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The title compound, (C6H9N2)[ZnCl3(C6H8N2)], consists of one 2-amino-5-methyl­pyridinium cation and one (2-amino-5-methyl­pyridine)trichloro­zincate(II) anion, which are held together by N—H...Cl hydrogen bonds and π–π inter­actions. The cation and the pyridine ligand show similar geometric features, except for the N—C bond lengths. Mol­ecules of the title compound are connected by N—H...Cl hydrogen bonds to form chiral chains; these chains are associated further by C—H...Cl hydrogen bonds to form layers, which are in turn linked by π–π inter­actions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105006694/hj1045sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105006694/hj1045Isup2.hkl
Contains datablock I

CCDC reference: 269019

Comment top

There are numerous examples of 2-amino-substituted pyridine compounds in which the 2-aminopyridines act as ligands (Ranninger et al., 1985; Krizanovic et al., 1993; Luque et al., 1997; Qin et al., 1999; Yip et al., 1999; Lah et al., 2002; Ren et al., 2002; Rivas et al., 2003) or as protonated cations (Luque et al., 1997; Jin et al., 2000, 2001, 2002, 2005; Albrecht et al., 2003). All of these studies provide important references to further research of 2-aminopyridines. We have synthesized the title compound, (I), where 2-amino-5-methylpyridine (AMP) appears both as a ligand and as a protonated cation.

The title compound consists of one AMP cation (HAMP) and one AMP ligand (LAMP) coordinated with a [ZnCl3] anion. These two moieties are held together by N2—H2A···Cl3 [3.301 (3) Å] and N4—H4B···Cl2 [3.322 (3) Å] hydrogen bonds, and by ππ interaction with a separation of 3.623 (3) Å between the centroids of the HAMP and LAMP moieties (Fig. 1 and Table 2). In the formula unit, the LAMP molecule lies almost perfectly parallel to the HAMP cation, as indicated by the dihedral angle of 0.6 (3)° between them. Atom Cl3 lies 0.708 (4) Å out of the LAMP ring plane, while atom Cl2 lies 1.089 (4) Å out of the HAMP ring plane.

In the HAMP cation, the N4—C11 bond length [1.329 (4) Å] is shorter than those of N3—C11 [1.342 (3) Å] and N3—C7 [1.349 (4) Å], and the C10—C11 [1.398 (4) Å] and C8—C9 [1.399 (4) Å] bond lengths are significantly longer than those of C9—C10 [1.351 (4) Å] and C7—C8 [1.347 (4) Å]. In the LAMP molecule, all the C—N bonds are comparable with one another, and the C—C bond length features are similar to those in the HAMP cation (Table 1). In contrast, in the solid-state structure of AMP (Nahringbauer & Kvick, 1977), the N—C bond length out of the ring is clearly longer than that in the ring, and the C—C bond-length differences are less pronounced. The geometric features of the HAMP cation resemble those observed in other 2-aminopyridine structures (Luque et al., 1997; Jin et al., 2000, 2001, 2002, 2005; Albrecht et al., 2003), which are believed to be involved in amino–imino tautomerism (Inuzuka & Fujimoto, 1986, 1990; Ishikawa et al., 2002). The geometric features of the LAMP molecule are similar to those of some other coordinated 2-aminopyridines (Ranninger et al., 1985; Krizanovic et al., 1993; Qin et al., 1999; Yip et al., 1999; Lah et al., 2002; Ren et al., 2002). The reason for deviations of the LAMP geometry from that of a normal AMP molecule remains unknown.

Molecules of (I) are connected to form a one-dimensional chiral chain along the [010] direction via N3—H3N···Cl3i, N2—H2B···Cl2i and N4—H4A···Cl1i hydrogen bonds (Fig. 2; symmetry code as in Table 2). Between two adjacent molecule of (I) in the chain, three hydrogen-bonded rings, R44(12), R22(8) and R11(6) [using the notation of Etter (1990) and Grell et al. (2000)], are embedded in a larger, R43(14), hydrogen-bonded ring (Fig. 3). Two neighboring chains, which are inversely related, are associated by a C9—H9···Cl1ii contact, and therefore the chirality is countervailed. A layer of (I) parallel to (101) is established by translation of the two inversely related chains. Finally, the whole structure is established by translation of the layer. There are ππ interactions (Sharma et al., 1993; Pedireddi et al., 1996) between neighboring layers, with a centroid-to-centroid distance of 3.908 (4) Å between the LAMP and HAMP moieties. A C12—H12B···π contact (LAMP; symmetry code: 1/2 + x, −1/2 − y, 1/2 + z) [with a distance of 3.325 (3) Å between the H atom and the centriod of LAMP] plays a subordinative role in stabilizing the structure.

