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

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ISSN: 2056-9890

Ethanaminium 3,4,5,6-tetra­bromo-2-(meth­­oxy­carbon­yl)benzoate methanol monosolvate

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

(Received 10 December 2010; accepted 15 December 2010; online 18 December 2010)

In the crystal structure of the title compound, C2H8N+·C9H3Br4O4·CH4O, inter­molecular N—H⋯O and O—H⋯O hydrogen bonds link the components into chains along [001]. Additional stabilization is supplied by weak C—H⋯O and C—H⋯Br inter­actions.

Related literature

For a related structure, see: Liang (2008[Liang, Z.-P. (2008). Acta Cryst. E64, o2416.]).

[Scheme 1]

Experimental

Crystal data
  • C2H8N+·C9H3Br4O4·CH4O

  • Mr = 572.89

  • Monoclinic, P 21 /c

  • a = 9.4651 (8) Å

  • b = 25.6544 (19) Å

  • c = 8.3365 (6) Å

  • β = 112.787 (1)°

  • V = 1866.3 (2) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 8.64 mm−1

  • T = 298 K

  • 0.40 × 0.35 × 0.33 mm

Data collection
  • Bruker SMART CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 1997[Bruker (1997). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.130, Tmax = 0.163

  • 9436 measured reflections

  • 3295 independent reflections

  • 1454 reflections with I > 2σ(I)

  • Rint = 0.086

Refinement
  • R[F2 > 2σ(F2)] = 0.042

  • wR(F2) = 0.068

  • S = 0.99

  • 3295 reflections

  • 200 parameters

  • H-atom parameters constrained

  • Δρmax = 0.49 e Å−3

  • Δρmin = −0.51 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1A⋯O4i 0.89 1.94 2.772 (9) 155
N1—H1B⋯O5 0.89 1.92 2.810 (9) 174
N1—H1C⋯O3ii 0.89 1.99 2.871 (7) 170
N1—H1C⋯O4ii 0.89 2.58 3.249 (8) 132
O5—H5⋯O3 0.82 1.90 2.705 (8) 165
C10—H10A⋯Br3iii 0.97 2.92 3.736 (8) 143
C11—H11B⋯O2iv 0.96 2.47 3.357 (10) 153
Symmetry codes: (i) x, y, z+1; (ii) [x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]; (iii) -x+1, -y+2, -z+1; (iv) x-1, y, z.

Data collection: SMART (Bruker, 1997[Bruker (1997). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 1997[Bruker (1997). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

4,5,6,7-Tetrabromo-2-ethylisoindoline-1,3-dione is an important flame retardant. 2-(Methoxycarbonyl)-3,4,5,6-tetrabromobenzoic acid is an intermediate in the sytnthesis of this flame retardant. In this paper, the structure of the title compound is reported. The asymmetric unit of the title compound (I) contains one ethanaminium cation, one 2-(methoxycarbonyl)-3,4,5,6-tetrabromobenzoate anion and one methanol solvent molecule (Fig. 1). The bond lengths and angles agree with those in ethane-1,2-diaminium 2-(methoxycarbonyl)-3,4,5,6-tetrabromo benzoate methanol solvate (Liang, 2008). In the crystal structure, intermolecular N—H···O and O—H···O hydrogen bonds link the components of the structure into one-dimensional chains along [001](see fig. 2). Additional stabilization is supplied by weak C—H···O and C—H···Br interactions.

Related literature top

For a related structure, see: Liang (2008).

Experimental top

A mixture of 4,5,6,7-tetrabromoisobenzofuran-1,3-dione (4.64 g, 0.01 mol) and methanol (15 ml) was refluxed for 0.5 h. And then ethanamine (0.45 g, 0.01 mol) was added to the above solution, and mixed for 10 min at room temperature. The solution was kept at room temperature for 3 d. Natural evaporation gave colourless single crystals of the title compound, suitable for X-ray analysis.

Refinement top

H atoms were initially located from difference maps and then refined in a riding model with C—H = 0.96–0.97 Å, N—H = 0.89 Å, O-H = 0.82Å and Uiso(H) = 1.2Ueq(C) or 1.5Ueq(O, N, methyl C).

Structure description top

4,5,6,7-Tetrabromo-2-ethylisoindoline-1,3-dione is an important flame retardant. 2-(Methoxycarbonyl)-3,4,5,6-tetrabromobenzoic acid is an intermediate in the sytnthesis of this flame retardant. In this paper, the structure of the title compound is reported. The asymmetric unit of the title compound (I) contains one ethanaminium cation, one 2-(methoxycarbonyl)-3,4,5,6-tetrabromobenzoate anion and one methanol solvent molecule (Fig. 1). The bond lengths and angles agree with those in ethane-1,2-diaminium 2-(methoxycarbonyl)-3,4,5,6-tetrabromo benzoate methanol solvate (Liang, 2008). In the crystal structure, intermolecular N—H···O and O—H···O hydrogen bonds link the components of the structure into one-dimensional chains along [001](see fig. 2). Additional stabilization is supplied by weak C—H···O and C—H···Br interactions.

