The crystal structure of the title compound, C
46H
34N
4O
2S
2, 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
CCDC reference: 672828
Key indicators
- Single-crystal X-ray study
- T = 153 K
- Mean (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
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.
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.
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).
4,4'-Bis[2-(benzylsulfanyl)phenylhydrazono]-2,2'-binaphthalene-
1,1'(4
H,4'H)-dione
top
Crystal data top
C46H34N4O2S2 | F(000) = 772 |
Mr = 738.89 | Dx = 1.408 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3027 reflections |
a = 19.184 (4) Å | θ = 2.1–25.0° |
b = 4.6066 (10) Å | µ = 0.20 mm−1 |
c = 21.734 (5) Å | T = 153 K |
β = 114.838 (4)° | Needle, red |
V = 1743.0 (7) Å3 | 0.42 × 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 tube | 1893 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.061 |
phi and ω scans | θmax = 25.0°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −14→22 |
Tmin = 0.926, Tmax = 0.964 | k = −5→5 |
6195 measured reflections | l = −24→25 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.065 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.139 | H 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 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.29 e Å−3 |
Crystal data top
C46H34N4O2S2 | V = 1743.0 (7) Å3 |
Mr = 738.89 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 19.184 (4) Å | µ = 0.20 mm−1 |
b = 4.6066 (10) Å | T = 153 K |
c = 21.734 (5) Å | 0.42 × 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 = 0.964 | Rint = 0.061 |
6195 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.065 | 0 restraints |
wR(F2) = 0.139 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.97 | Δρmax = 0.32 e Å−3 |
3027 reflections | Δρmin = −0.29 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
H02 | 0.298 (2) | 0.649 (8) | 0.5023 (18) | 0.035 (12)* | |
S1 | 0.15711 (5) | 0.7308 (2) | 0.42556 (4) | 0.0214 (3) | |
N1 | 0.37643 (16) | 0.4567 (6) | 0.58144 (14) | 0.0228 (8) | |
C12 | 0.1686 (2) | 0.4824 (8) | 0.49127 (17) | 0.0201 (9) | |
C1 | 0.43806 (19) | 0.5734 (8) | 0.57898 (17) | 0.0204 (9) | |
C3 | 0.50221 (19) | 0.8952 (8) | 0.52663 (16) | 0.0189 (8) | |
C10 | 0.5114 (2) | 0.4860 (8) | 0.63407 (17) | 0.0195 (9) | |
C11 | 0.2422 (2) | 0.4009 (8) | 0.53961 (17) | 0.0196 (8) | |
N2 | 0.30659 (17) | 0.5246 (7) | 0.53532 (16) | 0.0234 (8) | |
C8 | 0.5156 (2) | 0.2926 (8) | 0.68462 (17) | 0.0237 (9) | |
H8 | 0.4709 | 0.2088 | 0.6834 | 0.028* | |
C9 | 0.5792 (2) | 0.6001 (8) | 0.63453 (17) | 0.0210 (9) | |
C15 | 0.1852 (2) | 0.0758 (9) | 0.59165 (18) | 0.0258 (9) | |
H15 | 0.1905 | −0.0625 | 0.6245 | 0.031* | |
O1 | 0.64011 (15) | 0.8716 (7) | 0.58070 (15) | 0.0543 (10) | |
C16 | 0.2494 (2) | 0.1971 (8) | 0.58925 (17) | 0.0225 (9) | |
H16 | 0.2979 | 0.1429 | 0.6210 | 0.027* | |
C4 | 0.5785 (2) | 0.7989 (8) | 0.58052 (18) | 0.0249 (9) | |
C14 | 0.1119 (2) | 0.1591 (8) | 0.54492 (18) | 0.0255 (10) | |
H14 | 0.0686 | 0.0787 | 0.5471 | 0.031* | |
C20 | 0.1604 (2) | 0.9702 (8) | 0.22193 (18) | 0.0243 (9) | |
H20 | 0.1898 | 1.1158 | 0.2148 | 0.029* | |
C2 | 0.4387 (2) | 0.7774 (8) | 0.52924 (17) | 0.0231 (9) | |
H2 | 0.3913 | 0.8339 | 0.4959 | 0.028* | |
C6 | 0.6527 (2) | 0.3442 (8) | 0.73783 (18) | 0.0268 (10) | |
H6 | 0.6998 | 0.2997 | 0.7731 | 0.032* | |
C18 | 0.1411 (2) | 0.6237 (8) | 0.29665 (17) | 0.0196 (8) | |
C13 | 0.1043 (2) | 0.3600 (8) | 0.49592 (17) | 0.0207 (9) | |
H13 | 0.0555 | 0.4158 | 0.4652 | 0.025* | |
C7 | 0.5857 (2) | 0.2237 (9) | 0.73672 (17) | 0.0260 (9) | |
H7 | 0.5880 | 0.0974 | 0.7709 | 0.031* | |
C5 | 0.6494 (2) | 0.5284 (8) | 0.68709 (18) | 0.0250 (9) | |
H5 | 0.6945 | 0.6060 | 0.6878 | 0.030* | |
C17 | 0.1672 (2) | 0.4796 (8) | 0.36412 (17) | 0.0266 (10) | |
H17A | 0.2204 | 0.4212 | 0.3798 | 0.032* | |
H17B | 0.1366 | 0.3070 | 0.3602 | 0.032* | |
C23 | 0.0728 (2) | 0.5399 (8) | 0.24326 (18) | 0.0244 (9) | |
H23 | 0.0428 | 0.3965 | 0.2503 | 0.029* | |
C22 | 0.0486 (2) | 0.6662 (8) | 0.17986 (18) | 0.0238 (9) | |
H22 | 0.0032 | 0.6062 | 0.1445 | 0.029* | |
C21 | 0.0926 (2) | 0.8822 (8) | 0.16946 (18) | 0.0254 (9) | |
H21 | 0.0764 | 0.9686 | 0.1270 | 0.031* | |
C19 | 0.1846 (2) | 0.8421 (8) | 0.28492 (17) | 0.0225 (9) | |
H19 | 0.2304 | 0.9018 | 0.3200 | 0.027* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0238 (5) | 0.0194 (5) | 0.0204 (5) | 0.0035 (4) | 0.0086 (4) | 0.0017 (4) |
N1 | 0.0170 (17) | 0.0224 (18) | 0.0239 (17) | −0.0004 (14) | 0.0036 (14) | 0.0034 (15) |
C12 | 0.018 (2) | 0.020 (2) | 0.0208 (19) | 0.0020 (16) | 0.0069 (16) | −0.0019 (17) |
C1 | 0.0156 (19) | 0.019 (2) | 0.026 (2) | 0.0027 (16) | 0.0077 (16) | −0.0025 (18) |
C3 | 0.0184 (19) | 0.018 (2) | 0.021 (2) | −0.0009 (16) | 0.0090 (16) | −0.0041 (16) |
C10 | 0.025 (2) | 0.017 (2) | 0.0181 (19) | 0.0009 (17) | 0.0109 (16) | −0.0053 (17) |
C11 | 0.018 (2) | 0.022 (2) | 0.0200 (19) | −0.0032 (17) | 0.0095 (16) | −0.0048 (17) |
N2 | 0.0192 (18) | 0.027 (2) | 0.0222 (18) | 0.0024 (15) | 0.0066 (15) | 0.0085 (16) |
C8 | 0.023 (2) | 0.020 (2) | 0.028 (2) | 0.0010 (17) | 0.0105 (17) | −0.0042 (18) |
C9 | 0.023 (2) | 0.018 (2) | 0.024 (2) | −0.0042 (17) | 0.0116 (17) | −0.0008 (17) |
C15 | 0.029 (2) | 0.026 (2) | 0.024 (2) | −0.0030 (19) | 0.0118 (18) | 0.0000 (18) |
O1 | 0.0198 (16) | 0.075 (2) | 0.059 (2) | −0.0034 (16) | 0.0080 (14) | 0.0415 (19) |
C16 | 0.0178 (19) | 0.026 (2) | 0.021 (2) | −0.0006 (17) | 0.0057 (16) | 0.0018 (17) |
C4 | 0.018 (2) | 0.023 (2) | 0.033 (2) | −0.0027 (18) | 0.0111 (17) | 0.0056 (18) |
C14 | 0.019 (2) | 0.034 (3) | 0.026 (2) | −0.0074 (17) | 0.0110 (17) | −0.0045 (19) |
C20 | 0.025 (2) | 0.024 (2) | 0.027 (2) | −0.0033 (18) | 0.0136 (18) | 0.0017 (19) |
C2 | 0.0180 (19) | 0.024 (2) | 0.025 (2) | 0.0024 (18) | 0.0062 (16) | −0.0033 (19) |
C6 | 0.019 (2) | 0.031 (2) | 0.023 (2) | 0.0045 (18) | 0.0014 (17) | −0.0008 (19) |
C18 | 0.024 (2) | 0.016 (2) | 0.021 (2) | 0.0086 (17) | 0.0121 (17) | 0.0006 (17) |
C13 | 0.0169 (19) | 0.029 (2) | 0.0130 (19) | −0.0043 (17) | 0.0029 (15) | −0.0055 (17) |
C7 | 0.032 (2) | 0.028 (2) | 0.021 (2) | 0.007 (2) | 0.0128 (17) | 0.0062 (19) |
C5 | 0.018 (2) | 0.022 (2) | 0.031 (2) | −0.0033 (17) | 0.0066 (17) | −0.0005 (19) |
C17 | 0.037 (2) | 0.020 (2) | 0.025 (2) | 0.0061 (18) | 0.0153 (18) | −0.0008 (18) |
C23 | 0.024 (2) | 0.023 (2) | 0.033 (2) | −0.0011 (18) | 0.0192 (18) | −0.0004 (19) |
C22 | 0.021 (2) | 0.031 (2) | 0.022 (2) | 0.0067 (18) | 0.0108 (16) | 0.0009 (18) |
C21 | 0.030 (2) | 0.029 (2) | 0.020 (2) | 0.0127 (19) | 0.0142 (18) | 0.0057 (18) |
C19 | 0.024 (2) | 0.021 (2) | 0.021 (2) | 0.0052 (17) | 0.0083 (17) | −0.0019 (17) |
Geometric parameters (Å, º) top
S1—C12 | 1.770 (4) | C16—H16 | 0.9300 |
S1—C17 | 1.837 (4) | C14—C13 | 1.372 (5) |
N1—C1 | 1.320 (4) | C14—H14 | 0.9300 |
N1—N2 | 1.330 (4) | C20—C19 | 1.380 (5) |
C12—C13 | 1.398 (5) | C20—C21 | 1.383 (5) |
C12—C11 | 1.411 (5) | C20—H20 | 0.9300 |
C1—C2 | 1.436 (5) | C2—H2 | 0.9300 |
C1—C10 | 1.469 (5) | C6—C5 | 1.372 (5) |
C3—C2 | 1.357 (5) | C6—C7 | 1.392 (5) |
C3—C3i | 1.482 (7) | C6—H6 | 0.9300 |
C3—C4 | 1.507 (5) | C18—C23 | 1.391 (5) |
C10—C8 | 1.390 (5) | C18—C19 | 1.398 (5) |
C10—C9 | 1.399 (5) | C18—C17 | 1.491 (5) |
C11—C16 | 1.393 (5) | C13—H13 | 0.9300 |
C11—N2 | 1.398 (4) | C7—H7 | 0.9300 |
N2—H02 | 0.88 (4) | C5—H5 | 0.9300 |
C8—C7 | 1.382 (5) | C17—H17A | 0.9700 |
C8—H8 | 0.9300 | C17—H17B | 0.9700 |
C9—C5 | 1.392 (5) | C23—C22 | 1.384 (5) |
C9—C4 | 1.484 (5) | C23—H23 | 0.9300 |
C15—C16 | 1.372 (5) | C22—C21 | 1.383 (5) |
C15—C14 | 1.399 (5) | C22—H22 | 0.9300 |
C15—H15 | 0.9300 | C21—H21 | 0.9300 |
O1—C4 | 1.227 (4) | C19—H19 | 0.9300 |
| | | |
C12—S1—C17 | 99.43 (17) | C19—C20—H20 | 120.0 |
C1—N1—N2 | 120.6 (3) | C21—C20—H20 | 120.0 |
C13—C12—C11 | 118.4 (3) | C3—C2—C1 | 125.8 (3) |
C13—C12—S1 | 120.3 (3) | C3—C2—H2 | 117.1 |
C11—C12—S1 | 121.3 (3) | C1—C2—H2 | 117.1 |
N1—C1—C2 | 126.0 (3) | C5—C6—C7 | 120.2 (3) |
N1—C1—C10 | 115.0 (3) | C5—C6—H6 | 119.9 |
C2—C1—C10 | 119.0 (3) | C7—C6—H6 | 119.9 |
C2—C3—C3i | 122.4 (4) | C23—C18—C19 | 118.2 (3) |
C2—C3—C4 | 116.5 (3) | C23—C18—C17 | 120.4 (3) |
C3i—C3—C4 | 121.2 (4) | C19—C18—C17 | 121.3 (3) |
C8—C10—C9 | 119.3 (3) | C14—C13—C12 | 121.3 (3) |
C8—C10—C1 | 122.6 (3) | C14—C13—H13 | 119.4 |
C9—C10—C1 | 118.1 (3) | C12—C13—H13 | 119.4 |
C16—C11—N2 | 121.6 (3) | C8—C7—C6 | 119.7 (3) |
C16—C11—C12 | 119.9 (3) | C8—C7—H7 | 120.1 |
N2—C11—C12 | 118.5 (3) | C6—C7—H7 | 120.1 |
N1—N2—C11 | 119.5 (3) | C6—C5—C9 | 120.5 (4) |
N1—N2—H02 | 123 (3) | C6—C5—H5 | 119.7 |
C11—N2—H02 | 117 (3) | C9—C5—H5 | 119.7 |
C7—C8—C10 | 120.6 (4) | C18—C17—S1 | 109.9 (3) |
C7—C8—H8 | 119.7 | C18—C17—H17A | 109.7 |
C10—C8—H8 | 119.7 | S1—C17—H17A | 109.7 |
C5—C9—C10 | 119.6 (3) | C18—C17—H17B | 109.7 |
C5—C9—C4 | 118.6 (3) | S1—C17—H17B | 109.7 |
C10—C9—C4 | 121.8 (3) | H17A—C17—H17B | 108.2 |
C16—C15—C14 | 120.3 (4) | C22—C23—C18 | 121.2 (4) |
C16—C15—H15 | 119.8 | C22—C23—H23 | 119.4 |
C14—C15—H15 | 119.8 | C18—C23—H23 | 119.4 |
C15—C16—C11 | 120.4 (3) | C21—C22—C23 | 119.6 (3) |
C15—C16—H16 | 119.8 | C21—C22—H22 | 120.2 |
C11—C16—H16 | 119.8 | C23—C22—H22 | 120.2 |
O1—C4—C9 | 118.5 (3) | C22—C21—C20 | 120.2 (3) |
O1—C4—C3 | 122.8 (3) | C22—C21—H21 | 119.9 |
C9—C4—C3 | 118.7 (3) | C20—C21—H21 | 119.9 |
C13—C14—C15 | 119.7 (4) | C20—C19—C18 | 120.8 (3) |
C13—C14—H14 | 120.2 | C20—C19—H19 | 119.6 |
C15—C14—H14 | 120.2 | C18—C19—H19 | 119.6 |
C19—C20—C21 | 120.0 (4) | | |
| | | |
C17—S1—C12—C13 | −95.4 (3) | C2—C3—C4—O1 | 174.2 (4) |
C17—S1—C12—C11 | 83.9 (3) | C3i—C3—C4—O1 | −5.1 (7) |
N2—N1—C1—C2 | 0.0 (6) | C2—C3—C4—C9 | −3.8 (5) |
N2—N1—C1—C10 | 178.3 (3) | C3i—C3—C4—C9 | 176.9 (4) |
N1—C1—C10—C8 | 0.7 (5) | C16—C15—C14—C13 | 1.0 (5) |
C2—C1—C10—C8 | 179.2 (3) | C3i—C3—C2—C1 | 179.9 (4) |
N1—C1—C10—C9 | 179.7 (3) | C4—C3—C2—C1 | 0.7 (5) |
C2—C1—C10—C9 | −1.8 (5) | N1—C1—C2—C3 | −179.5 (3) |
C13—C12—C11—C16 | 1.7 (5) | C10—C1—C2—C3 | 2.2 (6) |
