research communications
of 4,4′-(diazenediyl)dipyridinium nitrate perchlorate
aSchool of Science, China University of Geosciences, Beijing 100083, People's Republic of China, and bBeijing Chaoyang Foreign Language School, Beijing 100101, People's Republic of China
*Correspondence e-mail: qiuqiming890521@163.com
The title compound, C10H10N42+·NO3−·ClO4−, was obtained unexpectedly by the reaction of Co(ClO4)2·6H2O and cytidine-5′-monophosphate with 4,4′-azopyridine in an aqueous solution of nitric acid. The molecular structure comprises two planar 4,4′-diazenediyldipyridinium dications lying on inversion centres and perchlorate and nitrate anions in general positions. In the crystal, N—H⋯O hydrogen bonds between dications and anions lead to the formation of [232] chains.
Keywords: crystal structure; 4,4′-azopyridine; hydrogen bonds.
CCDC reference: 2163316
1. Chemical context
If a molecule contains two connected six-membered rings, and each of them contains N atoms, this molecule can coordinate various metal ions in different ways. In particular, molecules containing two or more pyridine rings are perfect bridging ligands to form supramolecular structures (Zhang et al., 2005; Rusu et al., 2012; Theilmann et al., 2009; Aakeröy et al., 2013a,b; Huang et al., 2016; Santana et al., 2017; Hutchins et al., 2018). In our previous work (Qiu et al., 2017), we used, together with a cytidine-5′-monophosphate mononucleotide (CMP), an auxiliary ligands, namely 4,4′-azopyridine (azpy), to completely coordinate a metal ion to restrain the non-enzymatic hydrolysis of the phosphate group catalyzed by these ions, and we obtained the complex Co-CMP-azpy under pH = 5. As a result of the different charge states of CMP in aqueous solution, it seems to be meaningful to study nucleotide complexes at other pH values. Unexpectedly, single crystals of the title compound were obtained in a more acidic medium (pH = 3). The title compound is the first example of a salt of 4,4′-diazenediyldipyridinium dication with two different anions.
2. Structural commentary
The molecular structure of the title compound comprises two planar [within 0.261 (5) Å] 4,4′-diazenediyldipyridinium dications lying on inversion centers and perchlorate and nitrate anions in general positions (Fig. 1). A planar conformation of the 4,4′-diazenediyldipyridinium dications is commonly observed for this type of compound. However, in the structure of bis(4,4′-diazenediyldipyridinium) bis(μ-chloro)octachlorodibismuth (POPHIO; Klein, 2019a) pyridinium rings are twisted by 19.0 (4)°, whereas in the structure of 4,4′-diazenediyldipyridinium bis(iodide) (POPKEN; Klein, 2019b) the mean planes of the pyridinium rings form a dihedral angle of 84.1 (2)°. In the title 4,4'-diazenediyldipyridinium, the value of the dihedral angle between the planes passing through the pyridine rings is 0°.
3. Supramolecular features
The 4,4′-diazenediyldipyridinium dications are connected by N—H⋯O hydrogen bonds with nitrate anions thus forming chains directed along [232] (Fig. 2, Table 1). The perchlorate anions are attached to these chains via N—H⋯O hydrogen bonds. C—H⋯O interactions are also observed.
4. Database survey
A search of the Cambridge Structural Database (CSD version 5.40, update of March 2020; Groom et al., 2016) for the 4,4′-diazenediyldipyridinium dication gave 17 hits, of which four purely organic structures are closely related to the title compound. In the crystal of 4,4′-diazenediyldipyridinium dinitrate (HUKQIN; Felloni et al., 2002), N—H⋯O hydrogen bonds connect the dication to two anions, thus forming an island structure. The same type of structure is present in 4,4′-diazenediyldipyridinium dichloride (POPBUU; Klein, 2019c) and 4,4′-diazenediyldipyridinium diiodide (POPKEN; Klein, 2019b). In the salt with partially deprotonated 1,2,4,5-benzenetetracarboxylic acid (BULJEZ; Ravat et al., 2015), the 4,4′-diazenediyldipyridinium dications act as the spacers that join the layers of hydrogen-bonded anions into a three-dimensional structure.
