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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 68| Part 7| July 2012| Page o2087
https://doi.org/10.1107/S1600536812025524

(E,E)-1,2-Bis[3-(prop-2-yn-1-yl­­oxy)benzyl­­idene]hydrazine

Wisam Naji Atiyah Al-Mehana,a Rosiyah Yahya,a Faridah Sonsudinb and Kong Mun Loa*

aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and bCentre for Foundation Studies in Science, University of Malaya, 50603 Kuala Lumpur, Malaysia
*Correspondence e-mail: kmlo@um.edu.my

(Received 15 May 2012; accepted 5 June 2012; online 13 June 2012)

The mol­ecule of the title compound, C20H16N2O2, is centrosymmetric, the inversion center being located at the mid-point of the central azine bond. The conformation around the C=N bond is E. The whole mol­ecule (except for the H atoms) is essentially planar, with an r.m.s. deviation of 0.07 Å. In the crystal, mol­ecules are linked head-to-tail by pairs of C—H⋯O hydrogen bonds, forming inversion dimers, and resulting in the formation of chains propagating along [011].

Related literature

For biological properties and practical appplications of diacetyl­ene compounds, see: Zloh et al. (2007[Zloh, M., Bucar, F. & Gibbons, S. (2007). J. Theor. Chem. Acc.117, 247-252.]); Buckley & Neumeister (1992[Buckley, L. J. & Neumeister, G. C. (1992). J. Smart Mat. Struct. pp. 1-4.]). For the structure of (E,E)-1,2-bis­[3-(prop-2-yn-1-yl­oxy)benzyl­indene]­hydrazine see: Al-Mehana et al. (2011[Al-Mehana, W. N. A., Yahya, R. & Lo, K. M. (2011). Acta Cryst. E67, o2900.]).

[Scheme 1]

Experimental

Crystal data

  • C20H16N2O2

  • Mr = 316.35

  • Triclinic, [P \overline 1]

  • a = 4.5700 (3) Å

  • b = 9.4947 (7) Å

  • c = 9.8920 (8) Å

  • α = 67.986 (7)°

  • β = 77.487 (6)°

  • γ = 84.132 (6)°

  • V = 388.37 (5) Å3

  • Z = 1

  • Mo Kα radiation

  • μ = 0.09 mm−1

  • T = 100 K

  • 0.1 × 0.08 × 0.08 mm
Data collection

  • Agilent SuperNova Dual (Cu) Atlas diffractometer

  • Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012[Agilent (2012). CrysAlis PRO. Agilent Technologies, Yarnton, England.]) Tmin = 0.440, Tmax = 1.000

  • 2956 measured reflections

  • 1710 independent reflections

  • 1508 reflections with I > 2σ(I)

  • Rint = 0.027
Refinement

  • R[F2 > 2σ(F2)] = 0.041

  • wR(F2) = 0.122

  • S = 1.02

  • 1710 reflections

  • 109 parameters

  • H-atom parameters constrained

  • Δρmax = 0.23 e Å−3

  • Δρmin = −0.29 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
C5—H5⋯O1i 0.93 2.52 3.4467 (16) 177
Symmetry code: (i) -x, -y+2, -z+1.

Data collection: CrysAlis PRO (Agilent, 2012[Agilent (2012). CrysAlis PRO. Agilent Technologies, Yarnton, England.]); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: X-SEED (Barbour, 2001[Barbour, L. J. (2001). J. Supramol. Chem. 1, 189-191.]); software used to prepare material for publication: pubCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812025524/su2430sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812025524/su2430Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812025524/su2430Isup3.cml

checkCIF report


Comment top

Diacetylene compounds are known to have antitumour and antimicrobial activities (Zloh et al., 2007). In addition to their biological activities, diacetylenes are also used as coating and surface treatment agents and as inner cladding material for silica fibre-optic cores (Buckley & Neumeister, 1992). A recent study detailed the crystal structure of (E,E)-1,2-Bis[4-(prop-2-yn-1-yloxy)benzylindene]hydrazine (Al-Mehana et al., 2011). Herein we report on the synthesis and crystal structure of the 3-substituted isomer of this diacetylene compound.

Like the above mentioned compound, the title compound, Fig. 1, is also centrosymmetric around the central azine bond [N1—N1i = 1.415 (1) Å; Symmetry code: (i) -x+2, -y+1, -z+2], with an E conformation about the N1═C10 bond [1.2810 (18) Å].

The title compound differs from the 4-substituted isomer (Al-Mehana et al., 2011) as it adopts a different type of C—H···O interaction in its crystal packing. Here, one of the aromatic H atoms is a hydrogen bond donor to the adjacent phenoxy O atom resulting in the formation of an infinite polymeric chain propagating along [011] (Table 1 and Fig. 2).

Related literature top

For biological properties and practical appplications of diacetylene compounds, see: Zloh et al. (2007); Buckley & Neumeister (1992). For the structure of (E,E)-1,2-bis[3-(prop-2-yn-1-yloxy)benzylindene]hydrazine see: Al-Mehana et al. (2011).

Experimental top

3,3'-(E, E)-hydrazine-1,2-diylidene bis(methan-1-yl-1-ylidene)diphenol (L1) was prepared by stirring 3-hydroxybenzaldehyde (3 g, 24.5 mmol), hydrazine sulfate (1.65 g, 12.6 mmol) and 1.5 ml of concentrated ammonium solution in a mixture of ethanol and water (20 ml) for 3 h. The product was obtained as a yellow crystalline solid, m.p. 487 - 488 K. A mixture of the diphenol, L1 (2 g, 8.3 mmol) and anhydrous potassium carbonate (1.84 g, 8.6 mmol) in 20 ml of dry acetone was stirred for 30 minutes. Then an excess of propargyl bromide (2.28 g, 19.2 mmol) was added drop wise and the resulting mixture was left under reflux for 48 h. The solvent was then evaporated under reduced pressure. The product was extracted with 100 ml of diethyl ether. The organic layer was washed with brine and dried with MgSO4. A yellow amorphous solid was obtained upon slow evaporation of the ethereal solution and was recrystallized with a 1:1 ethyl acetate-methanol mixture, to yield pure yellow block-like crystals of the title compound [M.p. 401 - 403 K].

Refinement top

Hydrogen atoms were included in calculated positions and treated as riding atoms: C–H 0.93 Å (CH) and 0.97 Å (CH2) with Uiso(H) = 1.2Ueq(C).

Structure description top

Diacetylene compounds are known to have antitumour and antimicrobial activities (Zloh et al., 2007). In addition to their biological activities, diacetylenes are also used as coating and surface treatment agents and as inner cladding material for silica fibre-optic cores (Buckley & Neumeister, 1992). A recent study detailed the crystal structure of (E,E)-1,2-Bis[4-(prop-2-yn-1-yloxy)benzylindene]hydrazine (Al-Mehana et al., 2011). Herein we report on the synthesis and crystal structure of the 3-substituted isomer of this diacetylene compound.

Like the above mentioned compound, the title compound, Fig. 1, is also centrosymmetric around the central azine bond [N1—N1i = 1.415 (1) Å; Symmetry code: (i) -x+2, -y+1, -z+2], with an E conformation about the N1═C10 bond [1.2810 (18) Å].

The title compound differs from the 4-substituted isomer (Al-Mehana et al., 2011) as it adopts a different type of C—H···O interaction in its crystal packing. Here, one of the aromatic H atoms is a hydrogen bond donor to the adjacent phenoxy O atom resulting in the formation of an infinite polymeric chain propagating along [011] (Table 1 and Fig. 2).

For biological properties and practical appplications of diacetylene compounds, see: Zloh et al. (2007); Buckley & Neumeister (1992). For the structure of (E,E)-1,2-bis[3-(prop-2-yn-1-yloxy)benzylindene]hydrazine see: Al-Mehana et al. (2011).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: pubCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title molecule, with the atom numbering. The displacement ellipsoids are drawn at the 50% probability level [symmetry code: (i) -x+2, -y+1, -z+2].
[Figure 2] Fig. 2. A partial view along the a axis of the crystal packing of the title compound, illustrating the formation of the intermolecular chain along [011]. The C—H···O interactions are shown as red lines; see Table 1 for details.
(E,E)-1,2-Bis[3-(prop-2-yn-1-yloxy)benzylidene]hydrazine top
Crystal data top
C20H16N2O2Z = 1
Mr = 316.35F(000) = 166
Triclinic, P1Dx = 1.353 Mg m−3
Hall symbol: -P 1Melting point = 401–403 K
a = 4.5700 (3) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.4947 (7) ÅCell parameters from 1636 reflections
c = 9.8920 (8) Åθ = 2.3–29.1°
α = 67.986 (7)°µ = 0.09 mm−1
β = 77.487 (6)°T = 100 K
γ = 84.132 (6)°Block, colourless
V = 388.37 (5) Å30.1 × 0.08 × 0.08 mm
Data collection top
Agilent SuperNova Dual (Cu at zero) Atlas
diffractometer		1710 independent reflections
Radiation source: SuperNova (Mo) X-ray Source1508 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.027
ω scansθmax = 27.5°, θmin = 2.3°
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2012)		h = −5→4
Tmin = 0.440, Tmax = 1.000k = −12→12
2956 measured reflectionsl = −12→12
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)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.122H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0756P)2 + 0.0718P]
where P = (Fo2 + 2Fc2)/3
1710 reflections(Δ/σ)max < 0.001
109 parametersΔρmax = 0.23 e Å−3
0 restraintsΔρmin = −0.29 e Å−3
Crystal data top
C20H16N2O2γ = 84.132 (6)°
Mr = 316.35V = 388.37 (5) Å3
Triclinic, P1Z = 1
a = 4.5700 (3) ÅMo Kα radiation
b = 9.4947 (7) ŵ = 0.09 mm−1
c = 9.8920 (8) ÅT = 100 K
α = 67.986 (7)°0.1 × 0.08 × 0.08 mm
β = 77.487 (6)°
Data collection top
Agilent SuperNova Dual (Cu at zero) Atlas
diffractometer		1710 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2012)		1508 reflections with I > 2σ(I)
Tmin = 0.440, Tmax = 1.000Rint = 0.027
2956 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.122H-atom parameters constrained
S = 1.02Δρmax = 0.23 e Å−3
1710 reflectionsΔρmin = −0.29 e Å−3
109 parameters
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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*/Ueq
O10.26162 (18)0.81143 (9)0.53750 (8)0.0186 (3)
N10.9141 (2)0.53809 (10)0.94457 (10)0.0154 (3)
C10.1926 (3)0.64779 (13)0.28726 (13)0.0223 (3)
C20.2727 (3)0.67068 (13)0.38360 (13)0.0201 (3)
C30.3877 (3)0.68058 (13)0.50670 (13)0.0202 (3)
C40.3322 (2)0.82703 (12)0.65948 (12)0.0150 (3)
C50.1900 (3)0.94943 (13)0.69477 (13)0.0173 (3)
C60.2352 (3)0.97068 (12)0.81942 (13)0.0186 (3)
C70.4213 (3)0.87082 (13)0.90930 (13)0.0176 (3)
C80.5677 (2)0.75107 (12)0.87209 (12)0.0151 (3)
C90.5252 (2)0.72894 (12)0.74544 (12)0.0148 (3)
C100.7639 (2)0.65050 (12)0.96900 (12)0.0150 (3)
H10.130000.629900.211900.0270*
H3A0.336300.590000.594400.0240*
H3B0.604400.687000.480800.0240*
H50.065801.016200.634900.0210*
H60.140901.052100.843500.0220*
H70.447500.884400.994200.0210*
H90.624800.649700.719200.0180*
H100.780300.669301.052800.0180*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0223 (5)0.0187 (4)0.0173 (4)0.0091 (3)−0.0109 (3)−0.0080 (3)
N10.0141 (5)0.0152 (5)0.0162 (5)0.0017 (4)−0.0086 (4)−0.0022 (4)
C10.0254 (6)0.0225 (6)0.0209 (6)0.0061 (5)−0.0105 (5)−0.0083 (5)
C20.0206 (6)0.0183 (6)0.0204 (6)0.0069 (4)−0.0071 (4)−0.0061 (5)
C30.0218 (6)0.0209 (6)0.0208 (6)0.0085 (5)−0.0101 (5)−0.0098 (5)
C40.0146 (5)0.0156 (5)0.0135 (5)−0.0005 (4)−0.0045 (4)−0.0027 (4)
C50.0166 (6)0.0146 (5)0.0184 (6)0.0037 (4)−0.0076 (4)−0.0021 (4)
C60.0205 (6)0.0132 (5)0.0225 (6)0.0049 (4)−0.0069 (5)−0.0069 (4)
C70.0194 (6)0.0170 (5)0.0184 (5)0.0014 (4)−0.0082 (4)−0.0065 (4)
C80.0126 (5)0.0136 (5)0.0175 (5)−0.0001 (4)−0.0050 (4)−0.0028 (4)
C90.0142 (5)0.0128 (5)0.0166 (5)0.0026 (4)−0.0044 (4)−0.0044 (4)
C100.0150 (5)0.0152 (5)0.0160 (5)0.0000 (4)−0.0067 (4)−0.0050 (4)
Geometric parameters (Å, º) top
O1—C31.4247 (16)C8—C91.4009 (16)
O1—C41.3763 (13)C8—C101.4649 (15)
N1—C101.2808 (15)C1—H10.9300
N1—N1i1.4158 (13)C3—H3A0.9700
C1—C21.1883 (18)C3—H3B0.9700
C2—C31.4632 (18)C5—H50.9300
C4—C51.3951 (18)C6—H60.9300
C4—C91.3899 (15)C7—H70.9300
C5—C61.3817 (17)C9—H90.9300
C6—C71.3941 (18)C10—H100.9300
C7—C81.3883 (18)
C3—O1—C4115.61 (9)O1—C3—H3A110.00
N1i—N1—C10111.29 (9)O1—C3—H3B110.00
C1—C2—C3173.13 (14)C2—C3—H3A110.00
O1—C3—C2109.82 (11)C2—C3—H3B110.00
O1—C4—C5115.01 (10)H3A—C3—H3B108.00
O1—C4—C9124.05 (11)C4—C5—H5120.00
C5—C4—C9120.93 (11)C6—C5—H5120.00
C4—C5—C6119.44 (12)C5—C6—H6120.00
C5—C6—C7120.38 (12)C7—C6—H6120.00
C6—C7—C8120.04 (11)C6—C7—H7120.00
C7—C8—C9120.09 (10)C8—C7—H7120.00
C7—C8—C10117.97 (10)C4—C9—H9120.00
C9—C8—C10121.94 (10)C8—C9—H9120.00
C4—C9—C8119.08 (11)N1—C10—H10118.00
N1—C10—C8123.54 (10)C8—C10—H10118.00
C2—C1—H1180.00
C3—O1—C4—C93.31 (15)C4—C5—C6—C70.0 (2)
C4—O1—C3—C2174.74 (10)C5—C6—C7—C81.4 (2)
C3—O1—C4—C5−175.53 (10)C6—C7—C8—C10179.20 (11)
C10—N1—N1i—C10i179.98 (10)C6—C7—C8—C9−0.97 (18)
N1i—N1—C10—C8179.47 (9)C7—C8—C9—C4−0.85 (16)
O1—C4—C5—C6177.00 (11)C7—C8—C10—N1−178.79 (11)
C9—C4—C5—C6−1.88 (18)C9—C8—C10—N11.38 (17)
C5—C4—C9—C82.29 (16)C10—C8—C9—C4178.97 (10)
O1—C4—C9—C8−176.49 (10)
Symmetry code: (i) −x+2, −y+1, −z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5—H5···O1ii0.932.523.4467 (16)177
Symmetry code: (ii) −x, −y+2, −z+1.

Experimental details

Crystal data
Chemical formulaC20H16N2O2
Mr316.35
Crystal system, space groupTriclinic, P1
Temperature (K)100
a, b, c (Å)4.5700 (3), 9.4947 (7), 9.8920 (8)
α, β, γ (°)67.986 (7), 77.487 (6), 84.132 (6)
V (Å3)388.37 (5)
Z1
Radiation typeMo Kα
µ (mm−1)0.09
Crystal size (mm)0.1 × 0.08 × 0.08
Data collection
DiffractometerAgilent SuperNova Dual (Cu at zero) Atlas
Absorption correctionMulti-scan
(CrysAlis PRO; Agilent, 2012)
Tmin, Tmax0.440, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections		2956, 1710, 1508
Rint0.027
(sin θ/λ)max (Å−1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.122, 1.02
No. of reflections1710
No. of parameters109
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.23, −0.29

Computer programs: CrysAlis PRO (Agilent, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), pubCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5—H5···O1i0.932.523.4467 (16)177
Symmetry code: (i) −x, −y+2, −z+1.
 

Acknowledgements

We thank the University of Malaya (FRGS grant No. FP001/2010 A) and the Ministry of Higher Education of Malaysia (grant No. UM.C/HIR/MOHE/SC/12) for supporting this study.

References

First citationAgilent (2012). CrysAlis PRO. Agilent Technologies, Yarnton, England.  Google Scholar
 First citationAl-Mehana, W. N. A., Yahya, R. & Lo, K. M. (2011). Acta Cryst. E67, o2900.  Web of Science CSD CrossRef IUCr Journals Google Scholar
 First citationBarbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.  CrossRef CAS Google Scholar
 First citationBuckley, L. J. & Neumeister, G. C. (1992). J. Smart Mat. Struct. pp. 1–4.  CrossRef Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationZloh, M., Bucar, F. & Gibbons, S. (2007). J. Theor. Chem. Acc.117, 247-252.  Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 68| Part 7| July 2012| Page o2087
https://doi.org/10.1107/S1600536812025524
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