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Acta Crystallogr Sect E Struct Rep Online. 2009 August 1; 65(Pt 8): o1844.
Published online 2009 July 11. doi:  10.1107/S1600536809025677
PMCID: PMC2977253

N 2,N 2,N 4,N 4-Tetra­ethyl-6-{2-[(E)-1-(4-nitro­phen­yl)ethyl­idene]hydrazino}-1,3,5-triazine-2,4-diamine

Abstract

The title compound, C19H28N8O2, was prepared by the reaction of N 2,N 2,N 4,N 4-tetra­ethyl-6-hydrazino-1,3,5-triazine-2,4-diamine and 1-(4-nitro­phen­yl)ethanone in ethanol at room temperature. The mol­ecular conformation is stabilized by intra­molecular C—H(...)N hydrogen-bonding inter­actions. There are also inter­molecular N—H(...)O hydrogen bonds, and C—H(...)π and π–π inter­actions, which help to stabilize the crystal structure. The centroid–centroid distance is 3.6172 (10) Å between adjacent benzene and 1,3,5-triazine rings.

Related literature

For the antimicrobial and anticancer applications of Schiff bases, see: Tarafder et al. (2000 [triangle]); Deschamps et al. (2003 [triangle]). For the ability of Schiff bases to form intramolecular hydrogen bonds by electron coupling between acid–base centers, see: Rozwadowski et al. (1999 [triangle]). For a related structure, see: Jian et al. (2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o1844-scheme1.jpg

Experimental

Crystal data

  • C19H28N8O2
  • M r = 400.49
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1844-efi1.jpg
  • a = 12.333 (3) Å
  • b = 9.5286 (19) Å
  • c = 17.407 (4) Å
  • β = 92.12 (3)°
  • V = 2044.3 (7) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 293 K
  • 0.22 × 0.18 × 0.10 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: none
  • 19318 measured reflections
  • 4667 independent reflections
  • 4054 reflections with I > 2σ(I)
  • R int = 0.018

Refinement

  • R[F 2 > 2σ(F 2)] = 0.036
  • wR(F 2) = 0.104
  • S = 1.05
  • 4667 reflections
  • 278 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.35 e Å−3
  • Δρmin = −0.24 e Å−3

Data collection: SMART (Bruker, 1997 [triangle]); cell refinement: SAINT (Bruker, 1997 [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: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809025677/at2835sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809025677/at2835Isup2.hkl

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

Acknowledgments

The authors thank Weifang University for support of this research (grant No. 2008Z14) and the Natural Science Foundation of Shandong Province (grant No. Y2008B29).

supplementary crystallographic information

Comment

Schiff bases have antimicrobial (Tarafder et al., 2000) and anticancer applications (Deschamps et al., 2003). The recent growing interest in Schiff bases is also due to their ability to form intramolecular hydrogen bonds by electron coupling between acid-base centers (Rozwadowski et al., 1999). The part of our research is to find Schiff base with higher biological activity, we sythesized the title compound (I) and report its crystal structure here.

In the crystal structure of compound (I) (Fig. 1), the dihedral angle formed by the C14 –C19 and N4–N6/C9–C11 rings was 10.76 (1)°. The C═N bond length [1.2910 (17) Å] is in agreement with that observed before (Jian et al., 2006). There are intermolecular N—H···O hydrogen-bonds, C—H···π and π—π interactions to stabilize the crystal structure. The centroid–centroid distance iss 3.6172 (10) Å between the adjacent benzene and 1,3,5-triazine rings.

Experimental

A mixture of N2,N2,N4,N4-tetraethyl-6-hydrazinyl-1,3,5-triazine-2,4-diamine (0.02 mol) and 1-(4-nitrophenyl)ethanone (0.02 mol) was stirred with ethanol (50 mL) at 298 K for 2 h, affording the title compound (6.40 g, yield 80.0%). Single crystals suitable for X-ray measurements were obtained by recrystallization from ethanol at room temperature.

Refinement

The title compound, C19H28N8O2, was prepared by the reaction of N2,N2,N4,N4-tetraethyl-6-hydrazino-1,3,5-triazine-2,4-diamine and 1-(4-nitrophenyl)ethanone with ethanol at room temperature. The molecular conformation is stabilized by intramolecular C—H···N hydrogen-bonding interactions. There are also intermolecular N—H···O hydrogen bonds, and C—H···π and π–π interactions, which help to stabilize the crystal structure. The centroid–centroid distance is 3.6172 (10) Å between adjacent benzene and 1,3,5-triazine rings.

Figures

Fig. 1.
The structure of the title compound showing 30% probability displacement ellipsoids and the atom-numbering scheme.

Crystal data

C19H28N8O2F(000) = 856
Mr = 400.49Dx = 1.301 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 4667 reflections
a = 12.333 (3) Åθ = 3.2–27.5°
b = 9.5286 (19) ŵ = 0.09 mm1
c = 17.407 (4) ÅT = 293 K
β = 92.12 (3)°Block, yellow
V = 2044.3 (7) Å30.22 × 0.18 × 0.10 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer4054 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.018
graphiteθmax = 27.5°, θmin = 3.2°
[var phi] and ω scansh = −16→15
19318 measured reflectionsk = −12→12
4667 independent reflectionsl = −22→22

