Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105006694/hj1045sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105006694/hj1045Isup2.hkl |
CCDC reference: 269019
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.
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.
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.
(C6H9N2)[ZnCl3(C6H8N2)] | F(000) = 792 |
Mr = 389.02 | Dx = 1.536 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 3253 reflections |
a = 9.254 (3) Å | θ = 2.4–26.0° |
b = 13.726 (4) Å | µ = 1.93 mm−1 |
c = 13.572 (5) Å | T = 293 K |
β = 102.57 (3)° | Prism, colorless |
V = 1682.6 (10) Å3 | 0.30 × 0.25 × 0.22 mm |
Z = 4 |
Bruker SMART Apex CCD area-detector diffractometer | 3304 independent reflections |
Radiation source: sealed tube | 2518 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.049 |
ϕ and ω scans | θmax = 26.0°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −11→10 |
Tmin = 0.57, Tmax = 0.65 | k = −15→16 |
8903 measured reflections | l = −14→16 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.072 | H 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 parameters | Δρmax = 0.35 e Å−3 |
101 restraints | Δρmin = −0.25 e Å−3 |
(C6H9N2)[ZnCl3(C6H8N2)] | V = 1682.6 (10) Å3 |
Mr = 389.02 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.254 (3) Å | µ = 1.93 mm−1 |
b = 13.726 (4) Å | T = 293 K |
c = 13.572 (5) Å | 0.30 × 0.25 × 0.22 mm |
β = 102.57 (3)° |
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 = 0.65 | Rint = 0.049 |
8903 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 101 restraints |
wR(F2) = 0.072 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.93 | Δρmax = 0.35 e Å−3 |
3304 reflections | Δρmin = −0.25 e Å−3 |
203 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Zn | 0.84505 (3) | 0.46058 (2) | 0.76390 (2) | 0.04605 (12) | |
Cl1 | 1.01068 (8) | 0.58350 (5) | 0.78368 (6) | 0.0614 (2) | |
Cl2 | 0.63306 (8) | 0.49257 (5) | 0.64987 (6) | 0.0584 (2) | |
Cl3 | 0.79975 (8) | 0.42665 (5) | 0.91729 (6) | 0.0596 (2) | |
C1 | 1.0212 (3) | 0.3738 (2) | 0.6350 (2) | 0.0506 (6) | |
H1 | 1.0320 | 0.4399 | 0.6233 | 0.061* | |
C2 | 1.0866 (3) | 0.3098 (2) | 0.5812 (2) | 0.0565 (7) | |
C3 | 1.0699 (3) | 0.2114 (2) | 0.6019 (2) | 0.0627 (7) | |
H3 | 1.1133 | 0.1645 | 0.5682 | 0.075* | |
C4 | 0.9915 (3) | 0.1836 (2) | 0.6702 (2) | 0.0602 (7) | |
H4 | 0.9803 | 0.1177 | 0.6828 | 0.072* | |
C5 | 0.9269 (3) | 0.25364 (18) | 0.7221 (2) | 0.0476 (6) | |
C6 | 1.1708 (3) | 0.3442 (3) | 0.5053 (2) | 0.0823 (10) | |
H6A | 1.1898 | 0.4128 | 0.5139 | 0.123* | |
H6B | 1.1136 | 0.3322 | 0.4384 | 0.123* | |
H6C | 1.2631 | 0.3098 | 0.5148 | 0.123* | |
C7 | 0.7432 (3) | 0.1169 (2) | 0.4193 (2) | 0.0598 (7) | |
H7 | 0.7554 | 0.0505 | 0.4101 | 0.072* | |
C8 | 0.8044 (3) | 0.1808 (2) | 0.3650 (2) | 0.0595 (7) | |
C9 | 0.7798 (3) | 0.2795 (2) | 0.3815 (2) | 0.0587 (7) | |
H9 | 0.8188 | 0.3260 | 0.3447 | 0.070* | |
C10 | 0.7012 (3) | 0.3094 (2) | 0.4489 (2) | 0.0552 (7) | |
H10 | 0.6866 | 0.3756 | 0.4578 | 0.066* | |
C11 | 0.6419 (3) | 0.24088 (19) | 0.5052 (2) | 0.0505 (6) | |
C12 | 0.8961 (4) | 0.1478 (3) | 0.2923 (3) | 0.0860 (10) | |
H12A | 0.9990 | 0.1587 | 0.3215 | 0.129* | |
H12B | 0.8682 | 0.1841 | 0.2306 | 0.129* | |
H12C | 0.8796 | 0.0797 | 0.2785 | 0.129* | |
N1 | 0.9421 (2) | 0.34871 (14) | 0.70374 (16) | 0.0431 (5) | |
N2 | 0.8468 (3) | 0.22852 (18) | 0.7900 (2) | 0.0624 (7) | |
N3 | 0.6645 (3) | 0.14677 (17) | 0.4865 (2) | 0.0549 (6) | |
N4 | 0.5635 (3) | 0.2642 (2) | 0.5730 (2) | 0.0631 (7) | |
H2B | 0.845 (3) | 0.1667 (15) | 0.805 (3) | 0.089 (11)* | |
H4B | 0.562 (4) | 0.3254 (16) | 0.598 (3) | 0.095 (12)* | |
H2A | 0.825 (3) | 0.2756 (18) | 0.8367 (19) | 0.073 (10)* | |
H4A | 0.532 (3) | 0.2184 (19) | 0.618 (2) | 0.092 (11)* | |
H3N | 0.623 (3) | 0.1058 (18) | 0.520 (2) | 0.074 (10)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn | 0.0580 (2) | 0.03524 (18) | 0.0481 (2) | 0.00135 (13) | 0.01856 (15) | −0.00093 (14) |
Cl1 | 0.0750 (5) | 0.0420 (4) | 0.0710 (5) | −0.0115 (3) | 0.0243 (4) | −0.0052 (3) |
Cl2 | 0.0644 (5) | 0.0443 (4) | 0.0640 (5) | 0.0068 (3) | 0.0081 (4) | −0.0025 (3) |
Cl3 | 0.0809 (5) | 0.0539 (4) | 0.0505 (5) | −0.0042 (4) | 0.0286 (4) | −0.0020 (3) |
C1 | 0.0545 (14) | 0.0474 (13) | 0.0520 (15) | 0.0016 (11) | 0.0159 (12) | 0.0009 (12) |
C2 | 0.0548 (14) | 0.0650 (15) | 0.0512 (15) | 0.0075 (12) | 0.0151 (12) | −0.0043 (13) |
C3 | 0.0668 (16) | 0.0614 (15) | 0.0590 (17) | 0.0181 (13) | 0.0120 (13) | −0.0149 (14) |
C4 | 0.0714 (16) | 0.0439 (13) | 0.0628 (17) | 0.0088 (12) | 0.0092 (13) | −0.0087 (13) |
C5 | 0.0539 (13) | 0.0356 (12) | 0.0523 (14) | 0.0018 (11) | 0.0093 (12) | −0.0042 (11) |
C6 | 0.080 (2) | 0.110 (3) | 0.065 (2) | 0.0131 (19) | 0.0340 (18) | 0.000 (2) |
C7 | 0.0627 (15) | 0.0516 (14) | 0.0613 (16) | 0.0018 (12) | 0.0052 (13) | −0.0035 (13) |
C8 | 0.0523 (14) | 0.0691 (15) | 0.0555 (15) | 0.0026 (12) | 0.0081 (12) | −0.0001 (13) |
C9 | 0.0546 (15) | 0.0628 (15) | 0.0592 (16) | −0.0064 (12) | 0.0136 (13) | 0.0120 (13) |
C10 | 0.0572 (15) | 0.0473 (13) | 0.0599 (16) | −0.0058 (12) | 0.0103 (12) | 0.0083 (12) |
C11 | 0.0528 (13) | 0.0447 (13) | 0.0532 (15) | −0.0056 (11) | 0.0094 (12) | 0.0034 (12) |
C12 | 0.072 (2) | 0.114 (3) | 0.074 (2) | 0.014 (2) | 0.0209 (18) | −0.010 (2) |
N1 | 0.0490 (11) | 0.0348 (10) | 0.0472 (12) | 0.0019 (9) | 0.0141 (9) | −0.0013 (9) |
N2 | 0.0856 (19) | 0.0357 (14) | 0.0727 (19) | −0.0077 (12) | 0.0320 (15) | 0.0017 (13) |
N3 | 0.0613 (13) | 0.0437 (12) | 0.0591 (14) | −0.0082 (11) | 0.0119 (11) | 0.0058 (11) |
N4 | 0.0740 (17) | 0.0548 (16) | 0.0654 (18) | −0.0058 (13) | 0.0264 (14) | −0.0006 (14) |
Zn—N1 | 2.037 (2) | C7—N3 | 1.349 (4) |
Zn—Cl1 | 2.2558 (9) | C7—H7 | 0.9300 |
Zn—Cl3 | 2.2597 (11) | C8—C9 | 1.399 (4) |
Zn—Cl2 | 2.2617 (12) | C8—C12 | 1.504 (4) |
C1—N1 | 1.351 (3) | C9—C10 | 1.351 (4) |
C1—C2 | 1.364 (4) | C9—H9 | 0.9300 |
C1—H1 | 0.9300 | C10—C11 | 1.398 (4) |
C2—C3 | 1.394 (4) | C10—H10 | 0.9300 |
C2—C6 | 1.498 (4) | C11—N4 | 1.329 (4) |
C3—C4 | 1.352 (4) | C11—N3 | 1.342 (3) |
C3—H3 | 0.9300 | C12—H12A | 0.9600 |
C4—C5 | 1.401 (4) | C12—H12B | 0.9600 |
C4—H4 | 0.9300 | C12—H12C | 0.9600 |
C5—N1 | 1.342 (3) | N2—H2B | 0.873 (19) |
C5—N2 | 1.347 (4) | N2—H2A | 0.955 (18) |
C6—H6A | 0.9600 | N3—H3N | 0.864 (18) |
C6—H6B | 0.9600 | N4—H4B | 0.905 (19) |
C6—H6C | 0.9600 | N4—H4A | 0.963 (19) |
C7—C8 | 1.347 (4) | ||
N1—Zn—Cl1 | 105.31 (6) | C7—C8—C9 | 116.1 (3) |
N1—Zn—Cl3 | 113.59 (7) | C7—C8—C12 | 121.8 (3) |
Cl1—Zn—Cl3 | 107.58 (4) | C9—C8—C12 | 122.0 (3) |
N1—Zn—Cl2 | 105.33 (6) | C10—C9—C8 | 122.2 (3) |
Cl1—Zn—Cl2 | 113.70 (4) | C10—C9—H9 | 118.9 |
Cl3—Zn—Cl2 | 111.30 (4) | C8—C9—H9 | 118.9 |
N1—C1—C2 | 125.2 (3) | C9—C10—C11 | 119.9 (3) |
N1—C1—H1 | 117.4 | C9—C10—H10 | 120.0 |
C2—C1—H1 | 117.4 | C11—C10—H10 | 120.0 |
C1—C2—C3 | 115.8 (3) | N4—C11—N3 | 119.6 (3) |
C1—C2—C6 | 121.5 (3) | N4—C11—C10 | 123.7 (3) |
C3—C2—C6 | 122.7 (3) | N3—C11—C10 | 116.7 (3) |
C4—C3—C2 | 120.8 (3) | C8—C12—H12A | 109.5 |
C4—C3—H3 | 119.6 | C8—C12—H12B | 109.5 |
C2—C3—H3 | 119.6 | H12A—C12—H12B | 109.5 |
C3—C4—C5 | 120.2 (3) | C8—C12—H12C | 109.5 |
C3—C4—H4 | 119.9 | H12A—C12—H12C | 109.5 |
C5—C4—H4 | 119.9 | H12B—C12—H12C | 109.5 |
N1—C5—N2 | 118.1 (2) | C5—N1—C1 | 118.1 (2) |
N1—C5—C4 | 120.1 (3) | C5—N1—Zn | 125.85 (18) |
N2—C5—C4 | 121.8 (3) | C1—N1—Zn | 115.96 (16) |
C2—C6—H6A | 109.5 | C5—N2—H2B | 117 (2) |
C2—C6—H6B | 109.5 | C5—N2—H2A | 120.3 (17) |
H6A—C6—H6B | 109.5 | H2B—N2—H2A | 119 (3) |
C2—C6—H6C | 109.5 | C11—N3—C7 | 123.3 (3) |
H6A—C6—H6C | 109.5 | C11—N3—H3N | 115 (2) |
H6B—C6—H6C | 109.5 | C7—N3—H3N | 122 (2) |
C8—C7—N3 | 121.7 (3) | C11—N4—H4B | 122 (2) |
C8—C7—H7 | 119.2 | C11—N4—H4A | 124.4 (19) |
N3—C7—H7 | 119.2 | H4B—N4—H4A | 110 (3) |
N1—C1—C2—C3 | −1.0 (4) | C4—C5—N1—C1 | −0.4 (4) |
N1—C1—C2—C6 | 179.2 (3) | N2—C5—N1—Zn | −3.5 (4) |
C1—C2—C3—C4 | 0.9 (4) | C4—C5—N1—Zn | 175.5 (2) |
C6—C2—C3—C4 | −179.2 (3) | C2—C1—N1—C5 | 0.7 (4) |
C2—C3—C4—C5 | −0.7 (5) | C2—C1—N1—Zn | −175.5 (2) |
C3—C4—C5—N1 | 0.4 (4) | Cl1—Zn—N1—C5 | 145.78 (19) |
C3—C4—C5—N2 | 179.4 (3) | Cl3—Zn—N1—C5 | 28.3 (2) |
N3—C7—C8—C9 | −1.0 (4) | Cl2—Zn—N1—C5 | −93.7 (2) |
N3—C7—C8—C12 | 178.1 (3) | Cl1—Zn—N1—C1 | −38.3 (2) |
C7—C8—C9—C10 | 1.0 (4) | Cl3—Zn—N1—C1 | −155.77 (17) |
C12—C8—C9—C10 | −178.0 (3) | Cl2—Zn—N1—C1 | 82.18 (19) |
C8—C9—C10—C11 | 0.2 (4) | N4—C11—N3—C7 | −179.7 (3) |
C9—C10—C11—N4 | 179.9 (3) | C10—C11—N3—C7 | 1.7 (4) |
C9—C10—C11—N3 | −1.5 (4) | C8—C7—N3—C11 | −0.4 (4) |
N2—C5—N1—C1 | −179.4 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···Cl3 | 0.96 (2) | 2.38 (2) | 3.301 (3) | 162 (2) |
N2—H2B···Cl2i | 0.87 (2) | 2.47 (2) | 3.335 (3) | 174 (3) |
N3—H3N···Cl3i | 0.86 (2) | 2.65 (2) | 3.279 (3) | 131 (2) |
N4—H4B···Cl2 | 0.91 (2) | 2.45 (2) | 3.322 (3) | 162 (3) |
N4—H4A···Cl1i | 0.96 (2) | 2.37 (2) | 3.315 (3) | 168 (3) |
C9—H9···Cl1ii | 0.93 | 2.88 | 3.770 (3) | 162 |
Symmetry codes: (i) −x+3/2, y−1/2, −z+3/2; (ii) −x+2, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | (C6H9N2)[ZnCl3(C6H8N2)] |
Mr | 389.02 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 9.254 (3), 13.726 (4), 13.572 (5) |
β (°) | 102.57 (3) |
V (Å3) | 1682.6 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.93 |
Crystal size (mm) | 0.30 × 0.25 × 0.22 |
Data collection | |
Diffractometer | Bruker SMART Apex CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.57, 0.65 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8903, 3304, 2518 |
Rint | 0.049 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.072, 0.93 |
No. of reflections | 3304 |
No. of parameters | 203 |
No. of restraints | 101 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.35, −0.25 |
Computer programs: SMART (Bruker, 2000), SMART, SAINT (Bruker, 2000), SHELXTL (Bruker, 2000), SHELXL97 (Sheldrick, 1997), SHELXTL.
Zn—N1 | 2.037 (2) | C5—N1 | 1.342 (3) |
Zn—Cl1 | 2.2558 (9) | C5—N2 | 1.347 (4) |
Zn—Cl3 | 2.2597 (11) | C7—C8 | 1.347 (4) |
Zn—Cl2 | 2.2617 (12) | C7—N3 | 1.349 (4) |
C1—N1 | 1.351 (3) | C8—C9 | 1.399 (4) |
C1—C2 | 1.364 (4) | C8—C12 | 1.504 (4) |
C2—C3 | 1.394 (4) | C9—C10 | 1.351 (4) |
C2—C6 | 1.498 (4) | C10—C11 | 1.398 (4) |
C3—C4 | 1.352 (4) | C11—N4 | 1.329 (4) |
C4—C5 | 1.401 (4) | C11—N3 | 1.342 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···Cl3 | 0.955 (18) | 2.38 (2) | 3.301 (3) | 162 (2) |
N2—H2B···Cl2i | 0.873 (19) | 2.47 (2) | 3.335 (3) | 174 (3) |
N3—H3N···Cl3i | 0.864 (18) | 2.65 (2) | 3.279 (3) | 131 (2) |
N4—H4B···Cl2 | 0.905 (19) | 2.45 (2) | 3.322 (3) | 162 (3) |
N4—H4A···Cl1i | 0.963 (19) | 2.37 (2) | 3.315 (3) | 168 (3) |
C9—H9···Cl1ii | 0.93 | 2.88 | 3.770 (3) | 162 |
Symmetry codes: (i) −x+3/2, y−1/2, −z+3/2; (ii) −x+2, −y+1, −z+1. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- Purchase subscription
- Reduced-price subscriptions
- If you have already subscribed, you may need to register
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 π–π 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 π–π 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.