(E)-tert-Butyl 2-(5-{[4-(dimethylamino)phenyl]diazenyl}-2,6-dioxo-1H-pyrimid­in-3-yl)acetate dichloromethane monosolvate

Hudson, R.H.E.; Moustafa, M.E.; Boyle, P.D.

doi:10.1107/S1600536814007521

organic compounds

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ISSN: 2056-9890

Volume 70| Part 5| May 2014| Pages o556-o557

doi:10.1107/S1600536814007521

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(E)-tert-Butyl 2-(5-{[4-(dimethylamino)phenyl]diazenyl}-2,6-dioxo-1H-pyrimidin-3-yl)acetate dichloromethane monosolvate

Robert H. E. Hudson,^a ^* Mohamed E. Moustafa ^a and Paul D. Boyle ^a

^a1151 Richmond Street, Department of Chemistry, The University of Western Ontario, London, Ontario, N6A 5B7, Canada
^*Correspondence e-mail: robert.hudson@uwo.ca

(Received 11 March 2014; accepted 3 April 2014; online 16 April 2014)

In the title compound, C₁₈H₂₃N₅O₄·CH₂Cl₂, the dichloromethane solvent molecule is disordered over two sets of sites in a 0.630 (13):0.370 (13) ratio. The dihedral angle between the uracil and phenyl rings is 30.2 (1)°. In the crystal, the principal interactions are N—H⋯O hydrogen bonds, which link uracil units across centres of symmetry, forming eight-membered rings with an R²₂(8) graph-set motif. The structure also displays C—H⋯O and C—H⋯Cl hydrogen bonds. Intramolecular C—H⋯O short contacts are also observed.

CCDC reference: 995390

Related literature

As part of our program in the synthesis of modified nucleobases that possess intrinsic fluorescence while maintaining an unadultered base-paring face, we have prepared an asymmetrical azo compound as a hybrid between a nulceobase and the known fluorescence quencher 4-((4-(dimethylamino)phenyl)azo)benzoic acid (DABCYL), see: Dodd & Hudson(2009 ); Tyagi & Kramer (1996 ). For an azo-based fluorescence quencher in peptide nucleic acid, see: Moustafa & Hudson (2011 ). For an example of photoisomerization of azo groups in peptide nucleic acid, see: Yue et al. (2009 ), and in DNA, see: Asanuma et al. (1999 ). The title compound was prepared following standard procedures, see: Thurber & Townsend (1972 ), Tsupak et al. (2002 ) and Moustafa (2011 ).

Experimental

Crystal data

C₁₈H₂₃N₅O₄·CH₂Cl₂
M_r = 458.34
Monoclinic, P 2₁ /n
a = 13.208 (9) Å
b = 10.783 (6) Å
c = 17.255 (11) Å
β = 112.33 (2)°
V = 2273 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 150 K
0.20 × 0.18 × 0.15 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 )T_min = 0.689, T_max = 0.746
34970 measured reflections
5944 independent reflections
3567 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.128
S = 1.03
5944 reflections
374 parameters
12 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4A⋯O2ⁱ	0.84 (3)	2.02 (3)	2.851 (2)	171 (2)
C2—H2C⋯O1ⁱⁱ	1.03 (3)	2.62 (3)	3.189 (4)	115 (2)
C4—H4⋯Cl2Xⁱⁱⁱ	0.94 (2)	2.98 (2)	3.784 (4)	143.5 (17)
C12—H12⋯O1^iv	0.99 (2)	2.34 (2)	3.214 (3)	145.8 (18)
C13—H13B⋯Cl2X^v	0.96 (2)	2.99 (2)	3.895 (4)	158.6 (16)
C16—H16A⋯O3	0.98 (3)	2.51 (3)	3.042 (3)	114 (2)
C17—H17C⋯O3	0.96 (3)	2.48 (3)	2.994 (4)	113 (2)
C1X—H1X1⋯O3^vi	0.99	2.52	3.346 (4)	141
C1X—H1X2⋯O1ⁱⁱ	0.99	2.48	3.256 (4)	135
C1Y—H1Y1⋯O3^vi	0.99	2.50	3.346 (4)	143
Symmetry codes: (i) -x, -y+2, -z+1; (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) x, y+1, z; (iv) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (v) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (vi) -x+1, -y+1, -z+2.

