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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110010280/uk3019sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110010280/uk3019Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110010280/uk3019IIsup3.hkl
Contains datablock II

CCDC references: 779958; 779959

Comment top

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 ππ 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···O4iv = 3.180 (3) Å and C5···O3v = 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.

Experimental top

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).

Refinement top

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 Uiso(H) = 1.2Ueq(C,N) for both (I) and (II).

Computing details top

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 top
[Figure 1] 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].
[Figure 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.]
[Figure 3] 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.]
[Figure 4] 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 top
Crystal data top
C14H14N4O2F(000) = 284
Mr = 270.29Dx = 1.379 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 7355 reflections
a = 4.7578 (2) Åθ = 2.5–27.5°
b = 13.8845 (4) ŵ = 0.10 mm1
c = 10.1331 (3) ÅT = 150 K
β = 103.465 (2)°Block, colourless
V = 650.99 (4) Å30.30 × 0.25 × 0.15 mm
Z = 2
Data collection top
Nonius KappaCCD area-detector
diffractometer
1485 independent reflections
Radiation source: fine-focus sealed tube868 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.043
ω scansθmax = 27.5°, θmin = 2.5°
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
h = 66
Tmin = 0.972, Tmax = 0.986k = 1717
7355 measured reflectionsl = 1313
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.101H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0485P)2]
where P = (Fo2 + 2Fc2)/3
1485 reflections(Δ/σ)max < 0.001
91 parametersΔρmax = 0.14 e Å3
0 restraintsΔρmin = 0.19 e Å3
Crystal data top
C14H14N4O2V = 650.99 (4) Å3
Mr = 270.29Z = 2
Monoclinic, P21/cMo Kα radiation
a = 4.7578 (2) ŵ = 0.10 mm1
b = 13.8845 (4) ÅT = 150 K
c = 10.1331 (3) Å0.30 × 0.25 × 0.15 mm
β = 103.465 (2)°
Data collection top
Nonius KappaCCD area-detector
diffractometer
1485 independent reflections
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
868 reflections with I > 2σ(I)
Tmin = 0.972, Tmax = 0.986Rint = 0.043
7355 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0400 restraints
wR(F2) = 0.101H-atom parameters constrained
S = 1.03Δρmax = 0.14 e Å3
1485 reflectionsΔρmin = 0.19 e Å3
91 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
O10.3332 (2)0.44615 (7)0.84468 (10)0.0399 (3)
N10.0172 (3)0.75701 (10)0.51536 (12)0.0424 (4)
N20.6582 (2)0.56810 (8)0.88710 (11)0.0332 (3)
H20.76470.60530.94950.040*
C10.1514 (3)0.78547 (11)0.63302 (16)0.0447 (4)
H10.11770.84750.66570.054*
C20.3706 (3)0.73127 (11)0.71042 (17)0.0414 (4)
H2A0.48320.75590.79350.050*
C30.4257 (3)0.64065 (10)0.66615 (13)0.0303 (4)
C40.2493 (4)0.60952 (11)0.54642 (14)0.0407 (4)
H40.27560.54710.51300.049*
C50.0343 (3)0.66852 (12)0.47464 (15)0.0463 (5)
H50.08330.64510.39200.056*
C60.6693 (3)0.58036 (11)0.74618 (13)0.0352 (4)
H6A0.66330.51610.70310.042*
H6B0.85530.61100.74260.042*
C70.4898 (3)0.50156 (10)0.92348 (14)0.0303 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0489 (7)0.0389 (6)0.0301 (6)0.0069 (5)0.0057 (5)0.0051 (5)
N10.0437 (9)0.0468 (8)0.0368 (8)0.0078 (7)0.0094 (7)0.0086 (7)
N20.0377 (8)0.0354 (7)0.0247 (7)0.0028 (6)0.0036 (6)0.0006 (5)
C10.0424 (10)0.0323 (9)0.0568 (11)0.0007 (8)0.0063 (10)0.0002 (8)
C20.0382 (10)0.0355 (9)0.0452 (10)0.0010 (8)0.0011 (8)0.0054 (8)
C30.0303 (8)0.0350 (9)0.0272 (8)0.0007 (7)0.0099 (7)0.0047 (7)
C40.0479 (10)0.0442 (9)0.0297 (8)0.0111 (8)0.0083 (8)0.0050 (7)
C50.0475 (11)0.0627 (12)0.0267 (8)0.0112 (9)0.0047 (8)0.0041 (8)
C60.0366 (9)0.0412 (9)0.0288 (9)0.0042 (7)0.0096 (7)0.0033 (6)
C70.0325 (9)0.0280 (8)0.0293 (8)0.0057 (7)0.0051 (7)0.0005 (7)
Geometric parameters (Å, º) top
O1—C71.2280 (16)C2—H2A0.9500
N1—C11.3327 (19)C3—C41.374 (2)
N1—C51.3369 (19)C3—C61.5046 (19)
N2—C71.3301 (18)C4—C51.378 (2)
N2—C61.4511 (17)C4—H40.9500
N2—H20.8800C5—H50.9500
C1—C21.374 (2)C6—H6A0.9900
C1—H10.9500C6—H6B0.9900
C2—C31.381 (2)C7—C7i1.532 (3)
C1—N1—C5115.66 (13)C3—C4—H4119.8
C7—N2—C6121.09 (12)C5—C4—H4119.8
C7—N2—H2119.5N1—C5—C4123.39 (14)
C6—N2—H2119.5N1—C5—H5118.3
N1—C1—C2124.55 (15)C4—C5—H5118.3
N1—C1—H1117.7N2—C6—C3113.31 (12)
C2—C1—H1117.7N2—C6—H6A108.9
C1—C2—C3119.32 (14)C3—C6—H6A108.9
C1—C2—H2A120.3N2—C6—H6B108.9
C3—C2—H2A120.3C3—C6—H6B108.9
C4—C3—C2116.75 (14)H6A—C6—H6B107.7
C4—C3—C6122.43 (13)O1—C7—N2124.65 (13)
C2—C3—C6120.82 (13)O1—C7—C7i121.76 (17)
C3—C4—C5120.30 (14)N2—C7—C7i113.59 (16)
Symmetry code: (i) x+1, y+1, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O1i0.882.352.716 (2)105
N2—H2···N1ii0.882.203.006 (2)152
C1—H1···O1iii0.952.533.254 (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 top
Crystal data top
C14H16N4O22+·2NO3F(000) = 412
Mr = 396.33Dx = 1.544 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 7829 reflections
a = 5.3668 (5) Åθ = 2.3–27.5°
b = 10.7271 (10) ŵ = 0.13 mm1
c = 14.8628 (14) ÅT = 150 K
β = 94.746 (2)°Plate, colourless
V = 852.72 (14) Å30.50 × 0.22 × 0.01 mm
Z = 2
Data collection top
Nonius KappaCCD area-detector
diffractometer
1931 independent reflections
Radiation source: fine-focus sealed tube1293 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.066
ω scansθmax = 27.5°, θmin = 2.3°
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
h = 66
Tmin = 0.939, Tmax = 0.999k = 1313
7829 measured reflectionsl = 1719
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.052H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.140 w = 1/[σ2(Fo2) + (0.067P)2 + 0.2415P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
1931 reflectionsΔρmax = 0.22 e Å3
132 parametersΔρmin = 0.34 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.025 (5)
Crystal data top
C14H16N4O22+·2NO3V = 852.72 (14) Å3
Mr = 396.33Z = 2
Monoclinic, P21/cMo Kα radiation
a = 5.3668 (5) ŵ = 0.13 mm1
b = 10.7271 (10) ÅT = 150 K
c = 14.8628 (14) Å0.50 × 0.22 × 0.01 mm
β = 94.746 (2)°
Data collection top
Nonius KappaCCD area-detector
diffractometer
1931 independent reflections
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
1293 reflections with I > 2σ(I)
Tmin = 0.939, Tmax = 0.999Rint = 0.066
7829 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0520 restraints
wR(F2) = 0.140H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.22 e Å3
