Quantum chemical studies on the molecular structure, spectroscopic and electronic properties of (6-Methoxy-2-oxo-2H-chromen-4-yl)-methyl pyrrolidine-1-carbodithioate

Meryem Evecen; Hasan Tanak

Accès libre

Quantum chemical studies on the molecular structure, spectroscopic and electronic properties of (6-Methoxy-2-oxo-2H-chromen-4-yl)-methyl pyrrolidine-1-carbodithioate

Meryem Evecen

Hasan Tanak

| 19 déc. 2016

Materials Science-Poland

Édition 34 (2016): Edition 4 (December 2016)

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Publié en ligne: 19 déc. 2016

Pages: 886 - 904

Reçu: 05 mai 2016

Accepté: 09 oct. 2016

DOI: https://doi.org/10.1515/msp-2016-0115

Mots clés
coumarin, vibrational spectroscopy, density functional theory, chemical shifts, electronic properties

© Wroclaw University of Technology

This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 3.0 License.

(a) The experimental geometric structure of the title compound [18], (b) DFT optimized structure of the title compound, (c) HF optimized structure of the title compound.

Superimposition of the calculated HF (top) and DFT (bottom) and experimental structures of (6-Methoxy-2-oxo-2H-chromen-4-yl)-methyl pyrrolidine-1-carbodithioate.

Potential energy profile using the DFT/B3LYP method for the internal rotation around the C18– N6 and C17–C14 bonds.

Natural atomic charges of (6-Methoxy-2-oxo-2H-chromen-4-yl)-methyl pyrrolidine-1-carbodithioate.

Theoretical UV-Vis spectra of (6-Methoxy-2-oxo-2H-chromen-4-yl)-methyl pyrrolidine-1-carbodithioate. gas (top) and DSMO (bottom).

Molecular orbital surfaces and energy levels of (6-Methoxy-2-oxo-2H-chromen-4-yl)-methyl pyrrolidine-1-carbodithioate.

The total electron density mapped with electrostatic potential of the title compound.

Selected molecular structure parameters.

Parameters	Experimental [18]	Calculated 6-311++G(d,p)

		B3LYP	HF

Bond lengths [Â]
S1–C18	1.787 (2)	1.815	1.785
S1–C17	1.813 (2)	1.839	1.823
S2–C18	1.666 (2)	1.669	1.669
O3–C8	1.358 (3)	1.364	1.347
O3–C7	1.403 (3)	1.421	1.398
O4–C16	1.364 (3)	1.390	1.344
O4–C11	1.375 (3)	1.365	1.353
O5–C16	1.199 (3)	1.204	1.180
N6–C18	1.313 (3)	1.341	1.320
N6–C19	1.465 (3)	1.479	1.472
N6–C22	1.480 (3)	1.478	1.472
C8–C9	1.386 (3)	1.388	1.374
C8–C13	1.391 (3)	1.406	1.399
C9–C10	1.395 (3)	1.411	1.405
C10–C11	1.395 (3)	1.400	1.377
C10–C14	1.445 (3)	1.411	1.405
C11–C12	1.385 (3)	1.396	1.390
C12–C13	1.361 (3)	1.380	1.369
C14–C15	1.341 (3)	1.355	1.332
C14–C17	1.502 (3)	1.504	1.507
C15–C16	1.446 (4)	1.455	1.466
C19–C20	1.507 (4)	1.532	1.526
C20–C21	1.474 (5)	1.535	1.527
C21–C22	1.505 (5)	1.531	1.525

Max. difference Maximum differences between the bond lengths and angles computed using theoretical methods and those obtained from X-ray diffraction		0.061	0.053

RMSE		0.021	0.018

Bond angles [°]

