Butane-1,4-diaminium bis­[3,4,5,6-tetra­chloro-2-(meth­oxy­carbon­yl)benzoate]

Liang, Z.P.

doi:10.1107/S1600536811016795

organic compounds

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doi:10.1107/S1600536811016795

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Butane-1,4-diaminium bis[3,4,5,6-tetrachloro-2-(methoxycarbonyl)benzoate]

Zu Pei Liang ^a ^*

^aDepartment of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, People's Republic of China
^*Correspondence e-mail: lzpwfu@163.com

(Received 29 April 2011; accepted 3 May 2011; online 7 May 2011)

In the title salt, C₄H₁₄N₂⁺·2C₉H₃Cl₄O₄⁻, the cation lies on an inversion center. In the anion, the mean planes of methoxycarbonyl and carboxylate groups form dihedral angles of 64.9 (3) and 58.5 (3)°, respectively, with the benzene ring. In the crystal, intermolecular N—H⋯O hydrogen bonds connect the components into sheets parallel to (100).

Related literature

For a related structure, see: Li (2011 ).

Experimental

Crystal data

C₄H₁₄N₂²⁺·2C₉H₃Cl₄O₄⁻
M_r = 724.00
Monoclinic, P 2₁ /c
a = 14.4243 (13) Å
b = 6.1041 (6) Å
c = 16.9653 (15) Å
β = 97.056 (1)°
V = 1482.4 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.81 mm⁻¹
T = 298 K
0.46 × 0.43 × 0.40 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.708, T_max = 0.738
7307 measured reflections
2603 independent reflections
1908 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.096
S = 1.05
2603 reflections
183 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯O3ⁱ	0.89	1.85	2.735 (3)	172
N1—H1B⋯O4ⁱⁱ	0.89	1.94	2.823 (3)	174
N1—H1A⋯O4	0.89	1.88	2.761 (3)	169
Symmetry codes: (i) x, y+1, z; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); 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) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811016795/lh5244sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811016795/lh5244Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811016795/lh5244Isup3.cml

checkCIF report

Comment top

In the present work, the reaction of 3,4,5,6-tetrachloro-2-(methoxycarbonyl)benzoic acid and butane-1,4-diamine in methanol was expected to yield 4,5,6,7-tetrachloro-2-[4-(4,5,6,7- tetrachloro-1,3-dioxoisoindolin-2-yl)butanyl]isoindoline-1,3-dione. However, the product was the title compound and this may have occurred because of the reduced time and temperature of the reaction. The asymmetric unit of the title compound (I) contains one half of a butane-1,4-diaminium cation and one 3,4,5,6-tetrachloro-2-(methoxycarbonyl)benzoate anions (Fig. 1). In the anion, the mean planes of the methoxycarbonyl and carboxyl groups are aligned at dihedral angles of 64.9 (3) and 58.5 (3) °, respectively with the benzene ring. The bond lengths and angles are in agreement with those which are related in hexane-1,6-diaminium bis[3,4,5,6-tetrachloro-2-(methoxycarbonyl)benzoate](Li, 2011). In the crystal, intermolecular N—H···O hydrogen bonds connect the components into two-dimensional sheets parallel to (100) (Fig. 2 and Table 1).

Related literature top

For a related structure, see: Li (2011).

Experimental top

A mixture of 4,5,6,7-tetrachloroisobenzofuran-1,3-dione (2.86 g, 0.01 mol) and methanol (15 ml) was refluxed for 0.5 h. Then butane-1,4-diamine (0.44 g, 0.005 mol) was added to the above solution and mixed for 20 min at room temperature. The solution was kept at room temperature for 5 d. Natural evaporation gave colourless single crystals of the title compound, suitable for X-ray analysis.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of (I), drawn with 30% probability ellipsoids. The symmetry complete cation is shown with unlabeled atoms related by the symmetry operator (-x+1, -y+2, -z+1).
	Fig. 2. The crystal packing of (I) with hydrogen bonds shown as dashed lines. Only H atoms involved in hydrogen bonds are shown.

Butane-1,4-diaminium bis[3,4,5,6-tetrachloro-2-(methoxycarbonyl)benzoate] top

Crystal data top

C₄H₁₄N₂²⁺·2C₉H₃Cl₄O₄⁻	F(000) = 732
M_r = 724.00	D_x = 1.622 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2612 reflections
a = 14.4243 (13) Å	θ = 2.4–26.5°
b = 6.1041 (6) Å	µ = 0.81 mm⁻¹
c = 16.9653 (15) Å	T = 298 K
β = 97.056 (1)°	Block, colorless
V = 1482.4 (2) Å³	0.46 × 0.43 × 0.40 mm
Z = 2

Data collection top

Bruker SMART CCD diffractometer	2603 independent reflections
Radiation source: fine-focus sealed tube	1908 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −9→17
T_min = 0.708, T_max = 0.738	k = −7→7
7307 measured reflections	l = −18→20

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0373P)² + 1.0059P] where P = (F_o² + 2F_c²)/3
2603 reflections	(Δ/σ)_max < 0.001
183 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₄H₁₄N₂²⁺·2C₉H₃Cl₄O₄⁻	V = 1482.4 (2) Å³
M_r = 724.00	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.4243 (13) Å	µ = 0.81 mm⁻¹
b = 6.1041 (6) Å	T = 298 K
c = 16.9653 (15) Å	0.46 × 0.43 × 0.40 mm
β = 97.056 (1)°

Data collection top

Bruker SMART CCD diffractometer	2603 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	1908 reflections with I > 2σ(I)
T_min = 0.708, T_max = 0.738	R_int = 0.024
7307 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.096	H-atom parameters constrained
S = 1.05	Δρ_max = 0.23 e Å⁻³
2603 reflections	Δρ_min = −0.20 e Å⁻³
183 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
Cl1	0.27338 (6)	0.79357 (15)	0.17344 (4)	0.0617 (3)
Cl2	0.10875 (6)	1.10088 (15)	0.19656 (5)	0.0705 (3)
Cl3	0.01193 (5)	1.07644 (14)	0.34929 (5)	0.0642 (3)
Cl4	0.07322 (6)	0.72291 (15)	0.47687 (5)	0.0630 (3)
N1	0.46526 (16)	0.9951 (4)	0.31490 (13)	0.0465 (6)
H1A	0.4416	0.8603	0.3128	0.070*
H1B	0.5002	1.0132	0.2756	0.070*
H1C	0.4189	1.0923	0.3099	0.070*
O1	0.19109 (14)	0.3094 (3)	0.46777 (12)	0.0559 (5)
O2	0.32465 (15)	0.4957 (4)	0.48905 (13)	0.0675 (6)
O3	0.31815 (14)	0.2789 (3)	0.31198 (14)	0.0626 (6)
O4	0.41355 (12)	0.5599 (3)	0.30166 (11)	0.0459 (5)
C1	0.24890 (19)	0.4667 (5)	0.45324 (15)	0.0415 (6)
C2	0.33628 (19)	0.4761 (4)	0.30956 (14)	0.0379 (6)
C3	0.20896 (17)	0.6149 (4)	0.38674 (15)	0.0376 (6)