Data collection: COLLECT (Nonius, 1999 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008); molecular graphics: NRCVAX (Gabe et al., 1989 ); software used to prepare material for publication: cif2tables.py (Boyle, 2008 ).

Supporting information

CCDC reference: 995390

Crystal structure: contains datablock I. DOI: 10.1107/S1600536814007521/zp2013sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814007521/zp2013Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814007521/zp2013Isup3.cml

checkCIF report

Introduction top

Experimental top

The title compound was prepared following standard procedures see: Thurber & Townsend (1972), Tsupak et al. (2002) and Moustafa (2011).

Synthesis and crystallization top

The title compound was crystallized by slow diffusion of hexanes into a solution of dichloromethane. Orange plates of suitable quality for diffraction were obtained.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1.

Results and discussion top

The molecule resides at a general position in the lattice as does a disordered methylene chloride of solvation. Selected intermolecular hydrogen bonding interactions are mentioned briefly below. All potential hydrogen bonding interactions are listed in Table 1.

The principal intermolecular interactions are N—H···O hydrogen bonds which join uracil moieties across a centre of symmetry forming an eight membered ring, designated as R²₂(8) ring in graph set notation. This hydrogen bond consists of N4—H4A···O2 with an H···A distance of 2.02 (3) Å. The other uracil carbonyl oxygen, O1, participates in two intermolecular C—H···O hydrogen bonds. The shorter of the two interactions arises with the atoms C12—H12 acting as the donor group. The hydrogen bond pattern forms a C(5) chain. The H12···O1 distance is 2.34 (2) Å. The longer interaction is with the atom H1X1 from the CH₂Cl₂ of solvation. The H1X2···O1 distance is 2.48 Å.

Related literature top

As part of our program in the synthesis of modified nucleobases that possess intrinsic fluorescence while maintaining an unadultered base-paring face, we have prepared an asymmetrical azo compound as a hybrid between a nulceobase and the known fluorescence quencher 4-((4-(dimethylamino)phenyl)azo)benzoic acid (DABCYL), see: Dodd & Hudson(2009); Tyagi & Kramer (1996). For an azo-based fluorescence quencher in peptide nucleic acid, see: Moustafa & Hudson (2011). For an example of photoisomerization of azo groups in peptide nucleic acid, see: Yue et al. (2009), and in DNA, see: Asanuma et al. (1999). The title compound was prepared following standard procedures, see: Thurber & Townsend (1972), Tsupak et al. (2002) and Moustafa (2011). All references (aprt from computer programs) must be cited here. Please note that the scheme should show the title compound only (the solvent must be included)

Computing details top

Data collection: COLLECT (Nonius, 1999); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008); molecular graphics: NRCVAX (Gabe et al., 1989); software used to prepare material for publication: cif2tables.py (Boyle, 2008).

Figures top

	Fig. 1. ORTEP representation of the title compound showing the atom-numbering. The asymmetric unit contains an enclathrated CH₂Cl₂ also.
	Fig. 2. Reaction scheme.

(E)-tert-Butyl 2-(5-{[4-(dimethylamino)phenyl]diazenyl}-2,6-dioxo-1H-pyrimidin-3-yl)acetate dichloromethane monosolvate top

Crystal data top

C₁₈H₂₃N₅O₄·CH₂Cl₂	F(000) = 960
M_r = 458.34	D_x = 1.339 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 13.208 (9) Å	Cell parameters from 9939 reflections
b = 10.783 (6) Å	θ = 2.3–28.1°
c = 17.255 (11) Å	µ = 0.32 mm⁻¹
β = 112.33 (2)°	T = 150 K
V = 2273 (3) Å³	Prism, colourless
Z = 4	0.20 × 0.18 × 0.15 mm