C18–S1–C17	102.70 (11)	103.03	105.31
C8–O3–C7	118.4 (2)	118.57	119.95
C16–O4–C11	121.98 (18)	122.35	123.06
C18–N6–C19	126.0 (2)	126.05	126.07
C18–N6–C22	123.3 (2)	122.29	122.30
C19–N6–C22	110.6 (2)	111.64	111.61
O3–C8–C9	124.1 (2)	124.75	124.86
O3–C8–C13	115.9 (2)	115.39	115.54
C9–C8–C13	119.9 (2)	119.85	119.59
C8–C9–C10	120.1 (2)	120.49	120.54
C11–C10–C9	118.4 (2)	118.48	118.70
C11–C10–C14	117.6 (2)	117.46	117.19
C9–C10–C14	123.99 (19)	124.04	124.09
O4–C11–C12	116.88 (19)	116.76	116.65
O4–C11–C10	121.7 (2)	122.19	122.29
C12–C11–C10	121.4 (2)	121.03	121.04
C13–C12–C11	119.3 (2)	119.76	119.71
C12–C13–C8	120.9 (2)	120.35	120.38
C15–C14–C10	119.0 (2)	119.10	118.80
C15–C14–C17	121.1 (2)	119.94	120.25
C10–C14–C17	119.93 (19)	120.94	120.92
C14–C15–C16	123.0 (2)	122.99	122.28
O5–C16–O4	116.9 (2)	117.99	119.15
O5–C16–C15	126.6 (3)	126.11	124.49
O4–C16–C15	116.5 (2)	115.88	116.35
C14–C17–S1	110.94 (16)	112.80	113.25
N6–C18–S2	124.10 (18)	123.67	123.54
N6–C18–S1	111.67 (17)	111.57	112.58
S2–C18–S1	124.21 (15)	124.75	123.86
N6–C19–C20	104.6 (2)	103.67	103.58
C21–C20–C19	105.7 (3)	103.34	103.21
C20–C21–C22	105.6 (3)	103.57	103.41
N6–C22–C21	103.7 (2)	103.75	103.61

Max. Difference Maximum differences between the bond lengths and angles computed using theoretical methods and those obtained from X-ray diffraction		2.36	2.61

RMSE		0.831	1.168

Torsion angles [°]

C22–N6–C18–S1	178.00	178.48	178.56
N6–C18–S1–C17	–170.98	–176.56	–174.45
C18–S1–C17–C14	103.72	105.99	98.78
S1–C17–C14–C15	–99.35	–104.04	–107.40

Natural atomic charges (e) of (6-Methoxy-2-oxo-2H-chromen-4-yl)-methyl pyrrolidine-1-carbodithioate.

Atom	B3LYP	Atom	B3LYP	Atom	B3LYP
S1	0.24719	C10	−0.11967	C18	−0.05156
S2	−0.16350	C11	0.32460	C19	−0.17943
O3	−0.54097	C12	−0.19651	H19A	0.20289
O4	−0.51251	H12	0.22618	H19B	0.21295
O5	−0.56201	C13	−0.21046	C20	−0.38867
N6	−0.49501	H13	0.22257	H20A	0.19988
C7	−0.20596	C14	0.03099	H20B	0.21342
H7A	0.16955	C15	−0.28039	C21	−0.39439
H7B	0.19436	H15	0.23948	H21A	0.20043
H7C	0.16919	C16	0.75023	H21B	0.21463
C8	0.31283	C17	−0.53537	C22	−0.16780
C9	−0.25921	H17A	0.22481	H22A	0.20388
H9	0.21104	H17B	0.26817	H22B	0.22427

Comparison of the experimental and calculated vibrational frequencies [cm−1].

Assignments^a	Experimental [18]	Scaled frequencies with 6-311++G(d,p)

		B3LYP	HF
ν(C−H)ring	–	3089	3019
ν(C−H)ring	–	3083	3015
ν(C−H)ring	–	3078	2998
ν(C−H₃)as	–	3011	2924
ν(C−H₂)as	–	2985	2889
ν(C−H₂)s	–	2926	2887
ν(C−H₃)as	–	2938	2866
ν(C−H₂)s	–	2924	2883
ν(C−H₃)s	–	2883	2813
ν(C=O)	1708	1722	1767
ν(C=C)	–	1594	1604
ν(C=C)ring	–	1581	1566
ν(C=C)ring	–	1536	1475
ν(C=C)+α(C−H₃)	–	1460	–
ω(C−H₃)	–	1444	1450
ν(C−N)	–	1389	1389
ν(C−C)+γ(C−H)ring	–	1348	1344
ν(C−C)+ω(C−H₂)	–	1319	1335
γ(C−H)ring	–	1246	1251
ν(C−O)ring+ν(C−O)methoxy	1279	1214	1233
γ(C−H)ring+ω(C−H₂)+ω(C−H₃)	–	1184	1205
δ(C−H₂)+ω(C−H₃)	–	1158	1181
ν(C−N)+δ(C−H₂)	–	1128	1181
ω(C−H₃)	–	1120	1045
γ(C−H)ring	–	1109	1045
γ(C−H)ring+ν(C−O)ring	–	1092	1076
ν(C−O)methoxy	1036	1024	1045
ν(C=S)	–	974	972
ν(C−O)ring+γ(C−H₂)	–	900	935
ω(C−H)ring	–	871	887
ν(C−N)	842	835	843
ω(C−H)ring	–	816	832
ν(C−S)+β(C−H₂)	–	792	801
ω(C−H)ring	–	728	731
ν(C−S)	660	674	666

Selected second-order perturbation energies E(2) associated with i → j delocalization in gas phase.

Donor orbital (i)	Type	ED/e	Acceptor orbital (j)	Type	ED/e	E⁽²⁾ [kJ/mol] E⁽²⁾ energy of hyper conjugative interactions	E(j)-E(i) [a.u.] Energy difference between donor and acceptor i and j NBO orbitals	F(ij) [a.u.] Fij is the Fock matrix element between i and j NBO orbitals
S1–C17	σ	1.96731	C14–C15	π*	0.16017	13.08	0.78	0.046
S1–C18	σ	1.97456	N6–C22	σ*	0.03367	23.28	0.95	0.065
S2–C18	σ	1.98622	S2–C18	σ*	0.02661	19.18	0.22	0.033
S2–C18	π	1.98142	N6–C19	σ*	0.03696	20.06	1.02	0.063
O5–C16	π	1.97927	C14–C15	π*	0.16017	14.25	0.56	0.040
N6–C19	σ	1.98300	S2–C18	π*	0.02661	15.92	1.02	0.056
N6–C22	σ	1.98037	S1–C18	σ*	0.11776	15.29	0.87	0.052
N6–C22	σ	1.98037	C10–C14	σ*	0.03343	18.01	1.43	0.070
N6–C22	σ	1.98037	C14–C15	π*	0.16017	14.71	0.91	0.052
N6–C22	σ	1.98037	C14–C17	σ*	0.02814	31.35	1.60	0.098
N6–C22	σ	1.98037	C15–H15	σ*	0.01325	16.17	1.32	0.064
N6–C22	σ	1.98037	C22–H22A	σ*	0.02002	98.68	5.65	0.326
C7–H9	σ	1.99099	O3–C8	σ*	0.02948	14.50	0.89	0.050
C8–C9	σ	1.97744	C9–C10	σ*	0.02110	14.96	1.26	0.060
C8–C9	π	1.70329	C10–C11	π*	0.42279	73.94	0.31	0.069
C8–C9	π	1.70329	C12–C13	π*	0.29806	69.93	0.31	0.064
C8–C13	σ	1.97225	O3–C7	σ*	0.00895	13.04	0.99	0.050
C8–C13	σ	1.97225	C8–C9	σ*	0.02751	17.09	1.27	0.064
C9–H9	σ	1.97491	C8–C13	σ*	0.02300	16.55	1.09	0.059
C9–H9	σ	1.97491	C10–C11	σ*	0.03420	16.80	1.09	0.059
C9–C10	σ	1.96573	O3–C8	σ*	0.02948	17.89	1.05	0.060
C9–C10	σ	1.96573	O4–C11	σ*	0.03285	15.88	1.04	0.056
C9–C10	σ	1.96573	C8–C9	σ*	0.02751	14.25	1.26	0.059
C9–C10	σ	1.96573	C10–C11	σ*	0.03420	15.88	1.25	0.061
C9–C10	σ	1.96573	C10–C14	σ*	0.03343	13.00	1.40	0.059
C10–C11	σ	1.97068	C9–C10	σ*	0.02110	15.00	1.25	0.060
C10–C11	σ	1.97068	C11–C12	σ*	0.02153	18.09	1.25	0.066
C10–C11	π	1.61973	C8–C9	π*	0.36558	74.48	0.29	0.064
C10–C11	π	1.61973	C12–C13	π*	0.29806	71.68	0.30	0.066
C10–C11	π	1.61973	C14–C15	π*	0.16017	42.21	0.45	0.064
C10–C14	σ	1.96855	C9–C10	σ*	0.02110	15.29	1.22	0.060
C11–C12	σ	1.97260	C10–C11	σ*	0.03420	18.93	1.26	0.068
C12–H12	σ	1.97720	C8–C13	σ*	0.02300	14.67	1.07	0.055
C12–H12	σ	1.97720	C10–C11	σ*	0.03420	17.84	1.08	0.061
C12–C13	σ	1.97210	O3–C8	σ*	0.02948	13.50	1.07	0.052
C12–C13	σ	1.97210	O4–C11	σ*	0.03285	15.34	1.06	0.056
C12–C13	π	1.71752	C8–C9	π*	0.36558	80.67	0.28	0.067
C12–C13	π	1.71752	C10–C11	π*	0.42279	75.53	0.31	0.069
C13–H13	σ	1.97744	C8–C9	σ*	0.02751	17.93	1.09	0.061
C13–H13	σ	1.97744	C11–C12	σ*	0.02153	13.91	1.06	0.053
C14–C15	σ	1.97636	C9–C10	σ*	0.02110	13.33	1.29	0.057
C14–C15	π	1.80442	S1–C17	σ*	0.02626	20.27	0.42	0.042
C14–C15	π	1.80442	O5–C16	π*	0.28744	91.54	0.30	0.074
C14–C15	π	1.80442	C10–C11	π*	0.42279	43.76	0.32	0.055
C15–H15	σ	1.97420	O4–C16	σ*	0.12395	17.72	0.84	0.055
C15–H15	σ	1.97420	C10–C14	σ*	0.03343	19.52	1.23	0.068
C15–C16	σ	1.98160	C14–C15	σ*	0.01954	12.54	1.32	0.056
C15–C16	σ	1.98160	C14–C17	σ*	0.02814	14.33	1.56	0.066
C17–H17B	σ	1.97909	C10–C14	σ*	0.03343	14.96	1.23	0.059
C19–C20	σ	1.97909	N6–C18	σ*	0.05998	15.04	1.09	0.057
C21–C22	σ	1.98228	N6–C18	σ*	0.05998	14.08	1.09	0.055
C21–C22	σ	1.98228	C10–C14	σ*	0.03343	20.64	1.33	0.073
C21–C22	σ	1.98228	C14–C15	π*	0.16017	25.53	0.81	0.065
C21–C22	σ	1.98228	C14–C17	σ*	0.02814	41.00	1.49	0.108
C21–C22	σ	1.98228	C22–H22A	σ*	0.02002	100.57	5.55	0.326
C22–H22A	σ	1.98004	C10–C14	σ*	0.03343	18.93	1.22	0.067
C22–H22A	σ	1.98004	C14–C17	σ*	0.02814	38.58	1.39	0.101
C22–H22A	σ	1.98004	C15–H15	σ*	0.01325	14.79	1.12	0.056
C22–H22A	σ	1.98004	C21–H21A	σ*	0.01457	21.69	0.94	0.063
C22–H22A	σ	1.98004	C21–C22	σ*	0.01296	15.46	2.76	0.090
C22–H22A	σ	1.98004	C22–H22A	σ*	0.02002	66.54	5.44	0.263
C22–H22A	σ	1.98004	C22–H22B	σ*	0.02002	51.99	2.82	0.168
C22–H22B	σ	1.98156	C10–C14	σ*	0.03343	61.61	1.21	0.120
C22–H22B	σ	1.98156	C14–C15	π*	0.16017	52.54	0.70	0.087
C22–H22B	σ	1.98156	C14–C17	σ*	0.02814	118.16	1.38	0.177
C22–H22B	σ	1.98156	C15–H15	σ*	0.01325	46.94	1.11	0.100
C22–H22B	σ	1.98156	C22–H22A	σ*	0.02002	269.02	5.44	0.528
C22–H22B	σ	1.98156	C22–H22B	σ*	0.01560	33.27	2.82	0.134
S1	LP(1)	1.97272	S2–C18	π*	0.02661	28.34	0.93	0.071
S1	LP(2)	1.81217	S2–C18	σ*	0.50942	126.61	0.18	0.072
S2	LP(1)	1.97823	S1–C18	σ*	0.11776	19.35	0.86	0.058
S2	LP(1)	1.97823	N6–C18	σ*	0.05998	13.83	1.18	0.056
S2	LP(2)	1.82347	S1–C18	σ*	0.11776	69.05	0.35	0.068
S2	LP(2)	1.82347	N6–C18	σ*	0.05998	46.73	0.67	0.080
S2	LP(2)	1.82347	C17–H17B	σ*	0.03283	16.63	0.61	0.046
O3	LP(1)	1.96313	C8–C9	σ*	0.02751	29.05	1.11	0.079
O3	LP(2)	1.84590	C7–H7A	σ*	0.01902	23.36	0.69	0.057
O3	LP(2)	1.84590	C7–H7C	σ*	0.01908	23.53	0.69	0.058
O3	LP(2)	1.84590	C8–C9	π*	0.36558	125.23	0.34	0.095
O4	LP(1)	1.96311	C10–C11	σ*	0.03420	26.54	1.09	0.074
O4	LP(1)	1.96311	C15–C16	σ*	0.05477	18.76	1.00	0.060
O4	LP(2)	1.74309	O5–C16	π*	0.28744	146.13	0.35	0.100
O4	LP(2)	1.74309	C10–C11	π*	0.42279	113.65	0.37	0.094
O5	LP(2)	1.83314	O4–C16	σ*	0.12395	156.33	0.57	0.131
O5	LP(2)	1.83314	C15–C16	σ*	0.05477	66.75	0.70	0.097
N6	LP(1)	1.61189	S2–C18	σ*	0.50942	357.01	0.19	0.118
N6	LP(1)	1.61189	C19–H19A	σ*	0.02121	23.61	0.65	0.060
N6	LP(1)	1.61189	C19–H19B	σ*	0.01621	13.54	0.67	0.046
O4–C16	σ*	0.12395	O4–C11	σ*	0.03285	114.19	0.02	0.080
O5–C16	π*	0.28744	C14–C15	π*	0.16017	31.39	0.17	0.067
C8–C9	π*	0.36558	C10–C11	π*	0.42279	532.95	0.02	0.077
C8–C9	π*	0.36558	C12–C13	π*	0.29806	830.56	0.01	0.082
C10–C11	π*	0.42279	C14–C15	π*	0.16017	135.68	0.14	0.113
C10–C11	π*	0.42279	C14–C17	σ*	0.02814	14.08	0.83	0.099
C10–C11	π*	0.42279	C22–H22A	σ*	0.02002	18.68	4.89	0.280
C14–C15	π*	0.16017	C10–C14	σ*	0.03343	24.28	0.52	0.158
C14–C15	π*	0.16017	C14–C17	σ*	0.02814	36.65	0.69	0.226
C14–C15	π*	0.16017	C15–H15	σ*	0.01325	14.42	0.41	0.114
C14–C15	π*	0.16017	C22–H22A	σ*	0.02002	60.61	4.74	0.780

Thermodynamic properties at different temperatures at B3LYP/6-311++G(d,p) level.

T	$H_{m}^{0}$ ${\text{H}}_{\text{m}}^{\text{0}}$	$C_{p,m}^{0}$ ${\text{C}}_{{\text{p,m}}}^{\text{0}}$	$S_{m}^{0}$ ${\text{S}}_{\text{m}}^{\text{0}}$
[K]	[kJ⋅mol⁻¹]	[J⋅mol⁻¹⋅K⁻¹]	[J⋅mol⁻¹⋅K⁻¹]
200	29.30	237.84	545.94
250	42.84	287.79	606.22
300	58.89	338.28	664.70
350	77.45	387.27	721.80
400	98.39	433.17	777.68
450	121.55	475.18	832.15
500	146.67	513.09	885.07
550	173.63	547.07	936.40
600	202.18	577.55	986.06

Theoretical and experimental 1H and 13C isotropic chemical shifts (with respect to TMS values in ppm) for the title compound.

Atom	Gas		Ethanol		DMSO
Atom
	B3LYP	HF	B3LYP	HF	B3LYP	HF
H7A	3.75	3.67	3.92	3.65	3.93	3.63
H7B	4.14	4.04	4.24	4.03	4.24	4.03
H7C	3.69	3.64	3.88	3.62	3.89	3.65
H9	6.71	7.03	7.06	7.00	7.07	7.02
H12	7.37	7.81	7.48	7.80	7.49	7.80
H13	7.30	7.75	7.48	7.73	7.49	7.74
H15	6.80	6.73	6.77	6.73	6.77	6.72
H17A	4.00	4.03	4.33	3.99	4.35	4.01
H17B	5.50	5.24	5.46	5.23	5.45	5.23
H19A	3.40	3.08	3.47	3.06	3.47	3.06
H19B	3.76	3.46	3.82	3.44	3.82	3.45
H20A	1.98	1.87	2.11	1.85	2.12	1.86
H20B	2.07	1.94	2.13	1.93	2.13	1.93
H21A	1.89	1.73	2.00	1.71	2.00	1.71
H21B	1.95	1.92	2.08	1.91	2.08	1.91
H22A	3.75	3.39	3.77	3.38	3.77	3.38
H22B	4.30	3.88	4.24	3.88	4.18	3.87
C7	56.76	50.26	57.92	50.70	58.08	50.73
C8	163.38	159.94	164.94	160.39	165.10	160.41
C9	106.50	109.31	109.16	109.62	109.44	109.74
C10	126.16	122.12	126.87	122.58	127.00	122.60
C11	158.96	151.76	158.40	152.26	158.49	152.25
C12	124.72	127.27	124.96	127.81	125.04	127.77
C13	127.92	130.96	129.74	131.39	129.90	131.43
C14	159.64	164.12	164.81	164.28	165.16	164.50
C15	122.61	119.57	120.63	120.23	120.64	120.11
C16	163.72	164.98	167.21	165.29	167.44	165.41
C17	42.95	33.34	43.17	33.80	43.29	33.82
C18	205.44	226.88	206.75	227.35	206.97	227.36
C19	53.29	47.80	55.25	48.20	55.44	48.26
C20	30.86	26.30	31.46	26.76	31.59	26.78
C21	28.69	24.57	29.23	25.04	29.35	25.05
C22	60.29	53.03	62.20	53.45	62.38	53.50

eISSN:: 2083-134X
Langue:: Anglais

Périodicité:: 4 fois par an
Sujets de la revue:: Materials Sciences, other, Nanomaterials, Functional and Smart Materials, Materials Characterization and Properties

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Quantum chemical studies on the molecular structure, spectroscopic and electronic properties of (6-Methoxy-2-oxo-2H-chromen-4-yl)-methyl pyrrolidine-1-carbodithioate

Publié en ligne: 19 déc. 2016

Pages: 886 - 904

Reçu: 05 mai 2016

Accepté: 09 oct. 2016

DOI: https://doi.org/10.1515/msp-2016-0115

Mots cléscoumarin, vibrational spectroscopy, density functional theory, chemical shifts, electronic properties

© Wroclaw University of Technology

This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 3.0 License.

Selected molecular structure parameters.

Natural atomic charges (e) of (6-Methoxy-2-oxo-2H-chromen-4-yl)-methyl pyrrolidine-1-carbodithioate.

Comparison of the experimental and calculated vibrational frequencies [cm−1].

Selected second-order perturbation energies E(2) associated with i → j delocalization in gas phase.

Thermodynamic properties at different temperatures at B3LYP/6-311++G(d,p) level.

Theoretical and experimental 1H and 13C isotropic chemical shifts (with respect to TMS values in ppm) for the title compound.

Mots clés
coumarin, vibrational spectroscopy, density functional theory, chemical shifts, electronic properties