For a related structure, see: Liang (2008).

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
[Figure 1] Fig. 1. The asymmetric unit of (I), drawn with 30% probability ellipsoids.
[Figure 2] Fig. 2. The crystal packing of (I). Hydrogen bonds are indicated by dashed lines.
Ethanaminium 3,4,5,6-tetrabromo-2-(methoxycarbonyl)benzoate methanol monosolvate top
Crystal data top
C2H8N+·C9H3Br4O4·CH4OF(000) = 1096
Mr = 572.89Dx = 2.039 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1513 reflections
a = 9.4651 (8) Åθ = 2.3–20.6°
b = 25.6544 (19) ŵ = 8.64 mm1
c = 8.3365 (6) ÅT = 298 K
β = 112.787 (1)°Block, colorless
V = 1866.3 (2) Å30.40 × 0.35 × 0.33 mm
Z = 4
Data collection top
Bruker SMART CCD
diffractometer
3295 independent reflections
Radiation source: fine-focus sealed tube1454 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.086
φ and ω scansθmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
h = 911
Tmin = 0.130, Tmax = 0.163k = 3030
9436 measured reflectionsl = 98
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.068H-atom parameters constrained
S = 0.99 w = 1/[σ2(Fo2) + (0.0024P)2]
where P = (Fo2 + 2Fc2)/3
3295 reflections(Δ/σ)max = 0.001
200 parametersΔρmax = 0.49 e Å3
0 restraintsΔρmin = 0.51 e Å3
Crystal data top
C2H8N+·C9H3Br4O4·CH4OV = 1866.3 (2) Å3
Mr = 572.89Z = 4
Monoclinic, P21/cMo Kα radiation
a = 9.4651 (8) ŵ = 8.64 mm1
b = 25.6544 (19) ÅT = 298 K
c = 8.3365 (6) Å0.40 × 0.35 × 0.33 mm
β = 112.787 (1)°
Data collection top
Bruker SMART CCD
diffractometer
3295 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
1454 reflections with I > 2σ(I)
Tmin = 0.130, Tmax = 0.163Rint = 0.086
9436 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.068H-atom parameters constrained
S = 0.99Δρmax = 0.49 e Å3
3295 reflectionsΔρmin = 0.51 e Å3
200 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
xyzUiso*/Ueq
Br10.32729 (8)0.90633 (3)0.26426 (13)0.0702 (3)
Br20.40752 (9)1.03175 (3)0.25156 (12)0.0705 (3)
Br30.73585 (10)1.06551 (3)0.23297 (14)0.0807 (3)
Br40.98266 (9)0.97499 (3)0.23443 (13)0.0773 (3)
N10.5436 (6)0.7996 (2)0.8034 (8)0.0546 (19)
H1A0.53760.81330.89860.082*
H1B0.61860.81510.78200.082*
H1C0.56310.76560.81960.082*
O10.8313 (6)0.8333 (2)0.1273 (8)0.0672 (18)
O20.9937 (7)0.8565 (2)0.3871 (9)0.101 (3)
O30.6431 (6)0.8063 (2)0.3863 (8)0.076 (2)
O40.4945 (6)0.8125 (2)0.1079 (8)0.0713 (19)
O50.7663 (7)0.8481 (2)0.7090 (7)0.104 (2)
H50.74130.83830.60810.157*
C10.8783 (9)0.8620 (3)0.2667 (14)0.050 (3)
C20.5820 (10)0.8306 (3)0.2499 (14)0.050 (3)
C30.7630 (7)0.9042 (3)0.2521 (9)0.0369 (19)
C40.6200 (8)0.8886 (3)0.2517 (9)0.040 (2)
C50.5158 (7)0.9276 (3)0.2534 (9)0.040 (2)
C60.5515 (7)0.9794 (3)0.2527 (9)0.047 (2)
C70.6915 (8)0.9947 (3)0.2450 (10)0.045 (2)
C80.7960 (7)0.9565 (3)0.2469 (9)0.040 (2)
C90.9329 (9)0.7886 (3)0.1323 (11)0.097 (3)
H9A1.03670.80060.16850.146*
H9B0.90100.77340.01850.146*
H9C0.92660.76290.21310.146*
C100.3935 (9)0.8076 (3)0.6508 (10)0.056 (2)
H10A0.37300.84470.63330.068*
H10B0.40180.79370.54660.068*
C110.2643 (8)0.7820 (3)0.6773 (10)0.081 (3)
H11A0.27630.74490.67660.121*
H11B0.16970.79190.58540.121*
H11C0.26300.79260.78720.121*
C120.8988 (9)0.8774 (3)0.7572 (12)0.104 (4)
H12A0.91410.89590.86270.155*
H12B0.88990.90190.66670.155*
H12C0.98440.85480.77570.155*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0399 (5)0.0808 (7)0.1016 (9)0.0038 (5)0.0403 (6)0.0061 (6)
Br20.0615 (6)0.0617 (6)0.0956 (8)0.0286 (5)0.0386 (6)0.0063 (6)
Br30.0898 (7)0.0337 (5)0.1331 (10)0.0058 (5)0.0592 (7)0.0010 (6)
Br40.0455 (6)0.0699 (7)0.1306 (10)0.0122 (5)0.0496 (6)0.0070 (6)
N10.061 (5)0.042 (4)0.072 (6)0.011 (3)0.039 (4)0.000 (4)
O10.057 (4)0.063 (4)0.077 (5)0.027 (3)0.022 (4)0.014 (4)
O20.068 (4)0.114 (6)0.085 (6)0.048 (4)0.011 (4)0.033 (4)
O30.101 (5)0.044 (4)0.070 (5)0.006 (3)0.020 (4)0.019 (4)
O40.094 (5)0.062 (4)0.062 (5)0.038 (3)0.035 (4)0.021 (4)
O50.101 (5)0.150 (6)0.074 (6)0.064 (4)0.048 (4)0.018 (4)
C10.036 (6)0.042 (6)0.072 (9)0.003 (5)0.020 (6)0.009 (6)
C20.047 (6)0.036 (6)0.075 (9)0.006 (5)0.035 (6)0.005 (6)
C30.031 (4)0.028 (4)0.057 (6)0.003 (4)0.023 (4)0.005 (5)
C40.043 (5)0.032 (5)0.043 (6)0.007 (4)0.017 (5)0.002 (4)
C50.026 (4)0.038 (5)0.060 (6)0.007 (4)0.021 (4)0.004 (5)
C60.035 (5)0.045 (6)0.058 (6)0.014 (4)0.016 (5)0.001 (4)
C70.032 (5)0.033 (5)0.068 (6)0.003 (4)0.019 (5)0.003 (4)
C80.016 (4)0.041 (5)0.062 (6)0.001 (4)0.014 (4)0.002 (5)
C90.090 (7)0.080 (7)0.106 (9)0.045 (6)0.022 (6)0.025 (6)
C100.077 (6)0.046 (6)0.040 (6)0.018 (5)0.015 (6)0.009 (5)
C110.052 (6)0.097 (7)0.085 (8)0.013 (5)0.017 (6)0.016 (6)
C120.082 (7)0.100 (8)0.144 (10)0.050 (6)0.060 (7)0.030 (7)
Geometric parameters (Å, º) top
Br1—C51.902 (6)C3—C41.411 (8)
Br2—C61.911 (6)C4—C51.410 (8)
Br3—C71.876 (6)C5—C61.370 (8)
Br4—C81.871 (6)C6—C71.408 (7)
N1—C101.509 (8)C7—C81.389 (8)
N1—H1A0.8900C9—H9A0.9600
N1—H1B0.8900C9—H9B0.9600
N1—H1C0.8900C9—H9C0.9600
O1—C11.301 (9)C10—C111.478 (8)
O1—C91.487 (7)C10—H10A0.9700
O2—C11.171 (9)C10—H10B0.9700
O3—C21.227 (9)C11—H11A0.9600
O4—C21.241 (9)C11—H11B0.9600
O5—C121.381 (7)C11—H11C0.9600
O5—H50.8200C12—H12A0.9600
C1—C31.507 (9)C12—H12B0.9600
C2—C41.530 (9)C12—H12C0.9600
C3—C81.381 (7)
C10—N1—H1A109.5C6—C7—Br3120.5 (5)
C10—N1—H1B109.5C3—C8—C7121.2 (6)
H1A—N1—H1B109.5C3—C8—Br4118.6 (5)
C10—N1—H1C109.5C7—C8—Br4120.2 (5)
H1A—N1—H1C109.5O1—C9—H9A109.5
H1B—N1—H1C109.5O1—C9—H9B109.5
C1—O1—C9114.7 (6)H9A—C9—H9B109.5
C12—O5—H5109.5O1—C9—H9C109.5
O2—C1—O1125.5 (8)H9A—C9—H9C109.5
O2—C1—C3124.2 (9)H9B—C9—H9C109.5
O1—C1—C3110.4 (7)C11—C10—N1112.1 (6)
O3—C2—O4126.6 (8)C11—C10—H10A109.2
O3—C2—C4117.4 (8)N1—C10—H10A109.2
O4—C2—C4116.0 (8)C11—C10—H10B109.2
C8—C3—C4120.3 (6)N1—C10—H10B109.2
C8—C3—C1122.3 (6)H10A—C10—H10B107.9
C4—C3—C1117.4 (6)C10—C11—H11A109.5
C5—C4—C3118.2 (6)C10—C11—H11B109.5
C5—C4—C2121.9 (7)H11A—C11—H11B109.5
C3—C4—C2119.9 (6)C10—C11—H11C109.5
C6—C5—C4121.0 (6)H11A—C11—H11C109.5
C6—C5—Br1121.0 (5)H11B—C11—H11C109.5
C4—C5—Br1118.0 (5)O5—C12—H12A109.5
C5—C6—C7120.6 (6)O5—C12—H12B109.5
C5—C6—Br2120.3 (5)H12A—C12—H12B109.5
C7—C6—Br2119.0 (6)O5—C12—H12C109.5
C8—C7—C6118.8 (6)H12A—C12—H12C109.5
C8—C7—Br3120.8 (5)H12B—C12—H12C109.5
C9—O1—C1—O23.5 (13)C2—C4—C5—Br12.8 (10)
C9—O1—C1—C3176.8 (6)C4—C5—C6—C71.9 (11)
O2—C1—C3—C864.3 (12)Br1—C5—C6—C7179.9 (5)
O1—C1—C3—C8115.3 (8)C4—C5—C6—Br2179.1 (5)
O2—C1—C3—C4112.9 (10)Br1—C5—C6—Br22.9 (9)
O1—C1—C3—C467.5 (9)C5—C6—C7—C83.2 (11)
C8—C3—C4—C52.7 (10)Br2—C6—C7—C8179.6 (6)
C1—C3—C4—C5174.6 (7)C5—C6—C7—Br3177.0 (6)
C8—C3—C4—C2177.5 (7)Br2—C6—C7—Br30.2 (8)
C1—C3—C4—C25.3 (11)C4—C3—C8—C71.4 (11)
O3—C2—C4—C5104.5 (9)C1—C3—C8—C7175.7 (8)
O4—C2—C4—C577.2 (10)C4—C3—C8—Br4176.4 (5)
O3—C2—C4—C375.3 (10)C1—C3—C8—Br46.4 (11)
O4—C2—C4—C3103.0 (8)C6—C7—C8—C31.5 (11)
C3—C4—C5—C61.0 (10)Br3—C7—C8—C3178.7 (5)
C2—C4—C5—C6179.1 (7)C6—C7—C8—Br4179.3 (5)
C3—C4—C5—Br1177.0 (5)Br3—C7—C8—Br40.9 (9)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O4i0.891.942.772 (9)155
N1—H1B···O50.891.922.810 (9)174
N1—H1C···O3ii0.891.992.871 (7)170
N1—H1C···O4ii0.892.583.249 (8)132
O5—H5···O30.821.902.705 (8)165
C10—H10A···Br3iii0.972.923.736 (8)143
C11—H11B···O2iv0.962.473.357 (10)153
Symmetry codes: (i) x, y, z+1; (ii) x, y+3/2, z+1/2; (iii) x+1, y+2, z+1; (iv) x1, y, z.

Experimental details

Crystal data
Chemical formulaC2H8N+·C9H3Br4O4·CH4O
Mr572.89
Crystal system, space groupMonoclinic, P21/c
Temperature (K)298
a, b, c (Å)9.4651 (8), 25.6544 (19), 8.3365 (6)
β (°) 112.787 (1)
V3)1866.3 (2)
Z4
Radiation typeMo Kα
µ (mm1)8.64
Crystal size (mm)0.40 × 0.35 × 0.33
Data collection
DiffractometerBruker SMART CCD
Absorption correctionMulti-scan
(SADABS; Bruker, 1997)
Tmin, Tmax0.130, 0.163
No. of measured, independent and
observed [I > 2σ(I)] reflections
9436, 3295, 1454
Rint0.086
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.068, 0.99
No. of reflections3295
No. of parameters200
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.49, 0.51

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···AD—HH···AD···AD—H···A
N1—H1A···O4i0.891.942.772 (9)155
N1—H1B···O50.891.922.810 (9)174
N1—H1C···O3ii0.891.992.871 (7)170
N1—H1C···O4ii0.892.583.249 (8)132
O5—H5···O30.821.902.705 (8)165
C10—H10A···Br3iii0.972.923.736 (8)143
C11—H11B···O2iv0.962.473.357 (10)153
Symmetry codes: (i) x, y, z+1; (ii) x, y+3/2, z+1/2; (iii) x+1, y+2, z+1; (iv) x1, y, z.
 

Acknowledgements

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

References

First citationBruker (1997). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationLiang, Z.-P. (2008). Acta Cryst. E64, o2416.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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