Data collection top

Nonius KappaCCD diffractometer	3567 reflections with I > 2σ(I)
Radiation source: sealed tube	R_int = 0.054
phi and ω scans	θ_max = 29.6°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −18→17
T_min = 0.689, T_max = 0.746	k = −14→14
34970 measured reflections	l = −22→23
5944 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.128	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0446P)² + 1.4761P] where P = (F_o² + 2F_c²)/3
5944 reflections	(Δ/σ)_max = 0.001
374 parameters	Δρ_max = 0.53 e Å⁻³
12 restraints	Δρ_min = −0.59 e Å⁻³

Crystal data top

C₁₈H₂₃N₅O₄·CH₂Cl₂	V = 2273 (3) Å³
M_r = 458.34	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 13.208 (9) Å	µ = 0.32 mm⁻¹
b = 10.783 (6) Å	T = 150 K
c = 17.255 (11) Å	0.20 × 0.18 × 0.15 mm
β = 112.33 (2)°

Data collection top

Nonius KappaCCD diffractometer	5944 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	3567 reflections with I > 2σ(I)
T_min = 0.689, T_max = 0.746	R_int = 0.054
34970 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	12 restraints
wR(F²) = 0.128	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.53 e Å⁻³
5944 reflections	Δρ_min = −0.59 e Å⁻³
374 parameters

