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

Li, J.

doi:10.1107/S1600536811008506

organic compounds

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Volume 67| Part 4| April 2011| Page o901

doi:10.1107/S1600536811008506

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

Jian Li ^a ^*

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

(Received 13 February 2011; accepted 6 March 2011; online 15 March 2011)

In the anion of the title salt, C₆H₁₈N₂²⁺·2C₉H₃Cl₄O₄⁻, the methoxycarbonyl and carboxyl groups are aligned at dihedral angles of 71.0 (3) and 100.9 (3)°, respectively, with the aromatic ring. The asymmetric unit contains half a cation and one anion. In the crystal, intermolecular N—H⋯O, C—H⋯Cl and C—H⋯O hydrogen bonds link the components into a three-dimensional network.

Related literature

For related structures, see: Li (2011 ); Liang (2008 ).

Experimental

Crystal data

C₆H₁₈N₂²⁺·2C₉H₃Cl₄O₄⁻
M_r = 752.05
Monoclinic, C 2/c
a = 31.236 (3) Å
b = 5.8911 (4) Å
c = 18.3762 (18) Å
β = 107.118 (1)°
V = 3231.7 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.74 mm⁻¹
T = 298 K
0.37 × 0.28 × 0.15 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.770, T_max = 0.897
7618 measured reflections
2829 independent reflections
1817 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.154
S = 1.04
2829 reflections
192 parameters
H-atom parameters constrained
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O4	0.89	1.90	2.770 (5)	165
N1—H1B⋯O3ⁱ	0.89	1.87	2.757 (5)	171
C9—H9B⋯Cl4ⁱⁱ	0.96	2.75	3.677 (9)	161
C10—H10B⋯O2	0.97	2.58	3.208 (7)	122
Symmetry codes: (i) x, y-1, z; (ii) $[-x, y+1, -z+{\script{1\over 2}}]$ .

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); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811008506/bt5475sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811008506/bt5475Isup2.hkl

checkCIF report

Comment top

In the present work, the reaction of 3,4,5,6-tetrachloro-2-(methoxycarbonyl)benzoic acid and hexane-1,6-diamine in methanol is expected to yield 4,5,6,7-tetrachloro-2-[6-(4,5,6,7- tetrachloro-1,3-dioxoisoindolin-2-yl)hexyl]isoindoline-1,3-dione. However, the product is hexane-1,6-diaminium 3,4,5,6-tetrachloro-2-(methoxycarbonyl)benzoate (Scheme I, Fig. 1), this may be the reason of a shorter time and cooler temperature in the reaction. The asymmetric unit of the title compound (I) contains half a hexane-1,6-diaminium cation and one 3,4,5,6-tetrachloro-2-(methoxycarbonyl)benzoate anion (Fig. 1). In the anion of the title salt, the methoxycarbonyl and carboxyl groups are aligned at dihedral angles of 71.0 (3) and 100.9 (3) °, respectively, with the aromatic ring. The bond lengths and angles are in agreement with those in ethylammonium 2-(methoxycarbonyl)-3,4,5,6-tetrabromobenzoate methanol solvate (Li, 2011) and in ethane-1,2-diammonium bis(2-(methoxycarbonyl)-3,4,5,6-tetrabromobenzoate) methanol solvate (Liang, 2008). In the crystal structure, intermolecular N—H···O, C—H···Cl and C—H···O hydrogen bonds link the components of the structure into three-dimensional network (Fig. 2 and Table 1).

Related literature top

For related structures, see: Li (2011); Liang (2008).

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. And then hexane-1,6-diamine (0.58 g, 0.005 mol) was added to the above solution, being mixed round for 20 min at room temperature. And then the solution was kept at room temperature for 6 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); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), drawn with 30% probability ellipsoids.
	Fig. 2. The crystal packing of (I), viewed along b axis. Hydrogen bonds are indicated by dashed lines.

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

Crystal data top

C₆H₁₈N₂²⁺·2C₉H₃Cl₄O₄⁻	F(000) = 1528
M_r = 752.05	D_x = 1.546 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 31.236 (3) Å	Cell parameters from 2053 reflections
b = 5.8911 (4) Å	θ = 2.7–26.1°
c = 18.3762 (18) Å	µ = 0.74 mm⁻¹
β = 107.118 (1)°	T = 298 K
V = 3231.7 (5) Å³	Block, colorless
Z = 4	0.37 × 0.28 × 0.15 mm

Data collection top

Bruker SMART CCD diffractometer	2829 independent reflections
Radiation source: fine-focus sealed tube	1817 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −36→29
T_min = 0.770, T_max = 0.897	k = −6→7
7618 measured reflections	l = −21→21

