Supporting Information: coordinates of optimized geometries & total energies for [n]ladderanes. (x,y,z, in Angstroms; G3MP2B3 enthalpies in a.u.) [2]ladderane c c c c h h h h h h c h h c h h
NIMAG=0 x
y
1.335194 0.013892 -0.013928 1.284263 1.304967 2.194444 0.003782 -0.003754 1.175464 2.135962 -1.335168 -2.194530 -1.304907 -1.284238 -2.135907 -1.175611
0.760651 0.786482 -0.786519 -0.797947 1.276236 1.144117 1.388364 -1.388372 -1.245053 -1.277352 -0.760653 -1.144019 -1.276282 0.797974 1.277252 1.245181
total energy = -234.146228
[2]ladderane-open1 x c c h h h h c c h c h h c h h h c h h c h h h h
0.604498 -0.848166 1.280144 0.631854 -0.924997 -1.627113 -0.776547 0.784653 1.192222 1.605241 1.483018 1.216695 3.096631 3.663939 3.255874 3.528976 -1.474137 -1.187770 -1.124101 -3.002064 -3.476334 -3.322852 -3.395826 -1.134382
z -0.232149 0.579039 0.579032 -0.275061 -1.199291 0.327954 1.492391 1.492403 -1.270107 0.218133 -0.232156 0.327851 -1.199278 -0.275084 0.218297 -1.270086 ZPE=0.140100
y
NIMAG=0 z
1.463898 1.621930 2.317787 1.144894 2.380511 1.820534 0.175966 0.261588 0.629063 -0.946281 -1.761103 -1.327354 -0.623358 -1.502008 0.170397 -0.281883 -0.883370 -0.760119 -1.881928 -0.831806 -1.592514 -1.008052 0.144928 0.075442
-0.490224 0.029811 -0.374739 -1.539103 0.815964 -0.714983 0.610021 0.479272 1.431719 0.032469 0.760809 -0.921568 -0.122647 -0.450456 -0.862464 0.826112 -0.250181 -1.304306 0.045598 -0.131736 -0.762419 0.902486 -0.436920 1.643558
1
total energy = -313.843995
[3]ladderane
NIMAG=0 x
c c c c c c c c h h h h h h h h h h h h
ZPE= 0.216284
-1.991345 -1.992164 -0.578098 -0.578519 0.578138 0.578463 1.992093 1.991433 -2.060223 -2.063651 -0.444976 -0.445072 0.445319 0.444675 2.063400 2.060553 2.763669 2.763745 -2.763818 -2.763621
y
z
-0.778976 0.778346 -0.790789 0.791566 0.790847 -0.791473 -0.778414 0.778923 -1.261948 1.262094 -1.404110 1.406369 1.404230 -1.406220 -1.262076 1.261979 1.212292 -1.210442 1.210185 -1.212529
-0.128541 -0.128420 0.511104 0.509903 -0.510998 -0.509963 0.128357 0.128569 -1.110266 -1.109577 1.408985 1.406730 -1.408880 -1.406788 1.109568 1.110236 -0.515107 -0.516931 0.517021 0.514941
total energy = -311.401987
[3]ladderane-cis x c c c h h h h c h c h c h h c h h c h h
1.678383 0.851537 0.706483 1.327464 2.732839 1.300568 1.151635 -0.851527 -1.300625 -0.706466 -1.151510 -1.678262 -2.732696 -1.326998 -1.425349 -2.338493 -0.808946 1.425210 0.808524 2.338190
y
ZPE= 0.173718
NIMAG=0 z
0.703625 0.714434 -0.842942 1.341766 0.939758 1.218504 -1.501177 -0.714146 -1.217856 0.843204 1.501753 -0.703876 -0.940241 -1.342151 0.830638 1.433569 1.125851 -0.830877 -1.126083 -1.434050
total energy = -311.391472
-0.561620 0.749227 0.681933 -1.379547 -0.384187 1.610792 1.433945 0.749523 1.611264 0.681614 1.433417 -0.561408 -0.384163 -1.379076 -0.702224 -0.729824 -1.556786 -0.702002 -1.556354 -0.729739 ZPE= 0.173935
2
[4]ladderane
NIMAG=0 x
c c c c c c c c c c h h h h h h h h h h h h h h
-2.595948 -2.596212 -1.289829 -1.289784 0.000111 -0.000105 2.596182 2.595951 1.289790 1.289835 -2.523153 -2.524124 -1.288127 -1.288487 0.000495 -0.000460 2.524032 2.523251 1.288541 1.288081 -3.452610 -3.452830 3.452616 3.452826
y
z
-0.778885 0.778935 0.789373 -0.789815 -0.795933 0.795952 -0.778952 0.778839 0.789857 -0.789363 -1.261204 1.262535 1.402208 -1.403148 -1.421304 1.421315 -1.262579 1.261214 1.403236 -1.402191 -1.212539 1.211569 1.212426 -1.211588
-0.315656 -0.314763 0.521516 0.521077 -0.322684 -0.322693 -0.314767 -0.315671 0.521065 0.521556 -1.297341 -1.295881 1.429450 1.428678 -1.224050 -1.224067 -1.295867 -1.297336 1.428631 1.429492 0.210188 0.212012 0.210237 0.211967
total energy = -388.657800
[5]ladderane
NIMAG=0 x
c c c c c c c c c c c c h h h h h h h h h h
PE = 0.207003
6.898019 5.876146 6.970760 8.006827 8.816804 7.774768 10.783288 11.805161 10.710547 9.674480 8.864503 9.906539 7.103324 5.448051 6.722495 8.563353 9.074079 7.213170 10.577983 12.233256 10.958812 9.117954
y 1.885618 0.982643 -0.095045 0.820464 0.995875 0.075100 -1.885618 -0.982643 0.095045 -0.820464 -0.995875 -0.075100 2.863076 1.400417 -1.119787 0.506876 2.022479 0.378120 -2.863076 -1.400417 1.119787 -0.506876
z 4.098543 4.851772 5.067238 4.303528 5.603229 6.371338 8.070543 7.317314 7.101848 7.865558 6.565857 5.797748 4.550303 5.770393 4.770787 3.413833 5.891947 7.263668 7.618782 6.398693 7.398299 8.755253
3
h h h h h h
8.607228 10.468137 12.631541 6.640151 5.049766 11.041156
-2.022479 -0.378120 -0.642649 2.048006 0.642649 -2.048006
total energy = -465.913607
[6]ladderane -2.577492 -2.577492 -1.287780 -1.287781 0.000000 0.000000 3.883481 3.883481 2.577492 2.577492 1.287781 1.287780 -2.575754 -2.575758 -1.287820 -1.287822 0.000000 -0.000001 3.810706 3.810706 2.575757 2.575756 1.287821 1.287819 4.740205 4.740206 -3.883481 -4.740206 -3.810707 -3.883480 -3.810701 -4.740205
y
z
0.789783 -0.789784 -0.794450 0.794449 0.792701 -0.792701 -0.778965 0.778965 0.789785 -0.789783 -0.794451 0.794449 1.402992 -1.402996 -1.418802 1.418801 1.415767 -1.415766 -1.261753 1.261750 1.402997 -1.402991 -1.418803 1.418800 1.212276 -1.212273 0.778967 1.212274 1.261757 -0.778965 -1.261748 -1.212277
0.494102 0.494101 -0.350113 -0.350113 0.494840 0.494841 -0.342688 -0.342691 0.494100 0.494102 -0.350112 -0.350114 1.401668 1.401665 -1.252019 -1.252019 1.397681 1.397683 -1.324138 -1.324142 1.401664 1.401668 -1.252018 -1.252021 0.183339 0.183343 -0.342688 0.183344 -1.324136 -0.342692 -1.324144 0.183334
total energy = -543.169438
[7]ladderane
ZPE= 0.273734
NIMAG=0 x
c c c c c
ZPE= 0.250434
NIMAG=0 x
c c c c c c c c c c c c h h h h h h h h h h h h h h c h h c h h
6.277139 4.905418 7.949722 3.047080 4.219363 9.122005
-4.539179 -4.539169 -3.203849 -3.203832 -1.945498
y
z
0.778992 -0.778919 -0.789832 0.789767 0.794492
0.251779 0.251930 -0.537206 -0.537303 0.352990
4
c c c c c c c h h h h h h h h h h h h h h c h c h c h h c h h
-1.945491 1.945491 1.945499 0.628314 0.628320 -0.628320 -0.628310 -4.501882 -4.501799 -3.169128 -3.169045 -1.978219 -1.978166 1.978171 1.978207 0.595601 0.595640 -0.595640 -0.595592 -5.376406 -5.376420 3.203835 3.169052 3.203849 3.169122 4.539182 4.501892 5.376413 4.539160 4.501772 5.376415
-0.794483 -0.794483 0.794489 0.792839 -0.792866 -0.792864 0.792841 1.261802 -1.261525 -1.403184 1.403007 1.418833 -1.418764 -1.418766 1.418825 1.416048 -1.416095 -1.416092 1.416052 1.212338 -1.212406 0.789772 1.403021 -0.789824 -1.403168 0.778988 1.261810 1.212333 -0.778928 -1.261529 -1.212418
total energy = -620.425259
[8]ladderane
ZPE= 0.307075
NIMAG=0 x
c c c c c c c c c c c c h h h h h h h
0.353042 -0.353035 -0.352989 0.445331 0.445316 -0.445309 -0.445324 1.235219 1.235468 -1.443975 -1.444145 1.254314 1.254410 -1.254401 -1.254318 1.347364 1.347337 -1.347330 -1.347356 -0.304724 -0.304425 0.537297 1.444133 0.537211 1.443985 -0.251785 -1.235221 0.304712 -0.251941 -1.235479 0.304405
-5.170882 -5.170749 -3.865175 -3.865102 -2.575159 -2.575142 1.287735 1.287686 0.000013 -0.000019 -1.287697 -1.287730 -5.097932 -5.097364 -3.863938 -3.863429 -2.574854 -2.574736 1.287724
y
z
-0.779067 0.778941 0.789725 -0.789841 -0.794330 0.794651 0.792901 -0.792873 -0.792927 0.793062 0.792818 -0.792956 -1.261914 1.261639 1.402805 -1.403134 -1.418396 1.419138 1.416100
-0.358941 -0.359061 0.478386 0.478176 -0.365688 -0.365311 0.479895 0.479907 -0.365256 -0.365081 0.480070 0.479741 -1.340328 -1.340514 1.386035 1.385674 -1.267776 -1.267106 1.382527
5
h h h h h h h c h c h c h c h c h h c h h
1.287493 0.000087 -0.000100 -1.287539 -1.287681 -6.027706 -6.027731 2.575158 2.574842 2.575134 2.574739 3.865140 3.863685 3.865135 3.863712 5.170822 5.097635 6.027705 5.170824 6.027730 5.097706
-1.416060 -1.416162 1.416490 1.415828 -1.416338 -1.212214 1.212472 -0.794554 -1.418924 0.794439 1.418620 0.789861 1.403164 -0.789721 -1.402774 0.778934 1.261484 1.212348 -0.779038 -1.212296 -1.262019
total energy = -697.681082
1.382547 -1.267771 -1.267462 1.382832 1.382246 0.167036 0.166356 -0.365425 -1.267301 -0.365592 -1.267602 0.478153 1.385646 0.478397 1.386064 -0.359133 -1.340652 0.166530 -0.358856 0.166914 -1.340188 ZPE= 0.340419
6
+
4 CH4 = 4 C2H6
(1a)
-89.0 kJ/mol
8CH4 = 7C2H6
(1b)
-122.1 kJ/mol
+ +
12CH4 = 10C2H6
(1c)
+
(1d)
-202.4 kJ/mol
(1e)
-240.8 kJ/mol
16CH4 = 13C2H6 + 20CH4 = 16C2H6
+ 24CH4 = 19C2H6
28CH4 = 22C2H6
(1f)
(1g)
-161.8 kJ/mol
-280.2 kJ/mol
-319.7 kJ/mol
+ 32 CH4 = 25C2H6 (1h)
-359.2 kJmol
isodesmic reactions (BSE) used to calculate total strain energies Scheme A
7
(2a)
4 C2H6 = 4
-111.6 kJ/mol
+2
+ 7C2H6 = 4
(2b) -229.9 kJ/mol +4
+ 10C2H6 = 4
(2c) -332.0 kJ/mol
+6
+ 13C2H6 = 4
(2d) -434.0 kJ/mol
+8
+ 16C2H6 = 4
+ 19 C2H6 = 4
(2e) -536.0 kJ/mol
+ 10
+ 22 C2H6 = 4
+ 25 C2H6 = 4
(2f) -638.0 kJ/mol
+ 12
(2g) -739.9 kJ/mol
+ 14
homodesmotic reactions used to calculate total strain energy Scheme B
8
(2h) -841.9 kJ/mol
+
+
3 C2H6 =
+
3 C2H6 =
+
2 C2H6 =
-126.8 kJ/mol
+
2
3 C2H6 =
+
2 C2H6 =
+
3 C2H6 =
+
2 C2H6 =
-108.8 kJ/mol
-125.0 kJ/mol
2
+
+
2
+
2
-107.5 kJ/mol
-106.9 kJ/mol
+
+
2
-105.6 kJ/mol
+
2 C2H6 = 2
+
3C2H6=
+
2C2H6=
-107.6 kJ/mol
-88.8 kJ/mol
+ +
+ 2C2H6=
+
9
2
-107.3 kJ/mol
-105.6 kJ/mol
-87.5 kJ/mol
+
3C2H6=
+
2C2H6=
+ +
+ 2C2H6=
-87.5 kJ/mol
+
+ 2C2H6=
-105.7 kJ/mol
+
-87.5 kJ/mol
-86.2 kJ/mol
2
+ 3C2H6=
+
+ 2C2H6=
+
+
-107.2 kJ/mol
2
+
+ 2C2H6=
2C2H6=
-105.6 kJ/mol
+
+ 3C2H6=
+
-107.3 kJ/mol
2
+
2C 2H6=
+ 2C2H6=
+
homodesmotic reactions for calculating individual ring strain
Scheme C
10
2
-107.2 kJ/mol
-105.6 kJ/mol
-87.8 kJ/mol
-86.2 kJ/mol
