The experimental and theoretical charge densities of 1,4-bis(5-hexyl-2-thienyl)butane-1,4-dione, a precursor in the synthesis of thiophene-based semiconductors and organic solar cells, are presented. A dummy bond charges spherical atom model is applied besides the multipolar atom model. The results show that the dummy bond charges model is accurate enough to calculate electrostatic-derived properties which are comparable with those obtained by the multipolar atom model. The refinement statistics and the residual electron density values are found to be intermediate between the independent atom and the multipolar formalisms.
Supporting information
CCDC reference: 1430523
Program(s) used to refine structure: MoPro (J. Appl. Cryst. 2005, 38, 38-54).
1,4-bis (5-hexyl-2-thienyl) butane-1,4 dione
top
Crystal data top
C24H34O2S2 | γ = 95.39 (15)° |
Mr = 418.63 | V = 564.4 (9) Å3 |
Triclinic, P1 | Z = 1 |
Hall symbol: -P 1 | F(000) = 226 |
a = 5.047 (5) Å | Dx = 1.232 Mg m−3 |
b = 6.979 (6) Å | Mo Kα radiation, λ = 0.71073 Å |
c = 16.333 (9) Å | T = 100 K |
α = 98.79 (16)° | Rectangular block, yellow |
β = 93.52 (15)° | 0.43 × 0.14 × 0.08 mm |
Data collection top
Four-circle diffractometer | Rint = 0.053 |
Radiation source: fine-focus sealed tube | θmax = 46.9°, θmin = 3.4° |
ω scans | h = 0→10 |
70042 measured reflections | k = −14→14 |
9170 independent reflections | l = −33→33 |
9170 reflections with > 2.0σ(I) | |
Refinement top
Refinement on F2 | 342 restraints |
Least-squares matrix: full | Primary atom site location: structure-invariant direct methods |
R[F2 > 2σ(F2)] = 0.043 | Secondary atom site location: difference Fourier map |
wR(F2) = 0.072 | Hydrogen site location: difference Fourier map |
S = 1.05 | Only H-atom coordinates refined |
9169 reflections | w = 1/[σ2(Fo2) + (0.007P)2 + 0.4P] where P = (Fo2 + 2Fc2)/3 |
507 parameters | (Δ/σ)max < 0.001 |
Crystal data top
C24H34O2S2 | β = 93.52 (15)° |
Mr = 418.63 | γ = 95.39 (15)° |
Triclinic, P1 | V = 564.4 (9) Å3 |
a = 5.047 (5) Å | Z = 1 |
b = 6.979 (6) Å | Mo Kα radiation |
c = 16.333 (9) Å | T = 100 K |
α = 98.79 (16)° | 0.43 × 0.14 × 0.08 mm |
Data collection top
Four-circle diffractometer | 9170 reflections with > 2.0σ(I) |
70042 measured reflections | Rint = 0.053 |
9170 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.043 | 507 parameters |
wR(F2) = 0.072 | 342 restraints |
S = 1.05 | Only H-atom coordinates refined |
9169 reflections | |
Special details top
Refinement. Refinement of F2 against reflections. The threshold expression of F2 > σ(F2) is used for calculating R-factors(gt) 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 | |
S1 | −0.60821 (4) | 0.17676 (3) | 0.195386 (12) | 0.01319 (4) | |
O1 | −0.2860 (3) | −0.10723 (16) | 0.10469 (8) | 0.0203 (2) | |
C1 | −1.3157 (3) | 1.27357 (19) | 0.43468 (8) | 0.0266 (3) | |
