Supra­molecular hydrogen-bonded networks in cytosinium succinate and cytosinium 4-nitro­benzoate cytosine monohydrate

In cytosinium succinate (systematic name: 4-amino-2-oxo-2,3-dihydro­pyrimidin-1-ium 3-carboxy­propan­oate), C₄H₆N₃O⁺·C₄H₅O₄⁻, (I), the cytosinium cation forms one-dimensional self-assembling patterns by inter­molecular N—H...O hydrogen bonding, while in cytosinium 4-nitro­benzoate cytosine monohydrate [systematic name: 4-amino-2-oxo-2,3-dihydro­pyrimidin-1-ium 4-nitro­benzoate 4-amino­pyrimidin-2(1H)-one solvate monohydrate], C₄H₆N₃O⁺·C₇H₄NO₄⁻·C₄H₅N₃O·H₂O, (II), the cytosinium–cytosine base pair, held together by triple hydrogen bonds, leads to one-dimensional polymeric ribbons via double N—H...O hydrogen bonds. This study illustrates clearly the different alignment of cytosine mol­ecules in the crystal packing and their ability to form supra­molecular hydrogen-bonded networks with the anions.

S1. Comment

The protonated cytosine–cytosine base pair carries important structural implications for biological systems. In particular, this base pair is known to self-assemble in acidic media (Armentano et al., 2004) and is also found in RNA and DNA solutions. Furthermore, X-ray studies have revealed that the cytosine–cytosine base pair contributes to fully intercalated parallel-stranded duplexes of DNA structural motifs in crystals (Kang et al., 1994; Kang et al., 1995). Carboxylic acids belong to an important class of organic molecules and are believed to have existed in the prebiotic earth (Miller & Orgel, 1974; Kvenvolden et al., 1971). Succinic acid may bind to cations in either the monoanionic or the dianionic form, displaying a plethora of interesting structures. Succinic acid, with two carboxyl functions, can exist as a neutral molecule or as single negatively charged or double negatively charged ions (Prasad & Vijayan, 1991). 4-Nitrobenzoic acid can easily lose its acidic H atom and form complexes with other compounds through hydrogen bonding. The present study is a continuation of our ongoing programme on structure elucidation of nucleobases with the carboxylic and aromatic acids.

In the structures of (I) and (II), the bond lengths and angles (Table 1 and 3) correspond to those expected for the atom types and the type of hybridization (Allen et al., 1987). The asymmetric unit of (I) contains one cytosinium cation protonated at atom N3 and one succinate anion, with one of the carboxyl group deprotonated (Fig. 1), while (II) comprises one cytosinium cation (A), one cytosine molecule (B), one 4-nitrobenzoate anion and one water molecule (Fig. 2). As expected, both the succinate and the 4-nitrobenzoate anions of (I) and (II) are planar. In the succinate anion of (I), the two Csp²—Csp² single-bond distances of the carboxylate (C11—C12) and carboxyl (C13—C14) groups are not identical (Table 1). It is of interest to note that the shorter C13—C14 bond links the carboxyl group, while the longer C11—C12 bond links the carboxylate group. The C11—C12—C13—C14 unit is in a trans conformation in (I) (Table 1). In the 4-nitrobenzoate anion of (II), the mean planes of the carboxylate group (C11/O9/O10) and nitro group (N18/O19/O20) make dihedral angles of 1.9 (3) and 3.8 (2)°, respectively, with respect to the mean plane of the benzene ring (C12–C17). In (I), the O—H bond of the carboxyl group is in a trans conformation with respect to the C═O bond, as evidenced from the H16O—O16—C114—O15 torsion angle of 176.9 (6)°.

Cytosine is a quite strong base (pK_a1 = 1. 6 and pK_a2 = 12.2; Stecher, 1968) and, in the presence of acids, is readily protonated at the N3 ring position. The molecular geometries of the cytosine and cytosinium cation are in good agreement with those of similar structures (Görbitz & Sagstuen, 2004; Garcia-Teran et al., 2007). The N3 protonation or its absence reflects in the C2—N3—C4 bond angle. The N3 protonation of the cytosine ring is consistent with the larger C2—N3—C4 bond angle [124.0 (1)° in (I) and 123.6 (2)° in molecule A of (II)], while for unprotonated cytosine the angle is 119.3 (2)°, which agrees well with the reported value of the unprotonated cytosine molecule of 119.4° (McClure & Craven, 1973).