Special details top

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

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.9052 (2)	0.7150 (3)	1.05913 (18)	0.0474 (7)
H1A	0.873 (2)	0.777 (2)	1.0869 (16)	0.045 (7)*
H1B	0.929 (3)	0.766 (3)	1.020 (2)	0.084 (11)*
H1C	0.969 (3)	0.675 (3)	1.101 (2)	0.083 (11)*
C2	0.8704 (2)	0.4912 (3)	1.02020 (18)	0.0443 (7)
H2A	0.939 (3)	0.490 (3)	1.069 (2)	0.071 (9)*
H2B	0.891 (2)	0.465 (2)	0.9674 (18)	0.056 (8)*
H2C	0.817 (3)	0.427 (3)	1.0273 (19)	0.071 (10)*
N1	0.82913 (15)	0.61752 (19)	1.01530 (12)	0.0372 (5)
C3	0.72814 (16)	0.6469 (2)	0.95471 (13)	0.0279 (5)
C4	0.68748 (18)	0.7695 (2)	0.94533 (14)	0.0305 (5)
H4	0.7300 (18)	0.833 (2)	0.9799 (14)	0.028 (6)*
C5	0.58531 (18)	0.7985 (2)	0.88637 (14)	0.0293 (5)
H5	0.5580 (19)	0.877 (2)	0.8811 (15)	0.039 (7)*
C6	0.51979 (16)	0.70655 (18)	0.83333 (12)	0.0232 (4)
C7	0.56023 (17)	0.58499 (19)	0.84203 (14)	0.0261 (5)
H7	0.5167 (17)	0.524 (2)	0.8034 (14)	0.029 (6)*
C8	0.66189 (17)	0.5549 (2)	0.90144 (14)	0.0281 (5)
H8	0.6874 (18)	0.469 (2)	0.9054 (14)	0.034 (6)*
N2	0.41469 (13)	0.72338 (16)	0.77085 (10)	0.0250 (4)
N3	0.37871 (13)	0.83448 (15)	0.76006 (10)	0.0245 (4)
C9	0.26949 (15)	0.83883 (18)	0.69941 (12)	0.0213 (4)
C10	0.23176 (16)	0.95536 (18)	0.65479 (12)	0.0210 (4)
O1	0.28351 (11)	1.05269 (13)	0.66708 (9)	0.0269 (3)
N4	0.12641 (13)	0.94789 (16)	0.59289 (10)	0.0216 (4)
H4A	0.1030 (19)	1.012 (2)	0.5641 (16)	0.037 (7)*
C11	0.05549 (15)	0.84931 (18)	0.57493 (12)	0.0199 (4)
O2	−0.03756 (11)	0.85176 (13)	0.52046 (8)	0.0254 (3)
N5	0.09479 (13)	0.74509 (14)	0.62430 (10)	0.0207 (4)
C12	0.19932 (16)	0.74158 (19)	0.68434 (12)	0.0226 (4)
H12	0.2182 (18)	0.663 (2)	0.7162 (14)	0.033 (6)*
C13	0.01573 (17)	0.64735 (19)	0.61964 (14)	0.0229 (4)
H13A	0.0566 (19)	0.576 (2)	0.6456 (15)	0.036 (6)*
H13B	−0.0272 (17)	0.6270 (19)	0.5626 (14)	0.023 (5)*
C14	−0.05649 (16)	0.68765 (18)	0.66563 (12)	0.0220 (4)
O3	−0.03756 (12)	0.77674 (14)	0.71118 (9)	0.0318 (4)
O4	−0.14075 (11)	0.60916 (13)	0.64849 (8)	0.0245 (3)
C15	−0.21469 (16)	0.6153 (2)	0.69607 (13)	0.0271 (5)
C16	−0.1464 (2)	0.5914 (3)	0.78781 (16)	0.0456 (7)
H16A	−0.095 (2)	0.659 (3)	0.8133 (19)	0.066 (9)*
H16B	−0.104 (3)	0.516 (3)	0.7938 (19)	0.070 (10)*
H16C	−0.193 (3)	0.584 (3)	0.819 (2)	0.072 (10)*
C17	−0.2744 (2)	0.7388 (3)	0.6801 (2)	0.0440 (6)
H17A	−0.328 (2)	0.738 (3)	0.7089 (17)	0.057 (8)*
H17B	−0.311 (2)	0.755 (3)	0.6188 (19)	0.056 (8)*
H17C	−0.227 (3)	0.807 (3)	0.7051 (19)	0.065 (9)*
C18	−0.2945 (2)	0.5097 (3)	0.65820 (18)	0.0382 (6)
H18A	−0.256 (2)	0.432 (2)	0.6654 (15)	0.040 (7)*
H18B	−0.337 (2)	0.524 (3)	0.595 (2)	0.067 (9)*
H18C	−0.347 (2)	0.506 (3)	0.6847 (17)	0.054 (8)*
C1X	0.8190 (3)	0.1657 (3)	1.1140 (2)	0.0728 (10)	0.630 (13)
H1X1	0.8564	0.1666	1.1758	0.087*	0.630 (13)
H1X2	0.7807	0.2460	1.0970	0.087*	0.630 (13)
Cl1X	0.91767 (6)	0.15439 (9)	1.07048 (5)	0.0687 (3)	0.630 (13)
Cl2X	0.72201 (17)	0.0480 (2)	1.08651 (16)	0.0511 (7)	0.630 (13)
C1Y	0.8190 (3)	0.1657 (3)	1.1140 (2)	0.0728 (10)	0.370 (13)
H1Y1	0.8550	0.1888	1.1739	0.087*	0.370 (13)
H1Y2	0.7669	0.2326	1.0853	0.087*	0.370 (13)
Cl1Y	0.91767 (6)	0.15439 (9)	1.07048 (5)	0.0687 (3)	0.370 (13)
Cl2Y	0.7489 (11)	0.0313 (6)	1.1063 (8)	0.114 (2)	0.370 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0272 (13)	0.072 (2)	0.0370 (15)	−0.0029 (13)	0.0051 (12)	0.0058 (15)
C2	0.0346 (14)	0.0589 (18)	0.0386 (15)	0.0208 (13)	0.0128 (12)	0.0140 (13)
N1	0.0243 (9)	0.0461 (12)	0.0349 (11)	0.0039 (9)	0.0042 (8)	0.0078 (9)
C3	0.0231 (10)	0.0355 (12)	0.0267 (11)	0.0020 (9)	0.0112 (9)	0.0078 (9)
C4	0.0291 (11)	0.0286 (12)	0.0293 (11)	−0.0049 (10)	0.0061 (10)	−0.0004 (10)
C5	0.0305 (11)	0.0224 (11)	0.0322 (12)	0.0019 (9)	0.0087 (10)	0.0025 (9)
C6	0.0223 (10)	0.0211 (10)	0.0257 (10)	0.0003 (8)	0.0083 (8)	0.0028 (8)
C7	0.0241 (10)	0.0226 (11)	0.0331 (12)	−0.0018 (9)	0.0126 (9)	0.0001 (9)
C8	0.0274 (11)	0.0238 (11)	0.0362 (12)	0.0046 (9)	0.0154 (10)	0.0069 (9)
N2	0.0231 (9)	0.0244 (9)	0.0264 (9)	0.0010 (7)	0.0083 (7)	0.0023 (7)
N3	0.0241 (9)	0.0250 (9)	0.0238 (9)	0.0010 (7)	0.0085 (7)	0.0040 (7)
C9	0.0211 (9)	0.0227 (10)	0.0199 (10)	0.0007 (8)	0.0076 (8)	0.0011 (8)
C10	0.0250 (10)	0.0207 (10)	0.0196 (9)	0.0000 (8)	0.0109 (8)	−0.0008 (8)
O1	0.0308 (8)	0.0201 (7)	0.0284 (8)	−0.0036 (6)	0.0097 (6)	−0.0010 (6)
N4	0.0235 (8)	0.0181 (9)	0.0221 (9)	0.0009 (7)	0.0073 (7)	0.0038 (7)
C11	0.0233 (10)	0.0190 (10)	0.0206 (10)	0.0012 (8)	0.0117 (8)	0.0008 (8)
O2	0.0236 (7)	0.0233 (7)	0.0257 (7)	0.0011 (6)	0.0052 (6)	0.0032 (6)
N5	0.0211 (8)	0.0177 (8)	0.0237 (8)	−0.0002 (7)	0.0088 (7)	0.0026 (7)
C12	0.0251 (10)	0.0207 (11)	0.0226 (10)	0.0040 (8)	0.0096 (9)	0.0038 (8)
C13	0.0229 (10)	0.0170 (10)	0.0287 (11)	−0.0010 (8)	0.0097 (9)	0.0017 (9)
C14	0.0228 (10)	0.0193 (10)	0.0224 (10)	−0.0006 (8)	0.0068 (8)	0.0053 (8)
O3	0.0373 (9)	0.0270 (8)	0.0348 (8)	−0.0071 (7)	0.0179 (7)	−0.0087 (7)
O4	0.0248 (7)	0.0231 (7)	0.0287 (8)	−0.0038 (6)	0.0138 (6)	−0.0004 (6)
C15	0.0244 (10)	0.0315 (12)	0.0297 (11)	−0.0011 (9)	0.0151 (9)	0.0013 (9)
C16	0.0399 (15)	0.069 (2)	0.0298 (13)	−0.0125 (15)	0.0155 (12)	0.0091 (13)
C17	0.0367 (14)	0.0416 (16)	0.0602 (19)	0.0039 (12)	0.0255 (14)	−0.0042 (14)
C18	0.0325 (13)	0.0400 (15)	0.0457 (15)	−0.0086 (11)	0.0189 (12)	−0.0017 (12)
C1X	0.085 (2)	0.0521 (19)	0.105 (3)	−0.0259 (17)	0.063 (2)	−0.0354 (18)
Cl1X	0.0585 (5)	0.0981 (7)	0.0553 (5)	−0.0121 (4)	0.0282 (4)	−0.0193 (4)
Cl2X	0.0499 (14)	0.0513 (13)	0.0461 (11)	−0.0163 (7)	0.0114 (11)	−0.0014 (7)
C1Y	0.085 (2)	0.0521 (19)	0.105 (3)	−0.0259 (17)	0.063 (2)	−0.0354 (18)
Cl1Y	0.0585 (5)	0.0981 (7)	0.0553 (5)	−0.0121 (4)	0.0282 (4)	−0.0193 (4)
Cl2Y	0.232 (6)	0.0284 (17)	0.153 (5)	−0.024 (3)	0.155 (5)	−0.013 (3)

Geometric parameters (Å, º) top

C1—N1	1.452 (3)	C11—O2	1.232 (2)
C1—H1A	1.00 (3)	C11—N5	1.386 (2)
C1—H1B	1.01 (4)	N5—C12	1.376 (3)
C1—H1C	0.98 (4)	N5—C13	1.464 (3)
C2—N1	1.458 (3)	C12—H12	0.99 (2)
C2—H2A	0.98 (3)	C13—C14	1.518 (3)
C2—H2B	1.08 (3)	C13—H13A	0.95 (2)
C2—H2C	1.03 (3)	C13—H13B	0.96 (2)
N1—C3	1.383 (3)	C14—O3	1.206 (2)
C3—C8	1.408 (3)	C14—O4	1.339 (2)
C3—C4	1.414 (3)	O4—C15	1.497 (3)
C4—C5	1.382 (3)	C15—C16	1.517 (3)
C4—H4	0.94 (2)	C15—C17	1.518 (3)
C5—C6	1.403 (3)	C15—C18	1.521 (3)
C5—H5	0.91 (3)	C16—H16A	0.98 (3)
C6—C7	1.402 (3)	C16—H16B	0.97 (3)
C6—N2	1.409 (3)	C16—H16C	0.95 (3)
C7—C8	1.383 (3)	C17—H17A	1.00 (3)
C7—H7	0.95 (2)	C17—H17B	1.00 (3)
C8—H8	0.98 (2)	C17—H17C	0.96 (3)
N2—N3	1.276 (2)	C18—H18A	0.97 (3)
N3—C9	1.425 (3)	C18—H18B	1.03 (3)
C9—C12	1.358 (3)	C18—H18C	0.97 (3)
C9—C10	1.459 (3)	C1X—Cl2X	1.737 (3)
C10—O1	1.226 (2)	C1X—Cl1X	1.738 (3)
C10—N4	1.398 (3)	C1X—H1X1	0.9900
N4—C11	1.372 (3)	C1X—H1X2	0.9900
N4—H4A	0.84 (3)

N1—C1—H1A	113.5 (15)	C12—N5—C11	121.27 (16)
N1—C1—H1B	112.0 (19)	C12—N5—C13	120.81 (16)
H1A—C1—H1B	104 (2)	C11—N5—C13	117.19 (16)
N1—C1—H1C	108 (2)	C9—C12—N5	122.66 (18)
H1A—C1—H1C	110 (2)	C9—C12—H12	123.2 (13)
H1B—C1—H1C	109 (3)	N5—C12—H12	114.2 (13)
N1—C2—H2A	105.4 (19)	N5—C13—C14	110.01 (17)
N1—C2—H2B	113.6 (14)	N5—C13—H13A	107.0 (14)
H2A—C2—H2B	106 (2)	C14—C13—H13A	110.0 (14)
N1—C2—H2C	112.1 (17)	N5—C13—H13B	110.7 (13)
H2A—C2—H2C	110 (2)	C14—C13—H13B	111.1 (13)
H2B—C2—H2C	109 (2)	H13A—C13—H13B	107.9 (19)
C3—N1—C1	120.4 (2)	O3—C14—O4	126.64 (19)
C3—N1—C2	119.3 (2)	O3—C14—C13	123.57 (18)
C1—N1—C2	118.5 (2)	O4—C14—C13	109.78 (17)
N1—C3—C8	121.0 (2)	C14—O4—C15	120.76 (16)
N1—C3—C4	121.1 (2)	O4—C15—C16	108.16 (19)
C8—C3—C4	117.98 (19)	O4—C15—C17	109.97 (18)
C5—C4—C3	121.2 (2)	C16—C15—C17	113.6 (2)
C5—C4—H4	118.8 (13)	O4—C15—C18	102.75 (18)
C3—C4—H4	120.0 (13)	C16—C15—C18	111.2 (2)
C4—C5—C6	120.6 (2)	C17—C15—C18	110.6 (2)
C4—C5—H5	121.4 (15)	C15—C16—H16A	112.1 (18)
C6—C5—H5	118.0 (15)	C15—C16—H16B	110.1 (19)
C7—C6—C5	118.39 (19)	H16A—C16—H16B	108 (2)
C7—C6—N2	115.27 (18)	C15—C16—H16C	109.9 (19)
C5—C6—N2	126.34 (19)	H16A—C16—H16C	107 (3)
C8—C7—C6	121.4 (2)	H16B—C16—H16C	110 (3)
C8—C7—H7	121.1 (13)	C15—C17—H17A	108.7 (16)
C6—C7—H7	117.4 (13)	C15—C17—H17B	110.5 (17)
C7—C8—C3	120.4 (2)	H17A—C17—H17B	112 (2)
C7—C8—H8	119.0 (13)	C15—C17—H17C	112.6 (18)
C3—C8—H8	120.6 (13)	H17A—C17—H17C	104 (2)
N3—N2—C6	115.89 (16)	H17B—C17—H17C	108 (2)
N2—N3—C9	110.80 (16)	C15—C18—H18A	110.5 (15)
C12—C9—N3	122.83 (18)	C15—C18—H18B	110.8 (16)
C12—C9—C10	119.52 (18)	H18A—C18—H18B	109 (2)
N3—C9—C10	117.61 (17)	C15—C18—H18C	109.2 (17)
O1—C10—N4	120.61 (18)	H18A—C18—H18C	110 (2)
O1—C10—C9	126.13 (18)	H18B—C18—H18C	107 (2)
N4—C10—C9	113.26 (17)	Cl2X—C1X—Cl1X	115.3 (2)
C11—N4—C10	127.82 (17)	Cl2X—C1X—H1X1	108.5
C11—N4—H4A	116.1 (17)	Cl1X—C1X—H1X1	108.5
C10—N4—H4A	116.0 (17)	Cl2X—C1X—H1X2	108.5
O2—C11—N4	123.60 (18)	Cl1X—C1X—H1X2	108.5
O2—C11—N5	121.23 (17)	H1X1—C1X—H1X2	107.5
N4—C11—N5	115.15 (17)

C1—N1—C3—C8	168.5 (2)	N3—C9—C10—N4	175.99 (16)
C2—N1—C3—C8	4.1 (3)	O1—C10—N4—C11	−175.49 (18)
C1—N1—C3—C4	−12.6 (3)	C9—C10—N4—C11	4.9 (3)
C2—N1—C3—C4	−177.0 (2)	C10—N4—C11—O2	177.93 (19)
N1—C3—C4—C5	−178.2 (2)	C10—N4—C11—N5	−0.6 (3)
C8—C3—C4—C5	0.7 (3)	O2—C11—N5—C12	179.03 (18)
C3—C4—C5—C6	−0.9 (3)	N4—C11—N5—C12	−2.4 (3)
C4—C5—C6—C7	0.4 (3)	O2—C11—N5—C13	−10.7 (3)
C4—C5—C6—N2	−180.0 (2)	N4—C11—N5—C13	167.88 (17)
C5—C6—C7—C8	0.3 (3)	N3—C9—C12—N5	−178.38 (18)
N2—C6—C7—C8	−179.39 (19)	C10—C9—C12—N5	4.2 (3)
C6—C7—C8—C3	−0.5 (3)	C11—N5—C12—C9	0.5 (3)
N1—C3—C8—C7	178.9 (2)	C13—N5—C12—C9	−169.43 (19)
C4—C3—C8—C7	0.0 (3)	C12—N5—C13—C14	96.3 (2)
C7—C6—N2—N3	−177.35 (18)	C11—N5—C13—C14	−74.0 (2)
C5—C6—N2—N3	3.0 (3)	N5—C13—C14—O3	−12.2 (3)
C6—N2—N3—C9	−176.25 (16)	N5—C13—C14—O4	168.70 (15)
N2—N3—C9—C12	26.9 (3)	O3—C14—O4—C15	−8.9 (3)
N2—N3—C9—C10	−155.63 (17)	C13—C14—O4—C15	170.22 (16)
C12—C9—C10—O1	173.92 (19)	C14—O4—C15—C16	−60.9 (2)
N3—C9—C10—O1	−3.6 (3)	C14—O4—C15—C17	63.7 (2)
C12—C9—C10—N4	−6.5 (3)	C14—O4—C15—C18	−178.54 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···O2ⁱ	0.84 (3)	2.02 (3)	2.851 (2)	171 (2)
C2—H2C···O1ⁱⁱ	1.03 (3)	2.62 (3)	3.189 (4)	115 (2)
C4—H4···Cl2Xⁱⁱⁱ	0.94 (2)	2.98 (2)	3.784 (4)	143.5 (17)
C12—H12···O1^iv	0.99 (2)	2.34 (2)	3.214 (3)	145.8 (18)
C13—H13B···Cl2X^v	0.96 (2)	2.99 (2)	3.895 (4)	158.6 (16)
C16—H16A···O3	0.98 (3)	2.51 (3)	3.042 (3)	114 (2)
C17—H17C···O3	0.96 (3)	2.48 (3)	2.994 (4)	113 (2)
C1X—H1X1···O3^vi	0.99	2.52	3.346 (4)	141
C1X—H1X2···O1ⁱⁱ	0.99	2.48	3.256 (4)	135
C1Y—H1Y1···O3^vi	0.99	2.50	3.346 (4)	143

Symmetry codes: (i) −x, −y+2, −z+1; (ii) x+1/2, −y+3/2, z+1/2; (iii) x, y+1, z; (iv) −x+1/2, y−1/2, −z+3/2; (v) −x+1/2, y+1/2, −z+3/2; (vi) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···O2ⁱ	0.84 (3)	2.02 (3)	2.851 (2)	171 (2)
C2—H2C···O1ⁱⁱ	1.03 (3)	2.62 (3)	3.189 (4)	115 (2)
C4—H4···Cl2Xⁱⁱⁱ	0.94 (2)	2.98 (2)	3.784 (4)	143.5 (17)
C12—H12···O1^iv	0.99 (2)	2.34 (2)	3.214 (3)	145.8 (18)
C13—H13B···Cl2X^v	0.96 (2)	2.99 (2)	3.895 (4)	158.6 (16)
C16—H16A···O3	0.98 (3)	2.51 (3)	3.042 (3)	114 (2)
C17—H17C···O3	0.96 (3)	2.48 (3)	2.994 (4)	113 (2)
C1X—H1X1···O3^vi	0.99	2.52	3.346 (4)	140.7
C1X—H1X2···O1ⁱⁱ	0.99	2.48	3.256 (4)	135.3
C1Y—H1Y1···O3^vi	0.99	2.50	3.346 (4)	143.1

Symmetry codes: (i) −x, −y+2, −z+1; (ii) x+1/2, −y+3/2, z+1/2; (iii) x, y+1, z; (iv) −x+1/2, y−1/2, −z+3/2; (v) −x+1/2, y+1/2, −z+3/2; (vi) −x+1, −y+1, −z+2.

Acknowledgements

The authors thank NSERC Canada and the School of Graduate and Postdoctoral Studies (Western) for financial support of this work and the Egyptian Higher Education Ministry for scholarship support for MEM.

References

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Volume 70| Part 5| May 2014| Pages o556-o557

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

(E)-tert-Butyl 2-(5-{[4-(di­methylamino)phenyl]diazenyl}-2,6-dioxo-1H-pyrimid­in-3-yl)acetate di­chloro­methane monosolvate

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organic compounds

(E)-tert-Butyl 2-(5-{[4-(dimethylamino)phenyl]diazenyl}-2,6-dioxo-1H-pyrimidin-3-yl)acetate dichloromethane monosolvate