The title compound, C
20H
14O
2S, has been obtained in two monoclinic forms, which differ in their unit-cell dimensions, compactness of packing and conformation. Pairwise association of molecules occurs
via complementary O—H
O hydrogen bonding.
Supporting information
CCDC references: 659143; 659144
Form (Ia) was obtained in an attempt to grow crystals of Fe{η 5-C5H4P(—OC10H6(µ-S)C10H6O–)} (Punji et al., 2007) from a mixture of dichloromethane and petroleum ether. Form (Ib) was obtained in an attempt to crystallize {(–OC10H6(µ-S)C10H6O–)P(═ S)}2[µ-(–OC10 H6(µ-S)C10H6O–)] (Punji et al., 2007) in similar fashion. Both were additionally characterized by comparison of their melting points with that of an authentic sample.
H atoms attached to C atoms were placed in calculated positions (C—H = 0.95 Å) and included as riding contributions, with Uiso(H) values of 1.2Ueq of the attached C atoms. H atoms attached to O atoms were refined with isotropic displacement parameters.
Data collection: SMART (Bruker, 2000) for (Ia); APEX2 (Bruker, 2006) for (Ib). Cell refinement: SAINT-Plus (Bruker, 2004) for (Ia); APEX2 for (Ib). Data reduction: SAINT-Plus for (Ia); SAINT-Plus (Bruker, 2006) for (Ib). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: SHELXTL (Bruker, 2000) for (Ia); APEX2 for (Ib). Software used to prepare material for publication: SHELXTL for (Ia); APEX2 for (Ib).
(Ia) 1,1'-thiobis(2-naphthol)
top
Crystal data top
C20H14O2S | F(000) = 664 |
Mr = 318.37 | Dx = 1.444 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 4149 reflections |
a = 4.8053 (6) Å | θ = 2.4–28.2° |
b = 11.420 (1) Å | µ = 0.23 mm−1 |
c = 26.732 (3) Å | T = 100 K |
β = 93.181 (2)° | Plate, light brown |
V = 1464.7 (3) Å3 | 0.22 × 0.10 × 0.07 mm |
Z = 4 | |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 3339 independent reflections |
Radiation source: fine-focus sealed tube | 2472 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.052 |
phi and ω scans | θmax = 27.5°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | h = −6→6 |
Tmin = 0.953, Tmax = 0.987 | k = −14→14 |
12389 measured reflections | l = −33→34 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.106 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0503P)2 + 0.3449P] where P = (Fo2 + 2Fc2)/3 |
3339 reflections | (Δ/σ)max < 0.001 |
216 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
Crystal data top
C20H14O2S | V = 1464.7 (3) Å3 |
Mr = 318.37 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 4.8053 (6) Å | µ = 0.23 mm−1 |
b = 11.420 (1) Å | T = 100 K |
c = 26.732 (3) Å | 0.22 × 0.10 × 0.07 mm |
β = 93.181 (2)° | |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 3339 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | 2472 reflections with I > 2σ(I) |
Tmin = 0.953, Tmax = 0.987 | Rint = 0.052 |
12389 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.106 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.37 e Å−3 |
3339 reflections | Δρmin = −0.25 e Å−3 |
216 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. H-atoms were placed in calculated positions (C—H = 0.95 Å) and included as riding contributions with isotropic displacement parameters 1.2 times those of the attached carbon atoms. Those attached to oxygen were refined with isotropic displacement parameters. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.63179 (10) | 0.06039 (4) | 0.091079 (18) | 0.01418 (14) | |
O1 | 0.1705 (3) | 0.10880 (12) | 0.01702 (6) | 0.0190 (3) | |
H1 | 0.022 (7) | 0.123 (2) | 0.0006 (11) | 0.050 (9)* | |
O2 | 0.3124 (3) | −0.14148 (13) | 0.04670 (5) | 0.0176 (3) | |
H2 | 0.442 (6) | −0.095 (2) | 0.0387 (10) | 0.041 (8)* | |
C1 | 0.4929 (4) | 0.20012 (16) | 0.07384 (7) | 0.0137 (4) | |
C2 | 0.2772 (4) | 0.20957 (17) | 0.03784 (7) | 0.0149 (4) | |
C3 | 0.1780 (4) | 0.32021 (18) | 0.02190 (7) | 0.0164 (4) | |
H3 | 0.0262 | 0.3254 | −0.0023 | 0.020* | |
C4 | 0.2980 (4) | 0.41948 (18) | 0.04092 (7) | 0.0182 (4) | |
H4 | 0.2305 | 0.4935 | 0.0294 | 0.022* | |
C5 | 0.5229 (4) | 0.41472 (17) | 0.07776 (7) | 0.0148 (4) | |
C6 | 0.6486 (4) | 0.51749 (18) | 0.09808 (8) | 0.0197 (5) | |
H6 | 0.5828 | 0.5919 | 0.0868 | 0.024* | |
C7 | 0.8636 (4) | 0.51122 (18) | 0.13375 (7) | 0.0192 (5) | |
H7 | 0.9463 | 0.5809 | 0.1471 | 0.023* | |
C8 | 0.9620 (4) | 0.40112 (18) | 0.15064 (8) | 0.0190 (4) | |
H8 | 1.1109 | 0.3970 | 0.1755 | 0.023* | |
C9 | 0.8459 (4) | 0.30034 (17) | 0.13173 (7) | 0.0161 (4) | |
H9 | 0.9165 | 0.2269 | 0.1434 | 0.019* | |
C10 | 0.6204 (4) | 0.30343 (17) | 0.09482 (7) | 0.0140 (4) | |
C11 | 0.3527 (4) | −0.01347 (17) | 0.11877 (7) | 0.0146 (4) | |
C12 | 0.2380 (4) | −0.10835 (17) | 0.09357 (7) | 0.0146 (4) | |
C13 | 0.0309 (4) | −0.17787 (17) | 0.11432 (8) | 0.0175 (4) | |
H13 | −0.0463 | −0.2428 | 0.0962 | 0.021* | |
C14 | −0.0580 (4) | −0.15143 (18) | 0.16057 (8) | 0.0189 (5) | |
H14 | −0.1974 | −0.1986 | 0.1744 | 0.023* | |
C15 | 0.0531 (4) | −0.05489 (18) | 0.18849 (8) | 0.0175 (4) | |
C16 | −0.0407 (4) | −0.02594 (19) | 0.23601 (8) | 0.0213 (5) | |
H16 | −0.1784 | −0.0731 | 0.2503 | 0.026* | |
C17 | 0.0642 (4) | 0.0693 (2) | 0.26174 (8) | 0.0230 (5) | |
H17 | −0.0010 | 0.0881 | 0.2937 | 0.028* | |
C18 | 0.2681 (4) | 0.13923 (19) | 0.24090 (8) | 0.0215 (5) | |
H18 | 0.3391 | 0.2056 | 0.2588 | 0.026* | |
C19 | 0.3661 (4) | 0.11332 (18) | 0.19518 (8) | 0.0181 (4) | |
H19 | 0.5059 | 0.1612 | 0.1819 | 0.022* | |
C20 | 0.2612 (4) | 0.01570 (17) | 0.16735 (7) | 0.0149 (4) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0135 (2) | 0.0136 (2) | 0.0152 (3) | 0.0004 (2) | −0.00109 (18) | 0.0009 (2) |
O1 | 0.0200 (8) | 0.0170 (7) | 0.0191 (8) | −0.0012 (6) | −0.0068 (6) | 0.0000 (6) |
O2 | 0.0204 (8) | 0.0175 (8) | 0.0149 (7) | −0.0027 (6) | −0.0003 (6) | −0.0011 (6) |
C1 | 0.0145 (10) | 0.0143 (10) | 0.0122 (10) | 0.0009 (8) | 0.0007 (8) | 0.0021 (8) |
C2 | 0.0152 (10) | 0.0178 (10) | 0.0119 (10) | −0.0006 (8) | 0.0017 (8) | −0.0011 (8) |
C3 | 0.0145 (10) | 0.0218 (11) | 0.0128 (10) | 0.0025 (8) | −0.0018 (8) | 0.0017 (8) |
C4 | 0.0195 (11) | 0.0180 (11) | 0.0172 (11) | 0.0040 (8) | 0.0022 (8) | 0.0034 (8) |
C5 | 0.0152 (10) | 0.0140 (10) | 0.0153 (10) | 0.0013 (8) | 0.0030 (8) | 0.0003 (8) |
C6 | 0.0240 (11) | 0.0145 (10) | 0.0211 (11) | 0.0002 (9) | 0.0058 (9) | 0.0009 (8) |
C7 | 0.0236 (11) | 0.0170 (10) | 0.0172 (11) | −0.0058 (9) | 0.0027 (9) | −0.0039 (8) |
C8 | 0.0166 (11) | 0.0241 (11) | 0.0163 (10) | −0.0025 (9) | 0.0011 (8) | 0.0001 (9) |
C9 | 0.0162 (10) | 0.0173 (10) | 0.0147 (10) | 0.0004 (8) | 0.0005 (8) | 0.0012 (8) |
C10 | 0.0149 (10) | 0.0155 (10) | 0.0119 (10) | −0.0006 (8) | 0.0035 (8) | 0.0000 (8) |
C11 | 0.0136 (10) | 0.0141 (9) | 0.0159 (10) | 0.0011 (8) | −0.0010 (8) | 0.0046 (8) |
C12 | 0.0150 (10) | 0.0147 (10) | 0.0140 (10) | 0.0029 (8) | −0.0008 (8) | 0.0028 (8) |
C13 | 0.0191 (11) | 0.0124 (10) | 0.0205 (11) | −0.0012 (8) | −0.0037 (9) | 0.0033 (8) |
C14 | 0.0175 (11) | 0.0178 (11) | 0.0211 (11) | 0.0002 (9) | −0.0007 (9) | 0.0082 (9) |
C15 | 0.0155 (10) | 0.0197 (10) | 0.0170 (10) | 0.0034 (9) | −0.0015 (8) | 0.0057 (9) |
C16 | 0.0198 (11) | 0.0270 (12) | 0.0174 (11) | 0.0028 (9) | 0.0016 (9) | 0.0067 (9) |
C17 | 0.0234 (12) | 0.0311 (12) | 0.0145 (11) | 0.0065 (10) | 0.0001 (8) | 0.0006 (9) |
C18 | 0.0218 (11) | 0.0240 (11) | 0.0182 (11) | 0.0024 (9) | −0.0041 (9) | −0.0033 (9) |
C19 | 0.0176 (11) | 0.0188 (10) | 0.0174 (10) | 0.0015 (8) | −0.0027 (8) | 0.0019 (9) |
C20 | 0.0143 (10) | 0.0158 (10) | 0.0140 (10) | 0.0046 (8) | −0.0036 (8) | 0.0028 (8) |
Geometric parameters (Å, º) top
S1—C11 | 1.780 (2) | C8—H8 | 0.9500 |
S1—C1 | 1.780 (2) | C9—C10 | 1.425 (3) |
O1—C2 | 1.366 (2) | C9—H9 | 0.9500 |
O1—H1 | 0.83 (3) | C11—C12 | 1.375 (3) |
O2—C12 | 1.375 (2) | C11—C20 | 1.433 (3) |
O2—H2 | 0.86 (3) | C12—C13 | 1.411 (3) |
C1—C2 | 1.379 (3) | C13—C14 | 1.364 (3) |
C1—C10 | 1.430 (3) | C13—H13 | 0.9500 |
C2—C3 | 1.408 (3) | C14—C15 | 1.419 (3) |
C3—C4 | 1.358 (3) | C14—H14 | 0.9500 |
C3—H3 | 0.9500 | C15—C16 | 1.411 (3) |
C4—C5 | 1.422 (3) | C15—C20 | 1.425 (3) |
C4—H4 | 0.9500 | C16—C17 | 1.368 (3) |
C5—C6 | 1.415 (3) | C16—H16 | 0.9500 |
C5—C10 | 1.421 (3) | C17—C18 | 1.403 (3) |
C6—C7 | 1.369 (3) | C17—H17 | 0.9500 |
C6—H6 | 0.9500 | C18—C19 | 1.366 (3) |
C7—C8 | 1.409 (3) | C18—H18 | 0.9500 |
C7—H7 | 0.9500 | C19—C20 | 1.417 (3) |
C8—C9 | 1.364 (3) | C19—H19 | 0.9500 |
| | | |
C11—S1—C1 | 104.60 (9) | C9—C10—C1 | 122.96 (17) |
C2—O1—H1 | 109.7 (19) | C12—C11—C20 | 119.49 (18) |
C12—O2—H2 | 106.4 (18) | C12—C11—S1 | 117.42 (15) |
C2—C1—C10 | 119.89 (17) | C20—C11—S1 | 122.87 (15) |
C2—C1—S1 | 120.49 (15) | C11—C12—O2 | 123.10 (18) |
C10—C1—S1 | 119.46 (14) | C11—C12—C13 | 121.56 (18) |
O1—C2—C1 | 117.98 (17) | O2—C12—C13 | 115.34 (18) |
O1—C2—C3 | 121.30 (17) | C14—C13—C12 | 119.68 (19) |
C1—C2—C3 | 120.68 (18) | C14—C13—H13 | 120.2 |
C4—C3—C2 | 120.41 (18) | C12—C13—H13 | 120.2 |
C4—C3—H3 | 119.8 | C13—C14—C15 | 121.39 (19) |
C2—C3—H3 | 119.8 | C13—C14—H14 | 119.3 |
C3—C4—C5 | 121.19 (18) | C15—C14—H14 | 119.3 |
C3—C4—H4 | 119.4 | C16—C15—C14 | 121.73 (19) |
C5—C4—H4 | 119.4 | C16—C15—C20 | 119.40 (19) |
C6—C5—C10 | 119.51 (18) | C14—C15—C20 | 118.86 (18) |
C6—C5—C4 | 121.74 (18) | C17—C16—C15 | 120.8 (2) |
C10—C5—C4 | 118.74 (18) | C17—C16—H16 | 119.6 |
C7—C6—C5 | 120.94 (19) | C15—C16—H16 | 119.6 |
C7—C6—H6 | 119.5 | C16—C17—C18 | 119.9 (2) |
C5—C6—H6 | 119.5 | C16—C17—H17 | 120.0 |
C6—C7—C8 | 119.79 (19) | C18—C17—H17 | 120.0 |
C6—C7—H7 | 120.1 | C19—C18—C17 | 121.0 (2) |
C8—C7—H7 | 120.1 | C19—C18—H18 | 119.5 |
C9—C8—C7 | 120.76 (19) | C17—C18—H18 | 119.5 |
C9—C8—H8 | 119.6 | C18—C19—C20 | 120.6 (2) |
C7—C8—H8 | 119.6 | C18—C19—H19 | 119.7 |
C8—C9—C10 | 121.02 (18) | C20—C19—H19 | 119.7 |
C8—C9—H9 | 119.5 | C19—C20—C15 | 118.27 (18) |
C10—C9—H9 | 119.5 | C19—C20—C11 | 122.71 (18) |
C5—C10—C9 | 117.97 (17) | C15—C20—C11 | 119.02 (18) |
C5—C10—C1 | 119.06 (18) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2i | 0.83 (3) | 2.00 (3) | 2.826 (2) | 171 (3) |
Symmetry code: (i) −x, −y, −z. |
(Ib) 1,1'-thiobis(2-naphthol)
top
Crystal data top
C20H14O2S | F(000) = 664 |
Mr = 318.37 | Dx = 1.448 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 5540 reflections |
a = 13.6508 (9) Å | θ = 3.0–28.2° |
b = 5.2192 (3) Å | µ = 0.23 mm−1 |
c = 21.265 (1) Å | T = 100 K |
β = 105.409 (1)° | Column, colourless |
V = 1460.59 (15) Å3 | 0.20 × 0.09 × 0.05 mm |
Z = 4 | |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 3330 independent reflections |
Radiation source: fine-focus sealed tube | 2828 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.039 |
phi and ω scans | θmax = 27.5°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2007) | h = −17→17 |
Tmin = 0.922, Tmax = 0.988 | k = −6→6 |
23840 measured reflections | l = −27→27 |
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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.091 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0147P)2 + 2.0538P] where P = (Fo2 + 2Fc2)/3 |
3330 reflections | (Δ/σ)max = 0.001 |
216 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
Crystal data top
C20H14O2S | V = 1460.59 (15) Å3 |
Mr = 318.37 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 13.6508 (9) Å | µ = 0.23 mm−1 |
b = 5.2192 (3) Å | T = 100 K |
c = 21.265 (1) Å | 0.20 × 0.09 × 0.05 mm |
β = 105.409 (1)° | |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 3330 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2007) | 2828 reflections with I > 2σ(I) |
Tmin = 0.922, Tmax = 0.988 | Rint = 0.039 |
23840 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.091 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | Δρmax = 0.32 e Å−3 |
3330 reflections | Δρmin = −0.31 e Å−3 |
216 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. H-atoms attached to carbon were placed in calculated positions (C—H = 0.95 Å) and included as riding contributions with isotropic displacement parameters 1.2 times those of the attached atoms. H-atoms attached to oxygen were refined with isotropic displacement parameters. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.70872 (3) | 0.40125 (9) | 0.95382 (2) | 0.01721 (11) | |
O1 | 0.92640 (10) | 0.3062 (3) | 0.96499 (7) | 0.0215 (3) | |
H1 | 0.988 (2) | 0.298 (6) | 0.9612 (12) | 0.045 (8)* | |
O2 | 0.87525 (10) | 0.6943 (3) | 1.04306 (7) | 0.0209 (3) | |
H2 | 0.846 (2) | 0.685 (6) | 1.0036 (14) | 0.051 (9)* | |
C1 | 0.76113 (14) | 0.1558 (4) | 0.91397 (9) | 0.0174 (4) | |
C2 | 0.86561 (14) | 0.1377 (4) | 0.92395 (8) | 0.0174 (4) | |
C3 | 0.90827 (14) | −0.0575 (4) | 0.89310 (9) | 0.0193 (4) | |
H3 | 0.9800 | −0.0727 | 0.9019 | 0.023* | |
C4 | 0.84691 (15) | −0.2230 (4) | 0.85097 (9) | 0.0204 (4) | |
H4 | 0.8764 | −0.3535 | 0.8308 | 0.024* | |
C5 | 0.73946 (14) | −0.2039 (4) | 0.83666 (9) | 0.0186 (4) | |
C6 | 0.67535 (15) | −0.3720 (4) | 0.79194 (9) | 0.0227 (4) | |
H6 | 0.7046 | −0.5000 | 0.7708 | 0.027* | |
C7 | 0.57191 (16) | −0.3536 (4) | 0.77853 (10) | 0.0250 (4) | |
H7 | 0.5298 | −0.4670 | 0.7480 | 0.030* | |
C8 | 0.52810 (15) | −0.1657 (4) | 0.81014 (10) | 0.0238 (4) | |
H8 | 0.4562 | −0.1547 | 0.8012 | 0.029* | |
C9 | 0.58777 (14) | 0.0013 (4) | 0.85365 (9) | 0.0202 (4) | |
H9 | 0.5567 | 0.1278 | 0.8741 | 0.024* | |
C10 | 0.69569 (14) | −0.0120 (4) | 0.86864 (9) | 0.0171 (4) | |
C11 | 0.76333 (13) | 0.3332 (4) | 1.03806 (9) | 0.0174 (4) | |
C12 | 0.83999 (14) | 0.4917 (4) | 1.07206 (9) | 0.0176 (4) | |
C13 | 0.88508 (14) | 0.4567 (4) | 1.13942 (9) | 0.0206 (4) | |
H13 | 0.9391 | 0.5648 | 1.1619 | 0.025* | |
C14 | 0.85056 (14) | 0.2669 (4) | 1.17185 (9) | 0.0214 (4) | |
H14 | 0.8812 | 0.2439 | 1.2171 | 0.026* | |
C15 | 0.76989 (14) | 0.1024 (4) | 1.13979 (9) | 0.0195 (4) | |
C16 | 0.73244 (15) | −0.0933 (4) | 1.17345 (10) | 0.0232 (4) | |
H16 | 0.7617 | −0.1155 | 1.2189 | 0.028* | |
C17 | 0.65475 (15) | −0.2509 (4) | 1.14146 (10) | 0.0247 (4) | |
H17 | 0.6306 | −0.3815 | 1.1646 | 0.030* | |
C18 | 0.61079 (15) | −0.2183 (4) | 1.07393 (10) | 0.0224 (4) | |
H18 | 0.5570 | −0.3278 | 1.0519 | 0.027* | |
C19 | 0.64475 (14) | −0.0304 (4) | 1.03978 (9) | 0.0194 (4) | |
H19 | 0.6139 | −0.0110 | 0.9944 | 0.023* | |
C20 | 0.72507 (14) | 0.1352 (4) | 1.07113 (9) | 0.0170 (4) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0170 (2) | 0.0198 (2) | 0.0149 (2) | 0.00341 (18) | 0.00420 (16) | 0.00071 (19) |
O1 | 0.0159 (7) | 0.0264 (8) | 0.0220 (7) | −0.0010 (6) | 0.0048 (6) | −0.0041 (6) |
O2 | 0.0195 (7) | 0.0227 (7) | 0.0204 (7) | −0.0013 (6) | 0.0052 (6) | −0.0020 (6) |
C1 | 0.0198 (9) | 0.0197 (10) | 0.0133 (8) | 0.0039 (8) | 0.0054 (7) | 0.0022 (7) |
C2 | 0.0185 (9) | 0.0214 (10) | 0.0126 (8) | −0.0005 (8) | 0.0048 (7) | 0.0011 (7) |
C3 | 0.0189 (9) | 0.0230 (10) | 0.0173 (9) | 0.0040 (8) | 0.0072 (7) | 0.0025 (8) |
C4 | 0.0243 (10) | 0.0201 (10) | 0.0187 (9) | 0.0047 (8) | 0.0092 (8) | 0.0020 (8) |
C5 | 0.0226 (9) | 0.0204 (10) | 0.0140 (8) | 0.0007 (8) | 0.0067 (7) | 0.0031 (8) |
C6 | 0.0276 (10) | 0.0225 (10) | 0.0187 (9) | 0.0002 (8) | 0.0076 (8) | −0.0017 (8) |
C7 | 0.0263 (10) | 0.0264 (11) | 0.0205 (9) | −0.0047 (9) | 0.0028 (8) | −0.0027 (9) |
C8 | 0.0200 (9) | 0.0283 (11) | 0.0217 (9) | −0.0013 (8) | 0.0031 (8) | 0.0019 (9) |
C9 | 0.0194 (9) | 0.0227 (10) | 0.0190 (9) | 0.0022 (8) | 0.0058 (7) | 0.0018 (8) |
C10 | 0.0203 (9) | 0.0181 (9) | 0.0133 (8) | 0.0016 (7) | 0.0050 (7) | 0.0045 (7) |
C11 | 0.0148 (8) | 0.0224 (10) | 0.0156 (8) | 0.0051 (7) | 0.0048 (7) | −0.0008 (8) |
C12 | 0.0155 (8) | 0.0194 (9) | 0.0199 (9) | 0.0037 (7) | 0.0081 (7) | −0.0017 (8) |
C13 | 0.0156 (9) | 0.0280 (11) | 0.0176 (9) | 0.0047 (8) | 0.0031 (7) | −0.0055 (8) |
C14 | 0.0197 (9) | 0.0302 (11) | 0.0138 (8) | 0.0086 (8) | 0.0040 (7) | −0.0001 (8) |
C15 | 0.0168 (9) | 0.0244 (10) | 0.0186 (9) | 0.0074 (8) | 0.0068 (7) | 0.0015 (8) |
C16 | 0.0253 (10) | 0.0267 (11) | 0.0201 (9) | 0.0095 (9) | 0.0104 (8) | 0.0040 (9) |
C17 | 0.0266 (10) | 0.0234 (11) | 0.0295 (11) | 0.0070 (9) | 0.0167 (9) | 0.0072 (9) |
C18 | 0.0204 (9) | 0.0213 (10) | 0.0280 (10) | 0.0007 (8) | 0.0109 (8) | −0.0010 (9) |
C19 | 0.0177 (9) | 0.0229 (10) | 0.0184 (9) | 0.0044 (8) | 0.0063 (7) | −0.0010 (8) |
C20 | 0.0165 (8) | 0.0195 (10) | 0.0163 (8) | 0.0051 (7) | 0.0068 (7) | −0.0011 (7) |
Geometric parameters (Å, º) top
S1—C11 | 1.784 (2) | C8—H8 | 0.9500 |
S1—C1 | 1.787 (2) | C9—C10 | 1.424 (3) |
O1—C2 | 1.356 (2) | C9—H9 | 0.9500 |
O1—H1 | 0.86 (3) | C11—C12 | 1.378 (3) |
O2—C12 | 1.374 (2) | C11—C20 | 1.425 (3) |
O2—H2 | 0.83 (3) | C12—C13 | 1.413 (3) |
C1—C2 | 1.388 (2) | C13—C14 | 1.361 (3) |
C1—C10 | 1.427 (3) | C13—H13 | 0.9500 |
C2—C3 | 1.418 (3) | C14—C15 | 1.420 (3) |
C3—C4 | 1.361 (3) | C14—H14 | 0.9500 |
C3—H3 | 0.9500 | C15—C16 | 1.418 (3) |
C4—C5 | 1.420 (3) | C15—C20 | 1.436 (2) |
C4—H4 | 0.9500 | C16—C17 | 1.372 (3) |
C5—C6 | 1.414 (3) | C16—H16 | 0.9500 |
C5—C10 | 1.428 (3) | C17—C18 | 1.412 (3) |
C6—C7 | 1.368 (3) | C17—H17 | 0.9500 |
C6—H6 | 0.9500 | C18—C19 | 1.372 (3) |
C7—C8 | 1.409 (3) | C18—H18 | 0.9500 |
C7—H7 | 0.9500 | C19—C20 | 1.416 (3) |
C8—C9 | 1.371 (3) | C19—H19 | 0.9500 |
| | | |
C11—S1—C1 | 102.73 (9) | C1—C10—C5 | 119.07 (17) |
C2—O1—H1 | 110.6 (19) | C12—C11—C20 | 120.21 (17) |
C12—O2—H2 | 106 (2) | C12—C11—S1 | 117.64 (15) |
C2—C1—C10 | 119.67 (17) | C20—C11—S1 | 121.99 (14) |
C2—C1—S1 | 120.05 (15) | O2—C12—C11 | 122.28 (17) |
C10—C1—S1 | 120.17 (14) | O2—C12—C13 | 116.39 (17) |
O1—C2—C1 | 118.85 (17) | C11—C12—C13 | 121.32 (18) |
O1—C2—C3 | 120.48 (17) | C14—C13—C12 | 119.45 (19) |
C1—C2—C3 | 120.64 (18) | C14—C13—H13 | 120.3 |
C4—C3—C2 | 120.27 (18) | C12—C13—H13 | 120.3 |
C4—C3—H3 | 119.9 | C13—C14—C15 | 121.73 (18) |
C2—C3—H3 | 119.9 | C13—C14—H14 | 119.1 |
C3—C4—C5 | 121.09 (18) | C15—C14—H14 | 119.1 |
C3—C4—H4 | 119.5 | C16—C15—C14 | 122.07 (18) |
C5—C4—H4 | 119.5 | C16—C15—C20 | 119.06 (18) |
C6—C5—C4 | 121.34 (18) | C14—C15—C20 | 118.87 (18) |
C6—C5—C10 | 119.55 (18) | C17—C16—C15 | 121.11 (18) |
C4—C5—C10 | 119.11 (18) | C17—C16—H16 | 119.4 |
C7—C6—C5 | 121.13 (19) | C15—C16—H16 | 119.4 |
C7—C6—H6 | 119.4 | C16—C17—C18 | 119.72 (19) |
C5—C6—H6 | 119.4 | C16—C17—H17 | 120.1 |
C6—C7—C8 | 119.67 (19) | C18—C17—H17 | 120.1 |
C6—C7—H7 | 120.2 | C19—C18—C17 | 120.82 (19) |
C8—C7—H7 | 120.2 | C19—C18—H18 | 119.6 |
C9—C8—C7 | 120.89 (19) | C17—C18—H18 | 119.6 |
C9—C8—H8 | 119.6 | C18—C19—C20 | 121.01 (18) |
C7—C8—H8 | 119.6 | C18—C19—H19 | 119.5 |
C8—C9—C10 | 120.92 (19) | C20—C19—H19 | 119.5 |
C8—C9—H9 | 119.5 | C19—C20—C11 | 123.35 (17) |
C10—C9—H9 | 119.5 | C19—C20—C15 | 118.27 (18) |
C9—C10—C1 | 123.10 (18) | C11—C20—C15 | 118.38 (17) |
C9—C10—C5 | 117.83 (18) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2i | 0.86 (3) | 1.90 (3) | 2.7581 (19) | 175 (3) |
Symmetry code: (i) −x+2, −y+1, −z+2. |
Experimental details
| (Ia) | (Ib) |
Crystal data |
Chemical formula | C20H14O2S | C20H14O2S |
Mr | 318.37 | 318.37 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21/n |
Temperature (K) | 100 | 100 |
a, b, c (Å) | 4.8053 (6), 11.420 (1), 26.732 (3) | 13.6508 (9), 5.2192 (3), 21.265 (1) |
β (°) | 93.181 (2) | 105.409 (1) |
V (Å3) | 1464.7 (3) | 1460.59 (15) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.23 | 0.23 |
Crystal size (mm) | 0.22 × 0.10 × 0.07 | 0.20 × 0.09 × 0.05 |
|
Data collection |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2002) | Multi-scan (SADABS; Sheldrick, 2007) |
Tmin, Tmax | 0.953, 0.987 | 0.922, 0.988 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12389, 3339, 2472 | 23840, 3330, 2828 |
Rint | 0.052 | 0.039 |
(sin θ/λ)max (Å−1) | 0.650 | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.106, 1.02 | 0.044, 0.091, 1.09 |
No. of reflections | 3339 | 3330 |
No. of parameters | 216 | 216 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.37, −0.25 | 0.32, −0.31 |
Selected geometric parameters (Å, º) for (Ia) topS1—C11 | 1.780 (2) | S1—C1 | 1.780 (2) |
| | | |
C11—S1—C1 | 104.60 (9) | | |
Hydrogen-bond geometry (Å, º) for (Ia) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2i | 0.83 (3) | 2.00 (3) | 2.826 (2) | 171 (3) |
Symmetry code: (i) −x, −y, −z. |
Selected geometric parameters (Å, º) for (Ib) topS1—C11 | 1.784 (2) | S1—C1 | 1.787 (2) |
| | | |
C11—S1—C1 | 102.73 (9) | | |
Hydrogen-bond geometry (Å, º) for (Ib) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2i | 0.86 (3) | 1.90 (3) | 2.7581 (19) | 175 (3) |
Symmetry code: (i) −x+2, −y+1, −z+2. |
1,1'-Thiobis(2-naphthol), (I), has been obtained in two crystalline forms (Fig. 1, and Tables 1 and 3) with distinctly different unit cells. At first sight, form (Ia), with a short a axis, appears to exhibit a more compact packing than does form (Ib), with a short b axis, as is depicted in Figs. 2 and 3. However, simulated radial distribution functions of the two structures indicate a larger number of intermolecular contacts in the 3.5–5.0 Å range, suggesting that (Ib) possesses a slightly more compact structure.
Despite this, four contacts of 3.349 (2)–3.490 (2) Å occur between S1 and C12–C15 in the neighboring molecule at (1 + x, y, z) in (Ia), whereas in (Ib), S1 forms contacts with only C5 in the molecule at (x, 1 + y, z), at a distance of 3.344 (2) Å. These S····C contacts propagate parallel to a in (Ia) and parallel to b in (Ib). Additionally, besides the H1····O2 hydrogen bond that is seen in both forms (Tables 2 and 4), the pattern of potential interactions of H2 with its surroundings differs between (Ia) and (Ib). In the former, there is an intermolecular contact of 2.46 (3) Å with O1ii [O2—H2····O1ii = 134 (3)°; symmetry code: (ii) 1 − x, −y, −z] and an intramolecular contact of 2.41 (2) Å with S1 [O2—H2····S1 = 125 (2)°], while in the latter the closest contacts are both intramolecular [H2····O1 = 2.50 (2) Å and O2—H2····O1 = 104 (2) °; H2····S1 = 2.40 (2) Å and O2—H2····S1 = 126 (2)°]. In both instances, the H2····S1 contacts are comparable to previously reported O—H····S hydrogen bonds (Allen et al., 1997). The torsional orientation of the O2—H2 bond in both forms suggests a weak bifurcated hydrogen bond.
In both forms, the naphthyl groups are planar to within 0.004–0.01 Å, with dihedral angles between the mean planes of 100.0 (1)° for (Ia) and 96.5 (1)° in (Ib). Modest differences in the overall conformations of the molecule between the two forms are also seen in the C2—C1—S1—C11 and C12—C11—S1—C1 torsion angles, which are −64.8 (2) and 112.5 (2)°, respectively, in (Ia) and −60.5 (2) and 105.6 (2)°, respectively, in (Ib).