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)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.104H atoms treated by a mixture of independent and constrained refinement
S = 1.05w = 1/[σ2(Fo2) + (0.0544P)2 + 0.6629P] where P = (Fo2 + 2Fc2)/3
4667 reflections(Δ/σ)max = 0.001
278 parametersΔρmax = 0.35 e Å3
0 restraintsΔρmin = −0.24 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
N60.86798 (7)0.13524 (9)0.14238 (5)0.01620 (18)
O20.61084 (7)−0.21575 (10)−0.26492 (5)0.0282 (2)
O10.71950 (7)−0.38030 (9)−0.29988 (5)0.02543 (19)
N30.97484 (7)−0.06303 (10)0.12715 (5)0.01717 (19)
N50.91414 (7)0.28722 (9)0.24899 (5)0.01601 (19)
N41.01161 (7)0.07162 (9)0.23260 (5)0.01529 (18)
N71.05089 (7)0.22043 (9)0.33480 (5)0.01625 (19)
N20.91687 (7)−0.09648 (9)0.06200 (5)0.01611 (19)
C190.75621 (8)−0.27251 (11)−0.18232 (6)0.0168 (2)
N10.69125 (7)−0.29130 (10)−0.25356 (5)0.0200 (2)
N80.77480 (7)0.34066 (10)0.16191 (5)0.01862 (19)
C150.79067 (8)−0.14525 (11)−0.06617 (6)0.0180 (2)
H15A0.7718−0.0751−0.03200.022*
C110.94887 (8)0.05417 (11)0.16864 (6)0.0146 (2)
C160.88343 (8)−0.22754 (11)−0.04984 (6)0.0148 (2)
C170.90831 (8)−0.33498 (11)−0.10124 (6)0.0168 (2)
H17A0.9682−0.3920−0.09050.020*
C100.99015 (8)0.19185 (11)0.27004 (6)0.0145 (2)
C180.84541 (8)−0.35806 (11)−0.16793 (6)0.0175 (2)
H18A0.8628−0.4291−0.20200.021*
C120.95244 (8)−0.19665 (11)0.01989 (6)0.0151 (2)
C140.72719 (8)−0.16701 (12)−0.13212 (6)0.0188 (2)
H14A0.6662−0.1120−0.14270.023*
C90.85476 (8)0.25133 (11)0.18551 (6)0.0154 (2)
C21.13661 (8)0.12427 (11)0.36176 (6)0.0168 (2)
H2B1.19370.17800.38790.020*
H2C1.16760.07930.31760.020*
C131.05659 (10)−0.27421 (13)0.03706 (7)0.0226 (2)
C31.02715 (9)0.34442 (12)0.38092 (6)0.0200 (2)
H3D1.01630.42410.34680.024*
H3E1.08960.36460.41460.024*
C60.69842 (9)0.30243 (12)0.09900 (6)0.0217 (2)
H6B0.73670.25110.06020.026*
H6C0.66920.38720.07540.026*
C70.75666 (9)0.47314 (12)0.20190 (7)0.0212 (2)
H7A0.77530.46150.25620.025*
H7B0.68040.49750.19700.025*
C40.92728 (10)0.32834 (14)0.42962 (7)0.0270 (3)
H4B0.91650.41300.45820.040*
H4C0.93800.25120.46460.040*
H4D0.86460.31070.39670.040*
C50.60582 (10)0.21306 (14)0.12663 (8)0.0320 (3)
H5B0.55770.19010.08390.048*
H5C0.56680.26420.16430.048*
H5D0.63440.12830.14920.048*
C80.82384 (11)0.59180 (13)0.16992 (8)0.0321 (3)
H8A0.80990.67670.19760.048*
H8B0.80450.60500.11650.048*
H8C0.89950.56870.17550.048*
C11.09742 (10)0.01179 (12)0.41592 (7)0.0244 (2)
H1A1.1571−0.04780.43140.037*
H1B1.0420−0.04330.39010.037*
H1C1.06840.05530.46050.037*
H13A1.0787 (13)−0.3377 (19)−0.0021 (10)0.043 (5)*
H13B1.0561 (14)−0.325 (2)0.0845 (11)0.050 (5)*
H13C1.1172 (14)−0.2076 (19)0.0445 (10)0.046 (5)*
H3A1.0310 (12)−0.1104 (16)0.1438 (8)0.027 (4)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N60.0158 (4)0.0174 (4)0.0152 (4)0.0012 (3)−0.0017 (3)−0.0008 (3)
O20.0243 (4)0.0356 (5)0.0240 (4)0.0003 (3)−0.0093 (3)0.0004 (4)
O10.0308 (4)0.0284 (4)0.0169 (4)−0.0089 (3)−0.0008 (3)−0.0064 (3)
N30.0177 (4)0.0185 (4)0.0148 (4)0.0038 (3)−0.0056 (3)−0.0029 (3)
N50.0152 (4)0.0170 (4)0.0157 (4)0.0002 (3)−0.0001 (3)−0.0017 (3)
N40.0152 (4)0.0170 (4)0.0135 (4)0.0000 (3)−0.0011 (3)−0.0009 (3)
N70.0160 (4)0.0182 (4)0.0143 (4)0.0002 (3)−0.0022 (3)−0.0035 (3)
N20.0176 (4)0.0173 (4)0.0132 (4)−0.0008 (3)−0.0031 (3)−0.0010 (3)
C190.0178 (5)0.0198 (5)0.0125 (5)−0.0063 (4)−0.0017 (4)0.0007 (4)
N10.0208 (4)0.0233 (5)0.0156 (4)−0.0085 (4)−0.0025 (3)0.0010 (4)
N80.0173 (4)0.0187 (4)0.0196 (4)0.0037 (3)−0.0027 (3)−0.0018 (4)
C150.0192 (5)0.0177 (5)0.0171 (5)0.0014 (4)−0.0011 (4)−0.0035 (4)
C110.0145 (4)0.0161 (5)0.0133 (5)−0.0014 (4)0.0004 (4)0.0002 (4)
C160.0161 (5)0.0149 (5)0.0132 (5)−0.0017 (4)0.0000 (4)0.0010 (4)
C170.0166 (5)0.0161 (5)0.0179 (5)0.0003 (4)0.0008 (4)−0.0003 (4)
C100.0131 (4)0.0173 (5)0.0132 (5)−0.0028 (4)0.0017 (4)0.0003 (4)
C180.0199 (5)0.0166 (5)0.0162 (5)−0.0033 (4)0.0024 (4)−0.0037 (4)
C120.0164 (5)0.0154 (5)0.0134 (5)0.0000 (4)−0.0007 (4)0.0009 (4)
C140.0173 (5)0.0198 (5)0.0190 (5)0.0008 (4)−0.0025 (4)0.0005 (4)
C90.0141 (5)0.0170 (5)0.0150 (5)−0.0009 (4)0.0016 (4)0.0013 (4)
C20.0148 (5)0.0203 (5)0.0150 (5)−0.0008 (4)−0.0027 (4)−0.0009 (4)
C130.0232 (6)0.0256 (6)0.0185 (5)0.0084 (4)−0.0052 (4)−0.0043 (4)
C30.0209 (5)0.0204 (5)0.0184 (5)−0.0010 (4)−0.0028 (4)−0.0064 (4)
C60.0205 (5)0.0249 (6)0.0192 (5)0.0062 (4)−0.0054 (4)−0.0004 (4)
C70.0197 (5)0.0202 (5)0.0237 (5)0.0062 (4)0.0011 (4)−0.0026 (4)
C40.0279 (6)0.0320 (6)0.0213 (6)0.0027 (5)0.0039 (5)−0.0068 (5)
C50.0251 (6)0.0302 (7)0.0398 (7)−0.0021 (5)−0.0131 (5)0.0053 (5)
C80.0366 (7)0.0212 (6)0.0388 (7)0.0008 (5)0.0071 (6)−0.0016 (5)
C10.0276 (6)0.0234 (6)0.0223 (5)−0.0002 (4)0.0028 (4)0.0026 (4)

Geometric parameters (Å, °)

N6—C111.3294 (13)C12—C131.5023 (14)
N6—C91.3502 (14)C14—H14A0.9300
O2—N11.2354 (13)C2—C11.5182 (15)
O1—N11.2295 (13)C2—H2B0.9700
N3—N21.3562 (12)C2—H2C0.9700
N3—C111.3742 (14)C13—H13A0.958 (18)
N3—H3A0.868 (15)C13—H13B0.96 (2)
N5—C101.3466 (13)C13—H13C0.986 (18)
N5—C91.3470 (14)C3—C41.5285 (17)
N4—C111.3426 (13)C3—H3D0.9700
N4—C101.3490 (14)C3—H3E0.9700
N7—C101.3578 (13)C6—C51.5170 (18)
N7—C21.4632 (13)C6—H6B0.9700
N7—C31.4641 (13)C6—H6C0.9700
N2—C121.2902 (14)C7—C81.5195 (17)
C19—C181.3846 (15)C7—H7A0.9700
C19—C141.3876 (15)C7—H7B0.9700
C19—N11.4623 (13)C4—H4B0.9600
N8—C91.3549 (13)C4—H4C0.9600
N8—C71.4628 (14)C4—H4D0.9600
N8—C61.4639 (14)C5—H5B0.9600
C15—C141.3811 (15)C5—H5C0.9600
C15—C161.4072 (14)C5—H5D0.9600
C15—H15A0.9300C8—H8A0.9600
C16—C171.4011 (14)C8—H8B0.9600
C16—C121.4860 (14)C8—H8C0.9600
C17—C181.3897 (15)C1—H1A0.9600
C17—H17A0.9300C1—H1B0.9600
C18—H18A0.9300C1—H1C0.9600
C11—N6—C9112.92 (9)C1—C2—H2C108.9
N2—N3—C11120.30 (9)H2B—C2—H2C107.7
N2—N3—H3A123.2 (10)C12—C13—H13A115.6 (10)
C11—N3—H3A116.5 (10)C12—C13—H13B112.8 (11)
C10—N5—C9113.82 (9)H13A—C13—H13B108.0 (15)
C11—N4—C10112.86 (9)C12—C13—H13C110.4 (10)
C10—N7—C2120.71 (9)H13A—C13—H13C105.4 (14)
C10—N7—C3120.12 (9)H13B—C13—H13C103.7 (15)
C2—N7—C3119.08 (8)N7—C3—C4113.88 (9)
C12—N2—N3117.98 (9)N7—C3—H3D108.8
C18—C19—C14122.29 (9)C4—C3—H3D108.8
C18—C19—N1119.22 (10)N7—C3—H3E108.8
C14—C19—N1118.47 (10)C4—C3—H3E108.8
O1—N1—O2122.83 (9)H3D—C3—H3E107.7
O1—N1—C19118.75 (9)N8—C6—C5111.95 (10)
O2—N1—C19118.42 (9)N8—C6—H6B109.2
C9—N8—C7121.34 (9)C5—C6—H6B109.2
C9—N8—C6120.77 (9)N8—C6—H6C109.2
C7—N8—C6117.73 (9)C5—C6—H6C109.2
C14—C15—C16121.06 (10)H6B—C6—H6C107.9
C14—C15—H15A119.5N8—C7—C8111.88 (9)
C16—C15—H15A119.5N8—C7—H7A109.2
N6—C11—N4127.98 (10)C8—C7—H7A109.2
N6—C11—N3118.56 (9)N8—C7—H7B109.2
N4—C11—N3113.46 (9)C8—C7—H7B109.2
C17—C16—C15118.28 (9)H7A—C7—H7B107.9
C17—C16—C12122.27 (9)C3—C4—H4B109.5
C15—C16—C12119.44 (9)C3—C4—H4C109.5
C18—C17—C16121.36 (10)H4B—C4—H4C109.5
C18—C17—H17A119.3C3—C4—H4D109.5
C16—C17—H17A119.3H4B—C4—H4D109.5
N5—C10—N4126.06 (9)H4C—C4—H4D109.5
N5—C10—N7116.60 (9)C6—C5—H5B109.5
N4—C10—N7117.34 (9)C6—C5—H5C109.5
C19—C18—C17118.25 (10)H5B—C5—H5C109.5
C19—C18—H18A120.9C6—C5—H5D109.5
C17—C18—H18A120.9H5B—C5—H5D109.5
N2—C12—C16114.46 (9)H5C—C5—H5D109.5
N2—C12—C13123.85 (9)C7—C8—H8A109.5
C16—C12—C13121.66 (9)C7—C8—H8B109.5
C15—C14—C19118.74 (10)H8A—C8—H8B109.5
C15—C14—H14A120.6C7—C8—H8C109.5
C19—C14—H14A120.6H8A—C8—H8C109.5
N5—C9—N6126.22 (9)H8B—C8—H8C109.5
N5—C9—N8117.19 (9)C2—C1—H1A109.5
N6—C9—N8116.59 (9)C2—C1—H1B109.5
N7—C2—C1113.49 (9)H1A—C1—H1B109.5
N7—C2—H2B108.9C2—C1—H1C109.5
C1—C2—H2B108.9H1A—C1—H1C109.5
N7—C2—H2C108.9H1B—C1—H1C109.5

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N3—H3A···O1i0.868 (15)2.491 (15)3.2751 (15)150.7 (13)
N3—H3A···O2i0.868 (15)2.474 (15)3.2486 (15)149.0 (13)
C2—H2C···N40.972.382.7252 (15)100
C7—H7A···N50.972.392.7322 (16)100
C15—H15A···N20.932.392.7128 (15)100
C1—H1A···Cg2ii0.962.913.7486 (16)147
C7—H7B···Cg1iii0.972.713.3835 (15)127

Symmetry codes: (i) x+1/2, −y−1/2, z+1/2; (ii) x−1/2, −y−3/2, z−1/2; (iii) −x+3/2, y+1/2, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: AT2835).

References

  • Bruker (1997). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Deschamps, P., Kulkarni, P. P. & Sarkar, B. (2003). Inorg. Chem.42, 7366–7368. [PubMed]
  • Jian, F.-F., Zhuang, R.-R., Wang, K.-F., Zhao, P.-S. & Xiao, H.-L. (2006). Acta Cryst. E62, o3198–o3199.
  • Rozwadowski, Z., Majewski, E., Dziembowska, T. & Hansen, P. E. (1999). J. Chem. Soc. Perkin Trans. 2, pp. 2809–2817.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Tarafder, M. T. H., Ali, M. A., Wee, D. J., Azahari, K., Silong, S. & Crouse, K. A. (2000). Transition Met. Chem.25, 456–460.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography