Download citation
Download citation
link to html
The title compound, C21H17N3O2, is a norbornene derivative containing an azo group which is disordered over two sites in an approximate 2:1 ratio. The two aromatic rings are almost coplanar [dihedral angle 9.25 (10)°]. The crystal packing is stabilized by an inter­molecular C—H...O hydrogen bond.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807043863/bt2500sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807043863/bt2500Isup2.hkl
Contains datablock I

CCDC reference: 663753

Key indicators

  • Single-crystal X-ray study
  • T = 292 K
  • Mean [sigma](C-C) = 0.004 Å
  • Disorder in main residue
  • R factor = 0.059
  • wR factor = 0.139
  • Data-to-parameter ratio = 14.9

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT301_ALERT_3_C Main Residue Disorder ......................... 7.00 Perc.
Alert level G PLAT793_ALERT_1_G Check the Absolute Configuration of C14 = ... S PLAT793_ALERT_1_G Check the Absolute Configuration of C15 = ... R PLAT793_ALERT_1_G Check the Absolute Configuration of C17 = ... R PLAT793_ALERT_1_G Check the Absolute Configuration of C20 = ... S PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 2
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 5 ALERT level G = General alerts; check 4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

The family of azobenzenes has been investigated intensively due to the their remarkable photochemically induced trans to cis isomerism. Azo polymers are of interest in various fields (Zhao et al., 1999). As a part of our investigation of preparing azo polymers, we report the crystal structure of the title compound (Fig. 1).

Bond lengths and angles of the norbornene moiety are similar to those in other norbornene derivatives (Tian et al., 2007). By means of C–H···O hydrogen bonds, the molecules are linked into a ribbon. (Tab. 1, Fig. 2). The two aromatic rings are almost coplanar [dihedral angle 9.25 (10)°]. The dihedral angle between the rings C13—C14—C15—C16—N13 and C7—C8—C9—C10—C11—C12 is 64.32 (7)° (Fig. 1).

Related literature top

For related literature, see: Tian et al. (2007); Zhao et al. (1999).

Experimental top

The title compound was prepared from norbornene dianhydride and 4-azobenzene according to the literature method (Tian et al., 2007). Single crystals were obtained by slow evaporation of a ethanol solution.

Refinement top

All hydrogen atoms were located in a difference Fourier map, but they were constrained to ride on their parent atoms with C—Haryl, C—Hmethylene and C—Hmethine-H distances of 0.93, 0.97 and 0.98 Å, respectively. Uiso(H) was set to 1.2Ueq(C). The two N atoms of the azo moiety are disordered over two sites with occupancies of 0.681 (12) and 0.319 (12). The C—N bond distances of the disordered N atoms were restrained to be equal within 0.01 Å.

Structure description top

The family of azobenzenes has been investigated intensively due to the their remarkable photochemically induced trans to cis isomerism. Azo polymers are of interest in various fields (Zhao et al., 1999). As a part of our investigation of preparing azo polymers, we report the crystal structure of the title compound (Fig. 1).

Bond lengths and angles of the norbornene moiety are similar to those in other norbornene derivatives (Tian et al., 2007). By means of C–H···O hydrogen bonds, the molecules are linked into a ribbon. (Tab. 1, Fig. 2). The two aromatic rings are almost coplanar [dihedral angle 9.25 (10)°]. The dihedral angle between the rings C13—C14—C15—C16—N13 and C7—C8—C9—C10—C11—C12 is 64.32 (7)° (Fig. 1).

For related literature, see: Tian et al. (2007); Zhao et al. (1999).

Computing details top

Data collection: SMART (Bruker 2001); cell refinement: SMART (Bruker 2001); data reduction: SAINT (Bruker 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker 2001); software used to prepare material for publication: SHELXTL (Bruker 2001).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.
[Figure 2] Fig. 2. Crystal packing of the title compound.
N-(4-Azobenzenyl)-5-norbornene-2,3-dicarboximide top
Crystal data top
C21H17N3O2F(000) = 1440
Mr = 343.38Dx = 1.318 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1899 reflections
a = 25.190 (2) Åθ = 3.2–20.8°
b = 6.5076 (5) ŵ = 0.09 mm1
c = 24.2792 (19) ÅT = 292 K
β = 119.567 (1)°Block, red
V = 3461.7 (5) Å30.20 × 0.20 × 0.10 mm
Z = 8
Data collection top
CCD area detector
diffractometer
2363 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.041
Graphite monochromatorθmax = 27.0°, θmin = 1.9°
φ and ω scansh = 3232
13859 measured reflectionsk = 87
3778 independent reflectionsl = 3129
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.059Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.139H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0477P)2 + 1.3571P]
where P = (Fo2 + 2Fc2)/3
3778 reflections(Δ/σ)max = 0.001
254 parametersΔρmax = 0.16 e Å3
2 restraintsΔρmin = 0.18 e Å3
Crystal data top
C21H17N3O2V = 3461.7 (5) Å3
Mr = 343.38Z = 8
Monoclinic, C2/cMo Kα radiation
a = 25.190 (2) ŵ = 0.09 mm1
b = 6.5076 (5) ÅT = 292 K
c = 24.2792 (19) Å0.20 × 0.20 × 0.10 mm
β = 119.567 (1)°
Data collection top
CCD area detector
diffractometer
2363 reflections with I > 2σ(I)
13859 measured reflectionsRint = 0.041
3778 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0592 restraints
wR(F2) = 0.139H-atom parameters constrained
S = 1.06Δρmax = 0.16 e Å3
3778 reflectionsΔρmin = 0.18 e Å3
254 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
xyzUiso*/UeqOcc. (<1)
C10.08004 (11)0.3958 (5)0.69015 (11)0.0732 (7)
H10.10910.33730.72810.088*
C20.06036 (11)0.2911 (4)0.63479 (12)0.0678 (7)
H20.07670.16260.63510.081*
C30.01680 (10)0.3736 (4)0.57875 (10)0.0602 (6)
H30.00320.30050.54120.072*
C40.00677 (10)0.5639 (4)0.57788 (11)0.0618 (6)
H40.03630.62050.53980.074*
C50.01360 (11)0.6716 (4)0.63394 (13)0.0679 (7)
H50.00220.80100.63370.081*
C60.05724 (11)0.5864 (4)0.68998 (11)0.0688 (7)
C70.09946 (11)0.8942 (5)0.82488 (11)0.0725 (8)
C80.13603 (12)0.7963 (4)0.88181 (12)0.0699 (7)
H80.15040.66460.88210.084*
C90.15139 (10)0.8937 (3)0.93864 (10)0.0558 (6)
H90.17670.82950.97710.067*
C100.12857 (8)1.0860 (3)0.93703 (9)0.0430 (5)
C110.09270 (9)1.1846 (4)0.88030 (9)0.0554 (6)
H110.07791.31590.87980.067*
C120.07893 (10)1.0891 (5)0.82462 (10)0.0707 (7)
H120.05551.15700.78640.085*
C130.12212 (9)1.1082 (3)1.03599 (9)0.0504 (5)
C140.14222 (9)1.2552 (3)1.09033 (9)0.0522 (6)
H140.10701.31461.09140.063*
C150.17851 (9)1.4214 (3)1.07873 (9)0.0522 (5)
H150.16041.55731.07560.063*
C160.17573 (9)1.3640 (3)1.01730 (9)0.0470 (5)
C170.18936 (10)1.1676 (4)1.15637 (9)0.0629 (6)
H170.17251.08931.17870.075*
C180.23697 (11)1.0607 (4)1.14686 (10)0.0648 (7)
H180.24350.91971.14840.078*
C190.26790 (10)1.2020 (4)1.13589 (10)0.0639 (6)
H190.29981.17861.12780.077*
C200.24259 (10)1.4069 (4)1.13884 (10)0.0607 (6)
H200.26961.52501.14710.073*
C210.22356 (11)1.3637 (4)1.18850 (11)0.0750 (7)
H21A0.25801.33961.23040.090*
H21B0.19721.46931.19020.090*
N10.08481 (19)0.6515 (8)0.7579 (2)0.0587 (14)0.681 (12)
N20.07375 (17)0.8321 (8)0.75791 (19)0.0555 (14)0.681 (12)
N1'0.0608 (4)0.7694 (12)0.7278 (5)0.053 (3)0.319 (12)
N2'0.0990 (4)0.7111 (15)0.7852 (4)0.054 (3)0.319 (12)
N30.14098 (7)1.1850 (2)0.99484 (7)0.0426 (4)
O10.09449 (8)0.9498 (3)1.02764 (7)0.0773 (5)
O20.19937 (8)1.4485 (2)0.99100 (8)0.0686 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0621 (14)0.108 (2)0.0493 (14)0.0060 (14)0.0272 (11)0.0015 (14)
C20.0740 (16)0.0677 (16)0.0706 (17)0.0052 (13)0.0426 (14)0.0057 (13)
C30.0613 (13)0.0777 (17)0.0491 (13)0.0168 (12)0.0331 (11)0.0194 (12)
C40.0522 (13)0.0806 (17)0.0563 (14)0.0011 (12)0.0296 (11)0.0076 (13)
C50.0664 (15)0.0599 (15)0.101 (2)0.0058 (12)0.0591 (15)0.0159 (14)
C60.0588 (14)0.099 (2)0.0625 (15)0.0196 (14)0.0404 (13)0.0319 (15)
C70.0657 (15)0.113 (2)0.0516 (15)0.0391 (15)0.0388 (13)0.0333 (15)
C80.0912 (18)0.0579 (15)0.0824 (18)0.0183 (13)0.0594 (16)0.0232 (14)
C90.0693 (14)0.0482 (13)0.0553 (13)0.0041 (11)0.0349 (11)0.0018 (11)
C100.0445 (10)0.0465 (12)0.0406 (11)0.0080 (9)0.0229 (9)0.0039 (9)
C110.0469 (11)0.0739 (15)0.0454 (12)0.0032 (10)0.0227 (10)0.0055 (11)
C120.0510 (13)0.119 (2)0.0402 (12)0.0088 (14)0.0210 (10)0.0045 (14)
C130.0465 (11)0.0610 (14)0.0441 (11)0.0087 (10)0.0226 (9)0.0034 (10)
C140.0428 (11)0.0709 (15)0.0468 (12)0.0027 (10)0.0251 (9)0.0102 (10)
C150.0613 (13)0.0399 (12)0.0546 (12)0.0064 (10)0.0279 (10)0.0065 (10)
C160.0519 (12)0.0352 (11)0.0517 (12)0.0022 (9)0.0238 (10)0.0038 (9)
C170.0655 (14)0.0846 (17)0.0416 (12)0.0100 (13)0.0286 (11)0.0020 (12)
C180.0693 (15)0.0596 (15)0.0498 (13)0.0124 (12)0.0174 (11)0.0061 (11)
C190.0440 (12)0.0839 (18)0.0554 (13)0.0080 (12)0.0181 (10)0.0037 (13)
C200.0565 (13)0.0640 (15)0.0551 (13)0.0147 (11)0.0226 (11)0.0184 (11)
C210.0697 (15)0.099 (2)0.0496 (13)0.0036 (14)0.0244 (12)0.0237 (14)
N10.061 (3)0.067 (3)0.047 (3)0.010 (2)0.025 (2)0.000 (2)
N20.057 (2)0.062 (3)0.046 (3)0.0013 (17)0.025 (2)0.0017 (19)
N1'0.052 (4)0.067 (6)0.030 (5)0.005 (4)0.014 (4)0.007 (4)
N2'0.056 (5)0.068 (7)0.024 (5)0.003 (4)0.010 (4)0.009 (4)
N30.0480 (9)0.0428 (10)0.0373 (8)0.0031 (7)0.0213 (7)0.0001 (7)
O10.0894 (12)0.0902 (13)0.0616 (10)0.0448 (10)0.0443 (9)0.0165 (9)
O20.0898 (11)0.0520 (9)0.0711 (10)0.0171 (8)0.0450 (9)0.0034 (8)
Geometric parameters (Å, º) top
C1—C21.363 (3)C12—H120.9300
C1—C61.366 (4)C13—O11.204 (2)
C1—H10.9300C13—N31.393 (2)
C2—C31.368 (3)C13—C141.501 (3)
C2—H20.9300C14—C151.529 (3)
C3—C41.369 (3)C14—C171.558 (3)
C3—H30.9300C14—H140.9800
C4—C51.385 (3)C15—C161.505 (3)
C4—H40.9300C15—C201.555 (3)
C5—C61.375 (3)C15—H150.9800
C5—H50.9300C16—O21.200 (2)
C6—N1'1.480 (7)C16—N31.397 (2)
C6—N11.500 (5)C17—C181.499 (3)
C7—C121.369 (4)C17—C211.522 (3)
C7—C81.381 (4)C17—H170.9800
C7—N21.479 (5)C18—C191.314 (3)
C7—N2'1.529 (9)C18—H180.9300
C8—C91.389 (3)C19—C201.495 (3)
C8—H80.9300C19—H190.9300
C9—C101.370 (3)C20—C211.528 (3)
C9—H90.9300C20—H200.9800
C10—C111.377 (3)C21—H21A0.9700
C10—N31.432 (2)C21—H21B0.9700
C11—C121.368 (3)N1—N21.207 (9)
C11—H110.9300N1'—N2'1.298 (18)
C2—C1—C6120.2 (2)C15—C14—C17103.14 (16)
C2—C1—H1119.9C13—C14—H14110.9
C6—C1—H1119.9C15—C14—H14110.9
C1—C2—C3120.5 (2)C17—C14—H14110.9
C1—C2—H2119.7C16—C15—C14105.49 (16)
C3—C2—H2119.7C16—C15—C20115.72 (17)
C2—C3—C4120.0 (2)C14—C15—C20102.83 (17)
C2—C3—H3120.0C16—C15—H15110.8
C4—C3—H3120.0C14—C15—H15110.8
C3—C4—C5119.7 (2)C20—C15—H15110.8
C3—C4—H4120.2O2—C16—N3123.68 (19)
C5—C4—H4120.2O2—C16—C15128.39 (19)
C6—C5—C4119.7 (2)N3—C16—C15107.92 (17)
C6—C5—H5120.1C18—C17—C21100.03 (19)
C4—C5—H5120.1C18—C17—C14105.81 (17)
C1—C6—C5119.9 (2)C21—C17—C1499.88 (18)
C1—C6—N1'146.4 (5)C18—C17—H17116.2
C5—C6—N1'93.7 (5)C21—C17—H17116.2
C1—C6—N1106.7 (3)C14—C17—H17116.2
C5—C6—N1133.2 (3)C19—C18—C17107.8 (2)
C12—C7—C8119.7 (2)C19—C18—H18126.1
C12—C7—N2106.8 (3)C17—C18—H18126.1
C8—C7—N2133.5 (3)C18—C19—C20107.7 (2)
C12—C7—N2'146.5 (5)C18—C19—H19126.1
C8—C7—N2'93.8 (5)C20—C19—H19126.1
C7—C8—C9120.4 (2)C19—C20—C21100.4 (2)
C7—C8—H8119.8C19—C20—C15106.20 (17)
C9—C8—H8119.8C21—C20—C1599.63 (18)
C10—C9—C8118.8 (2)C19—C20—H20116.1
C10—C9—H9120.6C21—C20—H20116.1
C8—C9—H9120.6C15—C20—H20116.1
C9—C10—C11120.9 (2)C17—C21—C2093.94 (17)
C9—C10—N3119.84 (18)C17—C21—H21A112.9
C11—C10—N3119.27 (18)C20—C21—H21A112.9
C12—C11—C10119.8 (2)C17—C21—H21B112.9
C12—C11—H11120.1C20—C21—H21B112.9
C10—C11—H11120.1H21A—C21—H21B110.4
C11—C12—C7120.4 (2)N2—N1—C6107.1 (4)
C11—C12—H12119.8N1—N2—C7106.9 (4)
C7—C12—H12119.8N2'—N1'—C6102.5 (7)
O1—C13—N3124.03 (19)N1'—N2'—C7102.7 (8)
O1—C13—C14127.59 (19)C13—N3—C16112.89 (16)
N3—C13—C14108.38 (18)C13—N3—C10123.70 (16)
C13—C14—C15105.19 (16)C16—N3—C10123.35 (16)
C13—C14—C17115.26 (18)
C6—C1—C2—C31.3 (4)C14—C17—C18—C1969.5 (2)
C1—C2—C3—C40.9 (4)C17—C18—C19—C200.9 (2)
