Dimethyl 2,7-di-tert-butyl­pyrene-4,9-di­carboxyl­ate

Moriguchi, T.; Okuyama, R.; Sasaki, M.; Miyoshi, N.

doi:10.1107/S2414314626002488

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 11| Part 3| March 2026| x260248

https://doi.org/10.1107/S2414314626002488

Open

access

Dimethyl 2,7-di-tert-butylpyrene-4,9-dicarboxylate

Tetsuji Moriguchi,^a ^* Rea Okuyama,^a Misa Sasaki ^a and Noriko Miyoshi ^b

^aDepartment of Material Science, Faculty of Engineering, Kyushu Institute of, Technology, 1-1 Sensui-cho, Tobata-ku Kitakyushu, Fukuoka, Japan, and ^bTechnical Support Department, Management Headquarters, Kyushu Institute of, Technology, 1-1 Sensui-cho, Tobata-ku, Kitakyushu 804-8550, Japan
^*Correspondence e-mail: [email protected]

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 16 February 2026; accepted 9 March 2026; online 11 March 2026)

The complete molecule of the title compound, C₂₈H₃₀O₄, is generated by a crystallographic centre of symmetry and the ester moiety is twisted away from the fused-ring plane by 28.03 (8)° due to steric repulsion. In the crystal, a weak C—H⋯O hydrogen bond links the molecules into (001) sheets.

Keywords: crystal structure; polyaromatic hydrocarbon; pyrene dicarboxylic acid; dimethylester.

CCDC reference: 2535992

Structure description

In recent years, polycyclic aromatic hydrocarbons (PAHs) have attracted great interest owing to their significant photochemical and electrical properties (Dötz et al., 2000 ). In PAHs, pyrene is the most studied and an important class of polyaromatic hydrocarbon found in charcoal. Pyrene and its substituted derivatives have p-type semiconductor properties (Moriguchi et al., 2017 ). We reported substituted pyrene derivatives (Moriguchi et al., 2018 ) and we have also studied a lanthanide complex having four pyrene moieties (Moriguchi et al., 2014 ) in order to evaluate its fluorescence property.

As part of our ongoing studies of these systems, we now report the synthesis and crystal structure of the title compound, C₂₈H₃₀O₄ (I). The complete molecule (Fig. 1) is generated by a crystallographic centre of symmetry in the orthorhombic space group Pbca at the mid-point of the C6—C6ⁱ [symmetry code: (i) −x, 1 − y, 2 − z] bond. The C12 methyl group lies almost in the plane of the fused ring system, whereas C10 and C11 are equally displaced either side [deviations = 0.001 (2), −1.290 (2) and 1.210 (2) Å, respectively]. The twist angle between the fused ring system and the C13/O1/O2/C14 ester moiety is 28.03 (8)°. This twist appears to arise due to steric repulsion between the O atoms of the ester group and hydrogen atoms of the pyrene ring system (H7⋯O1 = 2.27 Å; H3⋯O2 = 2.36 Å).

Figure 1
The molecular structure of (I) with displacement ellipsoids shown at the 50% probability level. Symmetry code: (i) −x, 1 − y, 2 − z.

The packing of (I) is shown in Fig. 2. No intermolecular π–π stacking interactions between the pyrene rings are observed, but some short intermolecular contacts can be detected (Fig. 3), including a weak C1—H1⋯O1ⁱⁱ [symmetry code: (ii) = − $[{1\over 2}]$ + x, $[{3\over 2}]$ − y, 2 − z] hydrogen bond with H⋯O = 2.32 Å and C—H⋯O = 164°, which links the molecules into (001) sheets.

Figure 2
Crystal packing of (I).

Figure 3
Intermolecular short contacts in the crystal of (I).

Synthesis and crystallization

NaOH (5.00 mmol) was added to an absolute methanol solution (50 ml) of 2,7-di-t-butylpyrene-4,9-dicarboxylic acid (1.00 mmol) at room temperature. The reaction mixture was stirred for 10 h at 318 K. After completion of reaction, the resultant mixture was cooled to room temperature, then poured into ice-cold water. The precipitate was separated by filtration and then washed with cold water. The resulting precipitate was filtered and recrystallized from methanol solution. Single crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of dichloromethane solution at room temperature.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

