2-(1,4-Dioxo-1,4-dihydro-2-naphth­yl)-2-methyl­propanoic acid

Dempster-Rivett, K.J.; Main, L.; Nicholson, B.K.; Denny, W.A.

doi:10.1107/S1600536807048131

2-(1,4-Dioxo-1,4-dihydro-2-naphthyl)-2-methylpropanoic acid

K. J. Dempster-Rivett, L. Main, B. K. Nicholson and W. A. Denny

The sterically crowded title compound, C₁₄H₁₂O₄, crystallizes as centrosymmetric hydrogen-bonded dimers involving the carboxyl groups. The naphthoquinone ring system is folded by 11.5 (1)° about a vector joining the 1,4-C atoms, and the quinone O atoms are displaced from the ring plane, presumably because of steric interactions with the bulky substituent.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807048131/bi2238sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807048131/bi2238Isup2.hkl Contains datablock I

CCDC reference: 667303

checkCIF report

Key indicators

Single-crystal X-ray study
T = 200 K
Mean (C-C) = 0.002 Å
R factor = 0.033
wR factor = 0.092
Data-to-parameter ratio = 12.7

checkCIF/PLATON results

No syntax errors found



Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.790     0.990
            Tmin(prime) and Tmax expected:      0.962     0.990
            RR(prime) =      0.821
            Please check that your absorption correction is appropriate.
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.82
PLAT335_ALERT_2_C Large Benzene C-C Range .......  C1     -C9            0.16 Ang.
PLAT432_ALERT_2_C Short Inter X...Y Contact  O2     ..  C1      ..       2.99 Ang.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   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
   2 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

The title compound was prepared as part of a study to examine constrained conformational effects on lactonization of naphthohydroquinone carboxylic acid derivatives for comparison with related work on sterically crowded o-hydroxycinnamic acids and benzoquinone analogues with a "trimethyl-lock" effect (Karle & Karle, 1972; Wang et al., 1996).

The compound crystallizes as a dimer formed about an inversion centre by O—H···O hydrogen bonding between the carboxyl groups. The naphthoquinone ring is folded by 11.5 (1)° about a vector joining the 1,4-carbon atoms and the quinone O atoms are displaced from the ring plane, presumably because of steric interactions with the adjacent geminal dimethyl groups, and with the carboxyl group. Even with the bending, there is still a close intramolecular contact between O1 and O3 (2.922 (2) Å) which suggests that intramolecular O3—H1···O1 hydrogen bonding might be possible if the intermolecular dimer form was not preferred. Naphthoquinone itself, and other 2-substituted naphthoquinones (e.g. the 2-iodo derivative) are planar (Gaultier and Hauw, 1965; Gaultier et al., 1971). However, benzoquinones with tri-substituted carbon atoms in the 2-position also show displacement of the quinone O atoms from the plane of the ring (Wang et al., 1996).

Related literature top

For synthesis details, see: Petersen & Heitzer (1972). For related studies of o-hydroxycinnamic acids and benzoquinones, see: Karle & Karle (1972); Wang et al. (1996). For related naphthoquinone structures, see: Gaultier & Hauw (1965); Gaultier et al. (1971).

Experimental top

The title compound was prepared using the method of Petersen & Heitzer (1972). Crystals suitable for X-ray analysis were grown from a solution in toluene.

Structure description top

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement parameters drawn at the 30% probability level for non-H atoms.
	Fig. 2. Side-on view showing the folding of the aromatic ring.

2-(1,4-Dioxo-1,4-dihydro-2-naphthyl)-2-methylpropanoic acid top

Crystal data top

C₁₄H₁₂O₄	F(000) = 512
M_r = 244.24	D_x = 1.374 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3955 reflections
a = 8.3070 (2) Å	θ = 2–25°
b = 6.5027 (2) Å	µ = 0.10 mm⁻¹
c = 22.0392 (6) Å	T = 200 K
β = 97.219 (1)°	Needle, yellow
V = 1181.07 (6) Å³	0.38 × 0.18 × 0.10 mm
Z = 4

Data collection top

Siemens SMART CCD diffractometer	2145 independent reflections
Radiation source: fine-focus sealed tube	1722 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ω scans	θ_max = 25.4°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −9→9
T_min = 0.790, T_max = 0.990	k = 0→7
6372 measured reflections	l = 0→26

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.092	w = 1/[σ²(F_o²) + (0.0458P)² + 0.2618P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
2145 reflections	Δρ_max = 0.22 e Å⁻³
169 parameters	Δρ_min = −0.17 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.014 (2)

Crystal data top

C₁₄H₁₂O₄	V = 1181.07 (6) Å³
M_r = 244.24	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.3070 (2) Å	µ = 0.10 mm⁻¹
b = 6.5027 (2) Å	T = 200 K
c = 22.0392 (6) Å	0.38 × 0.18 × 0.10 mm
β = 97.219 (1)°

Data collection top

Siemens SMART CCD diffractometer	2145 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	1722 reflections with I > 2σ(I)
T_min = 0.790, T_max = 0.990	R_int = 0.021
6372 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.22 e Å⁻³
2145 reflections	Δρ_min = −0.17 e Å⁻³
169 parameters

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

	x	y	z	U_iso*/U_eq
O1	0.22816 (14)	0.56642 (15)	0.14194 (5)	0.0427 (3)
O2	0.40002 (14)	−0.08507 (17)	0.27913 (5)	0.0483 (3)
O3	0.03089 (13)	0.29681 (18)	0.05640 (5)	0.0412 (3)
O4	0.19621 (13)	0.46089 (17)	0.00002 (5)	0.0435 (3)
H1	−0.046 (2)	0.386 (3)	0.0360 (8)	0.050*
C1	0.24736 (16)	0.4101 (2)	0.17254 (6)	0.0307 (3)
C2	0.29793 (16)	0.2139 (2)	0.14460 (6)	0.0289 (3)
C3	0.33983 (17)	0.0523 (2)	0.18060 (6)	0.0330 (3)
H3	0.3707	−0.0713	0.1622	0.040*
C4	0.34047 (17)	0.0569 (2)	0.24761 (6)	0.0350 (3)
C5	0.23413 (19)	0.2327 (3)	0.33547 (7)	0.0469 (4)
H5	0.2649	0.1169	0.3605	0.056*
C6	0.1598 (2)	0.3998 (3)	0.35918 (7)	0.0540 (5)
H6	0.1387	0.3978	0.4006	0.065*
C7	0.11625 (19)	0.5692 (3)	0.32321 (8)	0.0507 (5)
H7	0.0662	0.6835	0.3401	0.061*
C8	0.14484 (18)	0.5740 (3)	0.26257 (7)	0.0400 (4)
H8	0.1146	0.6912	0.2380	0.048*
C9	0.21794 (16)	0.4066 (2)	0.23789 (6)	0.0328 (3)
C10	0.26363 (16)	0.2354 (2)	0.27450 (6)	0.0351 (3)
C11	0.17484 (18)	0.3414 (2)	0.04156 (6)	0.0322 (3)
C12	0.31285 (17)	0.2190 (2)	0.07637 (6)	0.0327 (3)
C13	0.47669 (18)	0.3179 (3)	0.06739 (7)	0.0423 (4)
H13A	0.4896	0.3180	0.0238	0.063*
H13B	0.5651	0.2390	0.0901	0.063*
H13C	0.4797	0.4597	0.0826	0.063*
C14	0.3015 (2)	0.0004 (3)	0.04859 (7)	0.0491 (4)
H14A	0.3959	−0.0803	0.0658	0.074*
H14B	0.2993	0.0095	0.0041	0.074*
H14C	0.2021	−0.0665	0.0582	0.074*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0608 (7)	0.0313 (6)	0.0360 (6)	0.0057 (5)	0.0062 (5)	0.0046 (4)
O2	0.0507 (7)	0.0516 (7)	0.0408 (6)	0.0089 (5)	−0.0010 (5)	0.0170 (5)
O3	0.0335 (6)	0.0501 (7)	0.0389 (6)	−0.0016 (5)	0.0012 (4)	0.0127 (5)
O4	0.0414 (6)	0.0559 (7)	0.0333 (6)	0.0028 (5)	0.0054 (4)	0.0165 (5)
C1	0.0292 (7)	0.0327 (8)	0.0294 (7)	−0.0012 (6)	0.0004 (5)	−0.0002 (6)
C2	0.0273 (7)	0.0312 (7)	0.0277 (7)	−0.0016 (5)	0.0013 (5)	−0.0001 (6)
C3	0.0347 (7)	0.0313 (7)	0.0322 (8)	0.0009 (6)	0.0009 (6)	0.0019 (6)
C4	0.0300 (7)	0.0400 (8)	0.0334 (8)	−0.0016 (6)	−0.0016 (6)	0.0085 (6)
C5	0.0378 (9)	0.0710 (12)	0.0310 (8)	0.0018 (8)	0.0008 (6)	0.0071 (8)
C6	0.0410 (9)	0.0934 (14)	0.0277 (8)	0.0036 (9)	0.0052 (7)	−0.0085 (9)
C7	0.0377 (9)	0.0736 (12)	0.0407 (9)	0.0059 (8)	0.0044 (7)	−0.0174 (9)
C8	0.0339 (8)	0.0476 (9)	0.0382 (8)	0.0022 (7)	0.0030 (6)	−0.0070 (7)
C9	0.0273 (7)	0.0399 (8)	0.0305 (7)	−0.0021 (6)	0.0015 (5)	−0.0024 (6)
C10	0.0277 (7)	0.0485 (9)	0.0280 (7)	−0.0017 (6)	−0.0003 (6)	0.0018 (6)
C11	0.0369 (8)	0.0352 (8)	0.0242 (7)	−0.0020 (6)	0.0025 (5)	−0.0009 (6)
C12	0.0381 (8)	0.0339 (8)	0.0261 (7)	0.0033 (6)	0.0034 (6)	0.0006 (6)
C13	0.0370 (8)	0.0554 (10)	0.0351 (8)	0.0052 (7)	0.0071 (6)	0.0072 (7)
C14	0.0724 (12)	0.0417 (9)	0.0321 (8)	0.0088 (8)	0.0024 (7)	−0.0062 (7)

Geometric parameters (Å, º) top

O1—C1	1.2193 (17)	C6—H6	0.950
O2—C4	1.2219 (17)	C7—C8	1.387 (2)
O3—C11	1.3113 (17)	C7—H7	0.950
O3—H1	0.935 (19)	C8—C9	1.391 (2)
O4—C11	1.2303 (17)	C8—H8	0.950
C1—C9	1.4910 (19)	C9—C10	1.399 (2)
C1—C2	1.4991 (19)	C11—C12	1.522 (2)
C2—C3	1.3364 (19)	C12—C13	1.540 (2)
C2—C12	1.5246 (18)	C12—C14	1.546 (2)
C3—C4	1.476 (2)	C13—H13A	0.980
C3—H3	0.950	C13—H13B	0.980
C4—C10	1.484 (2)	C13—H13C	0.980
C5—C6	1.384 (3)	C14—H14A	0.980
C5—C10	1.396 (2)	C14—H14B	0.980
C5—H5	0.950	C14—H14C	0.980
C6—C7	1.378 (3)

C11—O3—H1	109.5 (10)	C8—C9—C1	119.91 (13)
O1—C1—C9	121.39 (13)	C10—C9—C1	120.24 (13)
O1—C1—C2	120.41 (12)	C5—C10—C9	119.82 (14)
C9—C1—C2	118.18 (12)	C5—C10—C4	120.75 (14)
C3—C2—C1	119.38 (12)	C9—C10—C4	119.42 (12)
C3—C2—C12	123.74 (12)	O4—C11—O3	123.14 (13)
C1—C2—C12	116.64 (11)	O4—C11—C12	122.37 (13)
C2—C3—C4	123.10 (13)	O3—C11—C12	114.29 (12)
C2—C3—H3	118.4	C11—C12—C2	111.05 (11)
C4—C3—H3	118.4	C11—C12—C13	109.80 (12)
O2—C4—C3	120.25 (14)	C2—C12—C13	108.57 (11)
O2—C4—C10	121.85 (13)	C11—C12—C14	106.06 (12)
C3—C4—C10	117.88 (12)	C2—C12—C14	111.23 (12)
C6—C5—C10	119.63 (16)	C13—C12—C14	110.11 (13)
C6—C5—H5	120.2	C12—C13—H13A	109.5
C10—C5—H5	120.2	C12—C13—H13B	109.5
C7—C6—C5	120.48 (14)	H13A—C13—H13B	109.5
C7—C6—H6	119.8	C12—C13—H13C	109.5
C5—C6—H6	119.8	H13A—C13—H13C	109.5
C6—C7—C8	120.53 (16)	H13B—C13—H13C	109.5
C6—C7—H7	119.7	C12—C14—H14A	109.5
C8—C7—H7	119.7	C12—C14—H14B	109.5
C7—C8—C9	119.69 (16)	H14A—C14—H14B	109.5
C7—C8—H8	120.2	C12—C14—H14C	109.5
C9—C8—H8	120.2	H14A—C14—H14C	109.5
C8—C9—C10	119.84 (13)	H14B—C14—H14C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H1···O4ⁱ	0.935 (19)	1.711 (19)	2.6455 (15)	176.5 (16)

Symmetry code: (i) −x, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₂O₄
M_r	244.24
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	200
a, b, c (Å)	8.3070 (2), 6.5027 (2), 22.0392 (6)
β (°)	97.219 (1)
V (Å³)	1181.07 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.38 × 0.18 × 0.10

Data collection
Diffractometer	Siemens SMART CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.790, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	6372, 2145, 1722
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.092, 1.03
No. of reflections	2145
No. of parameters	169
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.17

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).