In (I), the cytosinium cation and succinate anion are held together by two N—H···O hydrogen bonds (Table 2), thereby generating an R₂²(8) motif (Bernstein et al., 1995), which is further interconnected by intermolecular N—H···O and O—H···O interactions involving the the cytosinium cations and succinate anions leading to the formation of a two-dimensional sheet containing R₄⁴(15) and R₄⁴(19) motifs (Fig. 3). In the case of (II), the cytosinium–cytosine dimers are formed by two N—H···O and one N—H···N hydrogen bonds (Table 4), thus resembling a pseudo-Watson–Crick pattern. Furthermore, adjacent cytosinium–cytosine base pairs are interlinked by double N—H···O hydrogen bonds (Table 4), leading to one-dimensional supramolecular polymeric ribbons with alternating neutral and protonated cytosine entities (Fig. 4).

In (II), atom N1 of the cytosinium cation forms an N—H···O hydrogen bond with the water molecule, while the corresponding atom of the cytosine molecule forms an N—H···O hydrogen bond with the 4-nitrobenzoate anion. The water molecule plays a dual role as both donor and acceptor in the hydrogen-bonding interactions (Table 4). It is involved in three hydrogen bonds, acting donor to two inversion-related 4-nitrobenzoate anions and acceptor to an adjacent cytosinium cation.

In (II), the combination of N—H···O, N—H···N and O—H···O hydrogen bonds involving the cytosinium–cytosine base pairs, the 4-nitrobnzoate anions and the water molecules leads to two-dimensional hydrogen-bonded network cavities, which extend parallel to the c axis. Each cavity is arranged like a hexamer hydrogen-bonded network consisting of two sets of parallel cytosinium–cytosine base pairs, which are sandwiched between the two 4-nitrobenzoate anions and two water molecules (Fig. 5). The one-dimension polymeric ribbon formed by the cytosinium–cytosine base pair interacts with adjacent ribbons through 4-nitrobenzoate anions and water molecules via N—H···O and O—H···O hydrogen bonds, thereby generating a two-dimensional supramolecular hydrogen-bonded network in the crystal structure. It is very interesting to note that the nitro group of the 4-nitrobenzoate anion does not participate in any conventional hydrogen-bonding interactions. In (II), the water molecule does not have any interaction with the cytosine molecule, while the 4-nitrobenzate anion links the cytosinium cation through a weak C—H···O interaction.

Related literature

For related literature, see: Allen et al. (1987); Armentano et al. (2004); Bernstein et al. (1995); Görbitz & Sagstuen (2004); Garcia-Teran, Castillo, Luque, Garcia-Coucerio, Beobide & Roman (2007); Kang et al. (1994, 1995); Kvenvolden et al. (1971); McClure & Craven (1973); Miller & Orgel (1974); Prasad & Vijayan (1991); Stecher (1968).

S2. Experimental

To obtain crystals of (I) suitable for X-ray study, cytosine (0.111 g, 1 mmol) and succinic acid (0.118 g, 1 mmol) were dissolved in water (10 ml) and the solution was allowed to evaporate slowly. Crystals of (II) were obtained by slow evaporation of an equimolar solution of cytosine (0.111 g, 2 mmol) and 4-nitrobenzoic acid (0.167 g, 1 mmol) in water (20 ml).

S3. Refinement

All N- and O-bound H atoms were located in a difference Fourier map and their positions and isotropic parameters were refined. All other H atoms were located in a difference density map but were positioned geometrically and included as riding atoms, with C—H distances in the range 0.93–0.97 Å, and with U_iso(H) = 1.2U_eq(C).

Computing details

For both compounds, data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. A view of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. Hydrogen bonds are shown as dashed lines.
	Fig. 2. A view of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. Hydrogen bond are shown as dashed lines.
	Fig. 3. A packing diagram for (I), viewed down the a axis. Dashed lines indicate O—H···O and N—H···O hydrogen bonds. H atoms not involved in hydrogen bonding have been omitted for clarity. Only atoms involved in the hydrogen bonds are labelled. [Symmetry codes: (i) x - 1/2, -y + 5/2, z - 1/2; (ii) x, y - 1, z; (iii) x, y + 1, z]
	Fig. 4. A packing diagram for (II), viewed down the b axis. Only atoms involved in the hydrogen bonds are labelled. H atoms not involved in hydrogen bonding have been omitted for clarity.[Symmetry codes: (i) x, y - 1, z; (ii) x, y + 1, z; (iii) -x + 1, -y, -z + 1; (iv) -x + 2, -y, -z + 1.]
	Fig. 5. A view of the hexamer hydrogen-bonded network cavity. Dashed lines indicate O—H···O, N—H···N and N—H···O hydrogen bonds. H atoms not involved in hydrogen bonding have been omitted for clarity.