Table 1
Experimental details

Crystal data
Chemical formula	C₂₈H₃₀O₄
M_r	430.52
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	90
a, b, c (Å)	9.9087 (10), 13.7094 (14), 16.7900 (17)
V (Å³)	2280.8 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.40 × 0.35 × 0.30

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.663, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	20373, 2009, 1686
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.092, 1.06
No. of reflections	2009
No. of parameters	149
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.20
Computer programs: APEX2 and SAINT (Bruker, 2009 ), SHELXS (Sheldrick, 2008 ), SHELXL2019/3 (Sheldrick, 2015 ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 2535992

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314626002488/hb4556sup1.cif

Supporting information file. DOI: https://doi.org/10.1107/S2414314626002488/hb4556Isup2.cml

checkCIF report

Computing details top

Dimethyl 2,7-di-tert-butylpyrene-4,9-dicarboxylate top

Crystal data top

C₂₈H₃₀O₄	D_x = 1.254 Mg m⁻³
M_r = 430.52	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 4114 reflections
a = 9.9087 (10) Å	θ = 2.8–26.5°
b = 13.7094 (14) Å	µ = 0.08 mm⁻¹
c = 16.7900 (17) Å	T = 90 K
V = 2280.8 (4) Å³	Prism, clear light yellow
Z = 4	0.40 × 0.35 × 0.30 mm
F(000) = 920

Data collection top

Bruker APEXII CCD diffractometer	2009 independent reflections
Radiation source: sealed tube	1686 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
Detector resolution: 8 pixels mm^-1	θ_max = 25.0°, θ_min = 2.8°
φ and ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −16→16
T_min = 0.663, T_max = 0.746	l = −19→19
20373 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.092	w = 1/[σ²(F_o²) + (0.0411P)² + 0.9455P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
2009 reflections	Δρ_max = 0.18 e Å⁻³
149 parameters	Δρ_min = −0.20 e Å⁻³
0 restraints

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.

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

	x	y	z	U_iso*/U_eq
O1	−0.00597 (11)	0.82315 (7)	0.89804 (6)	0.0251 (3)
O2	−0.22549 (10)	0.78601 (7)	0.90258 (6)	0.0213 (3)
C1	−0.27651 (14)	0.50355 (11)	1.08192 (8)	0.0182 (3)
H1	−0.354287	0.542997	1.089500	0.022*
C2	−0.17052 (14)	0.53904 (10)	1.03565 (8)	0.0166 (3)
C3	−0.17815 (15)	0.63220 (10)	0.99780 (8)	0.0173 (3)