C2—C3—C4—C50.2 (3)C18—C19—C20—C2132.3 (2)
C3—C4—C5—C60.1 (3)C18—C19—C20—C1571.1 (2)
C2—C1—C6—C51.0 (4)C16—C15—C20—C1948.1 (3)
C2—C1—C6—N1'174.7 (6)C14—C15—C20—C1966.3 (2)
C2—C1—C6—N1176.3 (3)C16—C15—C20—C21152.03 (19)
C4—C5—C6—C10.3 (4)C14—C15—C20—C2137.6 (2)
C4—C5—C6—N1'177.3 (3)C18—C17—C21—C2049.8 (2)
C4—C5—C6—N1174.1 (3)C14—C17—C21—C2058.39 (19)
C12—C7—C8—C90.8 (3)C19—C20—C21—C1749.44 (19)
N2—C7—C8—C9177.6 (3)C15—C20—C21—C1759.2 (2)
N2'—C7—C8—C9178.1 (4)C1—C6—N1—N2168.1 (3)
C7—C8—C9—C101.4 (3)C5—C6—N1—N217.6 (5)
C8—C9—C10—C112.2 (3)N1'—C6—N1—N24.2 (6)
C8—C9—C10—N3176.58 (18)C6—N1—N2—C7178.4 (3)
C9—C10—C11—C120.8 (3)C12—C7—N2—N1170.9 (3)
N3—C10—C11—C12177.98 (18)C8—C7—N2—N17.7 (5)
C10—C11—C12—C71.5 (3)N2'—C7—N2—N18.4 (6)
C8—C7—C12—C112.2 (3)C1—C6—N1'—N2'7.1 (10)
N2—C7—C12—C11176.6 (2)C5—C6—N1'—N2'176.6 (6)
N2'—C7—C12—C11175.8 (7)N1—C6—N1'—N2'6.4 (6)
O1—C13—C14—C15176.6 (2)C6—N1'—N2'—C7176.3 (5)
N3—C13—C14—C153.3 (2)C12—C7—N2'—N1'4.1 (11)
O1—C13—C14—C1763.8 (3)C8—C7—N2'—N1'174.2 (6)
N3—C13—C14—C17116.16 (19)N2—C7—N2'—N1'5.3 (5)
C13—C14—C15—C161.6 (2)O1—C13—N3—C16175.9 (2)
C17—C14—C15—C16122.73 (17)C14—C13—N3—C164.0 (2)
C13—C14—C15—C20120.09 (17)O1—C13—N3—C101.3 (3)
C17—C14—C15—C201.1 (2)C14—C13—N3—C10178.78 (16)
C14—C15—C16—O2177.8 (2)O2—C16—N3—C13175.6 (2)
C20—C15—C16—O264.9 (3)C15—C16—N3—C132.9 (2)
C14—C15—C16—N30.6 (2)O2—C16—N3—C101.7 (3)
C20—C15—C16—N3113.55 (19)C15—C16—N3—C10179.84 (16)
C13—C14—C17—C1846.5 (2)C9—C10—N3—C1362.1 (3)
C15—C14—C17—C1867.5 (2)C11—C10—N3—C13116.6 (2)
C13—C14—C17—C21150.03 (18)C9—C10—N3—C16114.8 (2)
C15—C14—C17—C2136.0 (2)C11—C10—N3—C1666.4 (2)
C21—C17—C18—C1933.9 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C9—H9···O2i0.932.533.155 (3)125
Symmetry code: (i) x, y1, z.

Experimental details

Crystal data
Chemical formulaC21H17N3O2
Mr343.38
Crystal system, space groupMonoclinic, C2/c
Temperature (K)292
a, b, c (Å)25.190 (2), 6.5076 (5), 24.2792 (19)
β (°) 119.567 (1)
V3)3461.7 (5)
Z8
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.20 × 0.20 × 0.10
Data collection
DiffractometerCCD area detector
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
13859, 3778, 2363
Rint0.041
(sin θ/λ)max1)0.639
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.059, 0.139, 1.06
No. of reflections3778
No. of parameters254
No. of restraints2
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.16, 0.18

Computer programs: SMART (Bruker 2001), SAINT (Bruker 2001), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker 2001).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C9—H9···O2i0.932.533.155 (3)124.9
Symmetry code: (i) x, y1, z.
 

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds