Ethane-1,2-diaminium 3,4,5,6-tetra­bromo-2-(methoxy­carbon­yl)benzoate methanol solvate

Liang, Z.-P.

doi:10.1107/S1600536808038166

organic compounds

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Volume 64| Part 12| December 2008| Page o2416

doi:10.1107/S1600536808038166

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Ethane-1,2-diaminium 3,4,5,6-tetrabromo-2-(methoxycarbonyl)benzoate methanol solvate

Zu-Pei Liang ^a ^*

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

(Received 12 July 2008; accepted 17 November 2008; online 22 November 2008)

In the title compound, C₂H₁₀N₂²⁺·2C₉H₃Br₄O₄⁻·CH₄O, the N atoms of the ethane-1,2-diamine molecule are protonated. The crystal structure is stabilized by N—H⋯O hydrogen bonds between the ethane-1,2-diaminium cations and 3,4,5,6-tetrabromo-2-(methoxycarbonyl)bromobenzoate anions, and by O—H⋯O and N—H⋯O hydrogen bonds between the methanol solvate and both the cation and the anion. In addition, the crystal structure exhibits a C—Br⋯O halogen bond [3.20 (3) Å] and a Br⋯Br interaction [3.560 (2) Å].

Related literature

For related structures, see: Liang et al. (2006 , 2007 ); For a review of halogen bonding, see: Politzer et al. (2007 ).

Experimental

Crystal data

C₂H₁₀N₂²⁺·2C₉H₃Br₄O₄⁻·CH₄O
M_r = 1083.67
Monoclinic, P 2₁ /c
a = 6.456 (2) Å
b = 19.036 (7) Å
c = 26.017 (9) Å
β = 96.002 (6)°
V = 3179.7 (19) Å³
Z = 4
Mo Kα radiation
μ = 10.14 mm⁻¹
T = 298 (2) K
0.41 × 0.25 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.062, T_max = 0.221
15827 measured reflections
5585 independent reflections
3448 reflections with I > 2σ(I)
R_int = 0.083

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.145
S = 0.98
5585 reflections
367 parameters
6 restraints
H-atom parameters constrained
Δρ_max = 1.18 e Å⁻³
Δρ_min = −0.72 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2ⁱ	0.89	1.87	2.748 (8)	167
N1—H1B⋯O5ⁱⁱ	0.89	2.04	2.857 (8)	153
N1—H1C⋯O6	0.89	1.86	2.734 (8)	166
N2—H2A⋯O9ⁱⁱⁱ	0.89	1.97	2.801 (9)	154
N2—H2B⋯O2ⁱⁱⁱ	0.89	1.93	2.795 (9)	163
N2—H2B⋯O3ⁱⁱⁱ	0.89	2.57	3.000 (9)	110
N2—H2C⋯O5^iv	0.89	1.90	2.747 (9)	159
O9—H9⋯O1^v	0.82	1.89	2.695 (8)	168
Symmetry codes: (i) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x+2, -y+1, -z+1; (iii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) -x+1, -y+1, -z+1; (v) x-1, y, z.

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 DIAMOND (Brandenburg, 1998 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808038166/lx2065sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808038166/lx2065Isup2.hkl

checkCIF report

Comment top

1,2-Bis(tetrabromophthalimido)ethane is an important flame retardant. 2-(Methoxycarbonyl)-3,4,5,6-tetrabromobenzoic acid is the intermediate of the flame retardant. In this paper, the structure of the title compound is reported.

The asymmetric unit of the title compound contains one ethane-1,2-diaminium, two 3,4,5,6-tetrabromo-2-(methoxycarbonyl)bromobenzoate and one methanol molecule (Fig. 1). The bond lengths and angles agree with those in those similar compounds 4-phthalimidobenzoic acid N,N-dimethylformamide solvate (Liang et al., 2006) and 4-(5-Bromo-1,3-dioxoisoindolin-2-yl)benzoic acid N,N-dimethylformamide solvate (Liang et al., 2007). The dihedral angle between two benzene rings is 74.6 (2)°.

The crystal structure is stabilized by various hydrogen bonds (Fig. 2 and Table 1; symmetry code as in Fig. 2); N—H···O hydrogen bonds between the ethane-1,2-diaminium and the 2-(methoxycarbonyl)-3,4,5,6-tetrabromobenzoate anions, O—H···O and N—H···O hydrogen bonds between the methanol and the 3,4,5,6-tetrabromo-2-(methoxycarbonyl)bromobenzoate anions and the ethane-1,2-diaminium. The further stability comes from a weak C—Br···O halogen bond (Fig. 2) (Politzer et al., 2007); between the bromine atom and the oxygen of a neighbouring methoxy group, i.e. C13—Br8···O4^v distance of 3.20 (3) Å and a C13—Br8···O4^v angle of 156.9 (3)°, and a Br2···Br6^vi interaction at 3.560 (2) Å (Fig. 2).

Related literature top

For related structures, see: Liang et al. (2006, 2007); For a review of halogen bonding, see: Politzer et al. (2007).

Experimental top

A mixture of 4,5,6,7-tetrabromoisobenzofuran-1,3-dione (46.4 g, 0.1 mol) and methanol (150 ml) was refluxed for 0.5 h. And then ethane-1,2-diamine (3 g, 0.05 mol) was added to the above solution, being mixed round for 4 h at room temperature. After filtration and the filtrate was kept at room temperature for 3 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: SMART (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 DIAMOND (Brandenburg, 1998); 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 a axis. Hydrogen bonds are indicated by dashed lines. [Symmetry code: (i) -x + 2, y - 1/2, -z + 1/2; (ii) -x + 2, -y + 1, -z + 1; (iii) -x + 1, y - 1/2, -z + 1/2; (iv) -x + 1, -y + 1, -z + 1; (v) x - 1, y, z; (vi) -x + 1, -y + 2, -z + 1.]

Ethane-1,2-diaminium 3,4,5,6-tetrabromo-2-(methoxycarbonyl)benzoate methanol solvate top

Crystal data top

C₂H₁₀N₂²⁺·2C₉H₃Br₄O₄⁻·CH₄O	F(000) = 2048
M_r = 1083.67	D_x = 2.264 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2716 reflections
a = 6.456 (2) Å	θ = 2.3–22.1°
b = 19.036 (7) Å	µ = 10.14 mm⁻¹
c = 26.017 (9) Å	T = 298 K
β = 96.002 (6)°	Block, colourless
V = 3179.7 (19) Å³	0.41 × 0.25 × 0.15 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	5585 independent reflections
Radiation source: fine-focus sealed tube	3448 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.083
Detector resolution: 10.0 pixels mm^-1	θ_max = 25.0°, θ_min = 1.6°
ϕ and ω scans	h = −7→6
Absorption correction: multi-scan (SADABS; Bruker, 1997)	k = −22→22
T_min = 0.062, T_max = 0.221	l = −30→25
15827 measured reflections

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.145	H-atom parameters constrained
S = 0.98	w = 1/[σ²(F_o²) + (0.0474P)²] where P = (F_o² + 2F_c²)/3
5585 reflections	(Δ/σ)_max < 0.001
367 parameters	Δρ_max = 1.18 e Å⁻³
6 restraints	Δρ_min = −0.72 e Å⁻³

Crystal data top

C₂H₁₀N₂²⁺·2C₉H₃Br₄O₄⁻·CH₄O	V = 3179.7 (19) Å³
M_r = 1083.67	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.456 (2) Å	µ = 10.14 mm⁻¹
b = 19.036 (7) Å	T = 298 K
c = 26.017 (9) Å	0.41 × 0.25 × 0.15 mm
β = 96.002 (6)°