Experimental top

2-Amino-5-methylpyridine, ZnCl2 and aqueous HCl in a molar ratio of 2:1:1 were mixed and dissolved in sufficient ethanol by heating to a temperature at which a clear solution resulted. Crystals of (I) were formed by gradual evaporation of ethanol over a period of one week at 303 K, with a yield of 56% based on AMP. IR (KBr, cm−1): 3415 (s), 3333 (s), 3284 (s), 3200 (s), 3081, 3053, 2924, 1670 (s), 1645 (s), 1617 (s), 1569, 1555, 1515 (s), 1463, 1406, 1347, 1329, 1279, 1239, 1210, 1154, 1091, 1041, 832, 777, 717, 667, 648, 510, 460, 437.

Refinement top

H atoms attaching to N atoms were located in difference Fourier maps and their parameters were refined freely. Other H atoms were placed in calculated positions and allowed to ride on their parent atoms at C—H distances of 0.93 (aromatic) and 0.96 Å (methyl), with Uiso(H) values of 1.2 or 1.5 times Ueq of the parent atoms.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The cell unit of (I), with atom labels, showing 40% probability displacement ellipsoids. Hydrogen bonds are shown as dashed lines.
[Figure 2] Fig. 2. The chiral hydrogen-bond chain of (I) along the [010] direction. Hydrogen bonds are shown as dashed lines.
[Figure 3] Fig. 3. Layer formation of (I), parallel to (101). Hydrogen bonds are shown as dashed lines.
2-Amino-5-methylpyridinium (2-amino-5-methylpyridine)trichlorozincate(II) top
Crystal data top
(C6H9N2)[ZnCl3(C6H8N2)]F(000) = 792
Mr = 389.02Dx = 1.536 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3253 reflections
a = 9.254 (3) Åθ = 2.4–26.0°
b = 13.726 (4) ŵ = 1.93 mm1
c = 13.572 (5) ÅT = 293 K
β = 102.57 (3)°Prism, colorless
V = 1682.6 (10) Å30.30 × 0.25 × 0.22 mm
Z = 4
Data collection top
Bruker SMART Apex CCD area-detector
diffractometer
3304 independent reflections
Radiation source: sealed tube2518 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.049
ϕ and ω scansθmax = 26.0°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 1110
Tmin = 0.57, Tmax = 0.65k = 1516
8903 measured reflectionsl = 1416
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)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.072H atoms treated by a mixture of independent and constrained refinement
S = 0.93 w = 1/[σ2(Fo2) + (0.0325P)2]
where P = (Fo2 + 2Fc2)/3
3304 reflections(Δ/σ)max = 0.001
203 parametersΔρmax = 0.35 e Å3
101 restraintsΔρmin = 0.25 e Å3
Crystal data top
(C6H9N2)[ZnCl3(C6H8N2)]V = 1682.6 (10) Å3
Mr = 389.02Z = 4
Monoclinic, P21/nMo Kα radiation
a = 9.254 (3) ŵ = 1.93 mm1
b = 13.726 (4) ÅT = 293 K
c = 13.572 (5) Å0.30 × 0.25 × 0.22 mm
β = 102.57 (3)°
Data collection top
Bruker SMART Apex CCD area-detector
diffractometer
3304 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
2518 reflections with I > 2σ(I)
Tmin = 0.57, Tmax = 0.65Rint = 0.049
8903 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.031101 restraints
wR(F2) = 0.072H atoms treated by a mixture of independent and constrained refinement
S = 0.93Δρmax = 0.35 e Å3
3304 reflectionsΔρmin = 0.25 e Å3
203 parameters
Special details top

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.

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
Zn0.84505 (3)0.46058 (2)0.76390 (2)0.04605 (12)
Cl11.01068 (8)0.58350 (5)0.78368 (6)0.0614 (2)
Cl20.63306 (8)0.49257 (5)0.64987 (6)0.0584 (2)
Cl30.79975 (8)0.42665 (5)0.91729 (6)0.0596 (2)
C11.0212 (3)0.3738 (2)0.6350 (2)0.0506 (6)
H11.03200.43990.62330.061*
C21.0866 (3)0.3098 (2)0.5812 (2)0.0565 (7)
C31.0699 (3)0.2114 (2)0.6019 (2)0.0627 (7)
H31.11330.16450.56820.075*
C40.9915 (3)0.1836 (2)0.6702 (2)0.0602 (7)
H40.98030.11770.68280.072*
C50.9269 (3)0.25364 (18)0.7221 (2)0.0476 (6)
C61.1708 (3)0.3442 (3)0.5053 (2)0.0823 (10)
H6A1.18980.41280.51390.123*
H6B1.11360.33220.43840.123*
H6C1.26310.30980.51480.123*
C70.7432 (3)0.1169 (2)0.4193 (2)0.0598 (7)
H70.75540.05050.41010.072*
C80.8044 (3)0.1808 (2)0.3650 (2)0.0595 (7)
C90.7798 (3)0.2795 (2)0.3815 (2)0.0587 (7)
H90.81880.32600.34470.070*
C100.7012 (3)0.3094 (2)0.4489 (2)0.0552 (7)
H100.68660.37560.45780.066*
C110.6419 (3)0.24088 (19)0.5052 (2)0.0505 (6)
C120.8961 (4)0.1478 (3)0.2923 (3)0.0860 (10)
H12A0.99900.15870.32150.129*
H12B0.86820.18410.23060.129*
H12C0.87960.07970.27850.129*
N10.9421 (2)0.34871 (14)0.70374 (16)0.0431 (5)
N20.8468 (3)0.22852 (18)0.7900 (2)0.0624 (7)
N30.6645 (3)0.14677 (17)0.4865 (2)0.0549 (6)
N40.5635 (3)0.2642 (2)0.5730 (2)0.0631 (7)
H2B0.845 (3)0.1667 (15)0.805 (3)0.089 (11)*
H4B0.562 (4)0.3254 (16)0.598 (3)0.095 (12)*
H2A0.825 (3)0.2756 (18)0.8367 (19)0.073 (10)*
H4A0.532 (3)0.2184 (19)0.618 (2)0.092 (11)*
H3N0.623 (3)0.1058 (18)0.520 (2)0.074 (10)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn0.0580 (2)0.03524 (18)0.0481 (2)0.00135 (13)0.01856 (15)0.00093 (14)
Cl10.0750 (5)0.0420 (4)0.0710 (5)0.0115 (3)0.0243 (4)0.0052 (3)
Cl20.0644 (5)0.0443 (4)0.0640 (5)0.0068 (3)0.0081 (4)0.0025 (3)
Cl30.0809 (5)0.0539 (4)0.0505 (5)0.0042 (4)0.0286 (4)0.0020 (3)
C10.0545 (14)0.0474 (13)0.0520 (15)0.0016 (11)0.0159 (12)0.0009 (12)
C20.0548 (14)0.0650 (15)0.0512 (15)0.0075 (12)0.0151 (12)0.0043 (13)
C30.0668 (16)0.0614 (15)0.0590 (17)0.0181 (13)0.0120 (13)0.0149 (14)
C40.0714 (16)0.0439 (13)0.0628 (17)0.0088 (12)0.0092 (13)0.0087 (13)
C50.0539 (13)0.0356 (12)0.0523 (14)0.0018 (11)0.0093 (12)0.0042 (11)
C60.080 (2)0.110 (3)0.065 (2)0.0131 (19)0.0340 (18)0.000 (2)
C70.0627 (15)0.0516 (14)0.0613 (16)0.0018 (12)0.0052 (13)0.0035 (13)
C80.0523 (14)0.0691 (15)0.0555 (15)0.0026 (12)0.0081 (12)0.0001 (13)
C90.0546 (15)0.0628 (15)0.0592 (16)0.0064 (12)0.0136 (13)0.0120 (13)
C100.0572 (15)0.0473 (13)0.0599 (16)0.0058 (12)0.0103 (12)0.0083 (12)
C110.0528 (13)0.0447 (13)0.0532 (15)0.0056 (11)0.0094 (12)0.0034 (12)
C120.072 (2)0.114 (3)0.074 (2)0.014 (2)0.0209 (18)0.010 (2)
N10.0490 (11)0.0348 (10)0.0472 (12)0.0019 (9)0.0141 (9)0.0013 (9)
N20.0856 (19)0.0357 (14)0.0727 (19)0.0077 (12)0.0320 (15)0.0017 (13)
N30.0613 (13)0.0437 (12)0.0591 (14)0.0082 (11)0.0119 (11)0.0058 (11)
N40.0740 (17)0.0548 (16)0.0654 (18)0.0058 (13)0.0264 (14)0.0006 (14)
Geometric parameters (Å, º) top
Zn—N12.037 (2)C7—N31.349 (4)
Zn—Cl12.2558 (9)C7—H70.9300
Zn—Cl32.2597 (11)C8—C91.399 (4)
Zn—Cl22.2617 (12)C8—C121.504 (4)
C1—N11.351 (3)C9—C101.351 (4)
C1—C21.364 (4)C9—H90.9300
C1—H10.9300C10—C111.398 (4)
C2—C31.394 (4)C10—H100.9300
C2—C61.498 (4)C11—N41.329 (4)
C3—C41.352 (4)C11—N31.342 (3)
C3—H30.9300C12—H12A0.9600
C4—C51.401 (4)C12—H12B0.9600
C4—H40.9300C12—H12C0.9600
C5—N11.342 (3)N2—H2B0.873 (19)
C5—N21.347 (4)N2—H2A0.955 (18)
C6—H6A0.9600N3—H3N0.864 (18)
C6—H6B0.9600N4—H4B0.905 (19)
C6—H6C0.9600N4—H4A0.963 (19)
C7—C81.347 (4)
N1—Zn—Cl1105.31 (6)C7—C8—C9116.1 (3)
N1—Zn—Cl3113.59 (7)C7—C8—C12121.8 (3)
Cl1—Zn—Cl3107.58 (4)C9—C8—C12122.0 (3)
N1—Zn—Cl2105.33 (6)C10—C9—C8122.2 (3)
Cl1—Zn—Cl2113.70 (4)C10—C9—H9118.9
Cl3—Zn—Cl2111.30 (4)C8—C9—H9118.9
N1—C1—C2125.2 (3)C9—C10—C11119.9 (3)
N1—C1—H1117.4C9—C10—H10120.0
C2—C1—H1117.4C11—C10—H10120.0
C1—C2—C3115.8 (3)N4—C11—N3119.6 (3)
C1—C2—C6121.5 (3)N4—C11—C10123.7 (3)
C3—C2—C6122.7 (3)N3—C11—C10116.7 (3)
C4—C3—C2120.8 (3)C8—C12—H12A109.5
C4—C3—H3119.6C8—C12—H12B109.5
C2—C3—H3119.6H12A—C12—H12B109.5
C3—C4—C5120.2 (3)C8—C12—H12C109.5
C3—C4—H4119.9H12A—C12—H12C109.5
C5—C4—H4119.9H12B—C12—H12C109.5
N1—C5—N2118.1 (2)C5—N1—C1118.1 (2)
N1—C5—C4120.1 (3)C5—N1—Zn125.85 (18)
N2—C5—C4121.8 (3)C1—N1—Zn115.96 (16)
C2—C6—H6A109.5C5—N2—H2B117 (2)
C2—C6—H6B109.5C5—N2—H2A120.3 (17)
H6A—C6—H6B109.5H2B—N2—H2A119 (3)
C2—C6—H6C109.5C11—N3—C7123.3 (3)
H6A—C6—H6C109.5C11—N3—H3N115 (2)
H6B—C6—H6C109.5C7—N3—H3N122 (2)
C8—C7—N3121.7 (3)C11—N4—H4B122 (2)
C8—C7—H7119.2C11—N4—H4A124.4 (19)
N3—C7—H7119.2H4B—N4—H4A110 (3)
N1—C1—C2—C31.0 (4)C4—C5—N1—C10.4 (4)
N1—C1—C2—C6179.2 (3)N2—C5—N1—Zn3.5 (4)
C1—C2—C3—C40.9 (4)C4—C5—N1—Zn175.5 (2)
C6—C2—C3—C4179.2 (3)C2—C1—N1—C50.7 (4)
C2—C3—C4—C50.7 (5)C2—C1—N1—Zn175.5 (2)
C3—C4—C5—N10.4 (4)Cl1—Zn—N1—C5145.78 (19)
C3—C4—C5—N2179.4 (3)Cl3—Zn—N1—C528.3 (2)
N3—C7—C8—C91.0 (4)Cl2—Zn—N1—C593.7 (2)
N3—C7—C8—C12178.1 (3)Cl1—Zn—N1—C138.3 (2)
C7—C8—C9—C101.0 (4)Cl3—Zn—N1—C1155.77 (17)
C12—C8—C9—C10178.0 (3)Cl2—Zn—N1—C182.18 (19)
C8—C9—C10—C110.2 (4)N4—C11—N3—C7179.7 (3)
C9—C10—C11—N4179.9 (3)C10—C11—N3—C71.7 (4)
C9—C10—C11—N31.5 (4)C8—C7—N3—C110.4 (4)
N2—C5—N1—C1179.4 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···Cl30.96 (2)2.38 (2)3.301 (3)162 (2)
N2—H2B···Cl2i0.87 (2)2.47 (2)3.335 (3)174 (3)
N3—H3N···Cl3i0.86 (2)2.65 (2)3.279 (3)131 (2)
N4—H4B···Cl20.91 (2)2.45 (2)3.322 (3)162 (3)
N4—H4A···Cl1i0.96 (2)2.37 (2)3.315 (3)168 (3)
C9—H9···Cl1ii0.932.883.770 (3)162
Symmetry codes: (i) x+3/2, y1/2, z+3/2; (ii) x+2, y+1, z+1.

