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The crystal structure of a new crystalline phase, polymorph (II) of isobutyl-6-amino-5-cyano-2-methyl-4-phenyl-4H-pyran-3-carboxylate, was accurately determined by single-crystal X-ray diffraction analysis providing a clean identification of polymorphic forms. Comparison with a known phase, referred to as polymorph (I), reveals the type of supramolecular assembly. Inter- and intramolecular hydrogen-bonding interactions exhibit various supramolecular architectures in crystal packing and these variations confirm well the polymorphism in isobutyl-6-amino-5-cyano-2-methyl-4-phenyl-4H-pyran-3-carboxylate (IAPC) crystal structure. Crystal cohesion is achieved by N—H...N, N—H...O and C—H...H—C interactions, responsible for the formation and strengthening of the supramolecular assembly. The objective of this investigation is to study crystalline forms which can offer enhanced physicochemical properties, and also to recognize the molecular orientations between such forms. The conformational polymorphs of IAPC were compared spectroscopically by FT–IR and FT–Raman. The bulk phases were studied by X-ray powder diffraction patterns. External morphology was investigated using scanning electron microscopic images. The molecular interactions were quantified using Hirshfeld surface and fingerprint analysis. Density functional theory (DFT) computations were used to optimize the structure. The optimized structure is further subjected to an analysis of Mulliken population, natural population and electrostatic potential.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2052520616003310/ao5008sup1.cif
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520616003310/ao5008Isup2.hkl
Contains datablock I

CCDC reference: 1415778

Computing details top

Program(s) used to solve structure: olex2.solve (Bourhis et al., 2015); program(s) used to refine structure: olex2.refine (Bourhis et al., 2015); molecular graphics: Olex2 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).

(I) top
Crystal data top
C18H20N2O3V = 1681.3 (6) Å3
Mr = 312.37Z = 4
Triclinic, P1F(000) = 664.3291
a = 8.476 (2) ÅDx = 1.234 Mg m3
b = 9.923 (2) ÅMo Kα radiation, λ = 0.71073 Å
c = 20.882 (4) ŵ = 0.09 mm1
α = 92.500 (3)°T = 298 K
β = 93.048 (3)°Irregular, metallic light yellow
γ = 106.171 (3)°0.3 × 0.3 × 0.25 mm
Data collection top
Bruker SMART APEX2 area detector
diffractometer
4642 reflections with I 2u(I)
