Download citation
Download citation
link to html
The crystal structure of the title compound, C46H34N4O2S2, shows that the mol­ecules exist in the hydrazone form and not the azo form. The title compound is actually a centrosymmetric dimer of 3-dehydro-1-[2-(benzyl­sulfan­yl)phenyl­hydra­zono]naphthalene-4-one connected through the C-3 position of the naphthalene unit. The hydrazone H atom and the sulfanyl S atom are linked by an intra­molecular N—H...S hydrogen bond. In each mol­ecule, there are two intra­molecular C—H...O inter­actions. The crystal packing is stabilized by three weak inter­molecular π–π inter­actions; the centroid–centroid distances are 3.808 (2), 3.955 (2) and 3.955 (2) Å; the corresponding perpendicular distances are 3.481, 3.535 and 3.584 Å.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807054499/at2453sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807054499/at2453Isup2.hkl
Contains datablock I

CCDC reference: 672828

Key indicators

  • Single-crystal X-ray study
  • T = 153 K
  • Mean [sigma](C-C) = 0.005 Å
  • R factor = 0.065
  • wR factor = 0.139
  • Data-to-parameter ratio = 12.2

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT333_ALERT_2_C Large Average Benzene C-C Dist. C1 -C10 1.45 Ang. PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 5 PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 1
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 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 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

Aryl diazenes are among the largest group of dyes. The extensive application of azo dyes in industry and analytical chemistry have attracted attention for decades (Sudesh Kumar & Neckers, 1989). Optically active azobenzene polymers are very important functional materials because of their photoresponsive properties. Generally arylazonaphthalenes have been found to exist in the hydrazo-keto form in the solid state (Liu et al., 2005). The position of azo and hydroxyl groups in arylazo compounds brings into play the azo-hydrazo equilibrium, which has been the subject of intensive investigation in recent years (Antonov et al., 1999). Here in, we report the crystal structure of the title compound where the hydrazo-keto form is dominant over the azo-enol form in the solid state.

The molecular structure of the title compound, (I), is shown in Fig. 1, with the atom-numbering scheme. Selected bond lengths are listed in Table 1. The packing arrangement of (I) is shown in Fig. 2. The title compound is actually the centro symmetric dimer of the asymmetric unit, 3-dehydro-1-[2-(benzylsulfanyl)phenylhydrazono]naphthalene-4-one and the centre of symmetry exists at the centre of the C3—C3i [symmetry code: (i) -x + 1, -y + 2, -z + 1] bond. In each dimer the asymmetric units are inter-connected by a C3—C3i [symmetry code: (i) -x + 1, -y + 2, -z + 1] bond of the naphthalene moiety and two C2—H···O1 interactions (Table 2, Fig. 1). Naphthyl and phenyl rings around the hydrazone group adopt a trans configuration. The hydrazone H atom and the sulfanyl S atom are linked by an intramolecular N—H···S hydrogen bond (Table 2, Fig. 1). The crystal packing is stabilized by three weak intermolecular ππ interactions (Bagchi et al., 2007); the Cg1—Cg1ii, Cg1—Cg2iii and Cg2—Cg1iv [Symmetry codes: (ii) 1 - x, 1 - y, 1 - z; (iii) x, 1 + y, z; (iv) x, -1 + y, z. Cg1 and Cg2 are the centroids of C1—C10 and C5—C9 rings respectively.] distances are 3.808 (2), 3.955 (2) and 3.955 (2) Å (Fig. 3); the corresponding perpendicular distances are 3.481 (with slippage of 1.544 Å), 3.535 and 3.584 Å, respectively.

Related literature top

For related literature, see: Antonov et al. (1999); Bagchi et al. (2007); Liu et al. (2005); Sudesh Kumar & Neckers (1989).

Experimental top

The title compound, (I) was prepared by coupling diazotized 2-benzylthioaniline with 1-naphthol at around 273–278 K. The product was isolated by column chromatography and crystallized from ethanol. Suitable crystals of (I) were obtained by slow diffusion of a dichloromethane solution into n-hexane.

Refinement top

The N-bound H atom was located in a difference Fourier map and its coordinates and isotropic displacement parameter were freely refined. C-bound H atoms were included at calculated positions as riding atoms with C—H set to 0.93 Å for aromatic and 0.97 Å for CH2. H atoms, with Uiso (H) = 1.2Ueq(C). Some low-angle reflections were excluded from the refinement, as they were probably obscured by the beam stop.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXL97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of (I), with displacement ellipsoids drawn at the 75% probability level. The C—H···O and N—H···S interactions are shown by dotted lines [symmetry code: (i) -x + 1, -y + 2, -z + 1].
[Figure 2] Fig. 2. The molecular arrangement of (I) in the ac plane.
[Figure 3] Fig. 3. The inter molecular ππ interaction for (I), indicated by the dotted line. [Symmetry codes: (ii) 1 - x, 1 - y, 1 - z; (iii) x, 1 + y, z; (iv) x, -1 + y, z. Cg1 and Cg2 are the centroids of C1—C10 and C5—C9 rings respectively.]
4,4'-Bis[2-(benzylsulfanyl)phenylhydrazono]-2,2'-binaphthalene- 1,1'(4H,4'H)-dione top
Crystal data top
C46H34N4O2S2F(000) = 772
Mr = 738.89Dx = 1.408 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3027 reflections
a = 19.184 (4) Åθ = 2.1–25.0°
b = 4.6066 (10) ŵ = 0.20 mm1
c = 21.734 (5) ÅT = 153 K
β = 114.838 (4)°Needle, red
V = 1743.0 (7) Å30.42 × 0.31 × 0.19 mm
Z = 2
Data collection top
Bruker SMART APEX CCD area detector
diffractometer
3027 independent reflections
Radiation source: fine-focus sealed tube1893 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.061
phi and ω scansθmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1422
Tmin = 0.926, Tmax = 0.964k = 55
6195 measured reflectionsl = 2425
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)] = 0.065Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.139H atoms treated by a mixture of independent and constrained refinement
S = 0.97 w = 1/[σ2(Fo2) + (0.0594P)2]
where P = (Fo2 + 2Fc2)/3
3027 reflections(Δ/σ)max < 0.001
248 parametersΔρmax = 0.32 e Å3
0 restraintsΔρmin = 0.29 e Å3
Crystal data top
C46H34N4O2S2V = 1743.0 (7) Å3
Mr = 738.89Z = 2
Monoclinic, P21/cMo Kα radiation
a = 19.184 (4) ŵ = 0.20 mm1
b = 4.6066 (10) ÅT = 153 K
c = 21.734 (5) Å0.42 × 0.31 × 0.19 mm
β = 114.838 (4)°
Data collection top
Bruker SMART APEX CCD area detector
diffractometer
3027 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1893 reflections with I > 2σ(I)
Tmin = 0.926, Tmax = 0.964Rint = 0.061
6195 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0650 restraints
wR(F2) = 0.139H atoms treated by a mixture of independent and constrained refinement
S = 0.97Δρmax = 0.32 e Å3
3027 reflectionsΔρmin = 0.29 e Å3
248 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
H020.298 (2)0.649 (8)0.5023 (18)0.035 (12)*
S10.15711 (5)0.7308 (2)0.42556 (4)0.0214 (3)
N10.37643 (16)0.4567 (6)0.58144 (14)0.0228 (8)
C120.1686 (2)0.4824 (8)0.49127 (17)0.0201 (9)
C10.43806 (19)0.5734 (8)0.57898 (17)0.0204 (9)
C30.50221 (19)0.8952 (8)0.52663 (16)0.0189 (8)
C100.5114 (2)0.4860 (8)0.63407 (17)0.0195 (9)
C110.2422 (2)0.4009 (8)0.53961 (17)0.0196 (8)
N20.30659 (17)0.5246 (7)0.53532 (16)0.0234 (8)
C80.5156 (2)0.2926 (8)0.68462 (17)0.0237 (9)
H80.47090.20880.68340.028*
C90.5792 (2)0.6001 (8)0.63453 (17)0.0210 (9)
C150.1852 (2)0.0758 (9)0.59165 (18)0.0258 (9)
H150.19050.06250.62450.031*
O10.64011 (15)0.8716 (7)0.58070 (15)0.0543 (10)
C160.2494 (2)0.1971 (8)0.58925 (17)0.0225 (9)
H160.29790.14290.62100.027*
C40.5785 (2)0.7989 (8)0.58052 (18)0.0249 (9)
C140.1119 (2)0.1591 (8)0.54492 (18)0.0255 (10)
H140.06860.07870.54710.031*
C200.1604 (2)0.9702 (8)0.22193 (18)0.0243 (9)
H200.18981.11580.21480.029*
C20.4387 (2)0.7774 (8)0.52924 (17)0.0231 (9)
H20.39130.83390.49590.028*
C60.6527 (2)0.3442 (8)0.73783 (18)0.0268 (10)
H60.69980.29970.77310.032*
C180.1411 (2)0.6237 (8)0.29665 (17)0.0196 (8)
C130.1043 (2)0.3600 (8)0.49592 (17)0.0207 (9)
H130.05550.41580.46520.025*
C70.5857 (2)0.2237 (9)0.73672 (17)0.0260 (9)
H70.58800.09740.77090.031*
C50.6494 (2)0.5284 (8)0.68709 (18)0.0250 (9)
H50.69450.60600.68780.030*
C170.1672 (2)0.4796 (8)0.36412 (17)0.0266 (10)
H17A0.22040.42120.37980.032*
H17B0.13660.30700.36020.032*
C230.0728 (2)0.5399 (8)0.24326 (18)0.0244 (9)
H230.04280.39650.25030.029*
C220.0486 (2)0.6662 (8)0.17986 (18)0.0238 (9)
H220.00320.60620.14450.029*
C210.0926 (2)0.8822 (8)0.16946 (18)0.0254 (9)
H210.07640.96860.12700.031*
C190.1846 (2)0.8421 (8)0.28492 (17)0.0225 (9)
H190.23040.90180.32000.027*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0238 (5)0.0194 (5)0.0204 (5)0.0035 (4)0.0086 (4)0.0017 (4)
N10.0170 (17)0.0224 (18)0.0239 (17)0.0004 (14)0.0036 (14)0.0034 (15)
C120.018 (2)0.020 (2)0.0208 (19)0.0020 (16)0.0069 (16)0.0019 (17)
C10.0156 (19)0.019 (2)0.026 (2)0.0027 (16)0.0077 (16)0.0025 (18)
C30.0184 (19)0.018 (2)0.021 (2)0.0009 (16)0.0090 (16)0.0041 (16)
C100.025 (2)0.017 (2)0.0181 (19)0.0009 (17)0.0109 (16)0.0053 (17)
C110.018 (2)0.022 (2)0.0200 (19)0.0032 (17)0.0095 (16)0.0048 (17)
N20.0192 (18)0.027 (2)0.0222 (18)0.0024 (15)0.0066 (15)0.0085 (16)
C80.023 (2)0.020 (2)0.028 (2)0.0010 (17)0.0105 (17)0.0042 (18)
C90.023 (2)0.018 (2)0.024 (2)0.0042 (17)0.0116 (17)0.0008 (17)
C150.029 (2)0.026 (2)0.024 (2)0.0030 (19)0.0118 (18)0.0000 (18)
O10.0198 (16)0.075 (2)0.059 (2)0.0034 (16)0.0080 (14)0.0415 (19)
C160.0178 (19)0.026 (2)0.021 (2)0.0006 (17)0.0057 (16)0.0018 (17)
C40.018 (2)0.023 (2)0.033 (2)0.0027 (18)0.0111 (17)0.0056 (18)
C140.019 (2)0.034 (3)0.026 (2)0.0074 (17)0.0110 (17)0.0045 (19)
C200.025 (2)0.024 (2)0.027 (2)0.0033 (18)0.0136 (18)0.0017 (19)
C20.0180 (19)0.024 (2)0.025 (2)0.0024 (18)0.0062 (16)0.0033 (19)
C60.019 (2)0.031 (2)0.023 (2)0.0045 (18)0.0014 (17)0.0008 (19)
C180.024 (2)0.016 (2)0.021 (2)0.0086 (17)0.0121 (17)0.0006 (17)
C130.0169 (19)0.029 (2)0.0130 (19)0.0043 (17)0.0029 (15)0.0055 (17)
C70.032 (2)0.028 (2)0.021 (2)0.007 (2)0.0128 (17)0.0062 (19)
C50.018 (2)0.022 (2)0.031 (2)0.0033 (17)0.0066 (17)0.0005 (19)
C170.037 (2)0.020 (2)0.025 (2)0.0061 (18)0.0153 (18)0.0008 (18)
C230.024 (2)0.023 (2)0.033 (2)0.0011 (18)0.0192 (18)0.0004 (19)
C220.021 (2)0.031 (2)0.022 (2)0.0067 (18)0.0108 (16)0.0009 (18)
C210.030 (2)0.029 (2)0.020 (2)0.0127 (19)0.0142 (18)0.0057 (18)
C190.024 (2)0.021 (2)0.021 (2)0.0052 (17)0.0083 (17)0.0019 (17)
Geometric parameters (Å, º) top
S1—C121.770 (4)C16—H160.9300
S1—C171.837 (4)C14—C131.372 (5)
N1—C11.320 (4)C14—H140.9300
N1—N21.330 (4)C20—C191.380 (5)
C12—C131.398 (5)C20—C211.383 (5)
C12—C111.411 (5)C20—H200.9300
C1—C21.436 (5)C2—H20.9300
C1—C101.469 (5)C6—C51.372 (5)
C3—C21.357 (5)C6—C71.392 (5)
C3—C3i1.482 (7)C6—H60.9300
C3—C41.507 (5)C18—C231.391 (5)
C10—C81.390 (5)C18—C191.398 (5)
C10—C91.399 (5)C18—C171.491 (5)
C11—C161.393 (5)C13—H130.9300
C11—N21.398 (4)C7—H70.9300
N2—H020.88 (4)C5—H50.9300
C8—C71.382 (5)C17—H17A0.9700
C8—H80.9300C17—H17B0.9700
C9—C51.392 (5)C23—C221.384 (5)
C9—C41.484 (5)C23—H230.9300
C15—C161.372 (5)C22—C211.383 (5)
C15—C141.399 (5)C22—H220.9300
C15—H150.9300C21—H210.9300
O1—C41.227 (4)C19—H190.9300
C12—S1—C1799.43 (17)C19—C20—H20120.0
C1—N1—N2120.6 (3)C21—C20—H20120.0
C13—C12—C11118.4 (3)C3—C2—C1125.8 (3)
C13—C12—S1120.3 (3)C3—C2—H2117.1
C11—C12—S1121.3 (3)C1—C2—H2117.1
N1—C1—C2126.0 (3)C5—C6—C7120.2 (3)
N1—C1—C10115.0 (3)C5—C6—H6119.9
C2—C1—C10119.0 (3)C7—C6—H6119.9
C2—C3—C3i122.4 (4)C23—C18—C19118.2 (3)
C2—C3—C4116.5 (3)C23—C18—C17120.4 (3)
C3i—C3—C4121.2 (4)C19—C18—C17121.3 (3)
C8—C10—C9119.3 (3)C14—C13—C12121.3 (3)
C8—C10—C1122.6 (3)C14—C13—H13119.4
C9—C10—C1118.1 (3)C12—C13—H13119.4
C16—C11—N2121.6 (3)C8—C7—C6119.7 (3)
C16—C11—C12119.9 (3)C8—C7—H7120.1
N2—C11—C12118.5 (3)C6—C7—H7120.1
N1—N2—C11119.5 (3)C6—C5—C9120.5 (4)
N1—N2—H02123 (3)C6—C5—H5119.7
C11—N2—H02117 (3)C9—C5—H5119.7
C7—C8—C10120.6 (4)C18—C17—S1109.9 (3)
C7—C8—H8119.7C18—C17—H17A109.7
C10—C8—H8119.7S1—C17—H17A109.7
C5—C9—C10119.6 (3)C18—C17—H17B109.7
C5—C9—C4118.6 (3)S1—C17—H17B109.7
C10—C9—C4121.8 (3)H17A—C17—H17B108.2
C16—C15—C14120.3 (4)C22—C23—C18121.2 (4)
C16—C15—H15119.8C22—C23—H23119.4
C14—C15—H15119.8C18—C23—H23119.4
C15—C16—C11120.4 (3)C21—C22—C23119.6 (3)
C15—C16—H16119.8C21—C22—H22120.2
C11—C16—H16119.8C23—C22—H22120.2
O1—C4—C9118.5 (3)C22—C21—C20120.2 (3)
O1—C4—C3122.8 (3)C22—C21—H21119.9
C9—C4—C3118.7 (3)C20—C21—H21119.9
C13—C14—C15119.7 (4)C20—C19—C18120.8 (3)
C13—C14—H14120.2C20—C19—H19119.6
C15—C14—H14120.2C18—C19—H19119.6
C19—C20—C21120.0 (4)
C17—S1—C12—C1395.4 (3)C2—C3—C4—O1174.2 (4)
C17—S1—C12—C1183.9 (3)C3i—C3—C4—O15.1 (7)
N2—N1—C1—C20.0 (6)C2—C3—C4—C93.8 (5)
N2—N1—C1—C10178.3 (3)C3i—C3—C4—C9176.9 (4)
N1—C1—C10—C80.7 (5)C16—C15—C14—C131.0 (5)
C2—C1—C10—C8179.2 (3)C3i—C3—C2—C1179.9 (4)
N1—C1—C10—C9179.7 (3)C4—C3—C2—C10.7 (5)
C2—C1—C10—C91.8 (5)N1—C1—C2—C3179.5 (3)
C13—C12—C11—C161.7 (5)C10—C1—C2—C32.2 (6)
S1—C12—C11—C16177.7 (3)C15—C14—C13—C120.5 (5)
C13—C12—C11—N2179.6 (3)C11—C12—C13—C141.8 (5)
S1—C12—C11—N21.0 (5)S1—C12—C13—C14177.6 (3)
C1—N1—N2—C11179.2 (3)C10—C8—C7—C61.4 (6)
C16—C11—N2—N13.1 (5)C5—C6—C7—C80.6 (6)
C12—C11—N2—N1178.2 (3)C7—C6—C5—C90.9 (6)
C9—C10—C8—C73.1 (5)C10—C9—C5—C60.9 (5)
C1—C10—C8—C7177.9 (3)C4—C9—C5—C6179.6 (3)
C8—C10—C9—C52.8 (5)C23—C18—C17—S1108.6 (3)
C1—C10—C9—C5178.1 (3)C19—C18—C17—S172.3 (4)
C8—C10—C9—C4177.7 (3)C12—S1—C17—C18166.4 (3)
C1—C10—C9—C41.4 (5)C19—C18—C23—C220.7 (5)
C14—C15—C16—C111.1 (6)C17—C18—C23—C22178.4 (3)
N2—C11—C16—C15179.0 (3)C18—C23—C22—C210.9 (5)
C12—C11—C16—C150.3 (5)C23—C22—C21—C200.4 (5)
C5—C9—C4—O16.6 (6)C19—C20—C21—C220.1 (5)
C10—C9—C4—O1173.9 (4)C21—C20—C19—C180.2 (5)
C5—C9—C4—C3175.3 (3)C23—C18—C19—C200.2 (5)
C10—C9—C4—C34.2 (5)C17—C18—C19—C20178.9 (3)
Symmetry code: (i) x+1, y+2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H02···S10.88 (4)2.54 (4)3.012 (4)115 (3)
C2—H2···O1i0.932.032.752 (5)133
Symmetry code: (i) x+1, y+2, z+1.

Experimental details

Crystal data
Chemical formulaC46H34N4O2S2
Mr738.89
Crystal system, space groupMonoclinic, P21/c
Temperature (K)153
a, b, c (Å)19.184 (4), 4.6066 (10), 21.734 (5)
β (°) 114.838 (4)
V3)1743.0 (7)
Z2
Radiation typeMo Kα
µ (mm1)0.20
Crystal size (mm)0.42 × 0.31 × 0.19
Data collection
DiffractometerBruker SMART APEX CCD area detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.926, 0.964
No. of measured, independent and
observed [I > 2σ(I)] reflections
6195, 3027, 1893
Rint0.061
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.065, 0.139, 0.97
No. of reflections3027
No. of parameters248
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.32, 0.29

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 2000), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997).

Selected bond lengths (Å) top
N1—C11.320 (4)C3—C3i1.482 (7)
N1—N21.330 (4)C11—N21.398 (4)
Symmetry code: (i) x+1, y+2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H02···S10.88 (4)2.54 (4)3.012 (4)115 (3)
C2—H2···O1i0.932.032.752 (5)133
Symmetry code: (i) x+1, y+2, z+1.
 

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds