Syntheses and crystal structures of 2,2,5-trimethyl-1,3-dioxane-5-carb­oxy­lic acid and 2,2,5-trimethyl-1,3-dioxane-5-carb­oxy­lic anhydride

Giesen, J.A.; Grayson, S.M.; Mague, J.T.

doi:10.1107/S2056989019016670

Syntheses and crystal structures of 2,2,5-trimethyl-1,3-dioxane-5-carboxylic acid and 2,2,5-trimethyl-1,3-dioxane-5-carboxylic anhydride

J. A. Giesen, S. M. Grayson and J. T. Mague

The title compounds, C₈H₁₄O₄ and C₁₆H₂₆O₇, are precursors to dendrimers. The strong and weak hydrogen bonds in their extended structures are described.

Keywords: crystal structure; anhydride; hydrogen bond; dioxane; carboxylic acid.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989019016670/hb7867sup1.cif Contains datablocks global, I, II
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989019016670/hb7867Isup2.hkl Contains datablock I
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989019016670/hb7867IIsup3.hkl Contains datablock II
	Microsoft Word (DOCX) file https://doi.org/10.1107/S2056989019016670/hb7867sup4.docx 13C and 1H NMR spectra

CCDC references: 1971440; 1971439

checkCIF report

Key indicators

Structure: I

Single-crystal X-ray study
T = 150 K
Mean (C-C) = 0.001 Å
R factor = 0.039
wR factor = 0.113
Data-to-parameter ratio = 14.3

Structure: II

Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.002 Å
R factor = 0.040
wR factor = 0.109
Data-to-parameter ratio = 20.2

checkCIF/PLATON results

No syntax errors found



Datablock: I


Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.44 Report

Alert level G
PLAT128_ALERT_4_G Alternate Setting for Input Space Group     C2/c       I2/a Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          7 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          6 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   3 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check




Datablock: II


Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C1       --C2       .        5.7 s.u.
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600         13 Report

Alert level G
PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical          ? Check
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          2 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600        660 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.         17 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   4 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Computing details top

For both structures, data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

2,2,5-Trimethyl-1,3-dioxane-5-carboxylic acid (I) top

Crystal data top

C₈H₁₄O₄	F(000) = 752
M_r = 174.19	D_x = 1.312 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 16.9457 (8) Å	Cell parameters from 8540 reflections
b = 9.6453 (5) Å	θ = 2.5–29.1°
c = 12.1052 (6) Å	µ = 0.11 mm⁻¹
β = 116.986 (1)°	T = 150 K
V = 1763.12 (15) Å³	Block, colourless
Z = 8	0.35 × 0.32 × 0.25 mm

Data collection top

Bruker SMART APEX CCD diffractometer	2367 independent reflections
Radiation source: fine-focus sealed tube	2035 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
Detector resolution: 8.3333 pixels mm^-1	θ_max = 29.1°, θ_min = 2.5°
φ and ω scans	h = −23→23
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −13→13
T_min = 0.91, T_max = 0.97	l = −16→16
16506 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.039	Hydrogen site location: difference Fourier map
wR(F²) = 0.113	All H-atom parameters refined
S = 1.07	w = 1/[σ²(F_o²) + (0.0774P)² + 0.3458P] where P = (F_o² + 2F_c²)/3
2367 reflections	(Δ/σ)_max = 0.001
165 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Special details top

Experimental. The diffraction data were obtained from 3 sets of 400 frames, each of width 0.5° in ω, colllected at φ = 0.00, 90.00 and 180.00° and 2 sets of 800 frames, each of width 0.45° in φ, collected at ω = –30.00 and 210.00°. The scan time was 10 sec/frame.

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.

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

	x	y	z	U_iso*/U_eq
O1	0.39277 (7)	0.35303 (8)	0.10104 (8)	0.0395 (2)
O2	0.35826 (5)	0.54688 (7)	0.16844 (7)	0.0280 (2)
H2	0.3661 (10)	0.5831 (16)	0.1048 (16)	0.044 (4)*
O3	0.36941 (4)	0.33124 (7)	0.47442 (6)	0.01898 (17)
O4	0.37935 (4)	0.12345 (7)	0.38268 (6)	0.01931 (17)
C1	0.36963 (6)	0.41082 (10)	0.16968 (8)	0.01841 (19)
C2	0.34712 (6)	0.33493 (9)	0.26155 (7)	0.01538 (18)
C3	0.38203 (6)	0.41384 (9)	0.38447 (8)	0.01846 (19)
H3	0.4442 (8)	0.4359 (13)	0.4139 (12)	0.025 (3)*
H3B	0.3511 (9)	0.5007 (14)	0.3792 (12)	0.028 (3)*
C4	0.41050 (6)	0.19614 (9)	0.49632 (8)	0.0176 (2)
C5	0.39283 (6)	0.19347 (9)	0.28855 (8)	0.0194 (2)
H5	0.4560 (9)	0.2045 (15)	0.3127 (13)	0.034 (3)*
H5B	0.3649 (9)	0.1329 (14)	0.2151 (13)	0.031 (3)*
C6	0.24588 (6)	0.31871 (11)	0.20277 (9)	0.0251 (2)
H6A	0.2160 (9)	0.4086 (15)	0.1885 (13)	0.031 (3)*
H6B	0.2316 (8)	0.2611 (14)	0.2616 (12)	0.028 (3)*
H6C	0.2246 (10)	0.2711 (16)	0.1240 (14)	0.042 (4)*
C7	0.37499 (7)	0.11697 (11)	0.57215 (9)	0.0252 (2)
H7A	0.3976 (10)	0.1590 (16)	0.6557 (15)	0.045 (4)*
H7B	0.3967 (10)	0.0208 (16)	0.5805 (14)	0.037 (4)*
H7C	0.3113 (10)	0.1106 (16)	0.5286 (14)	0.039 (4)*
C8	0.51093 (6)	0.20861 (11)	0.56270 (9)	0.0256 (2)
H8A	0.5272 (10)	0.2602 (16)	0.6373 (14)	0.039 (4)*
H8B	0.5353 (9)	0.2497 (15)	0.5103 (13)	0.034 (3)*
H8C	0.5394 (9)	0.1170 (16)	0.5863 (13)	0.034 (3)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0713 (6)	0.0306 (4)	0.0381 (5)	0.0155 (4)	0.0436 (5)	0.0086 (3)
O2	0.0493 (5)	0.0185 (3)	0.0265 (4)	0.0005 (3)	0.0263 (3)	0.0028 (3)
O3	0.0299 (3)	0.0157 (3)	0.0163 (3)	0.0032 (2)	0.0147 (3)	0.0010 (2)
O4	0.0287 (3)	0.0139 (3)	0.0173 (3)	−0.0008 (2)	0.0122 (3)	−0.0004 (2)
C1	0.0209 (4)	0.0207 (4)	0.0148 (4)	0.0014 (3)	0.0091 (3)	0.0013 (3)
C2	0.0189 (4)	0.0159 (4)	0.0134 (4)	0.0005 (3)	0.0091 (3)	0.0000 (3)
C3	0.0285 (4)	0.0144 (4)	0.0152 (4)	−0.0004 (3)	0.0123 (3)	−0.0001 (3)
C4	0.0229 (4)	0.0149 (4)	0.0158 (4)	0.0005 (3)	0.0094 (3)	0.0013 (3)
C5	0.0284 (4)	0.0163 (4)	0.0172 (4)	0.0037 (3)	0.0136 (3)	0.0003 (3)
C6	0.0195 (4)	0.0307 (5)	0.0232 (5)	−0.0006 (4)	0.0081 (4)	0.0039 (4)
C7	0.0348 (5)	0.0233 (5)	0.0227 (5)	−0.0022 (4)	0.0175 (4)	0.0037 (4)
C8	0.0219 (4)	0.0301 (5)	0.0207 (5)	−0.0002 (4)	0.0062 (4)	0.0055 (4)

Geometric parameters (Å, º) top

O1—C1	1.2043 (11)	C4—C7	1.5129 (12)
O2—C1	1.3255 (12)	C4—C8	1.5216 (12)
O2—H2	0.909 (17)	C5—H5	0.979 (14)
O3—C3	1.4414 (10)	C5—H5B	0.986 (14)
O3—C4	1.4442 (11)	C6—H6A	0.979 (14)
O4—C4	1.4155 (10)	C6—H6B	1.015 (13)
O4—C5	1.4294 (10)	C6—H6C	0.968 (15)
C1—C2	1.5176 (11)	C7—H7A	0.991 (16)
C2—C5	1.5293 (12)	C7—H7B	0.986 (15)
C2—C3	1.5312 (12)	C7—H7C	0.964 (15)
C2—C6	1.5382 (12)	C8—H8A	0.955 (15)
C3—H3	0.970 (13)	C8—H8B	0.984 (14)
C3—H3B	0.975 (13)	C8—H8C	0.985 (15)

C1—O2—H2	108.3 (10)	O4—C5—C2	110.07 (7)
C3—O3—C4	114.39 (6)	O4—C5—H5	111.2 (8)
C4—O4—C5	114.63 (7)	C2—C5—H5	110.2 (9)
O1—C1—O2	122.79 (8)	O4—C5—H5B	104.7 (8)
O1—C1—C2	123.44 (9)	C2—C5—H5B	110.3 (8)
O2—C1—C2	113.72 (7)	H5—C5—H5B	110.2 (11)
C1—C2—C5	108.39 (7)	C2—C6—H6A	111.8 (8)
C1—C2—C3	110.95 (7)	C2—C6—H6B	107.6 (7)
C5—C2—C3	107.51 (7)	H6A—C6—H6B	109.9 (11)
C1—C2—C6	107.98 (7)	C2—C6—H6C	110.0 (9)
C5—C2—C6	111.02 (8)	H6A—C6—H6C	108.3 (13)
C3—C2—C6	110.98 (7)	H6B—C6—H6C	109.3 (12)
O3—C3—C2	109.57 (7)	C4—C7—H7A	109.6 (9)
O3—C3—H3	110.6 (8)	C4—C7—H7B	107.7 (8)
C2—C3—H3	110.0 (7)	H7A—C7—H7B	109.1 (13)
O3—C3—H3B	105.3 (8)	C4—C7—H7C	110.8 (9)
C2—C3—H3B	113.8 (8)	H7A—C7—H7C	113.7 (13)
H3—C3—H3B	107.3 (11)	H7B—C7—H7C	105.7 (13)
O4—C4—O3	109.42 (7)	C4—C8—H8A	108.3 (9)
O4—C4—C7	105.31 (7)	C4—C8—H8B	112.8 (8)
O3—C4—C7	105.98 (7)	H8A—C8—H8B	112.0 (13)
O4—C4—C8	112.76 (7)	C4—C8—H8C	111.4 (8)
O3—C4—C8	110.86 (7)	H8A—C8—H8C	107.4 (13)
C7—C4—C8	112.14 (8)	H8B—C8—H8C	104.8 (12)

O1—C1—C2—C5	22.55 (12)	C5—O4—C4—O3	56.51 (9)
O2—C1—C2—C5	−159.88 (8)	C5—O4—C4—C7	170.04 (7)
O1—C1—C2—C3	140.38 (10)	C5—O4—C4—C8	−67.36 (10)
O2—C1—C2—C3	−42.05 (10)	C3—O3—C4—O4	−56.03 (9)
O1—C1—C2—C6	−97.79 (11)	C3—O3—C4—C7	−169.12 (7)
O2—C1—C2—C6	79.77 (10)	C3—O3—C4—C8	68.95 (9)
C4—O3—C3—C2	57.03 (9)	C4—O4—C5—C2	−58.36 (10)
C1—C2—C3—O3	−172.93 (7)	C1—C2—C5—O4	175.13 (7)
C5—C2—C3—O3	−54.57 (9)	C3—C2—C5—O4	55.13 (9)
C6—C2—C3—O3	67.02 (9)	C6—C2—C5—O4	−66.43 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3ⁱ	0.909 (17)	1.804 (17)	2.7086 (9)	172.6 (14)
C6—H6A···O4ⁱⁱ	0.979 (15)	2.527 (15)	3.4958 (13)	170.4 (12)
C8—H8B···O1ⁱⁱⁱ	0.984 (14)	2.405 (14)	3.3864 (12)	174.8 (11)

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

2,2,5-Trimethyl-1,3-dioxane-5-carboxylic anhydride (II) top

Crystal data top

C₁₆H₂₆O₇	Z = 4
M_r = 330.37	F(000) = 712
Triclinic, P1	D_x = 1.286 Mg m⁻³
a = 10.355 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.928 (5) Å	Cell parameters from 9690 reflections
c = 14.496 (6) Å	θ = 2.4–29.6°
α = 73.128 (5)°	µ = 0.10 mm⁻¹
β = 84.900 (5)°	T = 100 K
γ = 89.499 (6)°	Block, colourless
V = 1706.3 (11) Å³	0.30 × 0.30 × 0.22 mm

Data collection top

Bruker SMART APEX CCD diffractometer	8606 independent reflections
Radiation source: fine-focus sealed tube	7451 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
Detector resolution: 8.3333 pixels mm^-1	θ_max = 29.3°, θ_min = 2.0°
φ and ω scans	h = −13→14
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −16→15
T_min = 0.97, T_max = 0.98	l = −19→19
30041 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.109	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0556P)² + 0.3868P] where P = (F_o² + 2F_c²)/3
8606 reflections	(Δ/σ)_max = 0.001
427 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Special details top

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. H-atoms attached to carbon were placed in calculated positions (C—H = 0.95 - 0.98 Å). All were included as riding contributions with isotropic displacement parameters 1.2 - 1.5 times those of the attached atoms.

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

	x	y	z	U_iso*/U_eq
O1	0.61114 (7)	0.17397 (6)	0.38614 (5)	0.01811 (15)
O2	0.50096 (8)	0.34387 (7)	0.35198 (6)	0.02453 (17)
O3	0.20648 (6)	0.19286 (6)	0.24679 (5)	0.01536 (14)
O4	0.37528 (7)	0.08851 (6)	0.19282 (5)	0.01796 (15)
O5	0.69640 (8)	0.26493 (7)	0.48443 (6)	0.02468 (17)
O6	0.77584 (7)	0.26736 (6)	0.20400 (5)	0.01762 (15)
O7	0.85266 (7)	0.41175 (6)	0.26717 (5)	0.01698 (15)
C1	0.50623 (9)	0.24255 (9)	0.35590 (7)	0.01594 (19)
C2	0.40734 (9)	0.17221 (8)	0.32402 (7)	0.01479 (19)
C3	0.47061 (9)	0.13905 (9)	0.23488 (7)	0.01764 (19)
H3A	0.509546	0.209880	0.186491	0.021*
H3B	0.540504	0.082334	0.254818	0.021*
C4	0.26705 (9)	0.16139 (9)	0.16544 (7)	0.01538 (19)
C5	0.29198 (9)	0.25081 (9)	0.29146 (7)	0.01568 (19)
H5A	0.244737	0.268096	0.348059	0.019*
H5B	0.323569	0.325907	0.244884	0.019*
C6	0.36290 (10)	0.06178 (9)	0.40559 (8)	0.0201 (2)
H6A	0.437550	0.011721	0.423812	0.030*
H6B	0.298009	0.018822	0.383227	0.030*
H6C	0.324777	0.084269	0.461837	0.030*
C7	0.16859 (10)	0.08444 (9)	0.14008 (8)	0.0197 (2)
H7A	0.137648	0.022159	0.198378	0.030*
H7B	0.209200	0.049489	0.091533	0.030*
H7C	0.095236	0.131909	0.113908	0.030*
C8	0.30637 (11)	0.26922 (9)	0.08043 (7)	0.0213 (2)
H8A	0.231143	0.319476	0.065223	0.032*
H8B	0.337824	0.244353	0.023790	0.032*
H8C	0.375355	0.312944	0.097812	0.032*
C9	0.71419 (10)	0.22328 (9)	0.41881 (7)	0.01674 (19)
C10	0.84583 (9)	0.20922 (8)	0.36723 (7)	0.01496 (18)
C11	0.83536 (10)	0.17628 (8)	0.27399 (7)	0.01655 (19)
H11A	0.923038	0.161976	0.246924	0.020*
H11B	0.783369	0.102966	0.288491	0.020*
C12	0.84132 (10)	0.37818 (9)	0.18094 (7)	0.01700 (19)
C13	0.91677 (10)	0.32801 (8)	0.33964 (7)	0.01650 (19)
H13A	0.918581	0.355697	0.397628	0.020*
H13B	1.007414	0.319629	0.314757	0.020*
C14	0.92243 (10)	0.11550 (9)	0.43651 (8)	0.0221 (2)
H14A	0.925743	0.135002	0.497449	0.033*
H14B	1.010801	0.112858	0.406871	0.033*
H14C	0.879586	0.038874	0.449389	0.033*
C15	0.75121 (12)	0.46587 (10)	0.12292 (9)	0.0268 (2)
H15A	0.667202	0.462130	0.160693	0.040*
H15B	0.739079	0.447442	0.062590	0.040*
H15C	0.788927	0.544884	0.107845	0.040*
C16	0.97334 (11)	0.37799 (9)	0.12476 (8)	0.0216 (2)
H16A	1.013381	0.456339	0.107417	0.032*
H16B	0.961933	0.356256	0.065737	0.032*
H16C	1.029383	0.321247	0.165093	0.032*
O8	0.91353 (7)	0.66447 (6)	0.36711 (5)	0.01908 (16)
O9	0.80649 (8)	0.74653 (7)	0.47388 (6)	0.02506 (17)
O10	0.69272 (7)	0.91031 (6)	0.27307 (5)	0.01648 (15)
O11	0.78656 (7)	0.78188 (6)	0.19087 (5)	0.01714 (15)
O12	1.03035 (8)	0.83256 (7)	0.34106 (6)	0.02418 (17)
O13	1.20111 (7)	0.58226 (6)	0.17388 (5)	0.01848 (15)
O14	1.35295 (7)	0.69110 (6)	0.22514 (5)	0.01777 (15)
C17	0.80283 (10)	0.71100 (9)	0.40517 (7)	0.01728 (19)
C18	0.68200 (9)	0.70215 (8)	0.35467 (7)	0.01530 (19)
C19	0.71338 (10)	0.68437 (8)	0.25503 (7)	0.01675 (19)
H19A	0.763701	0.611930	0.261691	0.020*
H19B	0.631671	0.674776	0.227257	0.020*
C20	0.72594 (10)	0.89232 (9)	0.18016 (7)	0.01614 (19)
C21	0.61304 (10)	0.81907 (9)	0.33904 (7)	0.01696 (19)
H21A	0.529030	0.814447	0.312520	0.020*
H21B	0.595578	0.836590	0.401641	0.020*
C22	0.59509 (11)	0.60097 (9)	0.41984 (8)	0.0232 (2)
H22A	0.514044	0.598390	0.390309	0.035*
H22B	0.575684	0.613336	0.483547	0.035*
H22C	0.640143	0.526714	0.427203	0.035*
C23	0.83068 (11)	0.98287 (10)	0.13041 (8)	0.0226 (2)
H23A	0.903529	0.973284	0.170656	0.034*
H23B	0.795553	1.061567	0.120902	0.034*
H23C	0.860766	0.972364	0.067464	0.034*
C24	0.60689 (10)	0.90425 (9)	0.12294 (8)	0.0196 (2)
H24A	0.633618	0.901436	0.057087	0.029*
H24B	0.565364	0.979148	0.120183	0.029*
H24C	0.545396	0.839795	0.154879	0.029*
C25	1.02532 (10)	0.73291 (9)	0.34016 (7)	0.01695 (19)
C26	1.13437 (9)	0.66492 (8)	0.30582 (7)	0.01591 (19)
C27	1.09366 (9)	0.63078 (9)	0.21756 (7)	0.0179 (2)
H27A	1.021396	0.572587	0.238381	0.022*
H27B	1.062981	0.700902	0.169665	0.022*
C28	1.31372 (10)	0.65704 (9)	0.14491 (7)	0.0171 (2)
C29	1.25393 (10)	0.74666 (9)	0.27107 (8)	0.0182 (2)
H29A	1.229428	0.820862	0.224740	0.022*
H29B	1.287269	0.765368	0.326907	0.022*
C30	1.16462 (10)	0.55598 (9)	0.38751 (8)	0.0207 (2)
H30A	1.190672	0.580001	0.442426	0.031*
H30B	1.235311	0.513214	0.364143	0.031*
H30C	1.087204	0.505140	0.408148	0.031*
C31	1.29214 (11)	0.76289 (10)	0.05887 (8)	0.0236 (2)
H31A	1.221283	0.809470	0.077099	0.035*
H31B	1.269615	0.736065	0.004421	0.035*
H31C	1.371653	0.811087	0.039866	0.035*
C32	1.42178 (10)	0.58090 (9)	0.12077 (8)	0.0211 (2)
H32A	1.501898	0.627907	0.099325	0.032*
H32B	1.398129	0.549594	0.068966	0.032*
H32C	1.435184	0.515969	0.178409	0.032*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0127 (3)	0.0173 (3)	0.0257 (4)	0.0006 (3)	−0.0049 (3)	−0.0074 (3)
O2	0.0246 (4)	0.0174 (4)	0.0347 (4)	0.0021 (3)	−0.0099 (3)	−0.0105 (3)
O3	0.0121 (3)	0.0186 (3)	0.0166 (3)	0.0000 (3)	−0.0012 (2)	−0.0071 (3)
O4	0.0146 (3)	0.0178 (3)	0.0248 (4)	0.0030 (3)	−0.0044 (3)	−0.0107 (3)
O5	0.0211 (4)	0.0332 (4)	0.0234 (4)	0.0008 (3)	−0.0028 (3)	−0.0138 (3)
O6	0.0183 (3)	0.0160 (3)	0.0203 (3)	0.0012 (3)	−0.0070 (3)	−0.0066 (3)
O7	0.0213 (4)	0.0127 (3)	0.0178 (3)	0.0020 (3)	−0.0047 (3)	−0.0049 (3)
C1	0.0139 (4)	0.0172 (5)	0.0162 (4)	0.0006 (4)	−0.0013 (3)	−0.0041 (4)
C2	0.0124 (4)	0.0144 (4)	0.0178 (4)	0.0000 (3)	−0.0021 (3)	−0.0049 (3)
C3	0.0124 (4)	0.0200 (5)	0.0231 (5)	0.0012 (4)	−0.0020 (4)	−0.0103 (4)
C4	0.0140 (4)	0.0162 (4)	0.0166 (4)	0.0011 (3)	−0.0008 (3)	−0.0060 (4)
C5	0.0141 (4)	0.0160 (4)	0.0186 (4)	0.0017 (3)	−0.0034 (3)	−0.0073 (4)
C6	0.0196 (5)	0.0176 (5)	0.0207 (5)	−0.0032 (4)	−0.0043 (4)	−0.0011 (4)
C7	0.0183 (5)	0.0199 (5)	0.0226 (5)	−0.0022 (4)	−0.0039 (4)	−0.0082 (4)
C8	0.0240 (5)	0.0211 (5)	0.0172 (5)	−0.0030 (4)	0.0005 (4)	−0.0034 (4)
C9	0.0146 (4)	0.0161 (4)	0.0189 (5)	−0.0009 (4)	−0.0035 (3)	−0.0036 (4)
C10	0.0127 (4)	0.0143 (4)	0.0177 (4)	0.0005 (3)	−0.0037 (3)	−0.0037 (3)
C11	0.0168 (4)	0.0131 (4)	0.0204 (5)	0.0015 (3)	−0.0031 (4)	−0.0057 (4)
C12	0.0200 (5)	0.0147 (4)	0.0168 (4)	0.0030 (4)	−0.0042 (4)	−0.0047 (4)
C13	0.0158 (4)	0.0154 (4)	0.0179 (4)	−0.0013 (4)	−0.0054 (4)	−0.0032 (4)
C14	0.0179 (5)	0.0202 (5)	0.0244 (5)	0.0031 (4)	−0.0052 (4)	0.0005 (4)
C15	0.0323 (6)	0.0230 (5)	0.0254 (5)	0.0106 (5)	−0.0115 (5)	−0.0051 (4)
C16	0.0236 (5)	0.0200 (5)	0.0195 (5)	0.0001 (4)	0.0007 (4)	−0.0038 (4)
O8	0.0130 (3)	0.0183 (3)	0.0265 (4)	−0.0002 (3)	−0.0001 (3)	−0.0078 (3)
O9	0.0234 (4)	0.0331 (4)	0.0206 (4)	0.0007 (3)	−0.0015 (3)	−0.0110 (3)
O10	0.0210 (4)	0.0126 (3)	0.0167 (3)	−0.0014 (3)	−0.0006 (3)	−0.0059 (3)
O11	0.0163 (3)	0.0159 (3)	0.0197 (3)	−0.0001 (3)	0.0016 (3)	−0.0068 (3)
O12	0.0233 (4)	0.0181 (4)	0.0319 (4)	−0.0012 (3)	0.0012 (3)	−0.0095 (3)
O13	0.0138 (3)	0.0179 (3)	0.0250 (4)	−0.0027 (3)	0.0002 (3)	−0.0088 (3)
O14	0.0134 (3)	0.0195 (4)	0.0215 (4)	−0.0015 (3)	−0.0020 (3)	−0.0074 (3)
C17	0.0154 (4)	0.0160 (4)	0.0189 (5)	0.0000 (4)	0.0011 (4)	−0.0034 (4)
C18	0.0132 (4)	0.0132 (4)	0.0192 (4)	−0.0007 (3)	0.0007 (3)	−0.0048 (3)
C19	0.0168 (5)	0.0128 (4)	0.0222 (5)	−0.0005 (4)	−0.0016 (4)	−0.0075 (4)
C20	0.0181 (5)	0.0148 (4)	0.0163 (4)	−0.0009 (4)	−0.0008 (3)	−0.0059 (3)
C21	0.0164 (5)	0.0157 (4)	0.0184 (5)	0.0009 (4)	0.0011 (4)	−0.0051 (4)
C22	0.0207 (5)	0.0180 (5)	0.0267 (5)	−0.0051 (4)	0.0016 (4)	−0.0008 (4)
C23	0.0249 (5)	0.0215 (5)	0.0196 (5)	−0.0082 (4)	−0.0009 (4)	−0.0031 (4)
C24	0.0204 (5)	0.0201 (5)	0.0198 (5)	0.0002 (4)	−0.0045 (4)	−0.0074 (4)
C25	0.0152 (4)	0.0184 (5)	0.0168 (4)	−0.0007 (4)	−0.0028 (3)	−0.0039 (4)
C26	0.0136 (4)	0.0150 (4)	0.0190 (5)	−0.0010 (3)	−0.0023 (3)	−0.0045 (4)
C27	0.0129 (4)	0.0200 (5)	0.0226 (5)	−0.0009 (4)	−0.0022 (4)	−0.0086 (4)
C28	0.0158 (5)	0.0159 (5)	0.0192 (5)	−0.0023 (4)	−0.0022 (4)	−0.0044 (4)
C29	0.0155 (5)	0.0172 (5)	0.0228 (5)	−0.0024 (4)	−0.0007 (4)	−0.0074 (4)
C30	0.0188 (5)	0.0180 (5)	0.0229 (5)	0.0009 (4)	−0.0033 (4)	−0.0019 (4)
C31	0.0253 (5)	0.0213 (5)	0.0216 (5)	0.0008 (4)	−0.0028 (4)	−0.0020 (4)
C32	0.0171 (5)	0.0205 (5)	0.0254 (5)	0.0003 (4)	0.0005 (4)	−0.0068 (4)

