(3-Nitro­phen­yl)methanediyl diacetate

Mohammadi Ziarani, G.; Abbasi, A.; Badiei, A.; Ghorbi, S.; Shahjafari, F.

doi:10.1107/S1600536807060990

organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o16

https://doi.org/10.1107/S1600536807060990

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(3-Nitrophenyl)methanediyl diacetate

Ghodsi Mohammadi Ziarani,^a Alireza Abbasi,^b ^* Alireza Badiei,^b Shima Ghorbi ^a and Fatemeh Shahjafari ^a

^aDepartment of Chemistry, University of Alzahra, Tehran, Iran, and ^bSchool of Chemistry, University College of Science, University of Tehran, Tehran, Iran
^*Correspondence e-mail: aabbasi@khayam.ut.ac.ir

(Received 19 November 2007; accepted 20 November 2007; online 6 December 2007)

In the title compound, C₁₁H₁₁NO₆, only weak van der Waals interactions are found in the molecular packing. The compound is an efficient catalyst for the acetalization of the carbonyl group of aldehydes in nearly quantative yield.

Related literature

For background literature on silica-based sulfonic acid as catalyst in solvent-free acetalization, see: Karimi et al. (2000 ); Kumar et al. (2006 ); Smith & Reddy (2003 ).

Experimental

Crystal data

C₁₁H₁₁NO₆
M_r = 253.21
Triclinic, $[P \overline 1]$
a = 7.8959 (9) Å
b = 8.4779 (10) Å
c = 9.7788 (13) Å
α = 109.094 (11)°
β = 98.031 (10)°
γ = 99.963 (10)°
V = 595.55 (13) Å³
Z = 2
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 290 (2) K
0.3 × 0.2 × 0.2 mm

Data collection

Stoe IPDS diffractometer
Absorption correction: none
3869 measured reflections
2149 independent reflections
1224 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.098
S = 0.91
2149 reflections
166 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Data collection: IPDS Software (Stoe & Cie, 1997 ); cell refinement: IPDS Software; data reduction: IPDS Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2001 ); software used to prepare material for publication: PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536807060990/ng2384sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807060990/ng2384Isup2.hkl

checkCIF report

Comment top

Protection of aldehydes is important in organic chemistry. Many procedures have been done for this aim. In this work, silica based sulfonic acid was used as catalyst in solvent free condition for the acetalization of 3-nitro-benzaldehyde (Karimi, et al., 2000; Kumar, et al., 2006; Smith, & Reddy, 2003). The time of reaction was just 10 minutes at room temperature and the yield of reaction was more than 96%. Therefore, this catalyst was very efficient catalyst for acetalization of the carbonyl group of aldehydes.

The moleculare structure of (I) and the atom-numbering scheme are shown in Fig. 1. The nitro (NO₂) group is twisted regarding to phenyl ring by torsion angles of O3–N1–C3–C8, 4.8 (3)° and O6–N1–C3–C2, 7.1 (3)°. The methyne carbon are connected to two acetate ions and phenyl ring in a distorted tetrahedral configuration. The structure of the title compound was corroborated by IR and 1H NMR spectroscopies.

Related literature top

For background literature on silica-based sulfonic acid as catalyst in solvent-free acetalization, see: Karimi et al. (2000); Kumar et al. (2006); Smith & Reddy (2003).

Experimental top

The catalyst (0.02 gr) was activated under vacuum at 100 °C followed by cooling to room temperature and then 3-nitro-benzaldehyde (3 mmol) was added to the catalyst. The mixture was stirred for two minutes and acetic anhydride (0.6 ml) was then added and stirred for 10 more minutes. The obtained solid was diluted with dichloromethane and filtered to remove the catalyst. The organic layer was washed with saturated NaHCO₃ solution and dried with Na₂SO₄. The solvent was evaporated under reduced pressure to obtain the title compound in yield of 96%. Crystals suitable for crystallography was obtained by crystallization from CH₂Cl₂.

Structure description top

For background literature on silica-based sulfonic acid as catalyst in solvent-free acetalization, see: Karimi et al. (2000); Kumar et al. (2006); Smith & Reddy (2003).

Computing details top

Data collection: IPDS Software (Stoe & Cie, 1997); cell refinement: IPDS Software (Stoe & Cie, 1997); data reduction: IPDS Software (Stoe & Cie, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2001); software used to prepare material for publication: PLATON (Spek, 2003).

Figures top

Fig. 1. Molecular structure of (I), with 50% probability displacement ellipsoids. H atoms are shown as circles of arbitrary radii.

(3-Nitrophenyl)methanediyl diacetate top

Crystal data top

C₁₁H₁₁NO₆	Z = 2
M_r = 253.21	F(000) = 264
Triclinic, P1	D_x = 1.412 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.8959 (9) Å	Cell parameters from 1543 reflections
b = 8.4779 (10) Å	θ = 3.5–25.5°
c = 9.7788 (13) Å	µ = 0.12 mm⁻¹
α = 109.094 (11)°	T = 290 K
β = 98.031 (10)°	Block shape, colorless
γ = 99.963 (10)°	0.3 × 0.2 × 0.2 mm
V = 595.55 (13) Å³

Data collection top

STOE IPDS diffractometer	1224 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.024
Graphite monochromator	θ_max = 25.5°, θ_min = 3.8°
Area detector – phi oscillation scans	h = −9→8
3869 measured reflections	k = −7→10
2149 independent reflections	l = −11→11

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)] = 0.036	H-atom parameters constrained
wR(F²) = 0.098	w = 1/[σ²(F_o²) + (0.0565P)²] where P = (F_o² + 2F_c²)/3
S = 0.91	(Δ/σ)_max < 0.001
2149 reflections	Δρ_max = 0.19 e Å⁻³
166 parameters	Δρ_min = −0.14 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.100 (9)

Crystal data top

C₁₁H₁₁NO₆	γ = 99.963 (10)°
M_r = 253.21	V = 595.55 (13) Å³
Triclinic, P1	Z = 2
a = 7.8959 (9) Å	Mo Kα radiation
b = 8.4779 (10) Å	µ = 0.12 mm⁻¹
c = 9.7788 (13) Å	T = 290 K
α = 109.094 (11)°	0.3 × 0.2 × 0.2 mm
β = 98.031 (10)°

Data collection top

STOE IPDS diffractometer	1224 reflections with I > 2σ(I)
3869 measured reflections	R_int = 0.024
2149 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.098	H-atom parameters constrained
S = 0.91	Δρ_max = 0.19 e Å⁻³
2149 reflections	Δρ_min = −0.14 e Å⁻³
166 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
O1	0.30507 (14)	0.16974 (14)	−0.04836 (12)	0.0445 (3)
O2	0.59909 (14)	0.22011 (14)	0.05498 (12)	0.0457 (4)
O3	0.16732 (19)	0.6263 (2)	0.60185 (17)	0.0836 (5)
O4	0.43191 (18)	0.23344 (17)	−0.22188 (14)	0.0668 (4)
O5	0.75926 (17)	0.47383 (18)	0.07041 (18)	0.0791 (5)
O6	0.1787 (2)	0.7027 (2)	0.4140 (2)	0.1013 (6)
N1	0.2009 (2)	0.6066 (2)	0.4801 (2)	0.0651 (5)
C1	0.4464 (2)	0.2888 (2)	0.06532 (17)	0.0404 (4)
H1	0.4676	0.4004	0.0533	0.048*
C2	0.3243 (2)	0.4433 (2)	0.27690 (19)	0.0440 (5)
H2	0.3153	0.5260	0.2347	0.053*
C3	0.2703 (2)	0.4571 (2)	0.40713 (19)	0.0479 (5)
C4	0.3077 (3)	0.1635 (2)	−0.1894 (2)	0.0485 (5)
C5	0.3922 (2)	0.3050 (2)	0.20946 (17)	0.0394 (4)
C6	0.4043 (2)	0.1838 (2)	0.2739 (2)	0.0501 (5)
H6	0.4494	0.0901	0.2287	0.060*
C7	0.7489 (2)	0.3270 (3)	0.0531 (2)	0.0500 (5)
C8	0.2821 (2)	0.3387 (3)	0.4739 (2)	0.0580 (5)
H8	0.2456	0.3512	0.5625	0.070*
C9	0.3497 (2)	0.2009 (3)	0.4059 (2)	0.0595 (5)
H9	0.3587	0.1188	0.4487	0.071*
C10	0.1372 (3)	0.0604 (3)	−0.2909 (2)	0.0687 (6)
H10A	0.1573	0.0030	−0.3875	0.103*
H10B	0.0600	0.1348	−0.2973	0.103*
H10C	0.0842	−0.0233	−0.2535	0.103*
C11	0.8926 (2)	0.2351 (3)	0.0284 (3)	0.0726 (7)
H11A	0.9436	0.2246	0.1192	0.109*
H11B	0.9812	0.2985	−0.0039	0.109*
H11C	0.8457	0.1228	−0.0459	0.109*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0425 (7)	0.0528 (8)	0.0365 (7)	0.0072 (6)	0.0073 (6)	0.0162 (6)
O2	0.0396 (7)	0.0477 (7)	0.0545 (8)	0.0125 (6)	0.0163 (6)	0.0208 (6)
O3	0.0737 (11)	0.1055 (12)	0.0530 (9)	0.0200 (9)	0.0252 (8)	0.0001 (9)
O4	0.0720 (10)	0.0778 (10)	0.0515 (8)	0.0062 (8)	0.0219 (8)	0.0267 (8)
O5	0.0537 (9)	0.0547 (9)	0.1318 (14)	0.0070 (7)	0.0210 (9)	0.0398 (9)
O6	0.1370 (17)	0.0995 (14)	0.0925 (13)	0.0722 (13)	0.0492 (12)	0.0343 (12)
N1	0.0562 (11)	0.0744 (13)	0.0545 (12)	0.0175 (9)	0.0168 (9)	0.0068 (10)
C1	0.0376 (10)	0.0417 (10)	0.0424 (10)	0.0089 (8)	0.0088 (8)	0.0159 (8)
C2	0.0395 (10)	0.0474 (11)	0.0420 (11)	0.0066 (8)	0.0068 (8)	0.0147 (9)
C3	0.0360 (10)	0.0582 (12)	0.0415 (11)	0.0068 (9)	0.0086 (8)	0.0097 (9)
C4	0.0571 (13)	0.0512 (11)	0.0413 (12)	0.0190 (10)	0.0143 (10)	0.0172 (9)
C5	0.0327 (10)	0.0457 (10)	0.0362 (10)	0.0047 (8)	0.0040 (8)	0.0136 (8)
C6	0.0487 (11)	0.0535 (11)	0.0526 (12)	0.0128 (9)	0.0126 (9)	0.0238 (9)
C7	0.0397 (11)	0.0588 (13)	0.0508 (12)	0.0049 (10)	0.0111 (9)	0.0214 (10)
C8	0.0499 (12)	0.0771 (14)	0.0444 (11)	0.0082 (11)	0.0127 (10)	0.0206 (11)
C9	0.0589 (13)	0.0731 (14)	0.0570 (12)	0.0124 (11)	0.0149 (11)	0.0375 (11)
C10	0.0693 (15)	0.0789 (15)	0.0459 (12)	0.0100 (12)	0.0025 (11)	0.0145 (11)
C11	0.0469 (13)	0.0767 (15)	0.0971 (18)	0.0168 (11)	0.0275 (12)	0.0290 (13)

Geometric parameters (Å, º) top

O1—C4	1.366 (2)	C4—C10	1.488 (3)
O1—C1	1.4249 (19)	C5—C6	1.380 (2)
O2—C7	1.367 (2)	C6—C9	1.388 (2)
O2—C1	1.4287 (18)	C6—H6	0.9300
O3—N1	1.221 (2)	C7—C11	1.487 (2)
O4—C4	1.193 (2)	C8—C9	1.378 (2)
O5—C7	1.187 (2)	C8—H8	0.9300
O6—N1	1.215 (2)	C9—H9	0.9300
N1—C3	1.474 (2)	C10—H10A	0.9600
C1—C5	1.500 (2)	C10—H10B	0.9600
C1—H1	0.9800	C10—H10C	0.9600
C2—C3	1.374 (2)	C11—H11A	0.9600
C2—C5	1.381 (2)	C11—H11B	0.9600
C2—H2	0.9300	C11—H11C	0.9600
C3—C8	1.374 (3)

C4—O1—C1	116.57 (13)	C5—C6—H6	119.8
C7—O2—C1	116.69 (13)	C9—C6—H6	119.8
O6—N1—O3	123.62 (18)	O5—C7—O2	122.99 (17)
O6—N1—C3	117.60 (17)	O5—C7—C11	125.89 (18)
O3—N1—C3	118.8 (2)	O2—C7—C11	111.12 (17)
O1—C1—O2	107.75 (12)	C3—C8—C9	118.09 (17)
O1—C1—C5	106.49 (12)	C3—C8—H8	121.0
O2—C1—C5	111.36 (13)	C9—C8—H8	121.0
O1—C1—H1	110.4	C8—C9—C6	120.49 (18)
O2—C1—H1	110.4	C8—C9—H9	119.8
C5—C1—H1	110.4	C6—C9—H9	119.8
C3—C2—C5	119.16 (16)	C4—C10—H10A	109.5
C3—C2—H2	120.4	C4—C10—H10B	109.5
C5—C2—H2	120.4	H10A—C10—H10B	109.5
C8—C3—C2	122.43 (17)	C4—C10—H10C	109.5
C8—C3—N1	118.60 (18)	H10A—C10—H10C	109.5
C2—C3—N1	118.95 (18)	H10B—C10—H10C	109.5
O4—C4—O1	122.89 (18)	C7—C11—H11A	109.5
O4—C4—C10	126.65 (18)	C7—C11—H11B	109.5
O1—C4—C10	110.46 (16)	H11A—C11—H11B	109.5
C6—C5—C2	119.45 (16)	C7—C11—H11C	109.5
C6—C5—C1	121.85 (15)	H11A—C11—H11C	109.5
C2—C5—C1	118.68 (15)	H11B—C11—H11C	109.5
C5—C6—C9	120.38 (18)

C4—O1—C1—O2	−74.57 (15)	C3—C2—C5—C1	178.43 (15)
C4—O1—C1—C5	165.86 (13)	O1—C1—C5—C6	79.55 (18)
C7—O2—C1—O1	129.88 (14)	O2—C1—C5—C6	−37.7 (2)
C7—O2—C1—C5	−113.68 (15)	O1—C1—C5—C2	−98.83 (16)
C5—C2—C3—C8	0.4 (3)	O2—C1—C5—C2	143.97 (14)
C5—C2—C3—N1	178.90 (15)	C2—C5—C6—C9	−0.3 (2)
O6—N1—C3—C8	−174.42 (18)	C1—C5—C6—C9	−178.70 (16)
O3—N1—C3—C8	4.8 (3)	C1—O2—C7—O5	5.7 (3)
O6—N1—C3—C2	7.1 (3)	C1—O2—C7—C11	−174.89 (14)
O3—N1—C3—C2	−173.74 (16)	C2—C3—C8—C9	−0.5 (3)
C1—O1—C4—O4	10.7 (2)	N1—C3—C8—C9	−179.01 (15)
C1—O1—C4—C10	−169.00 (14)	C3—C8—C9—C6	0.2 (3)
C3—C2—C5—C6	0.0 (2)	C5—C6—C9—C8	0.2 (3)

Experimental details

Crystal data
Chemical formula	C₁₁H₁₁NO₆
M_r	253.21
Crystal system, space group	Triclinic, P1
Temperature (K)	290
a, b, c (Å)	7.8959 (9), 8.4779 (10), 9.7788 (13)
α, β, γ (°)	109.094 (11), 98.031 (10), 99.963 (10)
V (Å³)	595.55 (13)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.3 × 0.2 × 0.2

Data collection
Diffractometer	STOE IPDS
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	3869, 2149, 1224
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.098, 0.91
No. of reflections	2149
No. of parameters	166
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.14

Computer programs: IPDS Software (Stoe & Cie, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 2001), PLATON (Spek, 2003).

Selected bond lengths (Å) top

O1—C4	1.366 (2)	O4—C4	1.193 (2)
O1—C1	1.4249 (19)	O5—C7	1.187 (2)
O2—C7	1.367 (2)	O6—N1	1.215 (2)
O2—C1	1.4287 (18)	N1—C3	1.474 (2)
O3—N1	1.221 (2)

Acknowledgements

This work was supported by a grant from the University of Tehran and the University of Alzahra.

References

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