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The crystal structure of the title compound, C11H12N4, is stabilized by an N—H...N and three C—H...N inter­molecular hydrogen bonds. The N—H...N hydrogen bonds generate centrosymmetric R22(6) rings, while the three C—H...N hydrogen bonds forms edge-fused R22(7)R22(7)R22(10) ring motifs. Except for four H atoms of the methyl groups, all atoms are in the same plane and the dihedral angles between the aromatic and heterocyclic rings and the substituent group plane are 1.87 (5) and 1.53 (5)°, respectively.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807044807/at2397sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807044807/at2397Isup2.hkl
Contains datablock I

CCDC reference: 663787

Key indicators

  • Single-crystal X-ray study
  • T = 296 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.041
  • wR factor = 0.123
  • Data-to-parameter ratio = 12.9

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size ....... 0.78 mm PLAT153_ALERT_1_C The su's on the Cell Axes are Equal (x 100000) 400 Ang. PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 4000 Deg. PLAT480_ALERT_4_C Long H...A H-Bond Reported H11B .. N4 .. 2.80 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H10C .. N3 .. 2.79 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H11C .. N4 .. 2.88 Ang.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 6 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 2 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 1 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

Hydrazones and related compounds are known to possess antimicrobial, anticonvulsant, analgesic, anti-inflammatory, antiplatelet, antitubercular and antitumoral activities. For example, isonicotinoyl hydrazones are antitubercular; 4-hydroxybenzoic acid [(5-nitro-2-furyl) methylene]-hydrazide (nifuroxazide) is an intestinal antiseptic; 4-fluorobenzoic acid [(5-nitro-2-furyl)methylene]-hydrazide (Rollas et al., 2002) and 2,3,4-pentanetrione-3-[4-[[(5-nitro-2-furyl) methylene] hydrazino] carbonyl] phenyl]-hydrazone (Küçükgüzel et al., 1999) have antibacterial activity. A number of azine compounds containing both a diimine linkage and N—N bond have been investigated in terms of their crystallography and coordination chemistry (Kundu et al., 2005; Kesslen & Euler, 1999; Armstrong et al. 1998; Xu et al., 1997). The crystal structures of N,N-bis(4-chlorobenzylidene) hydrazine (Zheng et al., 2005a), N,N'-bis(3-nitrobenzylidene)hydrazine (Zheng et al. 2005b), N,N'-bis(3-hydroxy-4-methoxybenzylidene)hydrazine (Duan et al., 2005), 1,2-bis[4-(trifluoromethyl)benzylidene]hydrazine (Xu & Hu, 2007), isopropylidene-6-methoxy-2-naphthohydrazide (Sarojini, Narayana et al., 2007), 2-bromo-N'-isopropylidene-5- methoxybenzohydrazide (Sarojini, Yathirajan et al., 2007) have been reported. A new hydrazone, C11H12N4, (I) was synthesized and its crystal structure is reported.

The crystal packing is stabilized by an N—H···N and three C—H···N intermolecular hydrogen bonds. These hydrogen bonds generate centrosymmetric R22(6) and edge-fussed R22(7)R22(7)R22(10) ring motifs (Fig. 2) (Etter, 1990). Except the four protons of methyl groups, all atoms are in the same plane and the dihedral angles between the aromatic ring, heterocyclic ring and substituted group plane are 1.87 (5) ° and 1.53 (5) °, respectively. There are no C—H···π and π···π interactions in crystal packing.

Related literature top

For related structures, see: Zheng et al. (2005a,b); Duan et al. (2005); Xu & Hu, (2007); Sarojini, Narayana et al. (2007); Sarojini, Yathirajan et al. (2007); Rollas et al. (2002); Küçükgüzel et al. (1999); Kundu et al. (2005); Kesslen & Euler (1999); Armstrong et al. (1998); Xu et al. (1997). For related literature, see: Etter (1990).

Experimental top

A mixture of (1Z)-phthalazin-1(2H)-one hydrazone (3.20 g, 0.02 mol) and acetone (1.3 ml, 0.02 mol) in 15 ml of absolute ethanol containing 2 drops of sulfuric acid was refluxed for about 3 h. On cooling, the solid separated was filtered and recrystallized from acetone by slow evaporation [m.p.: 387–389 K]. Analysis for C11H12N4: Found (Calculated): C 65.89 (65.98), H 5.98 (6.04), N 27.91% (27.98%).

Refinement top

All C-bound H atoms except the methyl group and N-bound H atom were located in Fourier difference map and refined freely. The methyl group H atoms were refined using the riding model approximation with d(C—H) = 0.96 and Uiso(H) = 1.5Ueq(parent atom).

Structure description top

Hydrazones and related compounds are known to possess antimicrobial, anticonvulsant, analgesic, anti-inflammatory, antiplatelet, antitubercular and antitumoral activities. For example, isonicotinoyl hydrazones are antitubercular; 4-hydroxybenzoic acid [(5-nitro-2-furyl) methylene]-hydrazide (nifuroxazide) is an intestinal antiseptic; 4-fluorobenzoic acid [(5-nitro-2-furyl)methylene]-hydrazide (Rollas et al., 2002) and 2,3,4-pentanetrione-3-[4-[[(5-nitro-2-furyl) methylene] hydrazino] carbonyl] phenyl]-hydrazone (Küçükgüzel et al., 1999) have antibacterial activity. A number of azine compounds containing both a diimine linkage and N—N bond have been investigated in terms of their crystallography and coordination chemistry (Kundu et al., 2005; Kesslen & Euler, 1999; Armstrong et al. 1998; Xu et al., 1997). The crystal structures of N,N-bis(4-chlorobenzylidene) hydrazine (Zheng et al., 2005a), N,N'-bis(3-nitrobenzylidene)hydrazine (Zheng et al. 2005b), N,N'-bis(3-hydroxy-4-methoxybenzylidene)hydrazine (Duan et al., 2005), 1,2-bis[4-(trifluoromethyl)benzylidene]hydrazine (Xu & Hu, 2007), isopropylidene-6-methoxy-2-naphthohydrazide (Sarojini, Narayana et al., 2007), 2-bromo-N'-isopropylidene-5- methoxybenzohydrazide (Sarojini, Yathirajan et al., 2007) have been reported. A new hydrazone, C11H12N4, (I) was synthesized and its crystal structure is reported.

The crystal packing is stabilized by an N—H···N and three C—H···N intermolecular hydrogen bonds. These hydrogen bonds generate centrosymmetric R22(6) and edge-fussed R22(7)R22(7)R22(10) ring motifs (Fig. 2) (Etter, 1990). Except the four protons of methyl groups, all atoms are in the same plane and the dihedral angles between the aromatic ring, heterocyclic ring and substituted group plane are 1.87 (5) ° and 1.53 (5) °, respectively. There are no C—H···π and π···π interactions in crystal packing.

For related structures, see: Zheng et al. (2005a,b); Duan et al. (2005); Xu & Hu, (2007); Sarojini, Narayana et al. (2007); Sarojini, Yathirajan et al. (2007); Rollas et al. (2002); Küçükgüzel et al. (1999); Kundu et al. (2005); Kesslen & Euler (1999); Armstrong et al. (1998); Xu et al. (1997). For related literature, see: Etter (1990).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. A view of (I) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. Part of the crystal structure of (I), showing the formation of R22(6) and R22(7)R22(7)R22(10) motifs. [Symmetry codes: (i) 1 - x, -y, 1 - z (ii) 1 - x, -y, z + 1 (iii) -x, -y, z + 1].
[Figure 3] Fig. 3. Reaction scheme.
(1Z)-Phthalazin-1(2H)-one isopropylidenehydrazone top
Crystal data top
C11H12N4Z = 2
Mr = 200.25F(000) = 212
Triclinic, P1Dx = 1.246 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.176 (4) ÅCell parameters from 9440 reflections
b = 7.789 (4) Åθ = 2.7–27.8°
c = 9.800 (4) ŵ = 0.08 mm1
α = 79.74 (4)°T = 296 K
β = 84.40 (4)°Prism, yellow
γ = 83.53 (4)°0.78 × 0.55 × 0.19 mm
V = 533.9 (5) Å3
Data collection top
Stoe IPDS 2
diffractometer
2095 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus1679 reflections with I > 2σ(I)
Plane graphite monochromatorRint = 0.061
Detector resolution: 6.67 pixels mm-1θmax = 26.0°, θmin = 2.7°
ω scansh = 88
Absorption correction: integration
(X-RED32; Stoe & Cie, 2002)
k = 99
Tmin = 0.346, Tmax = 0.937l = 1212
9440 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.042H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.123 w = 1/[σ2(Fo2) + (0.0662P)2 + 0.04P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
2095 reflectionsΔρmax = 0.14 e Å3
163 parametersΔρmin = 0.11 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.046 (9)
Crystal data top
C11H12N4γ = 83.53 (4)°
Mr = 200.25V = 533.9 (5) Å3
Triclinic, P1Z = 2
a = 7.176 (4) ÅMo Kα radiation
b = 7.789 (4) ŵ = 0.08 mm1
c = 9.800 (4) ÅT = 296 K
α = 79.74 (4)°0.78 × 0.55 × 0.19 mm
β = 84.40 (4)°
Data collection top
Stoe IPDS 2
diffractometer
2095 independent reflections
Absorption correction: integration
(X-RED32; Stoe & Cie, 2002)
1679 reflections with I > 2σ(I)
Tmin = 0.346, Tmax = 0.937Rint = 0.061
9440 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.123H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.14 e Å3
2095 reflectionsΔρmin = 0.11 e Å3
163 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*/Ueq
C10.3460 (2)0.34934 (18)0.39909 (14)0.0546 (3)
C20.26486 (17)0.47918 (16)0.48054 (13)0.0483 (3)
C30.2234 (2)0.65485 (19)0.42177 (17)0.0605 (4)
C40.1516 (2)0.77485 (19)0.50384 (19)0.0683 (4)
C50.1182 (2)0.7230 (2)0.6451 (2)0.0703 (4)
C60.1561 (2)0.55094 (19)0.70560 (16)0.0594 (4)
C70.23084 (16)0.42685 (16)0.62321 (13)0.0466 (3)
C80.27783 (16)0.24291 (16)0.68173 (12)0.0455 (3)
C90.2846 (2)0.0619 (2)0.97379 (14)0.0614 (4)
C100.3412 (3)0.2538 (2)1.01029 (18)0.0827 (5)
H10A0.38390.30030.92700.124*
H10B0.23530.31191.05590.124*
H10C0.44100.27271.07140.124*
C110.2077 (2)0.0332 (3)1.08959 (15)0.0752 (5)
H11A0.17190.15371.05250.113*
H11B0.30210.02691.15380.113*
H11C0.09960.01991.13700.113*
N10.39192 (17)0.18830 (14)0.44897 (11)0.0552 (3)
N20.35559 (16)0.13888 (15)0.58826 (11)0.0532 (3)
N30.24853 (17)0.18648 (15)0.81368 (11)0.0561 (3)
N40.30515 (17)0.00592 (15)0.84518 (11)0.0589 (3)
H10.373 (2)0.381 (2)0.3020 (17)0.068 (4)*
H20.393 (2)0.031 (2)0.6218 (16)0.065 (4)*
H30.254 (3)0.688 (3)0.323 (2)0.088 (6)*
H40.125 (3)0.893 (2)0.4637 (18)0.081 (5)*
H50.076 (3)0.808 (3)0.701 (2)0.090 (6)*
H60.131 (2)0.509 (2)0.8036 (17)0.065 (4)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0641 (8)0.0528 (7)0.0437 (7)0.0047 (6)0.0006 (5)0.0086 (5)
C20.0461 (6)0.0462 (7)0.0530 (7)0.0001 (5)0.0048 (5)0.0112 (5)
C30.0643 (8)0.0508 (7)0.0637 (9)0.0011 (6)0.0082 (6)0.0053 (6)
C40.0710 (9)0.0448 (8)0.0892 (11)0.0039 (6)0.0112 (8)0.0152 (7)
C50.0710 (10)0.0559 (8)0.0898 (11)0.0039 (7)0.0035 (8)0.0362 (8)
C60.0618 (8)0.0599 (8)0.0601 (8)0.0025 (6)0.0010 (6)0.0249 (6)
C70.0412 (6)0.0487 (7)0.0520 (7)0.0030 (5)0.0024 (5)0.0154 (5)
C80.0422 (6)0.0500 (7)0.0453 (6)0.0034 (5)0.0012 (5)0.0130 (5)
C90.0602 (8)0.0741 (9)0.0485 (7)0.0118 (7)0.0055 (6)0.0029 (6)
C100.1079 (14)0.0743 (11)0.0616 (9)0.0125 (9)0.0128 (8)0.0057 (8)
C110.0716 (10)0.1004 (13)0.0491 (8)0.0029 (8)0.0031 (7)0.0082 (8)
N10.0664 (7)0.0509 (6)0.0447 (6)0.0070 (5)0.0035 (4)0.0107 (4)
N20.0655 (7)0.0448 (6)0.0454 (6)0.0046 (5)0.0026 (5)0.0070 (5)
N30.0642 (7)0.0584 (7)0.0446 (6)0.0027 (5)0.0002 (4)0.0102 (5)
N40.0695 (7)0.0584 (7)0.0468 (6)0.0045 (5)0.0037 (5)0.0050 (5)
Geometric parameters (Å, º) top
C1—N11.2809 (18)C8—N31.2941 (17)
C1—C21.4364 (19)C8—N21.3674 (17)
C1—H10.946 (16)C9—N41.2780 (18)
C2—C71.3904 (19)C9—C111.492 (2)
C2—C31.398 (2)C9—C101.493 (2)
C3—C41.366 (2)C10—H10A0.9600
C3—H30.96 (2)C10—H10B0.9600
C4—C51.376 (3)C10—H10C0.9600
C4—H40.943 (18)C11—H11A0.9600
C5—C61.374 (2)C11—H11B0.9600
C5—H50.94 (2)C11—H11C0.9600
C6—C71.3966 (19)N1—N21.3585 (16)
C6—H60.964 (16)N2—H20.870 (17)
C7—C81.4600 (19)N3—N41.4068 (18)
N1—C1—C2124.53 (12)N2—C8—C7115.36 (11)
N1—C1—H1115.2 (10)N4—C9—C11125.86 (15)
C2—C1—H1120.2 (10)N4—C9—C10116.67 (14)
C7—C2—C3119.55 (13)C11—C9—C10117.47 (13)
C7—C2—C1118.09 (12)C9—C10—H10A109.5
C3—C2—C1122.34 (13)C9—C10—H10B109.5
C4—C3—C2120.34 (15)H10A—C10—H10B109.5
C4—C3—H3121.8 (11)C9—C10—H10C109.5
C2—C3—H3117.8 (11)H10A—C10—H10C109.5
C3—C4—C5120.06 (14)H10B—C10—H10C109.5
C3—C4—H4120.0 (11)C9—C11—H11A109.5
C5—C4—H4120.0 (11)C9—C11—H11B109.5
C6—C5—C4120.90 (14)H11A—C11—H11B109.5
C6—C5—H5119.8 (11)C9—C11—H11C109.5
C4—C5—H5119.2 (11)H11A—C11—H11C109.5
C5—C6—C7119.73 (15)H11B—C11—H11C109.5
C5—C6—H6123.1 (10)C1—N1—N2116.62 (11)
C7—C6—H6117.1 (10)N1—N2—C8127.12 (11)
C2—C7—C6119.41 (13)N1—N2—H2115.9 (10)
C2—C7—C8118.27 (11)C8—N2—H2116.8 (10)
C6—C7—C8122.31 (12)C8—N3—N4110.64 (11)
N3—C8—N2123.62 (12)C9—N4—N3115.41 (13)
N3—C8—C7121.02 (12)
N1—C1—C2—C71.0 (2)C2—C7—C8—N3179.70 (11)
N1—C1—C2—C3177.64 (13)C6—C7—C8—N31.26 (19)
C7—C2—C3—C40.6 (2)C2—C7—C8—N21.14 (16)
C1—C2—C3—C4178.02 (13)C6—C7—C8—N2177.90 (11)
C2—C3—C4—C50.5 (2)C2—C1—N1—N21.8 (2)
C3—C4—C5—C60.0 (3)C1—N1—N2—C81.1 (2)
C4—C5—C6—C70.4 (2)N3—C8—N2—N1179.50 (12)
C3—C2—C7—C60.15 (19)C7—C8—N2—N10.36 (19)
C1—C2—C7—C6178.50 (12)N2—C8—N3—N40.75 (18)
C3—C2—C7—C8179.23 (11)C7—C8—N3—N4179.84 (10)
C1—C2—C7—C80.57 (18)C11—C9—N4—N30.1 (2)
C5—C6—C7—C20.4 (2)C10—C9—N4—N3179.27 (13)
C5—C6—C7—C8178.68 (12)C8—N3—N4—C9178.92 (11)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···N1i0.870 (17)2.322 (17)3.012 (2)136.4 (13)
C11—H11B···N4ii0.962.803.585 (3)139
C10—H10C···N3ii0.962.793.685 (3)156
C11—H11C···N4iii0.962.883.711 (3)145
Symmetry codes: (i) x+1, y, z+1; (ii) x+1, y, z+2; (iii) x, y, z+2.

Experimental details

Crystal data
Chemical formulaC11H12N4
Mr200.25
Crystal system, space groupTriclinic, P1
Temperature (K)296
a, b, c (Å)7.176 (4), 7.789 (4), 9.800 (4)
α, β, γ (°)79.74 (4), 84.40 (4), 83.53 (4)
V3)533.9 (5)
Z2
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.78 × 0.55 × 0.19
Data collection
DiffractometerStoe IPDS 2
Absorption correctionIntegration
(X-RED32; Stoe & Cie, 2002)
Tmin, Tmax0.346, 0.937
No. of measured, independent and
observed [I > 2σ(I)] reflections
9440, 2095, 1679
Rint0.061
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.123, 1.05
No. of reflections2095
No. of parameters163
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.14, 0.11

Computer programs: X-AREA (Stoe & Cie, 2002), X-RED32 (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···N1i0.870 (17)2.322 (17)3.012 (2)136.4 (13)
C11—H11B···N4ii0.962.803.585 (3)139.3
C10—H10C···N3ii0.962.793.685 (3)155.6
C11—H11C···N4iii0.962.883.711 (3)144.9
Symmetry codes: (i) x+1, y, z+1; (ii) x+1, y, z+2; (iii) x, y, z+2.
 

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