Crystal structure of 4-acetamido­benzoic acid monohydrate

Cai, W.-J.; Chi, S.-M.; Kou, J.-F.; Liu, F.-Y.

doi:10.1107/S1600536814021886

organic compounds

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Volume 70| Part 11| November 2014| Page o1154

doi:10.1107/S1600536814021886

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Crystal structure of 4-acetamidobenzoic acid monohydrate

Wen-Juan Cai,^a Shao-Ming Chi,^a Jun-Feng Kou ^a and Feng-Yi Liu ^a ^*

^aCollege of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming 650500, People's Republic of China
^*Correspondence e-mail: lfy20110407@163.com

Edited by D.-J. Xu, Zhejiang University (Yuquan Campus), China (Received 30 September 2014; accepted 4 October 2014; online 11 October 2014)

In the title compound, C₉H₉NO₃·H₂O, the plane of the acetamide group is oriented at 20.52 (8)° with respect to the benzene ring, whereas the plane of the carboxylic acid group is essentially coplanar with the benzene ring [maximum deviation = 0.033 (1) Å]. In the crystal, classical O—H⋯O and N—H⋯O hydrogen bonds and weak C—H⋯O hydrogen bonds link the organic molecules and water molecules of crystallization into a three-dimensional supramolecular architecture.

Keywords: crystal structure; 4-acetamidobenzoic acid; hydrogen bonding; hydrated carboxylic acid.

CCDC reference: 906509

1. Related literature

For applications of 4-acetamidobenzoic acid in coordination chemistry, see: Yin et al. (2011 ); Wang et al. (2009 ). For related structures, see: Kashino et al. (1986 ); Jedrzejas et al. (1995 ).

2. Experimental

2.1. Crystal data

C₉H₉NO₃·H₂O
M_r = 197.19
Monoclinic, P 2₁ /c
a = 6.6712 (13) Å
b = 28.870 (6) Å
c = 4.992 (1) Å
β = 100.01 (3)°
V = 946.8 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.31 × 0.28 × 0.26 mm

2.2. Data collection

Rigaku MM007-HF CCD (Saturn 724+) diffractometer
7525 measured reflections
1819 independent reflections
1448 reflections with I > 2σ(I)
R_int = 0.025

2.3. Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.116
S = 1.06
1819 reflections
140 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H4⋯O4ⁱ	0.89 (2)	2.17 (2)	3.003 (2)	155.4 (17)
O1—H1⋯O2ⁱⁱ	0.88 (2)	1.75 (2)	2.6285 (18)	174 (2)
O4—H2W⋯O4ⁱⁱⁱ	0.92 (2)	1.98 (2)	2.8920 (14)	176 (2)
O4—H1W⋯O3^iv	0.83 (3)	1.93 (3)	2.7549 (18)	173 (2)
C9—H9C⋯O3ⁱ	0.96	2.57	3.484 (2)	160
Symmetry codes: (i) x, y, z+1; (ii) -x+1, -y+1, -z; (iii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) x-1, y, z-1.

Data collection: CrystalStructure (Rigaku/MSC, 2006 ); cell refinement: CrystalStructure; data reduction: CrystalStructure; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXTL.

Supporting information

CCDC reference: 906509

Crystal structure: contains datablocks I, new_global_publ_block. DOI: 10.1107/S1600536814021886/xu5824sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814021886/xu5824Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814021886/xu5824Isup3.cml

checkCIF report

Comment top

In the past few years, 4-acetamidobenzoic acid has attracted increasing attention as a multifunctional ligand (Kashino et al., 1986; Jedrzejas et al., 1995). It shows potential diversified coordination and exhibits various coordination modes, such as monodentate, chelating, and multidentate bridging, etc in those reported complexes (Yin et al., 2011; Wang et al., 2009). Herein we report the synthesis and structure of the title compound.

The structure of the title compound is shown in Fig. 1, Fig. 2 and hydrogen bond geometry is given in Table 1. In the title compound, the acetamide moiety is oriented with respect to the benzene ring at 20.52 (8)° whereas the carboxyl group is essentially co-planar with the benzene ring [the maximum deviation = 0.033 (1) Å]. In the crystal, classic O—H···O, N—H···O hydrogen bonds and weak C—H···O hydrogen bond link organic molecules and crystalline water molecules into the three dimensional supramolecular architecture.

Related literature top

For applications of 4-acetamidobenzoic acid in coordination chemistry, see: Yin et al. (2011); Wang et al. (2009). For related structures, see: Kashino et al. (1986); Jedrzejas et al. (1995).

Experimental top

4-Aminobenzoic acid (5 mmol, 686 mg) was added to 20 ml acetic anhydride. The mixture was then refluxed under argon for 8 h. The excess of acetic anhydride was then evaporated under reduced pressure. Water was then added to the resulting solid. The colorless block crystals were obtained after 48 h. Yield: 90% (based on 4-aminobenzoic acid).

Computing details top

Data collection: CrystalStructure (Rigaku/MSC, 2006); cell refinement: CrystalStructure (Rigaku/MSC, 2006); data reduction: CrystalStructure (Rigaku/MSC, 2006); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, with atom labels and 30% probability displacement ellipsoids.

Fig. 2. Hydrogen bonds are shown as brown dashed lines.

Fig. 3. A view of the crystal packing.

4-Acetamidobenzoic acid monohydrate top

Crystal data top

C₉H₉NO₃·H₂O	F(000) = 416
M_r = 197.19	D_x = 1.383 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8729 reflections
a = 6.6712 (13) Å	θ = 3.1–26.0°
b = 28.870 (6) Å	µ = 0.11 mm⁻¹
c = 4.992 (1) Å	T = 293 K
β = 100.01 (3)°	Block, colorless
V = 946.8 (3) Å³	0.31 × 0.28 × 0.26 mm
Z = 4

Data collection top

Rigaku MM007-HF CCD (Saturn 724+) diffractometer	1448 reflections with I > 2σ(I)
Radiation source: rotating anode	R_int = 0.025
Confocal monochromator	θ_max = 26.0°, θ_min = 3.1°
ω scans at fixed χ = 45°	h = −8→8
7525 measured reflections	k = −35→35
1819 independent reflections	l = −6→5

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0607P)² + 0.1929P] where P = (F_o² + 2F_c²)/3
1819 reflections	(Δ/σ)_max < 0.001
140 parameters	Δρ_max = 0.16 e Å⁻³
1 restraint	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₉H₉NO₃·H₂O	V = 946.8 (3) Å³
M_r = 197.19	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.6712 (13) Å	µ = 0.11 mm⁻¹
b = 28.870 (6) Å	T = 293 K
c = 4.992 (1) Å	0.31 × 0.28 × 0.26 mm
β = 100.01 (3)°

Data collection top

Rigaku MM007-HF CCD (Saturn 724+) diffractometer	1448 reflections with I > 2σ(I)
7525 measured reflections	R_int = 0.025
1819 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	1 restraint
wR(F²) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.16 e Å⁻³
1819 reflections	Δρ_min = −0.21 e Å⁻³
140 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
C1	0.6802 (3)	0.43025 (5)	0.5354 (3)	0.0370 (4)
C2	0.8849 (3)	0.42983 (5)	0.6534 (3)	0.0432 (4)
H2	0.9751	0.4497	0.5886	0.052*
C3	0.9563 (3)	0.40000 (5)	0.8671 (3)	0.0420 (4)
H3	1.0932	0.4000	0.9459	0.050*
C4	0.8203 (2)	0.37010 (5)	0.9622 (3)	0.0346 (4)
C5	0.6157 (3)	0.37085 (6)	0.8459 (4)	0.0430 (4)
H5	0.5249	0.3511	0.9107	0.052*
C6	0.5461 (3)	0.40082 (6)	0.6342 (3)	0.0439 (4)
H6	0.4086	0.4012	0.5578	0.053*
C7	0.6019 (3)	0.46170 (5)	0.3049 (3)	0.0394 (4)
C8	1.0650 (2)	0.32340 (5)	1.2903 (3)	0.0344 (3)
C9	1.0717 (3)	0.29285 (6)	1.5361 (3)	0.0423 (4)
H9A	1.1507	0.2657	1.5161	0.063*
H9B	0.9358	0.2839	1.5528	0.063*
H9C	1.1329	0.3095	1.6961	0.063*
H1	0.684 (3)	0.5062 (7)	0.080 (4)	0.063*
H4	0.775 (3)	0.3275 (7)	1.251 (4)	0.051*
H1W	0.452 (4)	0.2928 (8)	0.293 (5)	0.063*
H2W	0.545 (4)	0.2597 (7)	0.471 (5)	0.063*
N1	0.8780 (2)	0.33893 (5)	1.1819 (3)	0.0386 (3)
O1	0.7308 (2)	0.48727 (4)	0.2144 (3)	0.0554 (4)
O2	0.4148 (2)	0.46159 (4)	0.2106 (3)	0.0546 (4)
O3	1.21944 (18)	0.33300 (4)	1.1992 (2)	0.0475 (3)
O4	0.5523 (2)	0.27530 (5)	0.3128 (3)	0.0486 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0446 (9)	0.0327 (7)	0.0322 (8)	0.0049 (6)	0.0030 (7)	0.0027 (6)
C2	0.0428 (9)	0.0409 (8)	0.0444 (9)	−0.0030 (7)	0.0037 (7)	0.0100 (7)
C3	0.0355 (8)	0.0426 (8)	0.0452 (9)	−0.0011 (6)	−0.0006 (7)	0.0091 (7)
C4	0.0379 (8)	0.0341 (7)	0.0311 (7)	0.0040 (6)	0.0041 (6)	0.0028 (6)
C5	0.0369 (9)	0.0463 (9)	0.0445 (9)	−0.0028 (7)	0.0031 (7)	0.0120 (7)
C6	0.0384 (9)	0.0465 (9)	0.0428 (9)	0.0018 (7)	−0.0037 (7)	0.0064 (7)
C7	0.0490 (10)	0.0339 (7)	0.0338 (8)	0.0049 (7)	0.0033 (7)	0.0020 (6)
C8	0.0387 (8)	0.0331 (7)	0.0297 (7)	0.0021 (6)	0.0012 (6)	−0.0010 (5)
C9	0.0467 (10)	0.0463 (9)	0.0326 (8)	0.0083 (7)	0.0035 (7)	0.0071 (6)
N1	0.0358 (7)	0.0428 (7)	0.0369 (7)	0.0029 (6)	0.0056 (6)	0.0113 (5)
O1	0.0595 (9)	0.0540 (7)	0.0495 (7)	−0.0018 (6)	0.0003 (7)	0.0215 (6)
O2	0.0504 (8)	0.0573 (7)	0.0515 (7)	0.0061 (6)	−0.0043 (6)	0.0177 (6)
O3	0.0349 (6)	0.0563 (7)	0.0500 (7)	0.0022 (5)	0.0041 (5)	0.0156 (5)
O4	0.0409 (7)	0.0569 (8)	0.0496 (7)	0.0028 (5)	0.0122 (6)	0.0053 (6)

Geometric parameters (Å, º) top

C1—C6	1.386 (2)	C7—O2	1.255 (2)
C1—C2	1.390 (2)	C7—O1	1.274 (2)
C1—C7	1.487 (2)	C8—O3	1.228 (2)
C2—C3	1.389 (2)	C8—N1	1.347 (2)
C2—H2	0.9300	C8—C9	1.505 (2)
C3—C4	1.394 (2)	C9—H9A	0.9600
C3—H3	0.9300	C9—H9B	0.9600
C4—C5	1.388 (2)	C9—H9C	0.9600
C4—N1	1.4193 (19)	N1—H4	0.89 (2)
C5—C6	1.382 (2)	O1—H1	0.881 (16)
C5—H5	0.9300	O4—H1W	0.83 (3)
C6—H6	0.9300	O4—H2W	0.92 (2)

C6—C1—C2	119.44 (14)	O2—C7—O1	123.84 (14)
C6—C1—C7	119.22 (16)	O2—C7—C1	118.76 (15)
C2—C1—C7	121.34 (15)	O1—C7—C1	117.40 (16)
C3—C2—C1	120.74 (15)	O3—C8—N1	123.64 (14)
C3—C2—H2	119.6	O3—C8—C9	121.75 (15)
C1—C2—H2	119.6	N1—C8—C9	114.60 (14)
C2—C3—C4	119.27 (16)	C8—C9—H9A	109.5
C2—C3—H3	120.4	C8—C9—H9B	109.5
C4—C3—H3	120.4	H9A—C9—H9B	109.5
C5—C4—C3	119.93 (14)	C8—C9—H9C	109.5
C5—C4—N1	116.64 (14)	H9A—C9—H9C	109.5
C3—C4—N1	123.41 (15)	H9B—C9—H9C	109.5
C6—C5—C4	120.34 (15)	C8—N1—C4	128.98 (14)
C6—C5—H5	119.8	C8—N1—H4	116.6 (13)
C4—C5—H5	119.8	C4—N1—H4	114.4 (13)
C5—C6—C1	120.27 (16)	C7—O1—H1	117.5 (15)
C5—C6—H6	119.9	H1W—O4—H2W	104 (2)
C1—C6—H6	119.9

C6—C1—C2—C3	0.6 (2)	C7—C1—C6—C5	179.16 (15)
C7—C1—C2—C3	−179.47 (15)	C6—C1—C7—O2	1.9 (2)
C1—C2—C3—C4	0.3 (3)	C2—C1—C7—O2	−178.08 (15)
C2—C3—C4—C5	−0.9 (2)	C6—C1—C7—O1	−177.98 (15)
C2—C3—C4—N1	−178.96 (15)	C2—C1—C7—O1	2.1 (2)
C3—C4—C5—C6	0.6 (3)	O3—C8—N1—C4	−3.9 (3)
N1—C4—C5—C6	178.79 (15)	C9—C8—N1—C4	176.06 (14)
C4—C5—C6—C1	0.3 (3)	C5—C4—N1—C8	163.45 (15)
C2—C1—C6—C5	−0.9 (2)	C3—C4—N1—C8	−18.4 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H4···O4ⁱ	0.89 (2)	2.17 (2)	3.003 (2)	155.4 (17)
O1—H1···O2ⁱⁱ	0.88 (2)	1.75 (2)	2.6285 (18)	174 (2)
O4—H2W···O4ⁱⁱⁱ	0.92 (2)	1.98 (2)	2.8920 (14)	176 (2)
O4—H1W···O3^iv	0.83 (3)	1.93 (3)	2.7549 (18)	173 (2)
C9—H9C···O3ⁱ	0.96	2.57	3.484 (2)	160

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H4···O4ⁱ	0.89 (2)	2.17 (2)	3.003 (2)	155.4 (17)
O1—H1···O2ⁱⁱ	0.881 (16)	1.751 (16)	2.6285 (18)	174 (2)
O4—H2W···O4ⁱⁱⁱ	0.92 (2)	1.98 (2)	2.8920 (14)	176 (2)
O4—H1W···O3^iv	0.83 (3)	1.93 (3)	2.7549 (18)	173 (2)
C9—H9C···O3ⁱ	0.96	2.57	3.484 (2)	160

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

Acknowledgements

The work was supported by the Natural Science Foundation of Yunnan Province, China (grant No. 2009CD048).

References

Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Jedrzejas, M. J., Luo, M., Singh, S., Brouillette, W. J. & Air, G. M. (1995). Acta Cryst. C51, 1910–1912. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Kashino, S., Matsushita, T., Iwamoto, T., Yamaguchi, K. & Haisa, M. (1986). Acta Cryst. C42, 457–462. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Rigaku/MSC. (2006). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, Z. H., Fan, J. & Zhang, W. G. (2009). Z. Anorg. Allg. Chem. 635, 2333–2339. Web of Science CSD CrossRef CAS Google Scholar
Yin, X., Fan, J., Wang, Z.-H. & Zhang, W.-G. (2011). Z. Anorg. Allg. Chem. 637, 773–777. Web of Science CSD CrossRef CAS Google Scholar