C4	0.25510 (17)	0.6303 (4)	0.31904 (15)	0.0358 (6)
C5	0.22239 (18)	0.7791 (4)	0.26073 (15)	0.0390 (6)
C6	0.14757 (18)	0.9170 (4)	0.26928 (16)	0.0428 (7)
C7	0.10285 (18)	0.9025 (4)	0.33718 (17)	0.0430 (7)
C8	0.13250 (18)	0.7475 (5)	0.39497 (16)	0.0415 (7)
C9	0.2212 (2)	0.1710 (6)	0.53489 (19)	0.0662 (9)
H9A	0.2630	0.0610	0.5195	0.099*
H9B	0.1679	0.1018	0.5529	0.099*
H9C	0.2529	0.2581	0.5770	0.099*
C10	0.5233 (2)	1.0276 (6)	0.39168 (18)	0.0619 (9)
H10A	0.5461	1.1772	0.3950	0.074*
H10B	0.5770	0.9309	0.3947	0.074*
C11	0.4702 (2)	0.9828 (6)	0.46041 (17)	0.0578 (8)
H11A	0.4477	0.8330	0.4572	0.069*
H11B	0.4163	1.0791	0.4572	0.069*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0654 (5)	0.0794 (6)	0.0435 (4)	0.0200 (4)	0.0191 (4)	0.0101 (4)
Cl2	0.0592 (5)	0.0752 (6)	0.0774 (6)	0.0234 (5)	0.0093 (4)	0.0269 (5)
Cl3	0.0443 (4)	0.0644 (5)	0.0856 (6)	0.0176 (4)	0.0143 (4)	−0.0125 (4)
Cl4	0.0541 (5)	0.0812 (6)	0.0597 (5)	0.0003 (4)	0.0309 (4)	−0.0073 (4)
N1	0.0478 (14)	0.0430 (13)	0.0528 (14)	0.0035 (11)	0.0233 (11)	0.0023 (11)
O1	0.0553 (13)	0.0521 (12)	0.0602 (13)	−0.0123 (11)	0.0065 (10)	0.0088 (10)
O2	0.0502 (13)	0.0832 (16)	0.0665 (14)	−0.0169 (12)	−0.0032 (11)	0.0221 (12)
O3	0.0513 (13)	0.0355 (12)	0.1034 (18)	0.0027 (10)	0.0198 (12)	−0.0069 (11)
O4	0.0376 (11)	0.0456 (11)	0.0581 (12)	0.0035 (9)	0.0206 (9)	−0.0009 (9)
C1	0.0385 (16)	0.0471 (17)	0.0407 (15)	−0.0064 (13)	0.0117 (13)	−0.0019 (12)
C2	0.0390 (16)	0.0385 (16)	0.0372 (14)	0.0043 (13)	0.0087 (12)	−0.0014 (11)
C3	0.0320 (14)	0.0382 (15)	0.0433 (14)	−0.0038 (12)	0.0076 (11)	−0.0036 (12)
C4	0.0319 (14)	0.0339 (14)	0.0424 (14)	−0.0005 (11)	0.0077 (11)	−0.0051 (11)
C5	0.0352 (15)	0.0435 (15)	0.0393 (14)	0.0011 (12)	0.0083 (11)	−0.0043 (12)
C6	0.0357 (15)	0.0415 (16)	0.0502 (16)	0.0029 (13)	0.0014 (12)	0.0003 (13)
C7	0.0308 (14)	0.0415 (16)	0.0572 (17)	0.0040 (12)	0.0074 (13)	−0.0096 (13)
C8	0.0335 (14)	0.0487 (17)	0.0448 (15)	−0.0025 (13)	0.0144 (12)	−0.0093 (13)
C9	0.077 (2)	0.062 (2)	0.063 (2)	−0.0074 (19)	0.0209 (18)	0.0136 (17)
C10	0.0485 (19)	0.082 (2)	0.057 (2)	−0.0095 (17)	0.0134 (15)	0.0004 (17)
C11	0.0532 (19)	0.067 (2)	0.0557 (18)	−0.0077 (17)	0.0179 (15)	0.0026 (16)

