Di-n-butyl 5-amino­isophthalate

Zhou, T.; Zhou, R.-J.; An, Z.

doi:10.1107/S1600536809024696

organic compounds

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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o1754

doi:10.1107/S1600536809024696

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Di-n-butyl 5-aminoisophthalate

Tian Zhou,^a ^* Ru-Jin Zhou ^a and Zhe An ^a

^aSchool of Chemistry and Life Science, Maoming University, Maoming 525000, People's Republic of China
^*Correspondence e-mail: zhoutian016@163.com

(Received 19 May 2009; accepted 26 June 2009; online 4 July 2009)

The title compound, C₁₆H₂₃NO₄, is essentially planar except for the last two C atoms in each n-butyl group (r.m.s. deviation from the least-squares plane = 0.02 Å for 17 non-H atoms). In the crystal, intermolecular N—H⋯O hydrogen bonds between the amine and carbonyl groups link the molecules into one-dimensional chains.

Related literature

For the related structure of 5-aminoisophthalic acid hemihydrate, see: Dobson & Gerkin (1998 ).

Experimental

Crystal data

C₁₆H₂₃NO₄
M_r = 293.35
Monoclinic, P 2₁ /c
a = 9.4350 (19) Å
b = 9.1640 (18) Å
c = 20.166 (4) Å
β = 94.67 (3)°
V = 1737.8 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 296 K
0.12 × 0.10 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.991, T_max = 0.994
8863 measured reflections
3169 independent reflections
1612 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.062
wR(F²) = 0.221
S = 1.04
3169 reflections
196 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.83 (5)	2.30 (6)	3.110 (4)	165 (6)
N1—H1B⋯O3ⁱⁱ	0.83 (6)	2.38 (6)	3.120 (4)	149 (5)
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) -x+1, -y+2, -z+1.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; 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/S1600536809024696/bi2379sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809024696/bi2379Isup2.hkl

checkCIF report

Comment top

As a part of our ongoing research on the synthesis and structure of Schiff-base ligands based on 5-aminoisophthalic acid, we obtained the title compound from acid-catalysed esterification in 1-butanol.

Related literature top

For the related structure of 5-aminoisophthalic acid hemihydrate, see: Dobson & Gerkin (1998).

Experimental top

5-Aminoisophthalic acid (10 g) was refluxed overnight in 1-butanol with catalysis of concentrated H₂SO₄. The solution was poured onto ice and adjusted to pH = 7, and the obtained powder was recrystallized from ethanol. Elemental analysis calculated: C 65.45, H 7.84, N 4.77%; found: C 65.42, H 7.81, N 4.70%.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); 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. Molecular structure with 30% probability displacement ellipsoids for non-H atoms.
	Fig. 2. One-dimensional hydrogen-bonded motif.

Di-n-butyl 5-aminoisophthalate top

Crystal data top

C₁₆H₂₃NO₄	F(000) = 632
M_r = 293.35	D_x = 1.121 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3119 reflections
a = 9.4350 (19) Å	θ = 2.0–25.5°
b = 9.1640 (18) Å	µ = 0.08 mm⁻¹
c = 20.166 (4) Å	T = 296 K
β = 94.67 (3)°	Block, colourless
V = 1737.8 (6) Å³	0.12 × 0.10 × 0.08 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	3169 independent reflections
Radiation source: fine-focus sealed tube	1612 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −7→11
T_min = 0.991, T_max = 0.994	k = −11→10
8863 measured reflections	l = −24→23

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.221	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.1119P)² + 0.1542P] where P = (F_o² + 2F_c²)/3
3169 reflections	(Δ/σ)_max < 0.001
196 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₁₆H₂₃NO₄	V = 1737.8 (6) Å³
M_r = 293.35	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.4350 (19) Å	µ = 0.08 mm⁻¹
b = 9.1640 (18) Å	T = 296 K
c = 20.166 (4) Å	0.12 × 0.10 × 0.08 mm
β = 94.67 (3)°

Data collection top

Bruker APEXII CCD diffractometer	3169 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1612 reflections with I > 2σ(I)
T_min = 0.991, T_max = 0.994	R_int = 0.029
8863 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	0 restraints
wR(F²) = 0.221	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.30 e Å⁻³
3169 reflections	Δρ_min = −0.16 e Å⁻³
196 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
O1	0.8685 (2)	0.3309 (2)	0.44186 (12)	0.1051 (8)
O2	0.6509 (2)	0.3015 (2)	0.39278 (11)	0.0938 (7)
O3	0.3317 (2)	0.8767 (3)	0.44890 (13)	0.1092 (8)
O4	0.29283 (19)	0.6651 (2)	0.39827 (11)	0.0944 (7)
N1	0.8560 (3)	0.8512 (4)	0.5269 (2)	0.1380 (15)
H1A	0.933 (6)	0.815 (7)	0.540 (3)	0.207*
H1B	0.831 (6)	0.926 (6)	0.546 (3)	0.207*
C1	0.7518 (3)	0.3783 (3)	0.42708 (14)	0.0759 (8)
C2	0.7015 (2)	0.5250 (3)	0.44442 (12)	0.0674 (7)
C3	0.7986 (3)	0.6180 (3)	0.47724 (14)	0.0768 (8)
H3A	0.8917	0.5868	0.4872	0.092*
C4	0.7598 (3)	0.7572 (3)	0.49558 (15)	0.0856 (9)
C5	0.6193 (3)	0.8002 (3)	0.47979 (15)	0.0808 (8)
H5A	0.5905	0.8928	0.4919	0.097*
C6	0.5223 (3)	0.7080 (3)	0.44666 (13)	0.0681 (7)
C7	0.5629 (3)	0.5693 (3)	0.42860 (12)	0.0675 (7)
H7A	0.4977	0.5068	0.4062	0.081*
C8	0.3749 (3)	0.7609 (3)	0.43193 (15)	0.0784 (8)
C9	0.1463 (3)	0.7056 (4)	0.38233 (19)	0.1024 (10)
H9A	0.1406	0.7901	0.3533	0.123*
H9B	0.1017	0.7296	0.4226	0.123*
C10	0.0741 (4)	0.5806 (5)	0.3489 (3)	0.1371 (16)
H10A	0.0657	0.5054	0.3822	0.165*
H10B	−0.0218	0.6115	0.3344	0.165*
C11	0.1293 (6)	0.5169 (9)	0.2960 (4)	0.220 (3)
H11A	0.2257	0.4870	0.3101	0.265*
H11B	0.1358	0.5912	0.2621	0.265*
C12	0.0559 (7)	0.3906 (9)	0.2644 (5)	0.300 (6)
H12A	0.1046	0.3602	0.2267	0.450*
H12B	−0.0401	0.4170	0.2499	0.450*
H12C	0.0553	0.3119	0.2958	0.450*
C13	0.6881 (4)	0.1552 (3)	0.3734 (2)	0.1112 (11)
H13A	0.7234	0.0992	0.4121	0.133*
H13B	0.7614	0.1584	0.3424	0.133*
C14	0.5572 (5)	0.0874 (4)	0.3415 (3)	0.1471 (16)
H14A	0.5822	−0.0100	0.3277	0.177*
H14B	0.4913	0.0762	0.3757	0.177*
C15	0.4815 (6)	0.1559 (6)	0.2858 (3)	0.175 (2)
H15A	0.5447	0.1639	0.2504	0.210*
H15B	0.4570	0.2542	0.2986	0.210*
C16	0.3471 (6)	0.0794 (7)	0.2586 (3)	0.205 (3)
H16A	0.3044	0.1331	0.2212	0.307*
H16B	0.2817	0.0740	0.2926	0.307*
H16C	0.3698	−0.0173	0.2447	0.307*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0690 (13)	0.0819 (14)	0.160 (2)	0.0183 (10)	−0.0158 (13)	−0.0206 (13)
O2	0.0795 (13)	0.0724 (13)	0.1264 (16)	0.0090 (10)	−0.0112 (11)	−0.0208 (11)
O3	0.0665 (12)	0.0882 (15)	0.169 (2)	0.0181 (11)	−0.0143 (12)	−0.0307 (14)
O4	0.0608 (11)	0.0900 (14)	0.1280 (17)	0.0102 (10)	−0.0193 (10)	−0.0165 (12)
N1	0.0748 (18)	0.093 (2)	0.237 (4)	0.0125 (15)	−0.046 (2)	−0.060 (2)
C1	0.0668 (17)	0.0684 (17)	0.0917 (19)	0.0034 (14)	0.0007 (14)	−0.0048 (14)
C2	0.0591 (14)	0.0654 (15)	0.0775 (16)	0.0036 (12)	0.0031 (12)	0.0013 (12)
C3	0.0570 (14)	0.0715 (18)	0.0993 (19)	0.0082 (12)	−0.0090 (13)	−0.0062 (14)
C4	0.0631 (16)	0.0731 (19)	0.117 (2)	0.0039 (14)	−0.0137 (15)	−0.0129 (16)
C5	0.0621 (16)	0.0667 (16)	0.111 (2)	0.0084 (13)	−0.0059 (14)	−0.0116 (15)
C6	0.0563 (14)	0.0651 (16)	0.0821 (17)	0.0020 (12)	−0.0004 (12)	0.0021 (13)
C7	0.0604 (15)	0.0667 (16)	0.0747 (16)	0.0012 (12)	0.0006 (12)	0.0007 (12)
C8	0.0611 (15)	0.0721 (19)	0.100 (2)	0.0036 (14)	−0.0054 (14)	−0.0018 (15)
C9	0.0600 (17)	0.119 (3)	0.123 (2)	0.0091 (17)	−0.0191 (16)	−0.007 (2)
C10	0.080 (2)	0.156 (4)	0.168 (4)	0.000 (2)	−0.030 (2)	−0.036 (3)
C11	0.127 (4)	0.280 (8)	0.248 (7)	−0.001 (5)	−0.022 (4)	−0.138 (7)
C12	0.173 (6)	0.301 (10)	0.410 (13)	−0.007 (5)	−0.074 (6)	−0.230 (10)
C13	0.114 (3)	0.073 (2)	0.143 (3)	0.0126 (18)	−0.009 (2)	−0.0249 (19)
C14	0.155 (4)	0.088 (3)	0.190 (4)	0.007 (2)	−0.038 (3)	−0.042 (3)
C15	0.168 (4)	0.148 (4)	0.197 (5)	0.010 (3)	−0.052 (4)	−0.041 (4)
C16	0.140 (4)	0.228 (6)	0.235 (6)	−0.002 (4)	−0.053 (4)	−0.094 (5)

Geometric parameters (Å, º) top

O1—C1	1.198 (3)	C9—H9B	0.970
O2—C1	1.331 (3)	C10—C11	1.357 (6)
O2—C13	1.448 (4)	C10—H10A	0.970
O3—C8	1.197 (3)	C10—H10B	0.970
O4—C8	1.321 (3)	C11—C12	1.468 (8)
O4—C9	1.442 (3)	C11—H11A	0.970
N1—C4	1.368 (4)	C11—H11B	0.970
N1—H1A	0.83 (5)	C12—H12A	0.960
N1—H1B	0.83 (6)	C12—H12B	0.960
C1—C2	1.478 (4)	C12—H12C	0.960
C2—C3	1.380 (4)	C13—C14	1.481 (5)
C2—C7	1.382 (3)	C13—H13A	0.970
C3—C4	1.385 (4)	C13—H13B	0.970
C3—H3A	0.930	C14—C15	1.426 (7)
C4—C5	1.395 (4)	C14—H14A	0.970
C5—C6	1.377 (4)	C14—H14B	0.970
C5—H5A	0.930	C15—C16	1.513 (7)
C6—C7	1.385 (3)	C15—H15A	0.970
C6—C8	1.480 (4)	C15—H15B	0.970
C7—H7A	0.930	C16—H16A	0.960
C9—C10	1.468 (5)	C16—H16B	0.960
C9—H9A	0.970	C16—H16C	0.960

C1—O2—C13	116.8 (2)	C9—C10—H10B	107.3
C8—O4—C9	117.0 (2)	H10A—C10—H10B	106.9
C4—N1—H1A	116 (4)	C10—C11—C12	118.9 (7)
C4—N1—H1B	122 (4)	C10—C11—H11A	107.6
H1A—N1—H1B	117 (5)	C12—C11—H11A	107.6
O1—C1—O2	122.8 (2)	C10—C11—H11B	107.6
O1—C1—C2	125.3 (3)	C12—C11—H11B	107.6
O2—C1—C2	112.0 (2)	H11A—C11—H11B	107.0
C3—C2—C7	120.6 (2)	C11—C12—H12A	109.5
C3—C2—C1	117.5 (2)	C11—C12—H12B	109.5
C7—C2—C1	121.9 (2)	H12A—C12—H12B	109.5
C2—C3—C4	121.1 (2)	C11—C12—H12C	109.5
C2—C3—H3A	119.4	H12A—C12—H12C	109.5
C4—C3—H3A	119.4	H12B—C12—H12C	109.5
N1—C4—C3	121.5 (2)	O2—C13—C14	107.1 (3)
N1—C4—C5	120.7 (3)	O2—C13—H13A	110.3
C3—C4—C5	117.8 (2)	C14—C13—H13A	110.3
C6—C5—C4	121.3 (3)	O2—C13—H13B	110.3
C6—C5—H5A	119.4	C14—C13—H13B	110.3
C4—C5—H5A	119.4	H13A—C13—H13B	108.6
C5—C6—C7	120.2 (2)	C15—C14—C13	120.2 (5)
C5—C6—C8	118.2 (2)	C15—C14—H14A	107.3
C7—C6—C8	121.5 (2)	C13—C14—H14A	107.3
C2—C7—C6	119.0 (2)	C15—C14—H14B	107.3
C2—C7—H7A	120.5	C13—C14—H14B	107.3
C6—C7—H7A	120.5	H14A—C14—H14B	106.9
O3—C8—O4	122.5 (2)	C14—C15—C16	115.7 (5)
O3—C8—C6	124.7 (3)	C14—C15—H15A	108.4
O4—C8—C6	112.8 (3)	C16—C15—H15A	108.4
O4—C9—C10	107.6 (3)	C14—C15—H15B	108.4
O4—C9—H9A	110.2	C16—C15—H15B	108.4
C10—C9—H9A	110.2	H15A—C15—H15B	107.4
O4—C9—H9B	110.2	C15—C16—H16A	109.5
C10—C9—H9B	110.2	C15—C16—H16B	109.5
H9A—C9—H9B	108.5	H16A—C16—H16B	109.5
C11—C10—C9	120.2 (4)	C15—C16—H16C	109.5
C11—C10—H10A	107.3	H16A—C16—H16C	109.5
C9—C10—H10A	107.3	H16B—C16—H16C	109.5
C11—C10—H10B	107.3

C13—O2—C1—O1	−0.1 (5)	C1—C2—C7—C6	179.6 (2)
C13—O2—C1—C2	−179.6 (3)	C5—C6—C7—C2	0.1 (4)
O1—C1—C2—C3	3.6 (4)	C8—C6—C7—C2	−179.1 (2)
O2—C1—C2—C3	−176.9 (2)	C9—O4—C8—O3	0.0 (4)
O1—C1—C2—C7	−176.5 (3)	C9—O4—C8—C6	179.1 (2)
O2—C1—C2—C7	3.0 (4)	C5—C6—C8—O3	−2.9 (5)
C7—C2—C3—C4	0.5 (4)	C7—C6—C8—O3	176.4 (3)
C1—C2—C3—C4	−179.6 (3)	C5—C6—C8—O4	178.0 (2)
C2—C3—C4—N1	−178.7 (3)	C7—C6—C8—O4	−2.7 (4)
C2—C3—C4—C5	0.0 (4)	C8—O4—C9—C10	−176.6 (3)
N1—C4—C5—C6	178.2 (3)	O4—C9—C10—C11	−51.7 (6)
C3—C4—C5—C6	−0.4 (5)	C9—C10—C11—C12	179.0 (7)
C4—C5—C6—C7	0.4 (4)	C1—O2—C13—C14	175.1 (3)
C4—C5—C6—C8	179.6 (3)	O2—C13—C14—C15	56.2 (6)
C3—C2—C7—C6	−0.5 (4)	C13—C14—C15—C16	−178.3 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.83 (5)	2.30 (6)	3.110 (4)	165 (6)
N1—H1B···O3ⁱⁱ	0.83 (6)	2.38 (6)	3.120 (4)	149 (5)

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

Experimental details

Crystal data
Chemical formula	C₁₆H₂₃NO₄
M_r	293.35
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	9.4350 (19), 9.1640 (18), 20.166 (4)
β (°)	94.67 (3)
V (Å³)	1737.8 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.12 × 0.10 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.991, 0.994
No. of measured, independent and observed [I > 2σ(I)] reflections	8863, 3169, 1612
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.221, 1.04
No. of reflections	3169
No. of parameters	196
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.16

Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2001), 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···O1ⁱ	0.83 (5)	2.30 (6)	3.110 (4)	165 (6)
N1—H1B···O3ⁱⁱ	0.83 (6)	2.38 (6)	3.120 (4)	149 (5)

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

Acknowledgements

The authors acknowledge financial support from the Science Foundation of Maoming University.

References

Bruker (2001). SADABS and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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