Geometric parameters (Å, º) top

O1—C1	1.3792 (12)	O8—C25	1.3820 (13)
O1—C9	1.4041 (12)	O8—C17	1.4073 (13)
O2—C1	1.1943 (13)	O9—C17	1.1939 (13)
O3—C4	1.4304 (12)	O10—C21	1.4321 (12)
O3—C5	1.4330 (12)	O10—C20	1.4360 (12)
O4—C4	1.4251 (12)	O11—C20	1.4274 (13)
O4—C3	1.4284 (12)	O11—C19	1.4333 (12)
O5—C9	1.1946 (13)	O12—C25	1.1942 (14)
O6—C12	1.4276 (13)	O13—C28	1.4301 (12)
O6—C11	1.4314 (12)	O13—C27	1.4318 (13)
O7—C13	1.4301 (12)	O14—C28	1.4296 (13)
O7—C12	1.4331 (13)	O14—C29	1.4341 (13)
C1—C2	1.5135 (14)	C17—C18	1.5239 (15)
C2—C5	1.5336 (14)	C18—C19	1.5264 (15)
C2—C6	1.5346 (14)	C18—C21	1.5278 (14)
C2—C3	1.5482 (14)	C18—C22	1.5378 (14)
C3—H3A	0.9900	C19—H19A	0.9900
C3—H3B	0.9900	C19—H19B	0.9900
C4—C7	1.5152 (14)	C20—C23	1.5140 (14)
C4—C8	1.5293 (14)	C20—C24	1.5290 (15)
C5—H5A	0.9900	C21—H21A	0.9900
C5—H5B	0.9900	C21—H21B	0.9900
C6—H6A	0.9800	C22—H22A	0.9800
C6—H6B	0.9800	C22—H22B	0.9800
C6—H6C	0.9800	C22—H22C	0.9800
C7—H7A	0.9800	C23—H23A	0.9800
C7—H7B	0.9800	C23—H23B	0.9800
C7—H7C	0.9800	C23—H23C	0.9800
C8—H8A	0.9800	C24—H24A	0.9800
C8—H8B	0.9800	C24—H24B	0.9800
C8—H8C	0.9800	C24—H24C	0.9800
C9—C10	1.5273 (15)	C25—C26	1.5163 (14)
C10—C11	1.5259 (14)	C26—C30	1.5346 (14)
C10—C13	1.5312 (14)	C26—C29	1.5369 (14)
C10—C14	1.5368 (14)	C26—C27	1.5432 (15)
C11—H11A	0.9900	C27—H27A	0.9900
C11—H11B	0.9900	C27—H27B	0.9900
C12—C15	1.5112 (14)	C28—C32	1.5154 (15)
C12—C16	1.5281 (15)	C28—C31	1.5264 (15)
C13—H13A	0.9900	C29—H29A	0.9900
C13—H13B	0.9900	C29—H29B	0.9900
C14—H14A	0.9800	C30—H30A	0.9800
C14—H14B	0.9800	C30—H30B	0.9800
C14—H14C	0.9800	C30—H30C	0.9800
C15—H15A	0.9800	C31—H31A	0.9800
C15—H15B	0.9800	C31—H31B	0.9800
C15—H15C	0.9800	C31—H31C	0.9800
C16—H16A	0.9800	C32—H32A	0.9800
C16—H16B	0.9800	C32—H32B	0.9800
C16—H16C	0.9800	C32—H32C	0.9800

C1—O1—C9	118.80 (8)	C25—O8—C17	118.48 (8)
C4—O3—C5	113.91 (7)	C21—O10—C20	114.29 (7)
C4—O4—C3	114.18 (8)	C20—O11—C19	114.15 (8)
C12—O6—C11	113.64 (8)	C28—O13—C27	114.50 (8)
C13—O7—C12	114.10 (8)	C28—O14—C29	114.37 (8)
O2—C1—O1	123.18 (9)	O9—C17—O8	121.02 (9)
O2—C1—C2	126.81 (9)	O9—C17—C18	125.63 (9)
O1—C1—C2	109.90 (8)	O8—C17—C18	113.21 (9)
C1—C2—C5	108.49 (8)	C17—C18—C19	112.87 (8)
C1—C2—C6	111.34 (8)	C17—C18—C21	106.98 (8)
C5—C2—C6	110.85 (8)	C19—C18—C21	106.97 (8)
C1—C2—C3	107.78 (8)	C17—C18—C22	108.84 (9)
C5—C2—C3	107.70 (8)	C19—C18—C22	110.24 (8)
C6—C2—C3	110.56 (9)	C21—C18—C22	110.90 (9)
O4—C3—C2	109.92 (8)	O11—C19—C18	111.17 (8)
O4—C3—H3A	109.7	O11—C19—H19A	109.4
C2—C3—H3A	109.7	C18—C19—H19A	109.4
O4—C3—H3B	109.7	O11—C19—H19B	109.4
C2—C3—H3B	109.7	C18—C19—H19B	109.4
H3A—C3—H3B	108.2	H19A—C19—H19B	108.0
O4—C4—O3	110.43 (8)	O11—C20—O10	110.54 (8)
O4—C4—C7	105.51 (8)	O11—C20—C23	105.06 (9)
O3—C4—C7	105.46 (8)	O10—C20—C23	105.60 (8)
O4—C4—C8	111.28 (8)	O11—C20—C24	111.92 (8)
O3—C4—C8	111.84 (8)	O10—C20—C24	110.91 (8)
C7—C4—C8	112.00 (9)	C23—C20—C24	112.51 (9)
O3—C5—C2	109.66 (8)	O10—C21—C18	109.60 (8)
O3—C5—H5A	109.7	O10—C21—H21A	109.7
C2—C5—H5A	109.7	C18—C21—H21A	109.7
O3—C5—H5B	109.7	O10—C21—H21B	109.7
C2—C5—H5B	109.7	C18—C21—H21B	109.7
H5A—C5—H5B	108.2	H21A—C21—H21B	108.2
C2—C6—H6A	109.5	C18—C22—H22A	109.5
C2—C6—H6B	109.5	C18—C22—H22B	109.5
H6A—C6—H6B	109.5	H22A—C22—H22B	109.5
C2—C6—H6C	109.5	C18—C22—H22C	109.5
H6A—C6—H6C	109.5	H22A—C22—H22C	109.5
H6B—C6—H6C	109.5	H22B—C22—H22C	109.5
C4—C7—H7A	109.5	C20—C23—H23A	109.5
C4—C7—H7B	109.5	C20—C23—H23B	109.5
H7A—C7—H7B	109.5	H23A—C23—H23B	109.5
C4—C7—H7C	109.5	C20—C23—H23C	109.5
H7A—C7—H7C	109.5	H23A—C23—H23C	109.5
H7B—C7—H7C	109.5	H23B—C23—H23C	109.5
C4—C8—H8A	109.5	C20—C24—H24A	109.5
C4—C8—H8B	109.5	C20—C24—H24B	109.5
H8A—C8—H8B	109.5	H24A—C24—H24B	109.5
C4—C8—H8C	109.5	C20—C24—H24C	109.5
H8A—C8—H8C	109.5	H24A—C24—H24C	109.5
H8B—C8—H8C	109.5	H24B—C24—H24C	109.5
O5—C9—O1	120.96 (9)	O12—C25—O8	123.29 (9)
O5—C9—C10	125.75 (9)	O12—C25—C26	126.46 (9)
O1—C9—C10	113.15 (9)	O8—C25—C26	110.18 (9)
C11—C10—C9	113.22 (8)	C25—C26—C30	110.55 (8)
C11—C10—C13	107.29 (8)	C25—C26—C29	108.29 (8)
C9—C10—C13	107.24 (8)	C30—C26—C29	111.02 (9)
C11—C10—C14	109.60 (9)	C25—C26—C27	108.45 (8)
C9—C10—C14	109.05 (8)	C30—C26—C27	111.08 (9)
C13—C10—C14	110.40 (8)	C29—C26—C27	107.34 (8)
O6—C11—C10	111.08 (8)	O13—C27—C26	110.17 (8)
O6—C11—H11A	109.4	O13—C27—H27A	109.6
C10—C11—H11A	109.4	C26—C27—H27A	109.6
O6—C11—H11B	109.4	O13—C27—H27B	109.6
C10—C11—H11B	109.4	C26—C27—H27B	109.6
H11A—C11—H11B	108.0	H27A—C27—H27B	108.1
O6—C12—O7	110.23 (8)	O14—C28—O13	110.38 (8)
O6—C12—C15	105.58 (9)	O14—C28—C32	105.13 (8)
O7—C12—C15	105.40 (8)	O13—C28—C32	105.60 (8)
O6—C12—C16	111.80 (8)	O14—C28—C31	111.89 (9)
O7—C12—C16	111.59 (9)	O13—C28—C31	111.58 (9)
C15—C12—C16	111.91 (9)	C32—C28—C31	111.90 (9)
O7—C13—C10	110.12 (8)	O14—C29—C26	109.88 (8)
O7—C13—H13A	109.6	O14—C29—H29A	109.7
C10—C13—H13A	109.6	C26—C29—H29A	109.7
O7—C13—H13B	109.6	O14—C29—H29B	109.7
C10—C13—H13B	109.6	C26—C29—H29B	109.7
H13A—C13—H13B	108.2	H29A—C29—H29B	108.2
C10—C14—H14A	109.5	C26—C30—H30A	109.5
C10—C14—H14B	109.5	C26—C30—H30B	109.5
H14A—C14—H14B	109.5	H30A—C30—H30B	109.5
C10—C14—H14C	109.5	C26—C30—H30C	109.5
H14A—C14—H14C	109.5	H30A—C30—H30C	109.5
H14B—C14—H14C	109.5	H30B—C30—H30C	109.5
C12—C15—H15A	109.5	C28—C31—H31A	109.5
C12—C15—H15B	109.5	C28—C31—H31B	109.5
H15A—C15—H15B	109.5	H31A—C31—H31B	109.5
C12—C15—H15C	109.5	C28—C31—H31C	109.5
H15A—C15—H15C	109.5	H31A—C31—H31C	109.5
H15B—C15—H15C	109.5	H31B—C31—H31C	109.5
C12—C16—H16A	109.5	C28—C32—H32A	109.5
C12—C16—H16B	109.5	C28—C32—H32B	109.5
H16A—C16—H16B	109.5	H32A—C32—H32B	109.5
C12—C16—H16C	109.5	C28—C32—H32C	109.5
H16A—C16—H16C	109.5	H32A—C32—H32C	109.5
H16B—C16—H16C	109.5	H32B—C32—H32C	109.5