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.154	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0489P)² + 12.9951P] where P = (F_o² + 2F_c²)/3
2829 reflections	(Δ/σ)_max < 0.001
192 parameters	Δρ_max = 0.51 e Å⁻³
0 restraints	Δρ_min = −0.41 e Å⁻³

Crystal data top

C₆H₁₈N₂²⁺·2C₉H₃Cl₄O₄⁻	V = 3231.7 (5) Å³
M_r = 752.05	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 31.236 (3) Å	µ = 0.74 mm⁻¹
b = 5.8911 (4) Å	T = 298 K
c = 18.3762 (18) Å	0.37 × 0.28 × 0.15 mm
β = 107.118 (1)°

Data collection top

Bruker SMART CCD diffractometer	2829 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	1817 reflections with I > 2σ(I)
T_min = 0.770, T_max = 0.897	R_int = 0.037
7618 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.154	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0489P)² + 12.9951P] where P = (F_o² + 2F_c²)/3
2829 reflections	Δρ_max = 0.51 e Å⁻³
192 parameters	Δρ_min = −0.41 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	0.16469 (4)	0.8320 (3)	0.02548 (7)	0.0738 (5)
Cl2	0.10240 (5)	0.4349 (3)	−0.04960 (8)	0.0845 (5)
Cl3	0.03378 (5)	0.2434 (2)	0.02771 (10)	0.0912 (6)
Cl4	0.02472 (5)	0.4714 (3)	0.17526 (10)	0.0918 (6)
N1	0.21033 (11)	0.4754 (6)	0.26915 (19)	0.0485 (9)
H1A	0.2012	0.6131	0.2512	0.073*
H1B	0.1918	0.3715	0.2417	0.073*
H1C	0.2379	0.4510	0.2662	0.073*
O1	0.06089 (14)	0.9497 (7)	0.2473 (2)	0.0906 (13)
O2	0.12386 (14)	0.7821 (10)	0.3033 (2)	0.1124 (18)
O3	0.14859 (11)	1.1892 (6)	0.1748 (2)	0.0769 (12)
O4	0.19786 (10)	0.9160 (5)	0.21430 (17)	0.0537 (8)
C1	0.09506 (15)	0.8248 (9)	0.2481 (3)	0.0558 (12)
C2	0.16017 (13)	0.9909 (7)	0.1788 (2)	0.0400 (10)
C3	0.09403 (13)	0.7360 (7)	0.1712 (2)	0.0432 (10)
C4	0.12605 (12)	0.8139 (6)	0.1380 (2)	0.0373 (9)
C5	0.12705 (13)	0.7243 (7)	0.0688 (2)	0.0458 (10)
C6	0.09835 (14)	0.5502 (7)	0.0339 (3)	0.0511 (12)
C7	0.06762 (15)	0.4685 (8)	0.0678 (3)	0.0559 (13)
C8	0.06449 (14)	0.5651 (8)	0.1346 (3)	0.0542 (12)
C9	0.0599 (3)	1.0419 (13)	0.3203 (3)	0.122 (3)
H9A	0.0605	0.9197	0.3552	0.184*
H9B	0.0330	1.1290	0.3134	0.184*
H9C	0.0855	1.1377	0.3405	0.184*
C10	0.21042 (15)	0.4596 (8)	0.3498 (3)	0.0531 (12)
H10A	0.2253	0.3210	0.3722	0.064*
H10B	0.1798	0.4547	0.3523	0.064*
C11	0.23434 (15)	0.6622 (8)	0.3940 (2)	0.0498 (11)
H11A	0.2645	0.6693	0.3894	0.060*
H11B	0.2188	0.7997	0.3718	0.060*
C12	0.23681 (14)	0.6522 (8)	0.4771 (2)	0.0517 (11)
H12A	0.2507	0.5102	0.4983	0.062*
H12B	0.2066	0.6541	0.4816	0.062*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0691 (9)	0.0891 (11)	0.0710 (8)	−0.0250 (7)	0.0329 (7)	−0.0234 (7)
Cl2	0.0825 (10)	0.0811 (11)	0.0783 (9)	−0.0055 (8)	0.0057 (8)	−0.0407 (8)
Cl3	0.0688 (9)	0.0500 (8)	0.1278 (13)	−0.0243 (7)	−0.0131 (9)	−0.0073 (8)
Cl4	0.0664 (9)	0.0909 (12)	0.1210 (13)	−0.0240 (8)	0.0322 (9)	0.0288 (10)
N1	0.044 (2)	0.033 (2)	0.060 (2)	0.0003 (16)	0.0021 (17)	−0.0084 (17)
O1	0.112 (3)	0.090 (3)	0.067 (2)	0.053 (3)	0.021 (2)	0.007 (2)
O2	0.094 (3)	0.181 (5)	0.058 (2)	0.071 (3)	0.016 (2)	0.010 (3)
O3	0.063 (2)	0.035 (2)	0.105 (3)	0.0031 (16)	−0.019 (2)	−0.0100 (18)
O4	0.0404 (17)	0.0431 (18)	0.0658 (19)	−0.0031 (14)	−0.0025 (15)	0.0026 (15)
C1	0.041 (3)	0.066 (3)	0.061 (3)	0.012 (2)	0.015 (2)	0.018 (3)
C2	0.038 (2)	0.035 (3)	0.043 (2)	−0.0057 (19)	0.0049 (18)	−0.0034 (19)
C3	0.034 (2)	0.037 (2)	0.054 (3)	0.0065 (19)	0.0067 (19)	0.010 (2)
C4	0.031 (2)	0.027 (2)	0.047 (2)	0.0021 (16)	0.0018 (17)	−0.0004 (18)
C5	0.037 (2)	0.041 (3)	0.055 (3)	−0.0035 (19)	0.007 (2)	−0.008 (2)
C6	0.041 (2)	0.036 (3)	0.065 (3)	0.002 (2)	−0.002 (2)	−0.011 (2)
C7	0.040 (3)	0.036 (3)	0.075 (3)	−0.004 (2)	−0.008 (2)	−0.003 (2)
C8	0.035 (2)	0.045 (3)	0.076 (3)	−0.003 (2)	0.007 (2)	0.019 (3)
C9	0.171 (7)	0.127 (6)	0.072 (4)	0.084 (6)	0.042 (4)	0.010 (4)
C10	0.048 (3)	0.046 (3)	0.063 (3)	−0.001 (2)	0.012 (2)	−0.003 (2)
C11	0.049 (3)	0.042 (3)	0.053 (3)	0.002 (2)	0.007 (2)	−0.007 (2)
C12	0.045 (3)	0.052 (3)	0.057 (3)	0.001 (2)	0.014 (2)	−0.007 (2)

Geometric parameters (Å, º) top

Cl1—C5	1.723 (5)	C4—C5	1.386 (6)
Cl2—C6	1.716 (5)	C5—C6	1.389 (6)
Cl3—C7	1.721 (4)	C6—C7	1.376 (7)
Cl4—C8	1.719 (5)	C7—C8	1.382 (7)
N1—C10	1.484 (5)	C9—H9A	0.9600
N1—H1A	0.8900	C9—H9B	0.9600
N1—H1B	0.8900	C9—H9C	0.9600
N1—H1C	0.8900	C10—C11	1.511 (6)
O1—C1	1.293 (5)	C10—H10A	0.9700
O1—C9	1.456 (7)	C10—H10B	0.9700
O2—C1	1.168 (5)	C11—C12	1.507 (6)
O3—C2	1.218 (5)	C11—H11A	0.9700
O4—C2	1.247 (5)	C11—H11B	0.9700
C1—C3	1.499 (6)	C12—C12ⁱ	1.519 (9)
C2—C4	1.521 (5)	C12—H12A	0.9700
C3—C4	1.394 (6)	C12—H12B	0.9700
C3—C8	1.397 (6)

C10—N1—H1A	109.5	C7—C8—C3	121.0 (4)
C10—N1—H1B	109.5	C7—C8—Cl4	120.2 (4)
H1A—N1—H1B	109.5	C3—C8—Cl4	118.8 (4)
C10—N1—H1C	109.5	O1—C9—H9A	109.5
H1A—N1—H1C	109.5	O1—C9—H9B	109.5
H1B—N1—H1C	109.5	H9A—C9—H9B	109.5
C1—O1—C9	116.3 (4)	O1—C9—H9C	109.5
O2—C1—O1	123.7 (5)	H9A—C9—H9C	109.5
O2—C1—C3	122.7 (4)	H9B—C9—H9C	109.5
O1—C1—C3	113.6 (4)	N1—C10—C11	110.0 (4)
O3—C2—O4	126.1 (4)	N1—C10—H10A	109.7
O3—C2—C4	118.3 (4)	C11—C10—H10A	109.7
O4—C2—C4	115.6 (4)	N1—C10—H10B	109.7
C4—C3—C8	119.0 (4)	C11—C10—H10B	109.7
C4—C3—C1	118.6 (4)	H10A—C10—H10B	108.2
C8—C3—C1	122.2 (4)	C12—C11—C10	112.5 (4)
C5—C4—C3	119.3 (4)	C12—C11—H11A	109.1
C5—C4—C2	120.8 (4)	C10—C11—H11A	109.1
C3—C4—C2	120.0 (4)	C12—C11—H11B	109.1
C4—C5—C6	121.3 (4)	C10—C11—H11B	109.1
C4—C5—Cl1	119.1 (3)	H11A—C11—H11B	107.8
C6—C5—Cl1	119.6 (3)	C11—C12—C12ⁱ	113.0 (5)
C7—C6—C5	119.4 (4)	C11—C12—H12A	109.0
C7—C6—Cl2	120.7 (3)	C12ⁱ—C12—H12A	109.0
C5—C6—Cl2	119.9 (4)	C11—C12—H12B	109.0
C6—C7—C8	120.0 (4)	C12ⁱ—C12—H12B	109.0
C6—C7—Cl3	119.9 (4)	H12A—C12—H12B	107.8
C8—C7—Cl3	120.1 (4)

C9—O1—C1—O2	1.0 (9)	C4—C5—C6—C7	1.5 (6)
C9—O1—C1—C3	−179.9 (5)	Cl1—C5—C6—C7	−178.4 (3)
O2—C1—C3—C4	−68.0 (7)	C4—C5—C6—Cl2	−177.0 (3)
O1—C1—C3—C4	112.9 (5)	Cl1—C5—C6—Cl2	3.1 (5)
O2—C1—C3—C8	106.7 (6)	C5—C6—C7—C8	2.3 (6)
O1—C1—C3—C8	−72.4 (6)	Cl2—C6—C7—C8	−179.3 (3)
C8—C3—C4—C5	1.6 (6)	C5—C6—C7—Cl3	−176.7 (3)
C1—C3—C4—C5	176.5 (4)	Cl2—C6—C7—Cl3	1.7 (5)
C8—C3—C4—C2	−176.8 (4)	C6—C7—C8—C3	−4.1 (7)
C1—C3—C4—C2	−1.8 (5)	Cl3—C7—C8—C3	174.9 (3)
O3—C2—C4—C5	101.7 (5)	C6—C7—C8—Cl4	177.5 (3)
O4—C2—C4—C5	−79.0 (5)	Cl3—C7—C8—Cl4	−3.6 (5)
O3—C2—C4—C3	−79.9 (5)	C4—C3—C8—C7	2.1 (6)
O4—C2—C4—C3	99.4 (4)	C1—C3—C8—C7	−172.6 (4)
C3—C4—C5—C6	−3.4 (6)	C4—C3—C8—Cl4	−179.4 (3)
C2—C4—C5—C6	174.9 (4)	C1—C3—C8—Cl4	5.9 (6)
C3—C4—C5—Cl1	176.5 (3)	N1—C10—C11—C12	−178.2 (4)
C2—C4—C5—Cl1	−5.2 (5)	C10—C11—C12—C12ⁱ	176.6 (5)

Symmetry code: (i) −x+1/2, −y+3/2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4	0.89	1.90	2.770 (5)	165
N1—H1B···O3ⁱⁱ	0.89	1.87	2.757 (5)	171
C9—H9B···Cl4ⁱⁱⁱ	0.96	2.75	3.677 (9)	161
C10—H10B···O2	0.97	2.58	3.208 (7)	122

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

Experimental details

Crystal data
Chemical formula	C₆H₁₈N₂²⁺·2C₉H₃Cl₄O₄⁻
M_r	752.05
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	31.236 (3), 5.8911 (4), 18.3762 (18)
β (°)	107.118 (1)
V (Å³)	3231.7 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.74
Crystal size (mm)	0.37 × 0.28 × 0.15

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.770, 0.897
No. of measured, independent and observed [I > 2σ(I)] reflections	7618, 2829, 1817
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.154, 1.04
No. of reflections	2829
No. of parameters	192
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0489P)² + 12.9951P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.41

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4	0.89	1.90	2.770 (5)	165
N1—H1B···O3ⁱ	0.89	1.87	2.757 (5)	171
C9—H9B···Cl4ⁱⁱ	0.96	2.75	3.677 (9)	161
C10—H10B···O2	0.97	2.58	3.208 (7)	122

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

Acknowledgements

The author thanks Shandong Provincial Natural Science Foundation, China (ZR2009BL027) for support.

References

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