Experimental details

Crystal data
Chemical formula(C6H9N2)[ZnCl3(C6H8N2)]
Mr389.02
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)9.254 (3), 13.726 (4), 13.572 (5)
β (°) 102.57 (3)
V3)1682.6 (10)
Z4
Radiation typeMo Kα
µ (mm1)1.93
Crystal size (mm)0.30 × 0.25 × 0.22
Data collection
DiffractometerBruker SMART Apex CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2000)
Tmin, Tmax0.57, 0.65
No. of measured, independent and
observed [I > 2σ(I)] reflections
8903, 3304, 2518
Rint0.049
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.031, 0.072, 0.93
No. of reflections3304
No. of parameters203
No. of restraints101
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.35, 0.25

Computer programs: SMART (Bruker, 2000), SMART, SAINT (Bruker, 2000), SHELXTL (Bruker, 2000), SHELXL97 (Sheldrick, 1997), SHELXTL.

Selected bond lengths (Å) top
Zn—N12.037 (2)C5—N11.342 (3)
Zn—Cl12.2558 (9)C5—N21.347 (4)
Zn—Cl32.2597 (11)C7—C81.347 (4)
Zn—Cl22.2617 (12)C7—N31.349 (4)
C1—N11.351 (3)C8—C91.399 (4)
C1—C21.364 (4)C8—C121.504 (4)
C2—C31.394 (4)C9—C101.351 (4)
C2—C61.498 (4)C10—C111.398 (4)
C3—C41.352 (4)C11—N41.329 (4)
C4—C51.401 (4)C11—N31.342 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···Cl30.955 (18)2.38 (2)3.301 (3)162 (2)
N2—H2B···Cl2i0.873 (19)2.47 (2)3.335 (3)174 (3)
N3—H3N···Cl3i0.864 (18)2.65 (2)3.279 (3)131 (2)
N4—H4B···Cl20.905 (19)2.45 (2)3.322 (3)162 (3)
N4—H4A···Cl1i0.963 (19)2.37 (2)3.315 (3)168 (3)
C9—H9···Cl1ii0.932.883.770 (3)162
Symmetry codes: (i) x+3/2, y1/2, z+3/2; (ii) x+2, y+1, z+1.
 

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