C2 | −1.2949 (2) | 1.05489 (14) | 0.42037 (6) | 0.01927 (17) | |
C3 | −1.11326 (19) | 0.98952 (13) | 0.35267 (5) | 0.01719 (15) | |
C4 | −1.08483 (18) | 0.77169 (12) | 0.34286 (5) | 0.01648 (15) | |
C5 | −0.91139 (17) | 0.70154 (12) | 0.27343 (5) | 0.01541 (14) | |
C6 | −0.87406 (17) | 0.48593 (11) | 0.26930 (5) | 0.01529 (14) | |
C7 | −0.69141 (16) | 0.41264 (11) | 0.20516 (5) | 0.01324 (13) | |
C8 | −0.56520 (19) | 0.51301 (12) | 0.14994 (6) | 0.01622 (15) | |
C9 | −0.39934 (18) | 0.39915 (12) | 0.09997 (5) | 0.01545 (15) | |
C10 | −0.40116 (15) | 0.21217 (10) | 0.11753 (4) | 0.01272 (12) | |
C11 | −0.25567 (16) | 0.05170 (12) | 0.08131 (5) | 0.01291 (13) | |
C12 | −0.07096 (16) | 0.08862 (11) | 0.01483 (5) | 0.01295 (12) | |
H1A | −1.4447 (18) | 1.3117 (17) | 0.4819 (5) | 0.04489 | |
H1B | −1.1265 (11) | 1.3522 (14) | 0.4531 (8) | 0.04769 | |
H1C | −1.391 (2) | 1.3194 (16) | 0.3796 (4) | 0.04903 | |
H2A | −1.220 (3) | 1.0126 (14) | 0.4785 (2) | 0.03239 | |
H2B | −1.4932 (6) | 0.9775 (11) | 0.4041 (9) | 0.03351 | |
H3A | −0.9155 (7) | 1.0701 (11) | 0.3677 (9) | 0.03618 | |
H3B | −1.194 (3) | 1.0238 (15) | 0.2936 (2) | 0.03684 | |
H4A | −1.2833 (7) | 0.6916 (10) | 0.3301 (8) | 0.02987 | |
H4B | −0.998 (2) | 0.7395 (14) | 0.4014 (2) | 0.02943 | |
H5A | −0.7164 (8) | 0.7871 (9) | 0.2837 (9) | 0.03161 | |
H5B | −1.004 (2) | 0.7246 (14) | 0.2140 (2) | 0.03174 | |
H6A | −0.794 (3) | 0.4644 (14) | 0.33051 (19) | 0.02836 | |
H6B | −1.0704 (7) | 0.4027 (9) | 0.2561 (9) | 0.02845 | |
H8 | −0.586 (2) | 0.6645 (6) | 0.1461 (7) | 0.03114 | |
H9 | −0.284 (2) | 0.4525 (12) | 0.0529 (6) | 0.02986 | |
H12A | 0.074 (2) | 0.2126 (14) | 0.0402 (8) | 0.03017 | |
H12B | −0.189 (2) | 0.131 (2) | −0.0366 (5) | 0.02884 | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.01592 (8) | 0.01142 (7) | 0.01319 (7) | 0.00276 (5) | 0.00391 (5) | 0.00308 (5) |
O1 | 0.0247 (4) | 0.0130 (3) | 0.0262 (4) | 0.0048 (3) | 0.0126 (5) | 0.0071 (3) |
C1 | 0.0371 (6) | 0.0204 (4) | 0.0229 (4) | 0.0134 (4) | 0.0041 (4) | −0.0013 (3) |
C2 | 0.0208 (3) | 0.0188 (3) | 0.0183 (3) | 0.0073 (3) | 0.0034 (3) | −0.0009 (2) |
C3 | 0.0199 (3) | 0.0163 (3) | 0.0163 (3) | 0.0071 (2) | 0.0030 (2) | 0.0015 (2) |
C4 | 0.0189 (3) | 0.0153 (3) | 0.0157 (3) | 0.0057 (2) | 0.0035 (2) | 0.0009 (2) |
C5 | 0.0176 (3) | 0.0138 (2) | 0.0153 (3) | 0.0051 (2) | 0.0031 (2) | 0.0013 (2) |
C6 | 0.0180 (3) | 0.0135 (2) | 0.0150 (3) | 0.0041 (2) | 0.0048 (2) | 0.00158 (19) |
C7 | 0.0157 (3) | 0.0115 (2) | 0.0130 (2) | 0.00263 (19) | 0.0038 (2) | 0.00168 (18) |
C8 | 0.0199 (3) | 0.0118 (2) | 0.0186 (3) | 0.0040 (2) | 0.0070 (3) | 0.0041 (2) |
C9 | 0.0182 (3) | 0.0124 (2) | 0.0174 (3) | 0.0031 (2) | 0.0065 (3) | 0.0043 (2) |
C10 | 0.0139 (2) | 0.0112 (2) | 0.0136 (2) | 0.00213 (19) | 0.00347 (19) | 0.00217 (18) |
C11 | 0.0138 (3) | 0.0113 (2) | 0.0141 (3) | 0.0020 (2) | 0.0034 (2) | 0.0023 (2) |
C12 | 0.0139 (2) | 0.0120 (2) | 0.0134 (2) | 0.0025 (2) | 0.0027 (2) | 0.00221 (19) |
H1A | 0.05356 | 0.03979 | 0.04380 | 0.01767 | 0.02140 | −0.00033 |
H1B | 0.04255 | 0.03238 | 0.06531 | 0.00461 | 0.00624 | −0.00246 |
H1C | 0.07400 | 0.04017 | 0.03696 | 0.02443 | 0.00375 | 0.00793 |
H2A | 0.03640 | 0.03618 | 0.02434 | 0.01180 | −0.00200 | 0.00087 |
H2B | 0.02752 | 0.03747 | 0.03309 | 0.00782 | −0.00123 | −0.00343 |
H3A | 0.03335 | 0.02841 | 0.04461 | 0.00227 | 0.00731 | −0.00224 |
H3B | 0.05001 | 0.03687 | 0.02744 | 0.01983 | 0.00428 | 0.00739 |
H4A | 0.02314 | 0.03234 | 0.03174 | 0.00291 | 0.00015 | −0.00171 |
H4B | 0.03326 | 0.03359 | 0.02159 | 0.01014 | −0.00270 | 0.00279 |
H5A | 0.02745 | 0.02581 | 0.03985 | 0.00006 | 0.00587 | 0.00018 |
H5B | 0.04059 | 0.03426 | 0.02277 | 0.01471 | 0.00075 | 0.00629 |
H6A | 0.03361 | 0.03223 | 0.02025 | 0.00976 | −0.00119 | 0.00482 |
H6B | 0.02214 | 0.02828 | 0.03266 | −0.00021 | 0.00192 | −0.00049 |
H8 | 0.04230 | 0.01821 | 0.03692 | 0.00963 | 0.01295 | 0.00919 |
H9 | 0.03616 | 0.02555 | 0.03164 | 0.00414 | 0.01642 | 0.01048 |
H12A | 0.02627 | 0.02595 | 0.03524 | −0.00374 | 0.00532 | −0.00204 |
H12B | 0.02976 | 0.03388 | 0.02511 | 0.00871 | 0.00290 | 0.00820 |
Geometric parameters (Å, º) top
S1—C7 | 1.7232 (13) | C5—C6 | 1.5258 (11) |
S1—C10 | 1.7264 (11) | C5—H5A | 1.0914 (14) |
O1—C11 | 1.2265 (10) | C5—H5B | 1.0924 (10) |
C1—C2 | 1.5227 (12) | C6—C7 | 1.5007 (11) |
C1—H1B | 1.0577 (14) | C6—H6A | 1.0916 (10) |
C1—H1A | 1.0587 (11) | C6—H6B | 1.0926 (14) |
C1—H1C | 1.0608 (10) | C7—C8 | 1.3747 (9) |
C2—C3 | 1.5231 (11) | C8—C9 | 1.4174 (11) |
C2—H2B | 1.0892 (14) | C8—H8 | 1.0831 (11) |
C2—H2A | 1.0920 (10) | C9—C10 | 1.3776 (10) |
C3—C4 | 1.5253 (12) | C9—H9 | 1.0831 (11) |
C3—H3B | 1.0918 (10) | C10—C11 | 1.4659 (12) |
C3—H3A | 1.0932 (14) | C11—C12 | 1.5097 (10) |
C4—C5 | 1.5246 (11) | C12—H12A | 1.0916 (14) |
C4—H4B | 1.0919 (10) | C12—H12B | 1.0924 (11) |
C4—H4A | 1.0921 (14) | | |
| | | |
C7—S1—C10 | 92.24 (17) | C5—C4—H4B | 109 (2) |
C2—C1—H1B | 111 (3) | C5—C4—H4A | 109 (2) |
C2—C1—H1A | 111 (3) | H4B—C4—H4A | 108 (4) |
C2—C1—H1C | 111 (2) | C6—C5—H5A | 109 (2) |
H1B—C1—H1A | 108 (4) | C6—C5—H5B | 109 (2) |
H1B—C1—H1C | 108 (4) | H5A—C5—H5B | 108 (4) |
H1A—C1—H1C | 108 (4) | C7—C6—C5 | 113.8 (3) |
C3—C2—C1 | 113.7 (4) | C7—C6—H6A | 109 (2) |
C3—C2—H2B | 109 (2) | C7—C6—H6B | 110 (2) |
C3—C2—H2A | 109 (2) | H6A—C6—H6B | 108 (5) |
H2B—C2—H2A | 107 (5) | C9—C8—H8 | 124 (2) |
C4—C3—H3B | 109 (2) | C10—C9—C8 | 112.7 (4) |
C4—C3—H3A | 109 (2) | C10—C9—H9 | 123 (2) |
H3B—C3—H3A | 108 (5) | C11—C10—C9 | 129.8 (5) |
C5—C4—C3 | 113.5 (3) | H12A—C12—H12B | 107 (5) |
| | | |
S1—C7—C6—C5 | 176.04 (4) | C7—S1—C10—C9 | −0.36 (5) |
S1—C7—C6—H6A | 55.3 (4) | C7—C6—C5—H5A | −55.5 (4) |
S1—C7—C6—H6B | −63.0 (4) | C7—C6—C5—H5B | 62.4 (4) |
S1—C7—C8—C9 | −0.40 (5) | C7—C8—C9—C10 | 0.13 (6) |
S1—C7—C8—H8 | −178.9 (2) | C7—C8—C9—H9 | −180.0 (3) |
S1—C10—C11—O1 | 1.79 (6) | C8—C7—S1—C10 | 0.43 (5) |
S1—C10—C11—C12 | −178.52 (8) | C8—C7—C6—H6A | −123.0 (8) |
S1—C10—C9—C8 | 0.20 (5) | C8—C7—C6—H6B | 118.8 (8) |
S1—C10—C9—H9 | −179.7 (2) | C8—C9—C10—C11 | −178.94 (6) |
O1—C11—C10—C9 | −179.13 (6) | C9—C10—C11—C12 | 0.55 (5) |
O1—C11—C12—H12A | −123.6 (8) | C10—C11—C12—H12A | 56.7 (7) |
O1—C11—C12—H12B | 120.4 (8) | C10—C11—C12—H12B | −59.2 (7) |
C1—C2—C3—C4 | 176.99 (8) | C10—C9—C8—H8 | 178.6 (3) |
C1—C2—C3—H3B | −61.8 (5) | C11—C10—C9—H9 | 1.2 (4) |
C1—C2—C3—H3A | 56.1 (5) | H1A—C1—C2—H2B | 57.7 (8) |
C2—C3—C4—C5 | 178.04 (7) | H1A—C1—C2—H2A | −58.9 (8) |
C2—C3—C4—H4B | −60.8 (5) | H1B—C1—C2—H2B | 177.6 (7) |
C2—C3—C4—H4A | 56.8 (5) | H1B—C1—C2—H2A | 61 (1) |
C3—C2—C1—H1B | −60.5 (7) | H1C—C1—C2—H2B | −62 (1) |
C3—C2—C1—H1A | 179.63 (11) | H1C—C1—C2—H2A | −179.0 (5) |
C3—C2—C1—H1C | 59.5 (6) | H2A—C2—C3—H3B | 176.7 (10) |
C3—C4—C5—C6 | 176.44 (6) | H2A—C2—C3—H3A | −65 (1) |
C3—C4—C5—H5A | 55.4 (4) | H2B—C2—C3—H3B | 60 (1) |
C3—C4—C5—H5B | −62.7 (5) | H2B—C2—C3—H3A | 178 (1) |
C4—C5—C6—C7 | −176.59 (6) | H3A—C3—C4—H4B | 60 (1) |
C4—C5—C6—H6A | −55.0 (4) | H3A—C3—C4—H4A | 178 (1) |
C4—C5—C6—H6B | 61.6 (5) | H3B—C3—C4—H4B | 178 (1) |
C4—C3—C2—H2B | −60.8 (5) | H3B—C3—C4—H4A | −65 (1) |
C4—C3—C2—H2A | 55.5 (4) | H4A—C4—C5—H5A | 177 (1) |
C5—C4—C3—H3B | 56.7 (5) | H4A—C4—C5—H5B | 59 (1) |
C5—C4—C3—H3A | −60.8 (5) | H4B—C4—C5—H5A | −66 (1) |
C5—C6—C7—C8 | −2.17 (5) | H4B—C4—C5—H5B | 176.3 (9) |
C6—C7—S1—C10 | −178.06 (5) | H5A—C5—C6—H6A | 66 (1) |
C6—C7—C8—C9 | 177.95 (6) | H5A—C5—C6—H6B | −177 (1) |
C6—C7—C8—H8 | −0.5 (4) | H5B—C5—C6—H6A | −176.0 (8) |
C6—C5—C4—H4B | 55.4 (4) | H5B—C5—C6—H6B | −59 (1) |
C6—C5—C4—H4A | −62.4 (5) | H8—C8—C9—H9 | −1.5 (5) |
C7—S1—C10—C11 | 178.88 (5) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···O1i | 1.08 (1) | 2.30 (1) | 3.095 (2) | 129 (1) |
Symmetry code: (i) x, y+1, z. |
Experimental details
Crystal data |
Chemical formula | C24H34O2S2 |
Mr | 418.63 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 5.047 (5), 6.979 (6), 16.333 (9) |
α, β, γ (°) | 98.79 (16), 93.52 (15), 95.39 (15) |
V (Å3) | 564.4 (9) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | ? |
Crystal size (mm) | 0.43 × 0.14 × 0.08 |
|
Data collection |
Diffractometer | Four-circle diffractometer |
Absorption correction | – |
No. of measured, independent and observed [ > 2.0σ(I)] reflections | 70042, 9170, 9170 |
Rint | 0.053 |
(sin θ/λ)max (Å−1) | 1.026 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.072, 1.05 |
No. of reflections | 9169 |
No. of parameters | 507 |
No. of restraints | 342 |
H-atom treatment | Only H-atom coordinates refined |
Δρmax, Δρmin (e Å−3) | ?, ? |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···O1i | 1.0831 (11) | 2.301 (3) | 3.095 (2) | 128.6 (5) |
Symmetry code: (i) x, y+1, z. |