(I) 4-amino-2-oxo-2,3-dihydropyrimidin-1-ium 3-carboxypropanoate

Crystal data

C4H6N3O^+·C4H5O4^−	F(000) = 960
Mr = 229.20	Dx = 1.576 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2934 reflections
a = 15.666 (3) Å	θ = 3.0–27.7°
b = 6.6959 (9) Å	µ = 0.13 mm^−1
c = 18.726 (3) Å	T = 294 K
β = 100.480 (4)°	Block, colorless
V = 1931.5 (5) Å^3	0.23 × 0.17 × 0.13 mm
Z = 8

Data collection

Bruker SMART APEX CCD area-detector diffractometer	1607 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.021
Graphite monochromator	θmax = 25.0°, θmin = 2.2°
ω scan	h = −18→18
8824 measured reflections	k = −7→7
1697 independent reflections	l = −22→22

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ^2(Fo^2) + (0.0619P)^2 + 1.1366P] where P = (Fo^2 + 2Fc^2)/3
1697 reflections	(Δ/σ)max = 0.001
165 parameters	Δρmax = 0.22 e Å^−3
0 restraints	Δρmin = −0.19 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C2	0.24296 (11)	0.9672 (2)	0.36715 (9)	0.0431 (4)
C4	0.27374 (8)	0.6259 (2)	0.40047 (7)	0.0293 (3)
C5	0.21523 (9)	0.5640 (2)	0.33688 (8)	0.0339 (3)
H5	0.2055	0.4293	0.3263	0.041*
C6	0.17464 (9)	0.7058 (2)	0.29278 (8)	0.0348 (3)
H6	0.1365	0.6678	0.2510	0.042*
N1	0.18750 (8)	0.9025 (2)	0.30726 (7)	0.0379 (3)
H1N	0.1598 (14)	0.997 (4)	0.2797 (12)	0.067 (6)*
N3	0.28423 (8)	0.82252 (19)	0.41264 (7)	0.0342 (3)
H3N	0.3223 (14)	0.874 (4)	0.4538 (12)	0.067 (6)*
N7	0.31822 (9)	0.5027 (2)	0.44761 (7)	0.0381 (3)
H7N	0.3552 (12)	0.551 (3)	0.4872 (10)	0.048 (5)*
H8N	0.3103 (13)	0.372 (4)	0.4406 (11)	0.062 (6)*
O8	0.25613 (11)	1.14294 (19)	0.37986 (8)	0.0851 (6)
C11	0.43913 (9)	0.8917 (2)	0.56554 (7)	0.0323 (3)
C12	0.49945 (9)	1.0063 (2)	0.62368 (8)	0.0342 (4)
H12A	0.4889	0.9647	0.6709	0.041*
H12B	0.5589	0.9719	0.6210	0.041*
C13	0.48910 (9)	1.2286 (2)	0.61737 (8)	0.0354 (4)
H13B	0.5001	1.2696	0.5702	0.042*
H13A	0.4293	1.2621	0.6193	0.042*
C14	0.54742 (9)	1.3459 (2)	0.67471 (7)	0.0330 (3)
O9	0.39163 (7)	0.98932 (16)	0.51724 (6)	0.0445 (3)
O10	0.43902 (7)	0.70284 (16)	0.56806 (6)	0.0432 (3)
O15	0.59984 (7)	1.26888 (18)	0.72319 (6)	0.0441 (3)
O16	0.54141 (8)	1.54080 (17)	0.67157 (6)	0.0446 (3)
H16O	0.4996 (15)	1.600 (4)	0.6292 (13)	0.078 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C2	0.0540 (9)	0.0247 (8)	0.0411 (9)	−0.0002 (6)	−0.0161 (7)	0.0012 (6)
C4	0.0318 (7)	0.0244 (7)	0.0293 (7)	−0.0007 (5)	−0.0010 (5)	−0.0002 (5)
C5	0.0392 (8)	0.0253 (7)	0.0326 (7)	−0.0030 (6)	−0.0056 (6)	−0.0028 (6)
C6	0.0370 (7)	0.0329 (8)	0.0298 (7)	−0.0038 (6)	−0.0064 (6)	−0.0023 (6)
N1	0.0445 (7)	0.0282 (7)	0.0337 (7)	0.0002 (5)	−0.0123 (5)	0.0040 (5)
N3	0.0407 (7)	0.0239 (6)	0.0315 (6)	−0.0012 (5)	−0.0106 (5)	−0.0015 (5)
N7	0.0461 (7)	0.0243 (7)	0.0367 (7)	0.0008 (5)	−0.0116 (6)	0.0006 (5)
O8	0.1243 (13)	0.0215 (7)	0.0801 (10)	−0.0012 (7)	−0.0598 (9)	−0.0007 (6)
C11	0.0338 (7)	0.0312 (8)	0.0285 (7)	−0.0030 (6)	−0.0033 (6)	−0.0022 (6)
C12	0.0344 (7)	0.0336 (8)	0.0302 (7)	−0.0038 (6)	−0.0056 (6)	−0.0022 (6)
C13	0.0373 (7)	0.0319 (8)	0.0316 (7)	−0.0023 (6)	−0.0082 (6)	−0.0030 (6)
C14	0.0347 (7)	0.0331 (8)	0.0278 (7)	−0.0026 (6)	−0.0035 (5)	−0.0031 (6)
O9	0.0518 (7)	0.0330 (6)	0.0386 (6)	−0.0030 (5)	−0.0190 (5)	−0.0015 (5)
O10	0.0531 (7)	0.0283 (6)	0.0406 (6)	−0.0033 (5)	−0.0118 (5)	−0.0026 (4)
O15	0.0472 (6)	0.0365 (7)	0.0389 (6)	−0.0005 (5)	−0.0174 (5)	−0.0024 (5)
O16	0.0551 (7)	0.0301 (6)	0.0402 (6)	−0.0029 (5)	−0.0140 (5)	−0.0036 (5)

