Allyl 6-amino-5-cyano-2-methyl-4-phenyl-4H-pyran-3-carboxyl­ate

In the title compound, C₁₇H₁₆N₂O₃, the 4H-pyran ring adopts a boat conformation. In the crystal, N—H...N and N—H...O inter­actions link the mol­ecules, forming an infinite ribbon running along the a-axis direction with N—H...N inter­actions forming centrosymmetric R²₂(12) graph-set motifs. The allyl side chain is disordered over two sets of sites with occupancies of 0.720 (7) and 0.280 (7).

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• Disorder in main residue
• R factor = 0.052
• wR factor = 0.160
• Data-to-parameter ratio = 16.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT220_ALERT_2_C Non-Solvent  Resd 1  C   Ueq(max)/Ueq(min) Range        3.5 Ratio
PLAT905_ALERT_3_C Negative K value in the Analysis of Variance ...     -0.940 Report
PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L=    0.600          3 Report

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          6 Note
PLAT003_ALERT_2_G Number of Uiso or Uij Restrained non-H Atoms ...          6 Report
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          2 Report
PLAT175_ALERT_4_G The CIF-Embedded .res File Contains SAME Records          1 Report
PLAT177_ALERT_4_G The CIF-Embedded .res File Contains DELU Records          1 Report
PLAT178_ALERT_4_G The CIF-Embedded .res File Contains SIMU Records          1 Report
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT230_ALERT_2_G Hirshfeld Test Diff for    C11      --C12      .        5.1 s.u.
PLAT301_ALERT_3_G Main Residue  Disorder ..............(Resd  1  )        14% Note
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          2 Note
PLAT793_ALERT_4_G Model has Chirality at C7          (Centro SPGR)          S Verify
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............         79 Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          1 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         12 Note
PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ...          3 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          3 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   3 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  17 ALERT level G = General information/check it is not something unexpected

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   6 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
   7 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: APEX2 (Bruker, 2008); cell refinement: APEX2 and SAINT (Bruker, 2008); data reduction: SAINT and XPREP (Bruker, 2008); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Allyl 6-amino-5-cyano-2-methyl-4-phenyl-4H-pyran-3-carboxylate

Crystal data

C17H16N2O3	Z = 2
Mr = 296.32	F(000) = 312
Triclinic, P1	Dx = 1.285 Mg m^−3
a = 8.2151 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.2850 (5) Å	Cell parameters from 4207 reflections
c = 11.6086 (7) Å	θ = 2.5–23.4°
α = 108.184 (4)°	µ = 0.09 mm^−1
β = 103.004 (4)°	T = 293 K
γ = 105.089 (2)°	BLOCK, orange
V = 765.64 (8) Å^3	0.20 × 0.20 × 0.15 mm

Data collection

Bruker Kappa APEXII CCD diffractometer	2207 reflections with I > 2σ(I)
ω and φ scan	Rint = 0.053
Absorption correction: multi-scan (SADABS; Bruker, 2008)	θmax = 28.3°, θmin = 2.5°
Tmin = 0.956, Tmax = 0.960	h = −10→10
3789 measured reflections	k = −12→12
3789 independent reflections	l = −15→15

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.052	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.160	w = 1/[σ^2(Fo^2) + (0.071P)^2 + 0.1156P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
3789 reflections	Δρmax = 0.21 e Å^−3
237 parameters	Δρmin = −0.28 e Å^−3
79 restraints	Extinction correction: SHELXL-2018/3 (Sheldrick 2018), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.028 (6)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. The positions of the hydrogen atoms bound to the O and C atoms are identified from the difference electron density maps and their distances are geometrically optimized. The hydrogen atoms bound to the C atoms are treated as riding atoms, with d(C—H) = 0.93 Å and U_iso(H) = 1.2U_eq(C) for aromatic, d(C—H) = 0.97 Å and U_iso(H) = 1.2U_eq(C) for methylene and d(C—H) = 0.96 Å and U_iso(H) = 1.5U_eq(C) for methyl groups. The amine protons were refined isotropically.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.13227 (16)	0.88787 (15)	0.32279 (13)	0.0513 (4)
O2	0.72395 (18)	0.92452 (18)	0.36162 (17)	0.0742 (5)
O3	0.62148 (18)	1.06948 (19)	0.26548 (15)	0.0728 (5)
N1	−0.0492 (2)	0.7331 (2)	0.38698 (18)	0.0580 (5)
H1N1	−0.080 (3)	0.663 (3)	0.4157 (19)	0.057 (6)*
H1N2	−0.109 (3)	0.797 (3)	0.376 (2)	0.068 (6)*
N2	0.1936 (2)	0.4855 (2)	0.48236 (19)	0.0700 (6)
C1	0.3644 (2)	0.5954 (2)	0.21556 (18)	0.0474 (4)
C2	0.4475 (3)	0.4852 (3)	0.2186 (2)	0.0693 (6)
H2A	0.523004	0.495812	0.296026	0.083*
C3	0.4174 (4)	0.3571 (3)	0.1044 (3)	0.0938 (9)
H3A	0.472222	0.281595	0.106231	0.113*
C4	0.3083 (5)	0.3415 (3)	−0.0102 (3)	0.0942 (9)
H4A	0.290072	0.256420	−0.085936	0.113*
C5	0.2271 (4)	0.4499 (3)	−0.0129 (2)	0.0881 (8)
H5A	0.152576	0.439516	−0.090676	0.106*
C6	0.2543 (3)	0.5753 (3)	0.0988 (2)	0.0700 (6)
H6A	0.196780	0.648748	0.095559	0.084*
C7	0.3897 (2)	0.7335 (2)	0.33875 (16)	0.0424 (4)
H7A	0.494936	0.744799	0.405599	0.051*
C8	0.4222 (2)	0.8932 (2)	0.32389 (16)	0.0421 (4)
C9	0.2989 (2)	0.9618 (2)	0.31696 (17)	0.0454 (4)
C10	0.1074 (2)	0.7670 (2)	0.36705 (16)	0.0437 (4)
C11	0.2308 (2)	0.6973 (2)	0.38400 (16)	0.0426 (4)
C12	0.2067 (2)	0.5791 (2)	0.43693 (18)	0.0488 (4)
C13	0.3033 (3)	1.1169 (3)	0.3039 (2)	0.0652 (6)
H13A	0.425021	1.184266	0.324493	0.098*
H13B	0.251375	1.171848	0.361704	0.098*
H13C	0.236508	1.094610	0.217107	0.098*
C14	0.6031 (2)	0.9636 (2)	0.31985 (18)	0.0484 (4)
C15A	0.814 (5)	1.136 (3)	0.2707 (18)	0.084 (3)	0.280 (7)
H15A	0.885611	1.222435	0.354245	0.101*	0.280 (7)
H15B	0.864085	1.051113	0.257234	0.101*	0.280 (7)
