Crystal structure of diethylammonium 5-((4-fluorophenyl)(6-hydroxy-1,3-dimethyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-5-yl)methyl)-1,3-dimethyl-2,6-dioxo-1,2,3,6-tetrahydropyrimidin-4-olate, C23H30FN5O6

Assem Barakat; Hazem A. Ghabbour; Abdullah Mohammed Al-Majid; El Sayed H. El Ashry; Ismail Warad; Hoong-Kun Fun

doi:10.1515/ncrs-2015-0169

Abstract

C₂₃H₃₀FN₅O₆, monoclinic, P2₁/n (no. 14), a = 9.5772(3) Å, b = 15.9466(5) Å, c = 15.8380(5) Å, β = 103.951(1)°, V = 2347.49(13) Å³, Z = 4, R_gt(F) = 0.0423, wR(F²) = 0.192, T = 150 K.

The crystal structure is shown in the figure. Tables 1–3 contain details of the measurement method and a list of the atoms including atomic coordinates and displacement parameters.

Table 1

Data collection and handling.

Crystal:	Violet, block, size 0.417×0.512×0.74 mm
Wavelength:	Mo K_α radiation (0.71073 Å)
μ:	1.07 cm⁻¹
Diffractometer, scan mode:	D8 Venture area detector, φ and ω scans
2θ_max:	60°
N(hkl)_measured, N(hkl)_unique:	44751, 6815
Criterion for I_obs, N(hkl)_gt:	I_obs > 2 σ(I_obs), 6046
N(param)_refined:	359
Programs:	BRUKER programs [11], SHELXL [12]

Table 2

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²).

Atom	Site	x	y	z	U_iso
H(2A)^a	4e	0.6870	0.5790	0.8747	0.053
H(2B)^a	4e	0.7986	0.6473	0.9254	0.053
H(2C)^a	4e	0.8557	0.5588	0.8999	0.053
H(2Y)^b	4e	0.860(4)	0.627(2)	0.928(2)	0.029(9)
H(2X)^b	4e	0.696(4)	0.617(2)	0.893(2)	0.026(8)
H(2Z)^b	4e	0.806(4)	0.540(2)	0.885(2)	0.029(9)
H(4A)	4e	1.0721	0.6542	0.6219	0.052
H(4B)	4e	1.1332	0.6096	0.7139	0.052
H(4C)	4e	1.1431	0.7093	0.7057	0.052
H(7A)	4e	0.6059	0.7580	0.5462	0.022
H(10A)	4e	0.5181	0.5761	0.2935	0.052
H(10B)	4e	0.3956	0.6460	0.2660	0.052
H(10C)	4e	0.3530	0.5488	0.2615	0.052
H(12A)^a	4e	0.2069	0.4972	0.5837	0.059
H(12B)^a	4e	0.2503	0.4263	0.5232	0.059
H(12C)^a	4e	0.1157	0.4862	0.4854	0.059
H(12Y)^b	4e	0.132(4)	0.514(2)	0.534(2)	0.027(9)
H(12X)^b	4e	0.195(4)	0.435(2)	0.482(2)	0.032(9)
H(12Z)^b	4e	0.267(4)	0.465(2)	0.589(2)	0.030(9)
H(15A)	4e	0.6364	0.8539	0.6914	0.034
H(16A)	4e	0.5036	0.9575	0.7416	0.037
H(18A)	4e	0.1349	0.8464	0.6100	0.033
H(19A)	4e	0.2697	0.7443	0.5578	0.028
H(20A)	4e	1.0304	0.6543	0.3725	0.053
H(20B)	4e	0.9952	0.6782	0.4633	0.053
H(20C)	4e	1.0781	0.7436	0.4162	0.053
H(21A)	4e	0.8735	0.7656	0.3055	0.030
H(21B)	4e	0.7904	0.6913	0.3406	0.030
H(22A)	4e	0.8827	0.9086	0.3783	0.034
H(22B)	4e	0.9873	0.8649	0.4609	0.034
H(23A)	4e	0.8761	0.9848	0.5044	0.053
H(23B)	4e	0.8295	0.9023	0.5483	0.053
H(23C)	4e	0.7214	0.9438	0.4659	0.053
H(2N5)	4e	0.799(2)	0.773(1)	0.466(1)	0.041(4)
H(1N5)	4e	0.710(2)	0.813(1)	0.385(1)	0.029(4)
H(1O1)	4e	0.456(3)	0.623(2)	0.690(2)	0.075(7)

^aDisordered, occupancy factor: 0.54; ^bDisordered, occupancy factor: 0.46.

Table 3

Atomic displacement parameters (Å²).

Atom	Site	x	y	z	U₁₁	U₂₂	U₃₃	U₁₂	U₁₃	U₂₃
F(1)	4e	0.23009(9)	0.96747(5)	0.71192(6)	0.0476(5)	0.0315(4)	0.0527(5)	0.0133(3)	0.0212(4)	−0.0017(3)
O(1)	4e	0.55322(8)	0.64718(5)	0.75387(5)	0.0192(3)	0.0384(4)	0.0268(4)	0.0014(3)	0.0117(3)	0.0041(3)
O(2)	4e	1.03810(8)	0.61625(5)	0.84023(5)	0.0210(3)	0.0275(4)	0.0240(4)	0.0004(3)	−0.0006(3)	0.0034(3)
O(3)	4e	0.85762(8)	0.72953(6)	0.57420(5)	0.0184(3)	0.0486(5)	0.0236(4)	−0.0038(3)	0.0055(3)	0.0123(3)
O(4)	4e	0.56414(9)	0.70153(6)	0.40686(5)	0.0275(4)	0.0395(5)	0.0249(4)	−0.0107(3)	0.0063(3)	−0.0015(3)
O(5)	4e	0.2233(1)	0.49798(6)	0.35577(7)	0.0320(4)	0.0265(4)	0.0509(6)	−0.0054(3)	−0.0099(4)	−0.0060(4)
O(6)	4e	0.37235(9)	0.59100(5)	0.63272(6)	0.0218(4)	0.0325(4)	0.0358(4)	−0.0052(3)	0.0099(3)	0.0060(3)
N(1)	4e	0.79666(9)	0.63785(6)	0.79821(5)	0.0209(4)	0.0266(4)	0.0173(4)	0.0028(3)	0.0066(3)	0.0024(3)
N(2)	4e	0.94376(8)	0.66817(6)	0.70476(5)	0.0134(3)	0.0263(4)	0.0193(4)	−0.0019(3)	0.0029(3)	0.0015(3)
N(3)	4e	0.4043(1)	0.59500(6)	0.38363(6)	0.0217(4)	0.0249(4)	0.0282(4)	−0.0004(3)	−0.0006(3)	−0.0045(3)
N(4)	4e	0.3074(1)	0.54311(6)	0.49507(7)	0.0166(4)	0.0218(4)	0.0431(5)	−0.0046(3)	0.0028(4)	−0.0001(4)
C(1)	4e	0.6742(1)	0.65966(6)	0.73433(6)	0.0175(4)	0.0224(4)	0.0211(4)	0.0010(3)	0.0070(3)	−0.0001(3)
C(2)	4e	0.7834(1)	0.6029(1)	0.88144(8)	0.0329(6)	0.0541(8)	0.0219(5)	0.0074(5)	0.0121(4)	0.0121(5)
C(3)	4e	0.9325(1)	0.63983(6)	0.78432(6)	0.0189(4)	0.0187(4)	0.0193(4)	−0.0010(3)	0.0031(3)	−0.0008(3)
C(4)	4e	1.0847(1)	0.6596(1)	0.68490(8)	0.0144(4)	0.0602(8)	0.0300(5)	0.0017(5)	0.0061(4)	0.0129(5)
C(5)	4e	0.8283(1)	0.69950(6)	0.64071(6)	0.0155(4)	0.0230(4)	0.0186(4)	−0.0030(3)	0.0026(3)	0.0010(3)
C(6)	4e	0.6893(1)	0.69390(6)	0.65639(6)	0.0145(4)	0.0208(4)	0.0195(4)	−0.0006(3)	0.0038(3)	0.0014(3)
C(7)	4e	0.5613(1)	0.72419(6)	0.58597(6)	0.0135(4)	0.0208(4)	0.0210(4)	−0.0024(3)	0.0030(3)	0.0019(3)
C(8)	4e	0.4779(1)	0.65625(6)	0.52746(7)	0.0139(4)	0.0211(4)	0.0255(4)	−0.0021(3)	0.0034(3)	−0.0003(3)
C(9)	4e	0.4879(1)	0.65460(7)	0.43886(7)	0.0151(4)	0.0247(5)	0.0256(5)	−0.0007(3)	0.0005(3)	−0.0014(4)
C(10)	4e	0.4190(1)	0.59115(8)	0.29371(8)	0.0354(6)	0.0370(6)	0.0271(5)	0.0014(5)	−0.0026(4)	−0.0060(5)
C(11)	4e	0.3061(1)	0.54267(7)	0.40778(8)	0.0186(4)	0.0196(4)	0.0418(6)	0.0014(3)	−0.0036(4)	−0.0023(4)
C(12)	4e	0.2121(1)	0.48317(8)	0.5243(1)	0.0229(5)	0.0276(6)	0.0662(9)	−0.0098(4)	0.0093(5)	0.0028(6)
C(13)	4e	0.3905(1)	0.59852(6)	0.55434(7)	0.0137(4)	0.0210(4)	0.0337(5)	−0.0002(3)	0.0041(4)	0.0017(4)
C(14)	4e	0.4675(1)	0.78744(6)	0.61996(6)	0.0174(4)	0.0198(4)	0.0221(4)	0.0000(3)	0.0031(3)	0.0036(3)
C(15)	4e	0.5343(1)	0.85209(7)	0.67452(8)	0.0219(5)	0.0219(5)	0.0373(6)	−0.0011(4)	0.0020(4)	−0.0012(4)
C(16)	4e	0.4564(1)	0.91374(7)	0.70495(8)	0.0350(6)	0.0203(5)	0.0354(6)	0.0008(4)	0.0045(5)	−0.0012(4)
C(17)	4e	0.3085(1)	0.90934(7)	0.68026(8)	0.0339(6)	0.0224(5)	0.0312(5)	0.0087(4)	0.0114(4)	0.0059(4)
C(18)	4e	0.2371(1)	0.84770(7)	0.62630(8)	0.0216(5)	0.0301(5)	0.0309(5)	0.0065(4)	0.0056(4)	0.0050(4)
C(19)	4e	0.3179(1)	0.78688(7)	0.59581(7)	0.0172(4)	0.0261(5)	0.0243(5)	0.0011(3)	0.0017(3)	0.0020(4)
N(5)	4e	0.80259(9)	0.79860(6)	0.41309(6)	0.0164(4)	0.0259(4)	0.0186(4)	−0.0030(3)	0.0036(3)	0.0004(3)
C(20)	4e	1.0038(1)	0.70002(9)	0.40696(8)	0.0319(6)	0.0446(7)	0.0289(5)	0.0094(5)	0.0073(4)	−0.0020(5)
C(21)	4e	0.8609(1)	0.73713(7)	0.35873(7)	0.0228(5)	0.0331(5)	0.0208(4)	−0.0011(4)	0.0062(4)	−0.0029(4)
C(22)	4e	0.8856(1)	0.87782(7)	0.43296(8)	0.0254(5)	0.0272(5)	0.0326(5)	−0.0073(4)	0.0076(4)	−0.0007(4)
C(23)	4e	0.8226(1)	0.93196(8)	0.49320(9)	0.0340(6)	0.0317(6)	0.0394(6)	−0.0046(5)	0.0059(5)	−0.0103(5)

Source of material

The chemical reagents and solvents used in this study are commercially available. The synthesis of the title compound follows a known procedure [1].

Yield: 93%; m.p. 148 °C; ¹H-NMR (400 MHz, CDCl₃): δ 17.65 (1H, s, OH), 7.33 (2H,d, J = 8.8 Hz, C₆H₄), 7.01 (2H, d, J = 8.8 Hz, C₆H₄), 5.80(1H, s, C₆H₄CH), 3.35 (12H, s, 4CH₃), 3.08 (4H,q, J = 7.3 Hz, CH₂CH₃), 1.30 (6H, t, J = 7.3 Hz, CH₂CH₃); ¹³C-NMR (100 MHz, CDCl₃): δ = 165.4, 164.5, 151.6, 141.0, 131.2, 128.5, 119.5, 91.6, 42.0, 34.3, 29.2, 29.1, 12.0.

Experimental details

All hydrogen atoms were placed geometrically on calculated positions using a riding model with the help of the SHELXL program (AFIX 137 option for methyl groups, AFIX 43 option for aromatic H atoms, AFIX 13 for tertiary and AFIX 23 for secondary H atoms) [12]. The hydrogen atoms of two methyl groups (bonded to C2 and C12) are disordered.

Discussion

1,3-Dimethylbarbituric acid skeleton represents the key pharmacophore of several pharmaceutically agents. Thus, several substituted 1,3-dimethylbarbituric acid were reported to exhibit marked chemotherapeutic activities such as antioxidant, anti-inflammatory, HIV-1 and HIV-2 protease inhibitors, anticancer, anticonvulsant and sedative-hypnotic [2–5]. In continues of our research program we report the crystal structure of a target molecule in this class of compounds. This contribution is part of our continuing interest in pyrimidin-based compounds [6–10]. The title compound comprise of a pyrimidine dione anion and a diethylammonium cation. All rings in the anion (N1/N2/C1/C3/C5/C6, N3/N4/C8—C9/C11/C13 and C14—C19) are planar. The dihedral angle between two pyridmidine rings was found to be 68.34(2)°. The phenyl ring appears to be twisted with an angles of 77.15(3)° and 65.75(2)° with respect to the planes of two pyrimidine rings (N1/N2/C1/C3/C5/C6 and N3/N4/C8—C9/C11/C13), respectively. Cations and anions are connected by NH⋯O hydrogen bonds to form a chain.

Acknowledgements:

The authors gratefully acknowledge the financial support to the King Saud University, Deanship of Scientific Research, College of Science Research Center.

References

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Crystal structure of diethylammonium 5-((4-fluorophenyl)(6-hydroxy-1,3-dimethyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-5-yl)methyl)-1,3-dimethyl-2,6-dioxo-1,2,3,6-tetrahydropyrimidin-4-olate, C₂₃H₃₀FN₅O₆