5. Synthesis and crystallization
An aqueous solution (5 mL) of cytidine-5′-monophosphate (32 mg, 0.10 mmol) was added to an aqueous solution (5 mL) of Co(ClO4)2·6H2O (18 mg, 0.05 mmol). After stirring for 10 min, 4,4′-azopyridine (9 mg, 0.05 mmol) in distilled water (5 mL) was added to this mixture. Nitric acid was also dropped to it and the resulting solution (pH = 3) was stirred at room temperature for 30 min. Red block-shaped crystals were obtained by evaporation at room temperature for two weeks.
6. Refinement
Crystal data, data collection and structure . All H atoms were positioned geometrically (N—H = 0.86 Å, C—H = 0.93 Å) and refined using a riding model with Uiso(H) = 1.2Ueq(N,C).
details are summarized in Table 2
|
Supporting information
CCDC reference: 2163316
https://doi.org/10.1107/S2056989022007885/yk2173sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989022007885/yk2173Isup2.hkl
Data collection: SAINT (Bruker, 2006); cell
SAINT (Bruker, 2006); data reduction: APEX2 (Bruker, 2006); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C10H10N42+·NO3−·ClO4− | Z = 2 |
Mr = 347.68 | F(000) = 356 |
Triclinic, P1 | Dx = 1.622 Mg m−3 |
a = 8.3023 (8) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.0792 (9) Å | Cell parameters from 1709 reflections |
c = 10.1052 (9) Å | θ = 2.3–25.3° |
α = 116.966 (3)° | µ = 0.32 mm−1 |
β = 105.481 (2)° | T = 298 K |
γ = 92.871 (1)° | Block, red |
V = 711.77 (11) Å3 | 0.45 × 0.40 × 0.33 mm |
Bruker APEXII CCD diffractometer | 1896 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube, Bruker (Mo) X-ray Source | Rint = 0.034 |
phi and ω continuous scans | θmax = 25.1°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −9→9 |
Tmin = 0.873, Tmax = 0.904 | k = −11→7 |
3625 measured reflections | l = −12→12 |
2466 independent reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.081 | H-atom parameters constrained |
wR(F2) = 0.250 | w = 1/[σ2(Fo2) + (0.189P)2 + 0.2213P] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max < 0.001 |
2466 reflections | Δρmax = 0.63 e Å−3 |
208 parameters | Δρmin = −0.51 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.2913 (7) | 0.5983 (5) | 0.6432 (5) | 0.0737 (14) | |
H1A | 0.305031 | 0.544442 | 0.545363 | 0.088* | |
C2 | 0.3896 (6) | 0.7426 (5) | 0.7501 (5) | 0.0611 (11) | |
H2A | 0.469672 | 0.786844 | 0.725164 | 0.073* | |
C3 | 0.3655 (5) | 0.8180 (4) | 0.8929 (4) | 0.0494 (9) | |
C4 | 0.2457 (5) | 0.7514 (5) | 0.9279 (5) | 0.0583 (10) | |
H4 | 0.228689 | 0.802795 | 1.024639 | 0.070* | |
C5 | 0.1525 (6) | 0.6100 (6) | 0.8199 (6) | 0.0681 (13) | |
H5 | 0.071484 | 0.563924 | 0.842278 | 0.082* | |
C6 | 0.2190 (5) | 0.0818 (4) | 0.6583 (4) | 0.0539 (10) | |
H6 | 0.201694 | 0.007099 | 0.555676 | 0.065* | |
C7 | 0.3250 (5) | 0.2196 (5) | 0.7198 (4) | 0.0510 (9) | |
H7 | 0.377227 | 0.240802 | 0.658865 | 0.061* | |
C8 | 0.3518 (4) | 0.3251 (4) | 0.8734 (4) | 0.0424 (8) | |
C9 | 0.2710 (5) | 0.2956 (4) | 0.9628 (4) | 0.0465 (9) | |
H9 | 0.288421 | 0.367714 | 1.066539 | 0.056* | |
C10 | 0.1631 (5) | 0.1558 (4) | 0.8943 (5) | 0.0513 (9) | |
H10 | 0.106801 | 0.132813 | 0.951752 | 0.062* | |
N1 | 0.1780 (6) | 0.5378 (4) | 0.6816 (5) | 0.0723 (12) | |
H1B | 0.118526 | 0.448315 | 0.614476 | 0.087* | |
N2 | 0.1408 (4) | 0.0552 (3) | 0.7461 (4) | 0.0510 (8) | |
H2B | 0.073137 | −0.030783 | 0.704763 | 0.061* | |
N3 | 0.4662 (5) | 0.9644 (4) | 1.0220 (4) | 0.0617 (9) | |
N4 | 0.4601 (4) | 0.4702 (3) | 0.9303 (3) | 0.0464 (8) | |
N5 | 0.1514 (4) | 0.2180 (4) | 0.2959 (4) | 0.0529 (8) | |
O1 | 0.0745 (4) | 0.2327 (3) | 0.3941 (3) | 0.0592 (8) | |
O2 | 0.1175 (5) | 0.0958 (4) | 0.1741 (4) | 0.0848 (11) | |
O3 | 0.2412 (6) | 0.3270 (4) | 0.3114 (4) | 0.1011 (15) | |
Cl1 | 0.22108 (13) | 0.71463 (11) | 0.30697 (11) | 0.0595 (4) | |
O4 | 0.0952 (4) | 0.7204 (4) | 0.3809 (4) | 0.0798 (10) | |
O5 | 0.2642 (6) | 0.8577 (4) | 0.3160 (5) | 0.1046 (14) | |
O6 | 0.3646 (6) | 0.6719 (7) | 0.3762 (7) | 0.131 (2) | |
O7 | 0.1536 (7) | 0.6059 (5) | 0.1466 (5) | 0.1112 (15) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.106 (4) | 0.049 (3) | 0.042 (2) | 0.015 (3) | 0.015 (2) | 0.007 (2) |
C2 | 0.072 (3) | 0.045 (2) | 0.057 (2) | 0.004 (2) | 0.026 (2) | 0.0163 (19) |
C3 | 0.047 (2) | 0.0333 (18) | 0.051 (2) | 0.0021 (15) | 0.0095 (16) | 0.0102 (16) |
C4 | 0.052 (2) | 0.054 (2) | 0.064 (2) | 0.0061 (18) | 0.0195 (18) | 0.025 (2) |
C5 | 0.054 (3) | 0.056 (3) | 0.091 (4) | −0.001 (2) | 0.009 (2) | 0.043 (3) |
C6 | 0.058 (2) | 0.041 (2) | 0.0427 (19) | −0.0034 (17) | 0.0141 (17) | 0.0061 (16) |
C7 | 0.048 (2) | 0.048 (2) | 0.050 (2) | −0.0002 (16) | 0.0212 (16) | 0.0161 (18) |
C8 | 0.0385 (18) | 0.0290 (16) | 0.0469 (19) | 0.0011 (13) | 0.0086 (14) | 0.0114 (15) |
C9 | 0.051 (2) | 0.0363 (18) | 0.0387 (18) | 0.0029 (15) | 0.0151 (15) | 0.0075 (15) |
C10 | 0.055 (2) | 0.044 (2) | 0.057 (2) | 0.0035 (17) | 0.0230 (17) | 0.0241 (18) |
N1 | 0.076 (3) | 0.0365 (18) | 0.072 (3) | −0.0058 (17) | −0.013 (2) | 0.0219 (19) |
N2 | 0.0477 (18) | 0.0341 (16) | 0.0548 (18) | −0.0064 (13) | 0.0102 (14) | 0.0134 (15) |
N3 | 0.074 (3) | 0.050 (2) | 0.057 (2) | 0.0032 (17) | 0.0302 (17) | 0.0182 (17) |
N4 | 0.0490 (18) | 0.0371 (16) | 0.0453 (15) | 0.0039 (13) | 0.0147 (13) | 0.0144 (14) |
N5 | 0.058 (2) | 0.0440 (18) | 0.0464 (17) | −0.0044 (15) | 0.0227 (14) | 0.0116 (15) |
O1 | 0.0702 (19) | 0.0487 (16) | 0.0513 (15) | −0.0080 (13) | 0.0297 (14) | 0.0148 (13) |
O2 | 0.122 (3) | 0.0550 (19) | 0.0581 (18) | −0.0123 (18) | 0.0462 (19) | 0.0060 (15) |
O3 | 0.121 (3) | 0.067 (2) | 0.092 (3) | −0.031 (2) | 0.065 (2) | 0.0067 (19) |
Cl1 | 0.0639 (7) | 0.0527 (7) | 0.0564 (7) | 0.0023 (5) | 0.0317 (5) | 0.0162 (5) |
O4 | 0.078 (2) | 0.0570 (19) | 0.092 (2) | −0.0099 (15) | 0.0561 (19) | 0.0123 (17) |
O5 | 0.147 (4) | 0.063 (2) | 0.116 (3) | 0.003 (2) | 0.078 (3) | 0.036 (2) |
O6 | 0.087 (3) | 0.209 (6) | 0.172 (5) | 0.040 (3) | 0.057 (3) | 0.145 (5) |
O7 | 0.162 (4) | 0.081 (3) | 0.070 (2) | 0.012 (3) | 0.059 (3) | 0.010 (2) |
C1—N1 | 1.326 (7) | C8—N4 | 1.452 (4) |
C1—C2 | 1.391 (6) | C9—C10 | 1.388 (5) |
C1—H1A | 0.9300 | C9—H9 | 0.9300 |
C2—C3 | 1.369 (6) | C10—N2 | 1.327 (5) |
C2—H2A | 0.9300 | C10—H10 | 0.9300 |
C3—C4 | 1.379 (6) | N1—H1B | 0.8600 |
C3—N3 | 1.458 (5) | N2—H2B | 0.8600 |
C4—C5 | 1.360 (6) | N3—N3i | 1.188 (7) |
C4—H4 | 0.9300 | N4—N4ii | 1.216 (6) |
C5—N1 | 1.334 (7) | N5—O3 | 1.219 (4) |
C5—H5 | 0.9300 | N5—O2 | 1.232 (4) |
C6—N2 | 1.335 (5) | N5—O1 | 1.276 (4) |
C6—C7 | 1.377 (6) | Cl1—O6 | 1.405 (5) |
C6—H6 | 0.9300 | Cl1—O7 | 1.408 (4) |
C7—C8 | 1.373 (5) | Cl1—O5 | 1.424 (4) |
C7—H7 | 0.9300 | Cl1—O4 | 1.427 (3) |
C8—C9 | 1.379 (5) | ||
N1—C1—C2 | 119.7 (4) | C8—C9—C10 | 118.4 (3) |
N1—C1—H1A | 120.2 | C8—C9—H9 | 120.8 |
C2—C1—H1A | 120.2 | C10—C9—H9 | 120.8 |
C3—C2—C1 | 118.3 (4) | N2—C10—C9 | 119.4 (3) |
C3—C2—H2A | 120.9 | N2—C10—H10 | 120.3 |
C1—C2—H2A | 120.9 | C9—C10—H10 | 120.3 |
C2—C3—C4 | 120.2 (4) | C1—N1—C5 | 122.8 (4) |