C16A	0.8150 (18)	1.1965 (15)	0.1739 (11)	0.098 (3)	0.280 (7)
H16A	0.885497	1.304306	0.198254	0.117*	0.280 (7)
C17A	0.728 (2)	1.1155 (18)	0.0576 (11)	0.149 (5)	0.280 (7)
H17A	0.656193	1.007380	0.029871	0.179*	0.280 (7)
H17B	0.734994	1.163255	−0.001548	0.179*	0.280 (7)
C15B	0.7942 (19)	1.1526 (13)	0.2641 (6)	0.093 (2)	0.720 (7)
H15C	0.824470	1.268629	0.307193	0.111*	0.720 (7)
H15D	0.882796	1.122081	0.311836	0.111*	0.720 (7)
C16B	0.8014 (7)	1.1178 (6)	0.1398 (4)	0.1014 (17)	0.720 (7)
H16B	0.721066	1.016544	0.079943	0.122*	0.720 (7)
C17B	0.8942 (6)	1.1959 (7)	0.0949 (5)	0.1199 (19)	0.720 (7)
H17C	0.978344	1.298620	0.147859	0.144*	0.720 (7)
H17D	0.880257	1.152447	0.007964	0.144*	0.720 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0444 (7)	0.0617 (8)	0.0695 (9)	0.0266 (6)	0.0260 (6)	0.0421 (7)
O2	0.0458 (8)	0.0656 (9)	0.1176 (13)	0.0250 (7)	0.0311 (8)	0.0375 (9)
O3	0.0517 (8)	0.0913 (11)	0.0830 (10)	0.0102 (7)	0.0273 (7)	0.0531 (9)
N1	0.0509 (10)	0.0682 (12)	0.0831 (13)	0.0301 (9)	0.0369 (9)	0.0483 (10)
N2	0.0740 (12)	0.0741 (12)	0.0988 (15)	0.0377 (10)	0.0476 (11)	0.0585 (12)
C1	0.0468 (10)	0.0454 (10)	0.0596 (11)	0.0179 (8)	0.0293 (9)	0.0237 (9)
C2	0.0816 (15)	0.0599 (13)	0.0913 (16)	0.0384 (12)	0.0465 (13)	0.0384 (12)
C3	0.127 (2)	0.0589 (15)	0.127 (3)	0.0528 (16)	0.078 (2)	0.0362 (16)
C4	0.123 (2)	0.0610 (16)	0.090 (2)	0.0183 (16)	0.0658 (19)	0.0093 (14)
C5	0.0939 (19)	0.0846 (18)	0.0627 (15)	0.0207 (15)	0.0283 (13)	0.0073 (13)
C6	0.0752 (14)	0.0731 (15)	0.0587 (13)	0.0329 (12)	0.0226 (11)	0.0165 (11)
C7	0.0400 (9)	0.0474 (10)	0.0465 (10)	0.0199 (7)	0.0155 (7)	0.0228 (8)
C8	0.0421 (9)	0.0431 (9)	0.0429 (9)	0.0140 (7)	0.0165 (7)	0.0185 (8)
C9	0.0454 (10)	0.0489 (10)	0.0490 (10)	0.0179 (8)	0.0190 (8)	0.0252 (8)
C10	0.0441 (10)	0.0476 (10)	0.0464 (10)	0.0174 (8)	0.0192 (8)	0.0236 (8)
C11	0.0473 (10)	0.0440 (9)	0.0460 (10)	0.0201 (8)	0.0208 (8)	0.0229 (8)
C12	0.0496 (10)	0.0516 (11)	0.0595 (11)	0.0246 (8)	0.0273 (9)	0.0285 (9)
C13	0.0675 (13)	0.0634 (13)	0.0876 (16)	0.0319 (11)	0.0333 (12)	0.0467 (12)
C14	0.0458 (10)	0.0440 (10)	0.0512 (10)	0.0131 (8)	0.0194 (8)	0.0135 (8)
C15A	0.057 (5)	0.109 (5)	0.094 (5)	0.010 (4)	0.030 (4)	0.061 (4)
C16A	0.076 (4)	0.110 (5)	0.105 (5)	0.001 (5)	0.027 (4)	0.069 (4)
C17A	0.191 (10)	0.144 (8)	0.111 (6)	0.050 (8)	0.035 (8)	0.067 (7)
C15B	0.060 (4)	0.118 (3)	0.084 (2)	−0.006 (3)	0.029 (2)	0.047 (2)
C16B	0.093 (3)	0.098 (3)	0.096 (3)	0.007 (3)	0.049 (2)	0.027 (3)
C17B	0.095 (3)	0.175 (5)	0.099 (3)	0.018 (3)	0.042 (2)	0.085 (3)

Geometric parameters (Å, º)

O1—C10	1.361 (2)	C7—H7A	0.9800
O1—C9	1.389 (2)	C8—C9	1.331 (2)
O2—C14	1.197 (2)	C8—C14	1.477 (2)
O3—C14	1.319 (2)	C9—C13	1.486 (2)
O3—C15B	1.434 (13)	C10—C11	1.348 (2)
O3—C15A	1.52 (4)	C11—C12	1.409 (2)
N1—C10	1.333 (2)	C13—H13A	0.9600
N1—H1N1	0.83 (2)	C13—H13B	0.9600
N1—H1N2	0.88 (2)	C13—H13C	0.9600
N2—C12	1.143 (2)	C15A—C16A	1.404 (4)
C1—C2	1.375 (3)	C15A—H15A	0.9700
C1—C6	1.376 (3)	C15A—H15B	0.9700
C1—C7	1.521 (2)	C16A—C17A	1.245 (4)
C2—C3	1.396 (4)	C16A—H16A	0.9300
C2—H2A	0.9300	C17A—H17A	0.9300
C3—C4	1.367 (4)	C17A—H17B	0.9300
C3—H3A	0.9300	C15B—C16B	1.395 (4)
C4—C5	1.349 (4)	C15B—H15C	0.9700
C4—H4A	0.9300	C15B—H15D	0.9700
C5—C6	1.371 (3)	C16B—C17B	1.227 (3)
C5—H5A	0.9300	C16B—H16B	0.9300
C6—H6A	0.9300	C17B—H17C	0.9300
C7—C8	1.508 (2)	C17B—H17D	0.9300
C7—C11	1.511 (2)
C10—O1—C9	119.93 (13)	C11—C10—O1	121.05 (15)
C14—O3—C15B	120.1 (4)	C10—C11—C12	119.89 (15)
C14—O3—C15A	110.7 (7)	C10—C11—C7	121.69 (15)
C10—N1—H1N1	120.4 (14)	C12—C11—C7	118.27 (14)
C10—N1—H1N2	116.0 (14)	N2—C12—C11	177.5 (2)
H1N1—N1—H1N2	123 (2)	C9—C13—H13A	109.5
C2—C1—C6	118.3 (2)	C9—C13—H13B	109.5
C2—C1—C7	120.80 (19)	H13A—C13—H13B	109.5
C6—C1—C7	120.86 (16)	C9—C13—H13C	109.5
C1—C2—C3	119.4 (2)	H13A—C13—H13C	109.5
C1—C2—H2A	120.3	H13B—C13—H13C	109.5
C3—C2—H2A	120.3	O2—C14—O3	122.49 (17)
C4—C3—C2	120.8 (2)	O2—C14—C8	121.74 (17)
C4—C3—H3A	119.6	O3—C14—C8	115.75 (16)
C2—C3—H3A	119.6	C16A—C15A—O3	108 (2)
C5—C4—C3	119.7 (2)	C16A—C15A—H15A	110.1
C5—C4—H4A	120.1	O3—C15A—H15A	110.1
C3—C4—H4A	120.1	C16A—C15A—H15B	110.1
C4—C5—C6	120.1 (3)	O3—C15A—H15B	110.1
C4—C5—H5A	120.0	H15A—C15A—H15B	108.4
C6—C5—H5A	120.0	C17A—C16A—C15A	124.5 (11)
C5—C6—C1	121.7 (2)	C17A—C16A—H16A	117.7
C5—C6—H6A	119.1	C15A—C16A—H16A	117.7
C1—C6—H6A	119.1	C16A—C17A—H17A	120.0
C8—C7—C11	109.31 (13)	C16A—C17A—H17B	120.0
C8—C7—C1	112.26 (14)	H17A—C17A—H17B	120.0
C11—C7—C1	111.41 (14)	C16B—C15B—O3	112.7 (8)
C8—C7—H7A	107.9	C16B—C15B—H15C	109.1
C11—C7—H7A	107.9	O3—C15B—H15C	109.1
C1—C7—H7A	107.9	C16B—C15B—H15D	109.1
C9—C8—C14	124.63 (16)	O3—C15B—H15D	109.1
C9—C8—C7	122.28 (15)	H15C—C15B—H15D	107.8
C14—C8—C7	113.08 (15)	C17B—C16B—C15B	131.9 (8)
C8—C9—O1	120.91 (15)	C17B—C16B—H16B	114.0
C8—C9—C13	131.04 (17)	C15B—C16B—H16B	114.0
O1—C9—C13	108.05 (15)	C16B—C17B—H17C	120.0
N1—C10—C11	128.55 (17)	C16B—C17B—H17D	120.0
N1—C10—O1	110.40 (15)	H17C—C17B—H17D	120.0
C6—C1—C2—C3	−0.2 (3)	C9—O1—C10—N1	168.74 (16)
C7—C1—C2—C3	178.11 (18)	C9—O1—C10—C11	−11.9 (2)
C1—C2—C3—C4	0.8 (4)	N1—C10—C11—C12	−4.5 (3)
C2—C3—C4—C5	−0.7 (4)	O1—C10—C11—C12	176.32 (16)
C3—C4—C5—C6	0.1 (4)	N1—C10—C11—C7	171.01 (18)
C4—C5—C6—C1	0.4 (4)	O1—C10—C11—C7	−8.2 (3)
C2—C1—C6—C5	−0.4 (3)	C8—C7—C11—C10	21.4 (2)
C7—C1—C6—C5	−178.71 (19)	C1—C7—C11—C10	−103.26 (19)
C2—C1—C7—C8	135.66 (18)	C8—C7—C11—C12	−163.08 (15)
C6—C1—C7—C8	−46.0 (2)	C1—C7—C11—C12	72.3 (2)
C2—C1—C7—C11	−101.37 (19)	C15B—O3—C14—O2	−5.2 (5)
C6—C1—C7—C11	76.9 (2)	C15A—O3—C14—O2	−2.7 (9)
C11—C7—C8—C9	−17.1 (2)	C15B—O3—C14—C8	176.0 (4)
C1—C7—C8—C9	106.99 (19)	C15A—O3—C14—C8	178.4 (9)
C11—C7—C8—C14	162.07 (14)	C9—C8—C14—O2	158.52 (19)
C1—C7—C8—C14	−73.79 (18)	C7—C8—C14—O2	−20.7 (2)
C14—C8—C9—O1	−179.35 (15)	C9—C8—C14—O3	−22.6 (3)
C7—C8—C9—O1	−0.2 (3)	C7—C8—C14—O3	158.17 (15)
C14—C8—C9—C13	0.1 (3)	C14—O3—C15A—C16A	158.0 (12)
C7—C8—C9—C13	179.25 (19)	O3—C15A—C16A—C17A	−56 (3)
C10—O1—C9—C8	16.3 (2)	C14—O3—C15B—C16B	117.5 (6)
C10—O1—C9—C13	−163.28 (16)	O3—C15B—C16B—C17B	152.6 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···N2^i	0.83 (2)	2.24 (2)	3.051 (2)	166.0 (19)
N1—H1N2···O2^ii	0.88 (2)	2.04 (2)	2.919 (2)	171 (2)
C13—H13A···O3	0.96	2.27	2.868 (3)	120

Symmetry codes: (i) −x, −y+1, −z+1; (ii) x−1, y, z.