1931 reflectionsΔρmin = 0.34 e Å3
132 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
O10.4626 (3)0.64026 (13)0.05718 (11)0.0395 (4)
N10.9992 (3)0.38814 (16)0.40178 (14)0.0378 (5)
H11.019 (5)0.344 (3)0.452 (2)0.052 (7)*
N20.7707 (3)0.49515 (16)0.07772 (12)0.0335 (4)
H20.82100.42090.06170.040*
C10.8025 (4)0.35835 (19)0.34439 (15)0.0376 (5)
H1A0.68380.29900.36150.045*
C20.7725 (4)0.41321 (18)0.26149 (15)0.0354 (5)
H2A0.63370.39180.22060.042*
C30.9454 (4)0.50041 (17)0.23705 (14)0.0324 (5)
C41.1435 (4)0.53134 (19)0.29905 (15)0.0356 (5)
H41.26190.59240.28450.043*
C51.1667 (4)0.4731 (2)0.38125 (15)0.0387 (5)
H51.30260.49330.42380.046*
C60.9197 (4)0.56397 (19)0.14673 (14)0.0351 (5)
H6A0.84260.64690.15380.042*
H6B1.08860.57730.12630.042*
C70.5596 (4)0.54171 (19)0.03805 (14)0.0325 (5)
N31.2254 (3)0.27547 (17)0.60041 (13)0.0395 (5)
O21.0396 (3)0.23861 (14)0.54849 (11)0.0445 (4)
O31.3366 (3)0.37079 (14)0.58010 (12)0.0453 (4)
O41.2836 (4)0.2183 (2)0.67073 (15)0.0746 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0401 (9)0.0325 (8)0.0456 (9)0.0065 (6)0.0013 (7)0.0068 (6)
N10.0439 (11)0.0299 (9)0.0392 (11)0.0035 (7)0.0005 (8)0.0023 (8)
N20.0357 (9)0.0270 (8)0.0373 (10)0.0025 (7)0.0004 (7)0.0026 (7)
C10.0386 (12)0.0282 (10)0.0461 (13)0.0030 (8)0.0035 (9)0.0009 (9)
C20.0353 (11)0.0274 (10)0.0428 (12)0.0012 (8)0.0004 (9)0.0033 (9)
C30.0328 (11)0.0244 (10)0.0395 (12)0.0019 (8)0.0009 (9)0.0047 (8)
C40.0331 (11)0.0319 (11)0.0418 (13)0.0028 (8)0.0026 (9)0.0023 (9)
C50.0363 (12)0.0363 (11)0.0427 (13)0.0008 (9)0.0021 (9)0.0048 (10)
C60.0353 (11)0.0292 (10)0.0403 (12)0.0036 (8)0.0008 (9)0.0000 (9)
C70.0323 (11)0.0285 (10)0.0373 (11)0.0009 (8)0.0059 (9)0.0005 (9)
N30.0368 (10)0.0344 (10)0.0467 (11)0.0050 (7)0.0002 (8)0.0053 (8)
O20.0471 (9)0.0361 (8)0.0492 (10)0.0111 (7)0.0029 (7)0.0020 (7)
O30.0444 (9)0.0369 (9)0.0537 (10)0.0079 (7)0.0015 (7)0.0011 (7)
O40.0533 (11)0.0897 (15)0.0785 (14)0.0066 (10)0.0091 (10)0.0473 (12)
Geometric parameters (Å, º) top
O1—C71.222 (2)C3—C41.388 (3)
N1—C51.333 (3)C3—C61.502 (3)
N1—C11.340 (3)C4—C51.368 (3)
N1—H10.89 (3)C4—H40.9500
N2—C71.331 (3)C5—H50.9500
N2—C61.449 (3)C6—H6A0.9900
N2—H20.8800C6—H6B0.9900
C1—C21.363 (3)C7—C7i1.539 (4)
C1—H1A0.9500N3—O41.230 (3)
C2—C31.387 (3)N3—O31.234 (2)
C2—H2A0.9500N3—O21.272 (2)
C5—N1—C1121.9 (2)C3—C4—H4120.3
C5—N1—H1121.6 (17)N1—C5—C4120.2 (2)
C1—N1—H1116.4 (17)N1—C5—H5119.9
C7—N2—C6121.47 (17)C4—C5—H5119.9
C7—N2—H2119.3N2—C6—C3113.94 (17)
C6—N2—H2119.3N2—C6—H6A108.8
N1—C1—C2120.0 (2)C3—C6—H6A108.8
N1—C1—H1A120.0N2—C6—H6B108.8
C2—C1—H1A120.0C3—C6—H6B108.8
C1—C2—C3119.8 (2)H6A—C6—H6B107.7
C1—C2—H2A120.1O1—C7—N2125.80 (19)
C3—C2—H2A120.1O1—C7—C7i121.0 (2)
C2—C3—C4118.6 (2)N2—C7—C7i113.2 (2)
C2—C3—C6121.77 (18)O4—N3—O3121.8 (2)
C4—C3—C6119.57 (18)O4—N3—O2119.46 (19)
C5—C4—C3119.5 (2)O3—N3—O2118.67 (17)
C5—C4—H4120.3
Symmetry code: (i) x+1, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O20.89 (3)1.82 (3)2.701 (3)173 (3)
N1—H1···O30.89 (3)2.46 (3)3.089 (3)128 (2)
N2—H2···O1i0.882.332.699 (2)105
N2—H2···O2ii0.882.092.943 (2)162
C1—H1A···O1iii0.952.273.159 (3)156
C2—H2A···O4iv0.952.293.180 (3)156
C5—H5···O3v0.952.433.160 (3)134
Symmetry codes: (i) x+1, y+1, z; (ii) x, y+1/2, z1/2; (iii) x+1, y1/2, z+1/2; (iv) x1, y+1/2, z1/2; (v) x+3, y+1, z+1.

Experimental details

(I)(II)
Crystal data
Chemical formulaC14H14N4O2C14H16N4O22+·2NO3
Mr270.29396.33
Crystal system, space groupMonoclinic, P21/cMonoclinic, P21/c
Temperature (K)150150
a, b, c (Å)4.7578 (2), 13.8845 (4), 10.1331 (3)5.3668 (5), 10.7271 (10), 14.8628 (14)
β (°) 103.465 (2) 94.746 (2)
V3)650.99 (4)852.72 (14)
Z22
Radiation typeMo KαMo Kα
µ (mm1)0.100.13
Crystal size (mm)0.30 × 0.25 × 0.150.50 × 0.22 × 0.01
Data collection
DiffractometerNonius KappaCCD area-detector
diffractometer
Nonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SORTAV; Blessing, 1995)
Multi-scan
(SORTAV; Blessing, 1995)
Tmin, Tmax0.972, 0.9860.939, 0.999
No. of measured, independent and
observed [I > 2σ(I)] reflections
7355, 1485, 868 7829, 1931, 1293
Rint0.0430.066
(sin θ/λ)max1)0.6500.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.101, 1.03 0.052, 0.140, 1.04
No. of reflections14851931
No. of parameters91132
H-atom treatmentH-atom parameters constrainedH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.14, 0.190.22, 0.34

Computer programs: COLLECT (Nonius, 1998), DENZO-SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) for (I) top
O1—C71.2280 (16)N2—C61.4511 (17)
N2—C71.3301 (18)C7—C7i1.532 (3)
C7—N2—C6121.09 (12)O1—C7—C7i121.76 (17)
N2—C6—C3113.31 (12)N2—C7—C7i113.59 (16)
O1—C7—N2124.65 (13)
Symmetry code: (i) x+1, y+1, z+2.
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O1i0.882.352.716 (2)105
N2—H2···N1ii0.882.203.006 (2)152
C1—H1···O1iii0.952.533.254 (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.
Selected geometric parameters (Å, º) for (II) top
O1—C71.222 (2)N3—O41.230 (3)
N2—C71.331 (3)N3—O31.234 (2)
N2—C61.449 (3)N3—O21.272 (2)
C7—C7i1.539 (4)
C7—N2—C6121.47 (17)N2—C7—C7i113.2 (2)
N2—C6—C3113.94 (17)O4—N3—O3121.8 (2)
O1—C7—N2125.80 (19)O4—N3—O2119.46 (19)
O1—C7—C7i121.0 (2)O3—N3—O2118.67 (17)
Symmetry code: (i) x+1, y+1, z.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O20.89 (3)1.82 (3)2.701 (3)173 (3)
N1—H1···O30.89 (3)2.46 (3)3.089 (3)128 (2)
N2—H2···O1i0.882.332.699 (2)105
N2—H2···O2ii0.882.092.943 (2)162
C1—H1A···O1iii0.952.273.159 (3)156
C2—H2A···O4iv0.952.293.180 (3)156
C5—H5···O3v0.952.433.160 (3)134
Symmetry codes: (i) x+1, y+1, z; (ii) x, y+1/2, z1/2; (iii) x+1, y1/2, z+1/2; (iv) x1, y+1/2, z1/2; (v) x+3, y+1, z+1.
 

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