Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807044807/at2397sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807044807/at2397Isup2.hkl |
CCDC reference: 663787
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (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
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).
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%).
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).
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).
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).
C11H12N4 | Z = 2 |
Mr = 200.25 | F(000) = 212 |
Triclinic, P1 | Dx = 1.246 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.176 (4) Å | Cell parameters from 9440 reflections |
b = 7.789 (4) Å | θ = 2.7–27.8° |
c = 9.800 (4) Å | µ = 0.08 mm−1 |
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 |
Stoe IPDS 2 diffractometer | 2095 independent reflections |
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus | 1679 reflections with I > 2σ(I) |
Plane graphite monochromator | Rint = 0.061 |
Detector resolution: 6.67 pixels mm-1 | θmax = 26.0°, θmin = 2.7° |
ω scans | h = −8→8 |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | k = −9→9 |
Tmin = 0.346, Tmax = 0.937 | l = −12→12 |
9440 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.042 | H 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 reflections | Δρmax = 0.14 e Å−3 |
163 parameters | Δρmin = −0.11 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.046 (9) |
C11H12N4 | γ = 83.53 (4)° |
Mr = 200.25 | V = 533.9 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.176 (4) Å | Mo Kα radiation |
b = 7.789 (4) Å | µ = 0.08 mm−1 |
c = 9.800 (4) Å | T = 296 K |
α = 79.74 (4)° | 0.78 × 0.55 × 0.19 mm |
β = 84.40 (4)° |
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 = 0.937 | Rint = 0.061 |
9440 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.123 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.14 e Å−3 |
2095 reflections | Δρmin = −0.11 e Å−3 |
163 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.3460 (2) | 0.34934 (18) | 0.39909 (14) | 0.0546 (3) | |
C2 | 0.26486 (17) | 0.47918 (16) | 0.48054 (13) | 0.0483 (3) | |
C3 | 0.2234 (2) | 0.65485 (19) | 0.42177 (17) | 0.0605 (4) | |
C4 | 0.1516 (2) | 0.77485 (19) | 0.50384 (19) | 0.0683 (4) | |
C5 | 0.1182 (2) | 0.7230 (2) | 0.6451 (2) | 0.0703 (4) | |
C6 | 0.1561 (2) | 0.55094 (19) | 0.70560 (16) | 0.0594 (4) | |
C7 | 0.23084 (16) | 0.42685 (16) | 0.62321 (13) | 0.0466 (3) | |
C8 | 0.27783 (16) | 0.24291 (16) | 0.68173 (12) | 0.0455 (3) | |
C9 | 0.2846 (2) | −0.0619 (2) | 0.97379 (14) | 0.0614 (4) | |
C10 | 0.3412 (3) | −0.2538 (2) | 1.01029 (18) | 0.0827 (5) | |
H10A | 0.3839 | −0.3003 | 0.9270 | 0.124* | |
H10B | 0.2353 | −0.3119 | 1.0559 | 0.124* | |
H10C | 0.4410 | −0.2727 | 1.0714 | 0.124* | |
C11 | 0.2077 (2) | 0.0332 (3) | 1.08959 (15) | 0.0752 (5) | |
H11A | 0.1719 | 0.1537 | 1.0525 | 0.113* | |
H11B | 0.3021 | 0.0269 | 1.1538 | 0.113* | |
H11C | 0.0996 | −0.0199 | 1.1370 | 0.113* | |
N1 | 0.39192 (17) | 0.18830 (14) | 0.44897 (11) | 0.0552 (3) | |
N2 | 0.35559 (16) | 0.13888 (15) | 0.58826 (11) | 0.0532 (3) | |
N3 | 0.24853 (17) | 0.18648 (15) | 0.81368 (11) | 0.0561 (3) | |
N4 | 0.30515 (17) | 0.00592 (15) | 0.84518 (11) | 0.0589 (3) | |
H1 | 0.373 (2) | 0.381 (2) | 0.3020 (17) | 0.068 (4)* | |
H2 | 0.393 (2) | 0.031 (2) | 0.6218 (16) | 0.065 (4)* | |
H3 | 0.254 (3) | 0.688 (3) | 0.323 (2) | 0.088 (6)* | |
H4 | 0.125 (3) | 0.893 (2) | 0.4637 (18) | 0.081 (5)* | |
H5 | 0.076 (3) | 0.808 (3) | 0.701 (2) | 0.090 (6)* | |
H6 | 0.131 (2) | 0.509 (2) | 0.8036 (17) | 0.065 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0641 (8) | 0.0528 (7) | 0.0437 (7) | 0.0047 (6) | 0.0006 (5) | −0.0086 (5) |
C2 | 0.0461 (6) | 0.0462 (7) | 0.0530 (7) | −0.0001 (5) | −0.0048 (5) | −0.0112 (5) |
C3 | 0.0643 (8) | 0.0508 (7) | 0.0637 (9) | 0.0011 (6) | −0.0082 (6) | −0.0053 (6) |
C4 | 0.0710 (9) | 0.0448 (8) | 0.0892 (11) | 0.0039 (6) | −0.0112 (8) | −0.0152 (7) |
C5 | 0.0710 (10) | 0.0559 (8) | 0.0898 (11) | 0.0039 (7) | −0.0035 (8) | −0.0362 (8) |
C6 | 0.0618 (8) | 0.0599 (8) | 0.0601 (8) | −0.0025 (6) | 0.0010 (6) | −0.0249 (6) |
C7 | 0.0412 (6) | 0.0487 (7) | 0.0520 (7) | −0.0030 (5) | −0.0024 (5) | −0.0154 (5) |
C8 | 0.0422 (6) | 0.0500 (7) | 0.0453 (6) | −0.0034 (5) | −0.0012 (5) | −0.0130 (5) |
C9 | 0.0602 (8) | 0.0741 (9) | 0.0485 (7) | −0.0118 (7) | −0.0055 (6) | −0.0029 (6) |
C10 | 0.1079 (14) | 0.0743 (11) | 0.0616 (9) | −0.0125 (9) | −0.0128 (8) | 0.0057 (8) |
C11 | 0.0716 (10) | 0.1004 (13) | 0.0491 (8) | −0.0029 (8) | 0.0031 (7) | −0.0082 (8) |
N1 | 0.0664 (7) | 0.0509 (6) | 0.0447 (6) | 0.0070 (5) | 0.0035 (4) | −0.0107 (4) |
N2 | 0.0655 (7) | 0.0448 (6) | 0.0454 (6) | 0.0046 (5) | 0.0026 (5) | −0.0070 (5) |
N3 | 0.0642 (7) | 0.0584 (7) | 0.0446 (6) | −0.0027 (5) | −0.0002 (4) | −0.0102 (5) |
N4 | 0.0695 (7) | 0.0584 (7) | 0.0468 (6) | −0.0045 (5) | −0.0037 (5) | −0.0050 (5) |
C1—N1 | 1.2809 (18) | C8—N3 | 1.2941 (17) |
C1—C2 | 1.4364 (19) | C8—N2 | 1.3674 (17) |
C1—H1 | 0.946 (16) | C9—N4 | 1.2780 (18) |
C2—C7 | 1.3904 (19) | C9—C11 | 1.492 (2) |
C2—C3 | 1.398 (2) | C9—C10 | 1.493 (2) |
C3—C4 | 1.366 (2) | C10—H10A | 0.9600 |
C3—H3 | 0.96 (2) | C10—H10B | 0.9600 |
C4—C5 | 1.376 (3) | C10—H10C | 0.9600 |
C4—H4 | 0.943 (18) | C11—H11A | 0.9600 |
C5—C6 | 1.374 (2) | C11—H11B | 0.9600 |
C5—H5 | 0.94 (2) | C11—H11C | 0.9600 |
C6—C7 | 1.3966 (19) | N1—N2 | 1.3585 (16) |
C6—H6 | 0.964 (16) | N2—H2 | 0.870 (17) |
C7—C8 | 1.4600 (19) | N3—N4 | 1.4068 (18) |
N1—C1—C2 | 124.53 (12) | N2—C8—C7 | 115.36 (11) |
N1—C1—H1 | 115.2 (10) | N4—C9—C11 | 125.86 (15) |
C2—C1—H1 | 120.2 (10) | N4—C9—C10 | 116.67 (14) |
C7—C2—C3 | 119.55 (13) | C11—C9—C10 | 117.47 (13) |
C7—C2—C1 | 118.09 (12) | C9—C10—H10A | 109.5 |
C3—C2—C1 | 122.34 (13) | C9—C10—H10B | 109.5 |
C4—C3—C2 | 120.34 (15) | H10A—C10—H10B | 109.5 |
C4—C3—H3 | 121.8 (11) | C9—C10—H10C | 109.5 |
C2—C3—H3 | 117.8 (11) | H10A—C10—H10C | 109.5 |
C3—C4—C5 | 120.06 (14) | H10B—C10—H10C | 109.5 |
C3—C4—H4 | 120.0 (11) | C9—C11—H11A | 109.5 |
C5—C4—H4 | 120.0 (11) | C9—C11—H11B | 109.5 |
C6—C5—C4 | 120.90 (14) | H11A—C11—H11B | 109.5 |
C6—C5—H5 | 119.8 (11) | C9—C11—H11C | 109.5 |
C4—C5—H5 | 119.2 (11) | H11A—C11—H11C | 109.5 |
C5—C6—C7 | 119.73 (15) | H11B—C11—H11C | 109.5 |
C5—C6—H6 | 123.1 (10) | C1—N1—N2 | 116.62 (11) |
C7—C6—H6 | 117.1 (10) | N1—N2—C8 | 127.12 (11) |
C2—C7—C6 | 119.41 (13) | N1—N2—H2 | 115.9 (10) |
C2—C7—C8 | 118.27 (11) | C8—N2—H2 | 116.8 (10) |
C6—C7—C8 | 122.31 (12) | C8—N3—N4 | 110.64 (11) |
N3—C8—N2 | 123.62 (12) | C9—N4—N3 | 115.41 (13) |
N3—C8—C7 | 121.02 (12) | ||
N1—C1—C2—C7 | −1.0 (2) | C2—C7—C8—N3 | −179.70 (11) |
N1—C1—C2—C3 | 177.64 (13) | C6—C7—C8—N3 | 1.26 (19) |
C7—C2—C3—C4 | 0.6 (2) | C2—C7—C8—N2 | 1.14 (16) |
C1—C2—C3—C4 | −178.02 (13) | C6—C7—C8—N2 | −177.90 (11) |
C2—C3—C4—C5 | −0.5 (2) | C2—C1—N1—N2 | 1.8 (2) |
C3—C4—C5—C6 | 0.0 (3) | C1—N1—N2—C8 | −1.1 (2) |
C4—C5—C6—C7 | 0.4 (2) | N3—C8—N2—N1 | −179.50 (12) |
C3—C2—C7—C6 | −0.15 (19) | C7—C8—N2—N1 | −0.36 (19) |
C1—C2—C7—C6 | 178.50 (12) | N2—C8—N3—N4 | −0.75 (18) |
C3—C2—C7—C8 | −179.23 (11) | C7—C8—N3—N4 | −179.84 (10) |
C1—C2—C7—C8 | −0.57 (18) | C11—C9—N4—N3 | −0.1 (2) |
C5—C6—C7—C2 | −0.4 (2) | C10—C9—N4—N3 | 179.27 (13) |
C5—C6—C7—C8 | 178.68 (12) | C8—N3—N4—C9 | 178.92 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···N1i | 0.870 (17) | 2.322 (17) | 3.012 (2) | 136.4 (13) |
C11—H11B···N4ii | 0.96 | 2.80 | 3.585 (3) | 139 |
C10—H10C···N3ii | 0.96 | 2.79 | 3.685 (3) | 156 |
C11—H11C···N4iii | 0.96 | 2.88 | 3.711 (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 formula | C11H12N4 |
Mr | 200.25 |
Crystal system, space group | Triclinic, 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) |
V (Å3) | 533.9 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.78 × 0.55 × 0.19 |
Data collection | |
Diffractometer | Stoe IPDS 2 |
Absorption correction | Integration (X-RED32; Stoe & Cie, 2002) |
Tmin, Tmax | 0.346, 0.937 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9440, 2095, 1679 |
Rint | 0.061 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.123, 1.05 |
No. of reflections | 2095 |
No. of parameters | 163 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 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).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···N1i | 0.870 (17) | 2.322 (17) | 3.012 (2) | 136.4 (13) |
C11—H11B···N4ii | 0.96 | 2.80 | 3.585 (3) | 139.3 |
C10—H10C···N3ii | 0.96 | 2.79 | 3.685 (3) | 155.6 |
C11—H11C···N4iii | 0.96 | 2.88 | 3.711 (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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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.