tert-Butyl­ammonium 2,3,4,5-tetra­chloro-6-methoxy­carbonyl­benzoate

Abstract

In the title compound, C₄H₁₂N⁺·C₉H₃Cl₄O₄ ⁻, the benzene ring forms dihedral angles of 62.4 (2) and 64.0 (3)°, respectively, with the essentially planar methoxy­carbonyl and carboxyl­ate groups. In the crystal structure, inter­molecular N—H⋯O hydrogen bonds connect anions and cations, forming one-dimensional chains along [010].

Related literature

For background information, see: Ungwitayatorn et al. (2001 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

• C₄H₁₂N⁺·C₉H₃Cl₄O₄ ⁻

• M _r = 391.06

• Monoclinic,

• a = 9.0193 (14) Å

• b = 6.5084 (11) Å

• c = 14.5965 (15) Å

• β = 91.7570 (10)°

• V = 856.4 (2) ų

• Z = 2

• Mo Kα radiation

• μ = 0.70 mm⁻¹

• T = 298 (2) K

• 0.53 × 0.48 × 0.44 mm

Data collection

• Bruker SMART CCD diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.706, T _max = 0.747

• 4281 measured reflections

• 2790 independent reflections

• 2364 reflections with I > 2σ(I)

• R _int = 0.043

Refinement

• R[F ² > 2σ(F ²)] = 0.044

• wR(F ²) = 0.116

• S = 1.04

• 2790 reflections

• 205 parameters

• 1 restraint

• H-atom parameters constrained

• Δρ_max = 0.21 e Å⁻³

• Δρ_min = −0.28 e Å⁻³

• Absolute structure: Flack (1983 ▶), 1147 Friedel pairs

• Flack parameter: 0.00 (9)

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O4i	0.89	1.97	2.838 (4)	165
N1—H1B⋯O4ii	0.89	1.97	2.850 (4)	168
N1—H1C⋯O3iii	0.89	1.94	2.818 (4)	169

Symmetry codes: (i) ; (ii) ; (iii) .

supplementary crystallographic information

Comment

Phthalimides are compounds which can posses biological activity (see: e.g. Ungwitayatorn et al., 2001). 2-(Methoxycarbonyl)-3,4,5,6-tetrachlorobenzoic acid is an intermediate in the sysnthesis of tetrachlorophthalimides and their derivatives. In this paper, the structure of the title compound (I) is reported. The asymmetric unit contains one tert-butylammonium cation and one 2-(methoxycarbonyl)-3,4,5,6-tetrachlorobenzene-1-carboxylate anion (Fig. 1). The bond lengths in (I) are normal (Allen et al., 1987). In the crystal structure, intermolecular N-H···O hydrogen bonds connect anions and cations to form one-dimensional chains along [O10].

Experimental

A mixture of tetrachlorophthalic anhydride (2.86 g, 0.01 mol) and methanol (20 ml) was refluxed for 0.5 h and then tert-butylamine (0.73 g, 0.01 mol) was added and the mixture stirred for 4 h at room temperature. After filtration, the filtrate was kept at room temperature for 5 d. Natural evaporation gave colourless single crystals of the title compound, suitable for X-ray analysis.

Refinement

H atoms were initially located from difference maps and then refined in a riding-model approximation with C—H = 0.96 Å, N—H = 0.89 Å and U_iso(H) = 1.5U_eq(N, C).

Figures

Fig. 1.

The molecular structure of (I), drawn with 30% probability ellipsoids.

Fig. 2.

Part of the crystal structure of (I) with hydrogen bonds indicated by dashed lines.

Crystal data

C4H12N+·C9H3Cl4O4–	F000 = 400
Mr = 391.06	Dx = 1.516 Mg m−3
Monoclinic, P21	Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 2177 reflections
a = 9.0193 (14) Å	θ = 2.3–27.0º
b = 6.5084 (11) Å	µ = 0.71 mm−1
c = 14.5965 (15) Å	T = 298 (2) K
β = 91.7570 (10)º	Block, colorless
V = 856.4 (2) Å3	0.53 × 0.48 × 0.44 mm
Z = 2

Data collection

Bruker SMART CCD diffractometer	2790 independent reflections
Radiation source: fine-focus sealed tube	2364 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.043
T = 298(2) K	θmax = 25.0º
φ and ω scans	θmin = 2.3º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)	h = −10→10
Tmin = 0.706, Tmax = 0.747	k = −7→7
4281 measured reflections	l = −15→17

Refinement

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.044	w = 1/[σ2(Fo2) + (0.048P)2 + 0.2322P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.116	(Δ/σ)max < 0.001
S = 1.04	Δρmax = 0.21 e Å−3
2790 reflections	Δρmin = −0.28 e Å−3
205 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraint	Extinction coefficient: 0.075 (5)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1147 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: 0.00 (9)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cl1	−0.17713 (11)	0.5505 (2)	0.24305 (8)	0.0650 (4)
Cl2	−0.10033 (15)	0.2412 (2)	0.09021 (8)	0.0730 (4)
Cl3	0.20894 (14)	0.2526 (2)	0.00306 (8)	0.0670 (4)
Cl4	0.44428 (12)	0.5681 (2)	0.07197 (8)	0.0645 (4)
N1	0.9054 (3)	0.8116 (5)	0.5564 (2)	0.0332 (7)
H1A	0.9244	0.9328	0.5825	0.050*
H1B	0.9627	0.7954	0.5084	0.050*
H1C	0.9241	0.7119	0.5969	0.050*
O1	0.4059 (3)	0.9677 (5)	0.1703 (2)	0.0561 (8)
O2	0.4110 (3)	0.8206 (5)	0.30813 (19)	0.0555 (8)
O3	0.0729 (3)	1.0097 (4)	0.30549 (18)	0.0462 (7)
O4	0.0532 (3)	0.7277 (4)	0.39073 (15)	0.0375 (6)
C1	0.2425 (4)	0.6942 (6)	0.1932 (2)	0.0347 (9)
C2	0.1041 (4)	0.6869 (6)	0.2345 (2)	0.0323 (8)
C3	−0.0013 (4)	0.5489 (7)	0.1999 (2)	0.0375 (9)
C4	0.0307 (5)	0.4133 (7)	0.1295 (3)	0.0431 (10)
C5	0.1686 (5)	0.4186 (7)	0.0903 (2)	0.0408 (9)
C6	0.2727 (4)	0.5608 (7)	0.1215 (2)	0.0380 (9)
C7	0.3626 (4)	0.8340 (6)	0.2319 (3)	0.0378 (9)
C8	0.0731 (4)	0.8226 (6)	0.3175 (2)	0.0305 (8)
C9	0.5402 (5)	1.0814 (9)	0.1945 (4)	0.0701 (15)
H9A	0.6216	0.9874	0.2027	0.105*
H9B	0.5265	1.1554	0.2505	0.105*
H9C	0.5614	1.1766	0.1464	0.105*
C10	0.7440 (4)	0.8028 (6)	0.5251 (3)	0.0367 (9)
C11	0.7195 (5)	0.9690 (7)	0.4533 (3)	0.0511 (11)
H11A	0.7391	1.1011	0.4804	0.077*
H11B	0.6186	0.9642	0.4305	0.077*
H11C	0.7852	0.9469	0.4038	0.077*
C12	0.7164 (4)	0.5891 (7)	0.4845 (3)	0.0469 (10)
H12A	0.7874	0.5622	0.4383	0.070*
H12B	0.6180	0.5831	0.4576	0.070*
H12C	0.7264	0.4878	0.5321	0.070*
C13	0.6520 (4)	0.8364 (7)	0.6089 (3)	0.0487 (11)
H13A	0.5497	0.8082	0.5938	0.073*
H13B	0.6622	0.9763	0.6290	0.073*
H13C	0.6859	0.7459	0.6571	0.073*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl1	0.0399 (6)	0.0959 (10)	0.0596 (7)	−0.0201 (6)	0.0101 (5)	−0.0272 (7)
Cl2	0.0733 (8)	0.0769 (10)	0.0685 (8)	−0.0297 (7)	−0.0010 (6)	−0.0322 (7)
Cl3	0.0782 (8)	0.0697 (9)	0.0532 (6)	0.0129 (7)	0.0033 (5)	−0.0277 (7)
Cl4	0.0511 (6)	0.0811 (9)	0.0627 (7)	0.0029 (6)	0.0236 (5)	−0.0087 (7)
N1	0.0333 (15)	0.0302 (17)	0.0364 (16)	0.0004 (13)	0.0033 (12)	0.0002 (14)
O1	0.0603 (19)	0.059 (2)	0.0495 (17)	−0.0197 (15)	0.0029 (14)	0.0158 (15)
O2	0.0606 (18)	0.061 (2)	0.0437 (16)	−0.0225 (16)	−0.0119 (14)	0.0098 (15)
O3	0.0623 (18)	0.0323 (18)	0.0439 (15)	−0.0008 (13)	0.0001 (13)	−0.0013 (12)
O4	0.0446 (14)	0.0374 (15)	0.0308 (13)	0.0003 (13)	0.0076 (11)	−0.0008 (12)
C1	0.039 (2)	0.035 (2)	0.0301 (18)	0.0012 (16)	−0.0010 (15)	0.0053 (16)
C2	0.0373 (19)	0.034 (2)	0.0259 (17)	−0.0030 (16)	0.0004 (15)	0.0015 (15)
C3	0.0349 (19)	0.045 (2)	0.0321 (18)	−0.0021 (19)	0.0002 (14)	−0.0037 (19)
C4	0.050 (2)	0.042 (2)	0.036 (2)	−0.0076 (19)	−0.0054 (18)	−0.0059 (18)
C5	0.050 (2)	0.042 (2)	0.0309 (19)	0.0048 (19)	0.0001 (17)	−0.0057 (17)
C6	0.0403 (19)	0.045 (2)	0.0286 (17)	0.007 (2)	0.0061 (15)	0.0042 (19)
C7	0.036 (2)	0.040 (2)	0.038 (2)	−0.0019 (17)	0.0050 (17)	0.0023 (18)
C8	0.0290 (18)	0.028 (2)	0.0340 (19)	−0.0036 (16)	−0.0012 (15)	0.0000 (16)
C9	0.064 (3)	0.070 (4)	0.078 (3)	−0.032 (3)	0.022 (2)	0.003 (3)
C10	0.0268 (17)	0.033 (2)	0.050 (2)	0.0016 (16)	−0.0027 (15)	−0.0039 (18)
C11	0.045 (2)	0.050 (3)	0.057 (3)	0.007 (2)	−0.011 (2)	0.010 (2)
C12	0.039 (2)	0.042 (3)	0.059 (3)	−0.0065 (19)	−0.0001 (18)	−0.013 (2)
C13	0.040 (2)	0.045 (3)	0.062 (3)	0.006 (2)	0.0158 (19)	−0.007 (2)

Geometric parameters (Å, °)

Cl1—C3	1.724 (4)	C3—C4	1.392 (6)
Cl2—C4	1.714 (4)	C4—C5	1.385 (6)
Cl3—C5	1.718 (4)	C5—C6	1.385 (6)
Cl4—C6	1.729 (4)	C9—H9A	0.9600
N1—C10	1.513 (5)	C9—H9B	0.9600
N1—H1A	0.8900	C9—H9C	0.9600
N1—H1B	0.8900	C10—C13	1.515 (5)
N1—H1C	0.8900	C10—C11	1.517 (6)
O1—C7	1.319 (5)	C10—C12	1.529 (6)
O1—C9	1.455 (5)	C11—H11A	0.9600
O2—C7	1.186 (4)	C11—H11B	0.9600
O3—C8	1.230 (5)	C11—H11C	0.9600
O4—C8	1.252 (4)	C12—H12A	0.9600
C1—C6	1.394 (5)	C12—H12B	0.9600
C1—C2	1.404 (5)	C12—H12C	0.9600
C1—C7	1.511 (5)	C13—H13A	0.9600
C2—C3	1.391 (5)	C13—H13B	0.9600
C2—C8	1.532 (5)	C13—H13C	0.9600
C10—N1—H1A	109.5	O1—C9—H9A	109.5
C10—N1—H1B	109.5	O1—C9—H9B	109.5
H1A—N1—H1B	109.5	H9A—C9—H9B	109.5
C10—N1—H1C	109.5	O1—C9—H9C	109.5
H1A—N1—H1C	109.5	H9A—C9—H9C	109.5
H1B—N1—H1C	109.5	H9B—C9—H9C	109.5
C7—O1—C9	115.6 (3)	N1—C10—C13	107.2 (3)
C6—C1—C2	119.9 (3)	N1—C10—C11	107.5 (3)
C6—C1—C7	120.1 (3)	C13—C10—C11	112.5 (3)
C2—C1—C7	119.7 (3)	N1—C10—C12	107.2 (3)
C3—C2—C1	118.2 (3)	C13—C10—C12	110.9 (4)
C3—C2—C8	121.3 (3)	C11—C10—C12	111.2 (3)
C1—C2—C8	120.5 (3)	C10—C11—H11A	109.5
C2—C3—C4	121.5 (3)	C10—C11—H11B	109.5
C2—C3—Cl1	119.3 (3)	H11A—C11—H11B	109.5
C4—C3—Cl1	119.1 (3)	C10—C11—H11C	109.5
C5—C4—C3	119.8 (4)	H11A—C11—H11C	109.5
C5—C4—Cl2	119.8 (3)	H11B—C11—H11C	109.5
C3—C4—Cl2	120.3 (3)	C10—C12—H12A	109.5
C6—C5—C4	119.3 (4)	C10—C12—H12B	109.5
C6—C5—Cl3	120.4 (3)	H12A—C12—H12B	109.5
C4—C5—Cl3	120.2 (3)	C10—C12—H12C	109.5
C5—C6—C1	121.1 (3)	H12A—C12—H12C	109.5
C5—C6—Cl4	119.2 (3)	H12B—C12—H12C	109.5
C1—C6—Cl4	119.7 (3)	C10—C13—H13A	109.5
O2—C7—O1	125.4 (4)	C10—C13—H13B	109.5
O2—C7—C1	123.1 (4)	H13A—C13—H13B	109.5
O1—C7—C1	111.5 (3)	C10—C13—H13C	109.5
O3—C8—O4	127.6 (3)	H13A—C13—H13C	109.5
O3—C8—C2	117.2 (3)	H13B—C13—H13C	109.5
O4—C8—C2	115.2 (3)
C6—C1—C2—C3	−2.0 (5)	Cl3—C5—C6—C1	−179.0 (3)
C7—C1—C2—C3	−176.8 (3)	C4—C5—C6—Cl4	−179.6 (3)
C6—C1—C2—C8	175.9 (3)	Cl3—C5—C6—Cl4	−0.5 (5)
C7—C1—C2—C8	1.2 (5)	C2—C1—C6—C5	−0.5 (5)
C1—C2—C3—C4	3.3 (6)	C7—C1—C6—C5	174.2 (4)
C8—C2—C3—C4	−174.6 (4)	C2—C1—C6—Cl4	−179.1 (3)
C1—C2—C3—Cl1	−174.8 (3)	C7—C1—C6—Cl4	−4.3 (5)
C8—C2—C3—Cl1	7.3 (5)	C9—O1—C7—O2	11.0 (6)
C2—C3—C4—C5	−2.0 (6)	C9—O1—C7—C1	−168.3 (4)
Cl1—C3—C4—C5	176.1 (3)	C6—C1—C7—O2	−115.3 (4)
C2—C3—C4—Cl2	178.5 (3)	C2—C1—C7—O2	59.4 (5)
Cl1—C3—C4—Cl2	−3.4 (5)	C6—C1—C7—O1	64.0 (5)
C3—C4—C5—C6	−0.6 (6)	C2—C1—C7—O1	−121.3 (4)
Cl2—C4—C5—C6	178.8 (3)	C3—C2—C8—O3	−117.6 (4)
C3—C4—C5—Cl3	−179.8 (3)	C1—C2—C8—O3	64.5 (5)
Cl2—C4—C5—Cl3	−0.3 (5)	C3—C2—C8—O4	63.6 (5)
C4—C5—C6—C1	1.9 (6)	C1—C2—C8—O4	−114.3 (4)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4i	0.89	1.97	2.838 (4)	165
N1—H1B···O4ii	0.89	1.97	2.850 (4)	168
N1—H1C···O3iii	0.89	1.94	2.818 (4)	169

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