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Acta Crystallogr Sect E Struct Rep Online. 2008 June 1; 64(Pt 6): o1152.
Published online 2008 May 24. doi:  10.1107/S1600536808015201
PMCID: PMC2961518

Bis(isobutyl­ammonium) phthalate monohydrate

Abstract

N-Isobutyl­phthalimic acid hydrolyzes to the title salt, 2C4H12N+·C8H4O4 ·H2O, which adopts a hydrogen-bonded layer structure. In the anion, the carboxyl­ate groups are twisted with respect to the benzene ring [dihedral angles = 43.8 (1) and 50.9 (1)°].

Related literature

For kinetic studies relating to the hydrolysis of N-isobutyl­phthalimic acid, see: Ariffin & Khan (2005 [triangle]); Khan & Ariffin (2003 [triangle]).

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Object name is e-64-o1152-scheme1.jpg

Experimental

Crystal data

  • 2C4H12N+·C8H4O4 2−·H2O
  • M r = 330.42
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1152-efi1.jpg
  • a = 8.8647 (4) Å
  • b = 9.4340 (5) Å
  • c = 12.9119 (6) Å
  • α = 72.298 (3)°
  • β = 79.449 (3)°
  • γ = 69.059 (3)°
  • V = 957.37 (8) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 100 (2) K
  • 0.32 × 0.08 × 0.08 mm

Data collection

  • Bruker SMART APEX diffractometer
  • Absorption correction: none
  • 8057 measured reflections
  • 4343 independent reflections
  • 2454 reflections with I > 2σ(I)
  • R int = 0.050

Refinement

  • R[F 2 > 2σ(F 2)] = 0.061
  • wR(F 2) = 0.156
  • S = 0.97
  • 4343 reflections
  • 241 parameters
  • 15 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.33 e Å−3
  • Δρmin = −0.27 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2008 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808015201/lh2629sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808015201/lh2629Isup2.hkl

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

Acknowledgments

We acknowledge the SAGA grant (06–02-03–0147) for supporting this study, and the University of Malaya for the purchase of the diffractometer.

supplementary crystallographic information

Comment

The title salt (Fig. 1) was obtained as a wet crystalline compound when N-isobutylphthalimic acid was left aside for several years. The acid has been shown by kinetic studies to be converted to phthalic acid and isobutylamine under neutral and acidic conditions (Ariffin & Khan, 2005; Khan Ariffin, 2003). In the anion, the carboxyl –CO2 groups are twisted with respect to the phenylene ring [dihedral angles 43.8 (1) and 50.9 (1) °]. Hydrogen bonds which involve the ammonium cations and water molecules link the components of the salt into a layer motif (Table 1).

Experimental

N-Isobutylphthalimidic acid was synthesized as described earlier (Ariffin & Khan, 2005; Khan & Ariffin, 2003). The crystalline compound was left aside for several years. The hydrolyzed title salt was obtained as a wet crystalline compound.

Refinement

Carbon-bound H-atoms were placed in calculated positions (C—H 0.95 to 0.99 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2–1.5U(C). The oxygen- and nitrogen-bound H-atoms were located in a difference Fourier map, and were refined with restraints of O–H = N–H = 0.85±0.01 Å; H···H = 1.39±0.01 Å; their temperature factors were freely refined.

Figures

Fig. 1.
Thermal ellipsoid plot (Barbour, 2001) of [C4H12N]2[C8H4O4].H2O at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radiius.

Crystal data

2C4H12N+·C8H4O42–·H2OZ = 2
Mr = 330.42F000 = 360
Triclinic, P1Dx = 1.146 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 8.8647 (4) ÅCell parameters from 941 reflections
b = 9.4340 (5) Åθ = 2.5–22.7º
c = 12.9119 (6) ŵ = 0.08 mm1
α = 72.298 (3)ºT = 100 (2) K
β = 79.449 (3)ºPrism, colorless
γ = 69.059 (3)º0.32 × 0.08 × 0.08 mm
V = 957.37 (8) Å3

Data collection

Bruker SMART APEX diffractometer2454 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.050
Monochromator: graphiteθmax = 27.5º
T = 100(2) Kθmin = 2.5º
ω scansh = −11→11
Absorption correction: Nonek = −10→12
8057 measured reflectionsl = −16→16
4343 independent reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.061H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.156  w = 1/[σ2(Fo2) + (0.0703P)2] where P = (Fo2 + 2Fc2)/3
S = 0.97(Δ/σ)max = 0.001
4343 reflectionsΔρmax = 0.33 e Å3
241 parametersΔρmin = −0.27 e Å3
15 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.049 (5)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
O10.49468 (17)0.58257 (19)0.62388 (12)0.0271 (4)
O20.75147 (17)0.58034 (18)0.58411 (12)0.0250 (4)
O30.86510 (16)0.23828 (19)0.58460 (12)0.0254 (4)
O41.08162 (16)0.21636 (19)0.66133 (12)0.0285 (4)
O1w0.7147 (2)0.8989 (2)0.50641 (15)0.0342 (4)
H1w10.696 (3)0.811 (2)0.535 (2)0.078 (12)*
H1w20.785 (3)0.887 (3)0.4520 (18)0.096 (14)*
N10.4142 (2)0.8164 (2)0.43079 (16)0.0230 (5)
H1n10.448 (3)0.7460 (19)0.4886 (14)0.062 (10)*
H1n20.3266 (18)0.809 (2)0.4159 (16)0.034 (7)*
H1n30.391 (2)0.9076 (13)0.4421 (17)0.028 (7)*
N20.9312 (2)0.4473 (3)0.39672 (16)0.0259 (5)
H2n10.873 (2)0.5321 (15)0.4154 (19)0.054 (9)*
H2n21.0323 (12)0.440 (2)0.3961 (17)0.042 (8)*
H2n30.917 (2)0.3689 (16)0.4499 (14)0.037 (8)*
C10.6391 (3)0.5332 (3)0.64401 (17)0.0216 (5)
C20.6832 (2)0.4119 (3)0.75120 (17)0.0212 (5)
C30.5823 (3)0.4347 (3)0.84480 (18)0.0265 (5)
H30.48500.52150.83930.032*
C40.6217 (3)0.3327 (3)0.94606 (19)0.0338 (6)
H40.55090.34891.00920.041*
C50.7644 (3)0.2070 (3)0.95501 (19)0.0326 (6)
H50.79280.13781.02440.039*
C60.8653 (3)0.1828 (3)0.86233 (18)0.0268 (6)
H60.96300.09640.86880.032*
C70.8264 (2)0.2824 (3)0.76022 (17)0.0207 (5)
C80.9328 (2)0.2442 (3)0.66050 (18)0.0217 (5)
C90.5386 (2)0.7900 (3)0.33858 (17)0.0231 (5)
H9A0.55350.68650.32730.028*
H9B0.64300.78610.35840.028*
C100.4971 (3)0.9152 (3)0.23207 (19)0.0309 (6)
H100.38830.92360.21480.037*
C110.4909 (3)1.0755 (3)0.2390 (2)0.0464 (8)
H11A0.40911.10740.29700.070*
H11B0.46261.15290.16920.070*
H11C0.59721.06930.25530.070*
C120.6223 (3)0.8638 (3)0.14157 (19)0.0369 (7)
H12A0.62510.76050.13830.055*
H12B0.72930.85750.15650.055*
H12C0.59310.94050.07160.055*
C130.8993 (3)0.4525 (3)0.28710 (19)0.0308 (6)
H13A0.91740.54690.23400.037*
H13B0.78450.46110.28770.037*
C141.0072 (3)0.3079 (3)0.2514 (2)0.0397 (7)
H141.12140.29210.26270.048*
C150.9981 (5)0.3334 (5)0.1306 (3)0.0870 (13)
H15A1.02640.42770.08930.130*
H15B0.88780.34690.11740.130*
H15C1.07430.24210.10690.130*
C160.9674 (5)0.1631 (4)0.3167 (3)0.0663 (10)
H16A0.97320.14930.39440.100*
H16B1.04520.07150.29410.100*
H16C0.85760.17360.30430.100*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0211 (8)0.0247 (10)0.0298 (9)−0.0054 (7)−0.0062 (7)0.0010 (7)
O20.0246 (8)0.0226 (9)0.0271 (8)−0.0104 (7)−0.0012 (7)−0.0027 (7)
O30.0224 (8)0.0283 (10)0.0282 (9)−0.0094 (7)−0.0021 (7)−0.0094 (7)
O40.0175 (8)0.0308 (10)0.0379 (10)−0.0074 (7)−0.0028 (7)−0.0102 (8)
O1w0.0366 (10)0.0226 (11)0.0420 (11)−0.0109 (8)0.0042 (9)−0.0093 (9)
N10.0209 (10)0.0173 (12)0.0286 (12)−0.0047 (8)−0.0045 (9)−0.0031 (10)
N20.0240 (10)0.0219 (12)0.0325 (12)−0.0080 (9)−0.0040 (9)−0.0063 (10)
C10.0250 (11)0.0155 (12)0.0251 (12)−0.0066 (10)−0.0013 (10)−0.0068 (10)
C20.0227 (11)0.0195 (13)0.0227 (12)−0.0086 (10)−0.0027 (9)−0.0047 (10)
C30.0275 (12)0.0233 (14)0.0256 (13)−0.0045 (10)−0.0033 (10)−0.0060 (10)
C40.0405 (14)0.0363 (17)0.0227 (13)−0.0132 (12)0.0010 (11)−0.0059 (12)
C50.0423 (14)0.0301 (15)0.0227 (13)−0.0113 (12)−0.0097 (11)0.0005 (11)
C60.0286 (12)0.0230 (14)0.0292 (13)−0.0081 (10)−0.0092 (10)−0.0034 (11)
C70.0203 (11)0.0199 (13)0.0235 (12)−0.0093 (10)−0.0032 (9)−0.0039 (10)
C80.0200 (11)0.0136 (12)0.0295 (13)−0.0051 (9)−0.0045 (9)−0.0015 (10)
C90.0207 (11)0.0201 (13)0.0270 (12)−0.0065 (9)−0.0023 (9)−0.0038 (10)
C100.0253 (12)0.0320 (15)0.0301 (13)−0.0098 (11)−0.0068 (10)0.0027 (11)
C110.0577 (17)0.0253 (16)0.0409 (16)−0.0109 (13)0.0083 (14)0.0027 (13)
C120.0443 (15)0.0433 (18)0.0267 (13)−0.0213 (13)−0.0027 (12)−0.0059 (12)
C130.0396 (14)0.0233 (14)0.0286 (13)−0.0081 (11)−0.0115 (11)−0.0029 (11)
C140.0430 (15)0.0404 (18)0.0359 (15)−0.0071 (13)−0.0066 (12)−0.0156 (13)
C150.139 (4)0.091 (3)0.0396 (19)−0.038 (3)−0.001 (2)−0.031 (2)
C160.116 (3)0.0258 (18)0.060 (2)−0.0150 (18)−0.023 (2)−0.0156 (16)

Geometric parameters (Å, °)

O1—C11.243 (2)C7—C81.507 (3)
O2—C11.270 (2)C9—C101.519 (3)
O3—C81.263 (3)C9—H9A0.9900
O4—C81.251 (2)C9—H9B0.9900
O1w—H1w10.861 (10)C10—C121.522 (3)
O1w—H1w20.858 (10)C10—C111.523 (4)
N1—C91.483 (3)C10—H101.0000
N1—H1n10.852 (9)C11—H11A0.9800
N1—H1n20.865 (9)C11—H11B0.9800
N1—H1n30.861 (9)C11—H11C0.9800
N2—C131.477 (3)C12—H12A0.9800
N2—H2n10.860 (9)C12—H12B0.9800
N2—H2n20.874 (9)C12—H12C0.9800
N2—H2n30.873 (9)C13—C141.508 (4)
C1—C21.514 (3)C13—H13A0.9900
C2—C31.389 (3)C13—H13B0.9900
C2—C71.406 (3)C14—C161.496 (4)
C3—C41.386 (3)C14—C151.518 (4)
C3—H30.9500C14—H141.0000
C4—C51.384 (3)C15—H15A0.9800
C4—H40.9500C15—H15B0.9800
C5—C61.383 (3)C15—H15C0.9800
C5—H50.9500C16—H16A0.9800
C6—C71.386 (3)C16—H16B0.9800
C6—H60.9500C16—H16C0.9800
H1w1—O1w—H1w2107.2 (15)C9—C10—C12108.7 (2)
C9—N1—H1n1109.2 (17)C9—C10—C11112.0 (2)
C9—N1—H1n2108.1 (14)C12—C10—C11110.4 (2)
H1n1—N1—H1n2109.4 (13)C9—C10—H10108.5
C9—N1—H1n3113.4 (15)C12—C10—H10108.5
H1n1—N1—H1n3108.9 (13)C11—C10—H10108.5
H1n2—N1—H1n3107.9 (12)C10—C11—H11A109.5
C13—N2—H2n1111.6 (16)C10—C11—H11B109.5
C13—N2—H2n2109.3 (15)H11A—C11—H11B109.5
H2n1—N2—H2n2106.4 (13)C10—C11—H11C109.5
C13—N2—H2n3116.3 (15)H11A—C11—H11C109.5
H2n1—N2—H2n3107.0 (13)H11B—C11—H11C109.5
H2n2—N2—H2n3105.7 (13)C10—C12—H12A109.5
O1—C1—O2125.4 (2)C10—C12—H12B109.5
O1—C1—C2117.22 (19)H12A—C12—H12B109.5
O2—C1—C2117.30 (18)C10—C12—H12C109.5
C3—C2—C7119.0 (2)H12A—C12—H12C109.5
C3—C2—C1118.49 (19)H12B—C12—H12C109.5
C7—C2—C1122.38 (19)N2—C13—C14111.78 (19)
C4—C3—C2121.0 (2)N2—C13—H13A109.3
C4—C3—H3119.5C14—C13—H13A109.3
C2—C3—H3119.5N2—C13—H13B109.3
C5—C4—C3119.9 (2)C14—C13—H13B109.3
C5—C4—H4120.1H13A—C13—H13B107.9
C3—C4—H4120.1C16—C14—C13112.4 (2)
C6—C5—C4119.6 (2)C16—C14—C15110.8 (3)
C6—C5—H5120.2C13—C14—C15110.0 (3)
C4—C5—H5120.2C16—C14—H14107.8
C5—C6—C7121.2 (2)C13—C14—H14107.8
C5—C6—H6119.4C15—C14—H14107.8
C7—C6—H6119.4C14—C15—H15A109.5
C6—C7—C2119.3 (2)C14—C15—H15B109.5
C6—C7—C8119.4 (2)H15A—C15—H15B109.5
C2—C7—C8121.22 (19)C14—C15—H15C109.5
O4—C8—O3125.5 (2)H15A—C15—H15C109.5
O4—C8—C7117.10 (19)H15B—C15—H15C109.5
O3—C8—C7117.40 (18)C14—C16—H16A109.5
N1—C9—C10113.95 (18)C14—C16—H16B109.5
N1—C9—H9A108.8H16A—C16—H16B109.5
C10—C9—H9A108.8C14—C16—H16C109.5
N1—C9—H9B108.8H16A—C16—H16C109.5
C10—C9—H9B108.8H16B—C16—H16C109.5
H9A—C9—H9B107.7
O1—C1—C2—C3−43.9 (3)C1—C2—C7—C6174.98 (19)
O2—C1—C2—C3133.5 (2)C3—C2—C7—C8174.7 (2)
O1—C1—C2—C7139.7 (2)C1—C2—C7—C8−8.9 (3)
O2—C1—C2—C7−42.9 (3)C6—C7—C8—O4−51.4 (3)
C7—C2—C3—C40.4 (3)C2—C7—C8—O4132.5 (2)
C1—C2—C3—C4−176.1 (2)C6—C7—C8—O3126.5 (2)
C2—C3—C4—C50.8 (4)C2—C7—C8—O3−49.7 (3)
C3—C4—C5—C6−1.1 (4)N1—C9—C10—C12−172.76 (19)
C4—C5—C6—C70.1 (4)N1—C9—C10—C1165.0 (3)
C5—C6—C7—C21.2 (3)N2—C13—C14—C1668.6 (3)
C5—C6—C7—C8−175.0 (2)N2—C13—C14—C15−167.4 (2)
C3—C2—C7—C6−1.4 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1w—H1w1···O20.86 (1)1.97 (2)2.780 (2)156 (3)
O1w—H1w2···O4i0.86 (1)1.97 (2)2.780 (2)157 (3)
N1—H1n1···O10.85 (1)1.94 (1)2.788 (2)172 (2)
N1—H1n2···O3ii0.87 (1)1.91 (1)2.755 (2)167 (2)
N1—H1n3···O1wiii0.86 (1)1.99 (1)2.823 (3)164 (2)
N2—H2n1···O20.86 (1)2.35 (2)2.996 (2)132 (2)
N2—H2n1···O4i0.86 (1)2.42 (2)2.995 (3)124 (2)
N2—H2n2···O2i0.87 (1)1.91 (1)2.781 (2)172 (2)
N2—H2n3···O30.87 (1)1.89 (1)2.741 (2)166 (2)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LH2629).

References

  • Ariffin, A. & Khan, M. N. (2005). Bull. Kor. Chem. Soc.26, 1037–1043.
  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Bruker (2007). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Khan, M. N. & Ariffin, A. (2003). Org. Biomol. Chem.1, 1404–1408. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2008). publCIF In preparation.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography