3-(4-pyridyl)-2,4-pentanedione - a bridge between coordinative, … · 2013-08-09 · structural...

3-(4-pyridyl)-2,4-pentanedione - a bridge between coordinative, halo-gen, and hydrogen bonds†

Carina Merkens, Fangfang Pan, and Ulli Englert∗

Supplementary Information

Contents

Structural Information 21 Structural Information for 1 . . . . . . . . . . 22 Structural Information for 2 . . . . . . . . . . 23 Structural Information for 3 . . . . . . . . . . 3

3.1 Structural Information for the Byproduct 3

List of Figures

S1 Displacement ellipsoid plot of 1. . . . . . . . 2S2 Localization of the enol H by difference

fourier map . . . . . . . . . . . . . . . . . . 2S3 Displacement ellipsoid plot of 2. . . . . . . . 3S4 Displacement ellipsoid plot of 3. . . . . . . . 3S5 Structural components of the byproduct of 3 . 4S6 Halogen bond interaction of I3 and O1 . . . . 6S7 Gradient vector field, laplacian of the electron

density, and deformation density of halogeninteractions in 3 . . . . . . . . . . . . . . . . 7

List of Tables

T1 Properties of bond critical points in 3 . . . . . 4T2 Resolution and completeness statistics of 3 . . 8T3 Agreement factor statistics as function of res-

olution . . . . . . . . . . . . . . . . . . . . . 8

Institute of Inorganic Chemistry, RWTH Aachen University, Aachen,Germany. Fax: +49-241-8092288; Tel: +49-241-8094666; E-mail:[email protected]

1–8 | 1

Electronic Supplementary Material (ESI) for CrystEngCommThis journal is © The Royal Society of Chemistry 2013

Structural Information

1 Structural Information for 1

Fig. S1 Displacement ellipsoid plot of the molecular arrangement in 1. Ellipsoids are drawn at 60 % probability. Symmetry operation:a 2-x, -y, 1-z.

Fig. S2 Localization of the enol H by difference fourier map. The difference Fourier map in the plane of the acetylaceton moiety shows alocal maximum of electron density for the enol H atom.


The CHCl3 molecule in 2 is well-ordered, with only slightly elevated anisotropic displacement parameters for the Cl atoms. ItsH atom is engaged in a hydrogen bond with O2.

Hydrogen bond D-H· · ·A D-H H· · ·A D· · ·A D-H· · ·AC40-H40· · ·O2 1.00 A 2.23 A 3.081(4) A 142◦

Halogen bonds C-D· · ·X D· · ·X C-D· · ·X Symmetry operationC35i-F3i· · ·Cl1 3.007(2) 162.89(19) i = -x, 1-y, 2-zC14ii-O4ii· · ·Cl3 3.233(2) 100.45(18) ii = 1+x, y, zC40iii-Cl2iii· · ·Cl2 3.5136(18) 135.15(12) iii = 1-x, 1-y, 2-z

Two neighbouring CHCl3 molecules (interaction C40iii-Cl2iii· · ·Cl2) occupy a volume of 240 A3; the overall packing coeffi-cient of the structure amounts to 0.665.

2 | 1–8


Fig. S3 Displacement ellipsoid plot of the molecular arrangement in 2. Ellipsoids are drawn at 60 % probability. Hydrogen atoms have beenomitted for clarity.


Fig. S4 Displacement ellipsoid plot of the molecular arrangement in 3. Ellipsoids are drawn at 60 % probability. Hydrogen atoms of thetarget molecule have been omitted for clarity. Symmetry operation: a -x, 2-y, -z.

3.1 Structural Information for the Byproduct

1–8 | 3


Fig. S5 Structural components of the byproduct of 3. Formula:C44H32AlCl6F8I4N3O6. Cell parameters: a=11.8681(5) A, b=13.2965(6) A,c=19.4697(9) A; α=90.3109(7)◦, β=102.3354(7)◦, γ=113.2746(6)◦, V=2743.4(2) A3.

Table T1 Properties of bond critical points in 3. ρ(rb) is the electron density, ∇2ρ(rb) the Laplacian of the electron density at the bond criticalpoint, Di j the interatomic distance, Ri j the lenght of the bond path, and di the distance from the first atom to the (3,-1) critical point.Symmetry operations: a x-1, y-1, z+1., b x+1, y-1, z-1.

Bond ρ(rb)(e A−3) ∇2ρ(rb)(e A−5) Di j(A) Ri j(A) di(A)

AL(1)-O(1) 0.67(4) 1.97(9) 1.8940(18) 1.8956 0.8283AL(1)-O(2) 0.78(4) 0.83(9) 1.874(2) 1.8747 0.8126AL(1)-O(3) 0.65(4) 2.43(9) 1.872(2) 1.8722 0.8224AL(1)-O(4) 0.55(4) 2.80(9) 1.8805(18) 1.8917 0.8443AL(1)-O(5) 0.68(4) 3.78(9) 1.8573(19) 1.8583 0.8126AL(1)-O(6) 0.67(4) 2.42(9) 1.8558(19) 1.8565 0.8213I(1)-C(31) 0.87(6) 2.01(8) 2.096(2) 2.1117 1.1643I(2)-C(34) 0.91(6) 1.86(9) 2.078(2) 2.0998 1.1492I(3)-C(37) 0.95(6) 1.27(8) 2.0791(18) 2.1044 1.1886F(1)-C(32) 2.37(11) -18.8(5) 1.340(3) 1.341 0.7665F(2)-C(33) 2.00(14) -16.1(7) 1.338(4) 1.3388 0.8414F(3)-C(36) 2.30(12) -21.8(6) 1.340(4) 1.3405 0.7773F(4)-C(35) 2.06(13) -15.9(7) 1.337(3) 1.3371 0.8274F(5)-C(38) 2.06(12) -15.0(6) 1.336(3) 1.3361 0.7776F(6)-C(39) 1.94(11) -7.8(6) 1.349(4) 1.3537 0.7811O(1)-C(2) 2.63(15) -28.4(8) 1.275(2) 1.278 0.8311O(2)-C(4) 2.99(14) -42.9(7) 1.270(2) 1.2722 0.7833O(3)-C(12) 2.80(14) -36.4(7) 1.272(2) 1.2719 0.7558O(4)-C(14) 2.76(13) -32.8(7) 1.280(2) 1.2816 0.7861O(5)-C(22) 2.69(13) -35.8(7) 1.273(2) 1.2734 0.7733O(6)-C(24) 2.77(14) -40.9(8) 1.277(2) 1.278 0.8145N(1)-C(8) 2.27(13) -13.8(3) 1.333(4) 1.3338 0.6694

Continued on next page

4 | 1–8


Table T1 – Continued from previous page

Bond ρ(rb)(e A−3) ∇2ρ(rb)(e A−5) Di j(A) Ri j(A) di(A)

N(1)-C(9) 2.38(12) -14.4(3) 1.347(4) 1.3476 0.7179N(2)-C(18) 2.51(10) -22.0(3) 1.346(3) 1.3472 0.7282N(2)-C(19) 2.43(10) -20.0(2) 1.342(3) 1.3421 0.7093N(3)-C(28) 2.44(11) -16.7(3) 1.332(4) 1.3316 0.7113N(3)-C(29) 2.54(10) -22.16(17) 1.337(4) 1.3372 0.7348C(1)-C(2) 2.00(8) -17.29(17) 1.502(2) 1.5034 0.7691C(2)-C(3) 2.09(9) -17.2(3) 1.407(2) 1.4073 0.7899C(3)-C(4) 2.23(9) -22.4(3) 1.418(2) 1.4184 0.6397C(3)-C(6) 1.89(8) -12.09(18) 1.484(2) 1.4877 0.7548C(4)-C(5) 1.98(8) -19.77(18) 1.497(2) 1.4972 0.712C(6)-C(7) 2.13(11) -17.5(4) 1.397(2) 1.3968 0.7973C(6)-C(10) 2.13(9) -20.4(3) 1.392(2) 1.3929 0.7201C(7)-C(8) 2.06(9) -15.3(3) 1.386(3) 1.3865 0.6588C(9)-C(10) 2.19(9) -19.2(3) 1.390(3) 1.3901 0.7128C(11)-C(12) 2.04(8) -21.38(18) 1.493(2) 1.4932 0.7209C(12)-C(13) 2.08(9) -20.5(3) 1.412(2) 1.4124 0.7835C(13)-C(14) 2.42(8) -20.7 (2) 1.416(2) 1.4185 0.6902C(13)-C(16) 1.77(10) -15.5 (4) 1.485(2) 1.4858 0.8735C(14)-C(15) 1.769(7) -15.41 (16) 1.496(2) 1.4958 0.7409C(16)-C(17) 2.29(9) -22.2(3) 1.399(2) 1.3993 0.6892C(16)-C(20) 2.29(9) -22.3(3) 1.401(2) 1.4017 0.6672C(17)-C(18) 2.31(8) -23.15(19) 1.389(3) 1.3911 0.6979C(19)-C(20) 2.23(9) -21.1(3) 1.388(2) 1.3881 0.7148C(21)-C(22) 1.81(8) -14.26(17) 1.499(2) 1.4993 0.7334C(22)-C(23) 2.07(8) -16.9(3) 1.413(2) 1.4134 0.7357C(23)-C(24) 2.16(10) -23.8(4) 1.410(2) 1.4114 0.5755C(23)-C(26) 1.82(8) -13.7(2) 1.489(2) 1.4894 0.6947C(24)-C(25) 1.89(8) -18.79(18) 1.494(2) 1.4947 0.7716C(26)-C(27) 2.39(12) -27.9(5) 1.397(2) 1.3968 0.8293C(26)-C(30) 2.26(10) -22.2(4) 1.399(3) 1.4004 0.7675C(27)-C(28) 2.11(9) -17.9(3) 1.392(2) 1.3929 0.6604C(29)-C(30) 2.28(9) -21.9(2) 1.392(3) 1.3921 0.6951C(31)-C(32) 2.28(9) -21.2(3) 1.384(3) 1.3838 0.6523C(31)-C(36) 2.31(9) -23.2(3) 1.384(2) 1.3846 0.6552C(32)-C(33) 2.16(10) -20.9(3) 1.388(3) 1.391 0.6449C(33)-C(34) 2.26(9) -20.1(3) 1.392(3) 1.3924 0.6738C(34)-C(35) 2.30(13) -26.4(6) 1.386(3) 1.3879 0.5437C(35)-C(36) 2.39(11) -26.9(4) 1.386(3) 1.3882 0.6301C(37)-C(38) 1.87(11) -13.4(4) 1.392(3) 1.3925 0.7951C(37)-C(39) 1.96(11) -13.2(4) 1.388(3) 1.3886 0.6115C(38)-C(39) 2.16(18) -20.4(5) 1.382(3) 1.382 0.738I(1)-N(2) 0.154(12) 1.708(11) 2.833(3) 2.8527 1.5223I(2)-O(7)a 0.092(7) 0.856(9) 3.026(6) 3.0818 1.6303I(3)-O(1) 0.082(4) 1.063(7) 3.157(2) 3.1702 1.7442H(7E)-N(1) 0.25(6) 2.06(4) 1.94 1.9428 0.698H(7D)-N(2)b 0.051(11) 0.550(5) 2.60 2.6042 1.0884

1–8 | 5


Fig. S6 Short halogen bond interactions between I3 and O1 link the chains of TFDIB and Al(acacPy)3 into a 1D ladder structure.

6 | 1–8


Fig. S7 Left: Projections in the plane of the TFDIB to show the I1· · ·N2 halogen bond. Right:Projections in the plane of TFDIB to show theI3· · ·O1 halogen bond. Top: gradient vector field of the experimental charge density; bond path are shown as black lines, bond critical pointsas dark blue and ring critical points as green solid circles. Middle: Laplacian of the electron density (contours at ±2n ·10−3 e A−5,0 ≤ n ≤ 20.) Bottom: deformation density (intervals at 0.05 e A−3). Both quantities are given with positive values in blue.

1–8 | 7


Theta sin θ/λ Complete Expected Measured Missing

20.82 0.500 0.998 4520 4513 723.01 0.550 0.999 6037 6029 825.24 0.600 0.999 7827 7819 8 ACTA Min. Res.

27.51 0.650 0.999 9977 9964 1329.84 0.700 0.998 12412 12390 2232.21 0.750 0.997 15295 15242 5334.65 0.800 0.995 18577 18492 8537.17 0.850 0.993 22259 22110 14939.77 0.900 0.991 26445 26215 23042.47 0.950 0.989 31116 30763 35345.29 1.000 0.985 36290 35760 53048.27 1.050 0.982 41977 41220 75751.43 1.100 0.978 48276 47190 108652.23 1.112 0.967 49909 48264 1645

Note: The reported completeness refers to the actual H, K, L index range.

Table T2 Resolution and completeness statistics of 3. Cumulative and Friedel pairs averaged.

Theta sin θ/λ # R1 wR2 S av(I/σW) av(I) av(σW)

12.38 0.302 991 0.042 0.096 2.606 24.82 10030.86 296.1615.68 0.380 998 0.029 0.071 1.507 18.81 5007.76 186.6618.02 0.435 996 0.030 0.067 1.169 14.79 3302.28 152.4719.90 0.479 988 0.034 0.078 1.124 12.13 2340.26 131.8921.51 0.516 1005 0.037 0.085 1.070 10.34 1923.70 124.8922.94 0.548 1006 0.044 0.109 1.364 10.16 1375.86 100.7524.22 0.577 990 0.039 0.089 1.402 13.23 1220.36 69.1025.40 0.603 983 0.037 0.086 1.238 12.00 942.69 57.0026.49 0.628 1006 0.037 0.084 1.129 11.07 844.21 55.0427.52 0.650 1006 0.041 0.092 1.066 9.37 648.36 50.5028.49 0.671 982 0.038 0.089 1.002 9.00 620.59 49.6529.41 0.691 993 0.044 0.099 0.990 7.96 527.35 49.4830.28 0.709 988 0.046 0.104 0.968 7.23 473.92 47.3531.12 0.727 976 0.052 0.114 0.969 6.70 430.99 45.1231.93 0.744 990 0.054 0.126 0.925 5.76 355.58 42.8032.71 0.760 1003 0.055 0.127 0.908 5.55 351.78 43.7433.46 0.776 945 0.055 0.129 0.835 5.13 299.70 42.7034.20 0.791 1010 0.060 0.144 0.840 4.47 262.01 41.5334.91 0.805 994 0.062 0.151 0.832 4.23 247.35 41.5152.23 1.112 29414 0.102 0.283 0.872 2.06 84.10 29.10

From FCF: R1 = 0.0542 (27899), wR2 = 0.1177 (48264), S = 1.028From CIF: R1 = 0.0542 (27901), wR2 = 0.1175 (48264), S = 1.026, Npar = 538Non (SHELXL) optimized weights: wR2 = 0.1035, S = 1.128

Table T3 R-Value statistics as a function of resolution (in resolution shell)

8 | 1–8


3-(4-pyridyl)-2,4-pentanedione - a bridge between coordinative, … · 2013-08-09 · structural...

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