Literature DB >> 21578370

4-Bromo-N,N'-bis-(4-methoxy-phen-yl)benzamidine.

Amlan K Pal1, Garry S Hanan.   

Abstract

The title compound, C(21)H(19)BrN(2)O(2), is an amidine containing electron-donating meth-oxy groups and a bulky Br atom on the benzene rings. The solid-state structure reveals a non-centrosymmetric mol-ecule, with an E configuration around the C=N double bond. The C-N bonds show distinct amine [1.3689 (19) Å] and imine [1.285 (2) Å] characteristics. In the crystal, symmetry-related mol-ecules are linked via a very weak N-H⋯N inter-action, and C-H⋯O and C-H⋯π inter-actions.

Entities:  

Year:  2009        PMID： 21578370      PMCID： PMC2971424          DOI： 10.1107/S1600536809040112

Source DB:  PubMed          Journal:  Acta Crystallogr Sect E Struct Rep Online        ISSN： 1600-5368


Related literature

For the use of benzamidine ligands as dimetallic tetra­midinate complexes, see: Chartrand & Hanan (2008 ▶). For structural features of this kind of benzamidine ligand, see: Alcock et al. (1988 ▶, 1994 ▶), Bortoluzzi et al. (2004 ▶), Barker et al. (1999 ▶). For structural features of acetamidine and formamidine ligands see: Norrestam et al. (1983 ▶); Cotton et al. (1997 ▶).

Experimental

Crystal data

C21H19BrN2O2 M = 411.29 Orthorhombic, a = 9.2582 (6) Å b = 16.8837 (10) Å c = 23.9403 (14) Å V = 3742.2 (4) Å3 Z = 8 Cu Kα radiation μ = 3.13 mm−1 T = 150 K 0.14 × 0.14 × 0.03 mm

Data collection

Bruker Microstar diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.610, T max = 0.910 52443 measured reflections 3396 independent reflections 3299 reflections with I > 2σ(I) R int = 0.062

Refinement

R[F 2 > 2σ(F 2)] = 0.029 wR(F 2) = 0.080 S = 1.07 3396 reflections 237 parameters H-atom parameters constrained Δρmax = 0.33 e Å−3 Δρmin = −0.59 e Å−3 Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: UdMX (Maris, 2004 ▶). Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809040112/su2139sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536809040112/su2139Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report
C21H19BrN2O2F(000) = 1680
Mr = 411.29Dx = 1.460 Mg m−3
Orthorhombic, PbcaCu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ac 2abCell parameters from 36728 reflections
a = 9.2582 (6) Åθ = 4.8–67.9°
b = 16.8837 (10) ŵ = 3.13 mm−1
c = 23.9403 (14) ÅT = 150 K
V = 3742.2 (4) Å3Plate, colorless
Z = 80.14 × 0.14 × 0.03 mm
Bruker Microstar diffractometer3396 independent reflections
Radiation source: Rotating Anode3299 reflections with I > 2σ(I)
Helios opticsRint = 0.062
Detector resolution: 8.3 pixels mm-1θmax = 68.1°, θmin = 5.2°
ω scansh = −11→9
Absorption correction: multi-scan (SADABS; Bruker, 2001)k = −19→20
Tmin = 0.610, Tmax = 0.910l = −28→28
52443 measured reflections
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.080H-atom parameters constrained
S = 1.07w = 1/[σ2(Fo2) + (0.0478P)2 + 1.6131P] where P = (Fo2 + 2Fc2)/3
3396 reflections(Δ/σ)max = 0.001
237 parametersΔρmax = 0.33 e Å−3
0 restraintsΔρmin = −0.59 e Å−3
Experimental. X-ray crystallographic data for I were collected from a single-crystal sample, which was mounted on a loop fiber. Data were collected using a Bruker microstar diffractometer equiped with a Platinum 135 CCD Detector, a Helios optics and a Kappa goniometer. The crystal-to-detector distance was 4.0 cm, and the data collection was carried out in 512 x 512 pixel mode. The initial unit-cell parameters were determined by a least-squares fit of the angular setting of strong reflections, collected by a 10.0 degree scan in 33 frames over three different parts of the reciprocal space (99 frames total).
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.
xyzUiso*/Ueq
Br11.11149 (2)0.899798 (11)0.150666 (8)0.03899 (10)
O10.40209 (14)0.43856 (8)0.43426 (5)0.0390 (3)
O20.40707 (14)0.73586 (8)−0.00500 (5)0.0394 (3)
N10.72340 (15)0.60992 (8)0.27898 (5)0.0276 (3)
H10.80630.62590.29300.033*
N20.59343 (16)0.60447 (8)0.19620 (6)0.0306 (3)
C10.69482 (16)0.63517 (9)0.22578 (6)0.0252 (3)
C20.79459 (16)0.69987 (9)0.20695 (6)0.0248 (3)
C30.80061 (17)0.77121 (9)0.23594 (6)0.0296 (3)
H30.74070.77890.26770.035*
C40.89304 (17)0.83133 (10)0.21905 (7)0.0318 (4)
H40.89630.88020.23870.038*
C50.98037 (17)0.81875 (9)0.17299 (7)0.0285 (3)
C60.97609 (18)0.74872 (10)0.14314 (7)0.0297 (3)
H61.03650.74120.11150.036*
C70.88162 (17)0.68942 (10)0.16033 (7)0.0269 (3)
H70.87670.64120.13990.032*
C80.63946 (17)0.56199 (9)0.31467 (6)0.0245 (3)
C90.52398 (17)0.51543 (9)0.29732 (6)0.0266 (3)
H90.50040.51250.25880.032*
C100.44259 (18)0.47305 (9)0.33623 (7)0.0288 (3)
H100.36370.44150.32400.035*
C110.47627 (17)0.47678 (9)0.39259 (7)0.0284 (3)
C120.59362 (18)0.52215 (10)0.41022 (7)0.0292 (3)
H120.61820.52420.44870.035*
C130.67413 (17)0.56419 (9)0.37168 (7)0.0270 (3)
H130.75400.59500.38400.032*
C140.2813 (2)0.39151 (11)0.41797 (9)0.0407 (4)
H14A0.20950.42510.39940.061*
H14B0.23790.36710.45110.061*
H14C0.31330.35000.39220.061*
C150.55222 (17)0.64111 (10)0.14555 (6)0.0274 (3)
C160.49751 (18)0.71759 (10)0.14424 (6)0.0295 (3)
H160.49560.74790.17770.035*
C170.44532 (19)0.75103 (10)0.09498 (6)0.0309 (4)
H170.40660.80310.09510.037*
C180.45031 (17)0.70775 (10)0.04598 (6)0.0305 (3)
C190.50326 (18)0.63055 (10)0.04669 (6)0.0313 (4)
H190.50540.60050.01320.038*
C200.55266 (19)0.59746 (9)0.09586 (7)0.0305 (4)
H200.58730.54450.09600.037*
C210.3394 (3)0.81124 (14)−0.00580 (8)0.0532 (5)
H21A0.25660.81100.01970.080*
H21B0.30610.8230−0.04380.080*
H21C0.40860.85180.00610.080*
U11U22U33U12U13U23
Br10.03179 (15)0.02995 (14)0.05522 (16)−0.00738 (7)0.00078 (7)0.01143 (7)
O10.0405 (7)0.0416 (7)0.0348 (6)−0.0134 (5)0.0058 (5)0.0085 (5)
O20.0449 (7)0.0458 (7)0.0275 (6)−0.0014 (6)−0.0100 (5)0.0050 (5)
N10.0228 (7)0.0332 (7)0.0268 (6)−0.0063 (5)−0.0028 (5)0.0050 (5)
N20.0293 (7)0.0358 (8)0.0268 (7)−0.0084 (5)−0.0012 (6)0.0049 (5)
C10.0225 (7)0.0276 (8)0.0256 (7)−0.0012 (6)0.0017 (6)0.0018 (6)
C20.0210 (7)0.0272 (7)0.0262 (7)−0.0007 (6)−0.0033 (6)0.0036 (6)
C30.0278 (8)0.0323 (8)0.0287 (7)−0.0015 (7)0.0017 (6)−0.0016 (6)
C40.0329 (9)0.0270 (8)0.0357 (9)−0.0027 (6)−0.0027 (6)−0.0023 (7)
C50.0232 (7)0.0259 (8)0.0365 (8)−0.0026 (6)−0.0039 (6)0.0082 (6)
C60.0267 (8)0.0315 (8)0.0310 (8)0.0013 (7)0.0038 (6)0.0056 (6)
C70.0266 (8)0.0256 (8)0.0284 (7)0.0010 (6)−0.0004 (6)0.0022 (6)
C80.0223 (7)0.0245 (7)0.0266 (7)0.0008 (6)0.0010 (6)0.0026 (6)
C90.0277 (8)0.0240 (7)0.0282 (7)−0.0002 (6)−0.0012 (6)0.0000 (6)
C100.0283 (8)0.0232 (7)0.0349 (8)−0.0033 (6)−0.0013 (7)0.0006 (6)
C110.0285 (8)0.0250 (7)0.0318 (8)−0.0015 (6)0.0050 (6)0.0051 (6)
C120.0297 (8)0.0321 (8)0.0257 (7)−0.0012 (6)−0.0015 (6)0.0032 (6)
C130.0222 (8)0.0291 (8)0.0297 (8)−0.0020 (6)−0.0026 (6)0.0018 (6)
C140.0315 (10)0.0351 (9)0.0555 (11)−0.0073 (7)0.0091 (8)0.0081 (8)
C150.0218 (8)0.0353 (9)0.0252 (7)−0.0078 (7)−0.0001 (6)0.0042 (6)
C160.0259 (8)0.0357 (9)0.0268 (7)−0.0033 (7)−0.0001 (6)−0.0035 (6)
C170.0268 (9)0.0339 (9)0.0319 (8)−0.0009 (6)−0.0015 (6)0.0011 (7)
C180.0244 (8)0.0397 (9)0.0275 (8)−0.0064 (7)−0.0026 (6)0.0044 (6)
C190.0313 (8)0.0372 (9)0.0254 (7)−0.0053 (7)0.0001 (6)−0.0028 (6)
C200.0280 (9)0.0319 (9)0.0316 (8)−0.0036 (6)0.0007 (7)−0.0002 (6)
C210.0551 (12)0.0662 (14)0.0383 (10)0.0196 (11)−0.0079 (9)0.0126 (9)
Br1—C51.9057 (15)C9—H90.95
O1—C111.3723 (19)C10—C111.386 (2)
O1—C141.426 (2)C10—H100.95
O2—C181.369 (2)C11—C121.395 (2)
O2—C211.419 (3)C12—C131.382 (2)
N1—C11.3689 (19)C12—H120.95
N1—C81.410 (2)C13—H130.95
N1—H10.88C14—H14a0.98
N2—C11.285 (2)C14—H14b0.98
N2—C151.414 (2)C14—H14c0.98
C1—C21.500 (2)C15—C161.387 (3)
C2—C71.388 (2)C15—C201.399 (2)
C2—C31.391 (2)C16—C171.394 (2)
C3—C41.388 (2)C16—H160.95
C3—H30.95C17—C181.383 (2)
C4—C51.384 (2)C17—H170.95
C4—H40.95C18—C191.393 (2)
C5—C61.382 (2)C19—C201.381 (2)
C6—C71.392 (2)C19—H190.95
C6—H60.95C20—H200.95
C7—H70.95C21—H21a0.98
C8—C91.390 (2)C21—H21b0.98
C8—C131.403 (2)C21—H21c0.98
C9—C101.396 (2)
C11—O1—C14117.11 (14)C10—C11—C12119.65 (14)
C18—O2—C21116.88 (14)C13—C12—C11120.01 (15)
C1—N1—C8129.49 (13)C13—C12—H12120
C1—N1—H1115.3C11—C12—H12120
C8—N1—H1115.3C12—C13—C8120.83 (14)
C1—N2—C15119.55 (14)C12—C13—H13119.6
N2—C1—N1121.89 (14)C8—C13—H13119.6
N2—C1—C2125.31 (14)O1—C14—H14A109.5
N1—C1—C2112.80 (13)O1—C14—H14B109.5
C7—C2—C3119.20 (14)H14A—C14—H14B109.5
C7—C2—C1120.45 (14)O1—C14—H14C109.5
C3—C2—C1120.35 (14)H14A—C14—H14C109.5
C4—C3—C2120.83 (15)H14B—C14—H14C109.5
C4—C3—H3119.6C16—C15—C20118.17 (14)
C2—C3—H3119.6C16—C15—N2121.68 (14)
C5—C4—C3118.70 (15)C20—C15—N2119.86 (16)
C5—C4—H4120.6C15—C16—C17121.51 (15)
C3—C4—H4120.6C15—C16—H16119.2
C6—C5—C4121.78 (15)C17—C16—H16119.2
C6—C5—BR1119.18 (12)C18—C17—C16119.47 (16)
C4—C5—BR1119.04 (12)C18—C17—H17120.3
C5—C6—C7118.73 (15)C16—C17—H17120.3
C5—C6—H6120.6O2—C18—C17124.27 (16)
C7—C6—H6120.6O2—C18—C19115.98 (15)
C2—C7—C6120.74 (15)C17—C18—C19119.74 (15)
C2—C7—H7119.6C20—C19—C18120.37 (15)
C6—C7—H7119.6C20—C19—H19119.8
C9—C8—C13118.79 (14)C18—C19—H19119.8
C9—C8—N1124.55 (14)C19—C20—C15120.70 (15)
C13—C8—N1116.63 (14)C19—C20—H20119.7
C8—C9—C10120.38 (14)C15—C20—H20119.7
C8—C9—H9119.8O2—C21—H21A109.5
C10—C9—H9119.8O2—C21—H21B109.5
C11—C10—C9120.32 (15)H21A—C21—H21B109.5
C11—C10—H10119.8O2—C21—H21C109.5
C9—C10—H10119.8H21A—C21—H21C109.5
O1—C11—C10125.00 (15)H21B—C21—H21C109.5
O1—C11—C12115.35 (14)
C15—N2—C1—N1169.37 (15)C14—O1—C11—C100.0 (2)
C15—N2—C1—C2−11.6 (2)C14—O1—C11—C12180.00 (15)
C8—N1—C1—N2−13.9 (3)C9—C10—C11—O1178.93 (15)
C8—N1—C1—C2166.90 (14)C9—C10—C11—C12−1.1 (2)
N2—C1—C2—C7−58.9 (2)O1—C11—C12—C13−178.87 (15)
N1—C1—C2—C7120.22 (16)C10—C11—C12—C131.1 (2)
N2—C1—C2—C3120.87 (18)C11—C12—C13—C80.0 (2)
N1—C1—C2—C3−59.99 (19)C9—C8—C13—C12−1.2 (2)
C7—C2—C3—C4−0.5 (2)N1—C8—C13—C12176.93 (15)
C1—C2—C3—C4179.68 (14)C1—N2—C15—C16−61.3 (2)
C2—C3—C4—C5−0.6 (2)C1—N2—C15—C20125.04 (17)
C3—C4—C5—C61.0 (2)C20—C15—C16—C17−0.6 (2)
C3—C4—C5—BR1−178.30 (12)N2—C15—C16—C17−174.34 (15)
C4—C5—C6—C7−0.3 (2)C15—C16—C17—C18−1.2 (3)
BR1—C5—C6—C7178.98 (12)C21—O2—C18—C17−6.8 (2)
C3—C2—C7—C61.2 (2)C21—O2—C18—C19173.81 (17)
C1—C2—C7—C6−178.98 (14)C16—C17—C18—O2−177.47 (15)
C5—C6—C7—C2−0.8 (2)C16—C17—C18—C191.9 (2)
C1—N1—C8—C916.0 (3)O2—C18—C19—C20178.51 (15)
C1—N1—C8—C13−162.04 (15)C17—C18—C19—C20−0.9 (2)
C13—C8—C9—C101.3 (2)C18—C19—C20—C15−0.9 (3)
N1—C8—C9—C10−176.71 (15)C16—C15—C20—C191.6 (2)
C8—C9—C10—C11−0.2 (2)N2—C15—C20—C19175.47 (15)
D—H···AD—HH···AD···AD—H···A
N1—H1···N2i0.882.703.478 (2)149
C14—H14B···O2ii0.982.433.327 (2)151
C7—H7···Cg2iii0.952.673.3282 (18)127
C13—H13···Cg3iii0.952.693.6307 (17)171
Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯AD—HH⋯AD⋯AD—H⋯A
N1—H1⋯N2i0.882.703.478 (2)149
C14—H14B⋯O2ii0.982.433.327 (2)151
C7—H7⋯Cg2iii0.952.673.3282 (18)127
C13—H13⋯Cg3iii0.952.693.6307 (17)171

Symmetry codes: (i) ; (ii) ; (iii) . Cg2 and Cg3 are the centroids of the C8–C13 and C15–C20 rings, respectively.

  2 in total

1.  A short history of SHELX.

Authors:  George M Sheldrick
Journal:  Acta Crystallogr A       Date:  2007-12-21       Impact factor: 2.290

2.  Facile synthesis of multinuclear complexes based on a tetra(4-pyridyl)amidinate dirhodium(II) dimer.

Authors:  Daniel Chartrand; Garry S Hanan
Journal:  Chem Commun (Camb)       Date:  2008-02-14       Impact factor: 6.222
  2 in total

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