Hydrogen-bonded supra­molecular networks of N,N'-bis­(4-pyridyl­methyl)­oxalamide and 4,4'-{[oxalyl­bis(aza­nediyl)]dimethyl­ene}­dipyridin­ium dinitrate

The molecule of N,N'-bis­(4-pyridylmethyl)oxalamide, C₁₄H₁₄N₄O₂, (I) or 4py-ox, has an inversion center in the middle of the oxalamide group. Adjacent mol­ecules are then linked through inter­molecular N-H...N and C-H...O hydrogen bonds, forming an extended supra­molecular network. 4,4'-{[Oxalylbis(aza­nediyl)]dimethyl­ene}­dipyridin­ium dinitrate, C₁₄H₁₆N₄O₂²⁺·2NO₃^-, (II), contains a diproton­ated 4py-ox cation and two nitrate counter-anions. Each nitrate ion is hydrogen bonded to four 4py-ox cations via inter­molecular N-H...O and C-H...O inter­actions. Adjacent 4py-ox cations are linked through weak C-H...O hydrogen bonding between an [alpha]-pyridinium C atom and an oxalamide O atom, forming a two-dimensional extended supra­molecular network.

S1. Comment

Since Jean-Marie Lehn's famous description of supramolecular chemistry (Reference?), the chemistry of molecular assemblies and the intermolecular non-covalent binding interactions (i.e. hydrogen bonding, ionic interactions and π–π stacking) have attracted increasing attention in crystal engineering. In particular, hydrogen bonding, which is a powerful organizing force in designing various supramolecules and solid-state architectures (Subramanian & Zaworotko, 1994), is extensively used not only for networking numerous organic and organometallic compounds (Desiraju, 2000), but also for generating interesting supramolecular properties, such as electrical, optical and magnetic (Letard et al., 1998) properties. Pyridyl groups, with effective sites for coordination to transition metal ions, have been used for the construction of supramolecular coordination compounds (Maspoch et al., 2004; Barnett & Champness, 2003; Carlucci et al., 2003). In addition, organic amides have proved to be very useful in self-assembly through hydrogen bonding, and the assembled products have relevance to biological systems. Thus, dipyridylamide ligands have recently been designed and synthesized in crystal engineering; in these compounds, amide–amide hydrogen bonding has been demonstrated to increase supramolecular versatility (Burchell et al., 2004; Muthu et al., 2001, 2002; Nguyen et al., 1998, 2001).

The title compound, (I) (4py-ox), has been successfully employed in the synthesis of novel metal–organic frameworks (Tzeng et al., 2005, 2006, 2007). We have focused our attention on this organic ligand to obtain a one-dimensional zigzag chain structure with the Co²⁺ ion (Lee & Wang, 2007). In this work, we report a new crystal morphology constructed by 4py-ox, which is a polymorphic crystal of the previous work (Lee & Wang, 2007). The second title compound, (II), was obtained as a by-product in the course of attempts to prepare a coordination polymer by the reaction of Cd(NO₃)₂.4H₂O and 4py-ox. The molecular structures and the related supramolecular constructions of (I) and (II) are presented in detail and compared with that of the polymorphic crystal in the previous work.

The crystal structure of 4py-ox is shown in Fig. 1, and selected bond lengths and angles are listed in Table 1. No obvious differences in the C—O, C—N and C—C bonds are found compared with those of the two independent molecules of the previous work (Lee & Wang, 2007). In this study, 4py-ox has a crystallographic inversion center in the middle of the oxalamide group, and one half of the molecule is independent. Therefore, the two pyridyl rings separated by the oxalamide linkage in the molecule are parallel to each other. The central oxalamide group is planar. The C2—C3—C6—N2 torsion angle is 53.55 (18)°, which is between the corresponding values of the two independent molecules of the previous work [N1/C14 = 30.1 (3) and 32.9 (3)°; N5/C28 = 75.9 (2) and 80.8 (2)°; Lee & Wang, 2007]. The distance between the two pyridyl rings is 5.43 (1) Å, which is longer than the corresponding values of 4.63 (1) and 0.30 (1) Å [Very short - please check] in the previous work, and the terminal (pyridyl) N···N separation of 12.199 (2) Å is slightly shorter than those of the previous work [13.075 (2) and 12.951 (2) Å; Lee & Wang, 2007].

The two-dimensional array of 4py-ox molecules is presented in Fig. 2, showing a two-dimensional sheet-like supramolecular network formed through intermolecular hydrogen bonds. Details of the hydrogen-bonding geometry are given in Table 2. Two types of intermolecular hydrogen bonds are observed in the unit cell. One is between the N atom of the oxalamide part and the pyridyl N atom of a neighboring molecule [N2···N1ⁱⁱ = 3.006 (2) Å; symmetry code: (ii) x + 1,-y + 3/2, z + 1/2], and the other between the O atom of the oxalamide part and the α-pyridyl C atom of a neighboring molecule [C1···O1ⁱⁱⁱ = 3.254 (2) Å; symmetry code: (iii) -x, y + 1/2, -z + 3/2]. There is also an intramolecular hydrogen bond within the oxalamide group [N2···O1ⁱ = 2.716 (2) Å; symmetry code: (i) -x + 1, -y + 1, -z + 2], and thus atom H2 is involved in a bifurcated hydrogen bond. The 4py-ox molecules are then interlinked via four sets of combined N—H···N and C—H···O hydrogen bonds to form a two-dimensional supramolecular architecture. It is interesting to note that this two-dimensional array is different from that of the previous report (Lee & Wang, 2007), in which dimers of 4py-ox molecules, formed via a pair of N—H···O hydrogen bonds [N···O distances of 2.916 (2) and 2.888 (2) Å], act as the basic building units and are then interlinked via four sets of N—H···N hydrogen bonds [N···N distances of 2.903 (2) and 2.930 (2) Å] between the N atoms of the oxalamide part and the pyridyl N atoms of neighboring dimers to form its two-dimensional supramolecular network.

Slow diffusion of Cd(NO₃)₂.4H₂O into a solution of 4py-ox resulted in colorless crystals of the unexpected composition [H₂(4py-ox)](NO₃)₂, compound (II). The diprotonation process of 4py-ox was also observed in [H₂(4,4'-bipy)](NO₃)₂ (where 4,4'-bipy is 4,4'-bipyridine; Felloni et al., 2002; Iyere et al., 2003) and [H₂(bpe)](NO₃)₂ [where bpe is 1,2-bis(4-pyridyl)ethene; Felloni et al., 2002; Yan, 2006]. The molecular structure of (II) contains diprotonated 4py-ox and NO3^- counterions, as shown in Fig. 3. Structural determination reveals that there is an inversion center in the middle of the oxalamide group and the asymmetric unit contains one-half of an H₂(4py-ox) cation and one NO3^- anion. Bond lengths and angles (Table 3) are comparable with those of (I). Similar to (I), the central oxalamide group is planar. The dihedral angle between the pyridinium ring and the oxalamide group is 103.9 (1)°, which is slightly smaller than the corresponding angle in (I) [104.9 (1)°]. The shortest distance between two pyridyl rings in (II) is 0.26 (1) Å [Very short - please check] and the C2—C3—C6—N2 torsion angle is 23.3 (3)°, and these values are both less than those observed in (I), although they are comparable with those of one molecule (N1/C14) in the previous work [0.30 (1) Å, and 30.1 (3) and 32.9 (3)°, respectively; Lee & Wang, 2007].

There are two bifurcated hydrogen bonds in the structure of (II). One is between the nitrate anion and the N1—H1 group of the pyridinium ring of the [H₂(4py-ox)]²⁺ cation, with N1···O2 = 2.701 (3) Å and N1···O3 = 3.089 (3) Å. These results are similar to those found in [H₂(4,4'-bipy)](NO₃)₂ reported earlier [N1···O2 = 2.668 (2) Å and N1···O3 = 3.148 (2) Å; Iyere et al., 2003]. The other is found at the N2—H2 group of the oxalamide moiety, in which there is an intramolecular hydrogen bond [N2···O1ⁱ = 2.669 (2) Å; symmetry code: (i) -x + 1, -y + 1, -z] and an intermolecular hydrogen bond [N2···O2ⁱⁱ = 2.943 (2) Å; symmetry code: (ii) x, -y + 1/2, z - 1/2]. Thus, atoms H1 and H2 are involved in bifurcated hydrogen bonds.

The supramolecular aggregation of (II) in the packing (Fig. 4) is more complicated than that in (I). Each nitrate ion is hydrogen-bonded to four cations via three N—H···O contacts [N1···O2 = 2.701 (3) Å, N1···O3 = 3.089 (3) Å and N2···O2ⁱⁱ = 2.943 (2) Å] and two C—H···O interactions [C2···O4^iv = 3.180 (3) Å and C5···O3^v = 3.160 (3) Å; symmetry codes: (iv) x - 1, -y + 1/2, z - 1/2; (v) -x + 3, -y + 1, -z + 1]. Such coordination of each nitrate ion by four cations was also observed in the structure of [H₂(4,4'-bipy)](NO₃)₂ (Iyere et al., 2003). Furthermore, adjacent cations are linked via weak C—H···O hydrogen bonding [C1···O1ⁱⁱⁱ = 3.159 (3) Å; symmetry code: (iii) -x + 1, y - 1/2, -z + 1/2] between the α-pyridium C atoms and the oxalamide O atoms, forming an extended two-dimensional supramolecular network. Details of the hydrogen-bonding geometry are given in Table 4.

S2. Experimental

N,N'-bis(pyridin-4-ylmethyl)oxalamide was prepared from 4-(aminomethyl)pyridine and diethyl oxalate, according to the method described by Nguyen et al. (1998). Single crystals of (I) were obtained by the DMF/ether diffusion method.

A methanol solution (5 ml) of Cd(NO₃)₂.4H₂O (1 mmol) was mixed with a methanol solution (5 ml) of 4py-ox (3 mmol). Slow diffusion with ether resulted in large colorless crystals of the unexpected composition N,N'-bis(4-pyridiniummethyl)oxalamide dinitrate, (II).

S3. Refinement

The pyridinium H atom of (II) was located in a difference Fourier map and refined isotropically. Other H atoms attached to C and N atoms were positioned geometrically and refined using a riding model, with C—H = 0.95–0.99 Å and N—H = 0.88 Å, and with U_iso(H) = 1.2U_eq(C,N) for both (I) and (II).

Computing details

For both compounds, data collection: COLLECT (Nonius, 1998); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. [Symmetry code: (i) -x + 1, -y + 1, -z + 2].
	Fig. 2. A packing diagram for (I), viewed along the a axis. Dashed lines represent hydrogen bonds. [Symmetry codes: (i) -x + 1, -y + 1, -z + 2; (ii) x + 1, -y + 3/2, z + 1/2; (iii) -x, y + 1/2, -z + 3/2.]
	Fig. 3. The molecular structure of (II), showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Dashed lines represent hydrogen bonds. [Symmetry code: (i) -x + 1, -y + 1, -z.]
	Fig. 4. A packing diagram for (II), viewed along the a axis. Dashed lines represent hydrogen bonds. [Symmetry codes: (i) -x + 1, -y + 1, -z; (ii) x, -y + 1/2, z - 1/2; (iii) -x + 1, y - 1/2, -z + 1/2; (iv) x - 1, -y + 1/2, z - 1/2; (v) -x + 3, -y + 1, -z + 1.]

(I) N,N'-bis(4-pyridylmethyl)oxalamide

Crystal data

C14H14N4O2	F(000) = 284
Mr = 270.29	Dx = 1.379 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7355 reflections
a = 4.7578 (2) Å	θ = 2.5–27.5°
b = 13.8845 (4) Å	µ = 0.10 mm^−1
c = 10.1331 (3) Å	T = 150 K
β = 103.465 (2)°	Block, colourless
V = 650.99 (4) Å^3	0.30 × 0.25 × 0.15 mm
Z = 2

Data collection

Nonius KappaCCD area-detector diffractometer	1485 independent reflections
Radiation source: fine-focus sealed tube	868 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.043
ω scans	θmax = 27.5°, θmin = 2.5°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −6→6
Tmin = 0.972, Tmax = 0.986	k = −17→17
7355 measured reflections	l = −13→13

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.101	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0485P)^2] where P = (Fo^2 + 2Fc^2)/3
1485 reflections	(Δ/σ)max < 0.001
91 parameters	Δρmax = 0.14 e Å^−3
0 restraints	Δρmin = −0.19 e Å^−3

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
O1	0.3332 (2)	0.44615 (7)	0.84468 (10)	0.0399 (3)
N1	−0.0172 (3)	0.75701 (10)	0.51536 (12)	0.0424 (4)
N2	0.6582 (2)	0.56810 (8)	0.88710 (11)	0.0332 (3)
H2	0.7647	0.6053	0.9495	0.040*
C1	0.1514 (3)	0.78547 (11)	0.63302 (16)	0.0447 (4)
H1	0.1177	0.8475	0.6657	0.054*
C2	0.3706 (3)	0.73127 (11)	0.71042 (17)	0.0414 (4)
H2A	0.4832	0.7559	0.7935	0.050*
C3	0.4257 (3)	0.64065 (10)	0.66615 (13)	0.0303 (4)
C4	0.2493 (4)	0.60952 (11)	0.54642 (14)	0.0407 (4)
H4	0.2756	0.5471	0.5130	0.049*
C5	0.0343 (3)	0.66852 (12)	0.47464 (15)	0.0463 (5)
H5	−0.0833	0.6451	0.3920	0.056*
C6	0.6693 (3)	0.58036 (11)	0.74618 (13)	0.0352 (4)
H6A	0.6633	0.5161	0.7031	0.042*
H6B	0.8553	0.6110	0.7426	0.042*
C7	0.4898 (3)	0.50156 (10)	0.92348 (14)	0.0303 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0489 (7)	0.0389 (6)	0.0301 (6)	−0.0069 (5)	0.0057 (5)	−0.0051 (5)
N1	0.0437 (9)	0.0468 (8)	0.0368 (8)	0.0078 (7)	0.0094 (7)	0.0086 (7)
N2	0.0377 (8)	0.0354 (7)	0.0247 (7)	−0.0028 (6)	0.0036 (6)	−0.0006 (5)
C1	0.0424 (10)	0.0323 (9)	0.0568 (11)	0.0007 (8)	0.0063 (10)	−0.0002 (8)
C2	0.0382 (10)	0.0355 (9)	0.0452 (10)	−0.0010 (8)	−0.0011 (8)	−0.0054 (8)
C3	0.0303 (8)	0.0350 (9)	0.0272 (8)	0.0007 (7)	0.0099 (7)	0.0047 (7)
C4	0.0479 (10)	0.0442 (9)	0.0297 (8)	0.0111 (8)	0.0083 (8)	−0.0050 (7)
C5	0.0475 (11)	0.0627 (12)	0.0267 (8)	0.0112 (9)	0.0047 (8)	−0.0041 (8)
C6	0.0366 (9)	0.0412 (9)	0.0288 (9)	0.0042 (7)	0.0096 (7)	0.0033 (6)
C7	0.0325 (9)	0.0280 (8)	0.0293 (8)	0.0057 (7)	0.0051 (7)	−0.0005 (7)

Geometric parameters (Å, º)

O1—C7	1.2280 (16)	C2—H2A	0.9500
N1—C1	1.3327 (19)	C3—C4	1.374 (2)
N1—C5	1.3369 (19)	C3—C6	1.5046 (19)
N2—C7	1.3301 (18)	C4—C5	1.378 (2)
N2—C6	1.4511 (17)	C4—H4	0.9500
N2—H2	0.8800	C5—H5	0.9500
C1—C2	1.374 (2)	C6—H6A	0.9900
C1—H1	0.9500	C6—H6B	0.9900
C2—C3	1.381 (2)	C7—C7^i	1.532 (3)
C1—N1—C5	115.66 (13)	C3—C4—H4	119.8
C7—N2—C6	121.09 (12)	C5—C4—H4	119.8
C7—N2—H2	119.5	N1—C5—C4	123.39 (14)
C6—N2—H2	119.5	N1—C5—H5	118.3
N1—C1—C2	124.55 (15)	C4—C5—H5	118.3
N1—C1—H1	117.7	N2—C6—C3	113.31 (12)
C2—C1—H1	117.7	N2—C6—H6A	108.9
C1—C2—C3	119.32 (14)	C3—C6—H6A	108.9
C1—C2—H2A	120.3	N2—C6—H6B	108.9
C3—C2—H2A	120.3	C3—C6—H6B	108.9
C4—C3—C2	116.75 (14)	H6A—C6—H6B	107.7
C4—C3—C6	122.43 (13)	O1—C7—N2	124.65 (13)
C2—C3—C6	120.82 (13)	O1—C7—C7^i	121.76 (17)
C3—C4—C5	120.30 (14)	N2—C7—C7^i	113.59 (16)

Symmetry code: (i) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1^i	0.88	2.35	2.716 (2)	105
N2—H2···N1^ii	0.88	2.20	3.006 (2)	152
C1—H1···O1^iii	0.95	2.53	3.254 (2)	133

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

(II) 4,4'-{[oxalylbis(azanediyl)]dimethylene}dipyridinium dinitrate

Crystal data

C14H16N4O2^2+·2NO3^−	F(000) = 412
Mr = 396.33	Dx = 1.544 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7829 reflections
a = 5.3668 (5) Å	θ = 2.3–27.5°
b = 10.7271 (10) Å	µ = 0.13 mm^−1
c = 14.8628 (14) Å	T = 150 K
β = 94.746 (2)°	Plate, colourless
V = 852.72 (14) Å^3	0.50 × 0.22 × 0.01 mm
Z = 2

Data collection

Nonius KappaCCD area-detector diffractometer	1931 independent reflections
Radiation source: fine-focus sealed tube	1293 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.066
ω scans	θmax = 27.5°, θmin = 2.3°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −6→6
Tmin = 0.939, Tmax = 0.999	k = −13→13
7829 measured reflections	l = −17→19

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.052	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.140	w = 1/[σ^2(Fo^2) + (0.067P)^2 + 0.2415P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
1931 reflections	Δρmax = 0.22 e Å^−3
132 parameters	Δρmin = −0.34 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.025 (5)

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
O1	0.4626 (3)	0.64026 (13)	0.05718 (11)	0.0395 (4)
N1	0.9992 (3)	0.38814 (16)	0.40178 (14)	0.0378 (5)
H1	1.019 (5)	0.344 (3)	0.452 (2)	0.052 (7)*
N2	0.7707 (3)	0.49515 (16)	0.07772 (12)	0.0335 (4)
H2	0.8210	0.4209	0.0617	0.040*
C1	0.8025 (4)	0.35835 (19)	0.34439 (15)	0.0376 (5)
H1A	0.6838	0.2990	0.3615	0.045*
C2	0.7725 (4)	0.41321 (18)	0.26149 (15)	0.0354 (5)
H2A	0.6337	0.3918	0.2206	0.042*
C3	0.9454 (4)	0.50041 (17)	0.23705 (14)	0.0324 (5)
C4	1.1435 (4)	0.53134 (19)	0.29905 (15)	0.0356 (5)
H4	1.2619	0.5924	0.2845	0.043*
C5	1.1667 (4)	0.4731 (2)	0.38125 (15)	0.0387 (5)
H5	1.3026	0.4933	0.4238	0.046*
C6	0.9197 (4)	0.56397 (19)	0.14673 (14)	0.0351 (5)
H6A	0.8426	0.6469	0.1538	0.042*
H6B	1.0886	0.5773	0.1263	0.042*
C7	0.5596 (4)	0.54171 (19)	0.03805 (14)	0.0325 (5)
N3	1.2254 (3)	0.27547 (17)	0.60041 (13)	0.0395 (5)
O2	1.0396 (3)	0.23861 (14)	0.54849 (11)	0.0445 (4)
O3	1.3366 (3)	0.37079 (14)	0.58010 (12)	0.0453 (4)
O4	1.2836 (4)	0.2183 (2)	0.67073 (15)	0.0746 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0401 (9)	0.0325 (8)	0.0456 (9)	0.0065 (6)	0.0013 (7)	−0.0068 (6)
N1	0.0439 (11)	0.0299 (9)	0.0392 (11)	0.0035 (7)	0.0005 (8)	0.0023 (8)
N2	0.0357 (9)	0.0270 (8)	0.0373 (10)	0.0025 (7)	0.0004 (7)	−0.0026 (7)
C1	0.0386 (12)	0.0282 (10)	0.0461 (13)	−0.0030 (8)	0.0035 (9)	−0.0009 (9)
C2	0.0353 (11)	0.0274 (10)	0.0428 (12)	−0.0012 (8)	0.0004 (9)	−0.0033 (9)
C3	0.0328 (11)	0.0244 (10)	0.0395 (12)	0.0019 (8)	0.0009 (9)	−0.0047 (8)
C4	0.0331 (11)	0.0319 (11)	0.0418 (13)	−0.0028 (8)	0.0026 (9)	−0.0023 (9)
C5	0.0363 (12)	0.0363 (11)	0.0427 (13)	−0.0008 (9)	−0.0021 (9)	−0.0048 (10)
C6	0.0353 (11)	0.0292 (10)	0.0403 (12)	−0.0036 (8)	0.0008 (9)	0.0000 (9)
C7	0.0323 (11)	0.0285 (10)	0.0373 (11)	0.0009 (8)	0.0059 (9)	0.0005 (9)
N3	0.0368 (10)	0.0344 (10)	0.0467 (11)	0.0050 (7)	−0.0002 (8)	0.0053 (8)
O2	0.0471 (9)	0.0361 (8)	0.0492 (10)	−0.0111 (7)	−0.0029 (7)	0.0020 (7)
O3	0.0444 (9)	0.0369 (9)	0.0537 (10)	−0.0079 (7)	−0.0015 (7)	−0.0011 (7)
O4	0.0533 (11)	0.0897 (15)	0.0785 (14)	0.0066 (10)	−0.0091 (10)	0.0473 (12)

Geometric parameters (Å, º)

O1—C7	1.222 (2)	C3—C4	1.388 (3)
N1—C5	1.333 (3)	C3—C6	1.502 (3)
N1—C1	1.340 (3)	C4—C5	1.368 (3)
N1—H1	0.89 (3)	C4—H4	0.9500
N2—C7	1.331 (3)	C5—H5	0.9500
N2—C6	1.449 (3)	C6—H6A	0.9900
N2—H2	0.8800	C6—H6B	0.9900
C1—C2	1.363 (3)	C7—C7^i	1.539 (4)
C1—H1A	0.9500	N3—O4	1.230 (3)
C2—C3	1.387 (3)	N3—O3	1.234 (2)
C2—H2A	0.9500	N3—O2	1.272 (2)
C5—N1—C1	121.9 (2)	C3—C4—H4	120.3
C5—N1—H1	121.6 (17)	N1—C5—C4	120.2 (2)
C1—N1—H1	116.4 (17)	N1—C5—H5	119.9
C7—N2—C6	121.47 (17)	C4—C5—H5	119.9
C7—N2—H2	119.3	N2—C6—C3	113.94 (17)
C6—N2—H2	119.3	N2—C6—H6A	108.8
N1—C1—C2	120.0 (2)	C3—C6—H6A	108.8
N1—C1—H1A	120.0	N2—C6—H6B	108.8
C2—C1—H1A	120.0	C3—C6—H6B	108.8
C1—C2—C3	119.8 (2)	H6A—C6—H6B	107.7
C1—C2—H2A	120.1	O1—C7—N2	125.80 (19)
C3—C2—H2A	120.1	O1—C7—C7^i	121.0 (2)
C2—C3—C4	118.6 (2)	N2—C7—C7^i	113.2 (2)
C2—C3—C6	121.77 (18)	O4—N3—O3	121.8 (2)
C4—C3—C6	119.57 (18)	O4—N3—O2	119.46 (19)
C5—C4—C3	119.5 (2)	O3—N3—O2	118.67 (17)
C5—C4—H4	120.3

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.89 (3)	1.82 (3)	2.701 (3)	173 (3)
N1—H1···O3	0.89 (3)	2.46 (3)	3.089 (3)	128 (2)
N2—H2···O1^i	0.88	2.33	2.699 (2)	105
N2—H2···O2^ii	0.88	2.09	2.943 (2)	162
C1—H1A···O1^iii	0.95	2.27	3.159 (3)	156
C2—H2A···O4^iv	0.95	2.29	3.180 (3)	156
C5—H5···O3^v	0.95	2.43	3.160 (3)	134

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