (6), 15.5678 (19)
β (°)	92.885 (2)	94.469 (2)
V (Å³)	475.71 (10)	528.45 (11)
Z	2	2
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	0.13	0.12
Crystal size (mm)	0.21 × 0.07 × 0.03	0.39 × 0.15 × 0.05

Data collection
Diffractometer	Bruker SMART APEXII	Bruker SMART APEXII
Absorption correction	Multi-scan (SADABS; Bruker, 2008 )	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.827, 0.996	0.917, 0.995
No. of measured, independent and observed [I > 2σ(I)] reflections	4142, 2455, 1914	4329, 2612, 2503
R_int	0.030	0.015
(sin θ/λ)_max (Å⁻¹)	0.682	0.682

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.083, 1.06	0.028, 0.072, 1.05
No. of reflections	2455	2612
No. of parameters	144	153
No. of restraints	1	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.24	0.30, −0.20
Computer programs: APEX2 and SAINT (Bruker, 2008), SHELXS97 and SHELXTL (Sheldrick, 2008 ), SHELXL2017 (Sheldrick, 2015), Mercury (Macrae et al., 2008 ) and publCIF (Westrip, 2010 ).

Figure 2
The structure of (2R,3R)-1,4-dioxaspiro[4.4]nonane-2,3-dicarboxylic acid, (I)

. Displacement ellipsoids are drawn at the 50% probability level.

Figure 3
The structure of (2R,3R)-1,4-dioxaspiro[4.5]decane-2,3-dicarboxylic acid, (II)

. Displacement ellipsoids are drawn at the 50% probability level.

Figure 4
The packing of (I)

parallel to (010). Two interacting molecular layers are shown. Only the H atoms involved in hydrogen bonding (blue dashed lines) have been included. Displacement ellipsoids are drawn at the 50% probability level.

3. Supramolecular features

The molecules of both structures are packed in two-dimensional frameworks by four –CO—OH⋯O=C(OH)– hydrogen bonds between neighboring carboxyl groups (Tables 3 and 4). The packing diagrams for (I) (Figs. 4, 5a) are nearly identical to those of (II) (not shown). The molecules form double layers parallel to the ab plane and sterically shielded from other layers by the cycloalkane fragments (Fig. 4). Hydrogen-bonded chains within the same layer are formed via two interactions involving the O1—H1 and O3 atoms of each molecule. These chains are interconnected into a two-dimensional hydrogen-bonded double-layered framework parallel to (001) by the O4—H4 and O2 atoms. The complicated structure of the two-dimensional double-layered framework is shown in Fig. 5a, but it can best be visualized in the simplified scheme in Fig. 5b. It might be noted that some weak C—H⋯O intermolecular interactions are also present (see the supporting information).

Table 3
Hydrogen-bond geometry (Å, °) for (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O3ⁱ	0.78 (4)	1.87 (4)	2.620 (3)	159 (4)
O4—H4⋯O2ⁱⁱ	0.84 (4)	1.92 (4)	2.723 (3)	159 (3)
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+1]$ ; (ii) x+1, y-1, z.

Table 4
Hydrogen-bond geometry (Å, °) for (II)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O3ⁱ	0.84 (3)	1.80 (3)	2.6230 (16)	164 (3)
O4—H4⋯O2ⁱⁱ	0.85 (3)	1.88 (3)	2.7116 (16)	164 (2)
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+1]$ ; (ii) x+1, y-1, z.

Figure 5
(a) The packing of (I)

parallel to (001). Two interacting molecular layers are shown. Only the H atoms involved in hydrogen bonding (blue dashed lines) have been included. Displacement ellipsoids are drawn at the 50% probability level. (b) The simplified structure of the two-dimensional double-layered framework. Molecules (circles) and hydrogen bonds (solid lines) within the same layers are shown in the same colour (blue or red). Hydrogen bonds between two layers are shown as solid black lines.

4. Database survey

Twenty crystal structures of tartaric acid ester derivatives possessing the 1,3-dioxolane cycle, R′R′′C₃H₂O₂(COOR)₂, are known to date [Cambridge Structural Database (CSD) Version 5.39, latest update Feb 2018; Groom et al., 2016 ]. There are 10 crystal structures of esters bearing one substituent R′ (R′′ = H) at the 2-position of the 1,3-dioxolane fragment (acetals): CSD refcodes DAZJET (Lee et al., 1999 ), LACREM, LACRUC (Roush et al., 1992 ), LEPHAR, LEPHEV (Eissmann et al., 2012), OLEGAN (Karisalmi et al., 2003 ), WEGXOW (Belokon' et al., 2005 ), XEYSEA (Jiang et al., 2007 ), YAXHIQ (Lv et al., 2012 ) and YIVGUF (Barrett et al., 1995 ). The crystal structures of esters with two substituents R′ and R′′ (ketals) are represented by GAGHAY, GUHGUL (Pelphrey et al., 2004 ), KEMRID (Wink & Dewan, 1990 ), MIWDIF (Ates & Curran, 2001 ), NAFWEW (Mikołajczyk et al., 1996 ), QOTVUQ (Maezaki et al., 2000 ), VICXOU/VICXOU10 (Giordano et al., 1990 ; Ianelli et al., 1992 ), VIHVAL (Linker et al., 2013 ) and VUCHAC, VUCHEG (Ianelli et al., 1992). The crystal structures of 14 related amide derivatives R′R′′C₃H₂O₂(CONR₂)₂ are also known (see the CSD and also Eissmann et al., 2012 and references therein). However, established crystal structures of related acids, R′R′′C₃H₂O₂(COOH)₂, are limited to only one structure with R′ = –C₆H₄-4-COOH and R′′ = H (LEPHIZ; Eissmann et al., 2012). This fact can be explained by some subtle problems with the individual isolation of pure acid samples because of the facile hydrolysis of the 1,3-dioxolane fragment during their preparation. Therefore, the synthesis and especially the crystallization of R′R′′C₃H₂O₂(COOH)₂ acids is a challenging task.

5. Synthesis and crystallization

5.1. General experimental remarks

(+)-Diethyl L-tartrate [Sigma–Aldrich, >99%, found [α]_D^297K = +12° (acetone, 20.5mg ml⁻¹); lit. data [α]_D^293K = +10° (ethanol, 53 mg ml⁻¹), see Černý, 1977 ] was used as purchased. ¹H and ¹³C{¹H} NMR spectra were recorded with Bruker AM-300 and Bruker DRX-500 spectrometers in CDCl₃ (Cambridge Isotope Laboratories, Inc., 99.8% ²H) and in acetone-d₆ (Sigma–Aldrich, 99.9 atom % ²H).

5.2. Synthesis of (2R,3R)-diethyl 1,4-dioxaspiro[4.5]decane-2,3-dicarboxylate

A 1000 ml round-bottomed flask equipped with a reflux condenser and a Dean–Stark trap was charged with diethyl L-tartrate (85.56 ml, 500 mmol), cyclohexanone (51.82 ml, 500 mmol), toluene (600 ml) and p-toluenesulfonic acid monohydrate (2.80 g, 147 mmol). The mixture was refluxed for 62 h. The resulting dark-brown mixture was washed with a saturated aqueous solution of NaHCO₃ (2 × 100ml) and with water (2 × 100ml). The organic layer was dried over anhydrous Na₂SO₄. The solvent was removed on a rotary evaporator. The obtained dark-brown oil was distilled under reduced pressure (388–391 K, 250 Pa). The yield of the colourless liquid was 84% (120.25 g, 420 mmol). η_D^293K = 1.4625, [α]_D^297K = −28.7 (acetone, 20.5 mg ml⁻¹) [Lit. data η_D^293K = 1.4605, [α]_D^293K = −35.57 (Tsuzuki, 1937 )]. ¹H NMR (CDCl₃) δ: 1.12 (t, 6H, CH₃—CH₂–O), 1.30–1.45 (m, 10H, –C₅H₁₀–), 4.10 (quartet, 4H, CH₃—CH₂—O), 4.55 (s, 2H, CH).

5.3. Synthesis of (2R,3R)-diethyl 1,4-dioxaspiro[4.4]nonane-2,3-dicarboxylate

The synthesis of (2R,3R)-diethyl 1,4-dioxaspiro[4.4]nonane-2,3-dicarboxylate was carried out analogously to that of (2R,3R)-diethyl 1,4-dioxaspiro[4.5]decane-2,3-dicarboxylate, starting from 85.47 ml (500 mmol) of diethyl L-tartrate, 44.23 ml (500 mmol) of cyclopentanone, 600 ml of toluene and 2.80 g (14.7 mmol) of p-toluenesulfonic acid monohydrate. The yield of the colourless liquid after vacuum distillation (383–385 K, 265 Pa) was 78% (106.08 g, 390 mmol). ¹H NMR (CDCl₃) δ: 1.17 (t, 6H, CH₃—CH₂—O), 1.51–1.63 (m, 4H, –C₄H₈–), 1.64–1.77 (m, 2H, –C₄H₈–), 1.77–1.91 (m, 2H, –C₄H₈–), 4.12 (quartet, 4H, CH₃—CH₂—O), 4.57 (s, 2H, CH).

