Supporting Information. Crystalline Polymorph Selection and Discovery with Polymer Heteronuclei

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1 Supporting Information Crystalline Polymorph Selection and Discovery with Polymer Heteronuclei Christopher P. Price, Adam L. Grzesiak and Adam J. Matzger* Department of Chemistry and the Macromolecular Science and Engineering Program, The University of Michigan, Ann Arbor, Michigan Page S2. Table 1. Composition of library A. Page S3. Page S4. Page S5. Page S6. Page S7. Figure 1. Results from acetaminophen crystallizations from libraries BE. Figures 2 and 3. Raman spectra for ROY polymorphs. Figure 4 and Table 2. Raman spectra for sulfamethoxazole polymorphs. Figure 5. Powder X-ray diffraction data for sulfamethoxazole polymorphs. Table 3. Sulfamethoxazole polymorph distribution in the absence and presence of library A. S1

2 Table 1. Composition of Polymer Library A (from Scientific Polymer Products, Inc.). acrylonitrile/butadiene/styrene resin alginic acid, sodium salt butyl methacrylate/isobutyl methacrylate, 50/50 copolymer cellulose acetate cellulose acetate butyrate cellulose propionate cellulose triacetate ethyl cellulose ethylene/acrylic acid, 85/15 coplymer ethylene/ethyl acrylate, 82/18 copolymer ethylene/propylene, 60/40 copolymer ethylene/vinyl acetate, 86/14 copolymer ethylene/vinyl acetate, 82/18 copolymer ethylene/vinyl acetate, 75/25 copolymer ethylene/vinyl acetate, 72/28 copolymer ethylene/vinyl acetate, 67/33 copolymer ethylene/vinyl acetate, 60/40 copolymer hyroxybutyl methyl cellulose, 3.5% hydroxybutyl, 30% methoxyl hydroxypropyl cellulose hydroxypropyl methyl cellulose, 10% hydroxypropyl, 30% methoxyl methyl cellulose methyl vinyl ether/ maleic acid, 50/50 copolymer methyl vinyl ether/maleic anhydride, 50/50 copolymer Nylon 6 (polycaprolactam) Nylon 6/6 [poly(hexamethylene adipamide)] Nylon 6/9 [poly(hexamethylene nonanediamide)] Nylon 6/10 [poly(hexamethylene sebacamide)] Nylon 6/12 [poly(hexamethylene dodecanediamide)] Nylon 6/T [poly(trimethyl hexamethylene terephthalamide)] Nylon 11 (polyundecanoamide) Nylon 12 (polyauryllactam) phenoxy resin polyacetal polyacrylamide polyacrylamide, carboxyl modified (low content) polyacrylamide, carboxyl modified (high content) poly(acrylic acid) polyamide resin 1,2-polybutadiene poly(1-butene), isotactic poly(n-butyl methacrylate) polycaprolactone polycarbonate poly(diallyl isophthalate) poly(diallyl phthalate) poly(2,6-dimethyl-p-phenylene oxide) poly(4,4'-dipropoxy-2,2'-diphenyl propane fumarate) poly(ethyl methacrylate) polyethylene, high density polyethylene, chlorinated (25% Cl) polyethylene, chlorinated (36% Cl) polyethylene, chlorinated (42% Cl) polyethylene, chlorinated (48% Cl) polyethylene, chlorosulfonated poly(ethylene oxide) polyethylene, oxidized poly(ethylene terephthalate) poly(2-hydroxyethyl methacrylate) poly(isobutyl methacrylate) polyisoprene, chlorinated (65% Cl) poly(methyl methacrylate) poly(4-methyl-1-pentene) poly(α-methylstyrene) poly(p-phenylene ether sulphone) poly(phenylene sulfide) polypropylene, isotactic, chlorinated polypropylene, isotactic polystyrene polysulfone poly(tetrafluoroethylene) poly(2,4,6-tribromostyrene) poly(vinyl acetate) poly(vinyl alcohol), 99.7% hydrolyzed poly(vinyl alcohol), 98% hydrolyzed poly(vinyl butyral) poly(vinyl chloride) poly(vinyl chloride), carboxylated poly(vinyl formal) poly(vinyl pyrrolidone) poly(vinyl stearate) poly(vinylidene fluoride) styrene/acrylonitrile, 75/25 copolymer styrene/acrylonitrile, 68/32 copolymer styrene/allyl alcohol copolymer styrene/butadiene, ABA block copolymer (30% styrene) styrene/butyl methacrylate, 50/50 copolymer styrene/ethylene-butylene, ABA block copolymer (29% styrene) styrene/isoprene, ABA block copolymer (14% styrene) styrene/maleic anhydride, 50/50 copolymer vinyl alcohol/vinyl butyral, 20/80 copolymer vinyl chloride/ vinyl acetate, 90/10 copolymer vinyl chloride/ vinyl acetate, 88/12 copolymer vinyl chloride/ vinyl acetate, 90/10 copolymer vinyl chloride/ vinyl acetate, 86/13 copolymer, 1% carboxylated vinyl chloride/vinyl acetate/hydroxypropyl acrylate, 80/5/15 terpolymer vinyl chloride/vinyl acetate/vinyl alcohol, 91/3/6 terpolymer S2

