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BY 4.0 license Open Access Published by De Gruyter (O) April 20, 2022

The crystal structure of 2,4,4-triphenyl-4H-benzo[b][1,4]oxaphosphinin-4-ium bromide – dichloromethane (1/1), C27H22BrCl2OP

Fen Liu, Longgen Sun and Haiyang Huang ORCID logo

Abstract

C27H22BrCl2OP, monoclinic, P21/c (no. 14), a = 9.0066(2) Å, b = 15.4924(4) Å, c = 18.5110(4) Å, β = 95.487(2)°, V = 2571.06(11) Å3, Z = 4, R gt (F) = 0.0509, wR ref (F 2) = 0.1494, T = 296 K.

CCDC no.: 1510421

The asymmetric unit of the title crystal 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: Prism, colorless
Size: 0.2 × 0.18 × 0.16 mm
Wavelength: Cu Kα radiation (1.54184 Å)
μ: 4.81 mm−1
Diffractometer, scan mode: Xcalibur, ω-scans
θ max, completeness: 67.1°, >99%
N(hkl)measured , N(hkl)unique, R int: 10289, 4591, 0.030
Criterion for I obs, N(hkl)gt: I obs > 2 σ(I obs), 3819
N(param)refined: 289
Programs: CrysAlisPRO [1], OEX2 [2], SHELX [3], DIAMOND [4]

Table 2:

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

x y z U iso*/U eq
O1 0.4739 (3) 0.83242 (16) 0.49360 (12) 0.0441 (5)
P1 0.47020 (8) 0.88158 (5) 0.33166 (4) 0.03147 (19)
Cl1 0.79812 (17) 0.33266 (9) 0.57199 (8) 0.0838 (4)
Cl2 1.00386 (16) 0.19561 (9) 0.55015 (7) 0.0818 (4)
Br1 0.77134 (5) 0.67100 (3) 0.25904 (3) 0.06504 (19)
C1 0.6694 (4) 0.7176 (3) 0.5633 (2) 0.0508 (9)
H1 0.6569 0.7699 0.5866 0.061*
C2 0.7397 (5) 0.6499 (3) 0.6007 (2) 0.0657 (12)
H2 0.7757 0.6572 0.6491 0.079*
C3 0.7573 (6) 0.5721 (4) 0.5676 (3) 0.0824 (16)
H3 0.8042 0.5267 0.5936 0.099*
C4 0.7052 (7) 0.5613 (3) 0.4957 (3) 0.0818 (15)
H4 0.7168 0.5083 0.4733 0.098*
C5 0.6356 (5) 0.6287 (3) 0.4568 (2) 0.0622 (11)
H5 0.6014 0.6212 0.4081 0.075*
C6 0.6169 (4) 0.7074 (2) 0.49030 (19) 0.0440 (8)
C7 0.5454 (3) 0.7803 (2) 0.44931 (17) 0.0374 (7)
C8 0.5529 (4) 0.7931 (2) 0.37804 (17) 0.0380 (7)
H8 0.6043 0.7533 0.3523 0.046*
C9 0.3711 (3) 0.9319 (2) 0.39877 (16) 0.0350 (6)
C10 0.3868 (3) 0.9009 (2) 0.47002 (16) 0.0363 (6)
C11 0.3107 (4) 0.9398 (3) 0.52293 (18) 0.0482 (8)
H11 0.3223 0.9194 0.5704 0.058*
C12 0.2180 (5) 1.0085 (3) 0.5051 (2) 0.0554 (10)
H12 0.1669 1.0343 0.5407 0.066*
C13 0.1996 (5) 1.0399 (3) 0.4344 (2) 0.0545 (9)
H13 0.1368 1.0866 0.4229 0.065*
C14 0.2751 (4) 1.0015 (2) 0.38163 (19) 0.0444 (7)
H14 0.2622 1.0220 0.3342 0.053*
C15 0.6095 (3) 0.9509 (2) 0.29964 (15) 0.0350 (6)
C16 0.5705 (4) 1.0321 (3) 0.2716 (2) 0.0517 (9)
H16 0.4712 1.0496 0.2670 0.062*
C17 0.6790 (5) 1.0859 (3) 0.2511 (3) 0.0630 (11)
H17 0.6532 1.1407 0.2335 0.076*
C18 0.8261 (5) 1.0602 (3) 0.2560 (2) 0.0587 (10)
H18 0.8992 1.0972 0.2418 0.070*
C19 0.8636 (4) 0.9793 (3) 0.2819 (2) 0.0554 (9)
H19 0.9626 0.9614 0.2845 0.066*
C20 0.7572 (4) 0.9243 (2) 0.30427 (19) 0.0443 (7)
H20 0.7839 0.8698 0.3223 0.053*
C21 0.3434 (4) 0.8492 (2) 0.25575 (16) 0.0367 (7)
C22 0.3925 (5) 0.8433 (4) 0.1874 (2) 0.0677 (13)
H22 0.4891 0.8597 0.1799 0.081*
C23 0.2967 (6) 0.8126 (5) 0.1302 (2) 0.0873 (18)
H23 0.3282 0.8098 0.0839 0.105*
C24 0.1568 (5) 0.7864 (4) 0.1417 (2) 0.0715 (13)
H24 0.0939 0.7649 0.1031 0.086*
C25 0.1072 (4) 0.7913 (3) 0.2093 (2) 0.0582 (10)
H25 0.0108 0.7740 0.2164 0.070*
C26 0.2019 (4) 0.8222 (2) 0.26680 (19) 0.0435 (8)
H26 0.1698 0.8247 0.3130 0.052*
C27 0.9874 (6) 0.3055 (3) 0.5681 (3) 0.0733 (13)
H27A 1.0283 0.3388 0.5303 0.088*
H27B 1.0436 0.3194 0.6140 0.088*

Source of materials

A modified synthesis that was similar to our previous report was performed [5]. (2-Bromophenyl)diphenylphosphine (2 mmol) and 2-bromo-1-phenylethan-1-one (2.2 mmol) were dissolved in toluene (10 mL) in a Schlenk bottle. After stirring at 90 °C for 3 h, the reaction was cooled to room temperature and then toluene was removed under reduced pressure. The residue is cleaned and then filtered with Et2O to give the intermediate 2-bromophenyl)(2-oxo-2-phenylethyl)diphenylphosphonium bromide as white solid. The intermediate were dissolved in toluene (10 mL) again and then t-BuOK (4.5 mmol) and Pd(PPh3)3 (0.1 mmol) was added under argon gas atmosphere. The reaction mixture was stirred at 110 °C for 5 h, and then it was cooled to room temperature and the toluene was removed under reduced pressure. Some CH2Cl2 (10 mL) and water (10 mL) were subsequently added to the resulting mixture. The organic layer was separated, and the aqueous layer was extracted with CH2Cl2 (10 mL × 2). All combined organic solutions were dried with anhydrous Na2SO4, and the solvent was removed under reduced pressure. The residue was washed by Et2O to afford the title compound (362 mg, 69%). Crystals of the title compound were obtained by slow evaporation (n-hexane/Et2O/CHCl2) within three days.

Experimental details

Coordinates of hydrogen atoms were included using constraints or restraints. Their Uiso values were set to 1.2Ueq of the parent atoms.

Comment

Phosphacycle-based p-conjugated materials have become an attractive research area due to their unique structural and electronic properties of p-block elements [6]. In last decades, most of the research is focusing development of p-conjugated five-membered phosphacycles, especially (benzo)phospholes [7], [8], [9]. Very recently, the six-membered phosphacycles frameworks has gradually attracted attention from material and synthetic chemists [10, 11]. On the other hand, the p-conjugated molecules containing a cationic phosphorus center usually show tunable electron-accepting properties, defining the appealing photophysical and electrochemical characteristics of organophosphorus ionic chromophores [12]. Therefore, six-membered [1,4]oxaphosphonium salts skeletons could have many potential applications in the functional materials research field.

The title structure (see the Figure) contains one 2,4,4-triphenyl-benzo[b][1,4]phosphapyranium cation, one bromine anion, and one dichloromethane solvent molecule. The [1,4]phosphapyranium-core is not perfectly coplanar with a puckering angle of 6.8°. The phosphorous(V) with two phenyl substituents is in a tetrahedral structure. In addition, the obvious interactions between C8–H and bromine anion is observed (distance of C8H–Br is 2.7140(5) Å).


Corresponding author: Haiyang Huang, Jiangxi Key Laboratory of Organic Chemistry, Jiangxi Science & Technology Normal University, Nanchang, 330013, People’s Republic of China, E-mail:

  1. Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.

  2. Research funding: This work was supported by the PhD start-up fund (NO. 2018BSQD025) and innovation fund (NO. YC2020-S563) of Jiangxi Science & Technology Normal University.

  3. Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

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Received: 2022-03-14
Accepted: 2022-04-05
Published Online: 2022-04-20
Published in Print: 2022-08-26

© 2022 Fen Liu et al., published by De Gruyter, Berlin/Boston

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

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