5.4. Synthesis and crystallization of (2R,3R)-1,4-dioxaspiro[4.5]decane-2,3-dicarboxylic acid, (II)

A 100 ml round-bottomed flask was charged with 2.130 g (7.52 mmol) of (2R,3R)-diethyl 1,4-dioxaspiro[4.5]decane-2,3-dicarboxylate, 22.5 ml of THF, 22.5 ml of methanol and 22.5 ml of 2 M aqueous solution of LiOH. The reaction mixture was stirred for 6 h. It was then washed with diethyl ether (3 × 20 ml). The aqueous solution was acidified with a 2 M solution of HCl to pH ≃ 1 at 273 K. The formed acid was extracted with ethyl acetate (3 × 20 ml). The organic layer was dried over Na₂SO₄. The solution was removed on a rotary evaporator. The yield of the resulting white powder was 72% (1.250 g, 5.43 mmol). M.p. = 413K, [α]_D^297K = −27.3 (acetone, 20.5 mg ml⁻¹) [Lit. data [α]_D²⁰ = −24.0, ethanol, 304 mg ml⁻¹ (Innis & Lamaty, 1977 )]. ¹H NMR (acetone-d₆) δ: 1.36–1.44 (m, 2H, —C₅H₁₀—), 1.53-1.74 (m, 8H, –C₅H₁₀–), 4.82 (s, 2H, CH), 7.0 (br.s, 2H, –COOH). ¹³C{1H} NMR (acetone-d₆) δ: 24.6, 25.6, 36.8, 77.7, 114.7, 171.7. Crystals of (II) were grown from an ethyl acetate/hexane (1:1 v/v) mixture.

5.5. Synthesis and crystallization of (2R,3R)-1,4-dioxaspiro[4.4]nonane-2,3-dicarboxylic acid, (I)

The synthesis of (I) was carried out analogously to that of (II), starting from 2.723 g (10 mmol) of (2R,3R)-diethyl 1,4-dioxaspiro[4.4]nonane-2,3-dicarboxylate, 22.5 ml of THF, 22.5 ml of methanol and 22.5 ml of 2 M aqueous solution of LiOH. The yield of the resulting white powder was 50% (1.081 g, 5 mmol). ¹H NMR (acetone-d₆) δ: 1.59–1.72 (m, 4H, –C₄H₈–), 1.74–1.87 (m, 2H, –C₄H₈–), 1.90–2.02 (m, 2H, –C₄H₈–), 4.78 (s, 2H, CH), 7.5 (br.s, 2H, -COOH). ¹³C{1H} NMR (acetone-d₆) δ: 24.0, 37.4, 77.9, 123.6, 171.4. Crystals of (I) were grown from an ethyl acetate/hexane (1:1 v/v) mixture.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 5. The positions of all non-H and the hydroxy H atoms were found from the electron difference density maps. These atoms were refined with individual anisotropic (non-H) or isotropic (hydroxy H) displacement parameters. The positions of the other H atoms were also found from the difference map but they were positioned geometrically (C—H distance = 0.99 Å for methylene, 1.00 Å for tertiary hydrogen atoms) and refined as riding atoms with U_iso(H) = 1.2U_eq(C). Reflection (001) in (II) was affected by the beam stop, and was therefore omitted from the refinement.

Supporting information

CCDC references: 1853435; 1853434

Crystal structure: contains datablocks I, II, global. DOI: https://doi.org/10.1107/S2056989018009593/eb2009sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018009593/eb2009Isup2.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989018009593/eb2009IIsup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989018009593/eb2009Isup4.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989018009593/eb2009IIsup5.cml

checkCIF report

Computing details top

For both structures, data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2017 (Sheldrick, 2015) and publCIF (Westrip, 2010).

(2R,3R)-1,4-Dioxaspiro[4.4]nonane-2,3-dicarboxylic acid (I) top

Crystal data top

C₉H₁₂O₆	F(000) = 228
M_r = 216.19	D_x = 1.509 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 6.2930 (8) Å	Cell parameters from 621 reflections
b = 5.3712 (7) Å	θ = 3–29°
c = 14.0916 (17) Å	µ = 0.13 mm⁻¹
β = 92.885 (2)°	T = 100 K
V = 475.71 (10) Å³	Needle, colourless
Z = 2	0.21 × 0.07 × 0.03 mm

Data collection top

Bruker SMART APEXII diffractometer	2455 independent reflections
Radiation source: fine-focus sealed tube	1914 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ω scans	θ_max = 29.0°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −8→8
T_min = 0.827, T_max = 0.996	k = −7→7
4142 measured reflections	l = −14→19