Geometric parameters (Å, º)

C2—O8	1.211 (2)	N7—H8N	0.89 (3)
C2—N1	1.3586 (19)	C11—O9	1.2468 (18)
C2—N3	1.372 (2)	C11—O10	1.2653 (19)
C4—N7	1.3125 (19)	C11—C12	1.5141 (19)
C4—N3	1.3408 (19)	C12—C13	1.500 (2)
C4—C5	1.4258 (19)	C12—H12A	0.9700
C5—C6	1.341 (2)	C12—H12B	0.9700
C5—H5	0.9300	C13—C14	1.4993 (19)
C6—N1	1.352 (2)	C13—H13B	0.9700
C6—H6	0.9300	C13—H13A	0.9700
N1—H1N	0.88 (2)	C14—O15	1.2220 (18)
N3—H3N	0.95 (2)	C14—O16	1.3089 (19)
N7—H7N	0.91 (2)	O16—H16O	1.01 (3)
O8—C2—N1	122.20 (15)	H7N—N7—H8N	121.4 (18)
O8—C2—N3	121.34 (14)	O9—C11—O10	123.12 (13)
N1—C2—N3	116.46 (14)	O9—C11—C12	117.89 (13)
N7—C4—N3	118.00 (13)	O10—C11—C12	118.98 (12)
N7—C4—C5	124.10 (13)	C13—C12—C11	113.71 (12)
N3—C4—C5	117.90 (13)	C13—C12—H12A	108.8
C6—C5—C4	117.97 (13)	C11—C12—H12A	108.8
C6—C5—H5	121.0	C13—C12—H12B	108.8
C4—C5—H5	121.0	C11—C12—H12B	108.8
C5—C6—N1	121.99 (14)	H12A—C12—H12B	107.7
C5—C6—H6	119.0	C14—C13—C12	114.88 (13)
N1—C6—H6	119.0	C14—C13—H13B	108.5
C6—N1—C2	121.72 (13)	C12—C13—H13B	108.5
C6—N1—H1N	122.9 (15)	C14—C13—H13A	108.5
C2—N1—H1N	115.3 (15)	C12—C13—H13A	108.5
C4—N3—C2	123.95 (13)	H13B—C13—H13A	107.5
C4—N3—H3N	122.4 (14)	O15—C14—O16	119.16 (13)
C2—N3—H3N	113.6 (15)	O15—C14—C13	123.40 (14)
C4—N7—H7N	120.2 (12)	O16—C14—C13	117.43 (12)
C4—N7—H8N	118.4 (14)	C14—O16—H16O	117.3 (14)
N7—C4—C5—C6	−179.22 (14)	O8—C2—N3—C4	−178.39 (18)
N3—C4—C5—C6	0.5 (2)	N1—C2—N3—C4	1.1 (2)
C4—C5—C6—N1	−0.3 (2)	O9—C11—C12—C13	3.78 (19)
C5—C6—N1—C2	0.6 (2)	O10—C11—C12—C13	−176.15 (13)
O8—C2—N1—C6	178.57 (19)	C11—C12—C13—C14	179.41 (11)
N3—C2—N1—C6	−0.9 (2)	C12—C13—C14—O15	0.1 (2)
N7—C4—N3—C2	178.81 (14)	C12—C13—C14—O16	179.66 (13)
C5—C4—N3—C2	−0.9 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O15^i	0.88 (2)	2.02 (2)	2.9018 (18)	175 (2)
N3—H3N···O9	0.95 (2)	1.65 (2)	2.5916 (15)	172 (2)
N7—H7N···O10	0.91 (2)	2.08 (2)	2.9854 (18)	171.0 (17)
N7—H8N···O8^ii	0.89 (3)	2.00 (2)	2.8122 (19)	150.5 (19)
O16—H16O···O10^iii	1.01 (3)	1.51 (3)	2.5250 (16)	176 (2)
C5—H5···O8^ii	0.93	2.24	2.970 (2)	135

Symmetry codes: (i) x−1/2, −y+5/2, z−1/2; (ii) x, y−1, z; (iii) x, y+1, z.

(II) 4-amino-2-oxo-2,3-dihydropyrimidin-1-ium 4-nitrobenzoate 4-aminopyrimidin-2(1H)-one solvate monohydrate

Crystal data

C4H6N3O^+·C7H4NO4^−·C4H5N3O·H2O	Z = 2
Mr = 407.36	F(000) = 424
Triclinic, P1	Dx = 1.539 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.7154 (14) Å	Cell parameters from 7202 reflections
b = 7.4036 (16) Å	θ = 2.2–28.0°
c = 19.228 (4) Å	µ = 0.13 mm^−1
α = 85.525 (4)°	T = 294 K
β = 87.576 (4)°	Block, colorless
γ = 67.279 (3)°	0.19 × 0.16 × 0.08 mm
V = 879.0 (3) Å^3

Data collection

Bruker SMART APEX CCD area-detector diffractometer	2570 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.044
Graphite monochromator	θmax = 25.0°, θmin = 1.1°
ω scan	h = −7→7
8258 measured reflections	k = −8→8
3064 independent reflections	l = −22→22

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)] = 0.070	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.209	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ^2(Fo^2) + (0.1347P)^2 + 0.1481P] where P = (Fo^2 + 2Fc^2)/3
3064 reflections	(Δ/σ)max < 0.001
298 parameters	Δρmax = 0.43 e Å^−3
0 restraints	Δρmin = −0.45 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C2A	0.7429 (4)	0.1448 (3)	0.41776 (12)	0.0295 (5)
C4A	0.7629 (3)	−0.1877 (3)	0.42401 (12)	0.0287 (5)
C5A	0.7629 (4)	−0.1816 (4)	0.35042 (12)	0.0340 (6)
H5A	0.7711	−0.2902	0.3274	0.041*
C6A	0.7508 (4)	−0.0155 (4)	0.31490 (13)	0.0352 (6)
H6A	0.7502	−0.0091	0.2664	0.042*
N1A	0.7395 (3)	0.1446 (3)	0.34758 (11)	0.0355 (5)
H1A	0.721 (6)	0.256 (6)	0.320 (2)	0.069 (10)*
N3A	0.7537 (3)	−0.0254 (3)	0.45455 (10)	0.0293 (5)
H3A	0.756 (5)	−0.024 (5)	0.5046 (19)	0.059 (9)*
N7A	0.7693 (4)	−0.3395 (3)	0.46420 (12)	0.0369 (6)
O8A	0.7359 (3)	0.2871 (2)	0.44812 (9)	0.0411 (5)
H7A	0.772 (4)	−0.442 (5)	0.4462 (15)	0.043 (8)*
H8A	0.767 (4)	−0.333 (4)	0.5152 (15)	0.035 (7)*
C2B	0.7662 (4)	−0.2006 (3)	0.63813 (12)	0.0276 (5)
C4B	0.7400 (3)	0.1223 (3)	0.63833 (12)	0.0280 (5)
C5B	0.7524 (4)	0.1080 (4)	0.71189 (13)	0.0349 (6)
H5B	0.7499	0.2125	0.7363	0.042*
C6B	0.7679 (4)	−0.0635 (4)	0.74500 (13)	0.0365 (6)
H6B	0.7746	−0.0784	0.7934	0.044*
N1B	0.7739 (3)	−0.2145 (3)	0.70870 (10)	0.0352 (5)
H1B	0.770 (6)	−0.317 (6)	0.730 (2)	0.068 (10)*
N3B	0.7508 (3)	−0.0296 (3)	0.60271 (10)	0.0280 (5)
N7B	0.7188 (4)	0.2883 (3)	0.60162 (13)	0.0386 (6)
O8B	0.7726 (3)	−0.3444 (2)	0.60712 (9)	0.0400 (5)
H7B	0.713 (5)	0.386 (5)	0.6241 (17)	0.057 (9)*
H8B	0.714 (5)	0.294 (4)	0.5552 (17)	0.044 (8)*
C12	0.8120 (4)	−0.6443 (4)	0.90808 (13)	0.0396 (6)
C13	0.9478 (5)	−0.6793 (4)	0.96393 (15)	0.0496 (7)
H13	1.0716	−0.6517	0.9580	0.060*
C14	0.9056 (6)	−0.7532 (5)	1.02753 (15)	0.0584 (8)
H14	0.9971	−0.7742	1.0649	0.070*
C15	0.7226 (5)	−0.7960 (4)	1.03467 (14)	0.0503 (8)
C16	0.5867 (5)	−0.7661 (5)	0.98061 (17)	0.0556 (8)
H16	0.4649	−0.7966	0.9866	0.067*
C17	0.6309 (5)	−0.6902 (4)	0.91697 (15)	0.0504 (7)
H17	0.5388	−0.6698	0.8798	0.060*
C11	0.8610 (5)	−0.5530 (4)	0.83995 (14)	0.0445 (7)
N18	0.6759 (7)	−0.8751 (4)	1.10258 (15)	0.0748 (10)
O9	1.0263 (4)	−0.5173 (4)	0.83713 (12)	0.0805 (8)
O10	0.7289 (3)	−0.5132 (3)	0.79171 (9)	0.0497 (6)
O20	0.5082 (7)	−0.9016 (5)	1.10923 (16)	0.1112 (12)
O19	0.8051 (7)	−0.9097 (5)	1.14913 (14)	0.1159 (13)
O1W	0.6864 (4)	0.4584 (3)	0.25694 (11)	0.0500 (6)
H1W	0.570 (5)	0.469 (4)	0.2305 (17)	0.049 (8)*
H2W	0.771 (7)	0.477 (6)	0.225 (2)	0.091 (14)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C2A	0.0312 (12)	0.0247 (12)	0.0348 (13)	−0.0140 (10)	0.0018 (9)	0.0004 (9)
C4A	0.0295 (12)	0.0271 (12)	0.0336 (12)	−0.0147 (9)	−0.0001 (9)	−0.0057 (9)
C5A	0.0390 (13)	0.0332 (13)	0.0345 (13)	−0.0177 (11)	0.0005 (10)	−0.0092 (10)
C6A	0.0344 (13)	0.0444 (15)	0.0311 (12)	−0.0191 (11)	0.0008 (10)	−0.0071 (11)
N1A	0.0411 (12)	0.0346 (12)	0.0330 (11)	−0.0181 (10)	0.0002 (9)	0.0033 (9)
N3A	0.0378 (11)	0.0245 (11)	0.0299 (11)	−0.0164 (8)	−0.0008 (8)	−0.0033 (8)
N7A	0.0575 (14)	0.0228 (11)	0.0379 (13)	−0.0230 (10)	−0.0007 (10)	−0.0060 (9)
O8A	0.0622 (12)	0.0247 (9)	0.0444 (10)	−0.0251 (8)	0.0004 (8)	−0.0041 (7)
C2B	0.0332 (12)	0.0217 (11)	0.0320 (12)	−0.0149 (9)	0.0000 (9)	−0.0022 (9)
C4B	0.0258 (11)	0.0217 (11)	0.0390 (13)	−0.0116 (9)	0.0008 (9)	−0.0048 (9)
C5B	0.0406 (14)	0.0295 (13)	0.0387 (13)	−0.0162 (11)	−0.0005 (10)	−0.0120 (10)
C6B	0.0427 (14)	0.0415 (15)	0.0306 (12)	−0.0213 (11)	−0.0015 (10)	−0.0066 (10)
N1B	0.0504 (13)	0.0320 (12)	0.0306 (11)	−0.0246 (10)	−0.0017 (9)	0.0024 (9)
N3B	0.0342 (11)	0.0222 (10)	0.0317 (10)	−0.0149 (8)	0.0006 (8)	−0.0044 (8)
N7B	0.0567 (14)	0.0218 (11)	0.0434 (14)	−0.0208 (10)	−0.0040 (10)	−0.0056 (9)
O8B	0.0670 (12)	0.0264 (9)	0.0366 (10)	−0.0284 (9)	−0.0003 (8)	−0.0047 (7)
C12	0.0561 (16)	0.0327 (14)	0.0354 (13)	−0.0228 (12)	0.0027 (11)	−0.0050 (10)
C13	0.0610 (18)	0.0522 (17)	0.0448 (16)	−0.0322 (15)	−0.0040 (13)	0.0005 (13)
C14	0.086 (2)	0.060 (2)	0.0358 (15)	−0.0351 (18)	−0.0109 (14)	0.0032 (13)
C15	0.083 (2)	0.0368 (16)	0.0335 (14)	−0.0270 (15)	0.0111 (14)	−0.0034 (11)
C16	0.0612 (18)	0.0519 (18)	0.0613 (19)	−0.0322 (15)	0.0085 (15)	0.0035 (14)
C17	0.0615 (18)	0.0527 (18)	0.0457 (16)	−0.0328 (15)	−0.0068 (13)	0.0070 (13)
C11	0.0612 (17)	0.0425 (16)	0.0379 (14)	−0.0296 (13)	0.0013 (13)	−0.0001 (12)
N18	0.135 (3)	0.0566 (18)	0.0426 (17)	−0.0493 (19)	0.0248 (18)	−0.0073 (13)
O9	0.0813 (17)	0.128 (2)	0.0586 (14)	−0.0745 (17)	−0.0050 (12)	0.0229 (14)
O10	0.0778 (14)	0.0474 (12)	0.0380 (10)	−0.0404 (10)	−0.0100 (9)	0.0068 (8)
O20	0.158 (3)	0.125 (3)	0.0767 (19)	−0.089 (3)	0.046 (2)	−0.0007 (17)
O19	0.205 (4)	0.124 (3)	0.0387 (15)	−0.087 (3)	−0.0048 (19)	0.0130 (15)
O1W	0.0575 (13)	0.0507 (13)	0.0433 (11)	−0.0250 (10)	−0.0020 (10)	0.0107 (9)

Geometric parameters (Å, º)

C2A—O8A	1.228 (3)	C6B—H6B	0.9300
C2A—N1A	1.351 (3)	N1B—H1B	0.85 (4)
C2A—N3A	1.374 (3)	N7B—H7B	0.86 (4)
C4A—N7A	1.301 (3)	N7B—H8B	0.89 (3)
C4A—N3A	1.357 (3)	C12—C13	1.382 (4)
C4A—C5A	1.412 (3)	C12—C17	1.385 (4)
C5A—C6A	1.335 (4)	C12—C11	1.509 (4)
C5A—H5A	0.9300	C13—C14	1.364 (4)
C6A—N1A	1.359 (3)	C13—H13	0.9300
C6A—H6A	0.9300	C14—C15	1.382 (5)
N1A—H1A	0.91 (4)	C14—H14	0.9300
N3A—H3A	0.97 (4)	C15—C16	1.360 (4)
N7A—H7A	0.85 (3)	C15—N18	1.461 (4)
N7A—H8A	0.98 (3)	C16—C17	1.375 (4)
C2B—O8B	1.246 (3)	C16—H16	0.9300
C2B—N1B	1.354 (3)	C17—H17	0.9300
C2B—N3B	1.360 (3)	C11—O9	1.235 (4)
C4B—N7B	1.329 (3)	C11—O10	1.248 (3)
C4B—N3B	1.339 (3)	N18—O19	1.216 (5)
C4B—C5B	1.414 (3)	N18—O20	1.216 (5)
C5B—C6B	1.343 (4)	O1W—H1W	0.92 (3)
C5B—H5B	0.9300	O1W—H2W	0.85 (5)
C6B—N1B	1.350 (3)
O8A—C2A—N1A	123.2 (2)	C6B—N1B—C2B	121.9 (2)
O8A—C2A—N3A	120.8 (2)	C6B—N1B—H1B	120 (2)
N1A—C2A—N3A	116.0 (2)	C2B—N1B—H1B	118 (2)
N7A—C4A—N3A	118.1 (2)	C4B—N3B—C2B	119.34 (19)
N7A—C4A—C5A	123.7 (2)	C4B—N7B—H7B	118 (2)
N3A—C4A—C5A	118.2 (2)	C4B—N7B—H8B	119.6 (19)
C6A—C5A—C4A	118.1 (2)	H7B—N7B—H8B	123 (3)
C6A—C5A—H5A	121.0	C13—C12—C17	118.6 (3)
C4A—C5A—H5A	121.0	C13—C12—C11	119.6 (2)
C5A—C6A—N1A	121.9 (2)	C17—C12—C11	121.8 (2)
C5A—C6A—H6A	119.1	C14—C13—C12	121.9 (3)
N1A—C6A—H6A	119.1	C14—C13—H13	119.1
C2A—N1A—C6A	122.3 (2)	C12—C13—H13	119.1
C2A—N1A—H1A	121 (2)	C13—C14—C15	117.9 (3)
C6A—N1A—H1A	117 (2)	C13—C14—H14	121.0
C4A—N3A—C2A	123.6 (2)	C15—C14—H14	121.0
C4A—N3A—H3A	121 (2)	C16—C15—C14	121.8 (3)
C2A—N3A—H3A	115 (2)	C16—C15—N18	119.8 (3)
C4A—N7A—H7A	120 (2)	C14—C15—N18	118.3 (3)
C4A—N7A—H8A	119.4 (16)	C15—C16—C17	119.5 (3)
H7A—N7A—H8A	121 (3)	C15—C16—H16	120.3
O8B—C2B—N1B	119.4 (2)	C17—C16—H16	120.3
O8B—C2B—N3B	121.5 (2)	C16—C17—C12	120.2 (3)
N1B—C2B—N3B	119.2 (2)	C16—C17—H17	119.9
N7B—C4B—N3B	117.2 (2)	C12—C17—H17	119.9
N7B—C4B—C5B	120.9 (2)	O9—C11—O10	124.9 (3)
N3B—C4B—C5B	121.8 (2)	O9—C11—C12	117.0 (3)
C6B—C5B—C4B	117.0 (2)	O10—C11—C12	118.0 (2)
C6B—C5B—H5B	121.5	O19—N18—O20	123.8 (3)
C4B—C5B—H5B	121.5	O19—N18—C15	118.6 (4)
C5B—C6B—N1B	120.7 (2)	O20—N18—C15	117.6 (4)
C5B—C6B—H6B	119.7	H1W—O1W—H2W	101 (3)
N1B—C6B—H6B	119.7
N7A—C4A—C5A—C6A	178.5 (2)	N1B—C2B—N3B—C4B	−1.1 (3)
N3A—C4A—C5A—C6A	−0.9 (3)	C17—C12—C13—C14	−1.5 (5)
C4A—C5A—C6A—N1A	0.2 (4)	C11—C12—C13—C14	177.0 (3)
O8A—C2A—N1A—C6A	178.9 (2)	C12—C13—C14—C15	1.0 (5)
N3A—C2A—N1A—C6A	−1.4 (3)	C13—C14—C15—C16	−0.1 (5)
C5A—C6A—N1A—C2A	1.0 (4)	C13—C14—C15—N18	−180.0 (3)
N7A—C4A—N3A—C2A	−179.0 (2)	C14—C15—C16—C17	−0.3 (5)
C5A—C4A—N3A—C2A	0.5 (3)	N18—C15—C16—C17	179.5 (3)
O8A—C2A—N3A—C4A	−179.7 (2)	C15—C16—C17—C12	−0.2 (5)
N1A—C2A—N3A—C4A	0.7 (3)	C13—C12—C17—C16	1.1 (4)
N7B—C4B—C5B—C6B	178.3 (2)	C11—C12—C17—C16	−177.4 (3)
N3B—C4B—C5B—C6B	−2.3 (3)	C13—C12—C11—O9	1.5 (4)
C4B—C5B—C6B—N1B	0.8 (4)	C17—C12—C11—O9	180.0 (3)
C5B—C6B—N1B—C2B	0.5 (4)	C13—C12—C11—O10	−176.1 (3)
O8B—C2B—N1B—C6B	179.9 (2)	C17—C12—C11—O10	2.3 (4)
N3B—C2B—N1B—C6B	−0.3 (3)	C16—C15—N18—O19	176.4 (3)
N7B—C4B—N3B—C2B	−178.1 (2)	C14—C15—N18—O19	−3.7 (5)
C5B—C4B—N3B—C2B	2.4 (3)	C16—C15—N18—O20	−4.0 (5)
O8B—C2B—N3B—C4B	178.66 (19)	C14—C15—N18—O20	175.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···O1W	0.91 (4)	1.80 (4)	2.710 (3)	173 (3)
N3A—H3A···N3B	0.97 (4)	1.88 (4)	2.846 (3)	177 (3)
N7A—H7A···O8A^i	0.85 (3)	2.11 (3)	2.900 (3)	154 (3)
N7A—H8A···O8B	0.98 (3)	1.76 (3)	2.747 (3)	175 (2)
N1B—H1B···O10	0.85 (4)	1.90 (4)	2.731 (3)	169 (3)
N7B—H7B···O8B^ii	0.86 (4)	2.18 (4)	2.889 (3)	139 (3)
N7B—H8B···O8A	0.89 (3)	2.06 (3)	2.949 (3)	174 (3)
O1W—H1W···O10^iii	0.92 (3)	1.97 (3)	2.847 (3)	159 (3)
O1W—H2W···O9^iv	0.85 (5)	1.87 (5)	2.723 (3)	175 (4)
C5B—H5B···O10^ii	0.93	2.32	3.249 (3)	176
C6A—H6A···O19^v	0.93	2.38	3.262 (4)	159

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