4-Chloro­benzoic acid N,N-di­methyl­form­amide solvate

Xu, X.; Kennedy, A.R.; Florence, A.J.; Shankland, N.

doi:10.1107/S1600536804024511

organic compounds

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ISSN: 2056-9890

Volume 60| Part 11| November 2004| Pages o1950-o1951

https://doi.org/10.1107/S1600536804024511

4-Chlorobenzoic acid N,N-dimethylformamide solvate

Xuelian Xu,^a Alan R. Kennedy,^b ^* Alastair J. Florence ^a and Norman Shankland ^a

^aDepartment of Pharmaceutical Sciences, University of Strathclyde, 27 Taylor Street, Glasgow G4 0NR, Scotland, and ^bDepartment of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, Scotland
^*Correspondence e-mail: a.r.kennedy@strath.ac.uk

(Received 17 September 2004; accepted 30 September 2004; online 9 October 2004)

In the title compound, C₇H₅ClO₂.C₃H₇NO, the carboxylic acid group of 4-chlorobenzoic acid is hydrogen bonded to a molecule of N,N-dimethylformamide via an R₂²(7) O—H⋯O/C—H⋯O motif. This motif takes precedence over the R₂²(8) O—H⋯O dimer arrangement observed in 4-chlorobenzoic acid itself.

Comment

4-Chlorobenzoic acid (CBA) crystallizes as hydrogen-bonded R₂²(8) O—H⋯O dimers and dynamic proton transfer within the hydrogen bonds mediates the interconversion of two inequivalent dimeric forms (Horsewill et al., 2003 ; Wilson et al., 2004 ).

The title compound, (I), was crystallized to determine whether the R₂²(8) motif, and the proton-transfer process, is preserved in the solvate (Fig. 1). Significant deviations from idealized aromatic geometry in the CBA molecule of (I) include a marked widening of the internal ring angle at C4 [122.26 (12)°] and a concomitant narrowing of the angles ortho to this at C3 [118.25 (12)°] and C5 [118.81 (13)°]. Utilizing the angular substituent parameters for Cl and COOH (Domenicano, 1992 ), the corresponding predicted internal ring angles of 122.1 (C4) and 118.7° (C3 and C5) are in good agreement with the observed values. Thus, it may be concluded that the distortions from ideal sp² ring geometry are in line with expectations based on Domenicano's assessment of structural substituent effects in benzene derivatives. The R₂²(8) motif in CBA [Fig. 2, top, determined from single-crystal neutron diffraction data at 100 K (Wilson et al., 2004)] is not preserved in (I). Instead, one CBA molecule is replaced by one molecule of N,N-dimethylformamide (DMF), forming an R₂²(7) O—H⋯O/C—H⋯O motif (Fig. 2, bottom), eliminating the possibility of a concerted two-proton transfer process. This interaction with DMF is not unexpected, as the R₂²(7) motif has been observed to recur with a reasonable frequency in the DMF solvates of carboxylic acids (Dale & Elsegood, 2004 ).

Figure 1
The molecular structure of (I

), shown with 50% probability displacement ellipsoids.

Figure 2
Top: the R₂²(8) motif in CBA, with O⋯O = 2.588 (3) Å, O—H = 0.997 (6) Å and H⋯O = 1.595 (6) Å. Bottom: the R₂²(7) motif in (I

), with O⋯O = 2.5752 (14) Å, O—H = 0.92 (2) Å, (O)H⋯O = 1.66 (2) Å and (C—)H⋯O = 2.716 (14) Å.

Experimental

A single-crystal sample of the title compound was recrystallized from DMF solution by slow evaporation at room temperature.

Crystal data

C₇H₅ClO₂·C₃H₇NO
M_r = 229.66
Monoclinic, P2₁/c
a = 6.1269 (2) Å
b = 14.6159 (5) Å
c = 12.6541 (4) Å
β = 103.228 (2)°
V = 1103.11 (6) Å³
Z = 4
D_x = 1.383 Mg m⁻³
Mo Kα radiation
Cell parameters from 2512 reflections
θ = 1.0–27.5°
μ = 0.33 mm⁻¹
T = 123 (2) K
Cut fragment, colourless
0.50 × 0.45 × 0.40 mm

Data collection

Nonius KappaCCD diffractometer
φ and ω scans
Absorption correction: none
10331 measured reflections
2488 independent reflections
2049 reflections with I > 2σ(I)
R_int = 0.033
θ_max = 27.5°
h = −7 → 7
k = −18 → 18
l = −16 → 16

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.086
S = 1.02
2488 reflections
146 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + (0.0339P)² + 0.445P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

O1—C7	1.3257 (16)
O2—C7	1.2149 (16)
O3—C8	1.2400 (16)

C6—C1—C2	119.67 (12)
C3—C2—C1	120.76 (12)
C2—C3—C4	118.25 (12)
C5—C4—C3	122.26 (12)
C4—C5—C6	118.81 (13)
C5—C6—C1	120.25 (12)
O2—C7—O1	123.90 (12)
O2—C7—C1	123.13 (12)
O1—C7—C1	112.97 (11)

The H atoms involved in hydrogen bonding were located in a difference map and refined isotropically, but all other H atoms were constrained to idealized geometry with a riding model: for CH₃, U_iso(H) = 1.5U_eq(C) and C—H = 0.98 Å; for CH, U_iso(H) = 1.2U_eq(C) and C—H = 0.95 Å.

Data collection: DENZO (Hooft, 1988 ) and COLLECT (Otwinowski & Minor, 1997 ); cell refinement: DENZO and COLLECT; data reduction: DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536804024511/cf6379sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536804024511/cf6379Isup2.hkl

Computing details top

Data collection: DENZO (Hooft, 1988) and COLLECT (Otwinowski & Minor, 1997); cell refinement: DENZO and COLLECT; data reduction: DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

4-Chlorobenzoic acid N,N-dimethylformamide solvate top

Crystal data top

C₇H₅ClO₂·C₃H₇NO	F(000) = 480
M_r = 229.66	D_x = 1.383 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.1269 (2) Å	Cell parameters from 2512 reflections
b = 14.6159 (5) Å	θ = 1.0–27.5°
c = 12.6541 (4) Å	µ = 0.33 mm⁻¹
β = 103.228 (2)°	T = 123 K
V = 1103.11 (6) Å³	Cut fragment, colourless
Z = 4	0.50 × 0.45 × 0.40 mm

Data collection top

Nonius KappaCCD diffractometer	2049 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.033
Graphite monochromator	θ_max = 27.5°, θ_min = 2.2°
φ and ω scans	h = −7→7
10331 measured reflections	k = −18→18
2488 independent reflections	l = −16→16

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.086	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0339P)² + 0.445P] where P = (F_o² + 2F_c²)/3
2488 reflections	(Δ/σ)_max < 0.001
146 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

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
Cl1	0.48550 (7)	0.33679 (3)	0.46220 (3)	0.04267 (14)
O1	0.75372 (17)	0.42666 (7)	−0.00788 (8)	0.0317 (2)
O2	1.03650 (16)	0.33076 (7)	0.06058 (8)	0.0292 (2)
O3	−0.08773 (16)	0.06015 (7)	0.32101 (8)	0.0294 (2)
N1	0.17573 (19)	0.10376 (8)	0.23148 (9)	0.0240 (2)
C1	0.7701 (2)	0.36572 (9)	0.16601 (10)	0.0223 (3)
C2	0.8882 (2)	0.31796 (9)	0.25654 (11)	0.0248 (3)
H2	1.0282	0.2907	0.2550	0.030*
C3	0.8037 (2)	0.30975 (10)	0.34867 (11)	0.0269 (3)
H3	0.8840	0.2773	0.4104	0.032*
C4	0.5986 (2)	0.35026 (10)	0.34838 (11)	0.0270 (3)
C5	0.4786 (2)	0.39844 (10)	0.26020 (11)	0.0264 (3)
H5	0.3392	0.4259	0.2623	0.032*
C6	0.5655 (2)	0.40599 (9)	0.16836 (11)	0.0248 (3)
H6	0.4849	0.4388	0.1069	0.030*
C7	0.8688 (2)	0.37198 (9)	0.06848 (11)	0.0239 (3)
C8	0.0964 (2)	0.09489 (9)	0.31984 (11)	0.0246 (3)
C9	0.0485 (3)	0.07220 (12)	0.12662 (11)	0.0370 (4)
H9A	−0.0924	0.0447	0.1350	0.056*
H9B	0.1362	0.0265	0.0976	0.056*
H9C	0.0159	0.1241	0.0764	0.056*
C10	0.3929 (2)	0.14543 (11)	0.23470 (13)	0.0340 (3)
H10A	0.4643	0.1620	0.3097	0.051*
H10B	0.3723	0.2005	0.1893	0.051*
H10C	0.4882	0.1018	0.2072	0.051*
H8	0.194 (2)	0.1190 (10)	0.3852 (12)	0.025 (4)*
H1	0.823 (4)	0.4279 (15)	−0.0653 (18)	0.066 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0402 (2)	0.0637 (3)	0.02799 (19)	−0.00013 (19)	0.01599 (16)	0.00366 (18)
O1	0.0328 (5)	0.0397 (6)	0.0245 (5)	0.0101 (5)	0.0107 (4)	0.0074 (4)
O2	0.0267 (5)	0.0339 (6)	0.0279 (5)	0.0057 (4)	0.0082 (4)	−0.0019 (4)
O3	0.0279 (5)	0.0350 (6)	0.0273 (5)	−0.0034 (4)	0.0102 (4)	−0.0029 (4)
N1	0.0243 (6)	0.0241 (6)	0.0235 (5)	0.0002 (5)	0.0053 (4)	−0.0004 (5)
C1	0.0235 (6)	0.0198 (6)	0.0238 (6)	−0.0014 (5)	0.0053 (5)	−0.0014 (5)
C2	0.0238 (7)	0.0232 (7)	0.0266 (7)	0.0017 (5)	0.0042 (5)	−0.0005 (5)
C3	0.0292 (7)	0.0266 (7)	0.0236 (6)	−0.0009 (6)	0.0035 (5)	0.0026 (5)
C4	0.0287 (7)	0.0303 (8)	0.0231 (6)	−0.0064 (6)	0.0085 (5)	−0.0036 (6)
C5	0.0239 (7)	0.0264 (7)	0.0299 (7)	0.0006 (6)	0.0082 (5)	−0.0017 (6)
C6	0.0248 (7)	0.0230 (7)	0.0257 (6)	0.0004 (5)	0.0039 (5)	0.0019 (5)
C7	0.0238 (6)	0.0239 (7)	0.0233 (6)	−0.0011 (5)	0.0036 (5)	−0.0018 (5)
C8	0.0275 (7)	0.0228 (7)	0.0228 (6)	0.0003 (5)	0.0043 (5)	−0.0011 (5)
C9	0.0358 (8)	0.0513 (10)	0.0234 (7)	−0.0045 (7)	0.0056 (6)	−0.0031 (7)
C10	0.0303 (7)	0.0355 (9)	0.0380 (8)	−0.0060 (6)	0.0114 (6)	0.0000 (7)

Geometric parameters (Å, º) top

Cl1—C4	1.7463 (14)	C3—H3	0.950
O1—C7	1.3257 (16)	C4—C3	1.389 (2)
O1—H1	0.92 (2)	C4—C5	1.380 (2)
O2—C7	1.2149 (16)	C5—H5	0.950
O3—C8	1.2400 (16)	C6—C5	1.3889 (18)
N1—C8	1.3238 (17)	C6—H6	0.950
N1—C9	1.4518 (17)	C8—H8	0.969 (15)
N1—C10	1.4552 (18)	C9—H9A	0.980
C1—C6	1.3915 (18)	C9—H9B	0.980
C1—C7	1.4963 (18)	C9—H9C	0.980
C2—C1	1.3942 (18)	C10—H10A	0.980
C2—H2	0.950	C10—H10B	0.980
C3—C2	1.3848 (19)	C10—H10C	0.980

C7—O1—H1	108.8 (13)	C5—C6—H6	119.9
C8—N1—C9	121.11 (12)	C1—C6—H6	119.9
C8—N1—C10	121.84 (12)	O2—C7—O1	123.90 (12)
C9—N1—C10	117.05 (11)	O2—C7—C1	123.13 (12)
C6—C1—C2	119.67 (12)	O1—C7—C1	112.97 (11)
C6—C1—C7	121.86 (12)	O3—C8—N1	124.14 (12)
C2—C1—C7	118.47 (12)	O3—C8—H8	121.6 (9)
C3—C2—C1	120.76 (12)	N1—C8—H8	114.3 (9)
C3—C2—H2	119.6	N1—C9—H9A	109.5
C1—C2—H2	119.6	N1—C9—H9B	109.5
C2—C3—C4	118.25 (12)	H9A—C9—H9B	109.5
C2—C3—H3	120.9	N1—C9—H9C	109.5
C4—C3—H3	120.9	H9A—C9—H9C	109.5
C5—C4—C3	122.26 (12)	H9B—C9—H9C	109.5
C5—C4—Cl1	119.07 (11)	N1—C10—H10A	109.5
C3—C4—Cl1	118.64 (11)	N1—C10—H10B	109.5
C4—C5—C6	118.81 (13)	H10A—C10—H10B	109.5
C4—C5—H5	120.6	N1—C10—H10C	109.5
C6—C5—H5	120.6	H10A—C10—H10C	109.5
C5—C6—C1	120.25 (12)	H10B—C10—H10C	109.5

C7—C1—C6—C5	179.74 (13)	C4—C3—C2—C1	0.0 (2)
C2—C1—C6—C5	−0.2 (2)	C5—C4—C3—C2	−0.4 (2)
C2—C1—C7—O1	−173.46 (12)	Cl1—C4—C3—C2	177.67 (11)
C2—C1—C7—O2	6.8 (2)	Cl1—C4—C5—C6	−177.60 (11)
C6—C1—C7—O1	6.56 (18)	C3—C4—C5—C6	0.5 (2)
C6—C1—C7—O2	−173.18 (13)	C1—C6—C5—C4	−0.2 (2)
C3—C2—C1—C6	0.3 (2)	C9—N1—C8—O3	−0.1 (2)
C3—C2—C1—C7	−179.68 (12)	C10—N1—C8—O3	179.77 (13)

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