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)] = 0.043	Hydrogen site location: mixed
wR(F²) = 0.083	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.031P)²] where P = (F_o² + 2F_c²)/3
2455 reflections	(Δ/σ)_max < 0.001
144 parameters	Δρ_max = 0.29 e Å⁻³
1 restraint	Δρ_min = −0.24 e Å⁻³

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.3838 (4)	0.5521 (4)	0.45124 (15)	0.0153 (5)
H1	0.271 (6)	0.587 (8)	0.468 (3)	0.039 (13)*
O2	0.3808 (3)	0.8867 (4)	0.35486 (14)	0.0156 (5)
O3	0.9421 (3)	0.1722 (4)	0.44956 (14)	0.0133 (5)
O4	1.0688 (3)	0.2205 (4)	0.30548 (14)	0.0141 (5)
H4	1.173 (6)	0.144 (7)	0.332 (2)	0.026 (10)*
O5	0.7890 (3)	0.7805 (3)	0.30380 (14)	0.0123 (5)
O6	0.6993 (3)	0.4106 (4)	0.23156 (13)	0.0127 (4)
C1	0.4679 (4)	0.7060 (5)	0.38994 (19)	0.0108 (6)
C2	0.6954 (4)	0.6301 (5)	0.3722 (2)	0.0113 (6)
H2	0.782988	0.639980	0.433289	0.014*
C3	0.7155 (4)	0.3667 (5)	0.33022 (19)	0.0103 (6)
H3	0.591522	0.263933	0.348493	0.012*
C4	0.9202 (4)	0.2424 (5)	0.3672 (2)	0.0105 (6)
C5	0.7661 (4)	0.6609 (5)	0.2121 (2)	0.0124 (6)
C6	0.6025 (5)	0.7952 (6)	0.1454 (2)	0.0174 (7)
H6A	0.481549	0.683619	0.127887	0.021*
H6B	0.547171	0.945453	0.176471	0.021*
C7	0.7213 (5)	0.8670 (7)	0.0571 (2)	0.0276 (8)
H7A	0.704227	0.737514	0.007304	0.033*
H7B	0.669165	1.027909	0.030732	0.033*
C8	0.9535 (5)	0.8873 (7)	0.0939 (2)	0.0220 (7)
H8A	1.051505	0.869535	0.041494	0.026*
H8B	0.981059	1.048463	0.126290	0.026*
C9	0.9776 (4)	0.6711 (6)	0.1634 (2)	0.0161 (6)
H9A	1.097196	0.700938	0.210352	0.019*
H9B	1.003536	0.513540	0.129416	0.019*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0145 (11)	0.0154 (11)	0.0167 (13)	0.0014 (9)	0.0066 (9)	0.0018 (10)
O2	0.0148 (10)	0.0150 (10)	0.0172 (12)	0.0050 (9)	0.0011 (8)	0.0010 (10)
O3	0.0147 (10)	0.0140 (10)	0.0112 (11)	0.0015 (8)	0.0007 (8)	0.0017 (9)
O4	0.0120 (10)	0.0154 (11)	0.0153 (11)	0.0031 (8)	0.0034 (8)	0.0025 (9)
O5	0.0164 (10)	0.0109 (10)	0.0100 (11)	−0.0014 (8)	0.0030 (8)	−0.0012 (8)
O6	0.0178 (10)	0.0102 (9)	0.0099 (11)	−0.0003 (8)	−0.0003 (8)	−0.0005 (9)
C1	0.0146 (13)	0.0093 (12)	0.0085 (14)	−0.0004 (11)	−0.0002 (11)	−0.0040 (12)
C2	0.0136 (14)	0.0087 (13)	0.0117 (16)	0.0012 (10)	0.0015 (11)	−0.0005 (11)
C3	0.0127 (13)	0.0083 (12)	0.0103 (15)	−0.0005 (10)	0.0021 (11)	0.0001 (12)
C4	0.0100 (13)	0.0063 (13)	0.0151 (16)	−0.0005 (10)	0.0001 (11)	−0.0031 (12)
C5	0.0171 (14)	0.0110 (13)	0.0091 (15)	0.0011 (11)	0.0019 (11)	−0.0020 (12)
C6	0.0183 (15)	0.0182 (14)	0.0155 (17)	0.0050 (12)	−0.0003 (13)	−0.0006 (13)
C7	0.0310 (18)	0.035 (2)	0.0167 (18)	0.0068 (16)	0.0021 (14)	0.0092 (16)
C8	0.0258 (16)	0.0225 (16)	0.0185 (18)	0.0003 (14)	0.0089 (13)	0.0071 (15)
C9	0.0164 (14)	0.0163 (15)	0.0160 (17)	0.0014 (12)	0.0047 (12)	0.0012 (14)