C9—O1—C1—O2	3.46 (14)	C25—O8—C17—O9	−55.71 (13)
C9—O1—C1—C2	−179.97 (8)	C25—O8—C17—C18	128.37 (9)
O2—C1—C2—C5	−3.88 (14)	O9—C17—C18—C19	164.90 (10)
O1—C1—C2—C5	179.70 (7)	O8—C17—C18—C19	−19.41 (11)
O2—C1—C2—C6	−126.13 (11)	O9—C17—C18—C21	47.51 (13)
O1—C1—C2—C6	57.46 (10)	O8—C17—C18—C21	−136.79 (8)
O2—C1—C2—C3	112.47 (11)	O9—C17—C18—C22	−72.37 (13)
O1—C1—C2—C3	−63.95 (10)	O8—C17—C18—C22	103.33 (10)
C4—O4—C3—C2	56.70 (10)	C20—O11—C19—C18	−55.78 (11)
C1—C2—C3—O4	−171.01 (8)	C17—C18—C19—O11	−62.23 (11)
C5—C2—C3—O4	−54.14 (10)	C21—C18—C19—O11	55.16 (10)
C6—C2—C3—O4	67.10 (10)	C22—C18—C19—O11	175.83 (8)
C3—O4—C4—O3	−56.64 (10)	C19—O11—C20—O10	53.54 (10)
C3—O4—C4—C7	−170.13 (8)	C19—O11—C20—C23	167.00 (8)
C3—O4—C4—C8	68.19 (11)	C19—O11—C20—C24	−70.62 (11)
C5—O3—C4—O4	57.13 (10)	C21—O10—C20—O11	−55.42 (11)
C5—O3—C4—C7	170.65 (8)	C21—O10—C20—C23	−168.54 (8)
C5—O3—C4—C8	−67.37 (10)	C21—O10—C20—C24	69.31 (10)
C4—O3—C5—C2	−57.84 (10)	C20—O10—C21—C18	58.32 (10)
C1—C2—C5—O3	170.98 (7)	C17—C18—C21—O10	65.26 (10)
C6—C2—C5—O3	−66.48 (10)	C19—C18—C21—O10	−55.93 (10)
C3—C2—C5—O3	54.57 (10)	C22—C18—C21—O10	−176.18 (8)
C1—O1—C9—O5	57.23 (13)	C17—O8—C25—O12	−5.51 (15)
C1—O1—C9—C10	−126.81 (9)	C17—O8—C25—C26	177.25 (8)
O5—C9—C10—C11	−168.32 (10)	O12—C25—C26—C30	121.38 (11)
O1—C9—C10—C11	15.95 (11)	O8—C25—C26—C30	−61.49 (11)
O5—C9—C10—C13	−50.17 (13)	O12—C25—C26—C29	−0.44 (14)
O1—C9—C10—C13	134.10 (8)	O8—C25—C26—C29	176.69 (8)
O5—C9—C10—C14	69.39 (13)	O12—C25—C26—C27	−116.62 (11)
O1—C9—C10—C14	−106.34 (10)	O8—C25—C26—C27	60.51 (10)
C12—O6—C11—C10	56.87 (11)	C28—O13—C27—C26	−56.55 (11)
C9—C10—C11—O6	63.78 (10)	C25—C26—C27—O13	171.20 (8)
C13—C10—C11—O6	−54.34 (10)	C30—C26—C27—O13	−67.12 (10)
C14—C10—C11—O6	−174.23 (8)	C29—C26—C27—O13	54.41 (10)
C11—O6—C12—O7	−55.71 (10)	C29—O14—C28—O13	−55.94 (10)
C11—O6—C12—C15	−169.06 (8)	C29—O14—C28—C32	−169.37 (8)
C11—O6—C12—C16	69.02 (11)	C29—O14—C28—C31	68.96 (11)
C13—O7—C12—O6	56.53 (11)	C27—O13—C28—O14	55.42 (10)
C13—O7—C12—C15	170.01 (8)	C27—O13—C28—C32	168.54 (8)
C13—O7—C12—C16	−68.31 (10)	C27—O13—C28—C31	−69.66 (11)
C12—O7—C13—C10	−57.49 (11)	C28—O14—C29—C26	57.59 (10)
C11—C10—C13—O7	54.30 (10)	C25—C26—C29—O14	−171.68 (8)
C9—C10—C13—O7	−67.63 (10)	C30—C26—C29—O14	66.78 (11)
C14—C10—C13—O7	173.69 (8)	C27—C26—C29—O14	−54.79 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3B···O10ⁱ	0.99	2.54	3.5043 (16)	164
C5—H5A···O9ⁱⁱ	0.99	2.54	3.4723 (18)	156
C11—H11B···O10ⁱ	0.99	2.57	3.5152 (17)	161
C14—H14A···O12ⁱⁱⁱ	0.98	2.56	3.531 (2)	171
C16—H16C···O3^iv	0.98	2.53	3.4973 (16)	170
C19—H19A···O7	0.99	2.53	3.5095 (17)	168
C27—H27A···O7	0.99	2.52	3.5035 (16)	170

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

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Syntheses and crystal structures of 2,2,5-trimethyl-1,3-dioxane-5-carb­oxy­lic acid and 2,2,5-trimethyl-1,3-dioxane-5-carb­oxy­lic anhydride

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Syntheses and crystal structures of 2,2,5-trimethyl-1,3-dioxane-5-carboxylic acid and 2,2,5-trimethyl-1,3-dioxane-5-carboxylic anhydride