N-Tosyl-l-proline benzene hemisolvate: a rare example of a hydrogen-bonded carb­oxy­lic acid dimer with symmetrically disordered H atoms

Wojnarska, J.; Ostrowska, K.; Gryl, M.; Stadnicka, K.M.

doi:10.1107/S2053229619010829

N-Tosyl-L-proline benzene hemisolvate: a rare example of a hydrogen-bonded carboxylic acid dimer with symmetrically disordered H atoms

J. Wojnarska, K. Ostrowska, M. Gryl and K. M. Stadnicka

The carboxylic acid group is an example of a functional group which possess a good hydrogen-bond donor (–OH) and acceptor (C=O). For this reason, carboxylic acids have a tendency to self-assembly by the formation of hydrogen bonds between the donor and acceptor sites. We present here the crystal structure of N-tosyl-L-proline (TPOH) benzene hemisolvate {systematic name: (2S)-1-[(4-methylbenzene)sulfonyl]pyrrolidine-2-carboxylic acid benzene hemisolvate}, C₁₂H₁₅NO₄S·0.5C₆H₆, (I), in which a cyclic R₂²(8) hydrogen-bonded carboxylic acid dimer with a strong O—( $1 \over 2$ H)

( $1 \over 2$ H)—O hydrogen bond is observed. The compound was characterized by single-crystal X-ray diffraction and NMR spectroscopy, and crystallizes in the space group I2 with half a benzene molecule and one TPOH molecule in the asymmetric unit. The H atom of the carboxyl OH group is disordered over a twofold axis. An analysis of the intermolecular interactions using the noncovalent interaction (NCI) index showed that the TPOH molecules form dimers due to the strong O—( $1 \over 2$ H)

( $1 \over 2$ H)—O hydrogen bond, while the packing of the benzene solvent molecules is governed by weak dispersive interactions. A search of the Cambridge Structural Database revealed that the disordered dimeric motif observed in (I) was found previously only in six crystal structures.

Keywords: symmetric hydrogen bonds; crystal structure; H-atom disorder; carboxyl cyclic dimer; tosyl-L-proline; noncovalent interactions.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229619010829/yf3184sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229619010829/yf3184Isup2.hkl Contains datablock I

CCDC reference: 1921956

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2018 (Sheldrick, 2015b).

(2S)-1-[(4-Methylbenzene)sulfonyl]pyrrolidine-2-carboxylic acid benzene hemisolvate top

Crystal data top

C₁₂H₁₅NO₄S·0.5C₆H₆	F(000) = 652
M_r = 308.36	D_x = 1.362 Mg m⁻³
Monoclinic, I2	Cu Kα radiation, λ = 1.54184 Å
a = 7.6965 (1) Å	Cell parameters from 7445 reflections
b = 10.9470 (2) Å	θ = 4.7–74.5°
c = 18.0806 (3) Å	µ = 2.05 mm⁻¹
β = 99.098 (2)°	T = 130 K
V = 1504.19 (4) Å³	Block, colourless
Z = 4	0.20 × 0.10 × 0.06 mm

Data collection top

Rigaku OD SuperNova Dual source diffractometer with an Atlas detector	2947 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Cu) X-ray Source	2794 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.042
ω scans	θ_max = 72.0°, θ_min = 4.7°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	h = −9→9
T_min = 0.763, T_max = 1.000	k = −13→13
14284 measured reflections	l = −22→22

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.094	w = 1/[σ²(F_o²) + (0.0583P)² + 0.7682P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
2947 reflections	Δρ_max = 0.16 e Å⁻³
198 parameters	Δρ_min = −0.25 e Å⁻³
3 restraints	Absolute structure: Flack x determined using 1252 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: difference Fourier map	Absolute structure parameter: −0.014 (19)

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	Occ. (<1)
S1	0.20625 (9)	0.54940 (8)	0.73058 (4)	0.02313 (18)
O1	0.1232 (3)	0.4554 (2)	0.76792 (13)	0.0297 (5)
O2	0.1349 (3)	0.6710 (2)	0.72600 (14)	0.0320 (5)
O12	0.5122 (4)	0.3556 (2)	0.92834 (13)	0.0393 (6)
H12	0.517 (13)	0.365 (8)	0.9747 (12)	0.047*	0.5
O11	0.4971 (3)	0.5589 (3)	0.92622 (12)	0.0339 (5)
H11	0.521 (11)	0.566 (8)	0.9728 (10)	0.041*	0.5
N1	0.4078 (3)	0.5602 (3)	0.77370 (13)	0.0246 (5)
C2	0.2229 (4)	0.3773 (3)	0.62250 (18)	0.0263 (6)
H2	0.222288	0.318171	0.660931	0.032*
C1	0.2151 (4)	0.5004 (3)	0.63819 (17)	0.0236 (6)
C11	0.5009 (4)	0.4571 (3)	0.89442 (17)	0.0250 (6)
C4	0.2359 (4)	0.4272 (4)	0.49284 (18)	0.0320 (8)
C4A	0.000000	0.5847 (5)	1.000000	0.0361 (12)
H4A	0.000002	0.671449	1.000001	0.043*
C6	0.2147 (5)	0.5878 (3)	0.58237 (19)	0.0314 (8)
H6	0.207082	0.672224	0.593558	0.038*
C10	0.4966 (4)	0.4514 (3)	0.81035 (17)	0.0260 (6)
H10	0.436951	0.375012	0.789299	0.031*
C7	0.5324 (4)	0.6431 (3)	0.74423 (19)	0.0303 (7)
H7A	0.513636	0.728981	0.758247	0.036*
H7B	0.520593	0.637140	0.689024	0.036*
C3	0.2318 (4)	0.3414 (3)	0.54953 (19)	0.0325 (8)
H3	0.235221	0.256847	0.538021	0.039*
C9	0.6836 (5)	0.4603 (4)	0.7903 (2)	0.0343 (8)
H9A	0.771809	0.425754	0.830650	0.041*
H9B	0.691292	0.416629	0.742923	0.041*
C3A	0.0565 (5)	0.5215 (4)	0.9418 (2)	0.0372 (9)
H3A	0.094508	0.564869	0.901746	0.045*
C5	0.2256 (4)	0.5497 (5)	0.50985 (17)	0.0356 (7)
H5	0.226067	0.608817	0.471443	0.043*
C2A	0.0574 (5)	0.3960 (4)	0.9420 (2)	0.0382 (8)
H2A	0.097383	0.352768	0.902346	0.046*
C8	0.7111 (5)	0.5968 (4)	0.7818 (2)	0.0356 (9)
H8A	0.802599	0.613004	0.750239	0.043*
H8B	0.746309	0.635938	0.831257	0.043*
C1A	0.000000	0.3321 (6)	1.000000	0.0423 (12)
H1A	0.000000	0.245352	1.000000	0.051*
C41	0.2484 (6)	0.3864 (5)	0.4139 (2)	0.0471 (10)
H41A	0.200724	0.450222	0.378462	0.071*
H41B	0.180651	0.310980	0.402717	0.071*
H41C	0.371862	0.371399	0.409532	0.071*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0251 (3)	0.0248 (4)	0.0200 (3)	0.0011 (3)	0.0049 (2)	−0.0010 (3)
O1	0.0314 (12)	0.0333 (12)	0.0264 (11)	−0.0036 (10)	0.0106 (9)	−0.0002 (10)
O2	0.0351 (13)	0.0289 (13)	0.0318 (12)	0.0083 (10)	0.0048 (10)	−0.0029 (10)
O12	0.0606 (17)	0.0302 (14)	0.0245 (12)	−0.0026 (12)	−0.0011 (11)	0.0011 (10)
O11	0.0509 (13)	0.0296 (13)	0.0207 (9)	0.0040 (12)	0.0040 (9)	−0.0053 (11)
N1	0.0264 (11)	0.0257 (14)	0.0212 (11)	−0.0005 (13)	0.0018 (9)	0.0006 (12)
C2	0.0269 (15)	0.0267 (17)	0.0261 (15)	0.0016 (13)	0.0069 (12)	0.0017 (13)
C1	0.0242 (15)	0.0278 (15)	0.0187 (15)	−0.0002 (12)	0.0027 (11)	−0.0004 (12)
C11	0.0240 (14)	0.0270 (15)	0.0239 (15)	0.0006 (12)	0.0039 (11)	−0.0005 (13)
C4	0.0263 (16)	0.048 (2)	0.0222 (15)	0.0003 (14)	0.0043 (12)	−0.0062 (14)
C4A	0.037 (3)	0.035 (3)	0.038 (3)	0.000	0.013 (2)	0.000
C6	0.0371 (18)	0.0299 (19)	0.0263 (17)	−0.0025 (13)	0.0021 (14)	0.0014 (13)
C10	0.0311 (15)	0.0254 (16)	0.0209 (14)	0.0022 (13)	0.0021 (11)	−0.0024 (12)
C7	0.0298 (17)	0.0308 (18)	0.0308 (17)	−0.0053 (14)	0.0062 (13)	0.0001 (14)
C3	0.0321 (17)	0.035 (2)	0.0306 (18)	0.0023 (14)	0.0061 (13)	−0.0077 (14)
C9	0.0348 (18)	0.042 (2)	0.0274 (17)	0.0086 (16)	0.0092 (13)	−0.0029 (16)
C3A	0.0336 (17)	0.051 (3)	0.0284 (17)	0.0022 (15)	0.0097 (13)	0.0028 (14)
C5	0.0388 (16)	0.0447 (19)	0.0232 (14)	0.000 (2)	0.0045 (12)	0.0100 (19)
C2A	0.0342 (18)	0.043 (2)	0.038 (2)	0.0021 (16)	0.0072 (15)	−0.0075 (16)
C8	0.0277 (17)	0.048 (2)	0.0325 (18)	−0.0038 (15)	0.0079 (14)	−0.0031 (16)
C1A	0.037 (3)	0.038 (3)	0.051 (3)	0.000	0.006 (2)	0.000
C41	0.043 (2)	0.075 (3)	0.0234 (17)	0.007 (2)	0.0060 (14)	−0.0087 (18)

Geometric parameters (Å, º) top

S1—O1	1.435 (3)	C6—H6	0.9500
S1—O2	1.437 (3)	C10—C9	1.543 (5)
S1—N1	1.626 (2)	C10—H10	1.0000
S1—C1	1.766 (3)	C7—C8	1.522 (5)
O12—C11	1.265 (4)	C7—H7A	0.9900
O12—H12	0.840 (14)	C7—H7B	0.9900
O11—C11	1.257 (4)	C3—H3	0.9500
O11—H11	0.837 (14)	C9—C8	1.520 (6)
N1—C10	1.477 (4)	C9—H9A	0.9900
N1—C7	1.480 (4)	C9—H9B	0.9900
C2—C1	1.381 (5)	C3A—C2A	1.373 (5)
C2—C3	1.388 (5)	C3A—H3A	0.9500
C2—H2	0.9500	C5—H5	0.9500
C1—C6	1.390 (5)	C2A—C1A	1.389 (5)
C11—C10	1.516 (4)	C2A—H2A	0.9500
C4—C5	1.380 (6)	C8—H8A	0.9900
C4—C3	1.394 (5)	C8—H8B	0.9900
C4—C41	1.513 (5)	C1A—H1A	0.9500
C4A—C3Aⁱ	1.386 (4)	C41—H41A	0.9800
C4A—C3A	1.386 (4)	C41—H41B	0.9800
C4A—H4A	0.9500	C41—H41C	0.9800
C6—C5	1.391 (5)

O1—S1—O2	119.78 (15)	C8—C7—H7A	111.1
O1—S1—N1	106.76 (14)	N1—C7—H7B	111.1
O2—S1—N1	106.67 (16)	C8—C7—H7B	111.1
O1—S1—C1	108.31 (15)	H7A—C7—H7B	109.1
O2—S1—C1	107.34 (15)	C2—C3—C4	121.2 (3)
N1—S1—C1	107.41 (13)	C2—C3—H3	119.4
C11—O12—H12	112 (6)	C4—C3—H3	119.4
C11—O11—H11	122 (6)	C8—C9—C10	103.6 (3)
C10—N1—C7	112.1 (3)	C8—C9—H9A	111.0
C10—N1—S1	119.7 (2)	C10—C9—H9A	111.0
C7—N1—S1	119.7 (2)	C8—C9—H9B	111.0
C1—C2—C3	118.8 (3)	C10—C9—H9B	111.0
C1—C2—H2	120.6	H9A—C9—H9B	109.0
C3—C2—H2	120.6	C2A—C3A—C4A	120.0 (4)
C2—C1—C6	121.2 (3)	C2A—C3A—H3A	120.0
C2—C1—S1	120.0 (2)	C4A—C3A—H3A	120.0
C6—C1—S1	118.8 (3)	C4—C5—C6	121.0 (4)
O11—C11—O12	124.2 (3)	C4—C5—H5	119.5
O11—C11—C10	119.7 (3)	C6—C5—H5	119.5
O12—C11—C10	116.1 (3)	C3A—C2A—C1A	120.2 (4)
C5—C4—C3	118.8 (3)	C3A—C2A—H2A	119.9
C5—C4—C41	120.8 (4)	C1A—C2A—H2A	119.9
C3—C4—C41	120.4 (4)	C9—C8—C7	104.0 (3)
C3Aⁱ—C4A—C3A	120.1 (5)	C9—C8—H8A	111.0
C3Aⁱ—C4A—H4A	120.0	C7—C8—H8A	111.0
C3A—C4A—H4A	120.0	C9—C8—H8B	111.0
C1—C6—C5	119.0 (4)	C7—C8—H8B	111.0
C1—C6—H6	120.5	H8A—C8—H8B	109.0
C5—C6—H6	120.5	C2Aⁱ—C1A—C2A	119.6 (6)
N1—C10—C11	110.6 (3)	C2Aⁱ—C1A—H1A	120.2
N1—C10—C9	103.1 (3)	C2A—C1A—H1A	120.2
C11—C10—C9	111.1 (3)	C4—C41—H41A	109.5
N1—C10—H10	110.6	C4—C41—H41B	109.5
C11—C10—H10	110.6	H41A—C41—H41B	109.5
C9—C10—H10	110.6	C4—C41—H41C	109.5
N1—C7—C8	103.1 (3)	H41A—C41—H41C	109.5
N1—C7—H7A	111.1	H41B—C41—H41C	109.5

O1—S1—N1—C10	29.6 (3)	O11—C11—C10—N1	−26.5 (4)
O2—S1—N1—C10	158.8 (2)	O12—C11—C10—N1	155.0 (3)
C1—S1—N1—C10	−86.4 (2)	O11—C11—C10—C9	87.4 (4)
O1—S1—N1—C7	175.0 (2)	O12—C11—C10—C9	−91.1 (4)
O2—S1—N1—C7	−55.8 (3)	C10—N1—C7—C8	−14.0 (3)
C1—S1—N1—C7	59.0 (3)	S1—N1—C7—C8	−161.8 (2)
C3—C2—C1—C6	0.5 (5)	C1—C2—C3—C4	1.1 (5)
C3—C2—C1—S1	−179.3 (2)	C5—C4—C3—C2	−1.9 (5)
O1—S1—C1—C2	−28.4 (3)	C41—C4—C3—C2	179.1 (3)
O2—S1—C1—C2	−159.1 (3)	N1—C10—C9—C8	28.9 (3)
N1—S1—C1—C2	86.6 (3)	C11—C10—C9—C8	−89.7 (3)
O1—S1—C1—C6	151.9 (3)	C3Aⁱ—C4A—C3A—C2A	−0.4 (3)
O2—S1—C1—C6	21.2 (3)	C3—C4—C5—C6	1.2 (5)
N1—S1—C1—C6	−93.2 (3)	C41—C4—C5—C6	−179.8 (3)
C2—C1—C6—C5	−1.2 (5)	C1—C6—C5—C4	0.3 (5)
S1—C1—C6—C5	178.6 (3)	C4A—C3A—C2A—C1A	0.7 (6)
C7—N1—C10—C11	109.6 (3)	C10—C9—C8—C7	−38.1 (3)
S1—N1—C10—C11	−102.6 (3)	N1—C7—C8—C9	31.9 (3)
C7—N1—C10—C9	−9.3 (3)	C3A—C2A—C1A—C2Aⁱ	−0.4 (3)
S1—N1—C10—C9	138.5 (2)

Symmetry code: (i) −x, y, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O12—H12···O12ⁱⁱ	0.84 (1)	1.81 (3)	2.628 (5)	166 (9)
O11—H11···O11ⁱⁱ	0.84 (1)	1.85 (3)	2.661 (4)	162 (8)
C10—H10···O2ⁱⁱⁱ	1.00	2.31	3.267 (4)	161

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

Number of crystal structures found in the CSD versus the symmetry of the carboxyl cyclic dimer (compare with Fig. 6a) top

Symmetry element (with orientation)	Number of structures
-1	3066
1	931
2 (z)	87
2 (y)	6
2/m (z)	6
Sum	4096*

Note: (*) the sum of the observed symmetry dependance of the carboxyl cyclic dimer is bigger than the total number of entries retrieved from the CSD (4089) as in several crystal structures, more than one dimer fragment was observed.

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N-Tosyl-L-proline benzene hemisolvate: a rare example of a hydrogen-bonded carb­oxy­lic acid dimer with symmetrically disordered H atoms

Supporting information

N-Tosyl-L-proline benzene hemisolvate: a rare example of a hydrogen-bonded carboxylic acid dimer with symmetrically disordered H atoms