ESI: Fig. 1 Temperature dependence of the parameters a, b, and c (Å), β (°) and volume V (Å3) of the monoclinic unit cell of (S)-malic acid.

Electronic Supplementary Material (ESI) for CrystEngComm.This journal is © The Royal Society of Chemistry 2018

ESI: Fig. 2 Temperature dependence of the parameters a, b, and c (Å), β (°) and volume V (Å3) of the monoclinic unit cell of malic acid racemate RSI.

ESI: Fig. 3 Temperature dependence of the parameters a, b, and c (Å), β (°) and volume V (Å3) of the monoclinic unit cell of malic acid racemate RSII.

ESI: Fig. 4 Temperature dependence of the parameters a, b and c (Å), , β and (°) and volume V (Å3) of the triclinic unit cell of malic acids’ non-equimolar discrete compound S3R.

ESI: Fig. 5 Temperature dependence of the parameters a, b, and c (Å), β (°) and volume V (Å3) of the monoclinic unit cell of L-Val.

ESI: Fig. 6 Temperature dependence of the parameters a, b, and c (Å), β (°) and volume V (Å3) of the monoclinic unit cell of L-Ile.

ESI: Fig. 7 Temperature dependence of the parameters a, b, and c (Å), β (°) and volume V (Å3) of the monoclinic unit cell of the non-equimolar discrete compound V2I.

ESI: Fig. 8 Diffraction patterns of L-Val (A), L-Ile (B), and V2I (C) obtained at three selected temperatures.

ESI: Тable 1 Experimentally observed (obs) and calculated (calc) values of interplanar distances d (Å), diffraction angles 2CuKα () and their deviations (Δ), as well as hkl indices of corresponding diffraction maximums of S-malic acid (room temperature). Calculated unit cell parameters (S.G. P21): a = 5.043(2) Å, b = 9.183(2) Å, c = 11.851(5) Å, β = 94.28(3)°, V = 547.3(2) Å3.

No hkl d, Å (obs) d, Å (calc) Δd, Å 2θ, ° (obs) 2θ, ° (calc) Δ2θ, °

1 0 1 2 4.97328 4.96906 0.00422 17.820 17.835 -0.0152 0 2 0 4.58805 4.59135 -0.00330 19.330 19.316 0.014

3 1 1 0 4.41182 4.41104 0.00078 20.110 20.114 -0.0044 0 2 1 4.27717 4.27971 -0.00255 20.750 20.738 0.0125 1 1 -1 4.22681 4.22411 0.00270 21.000 21.014 -0.0146 1 1 1 4.04779 4.04672 0.00108 21.940 21.946 -0.0067 1 0 -2 3.97973 3.97922 0.00052 22.320 22.323 -0.0038 1 1 -2 3.65235 3.65115 0.00121 24.350 24.358 -0.0089 1 1 2 3.42808 3.42884 -0.00076 25.970 25.964 0.006

10 1 2 1 3.21778 3.21673 0.00105 27.700 27.709 -0.00911 1 1 -3 3.03749 3.03863 -0.00114 29.380 29.369 0.01112 1 2 -2 3.00549 3.00704 -0.00155 29.700 29.684 0.01613 1 1 3 2.84654 2.84708 -0.00054 31.400 31.394 0.00614 0 1 4 2.81336 2.81248 0.00088 31.780 31.790 -0.01015 1 2 -3 2.63608 2.63631 -0.00024 33.980 33.977 0.00316 1 2 3 2.50816 2.50828 -0.00012 35.770 35.768 0.00217 1 3 -2 2.42629 2.42615 0.00014 37.020 37.022 -0.00218 1 1 4 2.38347 2.38366 -0.00020 37.710 37.707 0.00319 2 1 1 2.34280 2.34287 -0.00007 38.390 38.389 0.00120 2 0 2 2.25321 2.25404 -0.00082 39.980 39.965 0.01521 0 4 1 2.25321 2.25355 -0.00034 39.980 39.974 0.00622 1 3 -3 2.21813 2.21851 -0.00038 40.640 40.633 0.00723 1 2 4 2.17413 2.17403 0.00010 41.500 41.502 -0.00224 0 4 2 2.13967 2.13986 -0.00018 42.200 42.196 0.00425 1 3 3 2.13967 2.14058 -0.00091 42.200 42.181 0.01926 2 0 4 1.84861 1.84809 0.00052 49.250 49.265 -0.01527 2 3 2 1.81516 1.81501 0.00014 50.220 50.224 -0.00428 0 5 1 1.81516 1.81476 0.00040 50.220 50.232 -0.01229 1 5 -2 1.66789 1.66751 0.00038 55.010 55.024 -0.014

ESI: Тable 2 Experimentally observed (obs) and calculated (calc) values of interplanar distances d (Å), diffraction angles 2CuKα () and their deviations (Δ), as well as hkl indices of corresponding diffraction maximums of malic acid racemate RSI (room temperature). Calculated unit cell parameters (S.G. P21/c): a = 4.893(2) Å, b = 8.824(2) Å, c = 13.056(3) Å, β = 102.86(2)°, V = 549.5(2) Å3.

No hkl d, Å (obs) d, Å (calc) Δd, Å 2θ,° (obs) 2θ,° (calc) Δ2θ, °

1 1 0 0 4.77407 4.76999 0.00408 18.570 18.586 -0.0162 0 2 0 4.41182 4.41192 -0.00010 20.110 20.110 0.0003 1 0 -2 4.30590 4.30413 0.00178 20.610 20.619 -0.0094 1 1 -1 4.24079 4.23957 0.00121 20.930 20.936 -0.0065 1 1 1 3.77300 3.77163 0.00137 23.560 23.569 -0.0096 0 2 2 3.62596 3.62583 0.00013 24.530 24.531 -0.0017 1 1 -3 3.32742 3.32677 0.00065 26.770 26.775 -0.0058 1 1 2 3.22463 3.22502 -0.00039 27.640 27.637 0.0039 0 0 4 3.18287 3.18202 0.00085 28.010 28.018 -0.008

10 1 1 3 2.72817 2.72832 -0.00015 32.800 32.798 0.00211 1 3 -1 2.51156 2.51272 -0.00116 35.720 35.703 0.01712 2 0 -2 2.41622 2.41706 -0.00084 37.180 37.167 0.01313 0 3 3 2.41622 2.41722 -0.00100 37.180 37.164 0.01614 1 1 -5 2.39510 2.39417 0.00092 37.520 37.535 -0.01515 1 3 2 2.24192 2.24227 -0.00035 40.190 40.184 0.00616 0 2 5 2.20566 2.20491 0.00075 40.880 40.894 -0.01417 0 4 0 2.20566 2.20596 -0.00030 40.880 40.874 0.00618 2 0 -4 2.15282 2.15206 0.00076 41.930 41.945 -0.01519 0 0 6 2.12098 2.12134 -0.00037 42.590 42.582 0.00820 1 0 -6 2.12098 2.12151 -0.00053 42.590 42.579 0.01121 0 4 2 2.08508 2.08429 0.00078 43.360 43.377 -0.01722 2 2 -3 2.04650 2.04660 -0.00009 44.220 44.218 0.00223 1 3 -5 1.89975 1.89932 0.00043 47.840 47.851 -0.01124 1 0 6 1.79578 1.79561 0.00018 50.800 50.805 -0.00525 2 0 -6 1.79578 1.79591 -0.00013 50.800 50.796 0.00426 0 2 7 1.68115 1.68112 0.00003 54.540 54.541 -0.00127 1 2 6 1.66288 1.66314 -0.00027 55.190 55.180 0.01028 2 2 -6 1.66288 1.66338 -0.00051 55.190 55.172 0.01829 0 5 3 1.62951 1.62943 0.00008 56.420 56.423 -0.00330 2 4 -2 1.62951 1.62938 0.00013 56.420 56.425 -0.005

ESI: Тable 3 Experimentally observed (obs) and calculated (calc) values of interplanar distances d (Å), diffraction angles 2CuKα () and their deviations (Δ), as well as hkl indices of corresponding diffraction maximums of malic acid racemate RSII (room temperature). Calculated unit cell parameters (S.G. Cc): a = 13.094(4) Å, b = 8.820(3) Å, c = 4.903(2) Å, β = 103.08(3)°, V = 551.5(3) Å3.

No hkl d, Å(obs) d, Å(calc) Δd, Å 2θ, °(obs) 2θ, ° (calc) Δ2θ, °

1 2 0 0 6.37945 6.37734 0.00211 13.870 13.875 -0.0052 0 2 0 4.40748 4.40980 -0.00232 20.130 20.119 0.0113 1 1 -1 4.24882 4.24786 0.00096 20.890 20.895 -0.0054 3 1 0 3.83073 3.82980 0.00093 23.200 23.206 -0.0065 1 1 1 3.77142 3.77210 -0.00068 23.570 23.566 0.0046 2 2 0 3.62887 3.62711 0.00176 24.510 24.522 -0.0127 3 1 -1 3.33721 3.33827 -0.00106 26.690 26.681 0.0098 4 0 0 3.18733 3.18867 -0.00134 27.970 27.958 0.0129 3 1 1 2.73060 2.72857 0.00203 32.770 32.795 -0.025

10 2 2 1 2.72413 2.72449 -0.00036 32.850 32.846 0.00411 1 3 -1 2.51292 2.51365 -0.00074 35.700 35.689 0.01112 4 2 -1 2.46880 2.47008 -0.00127 36.360 36.341 0.01913 3 3 0 2.41684 2.41807 -0.00123 37.170 37.150 0.02014 5 1 -1 2.40189 2.40268 -0.00079 37.410 37.397 0.01315 0 4 0 2.20515 2.20490 0.00025 40.890 40.895 -0.00516 1 1 2 2.18521 2.18608 -0.00087 41.280 41.263 0.01717 4 0 -2 2.15971 2.16020 -0.00049 41.790 41.780 0.01018 2 4 0 2.08462 2.08387 0.00076 43.370 43.387 -0.01719 5 1 1 2.00986 2.00996 -0.00009 45.070 45.068 0.00220 0 4 1 2.00187 2.00184 0.00003 45.260 45.261 -0.00121 5 3 -1 1.90275 1.90322 -0.00047 47.760 47.747 0.01322 6 0 -2 1.80408 1.80330 0.00077 50.550 50.573 -0.02323 7 1 0 1.78432 1.78441 -0.00010 51.150 51.147 0.00324 4 4 -1 1.77301 1.77284 0.00017 51.500 51.505 -0.00525 6 2 1 1.66454 1.66402 0.00052 55.130 55.149 -0.01926 4 4 1 1.62686 1.62733 -0.00047 56.520 56.502 0.01827 4 4 -2 1.54358 1.54305 0.00053 59.870 59.893 -0.023

ESI: Тable 4 Experimentally observed (obs) and calculated (calc) values of interplanar distances d (Å), diffraction angles 2CuKα () and their deviations (Δ), as well as hkl indices of corresponding diffraction maximums of non-equimolar discrete compound S3R formed in the system S-malic acidR-malic acid (room temperature). Calculated unit cell parameters (S.G. P1): a = 4.895(2) Å, b = 10.606(4) Å, c =11.193(4) Å, α = 106.76(4)°, β = 95.54(4)°, γ = 94.56(3)°, V = 550.3(3) Å3.

No hkl d, Å(obs) d, Å(calc) Δd, Å 2θ, °(obs) 2θ, ° (calc) Δ2θ, °

1 0 0 1 10.66955 10.63289 0.03666 8.280 8.309 -0.0292 0 1 0 10.08596 10.09134 -0.00537 8.760 8.755 0.0053 0 1 1 6.41627 6.42486 -0.00858 13.790 13.771 0.0194 0 1 -2 5.42025 5.41703 0.00322 16.340 16.350 -0.0105 0 0 2 5.31685 5.31645 0.00040 16.660 16.661 -0.0016 0 2 -1 5.19913 5.19856 0.00057 17.040 17.042 -0.0027 0 2 0 5.04347 5.04567 -0.00220 17.570 17.562 0.0088 1 0 0 4.84390 4.84124 0.00265 18.300 18.310 -0.0109 1 0 -1 4.63316 4.63002 0.00315 19.140 19.153 -0.013

10 1 -1 0 4.57399 4.57014 0.00385 19.390 19.407 -0.01711 0 2 -2 4.37309 4.36784 0.00524 20.290 20.315 -0.02512 1 1 -1 4.24681 4.24420 0.00261 20.900 20.913 -0.01313 0 1 2 4.21490 4.21371 0.00120 21.060 21.066 -0.00614 1 0 -2 3.82585 3.82584 0.00001 23.230 23.230 -0.00015 1 -2 0 3.70634 3.70802 -0.00168 23.990 23.979 0.01116 1 -2 1 3.64351 3.64379 -0.00027 24.410 24.408 0.00217 0 3 -1 3.52417 3.52364 0.00053 25.250 25.254 -0.00418 1 -1 2 3.49558 3.49506 0.00052 25.460 25.464 -0.00419 1 2 0 3.31043 3.31204 -0.00162 26.910 26.897 0.01320 0 1 3 3.07124 3.06993 0.00131 29.050 29.063 -0.01321 1 0 -3 3.04560 3.04740 -0.00179 29.050 29.282 0.01822 1 -3 1 2.95686 2.95853 -0.00167 30.200 30.183 0.01723 -1 -3 1 2.75019 2.75067 -0.00048 32.530 32.524 0.00624 -1 3 1 2.69384 2.69302 0.00082 33.230 33.240 -0.01025 1 3 0 2.62782 2.62733 0.00049 34.090 34.097 -0.00726 -1 -1 4 2.52318 2.52443 -0.00126 35.550 35.532 0.01827 0 4 0 2.52318 2.52283 0.00034 35.550 35.555 -0.00528 -1 -3 3 2.50140 2.50128 0.00012 35.870 35.872 -0.00229 -1 -2 4 2.43454 2.43438 0.00016 36.890 36.893 -0.00330 0 1 4 2.40003 2.40020 -0.00017 37.440 37.437 0.00331 -2 1 1 2.38469 2.38400 0.00069 37.690 37.701 -0.01132 2 -1 1 2.32937 2.32948 -0.00011 38.620 38.618 0.00233 2 1 0 2.29567 2.29597 -0.00030 39.210 39.205 0.00534 0 -4 4 2.18369 2.18392 -0.00023 41.310 41.305 0.00535 2 -1 2 2.15626 2.15675 -0.00049 41.860 41.850 0.010

ESI: Тable 5 Experimentally observed (obs) and calculated (calc) values of interplanar distances d (Å), diffraction angles 2CuKα () and their deviations (Δ), as well as hkl indices of corresponding diffraction maximums of L-valine (room temperature). Calculated unit cell parameters (S.G. P21): a = 9.653(6) Å, b = 5.248(3) Å, c = 11.996(8) Å, β = 90.62(7)°, V = 607.7(5) Å3.

No hkl d, Å (obs) d, Å (calc) Δd, Å 2θ,° (obs) 2θ,° (calc) Δ2θ, °

1 0 0 1 11.95240 11.99515 -0.04275 7.390 7.364 0.0262 0 0 2 5.99268 5.99758 -0.00490 14.770 14.758 0.0123 0 1 1 4.81002 4.80809 0.00194 18.430 18.437 -0.0074 1 1 0 4.60694 4.61067 -0.00373 19.250 19.234 0.0165 0 0 3 3.99564 3.99838 -0.00274 22.230 22.215 0.0156 0 1 2 3.94830 3.94954 -0.00124 22.500 22.493 0.0077 2 0 -2 3.77933 3.77991 -0.00058 23.520 23.516 0.0048 1 1 -2 3.66570 3.66450 0.00120 24.260 24.268 -0.0089 2 1 0 3.55185 3.55241 -0.00056 25.050 25.046 0.004

10 2 1 -1 3.41515 3.41356 0.00159 26.070 26.082 -0.01211 2 1 1 3.39723 3.39884 -0.00162 26.210 26.197 0.01312 3 0 1 3.10049 3.09920 0.00129 28.770 28.782 -0.01213 2 1 -2 3.06711 3.06718 -0.00007 29.090 29.089 0.00114 0 0 4 3.00055 2.99879 0.00176 29.750 29.768 -0.01815 3 1 0 2.74281 2.74297 -0.00016 32.620 32.618 0.00216 3 1 1 2.66888 2.66863 0.00025 33.550 33.553 -0.00317 2 1 3 2.64666 2.64527 0.00140 33.840 33.858 -0.01818 1 2 0 2.53214 2.53216 -0.00002 35.420 35.420 0.00019 3 1 2 2.48466 2.48584 -0.00119 36.120 36.102 0.01820 0 2 2 2.40437 2.40404 0.00032 37.370 37.375 -0.005

ESI: Тable 6 Experimentally observed (obs) and calculated (calc) values of interplanar distances d (Å), diffraction angles 2CuKα () and their deviations (Δ), as well as hkl indices of corresponding diffraction maximums of L-isoleucine (room temperature). Calculated unit cell parameters (S.G. P21): a = 9.686(9) Å, b = 5.310(4) Å, c = 14.017(8) Å, β = 95.65(9)°, V = 717.5(7) Å3.

No hkl d, Å (obs) d, Å (calc) Δd, Å 2θ, ° (obs) 2θ, ° (calc) Δ2θ, °

1 0 0 1 13.95133 13.94856 0.00277 6.330 6.331 -0.0012 0 0 2 6.96987 6.97428 -0.00441 12.690 12.682 0.0083 2 0 0 4.81780 4.81960 -0.00180 18.400 18.393 0.0074 1 1 0 4.64760 4.65117 -0.00357 19.080 19.065 0.0155 1 1 -1 4.47571 4.47664 -0.00093 19.820 19.816 0.0046 2 0 1 4.42270 4.42284 -0.00013 20.060 20.059 0.0017 1 0 -3 4.35186 4.35919 -0.00733 20.390 20.355 0.0358 1 1 1 4.35186 4.35071 0.00116 20.390 20.395 -0.0059 0 1 2 4.22681 4.22497 0.00184 21.000 21.009 -0.009

10 1 1 2 3.79045 3.78738 0.00307 23.450 23.469 -0.01911 2 0 -3 3.52692 3.52417 0.00275 25.230 25.250 -0.02012 0 0 4 3.48750 3.48714 0.00036 25.520 25.523 -0.00313 0 0 5 2.78943 2.78971 -0.00028 32.060 32.057 0.00314 3 1 -1 2.74118 2.74132 -0.00015 32.640 32.638 0.00215 2 0 -5 2.52524 2.52464 0.00059 35.520 35.529 -0.00916 2 2 0 2.32532 2.32558 -0.00026 38.690 38.685 0.005

ESI: Тable 7 Experimentally observed (obs) and calculated (calc) values of interplanar distances d (Å), diffraction angles 2CuKα () and their deviations (Δ), as well as hkl indices of corresponding diffraction maximums of non-equimolar discrete compound V2I formed in the system L-valineL-isoleucine (room temperature). Calculated unit cell parameters (S.G. C2): a = 25.86(13) Å, b = 5.27(2) Å, c = 9.64(3) Å, β = 96.7(4)°, V = 1305(7) Å3.

No hkl d, Å (obs) d, Å (calc) Δd, Å 2θ,° (obs) 2θ,° (calc) Δ2θ, °

1 2 0 0 12.76310 12.84208 -0.07898 6.920 6.877 0.0432 4 0 0 6.41627 6.42104 -0.00477 13.790 13.780 0.0103 0 0 2 4.78429 4.78858 -0.00429 18.530 18.513 0.0174 1 1 -1 4.59984 4.59068 0.00915 19.280 19.319 -0.0395 1 1 1 4.49142 4.50123 -0.00981 19.750 19.707 0.0436 3 1 0 4.49142 4.48887 0.00255 19.750 19.761 -0.0117 3 1 -1 4.16989 4.16401 0.00587 21.290 21.320 -0.0308 3 1 1 3.96920 3.97190 -0.00270 22.380 22.365 0.0159 4 0 2 3.64645 3.63978 0.00668 24.390 24.435 -0.045

10 1 1 -2 3.55325 3.55321 0.00004 25.040 25.040 -0.00011 1 1 2 3.46878 3.47072 -0.00194 25.660 25.645 0.01512 3 1 2 3.17731 3.17898 -0.00167 28.060 28.045 0.015