Mirror optics monochromatorRint = 0.020
Detector resolution: 7.9 pixels mm-1θmax = 25.1°, θmin = 2.0°
ω and φ scansh = 1010
16201 measured reflectionsk = 1111
5928 independent reflectionsl = 2424
Refinement top
Refinement on F254 constraints
Least-squares matrix: fullPrimary atom site location: iterative
R[F2 > 2σ(F2)] = 0.051H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.153 w = 1/[σ2(Fo2) + (0.0857P)2 + 0.2381P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.002
5928 reflectionsΔρmax = 0.27 e Å3
450 parametersΔρmin = 0.20 e Å3
0 restraints
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.22832 (13)0.04944 (12)0.41244 (6)0.0598 (3)
O40.23466 (13)0.46130 (11)0.08914 (5)0.0550 (3)
O60.74684 (13)0.65187 (12)0.11778 (6)0.0633 (3)
O30.28717 (15)0.12147 (13)0.37996 (7)0.0690 (4)
O50.78504 (14)0.46669 (13)0.06377 (7)0.0675 (4)
N30.01605 (17)0.28742 (19)0.05364 (8)0.0598 (4)
C320.69416 (19)0.52614 (16)0.08693 (8)0.0499 (4)
C260.51356 (18)0.46122 (16)0.08494 (7)0.0477 (4)
C100.2885 (2)0.18631 (18)0.43473 (8)0.0555 (4)
O20.31207 (16)0.06117 (15)0.43901 (8)0.0865 (5)
C290.17958 (18)0.32637 (16)0.06310 (7)0.0483 (4)
C120.2270 (2)0.00064 (18)0.41258 (8)0.0544 (4)
N10.4517 (2)0.2204 (2)0.44599 (9)0.0738 (5)
C270.40173 (19)0.53128 (16)0.09205 (7)0.0502 (4)
C90.0598 (2)0.01534 (17)0.41103 (7)0.0523 (4)
C80.04693 (19)0.06146 (16)0.41239 (7)0.0499 (4)
C280.28590 (19)0.25141 (16)0.05089 (7)0.0496 (4)
N40.1920 (2)0.00941 (18)0.00895 (9)0.0815 (5)
C70.01004 (19)0.22009 (17)0.41534 (8)0.0506 (4)
C10.01373 (18)0.27654 (16)0.35009 (8)0.0507 (4)
C170.0321 (2)0.16961 (18)0.40864 (9)0.0647 (5)
H17a0.0484 (16)0.2022 (3)0.36621 (19)0.0970 (7)*
H17b0.1085 (11)0.1923 (2)0.4390 (5)0.0970 (7)*
H17c0.0784 (6)0.2144 (2)0.4192 (6)0.0970 (7)*
C330.9242 (2)0.71603 (19)0.12238 (9)0.0627 (5)
H33a0.9799 (2)0.65275 (19)0.14138 (9)0.0753 (6)*
H33b0.9629 (2)0.73520 (19)0.07991 (9)0.0753 (6)*
C60.0504 (2)0.22972 (19)0.29653 (9)0.0631 (5)
H60.1079 (2)0.16290 (19)0.30079 (9)0.0757 (5)*
C250.46600 (18)0.30330 (16)0.07443 (8)0.0490 (4)
H250.53085 (18)0.27996 (16)0.04035 (8)0.0588 (5)*
C300.23041 (19)0.11719 (18)0.01833 (8)0.0572 (4)
C110.1870 (2)0.26846 (18)0.44191 (8)0.0546 (4)
C240.4608 (2)0.27145 (19)0.19355 (9)0.0656 (5)
H240.4097 (2)0.34279 (19)0.19744 (9)0.0787 (6)*
C310.4211 (2)0.68381 (18)0.10370 (10)0.0698 (5)
H31a0.3363 (11)0.7092 (3)0.0789 (5)0.1047 (8)*
H31b0.4126 (17)0.7044 (3)0.14852 (15)0.1047 (8)*
H31c0.5270 (7)0.73645 (19)0.0912 (6)0.1047 (8)*
C340.9607 (2)0.84938 (18)0.16312 (9)0.0632 (5)
H340.9065 (2)0.91236 (18)0.14190 (9)0.0758 (6)*
C50.0308 (3)0.2802 (2)0.23722 (9)0.0743 (5)
H50.0742 (3)0.2470 (2)0.20185 (9)0.0892 (7)*
C190.50383 (18)0.23319 (16)0.13393 (9)0.0538 (4)
C130.4643 (2)0.1817 (2)0.37641 (10)0.0725 (5)
H13a0.4991 (2)0.2190 (2)0.41716 (10)0.0871 (6)*
H13b0.5189 (2)0.1104 (2)0.36680 (10)0.0871 (6)*
C180.2497 (2)0.4060 (2)0.47083 (10)0.0668 (5)
N20.2972 (2)0.5162 (2)0.49528 (11)0.1001 (7)
C230.4931 (3)0.2045 (2)0.24769 (11)0.0893 (7)
H230.4637 (3)0.2308 (2)0.28765 (11)0.1071 (9)*
C20.0972 (2)0.37666 (19)0.34204 (10)0.0670 (5)
H20.1415 (2)0.41036 (19)0.37702 (10)0.0804 (6)*
C30.1150 (3)0.4270 (2)0.28204 (12)0.0819 (6)
H30.1707 (3)0.4949 (2)0.27720 (12)0.0983 (8)*
C140.5085 (3)0.2970 (2)0.32439 (12)0.0908 (7)
H140.4605 (3)0.2579 (2)0.28520 (12)0.1089 (9)*
C220.5684 (3)0.0995 (3)0.24180 (17)0.1070 (10)
H220.5914 (3)0.0549 (3)0.27794 (17)0.1284 (12)*
C40.0521 (3)0.3786 (2)0.23015 (11)0.0782 (6)
H40.0656 (3)0.4126 (2)0.19002 (11)0.0939 (7)*
C350.8988 (3)0.8276 (3)0.22828 (10)0.0902 (7)
H35a0.7827 (5)0.7818 (16)0.22448 (10)0.1353 (10)*
H35b0.9548 (15)0.7702 (15)0.2508 (3)0.1353 (10)*
H35c0.9190 (19)0.9170 (3)0.2517 (3)0.1353 (10)*
C361.1457 (3)0.9180 (2)0.16670 (13)0.0954 (8)
H36a1.2011 (3)0.8590 (10)0.1884 (8)0.1431 (12)*
H36b1.1821 (5)0.9304 (18)0.12403 (13)0.1431 (12)*
H36c1.1707 (4)1.0079 (9)0.1899 (8)0.1431 (12)*
C200.5789 (2)0.12639 (19)0.12952 (12)0.0788 (6)
H200.6089 (2)0.09900 (19)0.08988 (12)0.0945 (7)*
C210.6096 (3)0.0604 (3)0.18341 (19)0.1081 (10)
H210.6592 (3)0.0120 (3)0.17975 (19)0.1298 (12)*
C150.4395 (5)0.4144 (4)0.3403 (3)0.1515 (19)
H15a0.507 (6)0.442 (5)0.373 (2)0.227 (3)*
H15b0.473 (6)0.483 (5)0.311 (2)0.227 (3)*
C160.6912 (3)0.3463 (4)0.31132 (17)0.1325 (12)
H16a0.7413 (4)0.386 (3)0.3490 (5)0.1987 (18)*
H16b0.7313 (5)0.2683 (7)0.3003 (13)0.1987 (18)*
H16c0.7184 (4)0.417 (2)0.2763 (9)0.1987 (18)*
H3a0.034 (2)0.201 (2)0.0423 (9)0.061 (5)*
H3b0.035 (2)0.3532 (19)0.0557 (8)0.055 (5)*
H1a0.508 (3)0.305 (2)0.4590 (10)0.079 (7)*
H1b0.500 (2)0.153 (2)0.4441 (9)0.063 (5)*
H15c0.325 (5)0.376 (4)0.3509 (18)0.189 (16)*
H70.052 (2)0.2553 (17)0.4433 (8)0.055 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0443 (6)0.0604 (7)0.0735 (8)0.0159 (5)0.0026 (5)0.0084 (6)
O40.0424 (6)0.0519 (6)0.0676 (7)0.0112 (5)0.0010 (5)0.0142 (5)
O60.0419 (6)0.0579 (7)0.0800 (8)0.0009 (5)0.0020 (5)0.0183 (6)
O30.0479 (7)0.0634 (8)0.0870 (9)0.0056 (6)0.0007 (6)0.0176 (6)
O50.0445 (7)0.0594 (7)0.0956 (9)0.0115 (5)0.0084 (6)0.0108 (6)
N30.0418 (8)0.0564 (9)0.0774 (10)0.0118 (7)0.0035 (7)0.0138 (8)
C320.0432 (9)0.0477 (9)0.0548 (9)0.0074 (7)0.0011 (7)0.0012 (7)
C260.0435 (8)0.0461 (8)0.0492 (8)0.0070 (7)0.0010 (6)0.0057 (7)
C100.0472 (9)0.0619 (10)0.0540 (9)0.0125 (8)0.0035 (7)0.0060 (8)
O20.0484 (7)0.0755 (9)0.1296 (13)0.0117 (6)0.0111 (7)0.0275 (8)
C290.0433 (8)0.0499 (9)0.0474 (8)0.0085 (7)0.0014 (6)0.0077 (7)
C120.0481 (9)0.0540 (9)0.0595 (10)0.0127 (8)0.0013 (7)0.0003 (8)
N10.0455 (9)0.0712 (11)0.1014 (13)0.0166 (9)0.0110 (8)0.0130 (10)
C270.0443 (9)0.0477 (9)0.0542 (9)0.0080 (7)0.0006 (7)0.0071 (7)
C90.0480 (9)0.0578 (10)0.0486 (9)0.0126 (7)0.0008 (7)0.0022 (7)
C80.0455 (9)0.0533 (9)0.0482 (8)0.0109 (7)0.0006 (6)0.0022 (7)
C280.0426 (8)0.0476 (8)0.0541 (9)0.0083 (7)0.0032 (6)0.0099 (7)
N40.0583 (9)0.0670 (10)0.1098 (13)0.0110 (8)0.0072 (9)0.0391 (10)
C70.0412 (8)0.0532 (9)0.0557 (9)0.0128 (7)0.0015 (7)0.0097 (7)
C10.0384 (8)0.0442 (8)0.0642 (10)0.0052 (6)0.0037 (7)0.0039 (7)
C170.0646 (11)0.0588 (10)0.0711 (12)0.0202 (8)0.0037 (9)0.0002 (8)
C330.0417 (9)0.0643 (11)0.0719 (11)0.0007 (8)0.0046 (8)0.0060 (9)
C60.0674 (11)0.0612 (10)0.0631 (11)0.0235 (9)0.0001 (8)0.0003 (8)
C250.0373 (8)0.0473 (8)0.0590 (9)0.0087 (6)0.0018 (6)0.0123 (7)
C300.0405 (8)0.0579 (10)0.0690 (11)0.0112 (7)0.0048 (7)0.0148 (8)
C110.0451 (9)0.0593 (10)0.0546 (9)0.0100 (7)0.0034 (7)0.0096 (7)
C240.0614 (11)0.0562 (10)0.0711 (12)0.0063 (8)0.0093 (9)0.0014 (9)
C310.0612 (11)0.0501 (10)0.0964 (14)0.0158 (8)0.0011 (10)0.0104 (9)
C340.0535 (10)0.0538 (10)0.0744 (11)0.0042 (8)0.0024 (8)0.0012 (8)
C50.0828 (14)0.0762 (13)0.0611 (11)0.0182 (11)0.0013 (10)0.0058 (10)
C190.0359 (8)0.0421 (8)0.0763 (11)0.0029 (6)0.0080 (7)0.0047 (7)
C130.0469 (10)0.0686 (12)0.0936 (14)0.0051 (8)0.0021 (9)0.0062 (10)
C180.0461 (9)0.0722 (12)0.0762 (12)0.0122 (9)0.0067 (8)0.0181 (10)
N20.0687 (11)0.0840 (13)0.1336 (17)0.0103 (10)0.0144 (11)0.0466 (12)
C230.0855 (15)0.0784 (14)0.0819 (15)0.0101 (12)0.0187 (12)0.0128 (12)
C20.0553 (10)0.0580 (10)0.0901 (14)0.0204 (8)0.0044 (9)0.0030 (9)
C30.0690 (13)0.0664 (12)0.1152 (18)0.0260 (10)0.0027 (12)0.0230 (12)
C140.0627 (13)0.0856 (15)0.1069 (18)0.0022 (11)0.0021 (11)0.0236 (13)
C220.0895 (18)0.0728 (16)0.137 (2)0.0072 (13)0.0464 (17)0.0365 (16)
C40.0704 (13)0.0756 (13)0.0814 (14)0.0083 (10)0.0072 (10)0.0217 (11)
C350.0879 (15)0.0946 (16)0.0765 (14)0.0096 (12)0.0029 (11)0.0129 (12)
C360.0643 (13)0.0711 (13)0.129 (2)0.0124 (11)0.0035 (12)0.0197 (13)
C200.0547 (11)0.0557 (11)0.1248 (18)0.0176 (9)0.0081 (11)0.0034 (11)
C210.0765 (16)0.0639 (14)0.181 (3)0.0205 (12)0.0353 (18)0.0213 (18)
C150.093 (2)0.087 (2)0.266 (6)0.0235 (18)0.000 (3)0.053 (3)
C160.0742 (16)0.139 (3)0.158 (3)0.0026 (16)0.0126 (16)0.046 (2)
Geometric parameters (Å, º) top
O1—C101.362 (2)C11—C181.414 (2)
O1—C91.3919 (19)C24—H240.9300
O4—C291.3666 (18)C24—C191.383 (3)
O4—C271.3895 (18)C24—C231.388 (3)
O6—C321.3266 (19)C31—H31a0.9600
O6—C331.4566 (19)C31—H31b0.9600
O3—C121.319 (2)C31—H31c0.9600
O3—C131.450 (2)C34—H340.9800
O5—C321.2013 (19)C34—C351.487 (3)
N3—C291.332 (2)C34—C361.522 (3)
N3—H3a0.859 (19)C5—H50.9300
N3—H3b0.878 (19)C5—C41.361 (3)
C32—C261.484 (2)C19—C201.382 (2)
C26—C271.333 (2)C13—H13a0.9700
C26—C251.508 (2)C13—H13b0.9700
C10—N11.335 (2)C13—C141.496 (3)
C10—C111.349 (2)C18—N21.141 (2)
O2—C121.200 (2)C23—H230.9300
C29—C281.346 (2)C23—C221.370 (4)
C12—C81.477 (2)C2—H20.9300
N1—H1a0.86 (2)C2—C31.385 (3)
N1—H1b0.88 (2)C3—H30.9300
C27—C311.484 (2)C3—C41.359 (3)
C9—C81.336 (2)C14—H140.9800
C9—C171.481 (2)C14—C151.485 (5)
C8—C71.510 (2)C14—C161.495 (3)
C28—C251.516 (2)C22—H220.9300
C28—C301.413 (2)C22—C211.356 (4)
N4—C301.143 (2)C4—H40.9300
C7—C11.520 (2)C35—H35a0.9600
C7—C111.508 (2)C35—H35b0.9600
C7—H70.926 (17)C35—H35c0.9600
C1—C61.387 (2)C36—H36a0.9600
C1—C21.381 (2)C36—H36b0.9600
C17—H17a0.9600C36—H36c0.9600
C17—H17b0.9600C20—H200.9300
C17—H17c0.9600C20—C211.375 (4)
C33—H33a0.9700C21—H210.9300
C33—H33b0.9700C15—H15a0.91 (5)
C33—C341.489 (2)C15—H15b0.87 (4)
C6—H60.9300C15—H15c0.95 (4)
C6—C51.375 (3)C16—H16a0.9600
C25—H250.9800C16—H16b0.9600
C25—C191.513 (2)C16—H16c0.9600
C9—O1—C10119.46 (12)H31b—C31—C27109.5
C27—O4—C29119.78 (12)H31b—C31—H31a109.5
C33—O6—C32116.06 (13)H31c—C31—C27109.5
C13—O3—C12117.09 (14)H31c—C31—H31a109.5
H3a—N3—C29118.8 (12)H31c—C31—H31b109.5
H3b—N3—C29117.9 (11)H34—C34—C33108.13 (11)
H3b—N3—H3a123.0 (17)C35—C34—C33112.66 (16)
O5—C32—O6123.09 (14)C35—C34—H34108.13 (13)
C26—C32—O6114.88 (13)C36—C34—C33108.27 (16)
C26—C32—O5122.00 (14)C36—C34—H34108.13 (12)
C27—C26—C32125.15 (14)C36—C34—C35111.36 (18)
C25—C26—C32112.81 (13)H5—C5—C6119.91 (12)
C25—C26—C27122.04 (13)C4—C5—C6120.2 (2)
N1—C10—O1110.65 (16)C4—C5—H5119.91 (13)
C11—C10—O1120.76 (14)C24—C19—C25121.14 (15)
C11—C10—N1128.58 (17)C20—C19—C25120.44 (18)
N3—C29—O4110.55 (14)C20—C19—C24118.40 (19)
C28—C29—O4120.74 (13)H13a—C13—O3110.13 (10)
C28—C29—N3128.70 (15)H13b—C13—O3110.13 (10)
O2—C12—O3122.87 (15)H13b—C13—H13a108.4
C8—C12—O3115.31 (14)C14—C13—O3107.87 (16)
C8—C12—O2121.78 (15)C14—C13—H13a110.13 (13)
H1a—N1—C10121.2 (15)C14—C13—H13b110.13 (13)
H1b—N1—C10118.3 (12)N2—C18—C11178.2 (2)
H1b—N1—H1a120.1 (19)H23—C23—C24120.25 (15)
C26—C27—O4121.07 (13)C22—C23—C24119.5 (3)
C31—C27—O4108.07 (13)C22—C23—H23120.25 (18)
C31—C27—C26130.86 (15)H2—C2—C1119.87 (11)
C8—C9—O1120.55 (15)C3—C2—C1120.25 (19)
C17—C9—O1108.71 (14)C3—C2—H2119.87 (13)
C17—C9—C8130.73 (15)H3—C3—C2119.56 (13)
C9—C8—C12123.74 (15)C4—C3—C2120.88 (19)
C7—C8—C12114.65 (13)C4—C3—H3119.56 (12)
C7—C8—C9121.60 (14)H14—C14—C13107.82 (13)
C25—C28—C29121.74 (13)C15—C14—C13111.7 (3)
C30—C28—C29120.54 (14)C15—C14—H14107.8 (2)
C30—C28—C25117.63 (13)C16—C14—C13109.9 (2)
C1—C7—C8111.50 (13)C16—C14—H14107.82 (18)
C11—C7—C8108.79 (13)C16—C14—C15111.7 (2)
C11—C7—C1112.21 (13)H22—C22—C23119.92 (18)
H7—C7—C8109.3 (10)C21—C22—C23120.2 (2)
H7—C7—C1107.2 (10)C21—C22—H22119.92 (16)
H7—C7—C11107.8 (10)C3—C4—C5119.7 (2)
C6—C1—C7120.52 (14)H4—C4—C5120.16 (13)
C2—C1—C7121.73 (16)H4—C4—C3120.16 (12)
C2—C1—C6117.75 (17)H35a—C35—C34109.5
H17a—C17—C9109.5H35b—C35—C34109.5
H17b—C17—C9109.5H35b—C35—H35a109.5
H17b—C17—H17a109.5H35c—C35—C34109.5
H17c—C17—C9109.5H35c—C35—H35a109.5
H17c—C17—H17a109.5H35c—C35—H35b109.5
H17c—C17—H17b109.5H36a—C36—C34109.5
H33a—C33—O6110.04 (9)H36b—C36—C34109.5
H33b—C33—O6110.04 (9)H36b—C36—H36a109.5
H33b—C33—H33a108.4H36c—C36—C34109.5
C34—C33—O6108.30 (14)H36c—C36—H36a109.5
C34—C33—H33a110.04 (11)H36c—C36—H36b109.5
C34—C33—H33b110.04 (10)H20—C20—C19119.80 (13)
H6—C6—C1119.37 (10)C21—C20—C19120.4 (2)
C5—C6—C1121.26 (18)C21—C20—H20119.80 (18)
C5—C6—H6119.37 (12)C20—C21—C22120.8 (2)
C28—C25—C26108.86 (13)H21—C21—C22119.59 (16)
H25—C25—C26107.79 (8)H21—C21—C20119.59 (18)
H25—C25—C28107.79 (8)H15a—C15—C1494 (3)
C19—C25—C26112.11 (12)H15b—C15—C14110 (3)
C19—C25—C28112.29 (13)H15b—C15—H15a103 (4)
C19—C25—H25107.79 (9)H15c—C15—C14108 (2)
N4—C30—C28177.11 (18)H15c—C15—H15a118 (4)
C7—C11—C10121.08 (14)H15c—C15—H15b119 (4)
C18—C11—C10119.69 (15)H16a—C16—C14109.5
C18—C11—C7119.09 (15)H16b—C16—C14109.5
C19—C24—H24119.64 (11)H16b—C16—H16a109.5
C23—C24—H24119.64 (15)H16c—C16—C14109.5
C23—C24—C19120.7 (2)H16c—C16—H16a109.5
H31a—C31—C27109.5H16c—C16—H16b109.5
 

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