Propane-1,3-diyl bis­(4-amino­benzoate)

Abstract

Mol­ecules of the title compound, C₁₇H₁₈N₂O₄, lie on a twofold rotation axis that passes through the central methyl­ene C atom. The mol­ecules adopt a ‘V’ shape and the trimethyl­ene unit assumes a gauche–gauche conformation. The amino N atom shows a nonplanar coordination. Adjacent mol­ecules are connected by N—H⋯O hydrogen bonds into chains running along [001]. Furthermore, N—H⋯N hydrogen bonds connect these chains into a three-dimensional network.

Related literature

For the crystal structure of 1,3-propandiyl-bis­(benzoate), see: Pérez & Brisse (1977 ▶).

Experimental

Crystal data

• C₁₇H₁₈N₂O₄

• M _r = 314.33

• Monoclinic,

• a = 23.725 (5) Å

• b = 4.5109 (9) Å

• c = 8.2171 (17) Å

• β = 107.173 (3)°

• V = 840.2 (3) ų

• Z = 2

• Mo Kα radiation

• μ = 0.09 mm⁻¹

• T = 100 K

• 0.35 × 0.35 × 0.02 mm

Data collection

• Bruker SMART APEX diffractometer

• 3936 measured reflections

• 1082 independent reflections

• 788 reflections with I > 2σ(I)

• R _int = 0.090

Refinement

• R[F ² > 2σ(F ²)] = 0.043

• wR(F ²) = 0.109

• S = 0.96

• 1082 reflections

• 113 parameters

• 3 restraints

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.24 e Å⁻³

• Δρ_min = −0.24 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H11⋯O2i	0.86 (1)	2.15 (2)	2.958 (3)	157 (5)
N1—H12⋯N1ii	0.86 (1)	2.25 (1)	3.104 (3)	169 (2)

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

The chemical is a commercially available chemical that should be compable of condensing with carbonyl compounds to yield Schff bases; its special feature is its trimethylene portion, which assumes a V shape. The C₁₇H₁₈N₂O₄ molecule (Scheme I) lies on a twofold rotation axis that passes through the central methylene carbon atom; this symmetry element relates one 4-aminobenzoate unit to the other. The molecule assumes a V shape and the trimethylene portion assumes a gauche–gauche conformation. The amino nitrogen atom shows non-planar coordination (Fig. 1). Adjacent molecules are connected by N–H···O and N–H···N shydrogen bonds to form a three-dimensional network.

Experimental

The compound was returned unchanged but in a crystalline form in an unsuccessful condensation with o-vanillin in ethanol medium.

Refinement

Carbon-bound H-atoms were placed in calculated positions [C–H 0.95–0.99 Å, U(H) 1.2U(C)] and were included in the refinement in the riding model approximation. The amino H-atoms were located in a difference Fourier map, and were refined isotropically with a distance restraint of N–H 0.86±0.01 Å. 822 Friedel pairs were merged.

Figures

Fig. 1.

Anisotropic displacement ellipsoid plot (Barbour, 2001) of C17H18N2O4 at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

Crystal data

C17H18N2O4	F(000) = 332
Mr = 314.33	Dx = 1.242 Mg m−3
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2y	Cell parameters from 915 reflections
a = 23.725 (5) Å	θ = 2.6–26.8°
b = 4.5109 (9) Å	µ = 0.09 mm−1
c = 8.2171 (17) Å	T = 100 K
β = 107.173 (3)°	Plate, yellow
V = 840.2 (3) Å3	0.35 × 0.35 × 0.02 mm
Z = 2

Data collection

Bruker SMART APEX diffractometer	788 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.090
graphite	θmax = 27.5°, θmin = 1.8°
ω scans	h = −30→29
3936 measured reflections	k = −5→5
1082 independent reflections	l = −10→10

Refinement

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109	H atoms treated by a mixture of independent and constrained refinement
S = 0.96	w = 1/[σ2(Fo2) + (0.0523P)2] where P = (Fo2 + 2Fc2)/3
1082 reflections	(Δ/σ)max = 0.001
113 parameters	Δρmax = 0.24 e Å−3
3 restraints	Δρmin = −0.24 e Å−3

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.42724 (7)	0.4987 (4)	0.0488 (2)	0.0262 (5)
O2	0.35969 (8)	0.7580 (5)	−0.1476 (2)	0.0304 (5)
N1	0.29701 (11)	1.0783 (6)	0.5367 (3)	0.0298 (6)
C1	0.5000	0.1862 (10)	0.0000	0.0279 (10)
H1A	0.5095	0.0569	−0.0857	0.033*	0.50
H1B	0.4905	0.0569	0.0857	0.033*	0.50
C2	0.44676 (11)	0.3705 (7)	−0.0862 (3)	0.0263 (7)
H2A	0.4572	0.5279	−0.1562	0.032*
H2B	0.4153	0.2454	−0.1609	0.032*
C3	0.38135 (11)	0.6876 (7)	0.0010 (3)	0.0244 (7)
C4	0.36179 (11)	0.7924 (7)	0.1432 (3)	0.0228 (6)
C5	0.31600 (11)	0.9969 (7)	0.1134 (3)	0.0260 (7)
H5	0.2991	1.0721	0.0016	0.031*
C6	0.29486 (12)	1.0917 (7)	0.2423 (3)	0.0286 (7)
H6	0.2631	1.2289	0.2187	0.034*
C7	0.31969 (11)	0.9879 (7)	0.4094 (3)	0.0252 (7)
C8	0.36569 (11)	0.7851 (8)	0.4393 (3)	0.0295 (7)
H8	0.3830	0.7123	0.5514	0.035*
C9	0.38646 (11)	0.6885 (8)	0.3103 (3)	0.0282 (7)
H9	0.4179	0.5495	0.3338	0.034*
H11	0.3137 (17)	1.032 (12)	0.641 (2)	0.098 (16)*
H12	0.2748 (10)	1.233 (4)	0.519 (3)	0.025 (8)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0204 (9)	0.0351 (12)	0.0206 (9)	0.0041 (10)	0.0021 (7)	0.0031 (9)
O2	0.0239 (10)	0.0453 (13)	0.0165 (9)	0.0042 (10)	−0.0024 (7)	0.0029 (10)
N1	0.0272 (14)	0.0364 (17)	0.0227 (13)	0.0056 (12)	0.0025 (11)	0.0016 (12)
C1	0.021 (2)	0.030 (3)	0.029 (2)	0.000	0.0034 (16)	0.000
C2	0.0205 (13)	0.0329 (17)	0.0243 (14)	−0.0040 (13)	0.0046 (11)	−0.0024 (13)
C3	0.0172 (13)	0.0302 (17)	0.0224 (13)	−0.0048 (13)	0.0005 (11)	0.0009 (13)
C4	0.0163 (12)	0.0304 (17)	0.0183 (12)	−0.0025 (12)	−0.0001 (10)	0.0023 (11)
C5	0.0190 (13)	0.0322 (17)	0.0193 (13)	−0.0007 (14)	−0.0058 (11)	0.0043 (13)
C6	0.0191 (14)	0.0368 (19)	0.0236 (14)	0.0029 (13)	−0.0031 (12)	0.0038 (13)
C7	0.0186 (13)	0.0335 (18)	0.0202 (13)	−0.0060 (14)	0.0006 (10)	0.0005 (13)
C8	0.0218 (14)	0.043 (2)	0.0179 (13)	0.0039 (14)	−0.0026 (11)	0.0090 (14)
C9	0.0181 (14)	0.0397 (19)	0.0237 (14)	0.0030 (14)	0.0012 (11)	0.0050 (14)

Geometric parameters (Å, °)

O1—C3	1.347 (3)	C3—C4	1.457 (4)
O1—C2	1.444 (3)	C4—C5	1.391 (4)
O2—C3	1.219 (3)	C4—C9	1.405 (3)
N1—C7	1.372 (3)	C5—C6	1.368 (4)
N1—H11	0.858 (10)	C5—H5	0.9500
N1—H12	0.861 (10)	C6—C7	1.405 (4)
C1—C2	1.503 (4)	C6—H6	0.9500
C1—C2i	1.503 (4)	C7—C8	1.389 (4)
C1—H1A	0.9900	C8—C9	1.365 (4)
C1—H1B	0.9900	C8—H8	0.9500
C2—H2A	0.9900	C9—H9	0.9500
C2—H2B	0.9900
C3—O1—C2	116.39 (19)	C5—C4—C9	118.1 (2)
C7—N1—H11	121 (3)	C5—C4—C3	119.4 (2)
C7—N1—H12	118.1 (19)	C9—C4—C3	122.4 (2)
H11—N1—H12	116 (4)	C6—C5—C4	121.1 (2)
C2—C1—C2i	112.9 (4)	C6—C5—H5	119.4
C2—C1—H1A	109.0	C4—C5—H5	119.4
C2i—C1—H1A	109.0	C5—C6—C7	120.6 (3)
C2—C1—H1B	109.0	C5—C6—H6	119.7
C2i—C1—H1B	109.0	C7—C6—H6	119.7
H1A—C1—H1B	107.8	N1—C7—C8	121.7 (2)
O1—C2—C1	105.94 (18)	N1—C7—C6	120.0 (3)
O1—C2—H2A	110.5	C8—C7—C6	118.2 (2)
C1—C2—H2A	110.5	C9—C8—C7	121.2 (3)
O1—C2—H2B	110.5	C9—C8—H8	119.4
C1—C2—H2B	110.5	C7—C8—H8	119.4
H2A—C2—H2B	108.7	C8—C9—C4	120.7 (3)
O2—C3—O1	121.5 (2)	C8—C9—H9	119.7
O2—C3—C4	125.4 (3)	C4—C9—H9	119.7
O1—C3—C4	113.1 (2)
C3—O1—C2—C1	176.5 (2)	C3—C4—C5—C6	177.4 (3)
C2i—C1—C2—O1	−71.92 (18)	C4—C5—C6—C7	1.1 (4)
C2—O1—C3—O2	−3.8 (4)	C5—C6—C7—N1	−178.2 (3)
C2—O1—C3—C4	176.2 (2)	C5—C6—C7—C8	−0.6 (4)
O2—C3—C4—C5	−2.2 (4)	N1—C7—C8—C9	177.6 (3)
O1—C3—C4—C5	177.8 (3)	C6—C7—C8—C9	0.1 (5)
O2—C3—C4—C9	176.1 (3)	C7—C8—C9—C4	0.1 (5)
O1—C3—C4—C9	−4.0 (4)	C5—C4—C9—C8	0.3 (4)
C9—C4—C5—C6	−0.9 (4)	C3—C4—C9—C8	−177.9 (3)

Symmetry codes: (i) −x+1, y, −z.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11···O2ii	0.86 (1)	2.15 (2)	2.958 (3)	157 (5)
N1—H12···N1iii	0.86 (1)	2.25 (1)	3.104 (3)	169 (2)

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