C2—C3—N3 | 125.2 (4) | C1—N1—H1B | 118.6 |
C4—C3—N3 | 114.4 (3) | C5—N1—H1B | 118.6 |
C5—C4—C3 | 119.4 (4) | C10—N2—C6 | 122.9 (3) |
C5—C4—H4 | 120.3 | C10—N2—H2B | 118.6 |
C3—C4—H4 | 120.3 | C6—N2—H2B | 118.6 |
N1—C5—C4 | 119.6 (5) | N3i—N3—C3 | 112.2 (4) |
N1—C5—H5 | 120.2 | N4ii—N4—C8 | 112.6 (4) |
C4—C5—H5 | 120.2 | O3—N5—O2 | 119.4 (3) |
N2—C6—C7 | 120.0 (3) | O3—N5—O1 | 121.1 (3) |
N2—C6—H6 | 120.0 | O2—N5—O1 | 118.9 (3) |
C7—C6—H6 | 120.0 | O6—Cl1—O7 | 108.4 (3) |
C8—C7—C6 | 118.3 (4) | O6—Cl1—O5 | 111.8 (3) |
C8—C7—H7 | 120.9 | O7—Cl1—O5 | 107.3 (3) |
C6—C7—H7 | 120.9 | O6—Cl1—O4 | 110.1 (2) |
C7—C8—C9 | 121.0 (3) | O7—Cl1—O4 | 109.5 (3) |
C7—C8—N4 | 115.9 (3) | O5—Cl1—O4 | 109.7 (2) |
C9—C8—N4 | 123.0 (3) | ||
N1—C1—C2—C3 | 0.0 (7) | N4—C8—C9—C10 | 176.6 (3) |
C1—C2—C3—C4 | −0.4 (6) | C8—C9—C10—N2 | 0.0 (6) |
C1—C2—C3—N3 | 175.1 (4) | C2—C1—N1—C5 | 0.3 (7) |
C2—C3—C4—C5 | 0.4 (6) | C4—C5—N1—C1 | −0.2 (7) |
N3—C3—C4—C5 | −175.6 (4) | C9—C10—N2—C6 | 0.4 (6) |
C3—C4—C5—N1 | −0.1 (6) | C7—C6—N2—C10 | −1.5 (6) |
N2—C6—C7—C8 | 2.2 (6) | C2—C3—N3—N3i | 22.8 (7) |
C6—C7—C8—C9 | −1.8 (6) | C4—C3—N3—N3i | −161.4 (5) |
C6—C7—C8—N4 | −178.0 (3) | C7—C8—N4—N4ii | −149.2 (4) |
C7—C8—C9—C10 | 0.7 (5) | C9—C8—N4—N4ii | 34.8 (5) |
Symmetry codes: (i) −x+1, −y+2, −z+2; (ii) −x+1, −y+1, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2B···O2iii | 0.86 | 2.47 | 3.046 (5) | 125 |
N2—H2B···O1iii | 0.86 | 1.97 | 2.833 (4) | 177 |
N2—H2B···N5iii | 0.86 | 2.58 | 3.372 (4) | 153 |
N1—H1B···O4iv | 0.86 | 2.42 | 3.078 (5) | 134 |
N1—H1B···O1 | 0.86 | 2.22 | 2.989 (5) | 150 |
C10—H10···O2iii | 0.93 | 2.46 | 3.049 (5) | 122 |
C10—H10···O2v | 0.93 | 2.42 | 3.257 (5) | 150 |
C9—H9···O7v | 0.93 | 2.58 | 3.191 (6) | 124 |
C7—H7···O6vi | 0.93 | 2.45 | 3.285 (6) | 150 |
C6—H6···O5vii | 0.93 | 2.42 | 3.302 (6) | 159 |
C6—H6···O4vii | 0.93 | 2.56 | 3.318 (5) | 139 |
C6—H6···Cl1vii | 0.93 | 2.93 | 3.798 (4) | 156 |
C5—H5···O7iv | 0.93 | 2.53 | 3.447 (7) | 169 |
C1—H1A···O3 | 0.93 | 2.28 | 3.117 (5) | 150 |
Symmetry codes: (iii) −x, −y, −z+1; (iv) −x, −y+1, −z+1; (v) x, y, z+1; (vi) −x+1, −y+1, −z+1; (vii) x, y−1, z. |
Funding information
We gratefully acknowledge support by the Fundamental Research Funds for the Central Universities (grant No. 2–9–2021–008).
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