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

Raza Shah, M.; Ng, S.W.

doi:10.1107/S1600536810026024

organic compounds

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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Page o1940

https://doi.org/10.1107/S1600536810026024

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

Muhammad Raza Shah ^a and Seik Weng Ng ^b ^*

^aH. E. J. Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, Karachi 75270, Pakistan, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 30 June 2010; accepted 1 July 2010; online 7 July 2010)

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, C 2
a = 23.725 (5) Å
b = 4.5109 (9) Å
c = 8.2171 (17) Å
β = 107.173 (3)°
V = 840.2 (3) Å³
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[F² > 2σ(F²)] = 0.043
wR(F²) = 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

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) x, y, z+1; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+1]$ .

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810026024/bt5289sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810026024/bt5289Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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

Structure description top

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

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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).

Figures top

Fig. 1. Anisotropic displacement ellipsoid plot (Barbour, 2001) of C₁₇H₁₈N₂O₄ at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

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

Crystal data top

C₁₇H₁₈N₂O₄	F(000) = 332
M_r = 314.33	D_x = 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 top

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

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)] = 0.043	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(F_o²) + (0.0523P)²] where P = (F_o² + 2F_c²)/3
1082 reflections	(Δ/σ)_max = 0.001
113 parameters	Δρ_max = 0.24 e Å⁻³
3 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₇H₁₈N₂O₄	V = 840.2 (3) Å³
M_r = 314.33	Z = 2
Monoclinic, C2	Mo Kα radiation
a = 23.725 (5) Å	µ = 0.09 mm⁻¹
b = 4.5109 (9) Å	T = 100 K
c = 8.2171 (17) Å	0.35 × 0.35 × 0.02 mm
β = 107.173 (3)°

Data collection top

Bruker SMART APEX diffractometer	788 reflections with I > 2σ(I)
3936 measured reflections	R_int = 0.090
1082 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	3 restraints
wR(F²) = 0.109	H atoms treated by a mixture of independent and constrained refinement
S = 0.96	Δρ_max = 0.24 e Å⁻³
1082 reflections	Δρ_min = −0.24 e Å⁻³
113 parameters

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

	x	y	z	U_iso*/U_eq	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 (Å²) top

	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, º) top

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 code: (i) −x+1, y, −z.

Hydrogen-bond geometry (Å, º) top

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.

Experimental details

Crystal data
Chemical formula	C₁₇H₁₈N₂O₄
M_r	314.33
Crystal system, space group	Monoclinic, C2
Temperature (K)	100
a, b, c (Å)	23.725 (5), 4.5109 (9), 8.2171 (17)
β (°)	107.173 (3)
V (Å³)	840.2 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.35 × 0.35 × 0.02

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	3936, 1082, 788
R_int	0.090
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.109, 0.96
No. of reflections	1082
No. of parameters	113
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.24

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

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) x, y, z+1; (ii) −x+1/2, y+1/2, −z+1.

Acknowledgements

The authors thank the Higher Education Commission of Pakistan and the University of Malaya for supporting this study.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Pérez, S. & Brisse, F. (1977). Acta Cryst. B33, 3259–3262. CSD CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar