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Acta Crystallogr Sect E Struct Rep Online. 2009 December 1; 65(Pt 12): o3206.
Published online 2009 November 25. doi:  10.1107/S160053680904937X
PMCID: PMC2972161

N-[4-(Morpholinodiazen­yl)phen­yl]acetamide

Abstract

The title compound, C12H16N4O2, is a member of a family of morpholine-substituted aromatic diazenes. Conjugation of the diazene group π-system and the lone pair of electrons of the morpholine N atom is evidenced by a lengthened N=N double bond of 1.2707 (19) Å and a shortened N—N single bond of 1.346 (2) Å. The bond angles at the morpholine N atom range from 113.52 (14) to 121.12 (14)°, indicating some degree of sp 2 hybridization. The morpholine ring adopts a conventional chair conformation with the diazenyl group in the equatorial position. The diazenyl and acetamido groups are both twisted relative to the plane of the benzene ring by 12.3 (2) and 25.5 (3)°, respectively.

Related literature

The title compound was synthesized using a modification of the method of Sengupta et al. (1998 [triangle]). For similar structures, see: Little et al. (2008 [triangle]). For information about diazene derivatives, see: Chen et al. (2005 [triangle]); Lalezari & Afgahi (1975 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]).

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Object name is e-65-o3206-scheme1.jpg

Experimental

Crystal data

  • C12H16N4O2
  • M r = 248.29
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o3206-efi1.jpg
  • a = 12.6013 (4) Å
  • b = 10.6114 (3) Å
  • c = 9.2967 (2) Å
  • β = 93.874 (2)°
  • V = 1240.29 (6) Å3
  • Z = 4
  • Cu Kα radiation
  • μ = 0.77 mm−1
  • T = 90 K
  • 0.23 × 0.17 × 0.01 mm

Data collection

  • Bruker Kappa APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2004 [triangle]) T min = 0.843, T max = 0.992
  • 11437 measured reflections
  • 2249 independent reflections
  • 1655 reflections with I > 2σ(I)
  • R int = 0.053

Refinement

  • R[F 2 > 2σ(F 2)] = 0.038
  • wR(F 2) = 0.095
  • S = 1.03
  • 2249 reflections
  • 168 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.20 e Å−3
  • Δρmin = −0.20 e Å−3

Data collection: APEX2 (Bruker, 2006 [triangle]); cell refinement: SAINT (Bruker, 2006 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 [triangle]).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680904937X/gk2239sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680904937X/gk2239Isup2.hkl

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

Acknowledgments

RI acknowledges Whittier College for the faculty research grant that funded this research. TC thanks Whittier College for summer support. Mr Jonathan Attard is thanked for an initial trial synthesis of the title compound.

supplementary crystallographic information

Comment

Diazene derivatives have found utility in various research areas (Lalezari & Afgahi, 1975; Chen et al., 2005). Our research uses morpholine-substituted aryl diazenes as easily handled and prepared equivalents for the in situ generation of diazonium ions that are then used in the synthesis of novel derivatives of trans–stilbene via a Heck-type reaction (Sengupta et al., 1998).

The structure of the title compound is shown in Figure 1. The N–N double bond adopted a trans-configuration. A N3–N2–N1 bond angle of 113.93 (14) ° deviates from the optimal trigonal planar geometry by approximately 6°. The diazene moiety, N3–N2–N1, exhibits π –delocalization, evidenced by N1–N2 and N2–N3 bond lengths of 1.346 (2) and 1.2707 (19) Å respectively. These values are between literature value of 1.222 Å for a N–N double bond and 1.420 Å for a N(sp2)–N(sp3) single bond (Allen et al., 1987) Morpholine nitrogen bond angles that ranged from 113.52 (14)–121.12 (14)° indicated that the morpholine nitrogen had some degree of sp2 hybridization and participated in π –delocalization. The morpholine ring adopted a conventional chair conformation,with the diazenyl group in the equitorial postion on the morpholine nitrogen, N3. The acetamino and diazene groups were found to be twisted 25.5 (3)° and 12.3 (2)° respectively from the plane of the phenyl ring. The structure of the title compound is similar to the structure of related diazenes (Little et al., 2008).

Experimental

Synthetic procedures were carried out using standard techniques. Solvents and reagents were used as received. Melting points were determined in open capillaries and are uncorrected. 1H and 13C NMR spectra were recorded on a Jeol ECX 300 MHz spectrometer using TMS as the internal standard. The IR spectrum was recorded as a KBr disk on a JASCO 460 F T–IR.

4.26 g of N–(4-aminophenyl)acetamide (28.4 mmol) was added to 12.5 ml of 6 M HCl in an ice water bath and cooled to 0° C to yield a light pink precipitate. The solid was maintained at 0° C, and a solution of 2.08 g (30.09 mmol) of NaNO2 in 4.0 ml H2O was added dropwise with stirring over ten minutes; a dark green brown solution resulted. After stirring for twenty minutes, 2.70 ml morpholine (2.74 g, 31.42 mmol) was added dropwise in 10 minutes. Then saturated K2CO3 was added until pH of 8 was reached, and solution was stirred for ten minutes: a yellow brown suspension resulted. The tan solid was collected using vacuum filtration, washed well with water and dried in air. The crude product was recrystallized from a 1:3 benzene:cyclohexane mixture to give 3.55 g (50.4%) of 4-[(E)-(acetamidophenyl)diazenyl]-morpholine as a tan microcrystalline solid.

m.p. 448-449 K. IR (KBr) 3294, 3055, 2971, 1664, 1600 cm-1. 1H NMR (300 MHz, CD3CN): 2.03 (s, 3H), 3.67 (m, 4H), 3.77 (m, 4H), 7.33 (d, 2H), 7.51 (d, 2H), 8.33 (s, 1H). 13C NMR (75 MHz, DMSO–d6): 24.54, 48.33, 66.05, 119.89, 121.27, 138.28, 145.50, 168.75 p.p.m.. Rf = 0.61 (ethyl acetate)

Refinement

H atoms on C were placed in idealized positions with C—H distances 0.95 - 0.99 Å and thereafter treated as riding. A torsional parameter was refined for the methyl group. The N—H hydrogen atom was placed from a difference map, and its coordinates were refined. Uiso for H were assigned as 1.2 times Ueq of the attached atoms (1.5 for methyl).

Figures

Fig. 1.
Molecular structure of the title compound with displacement ellipsoids at the 50% probability level. H atoms are shown with arbitrary radius.

Crystal data

C12H16N4O2F(000) = 528
Mr = 248.29Dx = 1.330 Mg m3
Monoclinic, P21/cCu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybcCell parameters from 1544 reflections
a = 12.6013 (4) Åθ = 3.5–67.6°
b = 10.6114 (3) ŵ = 0.77 mm1
c = 9.2967 (2) ÅT = 90 K
β = 93.874 (2)°Plate, colorless
V = 1240.29 (6) Å30.23 × 0.17 × 0.01 mm
Z = 4

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer2249 independent reflections
Radiation source: fine-focus sealed tube1655 reflections with I > 2σ(I)
graphiteRint = 0.053
phi and ω scansθmax = 68.8°, θmin = 3.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)h = −15→14
Tmin = 0.843, Tmax = 0.992k = −12→12
11437 measured reflectionsl = −7→11

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.095w = 1/[σ2(Fo2) + (0.0421P)2 + 0.3P] where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
2249 reflectionsΔρmax = 0.20 e Å3
168 parametersΔρmin = −0.20 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0012 (2)

Special details

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)

xyzUiso*/Ueq
O10.58539 (10)0.71775 (12)0.68342 (13)0.0281 (3)
O20.91392 (10)−0.19398 (12)0.26306 (12)0.0260 (3)
N10.63437 (11)0.46590 (13)0.62337 (14)0.0203 (3)
N20.66849 (11)0.34581 (13)0.61964 (14)0.0198 (3)
N30.73809 (11)0.32649 (13)0.52939 (14)0.0204 (3)
N40.88774 (11)−0.17257 (13)0.50181 (15)0.0179 (3)
H4N0.8936 (14)−0.2115 (18)0.5884 (18)0.021*
C10.52108 (14)0.61813 (17)0.73287 (19)0.0249 (4)
H1A0.46090.60250.66100.030*
H1B0.49140.64340.82440.030*
C20.58485 (14)0.49823 (17)0.75637 (18)0.0224 (4)
H2A0.64040.51040.83570.027*
H2B0.53760.42890.78360.027*
C30.69258 (14)0.56752 (16)0.55717 (18)0.0218 (4)
H3A0.71160.54190.45980.026*
H3B0.75910.58590.61630.026*
C40.62278 (15)0.68384 (17)0.54677 (19)0.0258 (4)
H4A0.66370.75500.50950.031*
H4B0.56110.66790.47750.031*
C50.77020 (13)0.19715 (16)0.52560 (17)0.0181 (4)
C60.74615 (13)0.10620 (16)0.62701 (17)0.0199 (4)
H60.70410.12790.70440.024*
C70.78367 (13)−0.01525 (16)0.61454 (17)0.0192 (4)
H70.7660−0.07730.68260.023*
C80.84737 (13)−0.04798 (16)0.50304 (16)0.0169 (4)
C90.87227 (14)0.04281 (16)0.40320 (17)0.0188 (4)
H90.91550.02160.32700.023*
C100.83377 (13)0.16458 (16)0.41515 (17)0.0186 (4)
H100.85120.22650.34680.022*
C110.92053 (13)−0.23624 (16)0.38778 (17)0.0189 (4)
C120.96655 (14)−0.36422 (16)0.42131 (18)0.0217 (4)
H12A0.9306−0.42700.35790.033*
H12B0.9564−0.38550.52200.033*
H12C1.0427−0.36370.40580.033*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0306 (7)0.0194 (7)0.0348 (7)−0.0004 (6)0.0055 (6)−0.0053 (6)
O20.0442 (8)0.0191 (7)0.0147 (6)0.0039 (6)0.0025 (5)−0.0009 (5)
N10.0226 (7)0.0150 (7)0.0236 (7)0.0021 (6)0.0038 (6)−0.0025 (6)
N20.0215 (7)0.0184 (8)0.0195 (7)0.0007 (6)0.0002 (6)−0.0021 (6)
N30.0221 (7)0.0192 (8)0.0199 (7)0.0012 (6)0.0009 (6)−0.0028 (6)
N40.0243 (8)0.0160 (7)0.0136 (7)0.0016 (6)0.0025 (6)0.0012 (6)
C10.0229 (9)0.0227 (10)0.0293 (9)0.0014 (8)0.0027 (8)−0.0037 (8)
C20.0232 (9)0.0229 (10)0.0215 (9)0.0006 (7)0.0040 (7)−0.0033 (8)
C30.0244 (9)0.0168 (9)0.0247 (9)−0.0009 (8)0.0042 (8)−0.0008 (7)
C40.0296 (10)0.0185 (9)0.0294 (10)−0.0005 (8)0.0023 (8)−0.0016 (8)
C50.0173 (8)0.0173 (9)0.0190 (8)0.0002 (7)−0.0025 (7)−0.0032 (7)
C60.0197 (9)0.0225 (10)0.0179 (8)−0.0005 (7)0.0029 (7)−0.0027 (7)
C70.0218 (9)0.0198 (9)0.0162 (8)−0.0010 (7)0.0016 (7)0.0010 (7)
C80.0185 (8)0.0169 (9)0.0148 (8)−0.0001 (7)−0.0018 (7)−0.0022 (7)
C90.0214 (8)0.0198 (9)0.0152 (8)0.0001 (7)0.0018 (7)−0.0013 (7)
C100.0220 (8)0.0180 (9)0.0157 (8)−0.0021 (7)0.0001 (7)0.0023 (7)
C110.0207 (9)0.0180 (9)0.0179 (9)−0.0009 (7)0.0010 (7)−0.0009 (7)
C120.0277 (9)0.0182 (9)0.0194 (8)0.0023 (8)0.0030 (7)−0.0020 (8)

Geometric parameters (Å, °)

O1—C11.427 (2)C3—H3B0.9900
O1—C41.430 (2)C4—H4A0.9900
O2—C111.2407 (19)C4—H4B0.9900
N1—N21.346 (2)C5—C101.388 (2)
N1—C21.463 (2)C5—C61.397 (2)
N1—C31.463 (2)C6—C71.380 (2)
N2—N31.2707 (19)C6—H60.9500
N3—C51.432 (2)C7—C81.397 (2)
N4—C111.345 (2)C7—H70.9500
N4—C81.417 (2)C8—C91.388 (2)
N4—H4N0.903 (17)C9—C101.387 (2)
C1—C21.513 (2)C9—H90.9500
C1—H1A0.9900C10—H100.9500
C1—H1B0.9900C11—C121.501 (2)
C2—H2A0.9900C12—H12A0.9800
C2—H2B0.9900C12—H12B0.9800
C3—C41.515 (2)C12—H12C0.9800
C3—H3A0.9900
C1—O1—C4109.15 (13)O1—C4—H4B109.2
N2—N1—C2113.52 (14)C3—C4—H4B109.2
N2—N1—C3121.12 (14)H4A—C4—H4B107.9
C2—N1—C3115.93 (14)C10—C5—C6119.32 (16)
N3—N2—N1113.93 (14)C10—C5—N3115.78 (15)
N2—N3—C5112.31 (14)C6—C5—N3124.83 (14)
C11—N4—C8127.19 (14)C7—C6—C5119.82 (15)
C11—N4—H4N117.5 (12)C7—C6—H6120.1
C8—N4—H4N115.3 (12)C5—C6—H6120.1
O1—C1—C2111.22 (14)C6—C7—C8120.77 (16)
O1—C1—H1A109.4C6—C7—H7119.6
C2—C1—H1A109.4C8—C7—H7119.6
O1—C1—H1B109.4C9—C8—C7119.38 (16)
C2—C1—H1B109.4C9—C8—N4123.00 (15)
H1A—C1—H1B108.0C7—C8—N4117.55 (14)
N1—C2—C1109.14 (14)C10—C9—C8119.79 (15)
N1—C2—H2A109.9C10—C9—H9120.1
C1—C2—H2A109.9C8—C9—H9120.1
N1—C2—H2B109.9C9—C10—C5120.90 (16)
C1—C2—H2B109.9C9—C10—H10119.5
H2A—C2—H2B108.3C5—C10—H10119.5
N1—C3—C4108.78 (14)O2—C11—N4123.37 (15)
N1—C3—H3A109.9O2—C11—C12121.44 (15)
C4—C3—H3A109.9N4—C11—C12115.19 (14)
N1—C3—H3B109.9C11—C12—H12A109.5
C4—C3—H3B109.9C11—C12—H12B109.5
H3A—C3—H3B108.3H12A—C12—H12B109.5
O1—C4—C3111.89 (14)C11—C12—H12C109.5
O1—C4—H4A109.2H12A—C12—H12C109.5
C3—C4—H4A109.2H12B—C12—H12C109.5
C2—N1—N2—N3−159.87 (14)N3—C5—C6—C7−178.36 (16)
C3—N1—N2—N3−14.8 (2)C5—C6—C7—C81.3 (3)
N1—N2—N3—C5−178.35 (13)C6—C7—C8—C9−0.5 (2)
C4—O1—C1—C262.57 (18)C6—C7—C8—N4176.59 (16)
N2—N1—C2—C1−163.16 (14)C11—N4—C8—C9−25.5 (3)
C3—N1—C2—C149.87 (19)C11—N4—C8—C7157.45 (16)
O1—C1—C2—N1−55.31 (19)C7—C8—C9—C100.0 (2)
N2—N1—C3—C4166.58 (14)N4—C8—C9—C10−176.97 (16)
C2—N1—C3—C4−49.15 (19)C8—C9—C10—C5−0.2 (3)
C1—O1—C4—C3−62.36 (19)C6—C5—C10—C90.9 (2)
N1—C3—C4—O154.28 (19)N3—C5—C10—C9178.10 (15)
N2—N3—C5—C10170.70 (14)C8—N4—C11—O2−4.0 (3)
N2—N3—C5—C6−12.3 (2)C8—N4—C11—C12175.96 (16)
C10—C5—C6—C7−1.4 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N4—H4N···O2i0.903 (17)1.911 (18)2.8115 (18)174.5 (17)

Symmetry codes: (i) x, −y−1/2, z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: GK2239).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L. & Orpen, A. G. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Bruker (2006). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Chen, B., Flatt, A. K., Jian, H., Hudson, J. L. & Tour, J. M. (2005). Chem. Mater. 17, 4832–4836.
  • Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
  • Lalezari, I. & Afgahi, F. (1975). J. Pharm. Sci. 64, 698–699. [PubMed]
  • Little, V. R., Jenkins, H. & Vaughan, K. (2008). J. Chem. Crystallogr. 38, 447–452.
  • Sengupta, S., Bhattacharyya, S. & Sadhukhan, S. K. (1998). J. Chem. Soc. Perkin Trans. 1, pp. 275–277.
  • Sheldrick, G. (2004). SADABS. University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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