Geometric parameters (Å, º) top

Cl1—C5	1.735 (3)	C3—C8	1.389 (4)
Cl2—C6	1.711 (3)	C3—C4	1.400 (3)
Cl3—C7	1.719 (3)	C4—C5	1.382 (4)
Cl4—C8	1.725 (3)	C5—C6	1.390 (4)
N1—C10	1.473 (4)	C6—C7	1.390 (4)
N1—H1A	0.8900	C7—C8	1.391 (4)
N1—H1B	0.8900	C9—H9A	0.9600
N1—H1C	0.8900	C9—H9B	0.9600
O1—C1	1.314 (3)	C9—H9C	0.9600
O1—C9	1.441 (4)	C10—C11	1.497 (4)
O2—C1	1.196 (3)	C10—H10A	0.9700
O3—C2	1.234 (3)	C10—H10B	0.9700
O4—C2	1.248 (3)	C11—C11ⁱ	1.518 (6)
C1—C3	1.504 (4)	C11—H11A	0.9700
C2—C4	1.526 (3)	C11—H11B	0.9700

C10—N1—H1A	109.5	C6—C7—C8	119.6 (2)
C10—N1—H1B	109.5	C6—C7—Cl3	119.9 (2)
H1A—N1—H1B	109.5	C8—C7—Cl3	120.6 (2)
C10—N1—H1C	109.5	C3—C8—C7	120.3 (2)
H1A—N1—H1C	109.5	C3—C8—Cl4	120.6 (2)
H1B—N1—H1C	109.5	C7—C8—Cl4	119.1 (2)
C1—O1—C9	116.1 (2)	O1—C9—H9A	109.5
O2—C1—O1	125.0 (3)	O1—C9—H9B	109.5
O2—C1—C3	122.2 (3)	H9A—C9—H9B	109.5
O1—C1—C3	112.7 (2)	O1—C9—H9C	109.5
O3—C2—O4	126.8 (3)	H9A—C9—H9C	109.5
O3—C2—C4	115.5 (2)	H9B—C9—H9C	109.5
O4—C2—C4	117.7 (2)	N1—C10—C11	112.0 (2)
C8—C3—C4	120.5 (2)	N1—C10—H10A	109.2
C8—C3—C1	120.7 (2)	C11—C10—H10A	109.2
C4—C3—C1	118.6 (2)	N1—C10—H10B	109.2
C5—C4—C3	118.5 (2)	C11—C10—H10B	109.2
C5—C4—C2	121.9 (2)	H10A—C10—H10B	107.9
C3—C4—C2	119.6 (2)	C10—C11—C11ⁱ	112.1 (3)
C4—C5—C6	121.6 (2)	C10—C11—H11A	109.2
C4—C5—Cl1	120.1 (2)	C11ⁱ—C11—H11A	109.2
C6—C5—Cl1	118.3 (2)	C10—C11—H11B	109.2
C5—C6—C7	119.5 (2)	C11ⁱ—C11—H11B	109.2
C5—C6—Cl2	120.8 (2)	H11A—C11—H11B	107.9
C7—C6—Cl2	119.7 (2)

C9—O1—C1—O2	3.3 (4)	C4—C5—C6—C7	−1.5 (4)
C9—O1—C1—C3	−175.2 (2)	Cl1—C5—C6—C7	177.3 (2)
O2—C1—C3—C8	−112.4 (3)	C4—C5—C6—Cl2	179.6 (2)
O1—C1—C3—C8	66.2 (3)	Cl1—C5—C6—Cl2	−1.6 (3)
O2—C1—C3—C4	62.3 (4)	C5—C6—C7—C8	−1.2 (4)
O1—C1—C3—C4	−119.2 (3)	Cl2—C6—C7—C8	177.8 (2)
C8—C3—C4—C5	−0.4 (4)	C5—C6—C7—Cl3	178.6 (2)
C1—C3—C4—C5	−175.1 (2)	Cl2—C6—C7—Cl3	−2.5 (3)
C8—C3—C4—C2	−177.3 (2)	C4—C3—C8—C7	−2.2 (4)
C1—C3—C4—C2	8.0 (4)	C1—C3—C8—C7	172.4 (2)
O3—C2—C4—C5	−119.9 (3)	C4—C3—C8—Cl4	178.0 (2)
O4—C2—C4—C5	61.3 (3)	C1—C3—C8—Cl4	−7.5 (3)
O3—C2—C4—C3	56.9 (3)	C6—C7—C8—C3	3.0 (4)
O4—C2—C4—C3	−121.9 (3)	Cl3—C7—C8—C3	−176.8 (2)
C3—C4—C5—C6	2.3 (4)	C6—C7—C8—Cl4	−177.2 (2)
C2—C4—C5—C6	179.1 (2)	Cl3—C7—C8—Cl4	3.1 (3)
C3—C4—C5—Cl1	−176.52 (19)	N1—C10—C11—C11ⁱ	−179.8 (3)
C2—C4—C5—Cl1	0.3 (4)

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O3ⁱⁱ	0.89	1.85	2.735 (3)	172
N1—H1B···O4ⁱⁱⁱ	0.89	1.94	2.823 (3)	174
N1—H1A···O4	0.89	1.88	2.761 (3)	169

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

Experimental details

Crystal data
Chemical formula	C₄H₁₄N₂²⁺·2C₉H₃Cl₄O₄⁻
M_r	724.00
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	14.4243 (13), 6.1041 (6), 16.9653 (15)
β (°)	97.056 (1)
V (Å³)	1482.4 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.81
Crystal size (mm)	0.46 × 0.43 × 0.40

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.708, 0.738
No. of measured, independent and observed [I > 2σ(I)] reflections	7307, 2603, 1908
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.096, 1.05
No. of reflections	2603
No. of parameters	183
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.20

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O3ⁱ	0.89	1.85	2.735 (3)	172
N1—H1B···O4ⁱⁱ	0.89	1.94	2.823 (3)	174
N1—H1A···O4	0.89	1.88	2.761 (3)	169

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

Acknowledgements

The author thanks Shandong Provincial Natural Science Foundation, China (ZR2010BM033) for support.

References

Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Li, J. (2011). Acta Cryst. E67, o901. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

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