3 Library B MMA n -BuMA t -BuMA BzMA EEMA STY MMA n -BuMA t -BuMA BzMA EEMA STY Library C DMMAA DMAEMA MAM MAN 2VP 4VP DMMAA DMAEMA MAM MAN 2VP 4VP Library D EGMAP MAA HEMA AOS MMA STY EGMAP MAA HEMA AOS MMA STY Library E EEMA STY DMAEMA n -BuMA MAM MAA EEMA STY DMAEMA n -BuMA MAM MAA Figure 1. The occurrence rate of acetaminophen polymorphs grown from polymer libraries B-E based on a composite of three trails. Red = 100 % orthorhombic, orange = % orthorhombic, yellow = % orthorhombic or monoclinic, green = % monoclinic, blue = 100 % monoclinic, and white = no crystals. Percentages do not reflect the amount of DVB used in each polymer (see Experimental) and the large rectangles indicate when a monomer is copolymerized with DVB alone. S3

4 Figure 2. Raman spectra of six polymorphs of ROY. Figure 3. Raman spectra of six polymorphs of ROY (peaks from left to right: red prism, orangered plate, yellow needles, orange needles, orange plate, yellow prism) showing the difference in the nitrile stretch ( cm -1 ). S4

5 Figure 4. Raman spectra of the four polymorphs of sulfamethoxazole. Table 2. Selected Characteristic Regions of Raman Shifts for the Four Polymorphs of SMA. Raman Shift (cm -1 ) form I form II form III form IV Five peaks at 243, 260, 292, 328, and 352 Five peaks at 247, 264, 294, 329, and 347 Four peaks at 243, 264, 294, and Seven peaks at 502, 545, 593, 616, 633, 689, and Four peaks at 1093, 1143, 1157, and Three peaks at 1593, 1618, and and 3468 Eight peaks at 506, 547, 582, 615, 632, 675, 694, and 727 Four peaks at 1094, 1136, 1160, and 1188 Three peaks at 1596, 1616, and and 3478 Seven peaks at 507, 545, 583, 615, 633, 675, and 691 Four peaks at 1095, 1136, 1155, and and and 3478 Four peaks at 232, 263, 296, and 325 Seven peaks at 503, 554, 575, 614, 633, 679, and 774 Four peaks at 1091, 1145, 1160, and 1191 Three peaks at 1596, 1603, and and 3484 S5

6 Figure 5. Powder X-ray diffraction patterns of the four polymorphs of sulfamethoxazole. Data were recorded at room temperature on a Bruker AXS D 8 Advance powder diffractometer equipped with a CuKα source (λ = Å). S6

7 Table 3. Sulfamethoxazole Polymorph Distribution in the Absence and Presence of Library A. ethyl acetate methanol 2-propanol absence presence absence presence absence presence form I form II form III form IV 95 % 5 % 77 % 20 % ~1 % ~3 % 27 % 73 % 22 % 78 % 91 % 9 % 50 % 50 % S7