The molecular and supramolecular structures of the isomeric compounds 5,7-di­methoxy­imidazo­[1,2-c]­pyrimidine and 7-methoxy-1-methyl­imidazo­[1,2-a]­pyrimidin-5(1H)-one

The supramolecular structures of the isomeric compounds 5,7-di­methoxy­imidazo­[1,2-c]­pyrimidine, C₈H₉N₃O₂, (I), and 7-methoxy-1-methyl­imidazo­[1,2-a]­pyrimidin-5(1H)-one, C₈H₉N₃O₂, (II), are determined by weak C-H...N and C-H...O hydrogen bonds in (I), which generate alternating linked centrosymmetric R₂²(8) and R₂²(10) rings that form a ribbon running parallel to the c axis, and by C-H...O bonds in (II), which link the mol­ecules into sheets comprising centro­symmetric R₂²(10) and R₄⁴(22) rings.

S1. Comment

Imidazopyrimidine derivatives are a group of fused heterocyclic systems of particular interest due to their resemblance to the ubiquitous biologically important purine, and thence their potential as antimetabolites showing useful biological activities. In fact, some imidazo[1,2-a]pyrimidines have shown antifungal (Rival et al., 1991) and anti-inflammatory/analgesic activities (Sacchi et al., 1997). In this paper, we report the molecular and supramolecular structure of two isomeric examples of such fused heterocyclic derivatives, namely 5,7-dimethoxyimidazo[1,2-c]pyrimidine, (I), and 7-methoxy-1-methylimidazo [1,2-a]pyrimidin-5(1H)-one, (II). The former was prepared by reaction of commercial 4-amino-2,6-dimethoxypyrimidine with bromoacetaldehyde (Quijano et al. 1994). The latter was obtained in good yield by fusion of the crystalline intermediate 5,7-dimethoxyimidazo[1,2-a]pyrimidine, which was prepared by reaction of commercial 2-amino-4,6-dimethoxypyrimidine with bromoacetaldehyde.

There are no unusual bond lengths or angles in (I) and (II), however, the bond distances along the fused heterocycle perimeter of (I) show a clear alternation in single- and double-bond character, so pointing to the low aromatic nature of this compound (Table 1). In both compounds, the six- and five-membered rings are planar, with the angle between the rings in being 1.40 (10) and 3.13 (12)° in (I) and (II), respectively. In (I), the torsion angles about the C5—O5 and C7—O7 bonds show that the methoxy groups are coplanar with the ring system. In (II), however, the torsion angles about the C7—O7 bond show that the methoxy group is tilted out of the plane of the ring system (Table 3).

In the absence of any donors for conventional hydrogen bonds, the supramolecular structures are controlled by the formation of weak C—H···N and C—H···O hydrogen bonds in (I) and by weak C—H···O hydrogen bonds in (II). In the case of (I), these are weaker than in (II), as evidenced by the C8···N1 and C3···O5 distances of 3.476 (2) and 3.391 (2) Å, respectively, for (I), and the C3···O5 and C2···O5 distances of 3.104 (3) and 3.339 (3) Å, respectively, in for (II). Details of the hydrogen bonding are given in Tables 2 and 4.

In (I), the molecules are linked to form one-dimensional ribbons of centrosymmetric dimers which run parallel to the c axis (Fig. 3). Atom C8 in the molecule at (x, y, z) acts as a hydrogen-bond donor, via atom H8, to ring atom N1 in the molecule at (-x, 1 − y, 1 − z), so generating a centrosymmetric R²₂(8) ring (Bernstein et al., 1995) centred at (0, 1/2, 1/2). Atom C3 in the molecule at (x, y, z) acts as a hydrogen-bond donor, via atom H3, to methoxy atom O5 in the molecule at (-x, 1 − y, −z), so generating a centrosymmetric R²₂(10) ring centred at (0, 1/2, 0). Alternatively, the molecules can be viewed as being linked head-to-tail by two centrosymmetrically related C²₂(10) chains. There are no other direction-specific contacts in the structure.

In (II), atom C2 in the molecule at (x, y, z) acts as a hydrogen-bond donor, via atom H2, to O5 in the molecule at (x, 1.5 − y, 0.5 + z), so generating a C(6) chain which runs parallel to the c axis (Fig. 4). This chain is produced by the action of the c-glide plane at y = 0.75. This chain is then linked to an antiparallel chain produced by the action of centres-of-symmetry to form a corrugated ribbon which lies approximately parallel to the (010) plane. In the crosslink, atom C3 in the molecule at (x, y, z) acts as a hydrogen-bond donor, via atom H3, to atom O5 in the molecule at (1 − x, 1 − y, 1 − z), so generating a centrosymmetric R²₂(10) ring centred at (1/2, 1/2, 1/2). An R⁴₄(22) ring centred at (1/2, 1/2, 1) is also formed involving six molecules, with four C2–H2···O5 and two C3–H3···O5 interactions. In this ring, two molecules donate and accept one interaction each, two accept two interactions to the same atom and two donate two interactions via two different H atoms each (Fig. 4). These ribbons are then linked via further C3–H3···O5 crosslinks, extending the structure parallel to the b axis, thereby forming corrugated sheets which lie in the (100) plane.

The molecules stack above each other such that atom N4 of the five-membered ring lies almost directly above the centroid of the five-membered ring at (1 − x, 1 − y, −z). The inter-centroid distance is 3.5221 (14) Å, the perpedicular distance between the centroid of one ring and the plane of the other is 3.301 Å, and the offset between centroids is 1.228 Å. A view of the stacking is shown in Fig. 5. Fig. 6 shows a stereoview of the three-dimensional structure formed by the interaction of the sheets and also the molecular stacking.

S2. Experimental

For the preparation of 5,7-dimethoxyimidazo[1,2-c]pyrimidine, (I), a mixture of bromoacetaldehyde diethyl acetal (6.9 ml, 45.4 mmol) and water (25 ml) was treated with concentrated hydrochloric acid (2.5 ml) and heated until a homogeneous solution was obtained. The pH was adjusted to 5–6 by addition of solid sodium acetate and the resulting solution was added dropwise to a suspension of 4-amino-2,6-dimethoxypyrimidine (0.51 g, 3.2 mmol) in water (13 ml) containing sodium acetate (0.27 g, 3.2 mmol). The mixture was refluxed for 20 min and, after cooling, 1 N NaOH was added until a pH of 8 was achieved. The crude reaction mixture was extracted with dichloromethane. The extract was dried over anhydrous sodium sulfate and the solvent removed in vacuo. The residue was chromatographed on a silica-gel flash column to afford 0.214 g (1.19 mmol, 37%) of compound (I). ¹H NMR (300 MHz, CDCl₃/TMS): δ 3.92 (s, 3H, CH₃O-7), 4.21 (s, 3H, CH₃O-5), 6.37 (s, 1H, H-8), 7.42 (s, 2H, H-2 and H-3); ¹³C NMR (75 MHz, CDCl₃/TMS): δ 55.26, 55.87, 82.19, 107,02, 134.03, 148.13, 150.05, 160.56. Recrystallization from ethyl acetate produced a crystalline sample suitable for single-crystal X-ray diffraction analysis (m.p. 387 K).

7-Methoxy-1-methylimidazo[1,2-a]pyrimidin-5(1H)-one, (II), was prepared using a procedure similar to that for compound (I). 5,7-Dimethoxyimidazo[1,2-a]pyrimidine (150 mg, 0.837 mmol) was obtained from 2-amino-4,6-dimethoxypyrimidine (1.64 g, 10.3 mmol) and bromoacetaldehyde diethyl acetal (6.25 ml, 41.2 mmol) (reaction time: 40 min). M.p. 399 K. ¹H NMR (300 MHz, CDCl₃/TMS): δ 4.03 (s, 3H, CH₃O-7), 4.08 (s, 3H, CH₃O-5), 5.67 (s, 1H, H-6), 7.34 (d, J = 1,7 Hz, 1H, H-3), 7.42 (d, J = 1,7 Hz, 1H, H-2). ¹³C NMR (75 MHz, CDCl₃/TMS): δ 54.35, 56.72, 77.12, 105.87, 132.06, 149.06, 156.36, 165.12. This compound was placed in a Pyrex tube and heated in an oil bath at 403 K for 20 min. During this period, melting and resolidification of the starting material was observed. The solid residue was directly recrystallized from ethyl acetate to afford 113 mg (0.631 mmol, 75% yield) of compound (II) as crystals suitable for X-ray diffraction analysis (m. p. 449 K). ¹H NMR (300 MHz, CDCl₃/TMS): δ 3.67 (s, 3H, CH₃N), 3.89 (s, 3H, CH₃O), 5.39 (s, 1H, H-6), 6.86 (d, J = 3.1 Hz, 1H, H-2), 7.48 (d, J = 3.1 Hz, 1H, H-3). ¹³C NMR (75 MHz, CDCl₃/TMS): δ 31.51, 54.28, 80.01, 106.89, 118.28, 145.72, 158.97, 170.37

S3. Refinement

Compound (I) crystallized in the triclinic system; space group P1 was assumed and confirmed by the analysis. Compound (II) crystallized in the monoclinic system; space group P2₁/c was assumed from the systematic absences. In both compounds, H atoms were treated as riding atoms, with C—H distances of 0.95 (aromatic) and 0.98 Å (CH₃).

Computing details

For both compounds, data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and WORDPERFECT macro PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. A view of (I) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A view of (II) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 3. View of the ribbon structure running parallel to the c axis in (I). Atoms marked with an asterisk (*), hash (#) or ampersand (&) are at the symmetry positions (-x, 1 − y, −z), (-x, 1 − y, 1 − z) and (x, y, 1 + z), respectively.
	Fig. 4. View of the part of the sheet structure formed in (II) by two antiparallel C(6) chains linked by centrosymmetric R^22^(10) and R44(22) rings. Atoms marked with an asterisk (*), hash (#), ampersand (&), dollar sign ($) or `at' sign (@) are at the symmetry positions (x, 1.5 − y, 0.5 + z), (1 − x, 1 − y, 1 − z), (1 − x, −0.5 + y, 1.5 − z), (x, y, 1 + z) and (1 − x, 1 − y, 2 − z), respectively.
	Fig. 5. View of the stacking of the molecules in (II), showing the positon of atom N4 almost directly above the centroid of the five-membered ring. The molecule labelled with an asterisk (*) is at the symmetry position (1 − x, 1 − y, 1 − z).
	Fig. 6. Stereoview of the three-dimensional structure of (II), viewed down the a axis.

(I) 5,7-dimethoxyimidazo[1,2-c]pyrimidine

Crystal data

C8H9N3O2	Z = 2
Mr = 179.18	F(000) = 188
Triclinic, P1	Dx = 1.484 Mg m^−3
Hall symbol: -P 1	Melting point: 387 K
a = 3.8798 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.9183 (6) Å	Cell parameters from 1756 reflections
c = 12.6224 (11) Å	θ = 3.5–27.4°
α = 69.426 (3)°	µ = 0.11 mm^−1
β = 83.093 (4)°	T = 120 K
γ = 79.189 (4)°	Block, colourless
V = 400.94 (5) Å^3	0.22 × 0.14 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer	1182 reflections with I > 2σ(I)
Radiation source: fine-focus sealed X-ray tube	Rint = 0.058
Graphite monochromator	θmax = 27.4°, θmin = 3.5°
ϕ scans and ω scans with κ offsets	h = −5→4
6415 measured reflections	k = −11→11
1756 independent reflections	l = −16→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.134	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0751P)^2] where P = (Fo^2 + 2Fc^2)/3
1756 reflections	(Δ/σ)max < 0.001
120 parameters	Δρmax = 0.31 e Å^−3
0 restraints	Δρmin = −0.32 e Å^−3

Special details

Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm (Fox & Holmes, 1966) which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the 'size' command in the SHELXL97 input file.

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

	x	y	z	Uiso*/Ueq
N1	0.0425 (4)	0.37339 (18)	0.37285 (12)	0.0269 (4)
C2	−0.0218 (5)	0.3154 (2)	0.28995 (15)	0.0268 (5)
C3	0.0311 (5)	0.4191 (2)	0.18361 (15)	0.0258 (4)
N4	0.1346 (4)	0.55052 (17)	0.19891 (11)	0.0224 (4)
C5	0.2346 (5)	0.6905 (2)	0.12447 (14)	0.0216 (4)
O5	0.2332 (3)	0.70044 (14)	0.01661 (9)	0.0263 (4)
C51	0.3399 (5)	0.8458 (2)	−0.06818 (14)	0.0272 (5)
N6	0.3217 (4)	0.80121 (17)	0.15539 (11)	0.0235 (4)
C7	0.3118 (5)	0.7735 (2)	0.27021 (14)	0.0233 (4)
O7	0.3967 (3)	0.90308 (14)	0.28836 (9)	0.0282 (4)
C71	0.4070 (5)	0.8903 (2)	0.40490 (14)	0.0288 (5)
C8	0.2278 (5)	0.6363 (2)	0.35239 (15)	0.0245 (4)
C9	0.1371 (5)	0.5168 (2)	0.31598 (14)	0.0221 (4)
H2	−0.0954	0.2135	0.3060	0.032*
H3	0.0036	0.4051	0.1141	0.031*
H51A	0.1643	0.9401	−0.0676	0.041*
H51B	0.3592	0.8346	−0.1433	0.041*
H51C	0.5681	0.8605	−0.0508	0.041*
H71A	0.1755	0.8743	0.4438	0.043*
H71B	0.4695	0.9900	0.4081	0.043*
H71C	0.5828	0.7978	0.4422	0.043*
H8	0.2301	0.6217	0.4306	0.029*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0326 (9)	0.0241 (8)	0.0249 (8)	−0.0088 (7)	−0.0017 (7)	−0.0075 (6)
C2	0.0338 (11)	0.0220 (9)	0.0268 (10)	−0.0079 (8)	−0.0031 (8)	−0.0087 (8)
C3	0.0329 (11)	0.0224 (10)	0.0255 (9)	−0.0061 (8)	−0.0044 (8)	−0.0104 (8)
N4	0.0265 (9)	0.0204 (8)	0.0205 (8)	−0.0050 (7)	−0.0020 (6)	−0.0065 (6)
C5	0.0241 (10)	0.0227 (9)	0.0187 (9)	−0.0026 (8)	−0.0023 (7)	−0.0077 (7)
O5	0.0389 (8)	0.0238 (7)	0.0177 (6)	−0.0096 (6)	−0.0013 (5)	−0.0064 (5)
C51	0.0354 (11)	0.0250 (10)	0.0193 (9)	−0.0090 (8)	0.0016 (8)	−0.0040 (7)
N6	0.0295 (9)	0.0212 (8)	0.0206 (8)	−0.0065 (7)	−0.0019 (6)	−0.0064 (6)
C7	0.0263 (10)	0.0234 (9)	0.0223 (9)	−0.0037 (8)	−0.0041 (7)	−0.0095 (7)
O7	0.0424 (9)	0.0250 (7)	0.0211 (7)	−0.0118 (6)	−0.0027 (6)	−0.0088 (5)
C71	0.0381 (12)	0.0304 (11)	0.0230 (10)	−0.0099 (9)	−0.0044 (8)	−0.0121 (8)
C8	0.0279 (10)	0.0262 (10)	0.0201 (9)	−0.0047 (8)	−0.0021 (8)	−0.0084 (7)
C9	0.0231 (10)	0.0236 (9)	0.0188 (9)	−0.0018 (8)	−0.0032 (7)	−0.0064 (7)

Geometric parameters (Å, º)

N1—C9	1.324 (2)	C51—H51B	0.98
N1—C2	1.384 (2)	C51—H51C	0.98
C2—C3	1.353 (3)	N6—C7	1.379 (2)
C2—H2	0.95	C7—O7	1.358 (2)
C3—N4	1.388 (2)	C7—C8	1.362 (2)
C3—H3	0.95	O7—C71	1.4398 (19)
N4—C5	1.364 (2)	C71—H71A	0.98
N4—C9	1.402 (2)	C71—H71B	0.98
C5—N6	1.292 (2)	C71—H71C	0.98
C5—O5	1.3335 (19)	C8—C9	1.412 (2)
O5—C51	1.455 (2)	C8—H8	0.95
C51—H51A	0.98
C9—N1—C2	104.59 (15)	H51B—C51—H51C	109.5
C3—C2—N1	112.94 (16)	C5—N6—C7	117.12 (14)
C3—C2—H2	123.5	O7—C7—C8	125.53 (15)
N1—C2—H2	123.5	O7—C7—N6	109.84 (14)
C2—C3—N4	104.55 (15)	C8—C7—N6	124.63 (15)
C2—C3—H3	127.7	C7—O7—C71	116.35 (13)
N4—C3—H3	127.7	O7—C71—H71A	109.5
C5—N4—C3	132.45 (14)	O7—C71—H71B	109.5
C5—N4—C9	120.28 (14)	H71A—C71—H71B	109.5
C3—N4—C9	107.23 (13)	O7—C71—H71C	109.5
N6—C5—O5	123.74 (15)	H71A—C71—H71C	109.5
N6—C5—N4	123.52 (15)	H71B—C71—H71C	109.5
O5—C5—N4	112.75 (14)	C7—C8—C9	116.92 (16)
C5—O5—C51	116.14 (13)	C7—C8—H8	121.5
O5—C51—H51A	109.5	C9—C8—H8	121.5
O5—C51—H51B	109.5	N1—C9—N4	110.69 (14)
H51A—C51—H51B	109.5	N1—C9—C8	131.85 (16)
O5—C51—H51C	109.5	N4—C9—C8	117.44 (15)
H51A—C51—H51C	109.5
C9—N1—C2—C3	0.1 (2)	C5—N6—C7—C8	2.2 (3)
N1—C2—C3—N4	0.0 (2)	C8—C7—O7—C71	1.9 (3)
C2—C3—N4—C5	177.70 (18)	N6—C7—O7—C71	−178.37 (14)
C2—C3—N4—C9	0.0 (2)	O7—C7—C8—C9	178.19 (16)
C3—N4—C5—N6	179.63 (18)	N6—C7—C8—C9	−1.5 (3)
C9—N4—C5—N6	−2.9 (3)	C2—N1—C9—N4	−0.1 (2)
C3—N4—C5—O5	−0.5 (3)	C2—N1—C9—C8	178.37 (19)
C9—N4—C5—O5	177.01 (14)	C5—N4—C9—N1	−177.97 (15)
N6—C5—O5—C51	0.4 (2)	C3—N4—C9—N1	0.1 (2)
N4—C5—O5—C51	−179.47 (15)	C5—N4—C9—C8	3.3 (2)
O5—C5—N6—C7	−179.72 (16)	C3—N4—C9—C8	−178.62 (16)
N4—C5—N6—C7	0.1 (3)	C7—C8—C9—N1	−179.59 (19)
C5—N6—C7—O7	−177.62 (15)	C7—C8—C9—N4	−1.2 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···N1^i	0.95	2.59	3.476 (2)	155
C3—H3···O5^ii	0.95	2.50	3.391 (2)	157

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

(II) 7-methoxy-1-methylimidazo[1,2-a]pyrimidin-5(1H)-one

Crystal data

C8H9N3O2	F(000) = 376
Mr = 179.18	Dx = 1.436 Mg m^−3
Monoclinic, P21/c	Melting point: 449 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.5917 (6) Å	Cell parameters from 1855 reflections
b = 6.7484 (5) Å	θ = 3.3–27.5°
c = 14.3054 (14) Å	µ = 0.11 mm^−1
β = 91.648 (3)°	T = 120 K
V = 829.09 (12) Å^3	Plate, colourless
Z = 4	0.30 × 0.28 × 0.02 mm

Data collection

Nonius KappaCCD diffractometer	993 reflections with I > 2σ(I)
Radiation source: fine-focus sealed X-ray tube	Rint = 0.087
Graphite monochromator	θmax = 27.5°, θmin = 3.3°
ϕ scans and ω scans with κ offsets	h = −11→10
6217 measured reflections	k = −8→8
1855 independent reflections	l = −13→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.122	H-atom parameters constrained
S = 0.94	w = 1/[σ^2(Fo^2) + (0.0513P)^2] where P = (Fo^2 + 2Fc^2)/3
1855 reflections	(Δ/σ)max < 0.001
120 parameters	Δρmax = 0.21 e Å^−3
0 restraints	Δρmin = −0.29 e Å^−3

Special details

Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm (Fox & Holmes, 1966) which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the 'size' command in the SHELXL97 input file.

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

	x	y	z	Uiso*/Ueq
N1	0.6851 (2)	1.0258 (3)	0.62431 (13)	0.0233 (5)
C1	0.7393 (3)	1.1826 (3)	0.68716 (17)	0.0317 (6)
C2	0.5884 (3)	0.8698 (3)	0.64538 (17)	0.0249 (5)
C3	0.5694 (3)	0.7536 (3)	0.56916 (16)	0.0269 (6)
N4	0.6585 (2)	0.8409 (3)	0.49968 (12)	0.0223 (5)
C5	0.6857 (3)	0.7744 (3)	0.40684 (15)	0.0242 (5)
O5	0.61694 (19)	0.6226 (2)	0.37863 (11)	0.0310 (4)
C6	0.7908 (3)	0.8954 (3)	0.36131 (16)	0.0243 (5)
C7	0.8540 (3)	1.0617 (3)	0.40352 (16)	0.0236 (5)
O7	0.95467 (18)	1.1700 (2)	0.35333 (11)	0.0266 (4)
C71	1.0034 (3)	1.3575 (3)	0.39178 (17)	0.0316 (6)
N8	0.8256 (2)	1.1255 (3)	0.49053 (12)	0.0223 (5)
C9	0.7291 (2)	1.0068 (3)	0.53494 (16)	0.0210 (5)
H1A	0.6859	1.3067	0.6707	0.048*
H1B	0.8518	1.1999	0.6814	0.048*
H1C	0.7164	1.1467	0.7517	0.048*
H2	0.5425	0.8478	0.7041	0.030*
H3	0.5083	0.6366	0.5637	0.032*
H6	0.8198	0.8624	0.2996	0.029*
H71A	1.0548	1.3365	0.4530	0.047*
H71B	0.9123	1.4430	0.3989	0.047*
H71C	1.0763	1.4209	0.3497	0.047*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0243 (10)	0.0259 (10)	0.0195 (11)	−0.0008 (9)	−0.0002 (8)	−0.0026 (9)
C1	0.0351 (14)	0.0360 (14)	0.0240 (14)	−0.0051 (12)	0.0000 (11)	−0.0053 (11)
C2	0.0231 (12)	0.0298 (12)	0.0220 (13)	−0.0004 (11)	0.0032 (10)	0.0034 (11)
C3	0.0279 (12)	0.0284 (13)	0.0244 (14)	−0.0003 (11)	0.0033 (10)	0.0041 (11)
N4	0.0261 (10)	0.0243 (10)	0.0166 (10)	0.0018 (9)	0.0017 (8)	0.0009 (8)
C5	0.0276 (12)	0.0254 (12)	0.0196 (13)	0.0017 (11)	−0.0011 (10)	−0.0019 (10)
O5	0.0412 (10)	0.0283 (9)	0.0234 (9)	−0.0047 (8)	0.0021 (8)	−0.0033 (8)
C6	0.0270 (12)	0.0292 (13)	0.0169 (12)	0.0035 (11)	0.0011 (10)	−0.0002 (10)
C7	0.0224 (12)	0.0284 (12)	0.0198 (13)	0.0047 (11)	0.0002 (10)	0.0060 (10)
O7	0.0289 (9)	0.0295 (9)	0.0217 (9)	−0.0036 (7)	0.0052 (7)	0.0010 (7)
C71	0.0351 (14)	0.0317 (13)	0.0283 (14)	−0.0069 (12)	0.0041 (11)	−0.0009 (11)
N8	0.0212 (10)	0.0273 (10)	0.0186 (11)	0.0009 (9)	0.0014 (8)	0.0012 (8)
C9	0.0199 (11)	0.0233 (12)	0.0195 (12)	0.0045 (10)	−0.0023 (10)	0.0010 (10)

Geometric parameters (Å, º)

N1—C9	1.350 (3)	C5—O5	1.244 (3)
N1—C2	1.380 (3)	C5—C6	1.393 (3)
N1—C1	1.456 (3)	C6—C7	1.378 (3)
C1—H1A	0.98	C6—H6	0.95
C1—H1B	0.98	C7—N8	1.346 (3)
C1—H1C	0.98	C7—O7	1.354 (3)
C2—C3	1.349 (3)	O7—C71	1.437 (3)
C2—H2	0.95	C71—H71A	0.98
C3—N4	1.401 (3)	C71—H71B	0.98
C3—H3	0.95	C71—H71C	0.98
N4—C9	1.363 (3)	N8—C9	1.328 (3)
N4—C5	1.428 (3)
C9—N1—C2	108.71 (18)	O5—C5—N4	118.16 (19)
C9—N1—C1	124.14 (19)	C6—C5—N4	112.10 (19)
C2—N1—C1	127.10 (19)	C7—C6—C5	121.7 (2)
N1—C1—H1A	109.5	C7—C6—H6	119.2
N1—C1—H1B	109.5	C5—C6—H6	119.2
H1A—C1—H1B	109.5	N8—C7—O7	117.0 (2)
N1—C1—H1C	109.5	N8—C7—C6	125.9 (2)
H1A—C1—H1C	109.5	O7—C7—C6	117.1 (2)
H1B—C1—H1C	109.5	C7—O7—C71	117.10 (18)
C3—C2—N1	109.1 (2)	O7—C71—H71A	109.5
C3—C2—H2	125.5	O7—C71—H71B	109.5
N1—C2—H2	125.5	H71A—C71—H71B	109.5
C2—C3—N4	105.82 (19)	O7—C71—H71C	109.5
C2—C3—H3	127.1	H71A—C71—H71C	109.5
N4—C3—H3	127.1	H71B—C71—H71C	109.5
C9—N4—C3	109.22 (18)	C9—N8—C7	112.43 (18)
C9—N4—C5	121.30 (18)	N8—C9—N1	126.2 (2)
C3—N4—C5	129.39 (19)	N8—C9—N4	126.6 (2)
O5—C5—C6	129.7 (2)	N1—C9—N4	107.17 (18)
C9—N1—C2—C3	−0.8 (3)	C6—C7—O7—C71	171.5 (2)
C1—N1—C2—C3	−178.2 (2)	O7—C7—N8—C9	−178.21 (18)
N1—C2—C3—N4	0.4 (2)	C6—C7—N8—C9	1.2 (3)
C2—C3—N4—C9	0.1 (2)	C7—N8—C9—N1	176.4 (2)
C2—C3—N4—C5	176.8 (2)	C7—N8—C9—N4	−2.1 (3)
C9—N4—C5—O5	−179.57 (19)	C2—N1—C9—N8	−177.9 (2)
C3—N4—C5—O5	4.0 (3)	C1—N1—C9—N8	−0.5 (3)
C9—N4—C5—C6	0.9 (3)	C2—N1—C9—N4	0.8 (2)
C3—N4—C5—C6	−175.5 (2)	C1—N1—C9—N4	178.30 (19)
O5—C5—C6—C7	178.8 (2)	C3—N4—C9—N8	178.2 (2)
N4—C5—C6—C7	−1.8 (3)	C5—N4—C9—N8	1.1 (3)
C5—C6—C7—N8	0.8 (4)	C3—N4—C9—N1	−0.5 (2)
C5—C6—C7—O7	−179.8 (2)	C5—N4—C9—N1	−177.62 (18)
N8—C7—O7—C71	−9.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O5^i	0.95	2.22	3.104 (3)	153
C2—H2···O5^ii	0.95	2.57	3.339 (3)	139

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