Data collection top

Bruker SMART CCD area-detector diffractometer	5585 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	3448 reflections with I > 2σ(I)
T_min = 0.062, T_max = 0.221	R_int = 0.083
15827 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	6 restraints
wR(F²) = 0.145	H-atom parameters constrained
S = 0.98	Δρ_max = 1.18 e Å⁻³
5585 reflections	Δρ_min = −0.72 e Å⁻³
367 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
C13	0.2706 (12)	0.7587 (4)	0.4305 (3)	0.028 (2)
Br5	0.90144 (14)	0.74383 (5)	0.53528 (4)	0.0387 (3)
Br8	0.01592 (15)	0.76205 (5)	0.38806 (4)	0.0515 (3)
Br7	0.18589 (16)	0.89882 (5)	0.45626 (4)	0.0508 (3)
Br1	1.30682 (16)	1.00363 (5)	0.23756 (4)	0.0488 (3)
Br6	0.64413 (16)	0.89277 (5)	0.52383 (4)	0.0473 (3)
Br3	0.7771 (2)	1.01282 (6)	0.39936 (4)	0.0712 (4)
Br4	0.52006 (19)	0.87733 (7)	0.34731 (5)	0.0694 (4)
Br2	1.1722 (2)	1.07590 (7)	0.34433 (5)	0.0789 (4)
O5	0.7309 (8)	0.5905 (3)	0.5074 (2)	0.0316 (14)
O6	0.7401 (9)	0.6008 (3)	0.4220 (2)	0.0355 (15)
O2	0.9487 (9)	0.9138 (3)	0.1572 (2)	0.0366 (15)
O9	0.2812 (10)	0.7719 (3)	0.1141 (2)	0.0387 (15)
H9	0.2528	0.7917	0.1405	0.058*
C15	0.5347 (13)	0.8125 (4)	0.4890 (3)	0.029 (2)
N1	0.9242 (10)	0.4714 (3)	0.4311 (2)	0.0295 (17)
H1A	0.9667	0.4597	0.4008	0.044*
H1B	1.0283	0.4655	0.4559	0.044*
H1C	0.8841	0.5161	0.4303	0.044*
C14	0.3451 (13)	0.8158 (4)	0.4590 (3)	0.027 (2)
C4	0.7531 (14)	0.9129 (5)	0.3182 (3)	0.040 (2)
C5	0.8078 (13)	0.8814 (4)	0.2718 (3)	0.031 (2)
C11	0.3057 (13)	0.6319 (5)	0.4029 (3)	0.031 (2)
O1	1.1336 (11)	0.8281 (3)	0.1981 (2)	0.0498 (18)
C16	0.6458 (12)	0.7499 (4)	0.4910 (3)	0.0247 (18)
C19	0.5754 (12)	0.4323 (4)	0.3977 (3)	0.029 (2)
H19A	0.5067	0.4775	0.3995	0.035*
H19B	0.6339	0.4295	0.3649	0.035*
C17	0.5723 (12)	0.6915 (4)	0.4644 (3)	0.0234 (19)
N2	0.4214 (10)	0.3748 (3)	0.4012 (2)	0.0307 (17)
H2A	0.4809	0.3337	0.3956	0.046*
H2B	0.3132	0.3815	0.3776	0.046*
H2C	0.3779	0.3748	0.4326	0.046*
O4	0.7137 (11)	0.7667 (3)	0.2822 (3)	0.059 (2)
C18	0.6933 (12)	0.6221 (4)	0.4644 (3)	0.0236 (19)
O3	0.6344 (11)	0.8134 (4)	0.2056 (3)	0.061 (2)
C1	1.0757 (13)	0.9683 (5)	0.2702 (3)	0.034 (2)
C6	0.9726 (13)	0.9107 (4)	0.2478 (3)	0.0260 (19)
C12	0.3863 (12)	0.6964 (4)	0.4321 (3)	0.0212 (18)
C7	1.0268 (14)	0.8808 (5)	0.1962 (3)	0.030 (2)
O7	0.2565 (9)	0.5792 (3)	0.4236 (2)	0.0381 (15)
O8	0.2970 (10)	0.6420 (3)	0.3525 (2)	0.0475 (17)
C8	0.7027 (14)	0.8161 (5)	0.2485 (4)	0.039 (2)
C2	1.0236 (15)	0.9986 (5)	0.3156 (3)	0.039 (2)
C3	0.8613 (17)	0.9711 (5)	0.3390 (4)	0.046 (3)
C20	0.7472 (12)	0.4262 (4)	0.4415 (3)	0.029 (2)
H20A	0.6956	0.4404	0.4736	0.035*
H20B	0.7929	0.3777	0.4450	0.035*
C21	0.3236 (18)	0.7007 (5)	0.1248 (4)	0.059 (3)
H21A	0.4547	0.6966	0.1457	0.089*
H21B	0.3300	0.6757	0.0930	0.089*
H21C	0.2153	0.6813	0.1431	0.089*
C10	0.192 (2)	0.5888 (6)	0.3205 (4)	0.077 (4)
H10A	0.2580	0.5442	0.3279	0.116*
H10B	0.1982	0.6004	0.2848	0.116*
H10C	0.0488	0.5861	0.3274	0.116*
C9	0.605 (3)	0.7038 (7)	0.2652 (5)	0.112 (6)
H9A	0.4793	0.7160	0.2440	0.169*
H9B	0.5708	0.6776	0.2946	0.169*
H9C	0.6919	0.6759	0.2455	0.169*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C13	0.026 (5)	0.040 (5)	0.017 (4)	0.004 (4)	−0.001 (3)	0.010 (4)
Br5	0.0371 (5)	0.0371 (6)	0.0384 (6)	−0.0028 (4)	−0.0124 (4)	−0.0011 (4)
Br8	0.0390 (6)	0.0536 (7)	0.0570 (7)	0.0077 (5)	−0.0170 (5)	0.0117 (5)
Br7	0.0594 (7)	0.0334 (6)	0.0609 (7)	0.0211 (5)	0.0124 (5)	0.0069 (5)
Br1	0.0489 (6)	0.0493 (6)	0.0484 (7)	−0.0134 (5)	0.0065 (5)	−0.0022 (5)
Br6	0.0684 (7)	0.0281 (5)	0.0453 (6)	−0.0054 (5)	0.0055 (5)	−0.0119 (5)
Br3	0.1170 (11)	0.0641 (8)	0.0366 (6)	0.0414 (7)	0.0267 (6)	0.0001 (6)
Br4	0.0671 (8)	0.0844 (9)	0.0636 (8)	0.0141 (6)	0.0398 (6)	0.0286 (7)
Br2	0.1045 (11)	0.0677 (8)	0.0625 (8)	−0.0110 (7)	−0.0005 (7)	−0.0366 (7)
O5	0.038 (4)	0.032 (3)	0.025 (3)	0.006 (3)	0.003 (3)	0.004 (3)
O6	0.050 (4)	0.026 (3)	0.032 (4)	0.010 (3)	0.011 (3)	−0.001 (3)
O2	0.046 (4)	0.047 (4)	0.017 (3)	−0.008 (3)	0.003 (3)	0.009 (3)
O9	0.053 (4)	0.026 (3)	0.036 (4)	−0.003 (3)	0.005 (3)	−0.002 (3)
C15	0.044 (6)	0.022 (5)	0.023 (5)	0.004 (4)	0.008 (4)	0.000 (4)
N1	0.037 (4)	0.029 (4)	0.023 (4)	0.005 (3)	0.007 (3)	−0.004 (3)
C14	0.034 (5)	0.023 (5)	0.023 (5)	0.011 (4)	0.008 (4)	0.005 (4)
C4	0.037 (6)	0.059 (7)	0.027 (5)	0.022 (5)	0.012 (4)	0.023 (5)
C5	0.033 (5)	0.041 (6)	0.021 (5)	0.008 (4)	0.006 (4)	0.013 (4)
C11	0.034 (5)	0.037 (6)	0.023 (5)	−0.002 (4)	−0.001 (4)	0.001 (4)
O1	0.065 (5)	0.046 (4)	0.039 (4)	0.025 (4)	0.006 (3)	−0.006 (3)
C16	0.028 (4)	0.028 (5)	0.017 (4)	0.000 (4)	0.001 (3)	0.003 (4)
C19	0.037 (5)	0.021 (5)	0.030 (5)	0.001 (4)	0.005 (4)	0.006 (4)
C17	0.027 (5)	0.021 (5)	0.023 (5)	0.003 (3)	0.006 (4)	0.001 (4)
N2	0.033 (4)	0.035 (4)	0.022 (4)	0.000 (3)	−0.003 (3)	0.001 (3)
O4	0.078 (5)	0.043 (4)	0.055 (5)	−0.021 (4)	0.000 (4)	0.012 (4)
C18	0.022 (4)	0.022 (5)	0.026 (5)	−0.002 (3)	−0.002 (4)	0.000 (4)
O3	0.061 (5)	0.083 (6)	0.038 (4)	−0.036 (4)	0.002 (4)	−0.001 (4)
C1	0.034 (5)	0.046 (6)	0.023 (5)	0.009 (4)	0.004 (4)	0.008 (4)
C6	0.037 (5)	0.024 (5)	0.016 (4)	0.009 (4)	−0.002 (4)	0.001 (4)
C12	0.028 (5)	0.014 (4)	0.022 (5)	0.000 (3)	0.003 (4)	0.003 (3)
C7	0.037 (5)	0.034 (5)	0.021 (5)	−0.013 (4)	0.008 (4)	−0.008 (4)
O7	0.048 (4)	0.026 (3)	0.038 (4)	−0.004 (3)	−0.001 (3)	0.009 (3)
O8	0.069 (5)	0.044 (4)	0.026 (4)	−0.011 (3)	−0.011 (3)	−0.003 (3)
C8	0.039 (5)	0.053 (5)	0.025 (4)	−0.005 (4)	0.013 (4)	0.023 (4)
C2	0.051 (6)	0.040 (6)	0.025 (5)	0.009 (5)	−0.003 (4)	−0.007 (5)
C3	0.064 (7)	0.043 (6)	0.029 (6)	0.018 (5)	0.000 (5)	0.004 (5)
C20	0.034 (5)	0.037 (5)	0.015 (4)	0.002 (4)	0.001 (4)	−0.006 (4)
C21	0.096 (9)	0.028 (6)	0.052 (7)	−0.001 (6)	0.001 (6)	−0.007 (5)
C10	0.114 (11)	0.071 (9)	0.040 (7)	−0.029 (7)	−0.024 (7)	−0.014 (6)
C9	0.174 (17)	0.064 (9)	0.097 (11)	−0.052 (10)	0.006 (10)	0.011 (8)

Geometric parameters (Å, º) top

C13—C14	1.375 (11)	C16—C17	1.369 (10)
C13—C12	1.400 (10)	C19—N2	1.489 (10)
C13—Br8	1.883 (8)	C19—C20	1.509 (10)
Br5—C16	1.915 (8)	C19—H19A	0.9700
Br7—C14	1.882 (7)	C19—H19B	0.9700
Br1—C1	1.914 (9)	C17—C12	1.394 (11)
Br6—C15	1.877 (8)	C17—C18	1.533 (11)
Br3—C3	1.891 (10)	N2—H2A	0.8900
Br4—C4	1.880 (9)	N2—H2B	0.8900
Br2—C2	1.869 (9)	N2—H2C	0.8900
O5—C18	1.272 (9)	O4—C8	1.284 (10)
O6—C18	1.240 (9)	O4—C9	1.434 (13)
O2—C7	1.253 (10)	O3—C8	1.158 (10)
O9—C21	1.404 (10)	C1—C6	1.381 (11)
O9—H9	0.8200	C1—C2	1.387 (12)
C15—C14	1.382 (11)	C6—C7	1.532 (11)
C15—C16	1.389 (10)	O8—C10	1.436 (10)
N1—C20	1.478 (10)	C2—C3	1.369 (13)
N1—H1A	0.8900	C20—H20A	0.9700
N1—H1B	0.8900	C20—H20B	0.9700
N1—H1C	0.8900	C21—H21A	0.9600
C4—C3	1.388 (13)	C21—H21B	0.9600
C4—C5	1.424 (12)	C21—H21C	0.9600
C5—C6	1.405 (11)	C10—H10A	0.9600
C5—C8	1.512 (13)	C10—H10B	0.9600
C11—O7	1.197 (9)	C10—H10C	0.9600
C11—O8	1.321 (10)	C9—H9A	0.9600
C11—C12	1.506 (11)	C9—H9B	0.9600
O1—C7	1.215 (10)	C9—H9C	0.9600

C14—C13—C12	119.9 (7)	C6—C1—C2	122.7 (8)
C14—C13—Br8	121.6 (6)	C6—C1—Br1	117.1 (6)
C12—C13—Br8	118.5 (6)	C2—C1—Br1	120.1 (7)
C21—O9—H9	109.5	C1—C6—C5	118.8 (8)
C14—C15—C16	118.9 (7)	C1—C6—C7	121.4 (8)
C14—C15—Br6	120.1 (6)	C5—C6—C7	119.7 (7)
C16—C15—Br6	120.9 (6)	C17—C12—C13	119.9 (7)
C20—N1—H1A	109.5	C17—C12—C11	118.6 (7)
C20—N1—H1B	109.5	C13—C12—C11	121.3 (7)
H1A—N1—H1B	109.5	O1—C7—O2	128.7 (8)
C20—N1—H1C	109.5	O1—C7—C6	116.8 (8)
H1A—N1—H1C	109.5	O2—C7—C6	114.4 (8)
H1B—N1—H1C	109.5	C11—O8—C10	116.3 (8)
C13—C14—C15	120.5 (7)	O3—C8—O4	127.9 (10)
C13—C14—Br7	119.0 (6)	O3—C8—C5	122.3 (8)
C15—C14—Br7	120.5 (6)	O4—C8—C5	109.6 (8)
C3—C4—C5	120.4 (9)	C3—C2—C1	119.0 (9)
C3—C4—Br4	121.5 (7)	C3—C2—Br2	120.5 (7)
C5—C4—Br4	118.0 (8)	C1—C2—Br2	120.5 (8)
C6—C5—C4	118.5 (8)	C2—C3—C4	120.6 (9)
C6—C5—C8	118.4 (7)	C2—C3—Br3	120.6 (8)
C4—C5—C8	123.1 (8)	C4—C3—Br3	118.8 (8)
O7—C11—O8	125.6 (8)	N1—C20—C19	109.7 (6)
O7—C11—C12	123.4 (8)	N1—C20—H20A	109.7
O8—C11—C12	111.0 (7)	C19—C20—H20A	109.7
C17—C16—C15	121.9 (7)	N1—C20—H20B	109.7
C17—C16—Br5	119.1 (6)	C19—C20—H20B	109.7
C15—C16—Br5	118.9 (6)	H20A—C20—H20B	108.2
N2—C19—C20	109.9 (6)	O9—C21—H21A	109.5
N2—C19—H19A	109.7	O9—C21—H21B	109.5
C20—C19—H19A	109.7	H21A—C21—H21B	109.5
N2—C19—H19B	109.7	O9—C21—H21C	109.5
C20—C19—H19B	109.7	H21A—C21—H21C	109.5
H19A—C19—H19B	108.2	H21B—C21—H21C	109.5
C16—C17—C12	118.8 (7)	O8—C10—H10A	109.5
C16—C17—C18	123.3 (7)	O8—C10—H10B	109.5
C12—C17—C18	117.7 (7)	H10A—C10—H10B	109.5
C19—N2—H2A	109.5	O8—C10—H10C	109.5
C19—N2—H2B	109.5	H10A—C10—H10C	109.5
H2A—N2—H2B	109.5	H10B—C10—H10C	109.5
C19—N2—H2C	109.5	O4—C9—H9A	109.5
H2A—N2—H2C	109.5	O4—C9—H9B	109.5
H2B—N2—H2C	109.5	H9A—C9—H9B	109.5
C8—O4—C9	114.2 (9)	O4—C9—H9C	109.5
O6—C18—O5	125.7 (7)	H9A—C9—H9C	109.5
O6—C18—C17	117.0 (7)	H9B—C9—H9C	109.5
O5—C18—C17	117.2 (7)

C12—C13—C14—C15	0.6 (12)	C18—C17—C12—C11	5.4 (11)
Br8—C13—C14—C15	−178.6 (6)	C14—C13—C12—C17	2.8 (12)
C12—C13—C14—Br7	−179.8 (6)	Br8—C13—C12—C17	−178.0 (6)
Br8—C13—C14—Br7	1.0 (9)	C14—C13—C12—C11	177.7 (7)
C16—C15—C14—C13	−1.9 (12)	Br8—C13—C12—C11	−3.1 (10)
Br6—C15—C14—C13	175.4 (6)	O7—C11—C12—C17	62.5 (11)
C16—C15—C14—Br7	178.6 (6)	O8—C11—C12—C17	−117.7 (8)
Br6—C15—C14—Br7	−4.1 (10)	O7—C11—C12—C13	−112.4 (10)
C3—C4—C5—C6	−0.2 (12)	O8—C11—C12—C13	67.4 (10)
Br4—C4—C5—C6	175.6 (6)	C1—C6—C7—O1	101.9 (10)
C3—C4—C5—C8	177.3 (8)	C5—C6—C7—O1	−81.3 (10)
Br4—C4—C5—C8	−6.9 (11)	C1—C6—C7—O2	−79.9 (10)
C14—C15—C16—C17	−0.3 (13)	C5—C6—C7—O2	96.9 (9)
Br6—C15—C16—C17	−177.6 (6)	O7—C11—O8—C10	9.4 (13)
C14—C15—C16—Br5	−176.8 (6)	C12—C11—O8—C10	−170.4 (8)
Br6—C15—C16—Br5	5.9 (9)	C9—O4—C8—O3	−8.1 (16)
C15—C16—C17—C12	3.7 (12)	C9—O4—C8—C5	175.6 (10)
Br5—C16—C17—C12	−179.8 (6)	C6—C5—C8—O3	−54.1 (13)
C15—C16—C17—C18	178.1 (8)	C4—C5—C8—O3	128.5 (10)
Br5—C16—C17—C18	−5.4 (11)	C6—C5—C8—O4	122.5 (8)
C16—C17—C18—O6	−119.1 (9)	C4—C5—C8—O4	−55.0 (11)
C12—C17—C18—O6	55.3 (10)	C6—C1—C2—C3	−1.0 (13)
C16—C17—C18—O5	63.1 (11)	Br1—C1—C2—C3	−178.1 (7)
C12—C17—C18—O5	−122.5 (8)	C6—C1—C2—Br2	179.1 (6)
C2—C1—C6—C5	0.1 (12)	Br1—C1—C2—Br2	2.0 (10)
Br1—C1—C6—C5	177.3 (6)	C1—C2—C3—C4	1.3 (14)
C2—C1—C6—C7	176.9 (8)	Br2—C2—C3—C4	−178.8 (6)
Br1—C1—C6—C7	−5.9 (10)	C1—C2—C3—Br3	−177.4 (6)
C4—C5—C6—C1	0.5 (12)	Br2—C2—C3—Br3	2.4 (11)
C8—C5—C6—C1	−177.1 (7)	C5—C4—C3—C2	−0.7 (13)
C4—C5—C6—C7	−176.4 (7)	Br4—C4—C3—C2	−176.4 (7)
C8—C5—C6—C7	6.0 (12)	C5—C4—C3—Br3	178.0 (6)
C16—C17—C12—C13	−4.9 (12)	Br4—C4—C3—Br3	2.4 (10)
C18—C17—C12—C13	−179.6 (7)	N2—C19—C20—N1	166.0 (6)
C16—C17—C12—C11	−179.9 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.89	1.87	2.748 (8)	167
N1—H1B···O5ⁱⁱ	0.89	2.04	2.857 (8)	153
N1—H1C···O6	0.89	1.86	2.734 (8)	166
N2—H2A···O9ⁱⁱⁱ	0.89	1.97	2.801 (9)	154
N2—H2B···O2ⁱⁱⁱ	0.89	1.93	2.795 (9)	163
N2—H2B···O3ⁱⁱⁱ	0.89	2.57	3.000 (9)	110
N2—H2C···O5^iv	0.89	1.90	2.747 (9)	159
O9—H9···O1^v	0.82	1.89	2.695 (8)	168

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

Experimental details

Crystal data
Chemical formula	C₂H₁₀N₂²⁺·2C₉H₃Br₄O₄⁻·CH₄O
M_r	1083.67
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	6.456 (2), 19.036 (7), 26.017 (9)
β (°)	96.002 (6)
V (Å³)	3179.7 (19)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	10.14
Crystal size (mm)	0.41 × 0.25 × 0.15

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.062, 0.221
No. of measured, independent and observed [I > 2σ(I)] reflections	15827, 5585, 3448
R_int	0.083
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.145, 0.98
No. of reflections	5585
No. of parameters	367
No. of restraints	6
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.18, −0.72

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1998), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.89	1.87	2.748 (8)	166.6
N1—H1B···O5ⁱⁱ	0.89	2.04	2.857 (8)	152.5
N1—H1C···O6	0.89	1.86	2.734 (8)	166.4
N2—H2A···O9ⁱⁱⁱ	0.89	1.97	2.801 (9)	154.3
N2—H2B···O2ⁱⁱⁱ	0.89	1.93	2.795 (9)	162.5
N2—H2B···O3ⁱⁱⁱ	0.89	2.57	3.000 (9)	110.2
N2—H2C···O5^iv	0.89	1.90	2.747 (9)	159.0
O9—H9···O1^v	0.82	1.89	2.695 (8)	168.2

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

Acknowledgements

This work was supported by the Natural Science Foundation of Shandong Province (grant No. Y2007B61).

References

Brandenburg, K. (1998). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (1997). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Liang, Z.-P., Li, J. & Huang, B.-Y. (2006). Acta Cryst. E62, o4761–o4762. Web of Science CSD CrossRef IUCr Journals Google Scholar
Liang, Z.-P., Li, J., Hua, Y. & Wang, H.-L. (2007). Acta Cryst. E63, o3065. Web of Science CSD CrossRef IUCr Journals Google Scholar
Politzer, P., Lane, P., Concha, M. C., Ma, Y. & Murray, J. S. (2007). J. Mol. Model. 13, 305–11. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 64| Part 12| December 2008| Page o2416

doi:10.1107/S1600536808038166

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Ethane-1,2-diaminium 3,4,5,6-tetra­bromo-2-(meth­oxy­carbon­yl)benzoate methanol solvate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

Ethane-1,2-diaminium 3,4,5,6-tetrabromo-2-(methoxycarbonyl)benzoate methanol solvate