H3	−0.257346	0.670314	1.004777	0.021*
C4	−0.07638 (14)	0.66847 (10)	0.95215 (8)	0.0165 (3)
C5	0.04671 (14)	0.61282 (10)	0.94065 (8)	0.0155 (3)
C6	0.05351 (14)	0.51869 (10)	0.97619 (8)	0.0149 (3)
C7	0.15649 (14)	0.64500 (10)	0.89476 (8)	0.0171 (3)
H7	0.152365	0.707844	0.871049	0.021*
C8	0.27134 (14)	0.58810 (10)	0.88272 (8)	0.0173 (3)
C9	0.39102 (15)	0.62209 (11)	0.83199 (9)	0.0200 (3)
C10	0.41008 (17)	0.55038 (12)	0.76256 (9)	0.0278 (4)
H10A	0.329155	0.550616	0.729009	0.042*
H10B	0.424908	0.484584	0.783640	0.042*
H10C	0.488348	0.570193	0.730754	0.042*
C11	0.51910 (15)	0.62302 (12)	0.88319 (9)	0.0262 (4)
H11A	0.596640	0.641106	0.850099	0.039*
H11B	0.533827	0.558011	0.905842	0.039*
H11C	0.508712	0.670556	0.926348	0.039*
C12	0.36998 (16)	0.72414 (11)	0.79755 (10)	0.0262 (4)
H12A	0.289826	0.724224	0.763359	0.039*
H12B	0.449211	0.742784	0.766115	0.039*
H12C	0.357403	0.770847	0.841110	0.039*
C13	−0.09487 (14)	0.76657 (10)	0.91529 (8)	0.0178 (3)
C14	−0.25447 (16)	0.88024 (11)	0.86837 (9)	0.0252 (4)
H14A	−0.223178	0.931577	0.904554	0.038*
H14B	−0.351987	0.886744	0.860213	0.038*
H14C	−0.207928	0.886423	0.817121	0.038*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0216 (6)	0.0183 (6)	0.0356 (6)	−0.0033 (5)	0.0012 (5)	0.0032 (5)
O2	0.0196 (6)	0.0175 (5)	0.0268 (6)	0.0018 (4)	−0.0005 (4)	0.0051 (4)
C1	0.0155 (8)	0.0204 (8)	0.0189 (7)	0.0011 (6)	0.0002 (6)	−0.0021 (6)
C2	0.0165 (7)	0.0187 (8)	0.0145 (7)	−0.0011 (6)	−0.0019 (6)	−0.0022 (6)
C3	0.0157 (7)	0.0192 (8)	0.0169 (7)	0.0020 (6)	−0.0014 (6)	−0.0029 (6)
C4	0.0168 (7)	0.0174 (8)	0.0152 (7)	−0.0016 (6)	−0.0027 (6)	−0.0024 (6)
C5	0.0153 (7)	0.0178 (7)	0.0133 (7)	−0.0022 (6)	−0.0027 (6)	−0.0027 (6)
C6	0.0152 (7)	0.0170 (7)	0.0126 (7)	−0.0022 (6)	−0.0028 (5)	−0.0023 (5)
C7	0.0185 (8)	0.0177 (7)	0.0152 (7)	−0.0028 (6)	−0.0029 (6)	0.0006 (6)
C8	0.0164 (7)	0.0212 (8)	0.0143 (7)	−0.0032 (6)	−0.0012 (6)	−0.0025 (6)
C9	0.0185 (8)	0.0222 (8)	0.0194 (7)	−0.0033 (6)	0.0030 (6)	−0.0007 (6)
C10	0.0302 (9)	0.0299 (9)	0.0233 (8)	−0.0065 (7)	0.0085 (7)	−0.0022 (7)
C11	0.0185 (8)	0.0330 (9)	0.0270 (8)	−0.0046 (7)	0.0017 (6)	0.0014 (7)
C12	0.0246 (9)	0.0268 (9)	0.0273 (9)	−0.0044 (7)	0.0068 (7)	0.0053 (7)
C13	0.0176 (8)	0.0195 (8)	0.0164 (7)	−0.0003 (6)	0.0002 (6)	−0.0039 (6)
C14	0.0291 (9)	0.0189 (8)	0.0277 (8)	0.0067 (7)	0.0018 (7)	0.0040 (6)

Geometric parameters (Å, º) top

O1—C13	1.2088 (17)	C8—C9	1.533 (2)
O2—C13	1.3386 (17)	C9—C10	1.537 (2)
O2—C14	1.4426 (17)	C9—C11	1.533 (2)
C1—H1	0.9500	C9—C12	1.528 (2)
C1—C2	1.394 (2)	C10—H10A	0.9800
C1—C8ⁱ	1.391 (2)	C10—H10B	0.9800
C2—C3	1.428 (2)	C10—H10C	0.9800
C2—C6ⁱ	1.418 (2)	C11—H11A	0.9800
C3—H3	0.9500	C11—H11B	0.9800
C3—C4	1.361 (2)	C11—H11C	0.9800
C4—C5	1.452 (2)	C12—H12A	0.9800
C4—C13	1.492 (2)	C12—H12B	0.9800
C5—C6	1.423 (2)	C12—H12C	0.9800
C5—C7	1.404 (2)	C14—H14A	0.9800
C6—C6ⁱ	1.424 (3)	C14—H14B	0.9800
C7—H7	0.9500	C14—H14C	0.9800
C7—C8	1.394 (2)

C13—O2—C14	115.73 (11)	C12—C9—C10	108.40 (12)
C2—C1—H1	119.1	C12—C9—C11	108.51 (12)
C8ⁱ—C1—H1	119.1	C9—C10—H10A	109.5
C8ⁱ—C1—C2	121.70 (13)	C9—C10—H10B	109.5
C1—C2—C3	121.34 (13)	C9—C10—H10C	109.5
C1—C2—C6ⁱ	119.96 (13)	H10A—C10—H10B	109.5
C6ⁱ—C2—C3	118.69 (13)	H10A—C10—H10C	109.5
C2—C3—H3	118.7	H10B—C10—H10C	109.5
C4—C3—C2	122.55 (13)	C9—C11—H11A	109.5
C4—C3—H3	118.7	C9—C11—H11B	109.5
C3—C4—C5	120.37 (13)	C9—C11—H11C	109.5
C3—C4—C13	118.17 (13)	H11A—C11—H11B	109.5
C5—C4—C13	121.46 (12)	H11A—C11—H11C	109.5
C6—C5—C4	117.42 (12)	H11B—C11—H11C	109.5
C7—C5—C4	123.98 (13)	C9—C12—H12A	109.5
C7—C5—C6	118.57 (13)	C9—C12—H12B	109.5
C2ⁱ—C6—C5	119.08 (13)	C9—C12—H12C	109.5
C2ⁱ—C6—C6ⁱ	119.14 (16)	H12A—C12—H12B	109.5
C5—C6—C6ⁱ	121.78 (16)	H12A—C12—H12C	109.5
C5—C7—H7	118.8	H12B—C12—H12C	109.5
C8—C7—C5	122.42 (13)	O1—C13—O2	122.59 (13)
C8—C7—H7	118.8	O1—C13—C4	126.04 (13)
C1ⁱ—C8—C7	118.27 (13)	O2—C13—C4	111.37 (12)
C1ⁱ—C8—C9	118.91 (13)	O2—C14—H14A	109.5
C7—C8—C9	122.82 (13)	O2—C14—H14B	109.5
C8—C9—C10	108.80 (12)	O2—C14—H14C	109.5
C8—C9—C11	109.36 (12)	H14A—C14—H14B	109.5
C11—C9—C10	109.21 (13)	H14A—C14—H14C	109.5
C12—C9—C8	112.52 (12)	H14B—C14—H14C	109.5

C1—C2—C3—C4	−179.81 (13)	C5—C7—C8—C1ⁱ	−0.3 (2)
C1ⁱ—C8—C9—C10	59.99 (17)	C5—C7—C8—C9	179.30 (12)
C1ⁱ—C8—C9—C11	−59.22 (17)	C6ⁱ—C2—C3—C4	−1.3 (2)
C1ⁱ—C8—C9—C12	−179.88 (13)	C6—C5—C7—C8	0.1 (2)
C2—C3—C4—C5	−0.6 (2)	C7—C5—C6—C2ⁱ	0.20 (19)
C2—C3—C4—C13	179.95 (12)	C7—C5—C6—C6ⁱ	179.69 (15)
C3—C4—C5—C6	2.36 (19)	C7—C8—C9—C10	−119.65 (15)
C3—C4—C5—C7	−179.79 (13)	C7—C8—C9—C11	121.14 (15)
C3—C4—C13—O1	152.38 (14)	C7—C8—C9—C12	0.48 (19)
C3—C4—C13—O2	−27.83 (18)	C8ⁱ—C1—C2—C3	178.31 (13)
C4—C5—C6—C2ⁱ	178.17 (12)	C8ⁱ—C1—C2—C6ⁱ	−0.1 (2)
C4—C5—C6—C6ⁱ	−2.3 (2)	C13—C4—C5—C6	−178.16 (12)
C4—C5—C7—C8	−177.69 (13)	C13—C4—C5—C7	−0.3 (2)
C5—C4—C13—O1	−27.1 (2)	C14—O2—C13—O1	−1.3 (2)
C5—C4—C13—O2	152.68 (12)	C14—O2—C13—C4	178.87 (11)

Symmetry code: (i) −x, −y+1, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1ⁱⁱ	0.95	2.38	3.3057 (18)	164

Symmetry code: (ii) x−1/2, −y+3/2, −z+2.

Acknowledgements

We are grateful to the Center for Instrumental Analysis, Kyushu Institute of Technology (KITCIA) for the X-ray analysis.

References

Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Dötz, F., Brand, D. J., Ito, S., Gherghel, L. & Müllen, K. (2000). J. Am. Chem. Soc. 122, 7707–7717. Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef ICSD CAS IUCr Journals Google Scholar
Moriguchi, T., Higashi, M., Yakeya, D., Jalli, V., Tsuge, A., Okauchi, T., Nagamatsu, S. & Takashima, W. (2017). J. Mol. Struct. 1127, 413–418. Web of Science CSD CrossRef CAS Google Scholar
Moriguchi, T., Yakeya, D., Tsuge, A. & Jalli, V. (2018). J. Mol. Struct. 1157, 348–354. Web of Science CSD CrossRef CAS Google Scholar
Moriguchi, T., Yoza, K. & Tsuge, A. (2014). J. Crystallogr. Article ID 271238. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.