The title compound, C
12H
14N
3+·ClO
4−, crystallizes from a solution of bis(2-pyridylmethyl)amine and HClO
4 in water/DMF (3:1,
v/
v) with the secondary amine N atom protonated. The two pyridine arms of the ligand are held in a closed conformation through a strong bifurcated hydrogen bond from one of the ammonium H atoms. The ClO
4− anion is also hydrogen bonded to the same H atom of the ammonium N atom, with an N
O distance of 2.899 (4) Å. The other ammonium H atom is hydrogen bonded to an O atom of a symmetry-related perchlorate anion.
Supporting information
CCDC reference: 193748
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.006 Å
- Disorder in solvent or counterion
- R factor = 0.055
- wR factor = 0.156
- Data-to-parameter ratio = 9.8
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
PLAT_302 Alert C Anion/Solvent Disorder ....................... 24.00 Perc.
PLAT_420 Alert C D-H Without Acceptor N - H1N ?
PLAT_420 Alert C D-H Without Acceptor N - H2N ?
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
3 Alert Level C = Please check
Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: SHELXTL (Sheldrick, 1997); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
bis(2-pyridylmethyl)ammonium perchlorate
top
Crystal data top
C12H14N3+·ClO4− | Dx = 1.428 Mg m−3 |
Mr = 299.71 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 26 reflections |
a = 11.3201 (18) Å | θ = 11.6–13.0° |
b = 14.422 (2) Å | µ = 0.29 mm−1 |
c = 17.073 (3) Å | T = 293 K |
V = 2787.3 (7) Å3 | Plate, pale yellow |
Z = 8 | 0.84 × 0.56 × 0.10 mm |
F(000) = 1248 | |
Data collection top
Siemens P4S diffractometer | 1676 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.000 |
Graphite monochromator | θmax = 25.0°, θmin = 2.6° |
2θ/ω scans | h = −13→0 |
Absorption correction: part of the refinement model (ΔF) (SHELXTL; Sheldrick, 1997) | k = −17→0 |
Tmin = 0.728, Tmax = 0.971 | l = −20→0 |
2448 measured reflections | 3 standard reflections every 97 reflections |
2448 independent reflections | intensity decay: 1.0% |
Refinement top
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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.156 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.065P)2 + 2.1051P] where P = (Fo2 + 2Fc2)/3 |
2448 reflections | (Δ/σ)max = 0.001 |
250 parameters | Δρmax = 0.24 e Å−3 |
58 restraints | Δρmin = −0.27 e Å−3 |
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 | x | y | z | Uiso*/Ueq | Occ. (<1) |
Cl | 0.38743 (7) | 0.11220 (6) | 0.08135 (5) | 0.0592 (3) | |
O1A | 0.4293 (8) | 0.1513 (6) | 0.0094 (3) | 0.085 (3) | 0.47 |
O2A | 0.3456 (7) | 0.1850 (5) | 0.1313 (5) | 0.095 (3) | 0.47 |
O3A | 0.2926 (5) | 0.0494 (5) | 0.0651 (5) | 0.066 (2) | 0.47 |
O4A | 0.4814 (6) | 0.0637 (6) | 0.1193 (5) | 0.130 (9) | 0.47 |
O1B | 0.3085 (7) | 0.1575 (8) | 0.1347 (6) | 0.101 (6) | 0.29 |
O2B | 0.3281 (8) | 0.0355 (7) | 0.0455 (8) | 0.080 (5) | 0.29 |
O3B | 0.4236 (13) | 0.1766 (7) | 0.0222 (6) | 0.104 (6) | 0.29 |
O4B | 0.4888 (8) | 0.0796 (9) | 0.1231 (7) | 0.056 (4) | 0.29 |
O1C | 0.3846 (18) | 0.1955 (7) | 0.1269 (9) | 0.100 (10)* | 0.14 |
O2C | 0.4892 (10) | 0.0588 (12) | 0.1024 (11) | 0.066 (10)* | 0.14 |
O3C | 0.2829 (10) | 0.0592 (12) | 0.0962 (10) | 0.083 (10)* | 0.14 |
O4C | 0.3930 (15) | 0.1353 (13) | −0.0001 (3) | 0.056 (6)* | 0.14 |
O1D | 0.4179 (19) | 0.2072 (4) | 0.0950 (12) | 0.097 (11)* | 0.10 |
O2D | 0.4198 (18) | 0.0870 (14) | 0.0031 (4) | 0.060 (7)* | 0.10 |
O3D | 0.4493 (17) | 0.0544 (11) | 0.1358 (8) | 0.041 (7)* | 0.10 |
O4D | 0.2628 (4) | 0.1002 (16) | 0.0914 (12) | 0.16 (2)* | 0.10 |
N | 0.2353 (2) | 0.35208 (19) | 0.07550 (13) | 0.0523 (7) | |
H1N | 0.2552 | 0.4122 | 0.0809 | 0.063* | |
H2N | 0.2977 | 0.3179 | 0.0908 | 0.063* | |
N1A | 0.4140 (3) | 0.3867 (2) | −0.02112 (16) | 0.0605 (8) | |
N1B | 0.2690 (2) | 0.3938 (2) | 0.22490 (16) | 0.0611 (8) | |
C1A | 0.5074 (4) | 0.4094 (2) | −0.0653 (2) | 0.0693 (10) | |
H1AA | 0.5759 | 0.4285 | −0.0399 | 0.083* | |
C2A | 0.5084 (4) | 0.4063 (3) | −0.1443 (3) | 0.0792 (12) | |
H2AA | 0.5754 | 0.4232 | −0.1724 | 0.095* | |
C3A | 0.4074 (5) | 0.3774 (3) | −0.1824 (2) | 0.0863 (14) | |
H3AA | 0.4051 | 0.3744 | −0.2368 | 0.104* | |
C4A | 0.3095 (4) | 0.3529 (3) | −0.1386 (2) | 0.0707 (11) | |
H4AA | 0.2404 | 0.3330 | −0.1628 | 0.085* | |
C5A | 0.3166 (3) | 0.3585 (2) | −0.05823 (19) | 0.0547 (8) | |
C6A | 0.2128 (3) | 0.3336 (3) | −0.00790 (19) | 0.0702 (11) | |
H6AA | 0.1445 | 0.3690 | −0.0247 | 0.084* | |
H6AB | 0.1947 | 0.2683 | −0.0147 | 0.084* | |
C1B | 0.2940 (4) | 0.4151 (3) | 0.2995 (2) | 0.0710 (11) | |
H1BA | 0.3670 | 0.4418 | 0.3102 | 0.085* | |
C2B | 0.2187 (4) | 0.4000 (3) | 0.3608 (2) | 0.0729 (11) | |
H2BA | 0.2399 | 0.4168 | 0.4115 | 0.088* | |
C3B | 0.1119 (4) | 0.3598 (3) | 0.3461 (2) | 0.0725 (11) | |
H3BA | 0.0590 | 0.3486 | 0.3867 | 0.087* | |
C4B | 0.0839 (3) | 0.3361 (3) | 0.2706 (2) | 0.0635 (10) | |
H4BA | 0.0119 | 0.3081 | 0.2591 | 0.076* | |
C5B | 0.1643 (3) | 0.3546 (2) | 0.21190 (18) | 0.0511 (8) | |
C6B | 0.1354 (3) | 0.3320 (3) | 0.12818 (19) | 0.0640 (10) | |
H6BA | 0.1149 | 0.2669 | 0.1241 | 0.077* | |
H6BB | 0.0673 | 0.3680 | 0.1119 | 0.077* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl | 0.0588 (5) | 0.0616 (5) | 0.0571 (5) | 0.0029 (4) | −0.0055 (4) | 0.0037 (4) |
O1A | 0.071 (5) | 0.115 (7) | 0.070 (5) | −0.044 (5) | −0.010 (4) | 0.025 (4) |
O2A | 0.155 (8) | 0.058 (4) | 0.073 (5) | 0.029 (5) | −0.028 (5) | −0.018 (3) |
O3A | 0.038 (3) | 0.064 (5) | 0.096 (7) | −0.007 (3) | 0.019 (4) | 0.000 (4) |
O4A | 0.069 (9) | 0.213 (18) | 0.109 (11) | 0.047 (8) | −0.005 (8) | 0.050 (9) |
O1B | 0.045 (5) | 0.140 (14) | 0.119 (11) | 0.026 (7) | −0.008 (6) | −0.065 (10) |
O2B | 0.094 (11) | 0.069 (7) | 0.078 (8) | −0.021 (8) | 0.005 (8) | −0.021 (6) |
O3B | 0.130 (14) | 0.060 (7) | 0.123 (13) | −0.012 (8) | −0.007 (11) | 0.048 (8) |
O4B | 0.049 (8) | 0.069 (7) | 0.051 (7) | 0.013 (6) | 0.003 (6) | 0.007 (6) |
N | 0.0535 (15) | 0.0570 (15) | 0.0464 (14) | −0.0047 (13) | −0.0030 (12) | −0.0015 (12) |
N1A | 0.0644 (18) | 0.0656 (18) | 0.0516 (16) | −0.0069 (15) | 0.0017 (14) | −0.0036 (14) |
N1B | 0.0536 (17) | 0.0740 (19) | 0.0558 (16) | −0.0035 (15) | −0.0041 (13) | −0.0099 (14) |
C1A | 0.071 (2) | 0.063 (2) | 0.074 (3) | −0.0033 (19) | 0.015 (2) | −0.0041 (19) |
C2A | 0.100 (3) | 0.067 (3) | 0.071 (3) | 0.007 (2) | 0.026 (3) | 0.007 (2) |
C3A | 0.139 (4) | 0.076 (3) | 0.044 (2) | 0.021 (3) | 0.019 (3) | 0.0066 (19) |
C4A | 0.099 (3) | 0.070 (2) | 0.0428 (19) | −0.001 (2) | −0.007 (2) | 0.0003 (17) |
C5A | 0.068 (2) | 0.0519 (18) | 0.0438 (17) | 0.0012 (17) | −0.0023 (16) | −0.0013 (14) |
C6A | 0.070 (2) | 0.095 (3) | 0.0457 (19) | −0.018 (2) | −0.0086 (17) | −0.0031 (19) |
C1B | 0.070 (2) | 0.075 (2) | 0.068 (2) | 0.006 (2) | −0.018 (2) | −0.015 (2) |
C2B | 0.098 (3) | 0.073 (2) | 0.048 (2) | 0.027 (2) | −0.009 (2) | −0.0081 (18) |
C3B | 0.081 (3) | 0.080 (3) | 0.057 (2) | 0.016 (2) | 0.010 (2) | 0.004 (2) |
C4B | 0.060 (2) | 0.071 (2) | 0.059 (2) | 0.0053 (18) | 0.0058 (17) | 0.0081 (18) |
C5B | 0.0487 (18) | 0.0545 (18) | 0.0501 (19) | 0.0049 (16) | −0.0036 (15) | 0.0014 (15) |
C6B | 0.055 (2) | 0.085 (3) | 0.053 (2) | −0.0198 (19) | −0.0002 (16) | −0.0017 (18) |
Geometric parameters (Å, º) top
Cl—O1A | 1.432 (2) | N1B—C1B | 1.340 (4) |
Cl—O2A | 1.433 (2) | C1A—C2A | 1.350 (6) |
Cl—O3A | 1.432 (2) | C1A—H1AA | 0.930 |
Cl—O4A | 1.429 (2) | C2A—C3A | 1.380 (6) |
Cl—O1B | 1.433 (2) | C2A—H2AA | 0.930 |
Cl—O2B | 1.431 (2) | C3A—C4A | 1.383 (6) |
Cl—O3B | 1.432 (2) | C3A—H3AA | 0.930 |
Cl—O4B | 1.430 (2) | C4A—C5A | 1.376 (5) |
Cl—O1C | 1.432 (2) | C4A—H4AA | 0.930 |
Cl—O2C | 1.431 (2) | C5A—C6A | 1.500 (5) |
Cl—O3C | 1.431 (2) | C6A—H6AA | 0.970 |
Cl—O4C | 1.432 (2) | C6A—H6AB | 0.970 |
Cl—O1D | 1.431 (2) | C1B—C2B | 1.368 (5) |
Cl—O2D | 1.432 (2) | C1B—H1BA | 0.930 |
Cl—O3D | 1.432 (2) | C2B—C3B | 1.364 (5) |
Cl—O4D | 1.431 (2) | C2B—H2BA | 0.930 |
N—C6A | 1.471 (4) | C3B—C4B | 1.371 (5) |
N—C6B | 1.474 (4) | C3B—H3BA | 0.930 |
N—H1N | 0.900 | C4B—C5B | 1.380 (4) |
N—H2N | 0.900 | C4B—H4BA | 0.930 |
N1A—C5A | 1.335 (4) | C5B—C6B | 1.502 (4) |
N1A—C1A | 1.340 (4) | C6B—H6BA | 0.970 |
N1B—C5B | 1.332 (4) | C6B—H6BB | 0.970 |
| | | |
O1A—Cl—O2A | 109.44 (9) | C3A—C2A—H2AA | 120.9 |
O1A—Cl—O3A | 109.34 (9) | C2A—C3A—C4A | 119.1 (4) |
O1A—Cl—O4A | 109.57 (9) | C2A—C3A—H3AA | 120.4 |
O2A—Cl—O3A | 109.33 (9) | C4A—C3A—H3AA | 120.4 |
O2A—Cl—O4A | 109.58 (9) | C5A—C4A—C3A | 118.5 (4) |
O3A—Cl—O4A | 109.66 (9) | C5A—C4A—H4AA | 120.7 |
O1B—Cl—O2B | 109.34 (9) | C3A—C4A—H4AA | 120.7 |
O1B—Cl—O3B | 109.33 (9) | N1A—C5A—C4A | 122.6 (3) |
O1B—Cl—O4B | 109.54 (9) | N1A—C5A—C6A | 116.6 (3) |
O2B—Cl—O3B | 109.44 (9) | C4A—C5A—C6A | 120.7 (3) |
O2B—Cl—O4B | 109.63 (9) | N—C6A—C5A | 112.0 (3) |
O3B—Cl—O4B | 109.58 (9) | N—C6A—H6AA | 109.2 |
O1C—Cl—O2C | 109.46 (9) | C5A—C6A—H6AA | 109.2 |
O1C—Cl—O3C | 109.47 (9) | N—C6A—H6AB | 109.2 |
O1C—Cl—O4C | 109.45 (9) | C5A—C6A—H6AB | 109.2 |
O2C—Cl—O3C | 109.49 (9) | H6AA—C6A—H6AB | 107.9 |
O2C—Cl—O4C | 109.47 (9) | N1B—C1B—C2B | 124.0 (4) |
O3C—Cl—O4C | 109.49 (9) | N1B—C1B—H1BA | 118.0 |
O1D—Cl—O2D | 109.48 (9) | C2B—C1B—H1BA | 118.0 |
O1D—Cl—O3D | 109.48 (9) | C3B—C2B—C1B | 118.6 (3) |
O1D—Cl—O4D | 109.50 (9) | C3B—C2B—H2BA | 120.7 |
O2D—Cl—O3D | 109.44 (9) | C1B—C2B—H2BA | 120.7 |
O2D—Cl—O4D | 109.46 (9) | C2B—C3B—C4B | 119.0 (4) |
O3D—Cl—O4D | 109.47 (9) | C2B—C3B—H3BA | 120.5 |
C6A—N—C6B | 114.9 (3) | C4B—C3B—H3BA | 120.5 |
C6A—N—H1N | 108.5 | C3B—C4B—C5B | 118.8 (4) |
C6B—N—H1N | 108.5 | C3B—C4B—H4BA | 120.6 |
C6A—N—H2N | 108.5 | C5B—C4B—H4BA | 120.6 |
C6B—N—H2N | 108.5 | N1B—C5B—C4B | 123.3 (3) |
H1N—N—H2N | 107.5 | N1B—C5B—C6B | 116.4 (3) |
C5A—N1A—C1A | 117.3 (3) | C4B—C5B—C6B | 120.3 (3) |
C5B—N1B—C1B | 116.3 (3) | N—C6B—C5B | 111.7 (3) |
N1A—C1A—C2A | 124.1 (4) | N—C6B—H6BA | 109.3 |
N1A—C1A—H1AA | 117.9 | C5B—C6B—H6BA | 109.3 |
C2A—C1A—H1AA | 117.9 | N—C6B—H6BB | 109.3 |
C1A—C2A—C3A | 118.3 (4) | C5B—C6B—H6BB | 109.3 |
C1A—C2A—H2AA | 120.9 | H6BA—C6B—H6BB | 107.9 |
| | | |
C5A—N1A—C1A—C2A | 0.7 (6) | C5B—N1B—C1B—C2B | −0.8 (6) |
N1A—C1A—C2A—C3A | −0.5 (6) | N1B—C1B—C2B—C3B | 0.8 (6) |
C1A—C2A—C3A—C4A | 0.0 (6) | C1B—C2B—C3B—C4B | −0.1 (6) |
C2A—C3A—C4A—C5A | 0.1 (6) | C2B—C3B—C4B—C5B | −0.6 (6) |
C1A—N1A—C5A—C4A | −0.5 (5) | C1B—N1B—C5B—C4B | 0.1 (5) |
C1A—N1A—C5A—C6A | −179.9 (3) | C1B—N1B—C5B—C6B | 179.1 (3) |
C3A—C4A—C5A—N1A | 0.1 (6) | C3B—C4B—C5B—N1B | 0.6 (5) |
C3A—C4A—C5A—C6A | 179.5 (4) | C3B—C4B—C5B—C6B | −178.3 (3) |
C6B—N—C6A—C5A | 178.1 (3) | C6A—N—C6B—C5B | −178.7 (3) |
N1A—C5A—C6A—N | 4.4 (5) | N1B—C5B—C6B—N | 4.3 (5) |
C4A—C5A—C6A—N | −175.0 (3) | C4B—C5B—C6B—N | −176.7 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N—H1N···O3Ci | 0.90 | 2.18 | 3.015 (17) | 154 |
N—H1N···O2Bi | 0.90 | 2.10 | 2.789 (10) | 132 |
N—H1N···O3Ai | 0.90 | 2.07 | 2.869 (7) | 147 |
N—H2N···O1C | 0.90 | 2.11 | 2.953 (18) | 155 |
N—H2N···O1D | 0.90 | 2.10 | 2.958 (19) | 159 |
N—H2N···O2A | 0.90 | 2.11 | 2.875 (9) | 143 |
N—H2N···O1B | 0.90 | 2.43 | 3.095 (13) | 130 |
Symmetry code: (i) −x+1/2, y+1/2, z. |