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Acta Crystallogr Sect E Struct Rep Online. 2010 July 1; 66(Pt 7): o1730.
Published online 2010 June 23. doi:  10.1107/S1600536810022762
PMCID: PMC3007049

Dibutyl 5-[(4-ethoxycarbonylphenyl)diazenyl]benzene-1,3-dicarboxylate

Abstract

In the title compound, C25H30N2O6, the dihedral angle between the aromatic rings is 3.79 (1) Å and the N=N bond shows a trans conformation. Both butyl side chains show evidence of disorder.

Related literature

For general background to dendrimers related to the title compound, see: Tomalia et al. (1990 [triangle]); Bosman et al. (1999 [triangle]). For a related structure, see: Wang et al. (2004 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o1730-scheme1.jpg

Experimental

Crystal data

  • C25H30N2O6
  • M r = 454.51
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1730-efi1.jpg
  • a = 8.675 (2) Å
  • b = 11.299 (3) Å
  • c = 13.636 (3) Å
  • α = 97.311 (3)°
  • β = 94.806 (3)°
  • γ = 109.793 (2)°
  • V = 1235.8 (5) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 293 K
  • 0.12 × 0.10 × 0.08 mm

Data collection

  • Bruker APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2001 [triangle]) T min = 0.990, T max = 0.993
  • 8643 measured reflections
  • 4275 independent reflections
  • 2736 reflections with I > 2σ(I)
  • R int = 0.022

Refinement

  • R[F 2 > 2σ(F 2)] = 0.064
  • wR(F 2) = 0.218
  • S = 1.05
  • 4275 reflections
  • 302 parameters
  • 13 restraints
  • H-atom parameters constrained
  • Δρmax = 0.55 e Å−3
  • Δρmin = −0.32 e Å−3

Data collection: APEX2 (Bruker, 2004 [triangle]); cell refinement: SAINT-Plus (Bruker, 2001 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810022762/hb5477sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810022762/hb5477Isup2.hkl

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

Acknowledgments

Financial support from the National Natural Science Foundation of China (20501011) and Liaocheng University is gratefully acknowledged.

supplementary crystallographic information

Comment

Dendrimers have been the subject of intense investigation due to both interesting structural properties and promising applications in the areas of biological and material sciences (Tomalia et al., 1990; Bosman et al., 1999). Here, we describe the cystallization and structural characterization of the title compound.

As shown in Fig 1. the dihedral angle between the phenyl planes of the two benzene rings is 3.79 (1) Å. The mean deviations for the two phenyl planar are 0.0058 (1) and 0.0028 (1) Å, respectively. The C=O and C—O bond distances of carbonyl groups are 1.195 (3)—1.200 (3) and 1.324 (3)—1.452 (3) Å, respectively. The N=N and N—C bond distances are 1.240 (3) and 1.423 (3)—1.431 (3) Å, respectively, which are in the normal range compared to reported Dendrimer derivatives (Wang et al., 2004).

Experimental

A yellow powder of ethyl 4-((dibutyl-3',5'-biscarbonylphenyl)diazenyl)benzoate (Jinan Henghua Science & Technology Co. Ltd.) (1 mmol 0.45 g) was dissolved in 10 ml ethanol and evaporated in an open flask at room temperature. Three days later, orange blocks of (I) were obained. Anal. C25H30N2O6: C, 66.01; H, 6.60; N, 6.16%. Found: C, 65.98; H, 6.47; N, 6.05%.

Refinement

Hydrogen atoms were placed in geometrically calculated positions (C—H 0.95 Å for aromatic and formyl, 0.99 Å for methylene and 0.98 Å for methyl) and included in the refinement in a riding motion approximation with Uiso(H) = 1.2Ueq(C) [for methyl groups Uiso(H) = 1.5Ueq(C)].

Figures

Fig. 1.
The molecular sturcture of (I) with displacement ellipsoids drawn at the 30% probability level; H atoms are given as spheres of arbitrary radius.