Geometric parameters (Å, º) top

O1—C1	1.325 (3)	C3—H3	1.0000
O1—H1	0.78 (4)	C5—C9	1.529 (4)
O2—C1	1.208 (3)	C5—C6	1.539 (4)
O3—C4	1.222 (3)	C6—C7	1.533 (4)
O4—C4	1.314 (3)	C6—H6A	0.9900
O4—H4	0.84 (4)	C6—H6B	0.9900
O5—C2	1.409 (3)	C7—C8	1.529 (4)
O5—C5	1.443 (3)	C7—H7A	0.9900
O6—C3	1.409 (3)	C7—H7B	0.9900
O6—C5	1.439 (3)	C8—C9	1.522 (4)
C1—C2	1.521 (4)	C8—H8A	0.9900
C2—C3	1.541 (4)	C8—H8B	0.9900
C2—H2	1.0000	C9—H9A	0.9900
C3—C4	1.519 (4)	C9—H9B	0.9900

C1—O1—H1	117 (3)	O5—C5—C6	111.9 (2)
C4—O4—H4	108 (2)	C9—C5—C6	106.2 (2)
C2—O5—C5	109.3 (2)	C7—C6—C5	106.0 (2)
C3—O6—C5	109.7 (2)	C7—C6—H6A	110.5
O2—C1—O1	125.4 (2)	C5—C6—H6A	110.5
O2—C1—C2	124.0 (2)	C7—C6—H6B	110.5
O1—C1—C2	110.5 (2)	C5—C6—H6B	110.5
O5—C2—C1	112.8 (2)	H6A—C6—H6B	108.7
O5—C2—C3	102.6 (2)	C8—C7—C6	103.9 (3)
C1—C2—C3	113.9 (2)	C8—C7—H7A	111.0
O5—C2—H2	109.1	C6—C7—H7A	111.0
C1—C2—H2	109.1	C8—C7—H7B	111.0
C3—C2—H2	109.1	C6—C7—H7B	111.0
O6—C3—C4	115.5 (2)	H7A—C7—H7B	109.0
O6—C3—C2	102.8 (2)	C9—C8—C7	103.1 (3)
C4—C3—C2	110.9 (2)	C9—C8—H8A	111.1
O6—C3—H3	109.1	C7—C8—H8A	111.1
C4—C3—H3	109.1	C9—C8—H8B	111.1
C2—C3—H3	109.1	C7—C8—H8B	111.1
O3—C4—O4	123.4 (2)	H8A—C8—H8B	109.1
O3—C4—C3	121.0 (2)	C8—C9—C5	104.8 (2)
O4—C4—C3	115.6 (2)	C8—C9—H9A	110.8
O6—C5—O5	105.2 (2)	C5—C9—H9A	110.8
O6—C5—C9	112.9 (2)	C8—C9—H9B	110.8
O5—C5—C9	109.6 (2)	C5—C9—H9B	110.8
O6—C5—C6	111.2 (2)	H9A—C9—H9B	108.9

C5—O5—C2—C1	−95.7 (2)	C3—O6—C5—O5	−9.5 (3)
C5—O5—C2—C3	27.4 (3)	C3—O6—C5—C9	110.0 (2)
O2—C1—C2—O5	−5.2 (4)	C3—O6—C5—C6	−130.8 (2)
O1—C1—C2—O5	177.0 (2)	C2—O5—C5—O6	−12.6 (3)
O2—C1—C2—C3	−121.7 (3)	C2—O5—C5—C9	−134.3 (2)
O1—C1—C2—C3	60.5 (3)	C2—O5—C5—C6	108.2 (2)
C5—O6—C3—C4	−95.4 (3)	O6—C5—C6—C7	−120.1 (3)
C5—O6—C3—C2	25.5 (3)	O5—C5—C6—C7	122.6 (3)
O5—C2—C3—O6	−32.0 (2)	C9—C5—C6—C7	3.0 (3)
C1—C2—C3—O6	90.3 (3)	C5—C6—C7—C8	−26.1 (3)
O5—C2—C3—C4	92.0 (3)	C6—C7—C8—C9	39.3 (3)
C1—C2—C3—C4	−145.7 (2)	C7—C8—C9—C5	−37.6 (3)
O6—C3—C4—O3	−172.3 (2)	O6—C5—C9—C8	143.4 (3)
C2—C3—C4—O3	71.3 (3)	O5—C5—C9—C8	−99.7 (3)
O6—C3—C4—O4	8.6 (3)	C6—C5—C9—C8	21.4 (3)
C2—C3—C4—O4	−107.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3ⁱ	0.78 (4)	1.87 (4)	2.620 (3)	159 (4)
O4—H4···O2ⁱⁱ	0.84 (4)	1.92 (4)	2.723 (3)	159 (3)
C2—H2···O3ⁱⁱⁱ	1.00	2.34	3.315 (4)	166
C3—H3···O2^iv	1.00	2.43	3.358 (3)	155

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

(2R,3R)-1,4-Dioxaspiro[4.5]decane-2,3-dicarboxylic acid (II) top

Crystal data top

C₁₀H₁₄O₆	D_x = 1.447 Mg m⁻³
M_r = 230.21	Melting point: 413(1) K
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 6.4272 (8) Å	Cell parameters from 361 reflections
b = 5.2976 (6) Å	θ = 3–29°
c = 15.5678 (19) Å	µ = 0.12 mm⁻¹
β = 94.469 (2)°	T = 100 K
V = 528.45 (11) Å³	Needle, colourless
Z = 2	0.39 × 0.15 × 0.05 mm
F(000) = 244

Data collection top

Bruker SMART APEXII diffractometer	2612 independent reflections
Radiation source: fine-focus sealed tube	2503 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.015
ω scans	θ_max = 29.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −8→8
T_min = 0.917, T_max = 0.995	k = −7→5
4329 measured reflections	l = −21→20

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)] = 0.028	Hydrogen site location: mixed
wR(F²) = 0.072	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0411P)² + 0.0783P] where P = (F_o² + 2F_c²)/3
2612 reflections	(Δ/σ)_max < 0.001
153 parameters	Δρ_max = 0.30 e Å⁻³
1 restraint	Δρ_min = −0.20 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
O1	0.38484 (18)	0.5840 (2)	0.45476 (7)	0.0142 (2)
H1	0.275 (4)	0.638 (6)	0.4745 (17)	0.046 (8)*
O2	0.37180 (17)	0.9308 (2)	0.37124 (7)	0.0150 (2)
O3	0.92950 (17)	0.2135 (2)	0.45684 (7)	0.0124 (2)
O4	1.05961 (17)	0.2630 (2)	0.32878 (7)	0.0134 (2)
H4	1.158 (4)	0.171 (5)	0.3519 (15)	0.027 (6)*
O5	0.76550 (18)	0.8366 (2)	0.32166 (7)	0.0118 (2)
O6	0.70176 (17)	0.4547 (2)	0.25475 (7)	0.0116 (2)
C1	0.4607 (2)	0.7451 (3)	0.40041 (9)	0.0104 (3)
C2	0.6846 (2)	0.6758 (3)	0.38313 (9)	0.0099 (3)
H2	0.774689	0.688258	0.438295	0.012*
C3	0.7100 (2)	0.4108 (3)	0.34451 (9)	0.0099 (3)
H3	0.588324	0.303877	0.357764	0.012*
C4	0.9117 (2)	0.2852 (3)	0.38196 (10)	0.0103 (3)
C5	0.7505 (2)	0.7152 (3)	0.23867 (9)	0.0109 (3)
C6	0.9603 (2)	0.7413 (3)	0.20088 (9)	0.0145 (3)
H6A	1.069512	0.658928	0.239569	0.017*
H6B	0.996255	0.922393	0.196647	0.017*
C7	0.9553 (3)	0.6204 (4)	0.11126 (11)	0.0208 (4)
H7A	1.090749	0.648573	0.086579	0.025*
H7B	0.934204	0.435992	0.116324	0.025*
C8	0.7800 (3)	0.7324 (4)	0.05127 (10)	0.0233 (4)
H8A	0.775479	0.646187	−0.005267	0.028*
H8B	0.807902	0.913725	0.041928	0.028*
C9	0.5691 (3)	0.7025 (4)	0.08968 (10)	0.0191 (3)
H9A	0.535628	0.520808	0.094378	0.023*
H9B	0.458492	0.782178	0.050960	0.023*
C10	0.5734 (2)	0.8254 (3)	0.17929 (10)	0.0151 (3)
H10A	0.593000	1.009889	0.173941	0.018*
H10B	0.438602	0.795642	0.204323	0.018*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0135 (5)	0.0139 (6)	0.0160 (5)	0.0025 (5)	0.0065 (4)	0.0026 (5)
O2	0.0139 (5)	0.0142 (6)	0.0172 (5)	0.0044 (4)	0.0029 (4)	0.0027 (5)
O3	0.0127 (5)	0.0125 (6)	0.0122 (5)	0.0009 (4)	0.0014 (4)	0.0004 (4)
O4	0.0115 (5)	0.0133 (6)	0.0157 (5)	0.0032 (4)	0.0036 (4)	0.0017 (5)
O5	0.0156 (5)	0.0092 (5)	0.0111 (5)	−0.0026 (4)	0.0036 (4)	−0.0012 (4)
O6	0.0156 (5)	0.0087 (5)	0.0104 (5)	−0.0011 (4)	0.0005 (4)	0.0002 (4)
C1	0.0114 (6)	0.0102 (7)	0.0097 (6)	−0.0006 (5)	0.0010 (5)	−0.0031 (6)
C2	0.0101 (6)	0.0087 (7)	0.0110 (6)	0.0007 (5)	0.0020 (5)	0.0006 (5)
C3	0.0097 (6)	0.0090 (7)	0.0111 (6)	0.0015 (5)	0.0011 (5)	−0.0007 (5)
C4	0.0099 (6)	0.0066 (7)	0.0145 (7)	−0.0003 (5)	0.0008 (5)	−0.0011 (5)
C5	0.0125 (6)	0.0095 (7)	0.0108 (6)	0.0003 (5)	0.0020 (5)	−0.0007 (6)
C6	0.0141 (7)	0.0158 (8)	0.0142 (6)	−0.0018 (6)	0.0048 (5)	−0.0016 (6)
C7	0.0203 (8)	0.0265 (10)	0.0165 (7)	−0.0028 (7)	0.0079 (6)	−0.0053 (7)
C8	0.0288 (9)	0.0291 (10)	0.0126 (7)	−0.0068 (8)	0.0054 (6)	−0.0003 (7)
C9	0.0208 (8)	0.0239 (10)	0.0122 (7)	−0.0016 (7)	−0.0008 (6)	0.0028 (7)
C10	0.0149 (7)	0.0158 (8)	0.0145 (7)	0.0015 (6)	0.0000 (5)	0.0029 (6)

Geometric parameters (Å, º) top

O1—C1	1.322 (2)	C5—C10	1.525 (2)
O1—H1	0.84 (3)	C6—C7	1.533 (2)
O2—C1	1.208 (2)	C6—H6A	0.9900
O3—C4	1.2229 (19)	C6—H6B	0.9900
O4—C4	1.3135 (18)	C7—C8	1.526 (3)
O4—H4	0.85 (3)	C7—H7A	0.9900
O5—C2	1.4107 (18)	C7—H7B	0.9900
O5—C5	1.4398 (18)	C8—C9	1.532 (2)
O6—C3	1.4135 (17)	C8—H8A	0.9900
O6—C5	1.441 (2)	C8—H8B	0.9900
C1—C2	1.529 (2)	C9—C10	1.538 (2)
C2—C3	1.541 (2)	C9—H9A	0.9900
C2—H2	1.0000	C9—H9B	0.9900
C3—C4	1.532 (2)	C10—H10A	0.9900
C3—H3	1.0000	C10—H10B	0.9900
C5—C6	1.519 (2)

C1—O1—H1	112 (2)	C5—C6—H6A	109.4
C4—O4—H4	109.4 (15)	C7—C6—H6A	109.4
C2—O5—C5	109.65 (12)	C5—C6—H6B	109.4
C3—O6—C5	109.70 (12)	C7—C6—H6B	109.4
O2—C1—O1	125.41 (14)	H6A—C6—H6B	108.0
O2—C1—C2	123.59 (14)	C8—C7—C6	110.88 (15)
O1—C1—C2	110.89 (13)	C8—C7—H7A	109.5
O5—C2—C1	112.10 (12)	C6—C7—H7A	109.5
O5—C2—C3	103.28 (11)	C8—C7—H7B	109.5
C1—C2—C3	114.66 (12)	C6—C7—H7B	109.5
O5—C2—H2	108.9	H7A—C7—H7B	108.1
C1—C2—H2	108.9	C7—C8—C9	110.75 (14)
C3—C2—H2	108.9	C7—C8—H8A	109.5
O6—C3—C4	114.38 (12)	C9—C8—H8A	109.5
O6—C3—C2	103.84 (12)	C7—C8—H8B	109.5
C4—C3—C2	111.08 (12)	C9—C8—H8B	109.5
O6—C3—H3	109.1	H8A—C8—H8B	108.1
C4—C3—H3	109.1	C8—C9—C10	110.87 (14)
C2—C3—H3	109.1	C8—C9—H9A	109.5
O3—C4—O4	123.68 (14)	C10—C9—H9A	109.5
O3—C4—C3	120.74 (14)	C8—C9—H9B	109.5
O4—C4—C3	115.58 (13)	C10—C9—H9B	109.5
O5—C5—O6	105.80 (12)	H9A—C9—H9B	108.1
O5—C5—C6	107.89 (12)	C5—C10—C9	110.35 (14)
O6—C5—C6	111.46 (13)	C5—C10—H10A	109.6
O5—C5—C10	111.57 (13)	C9—C10—H10A	109.6
O6—C5—C10	108.05 (13)	C5—C10—H10B	109.6
C6—C5—C10	111.92 (13)	C9—C10—H10B	109.6
C5—C6—C7	110.97 (13)	H10A—C10—H10B	108.1

C5—O5—C2—C1	−99.25 (14)	C2—O5—C5—O6	−12.62 (15)
C5—O5—C2—C3	24.70 (14)	C2—O5—C5—C6	−132.02 (13)
O2—C1—C2—O5	−6.9 (2)	C2—O5—C5—C10	104.65 (14)
O1—C1—C2—O5	176.76 (12)	C3—O6—C5—O5	−6.39 (15)
O2—C1—C2—C3	−124.22 (16)	C3—O6—C5—C6	110.62 (13)
O1—C1—C2—C3	59.43 (16)	C3—O6—C5—C10	−126.00 (13)
C5—O6—C3—C4	−100.36 (14)	O5—C5—C6—C7	−178.91 (14)
C5—O6—C3—C2	20.87 (14)	O6—C5—C6—C7	65.34 (17)
O5—C2—C3—O6	−27.60 (14)	C10—C5—C6—C7	−55.80 (19)
C1—C2—C3—O6	94.65 (14)	C5—C6—C7—C8	55.80 (19)
O5—C2—C3—C4	95.81 (13)	C6—C7—C8—C9	−56.5 (2)
C1—C2—C3—C4	−141.94 (13)	C7—C8—C9—C10	56.9 (2)
O6—C3—C4—O3	−172.39 (14)	O5—C5—C10—C9	176.83 (13)
C2—C3—C4—O3	70.47 (18)	O6—C5—C10—C9	−67.27 (16)
O6—C3—C4—O4	7.99 (19)	C6—C5—C10—C9	55.82 (18)
C2—C3—C4—O4	−109.15 (15)	C8—C9—C10—C5	−56.08 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3ⁱ	0.84 (3)	1.80 (3)	2.6230 (16)	164 (3)
O4—H4···O2ⁱⁱ	0.85 (3)	1.88 (3)	2.7116 (16)	164 (2)
C2—H2···O3ⁱⁱⁱ	1.00	2.41	3.3818 (19)	164
C3—H3···O2^iv	1.00	2.44	3.392 (2)	160
C6—H6A···O4	0.99	2.52	3.255 (2)	131

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

Acknowledgements

Equipment from the collective exploitation center `New petrochemical processes, polymer composites and adhesives' of TIPS RAS was used.

Funding information

Funding for this research was provided by: the TIPS RAS State Plan.

References

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Volume 74| Part 8| August 2018| Pages 1058-1062

https://doi.org/10.1107/S2056989018009593

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

(2R,3R)-1,4-Dioxa­spiro­[4.4]nonane-2,3-di­carb­­oxy­lic and (2R,3R)-1,4-dioxa­spiro­[4.5]decane-2,3-di­carb­­oxy­lic acids

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

5.1. General experimental remarks

5.2. Synthesis of (2R,3R)-diethyl 1,4-dioxa­spiro­[4.5]decane-2,3-di­carboxyl­ate

5.3. Synthesis of (2R,3R)-diethyl 1,4-dioxa­spiro­[4.4]nonane-2,3-di­carboxyl­ate

5.4. Synthesis and crystallization of (2R,3R)-1,4-dioxa­spiro[4.5]decane-2,3-di­carb­oxy­lic acid, (II)

5.5. Synthesis and crystallization of (2R,3R)-1,4-dioxa­spiro[4.4]nonane-2,3-di­carb­oxy­lic acid, (I)

6. Refinement

Supporting information

Acknowledgements

Funding information

References

research communications

(2R,3R)-1,4-Dioxaspiro[4.4]nonane-2,3-dicarboxylic and (2R,3R)-1,4-dioxaspiro[4.5]decane-2,3-dicarboxylic acids

3. Supramolecular features

5.2. Synthesis of (2R,3R)-diethyl 1,4-dioxaspiro[4.5]decane-2,3-dicarboxylate

5.3. Synthesis of (2R,3R)-diethyl 1,4-dioxaspiro[4.4]nonane-2,3-dicarboxylate

5.4. Synthesis and crystallization of (2R,3R)-1,4-dioxaspiro[4.5]decane-2,3-dicarboxylic acid, (II)

5.5. Synthesis and crystallization of (2R,3R)-1,4-dioxaspiro[4.4]nonane-2,3-dicarboxylic acid, (I)