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Acta Crystallogr Sect E Struct Rep Online. 2008 July 1; 64(Pt 7): o1276.
Published online 2008 June 19. doi:  10.1107/S1600536808017625
PMCID: PMC2961687

N 2-o-Tolyl­benzamidine

Abstract

The asymmetric unit of the title compound, C14H14N2, contains two independent mol­ecules with slightly different conformations; the dihedral angles formed by aromatic rings in the two mol­ecules are 73.2 (1) and 75.0 (1)°. Inter­molecular N—H(...)N hydrogen bonds link the mol­ecules into chains extended in the [100] direction.

Related literature

For general background, see Bourget-Merle et al. (2002 [triangle]). For a related crystal structure, see Surma et al. (1988 [triangle]).

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Object name is e-64-o1276-scheme1.jpg

Experimental

Crystal data

  • C14H14N2
  • M r = 210.27
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1276-efi1.jpg
  • a = 10.347 (2) Å
  • b = 10.697 (2) Å
  • c = 11.495 (2) Å
  • α = 97.088 (4)°
  • β = 103.184 (4)°
  • γ = 95.898 (4)°
  • V = 1218.0 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.07 mm−1
  • T = 298 (2) K
  • 0.30 × 0.20 × 0.20 mm

Data collection

  • Siemens SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1997 [triangle]) T min = 0.980, T max = 0.986
  • 4978 measured reflections
  • 4158 independent reflections
  • 2913 reflections with I > 2σ(I)
  • R int = 0.021

Refinement

  • R[F 2 > 2σ(F 2)] = 0.073
  • wR(F 2) = 0.235
  • S = 1.09
  • 4158 reflections
  • 291 parameters
  • H-atom parameters constrained
  • Δρmax = 0.44 e Å−3
  • Δρmin = −0.46 e Å−3

Data collection: SMART (Siemens, 1996 [triangle]); cell refinement: SAINT (Siemens, 1996 [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 (Farrugia, 1997 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808017625/cv2419sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808017625/cv2419Isup2.hkl

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

Acknowledgments

We thank the Youth Foundation of Shanxi University (grant No. 2006026, China) for financial support.

supplementary crystallographic information

Comment

β-Diketiminate complexes are among the most common chelate systems in coordination chemistry (Bourget-Merle et al., 2002). Inspired by getting new chelate system with amidine motif, we got the title compound (I) by additional reaction of PhCN with o-methyl aniline lithium.

The asymmetric unit of (I) contains two independent molecules (Fig. 1), denoted A and B. The N=C bond lengths in both molecules (Table 1) agree well with the corresponding values reported for similar compounds (Surma et al., 1988). The conformations of the two independent molecules are slightly different. In molecule A, the mean plane N3/C22/N4 makes dihedral angles of 85.3 (1) and 21.5 (1)° with phenyl rings C16–C21and C23–C28, respectively. In molecule B, the mean plane N1/C8/N2 makes dihedral angles 86.8 (1) and 18.2 (1)° with phenyl rings C2–C7 and C9–C14, respectively.

In the crystal, intermolecular N—H···N hydrogen bonds (Table 1) link the molecules into chains extended in direction [100].

Experimental

All experiments were performed under an atmosphere of pure argon using Schlenk apparatus and a vacuum line, unless otherwise stated. The solvents used were of reagent grade or better and were freshly distilled under dry dinitrogen and degassed prior to use. Slowly added PhCN(1.03 g,10 mmol)to the solution of compound o-methyl-PhNHLi (1.13 g,10 mmol) in hexane (ca 40 ml)at -0°C., and then stirred for further 12 h.Add it to cold water, and then use chlorform to extract organic phase.The organic phase was slowly concentrated and get the crystal of the title compound.

Refinement

The H atoms were positioned geometrically and allowed to ride on their parent atoms, with N—H = 0.86 Å, C—H = 0.93–0.97 Å, and Uiso = 1.2–1.5 Ueq(parent atom).

Figures

Fig. 1.
Two independent molecules of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.

Crystal data

C14H14N2Z = 4
Mr = 210.27F000 = 448
Triclinic, P1Dx = 1.147 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 10.347 (2) ÅCell parameters from 2024 reflections
b = 10.697 (2) Åθ = 2.4–27.7º
c = 11.495 (2) ŵ = 0.07 mm1
α = 97.088 (4)ºT = 298 (2) K
β = 103.184 (4)ºPlate, colourless
γ = 95.898 (4)º0.30 × 0.20 × 0.20 mm
V = 1218.0 (4) Å3

Data collection

Siemens SMART CCD area-detector diffractometer4158 independent reflections
Radiation source: fine-focus sealed tube2913 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.021
T = 298(2) Kθmax = 25.0º
ω scansθmin = 1.8º
Absorption correction: multi-scan(SADABS; Sheldrick, 1997)h = −10→12
Tmin = 0.980, Tmax = 0.986k = −12→12
4978 measured reflectionsl = −13→13

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.073H-atom parameters constrained
wR(F2) = 0.235  w = 1/[σ2(Fo2) + (0.1497P)2] where P = (Fo2 + 2Fc2)/3
S = 1.09(Δ/σ)max < 0.001
4158 reflectionsΔρmax = 0.44 e Å3
291 parametersΔρmin = −0.46 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

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
N10.90491 (17)0.79986 (19)0.88806 (17)0.0538 (5)
N20.69224 (19)0.8197 (2)0.9148 (2)0.0688 (6)
H2A0.67260.85820.85300.083*
H2B0.63430.80550.95640.083*
C10.7749 (4)0.6552 (3)0.6545 (3)0.1043 (12)
H1A0.71960.62740.57440.156*
H1B0.72510.63620.71260.156*
H1C0.85270.61210.66590.156*
C20.8172 (3)0.7949 (3)0.6711 (2)0.0644 (7)
C30.8023 (3)0.8623 (3)0.5739 (3)0.0852 (9)
H30.76540.81800.49650.102*
C40.8387 (4)0.9873 (4)0.5865 (3)0.0972 (11)
H40.82481.02850.51890.117*
C50.8971 (4)1.0561 (3)0.7000 (3)0.0927 (10)
H50.92361.14330.70960.111*
C60.9149 (3)0.9920 (3)0.7983 (3)0.0680 (7)
H60.95431.03710.87490.082*
C70.8762 (2)0.8639 (2)0.7862 (2)0.0508 (6)
C80.81298 (19)0.7817 (2)0.9464 (2)0.0478 (5)
C90.8415 (2)0.7144 (2)1.05346 (19)0.0490 (6)
C100.9449 (3)0.6419 (2)1.0709 (2)0.0647 (7)
H100.99740.63531.01520.078*
C110.9718 (3)0.5790 (3)1.1693 (3)0.0786 (8)
H111.04270.53131.17960.094*
C120.8962 (3)0.5858 (3)1.2516 (3)0.0787 (8)
H120.91480.54271.31770.094*
C130.7939 (3)0.6555 (4)1.2367 (3)0.0889 (10)
H130.74110.65941.29220.107*
C140.7669 (3)0.7217 (3)1.1390 (3)0.0772 (8)
H140.69770.77151.13120.093*
N30.42879 (17)0.78365 (18)0.99087 (16)0.0513 (5)
N40.20510 (18)0.8125 (2)0.96875 (18)0.0692 (7)
H4A0.21610.83481.04520.083*
H4B0.12750.80980.92060.083*
C150.3694 (4)0.5807 (3)1.1207 (3)0.0896 (9)
H15A0.36150.52601.17960.134*
H15B0.43090.55191.07550.134*
H15C0.28320.57901.06670.134*
C160.4201 (2)0.7134 (3)1.1833 (2)0.0616 (7)
C170.4444 (3)0.7462 (4)1.3083 (3)0.0825 (9)
H170.42770.68301.35380.099*
C180.4913 (3)0.8661 (4)1.3665 (3)0.0901 (10)
H180.50500.88431.45000.108*
C190.5182 (3)0.9601 (3)1.3013 (3)0.0863 (9)
H190.55131.04241.34050.104*
C200.4963 (2)0.9325 (3)1.1778 (2)0.0642 (7)
H200.51550.99651.13400.077*
C210.44635 (19)0.8118 (2)1.1180 (2)0.0495 (6)
C220.3093 (2)0.7819 (2)0.9244 (2)0.0484 (6)
C230.2832 (2)0.7442 (2)0.7916 (2)0.0515 (6)
C240.1744 (3)0.7776 (3)0.7119 (2)0.0671 (7)
H240.11610.82620.74160.081*
C250.1519 (3)0.7395 (3)0.5887 (3)0.0783 (8)
H250.07830.76210.53640.094*
C260.2365 (3)0.6692 (3)0.5435 (3)0.0816 (9)
H260.22140.64420.46060.098*
C270.3439 (3)0.6357 (3)0.6208 (3)0.0833 (9)
H270.40200.58780.59000.100*
C280.3671 (3)0.6717 (3)0.7434 (2)0.0671 (7)
H280.44020.64710.79470.080*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0370 (9)0.0696 (13)0.0553 (11)0.0099 (8)0.0100 (8)0.0120 (9)
N20.0402 (10)0.0939 (16)0.0826 (15)0.0198 (10)0.0210 (9)0.0325 (12)
C10.136 (3)0.0662 (19)0.087 (2)−0.0047 (19)−0.008 (2)0.0009 (16)
C20.0606 (15)0.0661 (16)0.0609 (16)0.0095 (12)0.0040 (12)0.0082 (12)
C30.097 (2)0.090 (2)0.0601 (17)0.0134 (18)−0.0004 (15)0.0146 (15)
C40.113 (3)0.091 (2)0.085 (2)0.006 (2)0.0080 (19)0.0392 (19)
C50.104 (2)0.0664 (18)0.102 (3)−0.0002 (17)0.011 (2)0.0254 (18)
C60.0624 (15)0.0669 (17)0.0694 (17)0.0030 (12)0.0100 (12)0.0065 (13)
C70.0348 (10)0.0583 (14)0.0591 (14)0.0068 (9)0.0100 (9)0.0097 (11)
C80.0341 (10)0.0521 (12)0.0541 (13)0.0056 (9)0.0086 (9)0.0012 (10)
C90.0395 (11)0.0524 (13)0.0521 (13)0.0010 (9)0.0099 (9)0.0036 (10)
C100.0629 (15)0.0667 (15)0.0732 (17)0.0202 (12)0.0252 (12)0.0186 (13)
C110.084 (2)0.0766 (19)0.085 (2)0.0262 (15)0.0248 (16)0.0298 (16)
C120.081 (2)0.083 (2)0.0711 (18)0.0027 (16)0.0123 (15)0.0273 (15)
C130.081 (2)0.129 (3)0.0676 (18)0.020 (2)0.0328 (15)0.0283 (18)
C140.0590 (16)0.111 (2)0.0723 (18)0.0303 (16)0.0254 (13)0.0215 (16)
N30.0377 (10)0.0634 (12)0.0546 (11)0.0068 (8)0.0148 (8)0.0084 (9)
N40.0381 (10)0.1089 (17)0.0584 (12)0.0166 (11)0.0105 (9)0.0006 (12)
C150.102 (2)0.0692 (19)0.097 (2)−0.0074 (16)0.0294 (18)0.0172 (16)
C160.0501 (13)0.0753 (17)0.0631 (16)0.0099 (12)0.0184 (11)0.0142 (13)
C170.0803 (19)0.113 (3)0.0645 (18)0.0232 (18)0.0261 (15)0.0285 (18)
C180.091 (2)0.119 (3)0.0580 (17)0.020 (2)0.0182 (16)−0.0026 (19)
C190.083 (2)0.092 (2)0.074 (2)0.0097 (17)0.0135 (16)−0.0152 (17)
C200.0555 (14)0.0655 (16)0.0695 (17)0.0087 (12)0.0147 (12)0.0029 (13)
C210.0333 (10)0.0609 (14)0.0554 (14)0.0077 (9)0.0138 (9)0.0066 (11)
C220.0373 (11)0.0519 (12)0.0572 (14)0.0038 (9)0.0151 (9)0.0086 (10)
C230.0422 (12)0.0549 (13)0.0571 (14)−0.0001 (10)0.0140 (10)0.0094 (10)
C240.0588 (15)0.0825 (18)0.0636 (16)0.0168 (13)0.0156 (12)0.0177 (13)
C250.0736 (18)0.097 (2)0.0599 (17)0.0079 (16)0.0039 (14)0.0204 (15)
C260.083 (2)0.100 (2)0.0561 (16)−0.0026 (17)0.0186 (15)0.0018 (15)
C270.0714 (18)0.102 (2)0.0710 (19)0.0136 (16)0.0196 (15)−0.0133 (16)
C280.0532 (14)0.0801 (17)0.0639 (16)0.0121 (12)0.0113 (12)−0.0014 (13)

Geometric parameters (Å, °)

N1—C81.295 (3)N3—C221.294 (3)
N1—C71.417 (3)N3—C211.421 (3)
N2—C81.338 (3)N4—C221.346 (3)
N2—H2A0.8600N4—H4A0.8600
N2—H2B0.8600N4—H4B0.8600
C1—C21.490 (4)C15—C161.493 (4)
C1—H1A0.9600C15—H15A0.9600
C1—H1B0.9600C15—H15B0.9600
C1—H1C0.9600C15—H15C0.9600
C2—C31.391 (4)C16—C171.394 (4)
C2—C71.402 (3)C16—C211.405 (3)
C3—C41.332 (4)C17—C181.357 (5)
C3—H30.9300C17—H170.9300
C4—C51.386 (5)C18—C191.368 (5)
C4—H40.9300C18—H180.9300
C5—C61.379 (4)C19—C201.375 (4)
C5—H50.9300C19—H190.9300
C6—C71.369 (3)C20—C211.374 (3)
C6—H60.9300C20—H200.9300
C8—C91.489 (3)C22—C231.485 (3)
C9—C101.377 (3)C23—C281.384 (3)
C9—C141.381 (3)C23—C241.388 (3)
C10—C111.375 (4)C24—C251.383 (4)
C10—H100.9300C24—H240.9300
C11—C121.359 (4)C25—C261.359 (4)
C11—H110.9300C25—H250.9300
C12—C131.347 (4)C26—C271.364 (4)
C12—H120.9300C26—H260.9300
C13—C141.391 (4)C27—C281.373 (4)
C13—H130.9300C27—H270.9300
C14—H140.9300C28—H280.9300
C8—N1—C7118.20 (18)C22—N3—C21116.93 (17)
C8—N2—H2A120.0C22—N4—H4A120.0
C8—N2—H2B120.0C22—N4—H4B120.0
H2A—N2—H2B120.0H4A—N4—H4B120.0
C2—C1—H1A109.5C16—C15—H15A109.5
C2—C1—H1B109.5C16—C15—H15B109.5
H1A—C1—H1B109.5H15A—C15—H15B109.5
C2—C1—H1C109.5C16—C15—H15C109.5
H1A—C1—H1C109.5H15A—C15—H15C109.5
H1B—C1—H1C109.5H15B—C15—H15C109.5
C3—C2—C7117.1 (3)C17—C16—C21116.7 (3)
C3—C2—C1121.9 (3)C17—C16—C15122.3 (3)
C7—C2—C1121.0 (3)C21—C16—C15121.1 (2)
C4—C3—C2123.0 (3)C18—C17—C16122.9 (3)
C4—C3—H3118.5C18—C17—H17118.5
C2—C3—H3118.5C16—C17—H17118.5
C3—C4—C5120.2 (3)C17—C18—C19119.4 (3)
C3—C4—H4119.9C17—C18—H18120.3
C5—C4—H4119.9C19—C18—H18120.3
C6—C5—C4118.3 (3)C18—C19—C20119.8 (3)
C6—C5—H5120.9C18—C19—H19120.1
C4—C5—H5120.9C20—C19—H19120.1
C7—C6—C5121.8 (3)C21—C20—C19121.0 (3)
C7—C6—H6119.1C21—C20—H20119.5
C5—C6—H6119.1C19—C20—H20119.5
C6—C7—C2119.5 (2)C20—C21—C16120.1 (2)
C6—C7—N1120.1 (2)C20—C21—N3120.4 (2)
C2—C7—N1120.2 (2)C16—C21—N3119.4 (2)
N1—C8—N2123.3 (2)N3—C22—N4123.7 (2)
N1—C8—C9118.86 (18)N3—C22—C23119.19 (19)
N2—C8—C9117.84 (19)N4—C22—C23117.14 (19)
C10—C9—C14117.2 (2)C28—C23—C24117.7 (2)
C10—C9—C8120.7 (2)C28—C23—C22120.2 (2)
C14—C9—C8122.1 (2)C24—C23—C22122.1 (2)
C11—C10—C9121.2 (3)C25—C24—C23120.7 (3)
C11—C10—H10119.4C25—C24—H24119.7
C9—C10—H10119.4C23—C24—H24119.7
C12—C11—C10120.8 (3)C26—C25—C24120.5 (3)
C12—C11—H11119.6C26—C25—H25119.8
C10—C11—H11119.6C24—C25—H25119.8
C13—C12—C11119.5 (3)C25—C26—C27119.5 (3)
C13—C12—H12120.3C25—C26—H26120.2
C11—C12—H12120.3C27—C26—H26120.2
C12—C13—C14120.5 (3)C26—C27—C28120.8 (3)
C12—C13—H13119.8C26—C27—H27119.6
C14—C13—H13119.8C28—C27—H27119.6
C9—C14—C13120.9 (3)C27—C28—C23120.9 (3)
C9—C14—H14119.6C27—C28—H28119.6
C13—C14—H14119.6C23—C28—H28119.6
C7—C2—C3—C4−1.5 (5)C21—C16—C17—C18−0.1 (4)
C1—C2—C3—C4179.6 (3)C15—C16—C17—C18179.6 (3)
C2—C3—C4—C51.5 (6)C16—C17—C18—C19−0.9 (5)
C3—C4—C5—C6−0.6 (6)C17—C18—C19—C200.7 (5)
C4—C5—C6—C7−0.2 (5)C18—C19—C20—C210.6 (4)
C5—C6—C7—C20.2 (4)C19—C20—C21—C16−1.6 (3)
C5—C6—C7—N1175.4 (3)C19—C20—C21—N3−177.7 (2)
C3—C2—C7—C60.6 (4)C17—C16—C21—C201.4 (3)
C1—C2—C7—C6179.5 (3)C15—C16—C21—C20−178.3 (3)
C3—C2—C7—N1−174.6 (2)C17—C16—C21—N3177.5 (2)
C1—C2—C7—N14.3 (4)C15—C16—C21—N3−2.2 (3)
C8—N1—C7—C695.6 (3)C22—N3—C21—C20−98.8 (2)
C8—N1—C7—C2−89.2 (3)C22—N3—C21—C1685.1 (3)
C7—N1—C8—N20.4 (3)C21—N3—C22—N44.2 (3)
C7—N1—C8—C9179.91 (19)C21—N3—C22—C23−175.76 (19)
N1—C8—C9—C10−18.2 (3)N3—C22—C23—C2822.1 (3)
N2—C8—C9—C10161.3 (2)N4—C22—C23—C28−157.9 (2)
N1—C8—C9—C14161.7 (2)N3—C22—C23—C24−159.0 (2)
N2—C8—C9—C14−18.8 (3)N4—C22—C23—C2421.1 (3)
C14—C9—C10—C110.3 (4)C28—C23—C24—C25−0.1 (4)
C8—C9—C10—C11−179.8 (2)C22—C23—C24—C25−179.1 (2)
C9—C10—C11—C120.6 (5)C23—C24—C25—C26−0.4 (4)
C10—C11—C12—C13−0.3 (5)C24—C25—C26—C270.4 (5)
C11—C12—C13—C14−1.0 (5)C25—C26—C27—C280.2 (5)
C10—C9—C14—C13−1.5 (4)C26—C27—C28—C23−0.7 (5)
C8—C9—C14—C13178.5 (3)C24—C23—C28—C270.7 (4)
C12—C13—C14—C91.9 (5)C22—C23—C28—C27179.7 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2B···N30.862.253.049 (3)156
N4—H4B···N1i0.862.243.016 (3)151

Symmetry codes: (i) x−1, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CV2419).

References

  • Bourget-Merle, L., Lappert, M. F. & Severn, J. R. (2002). Chem. Rev.102, 3031–3065. [PubMed]
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Sheldrick, G. M. (1997). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Siemens (1996). SMART and SAINT Siemens Analytical X-ray Instruments Inc., Madison Wisconsin, USA.
  • Surma, K., Jaskólski, M., Kosturkiewicz, Z. & Oszczapowicz, J. (1988). Acta Cryst. C44, 1031–1033.

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