Butane-1,4-diaminium 2-(meth­oxy­carbon­yl)benzoate dihydrate

Li, J.

doi:10.1107/S1600536811003618

organic compounds

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Volume 67| Part 3| March 2011| Page o587

doi:10.1107/S1600536811003618

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Butane-1,4-diaminium 2-(methoxycarbonyl)benzoate dihydrate

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 23 January 2011; accepted 28 January 2011; online 9 February 2011)

In the title compound, C₄H₁₄N₂⁺·2C₉H₇O₄⁻·2H₂O, the butane-1,4-diaminium cation lies on an inversion center. In the crystal, intermolecular N—H⋯O and O—H⋯O hydrogen bonds link the components into layers parallel to (100). Addtional stabilization within these layers is provided by weak intermolecular C—H⋯O hydrogen bonds.

Related literature

For the appications of phthalimides and N-substituted phthalimides, see: Lima et al. (2002 ). For a related structure, see: Liang (2008 ).

Experimental

Crystal data

C₄H₁₄N₂²⁺·2C₉H₇O₄⁻·2H₂O
M_r = 484.50
Monoclinic, P 2₁ /c
a = 14.0344 (15) Å
b = 8.6746 (9) Å
c = 10.2304 (11) Å
β = 95.620 (1)°
V = 1239.5 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 298 K
0.50 × 0.48 × 0.47 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.950, T_max = 0.953
6001 measured reflections
2178 independent reflections
1601 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.123
S = 1.07
2178 reflections
157 parameters
H-atom parameters constrained
Δρ_max = 0.17 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—H1A⋯O4ⁱ	0.89	1.95	2.815 (2)	164
N1—H1B⋯O3	0.89	2.00	2.823 (2)	154
N1—H1C⋯O5	0.89	1.99	2.876 (2)	172
O5—H5C⋯O3ⁱⁱ	0.85	2.03	2.873 (2)	172
O5—H5D⋯O4ⁱⁱⁱ	0.85	1.96	2.808 (2)	172
C11—H11A⋯O2ⁱ	0.97	2.46	3.346 (2)	151
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) x, y-1, 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 PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811003618/lh5202sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811003618/lh5202Isup2.hkl

checkCIF report

Comment top

Phthalimides and N-substituted phthalimides are animportant class of compounds because of their interesting biological activities (Lima et al., 2002). 2-(Methoxycarbonyl)benzoic acid is an intermediate in the preparation of N-substituted phthalimides. In this paper, the structure of the title compound is reported. The asymmetric unit of the title compound (I) contains one half a butane-1,4-diaminium cation, a 2-(methoxycarbonyl)benzoate anion and a solvent water molecule (Fig. 1). The bond lengths and angles agree with those in ethane-1,2-diaminium 2-(methoxycarbonyl)-3,4,5,6-tetrabromobenzoate methanol solvate (Liang, 2008). In the crystal, intermolecular N—H···O and O—H···O hydrogen bonds link the components of the structure into two-dimensional layers parallel to (100) (Fig. 2 and Table 1). Addtional stabilization within these layers is provided by weak intermolecular C—H···O hydrogen bonds.

Related literature top

For the appications of phthalimides and N-substituted phthalimides, see: Lima et al. (2002). For a related structure, see: Liang (2008).

Experimental top

A mixture of phthalic anhydride (1.52 g, 0.01 mol) and methanol (15 ml) was refluxed for 0.5 h. 1,4-Butanediamine (0.44 g, 0.005 mol) was added to the above solution and mixed for 10 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.
	Fig. 2. Part of the crystal structure of the title compound with hydrogen bonds shown as dashed lines. Only H atoms involved in hydrogen bonds are shown.

Butane-1,4-diaminium 2-(methoxycarbonyl)benzoate dihydrate top

Crystal data top

C₄H₁₄N₂²⁺·2C₉H₇O₄⁻·2H₂O	F(000) = 516
M_r = 484.50	D_x = 1.298 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2198 reflections
a = 14.0344 (15) Å	θ = 2.8–27.5°
b = 8.6746 (9) Å	µ = 0.10 mm⁻¹
c = 10.2304 (11) Å	T = 298 K
β = 95.620 (1)°	Block, colorless
V = 1239.5 (2) Å³	0.50 × 0.48 × 0.47 mm
Z = 2

Data collection top

Bruker SMART CCD diffractometer	2178 independent reflections
Radiation source: fine-focus sealed tube	1601 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −12→16
T_min = 0.950, T_max = 0.953	k = −10→10
6001 measured reflections	l = −10→12

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.043	H-atom parameters constrained
wR(F²) = 0.123	w = 1/[σ²(F_o²) + (0.0556P)² + 0.314P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
2178 reflections	Δρ_max = 0.17 e Å⁻³
157 parameters	Δρ_min = −0.20 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.118 (8)

Crystal data top

C₄H₁₄N₂²⁺·2C₉H₇O₄⁻·2H₂O	V = 1239.5 (2) Å³
M_r = 484.50	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.0344 (15) Å	µ = 0.10 mm⁻¹
b = 8.6746 (9) Å	T = 298 K
c = 10.2304 (11) Å	0.50 × 0.48 × 0.47 mm
β = 95.620 (1)°

Data collection top

Bruker SMART CCD diffractometer	2178 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	1601 reflections with I > 2σ(I)
T_min = 0.950, T_max = 0.953	R_int = 0.037
6001 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.123	H-atom parameters constrained
S = 1.07	Δρ_max = 0.17 e Å⁻³
2178 reflections	Δρ_min = −0.20 e Å⁻³
157 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
N1	0.44862 (11)	0.25834 (17)	0.79462 (15)	0.0369 (4)
H1A	0.5061	0.2597	0.7647	0.055*
H1B	0.4252	0.3537	0.7944	0.055*
H1C	0.4094	0.1986	0.7432	0.055*
O1	0.13265 (10)	0.39089 (19)	0.54038 (16)	0.0622 (5)
O2	0.28346 (10)	0.43510 (19)	0.61583 (16)	0.0596 (5)
O3	0.37929 (10)	0.54277 (15)	0.88018 (14)	0.0458 (4)
O4	0.35667 (9)	0.74614 (15)	0.74950 (14)	0.0479 (4)
O5	0.33244 (12)	0.04093 (17)	0.63792 (15)	0.0628 (5)
H5C	0.3453	0.0256	0.5595	0.075*
H5D	0.3382	−0.0443	0.6790	0.075*
C1	0.19982 (14)	0.4525 (2)	0.62583 (19)	0.0376 (5)
C2	0.32751 (13)	0.6373 (2)	0.81441 (18)	0.0342 (4)
C3	0.15919 (12)	0.5400 (2)	0.73169 (18)	0.0351 (5)
C4	0.22064 (13)	0.6245 (2)	0.82091 (18)	0.0344 (5)
C5	0.18168 (15)	0.7007 (2)	0.9231 (2)	0.0490 (6)
H5	0.2216	0.7570	0.9833	0.059*
C6	0.08535 (16)	0.6941 (3)	0.9366 (2)	0.0587 (6)
H6	0.0608	0.7457	1.0056	0.070*
C7	0.02511 (16)	0.6117 (3)	0.8485 (2)	0.0565 (6)
H7	−0.0401	0.6075	0.8579	0.068*
C8	0.06155 (14)	0.5354 (2)	0.7462 (2)	0.0469 (5)
H8	0.0206	0.4804	0.6863	0.056*
C9	0.16701 (18)	0.2992 (4)	0.4371 (3)	0.0783 (9)
H9A	0.2048	0.3625	0.3851	0.117*
H9B	0.1135	0.2580	0.3825	0.117*
H9C	0.2055	0.2161	0.4751	0.117*
C10	0.45726 (13)	0.1967 (2)	0.93045 (17)	0.0337 (4)
H10A	0.3955	0.2014	0.9654	0.040*
H10B	0.5020	0.2592	0.9860	0.040*
C11	0.49175 (14)	0.0324 (2)	0.93138 (17)	0.0353 (5)
H11A	0.5510	0.0274	0.8901	0.042*
H11B	0.4447	−0.0306	0.8801	0.042*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0428 (9)	0.0320 (8)	0.0361 (9)	0.0064 (7)	0.0048 (7)	0.0075 (7)
O1	0.0412 (8)	0.0820 (12)	0.0614 (11)	−0.0001 (8)	−0.0048 (7)	−0.0318 (9)
O2	0.0391 (9)	0.0752 (11)	0.0644 (11)	−0.0021 (7)	0.0052 (7)	−0.0322 (9)
O3	0.0441 (8)	0.0439 (8)	0.0481 (9)	0.0115 (6)	−0.0026 (6)	0.0025 (7)
O4	0.0462 (9)	0.0374 (8)	0.0612 (10)	−0.0023 (6)	0.0106 (7)	0.0063 (7)
O5	0.0936 (13)	0.0428 (8)	0.0488 (10)	−0.0037 (8)	−0.0094 (8)	0.0011 (7)
C1	0.0365 (11)	0.0357 (10)	0.0398 (11)	−0.0011 (8)	0.0001 (8)	−0.0013 (8)
C2	0.0391 (10)	0.0279 (9)	0.0351 (10)	0.0004 (8)	0.0008 (8)	−0.0071 (8)
C3	0.0352 (10)	0.0325 (10)	0.0374 (11)	0.0026 (8)	0.0023 (8)	0.0043 (8)
C4	0.0382 (10)	0.0275 (9)	0.0372 (11)	0.0038 (8)	0.0024 (8)	0.0037 (8)
C5	0.0479 (13)	0.0505 (12)	0.0486 (13)	0.0046 (10)	0.0041 (10)	−0.0111 (10)
C6	0.0530 (14)	0.0701 (15)	0.0548 (15)	0.0104 (12)	0.0146 (11)	−0.0149 (12)
C7	0.0386 (12)	0.0694 (15)	0.0634 (15)	0.0079 (11)	0.0144 (10)	−0.0010 (13)
C8	0.0378 (11)	0.0493 (12)	0.0530 (14)	−0.0004 (9)	0.0014 (9)	0.0017 (10)
C9	0.0604 (16)	0.101 (2)	0.0702 (19)	0.0054 (14)	−0.0111 (13)	−0.0481 (16)
C10	0.0425 (11)	0.0302 (9)	0.0286 (10)	0.0033 (8)	0.0044 (8)	0.0020 (8)
C11	0.0457 (11)	0.0307 (9)	0.0295 (10)	0.0041 (8)	0.0035 (8)	0.0007 (8)

Geometric parameters (Å, º) top

N1—C10	1.483 (2)	C5—C6	1.373 (3)
N1—H1A	0.8900	C5—H5	0.9300
N1—H1B	0.8900	C6—C7	1.374 (3)
N1—H1C	0.8900	C6—H6	0.9300
O1—C1	1.333 (2)	C7—C8	1.378 (3)
O1—C9	1.443 (3)	C7—H7	0.9300
O2—C1	1.198 (2)	C8—H8	0.9300
O3—C2	1.248 (2)	C9—H9A	0.9600
O4—C2	1.246 (2)	C9—H9B	0.9600
O5—H5C	0.8500	C9—H9C	0.9600
O5—H5D	0.8500	C10—C11	1.505 (2)
C1—C3	1.481 (3)	C10—H10A	0.9700
C2—C4	1.512 (3)	C10—H10B	0.9700
C3—C8	1.393 (3)	C11—C11ⁱ	1.509 (3)
C3—C4	1.400 (3)	C11—H11A	0.9700
C4—C5	1.393 (3)	C11—H11B	0.9700

C10—N1—H1A	109.5	C7—C6—H6	119.9
C10—N1—H1B	109.5	C6—C7—C8	119.8 (2)
H1A—N1—H1B	109.5	C6—C7—H7	120.1
C10—N1—H1C	109.5	C8—C7—H7	120.1
H1A—N1—H1C	109.5	C7—C8—C3	120.6 (2)
H1B—N1—H1C	109.5	C7—C8—H8	119.7
C1—O1—C9	115.83 (17)	C3—C8—H8	119.7
H5C—O5—H5D	108.2	O1—C9—H9A	109.5
O2—C1—O1	121.97 (18)	O1—C9—H9B	109.5
O2—C1—C3	125.28 (17)	H9A—C9—H9B	109.5
O1—C1—C3	112.75 (16)	O1—C9—H9C	109.5
O4—C2—O3	125.51 (18)	H9A—C9—H9C	109.5
O4—C2—C4	117.28 (16)	H9B—C9—H9C	109.5
O3—C2—C4	117.10 (16)	N1—C10—C11	110.12 (14)
C8—C3—C4	119.66 (18)	N1—C10—H10A	109.6
C8—C3—C1	121.09 (17)	C11—C10—H10A	109.6
C4—C3—C1	119.22 (16)	N1—C10—H10B	109.6
C5—C4—C3	118.40 (17)	C11—C10—H10B	109.6
C5—C4—C2	117.51 (17)	H10A—C10—H10B	108.2
C3—C4—C2	124.08 (16)	C10—C11—C11ⁱ	112.22 (19)
C6—C5—C4	121.2 (2)	C10—C11—H11A	109.2
C6—C5—H5	119.4	C11ⁱ—C11—H11A	109.2
C4—C5—H5	119.4	C10—C11—H11B	109.2
C5—C6—C7	120.3 (2)	C11ⁱ—C11—H11B	109.2
C5—C6—H6	119.9	H11A—C11—H11B	107.9

C9—O1—C1—O2	1.4 (3)	O3—C2—C4—C5	86.2 (2)
C9—O1—C1—C3	−177.8 (2)	O4—C2—C4—C3	90.4 (2)
O2—C1—C3—C8	−170.6 (2)	O3—C2—C4—C3	−93.2 (2)
O1—C1—C3—C8	8.6 (3)	C3—C4—C5—C6	−0.2 (3)
O2—C1—C3—C4	7.4 (3)	C2—C4—C5—C6	−179.6 (2)
O1—C1—C3—C4	−173.44 (17)	C4—C5—C6—C7	−0.1 (4)
C8—C3—C4—C5	0.7 (3)	C5—C6—C7—C8	0.0 (4)
C1—C3—C4—C5	−177.31 (17)	C6—C7—C8—C3	0.5 (3)
C8—C3—C4—C2	−179.96 (17)	C4—C3—C8—C7	−0.8 (3)
C1—C3—C4—C2	2.1 (3)	C1—C3—C8—C7	177.12 (19)
O4—C2—C4—C5	−90.2 (2)	N1—C10—C11—C11ⁱ	176.08 (19)

Symmetry code: (i) −x+1, −y, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4ⁱⁱ	0.89	1.95	2.815 (2)	164
N1—H1B···O3	0.89	2.00	2.823 (2)	154
N1—H1C···O5	0.89	1.99	2.876 (2)	172
O5—H5C···O3ⁱⁱⁱ	0.85	2.03	2.873 (2)	172
O5—H5D···O4^iv	0.85	1.96	2.808 (2)	172
C11—H11A···O2ⁱⁱ	0.97	2.46	3.346 (2)	151

Symmetry codes: (ii) −x+1, y−1/2, −z+3/2; (iii) x, −y+1/2, z−1/2; (iv) x, y−1, z.

Experimental details

Crystal data
Chemical formula	C₄H₁₄N₂²⁺·2C₉H₇O₄⁻·2H₂O
M_r	484.50
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	14.0344 (15), 8.6746 (9), 10.2304 (11)
β (°)	95.620 (1)
V (Å³)	1239.5 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.50 × 0.48 × 0.47

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.950, 0.953
No. of measured, independent and observed [I > 2σ(I)] reflections	6001, 2178, 1601
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.123, 1.07
No. of reflections	2178
No. of parameters	157
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −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—H1A···O4ⁱ	0.89	1.95	2.815 (2)	164
N1—H1B···O3	0.89	2.00	2.823 (2)	154
N1—H1C···O5	0.89	1.99	2.876 (2)	172
O5—H5C···O3ⁱⁱ	0.85	2.03	2.873 (2)	172
O5—H5D···O4ⁱⁱⁱ	0.85	1.96	2.808 (2)	172
C11—H11A···O2ⁱ	0.97	2.46	3.346 (2)	151

Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) x, −y+1/2, z−1/2; (iii) x, y−1, z.

Acknowledgements

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

References

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