The crystal structure of 4-(pyren-1-yl)butyl-4-nitrobenzoate, C27H21NO4

Claudio Barrientos; Juan Arturo Squella; Silvana Moris

doi:10.1515/ncrs-2023-0034

Open Access Published by De Gruyter (O) February 28, 2023

The crystal structure of 4-(pyren-1-yl)butyl-4-nitrobenzoate, C₂₇H₂₁NO₄

Claudio Barrientos , Juan Arturo Squella and Silvana Moris

From the journal Zeitschrift für Kristallographie - New Crystal Structures

https://doi.org/10.1515/ncrs-2023-0034

Abstract

C₂₇H₂₁NO₄, triclinic, P 1 ‾ (no. 2), a = 7.3476(2) Å, b = 7.4894(2) Å, c = 20.5137(5) Å, α = 89.33000(10)°, β = 79.7070(10)°, γ = 67.5220(10)°, V = 1024.31(5) Å³, Z = 2, R _gt(F) = 0.0536, wR _ref(F ²) = 0.1792, T = 296.15 K.

CCDC no.: 2240071

The molecular structure is shown in the figure. Table 1 contains crystallographic data and Table 2 contains the list of the atoms including atomic coordinates and displacement parameters.

Table 1:

Data collection and handling.

Crystal:	Yellow plate
Size:	0.35 × 0.25 × 0.06 mm
Wavelength:	Mo Kα radiation (0.71073 Å)
μ:	0.09 mm⁻¹
Diffractometer, scan mode:	Bruker APEX-II, φ and ω
θ _max, completeness:	32.0°, 99%
N(hkl) _measured, N(hkl) _unique, R _int:	38,014, 7063, 0.040
Criterion for I _obs, N(hkl) _gt:	I _obs > 2 σ(I _obs), 5031
N(param)_refined:	289
Programs:	Olex2 [1, 2], SHELX [3]

Table 2:

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

Atom	x	y	z	U _iso*/U _eq
O1	0.4095 (2)	0.8490 (3)	1.08666 (5)	0.0987 (5)
O2	0.6965 (2)	0.7674 (2)	1.02432 (6)	0.0892 (4)
O3	0.01850 (13)	0.67382 (17)	0.82333 (5)	0.0648 (3)
O4	0.33353 (11)	0.54604 (12)	0.76573 (4)	0.04113 (19)
N1	0.5222 (2)	0.78884 (18)	1.03367 (5)	0.0564 (3)
C1	0.44000 (19)	0.74323 (17)	0.97852 (5)	0.0437 (3)
C2	0.2401 (2)	0.7740 (2)	0.98909 (6)	0.0531 (3)
H2	0.158519	0.820771	1.030400	0.064*
C3	0.16270 (19)	0.7339 (2)	0.93679 (6)	0.0511 (3)
H3	0.027484	0.754845	0.942625	0.061*
C4	0.28751 (16)	0.66242 (16)	0.87561 (5)	0.0384 (2)
C5	0.48893 (17)	0.63062 (17)	0.86679 (5)	0.0423 (2)
H5	0.571989	0.580763	0.825928	0.051*
C6	0.56792 (19)	0.67255 (19)	0.91844 (6)	0.0465 (3)
H6	0.702598	0.653632	0.912757	0.056*
C7	0.19537 (16)	0.62925 (17)	0.81986 (5)	0.0402 (2)
C8	0.25759 (15)	0.52075 (15)	0.70760 (5)	0.0358 (2)
H8A	0.185248	0.645771	0.691641	0.043*
H8B	0.166398	0.454702	0.718498	0.043*
C9	0.43361 (14)	0.40236 (14)	0.65491 (5)	0.0328 (2)
H9A	0.502114	0.275800	0.670577	0.039*
H9B	0.527700	0.465788	0.646040	0.039*
C10	0.36291 (14)	0.37930 (14)	0.59137 (5)	0.03200 (19)
H10A	0.294305	0.506381	0.576082	0.038*
H10B	0.267575	0.317386	0.600758	0.038*
C12	0.53513 (14)	0.25967 (14)	0.53653 (4)	0.03144 (19)
H12A	0.630883	0.321344	0.528407	0.038*
H12B	0.602484	0.133206	0.552462	0.038*
C13	0.47882 (13)	0.23119 (13)	0.47123 (4)	0.02908 (18)
C14	0.62853 (13)	0.12525 (13)	0.41680 (4)	0.02766 (18)
C15	0.57399 (13)	0.09871 (13)	0.35550 (4)	0.02739 (17)
C16	0.36996 (14)	0.17924 (14)	0.34853 (5)	0.03227 (19)
C17	0.22596 (14)	0.28310 (16)	0.40299 (5)	0.0387 (2)
H17	0.091561	0.336786	0.399302	0.046*
C18	0.28016 (14)	0.30759 (16)	0.46264 (5)	0.0367 (2)
H18	0.180442	0.377396	0.498101	0.044*
C19	0.83749 (14)	0.04039 (15)	0.42073 (5)	0.0351 (2)
H19	0.876289	0.055191	0.460395	0.042*
C20	0.97964 (14)	−0.06069 (16)	0.36817 (5)	0.0390 (2)
H20	1.113403	−0.112965	0.372651	0.047*
C21	0.92887 (14)	−0.08889 (15)	0.30599 (5)	0.0349 (2)
C22	0.72401 (13)	−0.00832 (13)	0.30033 (4)	0.02965 (18)
C23	0.66812 (16)	−0.03515 (15)	0.23939 (5)	0.0347 (2)
C24	0.46044 (17)	0.04475 (17)	0.23460 (5)	0.0406 (2)
H24	0.422564	0.025098	0.195258	0.049*
C25	0.31924 (16)	0.14804 (17)	0.28639 (5)	0.0399 (2)
H25	0.185593	0.200442	0.281771	0.048*
C26	0.81792 (19)	−0.13906 (18)	0.18585 (5)	0.0450 (3)
H26	0.782881	−0.157630	0.145840	0.054*
C27	1.01746 (19)	−0.2145 (2)	0.19172 (6)	0.0508 (3)
H27	1.115145	−0.281697	0.155408	0.061*
C28	1.07376 (17)	−0.19124 (18)	0.25090 (6)	0.0458 (3)
H28	1.208538	−0.243855	0.254145	0.055*

1 Source of materials

Equimolar quantities of the respective nitrobenzoyl chloride and 4-pyren-1-ylbutanol were mixed in a round bottom flask with dry THF to obtain the 4-(pyren-1-yl)butyl nitrobenzoate derivatives, according to previously reported methodology [4], [5], [6] 4-(pyren-1-yl)butyl-4-nitrobenzoate (4–NBPy) C₂₇H₂₁NO₄. Yellow powder, yield: 58.64%, mp: 168 °C–169 °C, ¹ H NMR (CDCl₃) d (ppm): 8.22–7.76 (m, 12H, Ar–H), 4.34, (t, 2 H, CH2–OR), 3.36, (t, 2 H, CH2-pyrene), 2.05–1.80 (m, 4H, 2xCH2). ¹³ C -NMR (75 MHz, CDCl₃ d [ppm]): 163.62, 149.34, 134.96, 134.54, 130.39, 129.80, 129.48, 128.92, 127.57, 126.46, 126.31, 125.71, 124.91, 124.00, 123.76, 122.37, 122.15, 94.06, 64.67, 63.55, 32.00, 28.68, 27.38, 26.88. Single crystals of 4-(pyren-1-yl)butyl-4-nitrobenzoate was prepared by dissolving the polycrystalline material in boiling chloroform (0.5 mL) and then hot methanol was added dropwise (0.5 mL) [5]. The mixture was allowed to crystallize for two weeks until the appearance of yellow plates.

2 Experimental details

For solving the structure OLEX2 was used [1] with the olex2.solve [2] and refined with the use of SHELX program package [3]. SADABS-2016/2 (Bruker, 2016/2) was used for absorption correction. H atoms were finally included in their calculated positions and treated as riding on their parent atom with constrained thermal parameters as U_iso(H) = 1.2 U_eq(C), the constraint distances of C–H ranging from 0.93 Å to 0.97 Å.

3 Comment

The pyrene ring and derivatives are well known for there properties in photochemistry field [7]. Excited state of pyrene in solution present an excimer formation which is used as a standard for micro-environmental changes [8, 9]. Pyrene is frequently used for supramolecular studies as a probe for proteins, peptides and lipid membranes and it is very sensible to environmental changes such as pH, pressure or temperature and used to identify guest molecules, metals or other substrates [10], [11], [12], [13], [14], [15]. Nitro compounds have an important role in organic synthesis due to their versatility to transform into other functional groups [16] and can be used as redox mediators for interesting biomolecules such as NADH [17]. The N–O bond lengths in the nitro group are 1.2144(16) and 1.2071(18) Å. In the crystal structure of the title compound, coplanarity of the nitro group with the pyrene group was observed (the C2–C1–N1–O1 torsion angle is 1.2(2)°).

Corresponding author: Silvana Moris, Centro de Investigación de Estudios Avanzados del Maule (CIEAM), Vicerrectoría de Investigación y Postgrado, Universidad Católica del Maule, Avenida San Miguel 3605, Talca 3480112, Chile, E-mail: smoris@ucm.cl

Funding source: FONDEQUIP

Award Identifier / Grant number: EQM200138

Acknowledgements

We gratefully acknowledge support by FONDEQUIP EQM200138 for D8 Venture diffractometer.

Author contribution: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.
Research funding: FONDEQUIP EQM200138.
Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

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Received: 2023-01-20

Accepted: 2023-02-06

Published Online: 2023-02-28

Published in Print: 2023-06-27

This work is licensed under the Creative Commons Attribution 4.0 International License.