S1—C12—C11—C16 | −177.7 (3) | C15—C14—C13—C12 | 0.5 (5) |
C13—C12—C11—N2 | −179.6 (3) | C11—C12—C13—C14 | −1.8 (5) |
S1—C12—C11—N2 | 1.0 (5) | S1—C12—C13—C14 | 177.6 (3) |
C1—N1—N2—C11 | −179.2 (3) | C10—C8—C7—C6 | −1.4 (6) |
C16—C11—N2—N1 | −3.1 (5) | C5—C6—C7—C8 | −0.6 (6) |
C12—C11—N2—N1 | 178.2 (3) | C7—C6—C5—C9 | 0.9 (6) |
C9—C10—C8—C7 | 3.1 (5) | C10—C9—C5—C6 | 0.9 (5) |
C1—C10—C8—C7 | −177.9 (3) | C4—C9—C5—C6 | −179.6 (3) |
C8—C10—C9—C5 | −2.8 (5) | C23—C18—C17—S1 | −108.6 (3) |
C1—C10—C9—C5 | 178.1 (3) | C19—C18—C17—S1 | 72.3 (4) |
C8—C10—C9—C4 | 177.7 (3) | C12—S1—C17—C18 | 166.4 (3) |
C1—C10—C9—C4 | −1.4 (5) | C19—C18—C23—C22 | 0.7 (5) |
C14—C15—C16—C11 | −1.1 (6) | C17—C18—C23—C22 | −178.4 (3) |
N2—C11—C16—C15 | −179.0 (3) | C18—C23—C22—C21 | −0.9 (5) |
C12—C11—C16—C15 | −0.3 (5) | C23—C22—C21—C20 | 0.4 (5) |
C5—C9—C4—O1 | 6.6 (6) | C19—C20—C21—C22 | 0.1 (5) |
C10—C9—C4—O1 | −173.9 (4) | C21—C20—C19—C18 | −0.2 (5) |
C5—C9—C4—C3 | −175.3 (3) | C23—C18—C19—C20 | −0.2 (5) |
C10—C9—C4—C3 | 4.2 (5) | C17—C18—C19—C20 | 178.9 (3) |
Symmetry code: (i) −x+1, −y+2, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H02···S1 | 0.88 (4) | 2.54 (4) | 3.012 (4) | 115 (3) |
C2—H2···O1i | 0.93 | 2.03 | 2.752 (5) | 133 |
Symmetry code: (i) −x+1, −y+2, −z+1. |
Experimental details
Crystal data |
Chemical formula | C46H34N4O2S2 |
Mr | 738.89 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 153 |
a, b, c (Å) | 19.184 (4), 4.6066 (10), 21.734 (5) |
β (°) | 114.838 (4) |
V (Å3) | 1743.0 (7) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.20 |
Crystal size (mm) | 0.42 × 0.31 × 0.19 |
|
Data collection |
Diffractometer | Bruker SMART APEX CCD area detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.926, 0.964 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6195, 3027, 1893 |
Rint | 0.061 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.065, 0.139, 0.97 |
No. of reflections | 3027 |
No. of parameters | 248 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.32, −0.29 |
Selected bond lengths (Å) topN1—C1 | 1.320 (4) | C3—C3i | 1.482 (7) |
N1—N2 | 1.330 (4) | C11—N2 | 1.398 (4) |
Symmetry code: (i) −x+1, −y+2, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H02···S1 | 0.88 (4) | 2.54 (4) | 3.012 (4) | 115 (3) |
C2—H2···O1i | 0.93 | 2.03 | 2.752 (5) | 133 |
Symmetry code: (i) −x+1, −y+2, −z+1. |
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 π–π 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.