Crystal data

C25H30N2O6Z = 2
Mr = 454.51F(000) = 484
Triclinic, P1Dx = 1.221 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.675 (2) ÅCell parameters from 2660 reflections
b = 11.299 (3) Åθ = 2.5–27.1°
c = 13.636 (3) ŵ = 0.09 mm1
α = 97.311 (3)°T = 293 K
β = 94.806 (3)°Block, yellow
γ = 109.793 (2)°0.12 × 0.10 × 0.08 mm
V = 1235.8 (5) Å3

Data collection

Bruker APEXII CCD diffractometer4275 independent reflections
Radiation source: fine-focus sealed tube2736 reflections with I > 2σ(I)
graphiteRint = 0.022
[var phi] and ω scansθmax = 25.0°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2001)h = −10→10
Tmin = 0.990, Tmax = 0.993k = −13→13
8643 measured reflectionsl = −15→16

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.064Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.218H-atom parameters constrained
S = 1.05w = 1/[σ2(Fo2) + (0.1149P)2 + 0.3064P] where P = (Fo2 + 2Fc2)/3
4275 reflections(Δ/σ)max < 0.001
302 parametersΔρmax = 0.55 e Å3
13 restraintsΔρmin = −0.32 e Å3

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
O11.0434 (3)0.2950 (2)0.48258 (15)0.0725 (6)
O20.8502 (3)0.3718 (2)0.52977 (16)0.0932 (8)
O30.7562 (3)−0.0204 (2)0.05822 (16)0.0871 (7)
O40.9356 (3)−0.0106 (2)0.18814 (15)0.0810 (7)
O5−0.2310 (2)0.3824 (2)0.02977 (15)0.0714 (6)
O6−0.1835 (3)0.5354 (2)0.1600 (2)0.0974 (8)
N10.4477 (3)0.2563 (2)0.19969 (16)0.0588 (6)
N20.4018 (3)0.3269 (2)0.25818 (16)0.0577 (6)
C11.3390 (8)−0.0964 (7)0.3283 (5)0.173 (3)
H1A1.3681−0.16210.29130.260*
H1B1.3211−0.11540.39400.260*
H1C1.4271−0.01590.33330.260*
C21.1938 (10)−0.0905 (10)0.2790 (6)0.225 (4)
H2A1.1052−0.15680.30040.270*
H2B1.1878−0.01050.31040.270*
C31.1450 (9)−0.0977 (7)0.1825 (5)0.189 (3)
H3A1.1593−0.17440.15070.227*
H3B1.2301−0.02750.16250.227*
C40.9940 (5)−0.0991 (4)0.1300 (3)0.0905 (11)
H4A0.9116−0.18430.11980.109*
H4B1.0129−0.07450.06520.109*
C51.2579 (9)0.1314 (8)0.5848 (7)0.207 (4)
H5A1.28090.16550.65480.311*
H5B1.30170.06430.57200.311*
H5C1.14050.09800.56460.311*
C61.3321 (7)0.2288 (7)0.5303 (5)0.149 (2)
H6A1.28230.20140.46110.179*
H6B1.44850.24070.53270.179*
C71.3166 (5)0.3532 (4)0.5670 (4)0.1102 (14)
H7A1.36490.41170.52230.132*
H7B1.38310.38660.63190.132*
C81.1471 (4)0.3556 (3)0.5769 (2)0.0842 (10)
H8A1.10250.31020.62980.101*
H8B1.15160.44290.59310.101*
C90.8992 (4)0.3119 (3)0.4689 (2)0.0642 (8)
C100.8072 (3)0.2505 (2)0.36752 (19)0.0545 (7)
C110.8557 (3)0.1654 (2)0.3055 (2)0.0552 (7)
H110.94630.14460.32740.066*
C120.7685 (3)0.1118 (2)0.21106 (19)0.0527 (6)
C130.8165 (3)0.0201 (3)0.1433 (2)0.0615 (7)
C140.6346 (3)0.1444 (2)0.1786 (2)0.0569 (7)
H140.57690.10950.11500.068*
C150.5867 (3)0.2286 (2)0.24046 (19)0.0523 (6)
C160.6712 (3)0.2805 (2)0.33568 (19)0.0532 (6)
H160.63670.33510.37790.064*
C170.2637 (3)0.3539 (2)0.21661 (19)0.0523 (6)
C180.1725 (3)0.2944 (3)0.1236 (2)0.0603 (7)
H180.20070.23340.08420.072*
C190.0408 (3)0.3268 (3)0.0906 (2)0.0608 (7)
H19−0.02070.28680.02870.073*
C20−0.0022 (3)0.4184 (2)0.1480 (2)0.0538 (6)
C210.0888 (3)0.4765 (3)0.2404 (2)0.0631 (7)
H210.06110.53800.27960.076*
C220.2203 (3)0.4437 (3)0.2744 (2)0.0623 (7)
H220.28020.48240.33690.075*
C23−0.1457 (4)0.4536 (3)0.1153 (2)0.0629 (7)
C24−0.3775 (4)0.4066 (4)−0.0072 (3)0.0835 (10)
H24A−0.34730.4937−0.01970.100*
H24B−0.45380.39480.04190.100*
C25−0.4555 (5)0.3171 (5)−0.0998 (4)0.1176 (15)
H25A−0.37720.3263−0.14670.176*
H25B−0.54910.3349−0.12760.176*
H25C−0.49130.2314−0.08600.176*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0697 (13)0.0861 (14)0.0657 (12)0.0446 (11)−0.0120 (10)−0.0074 (10)
O20.0977 (17)0.1285 (19)0.0641 (13)0.0739 (16)−0.0125 (12)−0.0253 (13)
O30.0918 (16)0.1085 (17)0.0657 (14)0.0566 (14)−0.0027 (12)−0.0195 (12)
O40.0927 (16)0.0967 (15)0.0693 (13)0.0649 (13)−0.0007 (11)−0.0106 (11)
O50.0609 (12)0.0868 (14)0.0751 (14)0.0419 (11)−0.0039 (10)0.0088 (11)
O60.0949 (17)0.1010 (17)0.1112 (19)0.0690 (15)−0.0067 (14)−0.0114 (14)
N10.0510 (13)0.0669 (14)0.0607 (14)0.0285 (11)0.0006 (10)0.0014 (11)
N20.0523 (13)0.0640 (13)0.0594 (13)0.0284 (11)0.0014 (10)0.0017 (10)
C10.140 (5)0.215 (7)0.181 (6)0.091 (5)−0.021 (4)0.043 (5)
C20.186 (7)0.343 (12)0.185 (7)0.177 (8)−0.038 (6)−0.012 (7)
C30.216 (6)0.243 (6)0.161 (5)0.188 (5)−0.031 (4)−0.049 (4)
C40.099 (3)0.097 (2)0.091 (2)0.065 (2)0.0094 (19)−0.0101 (18)
C50.173 (6)0.213 (7)0.302 (10)0.105 (6)0.090 (7)0.137 (8)
C60.108 (4)0.195 (6)0.185 (6)0.092 (4)0.028 (4)0.065 (5)
C70.080 (3)0.120 (3)0.124 (3)0.036 (2)−0.021 (2)0.019 (3)
C80.084 (2)0.092 (2)0.073 (2)0.0434 (19)−0.0254 (17)−0.0106 (17)
C90.0676 (18)0.0685 (17)0.0615 (17)0.0375 (15)−0.0027 (14)−0.0014 (13)
C100.0532 (15)0.0577 (15)0.0550 (15)0.0260 (12)0.0036 (12)0.0025 (12)
C110.0516 (15)0.0594 (15)0.0595 (16)0.0272 (12)0.0054 (12)0.0073 (12)
C120.0508 (15)0.0538 (14)0.0560 (15)0.0226 (12)0.0106 (12)0.0036 (11)
C130.0589 (17)0.0664 (17)0.0595 (18)0.0265 (14)0.0085 (14)−0.0010 (13)
C140.0537 (15)0.0601 (15)0.0551 (15)0.0213 (13)0.0033 (12)0.0027 (12)
C150.0460 (14)0.0568 (14)0.0560 (15)0.0224 (12)0.0043 (12)0.0067 (11)
C160.0524 (15)0.0555 (14)0.0548 (15)0.0259 (12)0.0070 (12)0.0011 (11)
C170.0455 (14)0.0607 (15)0.0524 (14)0.0227 (12)0.0033 (11)0.0066 (11)
C180.0578 (16)0.0670 (16)0.0602 (16)0.0338 (14)0.0028 (13)−0.0046 (13)
C190.0548 (16)0.0701 (17)0.0575 (16)0.0295 (13)−0.0034 (12)−0.0038 (13)
C200.0486 (14)0.0554 (14)0.0606 (16)0.0229 (12)0.0065 (12)0.0089 (12)
C210.0654 (18)0.0652 (16)0.0642 (17)0.0353 (14)0.0068 (14)−0.0034 (13)
C220.0608 (17)0.0711 (17)0.0546 (16)0.0312 (14)−0.0024 (13)−0.0064 (13)
C230.0593 (17)0.0638 (16)0.0738 (19)0.0322 (14)0.0088 (15)0.0110 (14)
C240.0625 (19)0.109 (3)0.094 (2)0.0478 (19)−0.0003 (17)0.027 (2)
C250.081 (3)0.141 (4)0.125 (3)0.045 (3)−0.026 (2)0.012 (3)

Geometric parameters (Å, °)

O1—C91.329 (3)C7—H7A0.9700
O1—C81.448 (3)C7—H7B0.9700
O2—C91.200 (3)C8—H8A0.9700
O3—C131.196 (3)C8—H8B0.9700
O4—C131.324 (3)C9—C101.492 (4)
O4—C41.447 (3)C10—C161.385 (3)
O5—C231.330 (3)C10—C111.394 (3)
O5—C241.452 (3)C11—C121.388 (4)
O6—C231.195 (3)C11—H110.9300
N1—N21.240 (3)C12—C141.388 (4)
N1—C151.431 (3)C12—C131.488 (3)
N2—C171.423 (3)C14—C151.383 (3)
C1—C21.403 (7)C14—H140.9300
C1—H1A0.9600C15—C161.386 (4)
C1—H1B0.9600C16—H160.9300
C1—H1C0.9600C17—C221.378 (3)
C2—C31.331 (7)C17—C181.393 (4)
C2—H2A0.9700C18—C191.372 (4)
C2—H2B0.9700C18—H180.9300
C3—C41.434 (7)C19—C201.388 (3)
C3—H3A0.9700C19—H190.9300
C3—H3B0.9700C20—C211.384 (4)
C4—H4A0.9700C20—C231.481 (4)
C4—H4B0.9700C21—C221.377 (4)
C5—C61.409 (8)C21—H210.9300
C5—H5A0.9600C22—H220.9300
C5—H5B0.9600C24—C251.465 (5)
C5—H5C0.9600C24—H24A0.9700
C6—C71.485 (7)C24—H24B0.9700
C6—H6A0.9700C25—H25A0.9600
C6—H6B0.9700C25—H25B0.9600
C7—C81.496 (5)C25—H25C0.9600
C9—O1—C8116.9 (2)O1—C9—C10111.9 (2)
C13—O4—C4117.4 (2)C16—C10—C11120.3 (2)
C23—O5—C24116.5 (2)C16—C10—C9118.2 (2)
N2—N1—C15114.7 (2)C11—C10—C9121.5 (2)
N1—N2—C17114.1 (2)C12—C11—C10119.8 (2)
C2—C1—H1A109.5C12—C11—H11120.1
C2—C1—H1B109.5C10—C11—H11120.1
H1A—C1—H1B109.5C14—C12—C11119.7 (2)
C2—C1—H1C109.5C14—C12—C13119.1 (2)
H1A—C1—H1C109.5C11—C12—C13121.1 (2)
H1B—C1—H1C109.5O3—C13—O4123.8 (2)
C3—C2—C1131.1 (7)O3—C13—C12124.4 (3)
C3—C2—H2A104.5O4—C13—C12111.9 (2)
C1—C2—H2A104.5C15—C14—C12120.2 (2)
C3—C2—H2B104.5C15—C14—H14119.9
C1—C2—H2B104.5C12—C14—H14119.9
H2A—C2—H2B105.6C14—C15—C16120.4 (2)
C2—C3—C4132.1 (6)C14—C15—N1115.8 (2)
C2—C3—H3A104.2C16—C15—N1123.8 (2)
C4—C3—H3A104.2C10—C16—C15119.6 (2)
C2—C3—H3B104.2C10—C16—H16120.2
C4—C3—H3B104.2C15—C16—H16120.2
H3A—C3—H3B105.5C22—C17—C18119.8 (2)
C3—C4—O4108.9 (3)C22—C17—N2116.3 (2)
C3—C4—H4A109.9C18—C17—N2123.9 (2)
O4—C4—H4A109.9C19—C18—C17119.3 (2)
C3—C4—H4B109.9C19—C18—H18120.3
O4—C4—H4B109.9C17—C18—H18120.3
H4A—C4—H4B108.3C18—C19—C20121.1 (2)
C6—C5—H5A109.5C18—C19—H19119.4
C6—C5—H5B109.5C20—C19—H19119.4
H5A—C5—H5B109.5C21—C20—C19119.1 (2)
C6—C5—H5C109.5C21—C20—C23118.5 (2)
H5A—C5—H5C109.5C19—C20—C23122.4 (2)
H5B—C5—H5C109.5C22—C21—C20120.2 (2)
C5—C6—C7114.3 (6)C22—C21—H21119.9
C5—C6—H6A108.7C20—C21—H21119.9
C7—C6—H6A108.7C21—C22—C17120.5 (2)
C5—C6—H6B108.7C21—C22—H22119.7
C7—C6—H6B108.7C17—C22—H22119.7
H6A—C6—H6B107.6O6—C23—O5123.0 (3)
C6—C7—C8118.0 (4)O6—C23—C20124.8 (3)
C6—C7—H7A107.8O5—C23—C20112.2 (2)
C8—C7—H7A107.8O5—C24—C25108.2 (3)
C6—C7—H7B107.8O5—C24—H24A110.1
C8—C7—H7B107.8C25—C24—H24A110.1
H7A—C7—H7B107.2O5—C24—H24B110.1
O1—C8—C7107.9 (3)C25—C24—H24B110.1
O1—C8—H8A110.1H24A—C24—H24B108.4
C7—C8—H8A110.1C24—C25—H25A109.5
O1—C8—H8B110.1C24—C25—H25B109.5
C7—C8—H8B110.1H25A—C25—H25B109.5
H8A—C8—H8B108.4C24—C25—H25C109.5
O2—C9—O1124.2 (3)H25A—C25—H25C109.5
O2—C9—C10123.8 (3)H25B—C25—H25C109.5
C15—N1—N2—C17179.9 (2)C12—C14—C15—N1179.7 (2)
C1—C2—C3—C4175.9 (8)N2—N1—C15—C14176.5 (2)
C2—C3—C4—O439.1 (12)N2—N1—C15—C16−3.3 (4)
C13—O4—C4—C3166.9 (4)C11—C10—C16—C15−2.1 (4)
C5—C6—C7—C8−54.1 (7)C9—C10—C16—C15177.7 (2)
C9—O1—C8—C7−165.9 (3)C14—C15—C16—C101.9 (4)
C6—C7—C8—O1−52.5 (5)N1—C15—C16—C10−178.3 (2)
C8—O1—C9—O2−1.0 (5)N1—N2—C17—C22−172.5 (2)
C8—O1—C9—C10177.2 (3)N1—N2—C17—C188.1 (4)
O2—C9—C10—C1610.6 (5)C22—C17—C18—C190.3 (4)
O1—C9—C10—C16−167.7 (2)N2—C17—C18—C19179.6 (2)
O2—C9—C10—C11−169.7 (3)C17—C18—C19—C200.5 (4)
O1—C9—C10—C1112.1 (4)C18—C19—C20—C21−0.7 (4)
C16—C10—C11—C120.8 (4)C18—C19—C20—C23−178.8 (3)
C9—C10—C11—C12−179.0 (3)C19—C20—C21—C220.1 (4)
C10—C11—C12—C140.7 (4)C23—C20—C21—C22178.2 (3)
C10—C11—C12—C13−179.7 (2)C20—C21—C22—C170.7 (5)
C4—O4—C13—O3−0.4 (5)C18—C17—C22—C21−0.9 (4)
C4—O4—C13—C12−179.8 (3)N2—C17—C22—C21179.7 (3)
C14—C12—C13—O36.7 (4)C24—O5—C23—O6−1.3 (5)
C11—C12—C13—O3−173.0 (3)C24—O5—C23—C20178.1 (2)
C14—C12—C13—O4−174.0 (2)C21—C20—C23—O65.3 (5)
C11—C12—C13—O46.4 (4)C19—C20—C23—O6−176.7 (3)
C11—C12—C14—C15−0.9 (4)C21—C20—C23—O5−174.1 (2)
C13—C12—C14—C15179.5 (2)C19—C20—C23—O53.9 (4)
C12—C14—C15—C16−0.5 (4)C23—O5—C24—C25−178.6 (3)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5477).

References

  • Bosman, A. W., Janssen, H. M. & Weijer, E. W. (1999). Chem. Rev.99, 1665–1688. [PubMed]
  • Bruker (2001). SAINT-Plus and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2004). APEX2 Bruker AXS Inc., Madison, Wisconsin, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Tomalia, D. A., Naylor, A. M. & Goddard, W. A. (1990). Angew. Chem. Int. Ed. Engl.29, 138–146.
  • Wang, S., Wang, X., Li, L. & Advincula, R. C. (2004). J. Org. Chem.69, 9073–9084. [PubMed]

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