Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107010098/av3074sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107010098/av3074Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107010098/av3074IIsup3.hkl |
CCDC references: 645587; 645588
For both compounds, data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXTL/PC (Bruker, 2000); program(s) used to refine structure: SHELXTL/PC; molecular graphics: ORTEP-3 (Farrugia, 1997), Mercury (Version 1.4.1; Macrae et al., 2006 ) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL/PC.
C6H7N2O+·ClO4− | F(000) = 456 |
Mr = 222.59 | Dx = 1.670 Mg m−3 Dm = 1.66 (1) Mg m−3 Dm measured by Flotation technique using a liquid-mixture of xylene and bromoform |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
a = 11.273 (5) Å | θ = 9.6–15.7° |
b = 9.858 (4) Å | µ = 0.43 mm−1 |
c = 8.077 (5) Å | T = 293 K |
β = 99.43 (3)° | Needle, colourless |
V = 885.5 (8) Å3 | 0.21 × 0.17 × 0.15 mm |
Z = 4 |
Nonius MACH3 diffractometer | 1038 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.037 |
Graphite monochromator | θmax = 25.0°, θmin = 2.8° |
ω–2θ scans | h = −13→13 |
Absorption correction: ψ scan (North et al., 1968) | k = −1→11 |
Tmin = 0.929, Tmax = 0.946 | l = 0→9 |
1895 measured reflections | 3 standard reflections every 60 min |
1562 independent reflections | intensity decay: none |
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)] = 0.071 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.220 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.1515P)2] where P = (Fo2 + 2Fc2)/3 |
1562 reflections | (Δ/σ)max < 0.001 |
127 parameters | Δρmax = 0.69 e Å−3 |
0 restraints | Δρmin = −0.58 e Å−3 |
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 | ||
N1 | 0.2316 (4) | 0.5216 (4) | 0.4476 (5) | 0.0460 (11) | |
H1 | 0.2256 | 0.6035 | 0.4104 | 0.055* | |
C2 | 0.3285 (4) | 0.4901 (5) | 0.5555 (6) | 0.0393 (12) | |
H2 | 0.3865 | 0.5555 | 0.5916 | 0.047* | |
C3 | 0.3429 (4) | 0.3570 (4) | 0.6147 (6) | 0.0336 (11) | |
C31 | 0.4487 (5) | 0.3117 (5) | 0.7359 (7) | 0.0423 (12) | |
N31 | 0.5251 (4) | 0.4023 (4) | 0.8059 (7) | 0.0647 (16) | |
H31A | 0.5854 | 0.3780 | 0.8794 | 0.078* | |
H31B | 0.5153 | 0.4864 | 0.7786 | 0.078* | |
O31 | 0.4599 (4) | 0.1912 (3) | 0.7716 (6) | 0.0579 (12) | |
C4 | 0.2536 (5) | 0.2651 (5) | 0.5532 (7) | 0.0427 (13) | |
H4 | 0.2615 | 0.1750 | 0.5872 | 0.051* | |
C5 | 0.1540 (5) | 0.3041 (6) | 0.4438 (7) | 0.0502 (14) | |
H5 | 0.0944 | 0.2413 | 0.4046 | 0.060* | |
C6 | 0.1426 (5) | 0.4371 (6) | 0.3920 (6) | 0.0489 (14) | |
H6 | 0.0745 | 0.4668 | 0.3201 | 0.059* | |
Cl1 | 0.16676 (11) | 0.87741 (12) | 0.41190 (15) | 0.0409 (5) | |
O1 | 0.0763 (4) | 0.7770 (4) | 0.3895 (7) | 0.0714 (14) | |
O2 | 0.1376 (4) | 0.9833 (4) | 0.2913 (5) | 0.0678 (13) | |
O3 | 0.2785 (4) | 0.8133 (4) | 0.3921 (7) | 0.0729 (14) | |
O4 | 0.1815 (5) | 0.9324 (5) | 0.5750 (6) | 0.0867 (16) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.061 (3) | 0.021 (2) | 0.050 (2) | 0.003 (2) | −0.008 (2) | 0.0024 (18) |
C2 | 0.045 (3) | 0.017 (2) | 0.052 (3) | 0.001 (2) | −0.002 (2) | 0.002 (2) |
C3 | 0.042 (3) | 0.015 (2) | 0.045 (3) | 0.0025 (19) | 0.010 (2) | −0.0041 (19) |
C31 | 0.043 (3) | 0.021 (3) | 0.060 (3) | 0.004 (2) | 0.001 (2) | −0.002 (2) |
N31 | 0.059 (3) | 0.025 (2) | 0.095 (4) | 0.003 (2) | −0.033 (3) | 0.005 (2) |
O31 | 0.061 (3) | 0.0175 (19) | 0.089 (3) | 0.0077 (16) | −0.005 (2) | 0.0101 (18) |
C4 | 0.050 (3) | 0.020 (2) | 0.059 (3) | −0.008 (2) | 0.008 (2) | 0.001 (2) |
C5 | 0.048 (3) | 0.043 (3) | 0.057 (3) | −0.016 (2) | −0.001 (3) | −0.006 (3) |
C6 | 0.046 (3) | 0.050 (3) | 0.046 (3) | 0.006 (3) | −0.005 (2) | 0.005 (3) |
Cl1 | 0.0473 (8) | 0.0255 (7) | 0.0470 (8) | −0.0008 (5) | −0.0010 (5) | 0.0013 (5) |
O1 | 0.062 (3) | 0.040 (2) | 0.107 (4) | −0.017 (2) | 0.000 (2) | 0.006 (2) |
O2 | 0.080 (3) | 0.045 (2) | 0.076 (3) | 0.007 (2) | 0.005 (2) | 0.030 (2) |
O3 | 0.051 (2) | 0.057 (3) | 0.108 (4) | 0.010 (2) | 0.002 (2) | 0.001 (3) |
O4 | 0.125 (4) | 0.078 (4) | 0.053 (3) | 0.001 (3) | 0.004 (3) | −0.009 (3) |
N1—C2 | 1.319 (6) | N31—H31B | 0.8600 |
N1—C6 | 1.324 (7) | C4—C5 | 1.365 (8) |
N1—H1 | 0.8600 | C4—H4 | 0.9300 |
C2—C3 | 1.397 (6) | C5—C6 | 1.377 (8) |
C2—H2 | 0.9300 | C5—H5 | 0.9300 |
C3—C4 | 1.385 (7) | C6—H6 | 0.9300 |
C3—C31 | 1.482 (7) | Cl1—O4 | 1.409 (5) |
C31—O31 | 1.224 (5) | Cl1—O1 | 1.412 (4) |
C31—N31 | 1.304 (7) | Cl1—O2 | 1.429 (4) |
N31—H31A | 0.8600 | Cl1—O3 | 1.441 (4) |
C2—N1—C6 | 125.2 (4) | C5—C4—C3 | 121.4 (5) |
C2—N1—H1 | 117.4 | C5—C4—H4 | 119.3 |
C6—N1—H1 | 117.4 | C3—C4—H4 | 119.3 |
N1—C2—C3 | 119.0 (4) | C4—C5—C6 | 119.4 (5) |
N1—C2—H2 | 120.5 | C4—C5—H5 | 120.3 |
C3—C2—H2 | 120.5 | C6—C5—H5 | 120.3 |
C4—C3—C2 | 117.0 (4) | N1—C6—C5 | 117.9 (5) |
C4—C3—C31 | 120.0 (4) | N1—C6—H6 | 121.0 |
C2—C3—C31 | 123.0 (4) | C5—C6—H6 | 121.0 |
O31—C31—N31 | 121.8 (5) | O4—Cl1—O1 | 111.2 (3) |
O31—C31—C3 | 119.2 (5) | O4—Cl1—O2 | 109.6 (3) |
N31—C31—C3 | 118.9 (4) | O1—Cl1—O2 | 110.1 (3) |
C31—N31—H31A | 120.0 | O4—Cl1—O3 | 107.5 (3) |
C31—N31—H31B | 120.0 | O1—Cl1—O3 | 107.7 (3) |
H31A—N31—H31B | 120.0 | O2—Cl1—O3 | 110.7 (3) |
C6—N1—C2—C3 | 1.9 (8) | C2—C3—C31—N31 | 8.3 (8) |
N1—C2—C3—C4 | 0.8 (7) | C2—C3—C4—C5 | −2.0 (8) |
N1—C2—C3—C31 | 179.9 (5) | C31—C3—C4—C5 | 178.8 (5) |
C4—C3—C31—O31 | 5.0 (8) | C3—C4—C5—C6 | 0.7 (8) |
C2—C3—C31—O31 | −174.1 (5) | C2—N1—C6—C5 | −3.3 (9) |
C4—C3—C31—N31 | −172.7 (5) | C4—C5—C6—N1 | 1.9 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1 | 0.86 | 2.39 | 3.058 (6) | 135 |
N1—H1···O3 | 0.86 | 2.16 | 2.971 (6) | 156 |
N31—H31A···O3i | 0.86 | 2.29 | 3.138 (7) | 170 |
N31—H31A···O4i | 0.86 | 2.65 | 3.302 (8) | 134 |
N31—H31B···O31ii | 0.86 | 2.09 | 2.927 (6) | 165 |
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+1, y+1/2, −z+3/2. |
C6H7N2O+·C2HO4− | F(000) = 440 |
Mr = 212.16 | Dx = 1.609 Mg m−3 Dm = 1.59 (1) Mg m−3 Dm measured by flotation technique using a liqiud-mixture of xylene and carbon tetrachloride |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
a = 12.8295 (7) Å | θ = 9.8–14.4° |
b = 6.3148 (5) Å | µ = 0.14 mm−1 |
c = 11.1883 (9) Å | T = 293 K |
β = 104.950 (12)° | Block, colourless |
V = 875.75 (11) Å3 | 0.22 × 0.19 × 0.14 mm |
Z = 4 |
Nonius MACH3 diffractometer | 1457 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.041 |
Graphite monochromator | θmax = 27.0°, θmin = 3.3° |
ω–2θ scans | h = −16→15 |
Absorption correction: ψ scan (North et al., 1968) | k = −1→8 |
Tmin = 0.962, Tmax = 0.983 | l = 0→14 |
2383 measured reflections | 3 standard reflections every 60 min |
1916 independent reflections | intensity decay: none |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.109 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0546P)2 + 0.2614P] where P = (Fo2 + 2Fc2)/3 |
1916 reflections | (Δ/σ)max < 0.001 |
137 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
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 | ||
O1A | 0.39687 (9) | 0.1942 (2) | 0.11029 (9) | 0.0326 (3) | |
O1B | 0.56161 (8) | 0.2088 (2) | 0.23860 (10) | 0.0363 (3) | |
C11 | 0.46189 (12) | 0.2062 (2) | 0.21507 (13) | 0.0245 (3) | |
C12 | 0.40854 (12) | 0.2259 (2) | 0.32440 (13) | 0.0240 (3) | |
O2A | 0.31123 (9) | 0.2332 (2) | 0.30730 (10) | 0.0350 (3) | |
O2B | 0.47857 (9) | 0.2395 (2) | 0.43052 (9) | 0.0353 (3) | |
H2B | 0.4472 | 0.2550 | 0.4851 | 0.053* | |
N1 | 0.29190 (11) | 0.7071 (2) | 0.04181 (13) | 0.0348 (3) | |
H1 | 0.3475 | 0.7455 | 0.0988 | 0.042* | |
C2 | 0.23827 (12) | 0.5350 (3) | 0.06054 (14) | 0.0282 (3) | |
H2 | 0.2611 | 0.4594 | 0.1340 | 0.034* | |
C3 | 0.14893 (11) | 0.4690 (3) | −0.02910 (14) | 0.0270 (3) | |
C31 | 0.08789 (13) | 0.2723 (3) | −0.01437 (14) | 0.0310 (4) | |
O31 | 0.00342 (10) | 0.2321 (2) | −0.09238 (12) | 0.0435 (3) | |
N31 | 0.12673 (12) | 0.1502 (3) | 0.08305 (14) | 0.0445 (4) | |
H31A | 0.0926 | 0.0376 | 0.0938 | 0.053* | |
H31B | 0.1861 | 0.1836 | 0.1356 | 0.053* | |
C4 | 0.11628 (13) | 0.5894 (3) | −0.13537 (15) | 0.0344 (4) | |
H4 | 0.0553 | 0.5503 | −0.1965 | 0.041* | |
C5 | 0.17344 (15) | 0.7666 (3) | −0.15131 (16) | 0.0418 (4) | |
H5 | 0.1512 | 0.8478 | −0.2227 | 0.050* | |
C6 | 0.26343 (15) | 0.8226 (3) | −0.06110 (17) | 0.0427 (5) | |
H6 | 0.3041 | 0.9397 | −0.0716 | 0.051* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1A | 0.0272 (6) | 0.0509 (7) | 0.0173 (5) | 0.0020 (5) | 0.0017 (4) | −0.0028 (5) |
O1B | 0.0217 (6) | 0.0619 (8) | 0.0242 (6) | 0.0044 (5) | 0.0041 (4) | −0.0038 (5) |
C11 | 0.0250 (7) | 0.0293 (8) | 0.0188 (7) | 0.0036 (6) | 0.0049 (5) | 0.0005 (6) |
C12 | 0.0238 (7) | 0.0282 (7) | 0.0191 (7) | 0.0000 (6) | 0.0036 (5) | 0.0023 (6) |
O2A | 0.0227 (6) | 0.0563 (8) | 0.0254 (6) | −0.0021 (5) | 0.0050 (4) | 0.0007 (5) |
O2B | 0.0248 (6) | 0.0635 (8) | 0.0163 (5) | 0.0024 (5) | 0.0029 (4) | 0.0001 (5) |
N1 | 0.0234 (6) | 0.0442 (9) | 0.0315 (7) | −0.0062 (6) | −0.0025 (5) | −0.0014 (6) |
C2 | 0.0219 (7) | 0.0356 (9) | 0.0244 (7) | 0.0026 (6) | 0.0010 (6) | 0.0006 (6) |
C3 | 0.0204 (6) | 0.0351 (8) | 0.0245 (7) | 0.0011 (6) | 0.0040 (6) | −0.0019 (6) |
C31 | 0.0244 (7) | 0.0387 (9) | 0.0276 (8) | −0.0024 (7) | 0.0027 (6) | −0.0014 (7) |
O31 | 0.0339 (6) | 0.0521 (8) | 0.0356 (7) | −0.0140 (6) | −0.0072 (5) | 0.0041 (6) |
N31 | 0.0372 (8) | 0.0463 (9) | 0.0412 (9) | −0.0139 (7) | −0.0058 (7) | 0.0105 (7) |
C4 | 0.0265 (8) | 0.0478 (10) | 0.0249 (8) | −0.0035 (7) | −0.0009 (6) | 0.0011 (7) |
C5 | 0.0412 (10) | 0.0511 (11) | 0.0284 (9) | −0.0084 (9) | 0.0005 (7) | 0.0096 (8) |
C6 | 0.0386 (10) | 0.0491 (11) | 0.0378 (10) | −0.0136 (8) | 0.0049 (8) | 0.0051 (8) |
O1A—C11 | 1.2535 (17) | C3—C4 | 1.382 (2) |
O1B—C11 | 1.2380 (18) | C3—C31 | 1.500 (2) |
C11—C12 | 1.553 (2) | C31—O31 | 1.2299 (18) |
C12—O2A | 1.2142 (18) | C31—N31 | 1.323 (2) |
C12—O2B | 1.2938 (17) | N31—H31A | 0.8600 |
O2B—H2B | 0.8200 | N31—H31B | 0.8600 |
N1—C2 | 1.331 (2) | C4—C5 | 1.375 (3) |
N1—C6 | 1.332 (2) | C4—H4 | 0.9300 |
N1—H1 | 0.8600 | C5—C6 | 1.369 (2) |
C2—C3 | 1.379 (2) | C5—H5 | 0.9300 |
C2—H2 | 0.9300 | C6—H6 | 0.9300 |
O1B—C11—O1A | 126.98 (14) | O31—C31—N31 | 122.71 (16) |
O1B—C11—C12 | 118.20 (13) | O31—C31—C3 | 118.83 (14) |
O1A—C11—C12 | 114.79 (13) | N31—C31—C3 | 118.46 (14) |
O2A—C12—O2B | 125.76 (14) | C31—N31—H31A | 120.0 |
O2A—C12—C11 | 121.54 (13) | C31—N31—H31B | 120.0 |
O2B—C12—C11 | 112.67 (12) | H31A—N31—H31B | 120.0 |
C12—O2B—H2B | 109.5 | C5—C4—C3 | 120.40 (15) |
C2—N1—C6 | 123.05 (14) | C5—C4—H4 | 119.8 |
C2—N1—H1 | 118.5 | C3—C4—H4 | 119.8 |
C6—N1—H1 | 118.5 | C6—C5—C4 | 119.41 (16) |
N1—C2—C3 | 119.92 (14) | C6—C5—H5 | 120.3 |
N1—C2—H2 | 120.0 | C4—C5—H5 | 120.3 |
C3—C2—H2 | 120.0 | N1—C6—C5 | 119.14 (17) |
C2—C3—C4 | 118.05 (15) | N1—C6—H6 | 120.4 |
C2—C3—C31 | 122.01 (14) | C5—C6—H6 | 120.4 |
C4—C3—C31 | 119.94 (13) | ||
O1B—C11—C12—O2A | 176.94 (15) | C4—C3—C31—O31 | −6.8 (2) |
O1A—C11—C12—O2A | −1.4 (2) | C2—C3—C31—N31 | −5.7 (2) |
O1B—C11—C12—O2B | −1.1 (2) | C4—C3—C31—N31 | 173.95 (17) |
O1A—C11—C12—O2B | −179.48 (14) | C2—C3—C4—C5 | 1.5 (3) |
C6—N1—C2—C3 | 0.1 (3) | C31—C3—C4—C5 | −178.16 (16) |
N1—C2—C3—C4 | −1.7 (2) | C3—C4—C5—C6 | 0.3 (3) |
N1—C2—C3—C31 | 177.93 (14) | C2—N1—C6—C5 | 1.7 (3) |
C2—C3—C31—O31 | 173.55 (16) | C4—C5—C6—N1 | −1.9 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2B—H2B···O1Ai | 0.82 | 1.72 | 2.531 (2) | 172 |
N1—H1···O1Bii | 0.86 | 1.90 | 2.681 (2) | 149 |
N31—H31A···O31iii | 0.86 | 2.10 | 2.953 (2) | 172 |
N31—H31B···O2A | 0.86 | 2.18 | 3.018 (2) | 163 |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, y+1/2, −z+1/2; (iii) −x, −y, −z. |