Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768199016547/cf0007sup1.cif | |
Structure factor file (SHELXL table format) https://doi.org/10.1107/S0108768199016547/cf0007168Ksup2.sft | |
Structure factor file (SHELXL table format) https://doi.org/10.1107/S0108768199016547/cf0007123Ksup3.sft |
CCDC references: 148908; 148909
For both compounds, data collection: 'Siemens P3-PC diffractometer program V.4.24'; cell refinement: 'Siemens P3-PC diffractometer program V.4.24'; data reduction: Siemens XDISK V.4.20.2 1991 PC; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).
C5H6N2 | Melting point: 242 K |
Mr = 94.12 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I4 | Cell parameters from 50 reflections |
a = 13.799 (2) Å | θ = 3–45° |
c = 10.876 (2) Å | µ = 0.08 mm−1 |
V = 2071.0 (6) Å3 | T = 168 K |
Z = 16 | Cylindrical, colorless |
F(000) = 800 | 0.15 mm (radius) |
Dx = 1.208 Mg m−3 |
Nicolet R3m/V four circle diffractometer | Rint = 0.023 |
Radiation source: fine-focus sealed tube | θmax = 22.6°, θmin = 2.1° |
Graphite monochromator | h = −11→14 |
Wyckoff scan mode | k = −11→14 |
2877 measured reflections | l = −10→11 |
1357 independent reflections | 2 standard reflections every 100 reflections |
1322 reflections with I > 2σ(I) | intensity decay: 2.7% |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.021 | w = 1/[σ2(Fo2) + (0.0324P)2 + 0.0103P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.050 | (Δ/σ)max = 0.009 |
S = 1.06 | Δρmax = 0.11 e Å−3 |
1357 reflections | Δρmin = −0.11 e Å−3 |
177 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0118 (11) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
Secondary atom site location: difference Fourier map | Absolute structure parameter: −0.2 (19) |
Experimental. The crystallization was performed on the diffractometer at a temperature of 230 K with a miniature zone melting procedure using focused infrared-laser radiation according to: R·Boese, M·Nussbaumer, "In Situ Crystallization Techniques", in: "Organic Crystal Chemistry", Ed. D·W. Jones, Oxford University Press, England, (1994) 20–37. |
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 | ||
N1A | 0.01817 (13) | 0.13390 (12) | 0.15819 (14) | 0.0518 (5) | |
C2A | 0.04174 (16) | 0.13994 (14) | 0.27625 (18) | 0.0414 (5) | |
C3A | −0.02827 (17) | 0.12962 (16) | 0.3652 (2) | 0.0504 (6) | |
H3A | −0.0129 (14) | 0.1323 (16) | 0.442 (2) | 0.046 (6)* | |
N4A | −0.12136 (14) | 0.11422 (17) | 0.34185 (16) | 0.0588 (6) | |
C5A | −0.14397 (19) | 0.10959 (18) | 0.2230 (2) | 0.0562 (6) | |
H5A | −0.2113 (19) | 0.1013 (16) | 0.200 (2) | 0.057 (6)* | |
C6A | −0.07612 (19) | 0.11796 (17) | 0.1336 (2) | 0.0560 (6) | |
H6A | −0.0946 (18) | 0.1145 (18) | 0.046 (3) | 0.077 (8)* | |
C7A | 0.14578 (19) | 0.1573 (2) | 0.3079 (2) | 0.0601 (7) | |
H7A1 | 0.193 (2) | 0.101 (2) | 0.268 (3) | 0.095 (9)* | |
H7A2 | 0.1588 (19) | 0.150 (2) | 0.404 (3) | 0.095 (9)* | |
H7A3 | 0.1667 (16) | 0.2122 (18) | 0.268 (2) | 0.056 (7)* | |
N1B | 0.47406 (14) | 0.12734 (14) | −0.09532 (14) | 0.0541 (5) | |
C2B | 0.44816 (16) | 0.13104 (15) | 0.0227 (2) | 0.0444 (5) | |
C3B | 0.51810 (16) | 0.12665 (16) | 0.1137 (2) | 0.0471 (5) | |
H3B | 0.5002 (15) | 0.1305 (14) | 0.204 (2) | 0.055 (6)* | |
N4B | 0.61292 (14) | 0.11852 (14) | 0.09180 (16) | 0.0515 (6) | |
C5B | 0.63781 (19) | 0.11532 (18) | −0.0264 (2) | 0.0525 (6) | |
H5B | 0.710 (2) | 0.110 (2) | −0.044 (3) | 0.083 (8)* | |
C6B | 0.56840 (17) | 0.11904 (17) | −0.1185 (2) | 0.0556 (6) | |
H6B | 0.5974 (16) | 0.1127 (18) | −0.196 (3) | 0.065 (8)* | |
C7B | 0.34303 (19) | 0.1395 (2) | 0.0527 (3) | 0.0585 (6) | |
H7B1 | 0.308 (3) | 0.127 (3) | −0.034 (4) | 0.143 (12)* | |
H7B2 | 0.318 (3) | 0.209 (3) | 0.056 (4) | 0.127 (12)* | |
H7B3 | 0.318 (2) | 0.093 (2) | 0.096 (3) | 0.110 (13)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1A | 0.0653 (14) | 0.0509 (12) | 0.0392 (11) | −0.0013 (10) | 0.0038 (8) | −0.0019 (9) |
C2A | 0.0526 (12) | 0.0372 (11) | 0.0343 (11) | 0.0004 (10) | 0.0004 (9) | −0.0003 (8) |
C3A | 0.0577 (16) | 0.0583 (13) | 0.0353 (13) | 0.0028 (10) | −0.0020 (10) | 0.0030 (10) |
N4A | 0.0506 (11) | 0.0764 (14) | 0.0494 (9) | −0.0009 (10) | 0.0011 (9) | 0.0045 (11) |
C5A | 0.0541 (15) | 0.0585 (15) | 0.0559 (14) | 0.0048 (14) | −0.0071 (12) | 0.0050 (13) |
C6A | 0.0734 (16) | 0.0601 (15) | 0.0346 (13) | 0.0020 (12) | −0.0136 (12) | 0.0010 (11) |
C7A | 0.0506 (14) | 0.0698 (18) | 0.0598 (16) | −0.0019 (13) | 0.0034 (12) | 0.0028 (15) |
N1B | 0.0702 (13) | 0.0622 (12) | 0.0299 (11) | 0.0027 (10) | −0.0048 (8) | −0.0043 (9) |
C2B | 0.0538 (13) | 0.0360 (11) | 0.0435 (14) | −0.0087 (11) | −0.0028 (10) | −0.0034 (9) |
C3B | 0.0605 (14) | 0.0521 (12) | 0.0288 (12) | −0.0030 (11) | −0.0001 (9) | −0.0010 (9) |
N4B | 0.0526 (12) | 0.0572 (11) | 0.0445 (10) | −0.0039 (9) | −0.0045 (8) | −0.0033 (9) |
C5B | 0.0577 (14) | 0.0488 (11) | 0.0510 (14) | 0.0008 (12) | 0.0109 (12) | −0.0040 (12) |
C6B | 0.0741 (17) | 0.0555 (15) | 0.0374 (14) | 0.0041 (13) | 0.0092 (13) | −0.0044 (10) |
C7B | 0.0545 (15) | 0.0566 (16) | 0.0644 (17) | 0.0017 (13) | 0.0008 (12) | 0.0002 (14) |
N1A—C2A | 1.327 (3) | N1B—C6B | 1.331 (3) |
N1A—C6A | 1.346 (3) | N1B—C2B | 1.333 (3) |
C2A—C3A | 1.374 (3) | C2B—C3B | 1.384 (3) |
C2A—C7A | 1.496 (3) | C2B—C7B | 1.492 (4) |
C3A—N4A | 1.326 (3) | C3B—N4B | 1.335 (3) |
N4A—C5A | 1.332 (3) | N4B—C5B | 1.331 (3) |
C5A—C6A | 1.354 (3) | C5B—C6B | 1.387 (3) |
C2A—N1A—C6A | 116.04 (19) | C6B—N1B—C2B | 116.6 (2) |
N1A—C2A—C3A | 120.13 (19) | N1B—C2B—C3B | 120.0 (2) |
N1A—C2A—C7A | 117.9 (2) | N1B—C2B—C7B | 118.3 (2) |
C3A—C2A—C7A | 122.0 (2) | C3B—C2B—C7B | 121.7 (2) |
N4A—C3A—C2A | 124.3 (2) | N4B—C3B—C2B | 124.1 (2) |
C3A—N4A—C5A | 114.8 (2) | C5B—N4B—C3B | 115.3 (2) |
N4A—C5A—C6A | 122.0 (2) | N4B—C5B—C6B | 121.2 (2) |
N1A—C6A—C5A | 122.7 (2) | N1B—C6B—C5B | 122.8 (2) |
C5H6N2 | Melting point: 242 K |
Mr = 94.12 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I4 | Cell parameters from 50 reflections |
a = 13.725 (2) Å | θ = 3–45° |
c = 10.859 (2) Å | µ = 0.08 mm−1 |
V = 2045.6 (6) Å3 | T = 123 K |
Z = 16 | Cylindrical, colorless |
F(000) = 800 | 0.15 mm (radius) |
Dx = 1.222 Mg m−3 |
Nicolet R3m/V four circle diffractometer | Rint = 0.024 |
Radiation source: fine-focus sealed tube | θmax = 22.5°, θmin = 2.1° |
Graphite monochromator | h = −14→10 |
Wyckoff scan mode | k = −10→14 |
1474 measured reflections | l = 0→11 |
1338 independent reflections | 2 standard reflections every 100 reflections |
1301 reflections with I > 2σ(I) | intensity decay: 0.7% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.026 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.068 | w = 1/[σ2(Fo2) + (0.0428P)2 + 0.2414P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.004 |
1338 reflections | Δρmax = 0.09 e Å−3 |
176 parameters | Δρmin = −0.12 e Å−3 |
0 restraints | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −6 (3) |
Experimental. The crystallization was performed on the diffractometer at a temperature of 230 K with a miniature zone melting procedure using focused infrared-laser radiation according to: R·Boese, M·Nussbaumer, "In Situ Crystallization Techniques", in: "Organic Crystal Chemistry", Ed. D·W. Jones, Oxford University Press, England, (1994) 20–37. |
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 | ||
N1A | 0.01857 (15) | 0.13349 (14) | 0.15884 (18) | 0.0377 (6) | |
C2A | 0.04218 (18) | 0.13973 (16) | 0.2772 (2) | 0.0310 (6) | |
C3A | −0.0289 (2) | 0.12985 (19) | 0.3668 (2) | 0.0381 (6) | |
H3A | −0.0139 (18) | 0.137 (2) | 0.443 (3) | 0.040 (7)* | |
N4A | −0.12254 (16) | 0.11445 (18) | 0.34271 (19) | 0.0437 (6) | |
C5A | −0.1452 (2) | 0.1090 (2) | 0.2227 (3) | 0.0427 (7) | |
H5A | −0.209 (2) | 0.0954 (19) | 0.198 (3) | 0.046 (8)* | |
C6A | −0.0756 (2) | 0.11701 (19) | 0.1330 (2) | 0.0416 (7) | |
H6A | −0.095 (2) | 0.111 (2) | 0.040 (3) | 0.077 (10)* | |
C7A | 0.1464 (2) | 0.1572 (3) | 0.3096 (3) | 0.0452 (8) | |
H7A1 | 0.190 (3) | 0.104 (3) | 0.270 (4) | 0.084 (11)* | |
H7A2 | 0.154 (2) | 0.156 (3) | 0.396 (3) | 0.067 (10)* | |
H7A3 | 0.166 (2) | 0.214 (2) | 0.273 (3) | 0.048 (9)* | |
N1B | −0.52689 (17) | 0.12727 (17) | −0.09554 (18) | 0.0414 (6) | |
C2B | −0.55250 (18) | 0.13104 (18) | 0.0227 (2) | 0.0349 (6) | |
C3B | −0.48228 (19) | 0.12616 (19) | 0.1148 (2) | 0.0369 (6) | |
H3B | −0.4996 (17) | 0.1288 (17) | 0.203 (2) | 0.034 (6)* | |
N4B | −0.38712 (16) | 0.11870 (17) | 0.09235 (19) | 0.0391 (6) | |
C5B | −0.3620 (2) | 0.11554 (19) | −0.0264 (3) | 0.0386 (6) | |
H5B | −0.287 (2) | 0.113 (2) | −0.041 (3) | 0.048 (7)* | |
C6B | −0.4314 (2) | 0.11949 (19) | −0.1188 (3) | 0.0432 (7) | |
H6B | −0.4053 (19) | 0.109 (2) | −0.196 (3) | 0.050 (9)* | |
C7B | −0.6584 (2) | 0.1387 (2) | 0.0524 (3) | 0.0438 (7) | |
H7B1 | −0.694 (3) | 0.113 (4) | −0.028 (5) | 0.136 (17)* | |
H7B2 | −0.683 (3) | 0.204 (3) | 0.053 (4) | 0.086 (12)* | |
H7B3 | −0.682 (3) | 0.090 (3) | 0.105 (4) | 0.099 (14)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1A | 0.0449 (15) | 0.0395 (13) | 0.0287 (12) | −0.0016 (11) | 0.0045 (9) | −0.0019 (10) |
C2A | 0.0393 (14) | 0.0276 (13) | 0.0261 (12) | 0.0004 (12) | −0.0001 (11) | −0.0002 (10) |
C3A | 0.0441 (17) | 0.0450 (15) | 0.0251 (15) | 0.0013 (12) | −0.0035 (12) | 0.0010 (13) |
N4A | 0.0391 (13) | 0.0563 (15) | 0.0359 (11) | −0.0011 (11) | 0.0001 (10) | 0.0050 (11) |
C5A | 0.0392 (17) | 0.0440 (17) | 0.0449 (16) | 0.0008 (15) | −0.0070 (15) | 0.0059 (14) |
C6A | 0.0583 (18) | 0.0411 (15) | 0.0253 (15) | 0.0018 (13) | −0.0089 (14) | 0.0010 (12) |
C7A | 0.0418 (16) | 0.053 (2) | 0.0409 (18) | −0.0026 (15) | 0.0044 (13) | −0.0006 (16) |
N1B | 0.0547 (16) | 0.0461 (14) | 0.0234 (12) | 0.0020 (11) | −0.0029 (10) | −0.0046 (10) |
C2B | 0.0425 (15) | 0.0287 (13) | 0.0334 (16) | −0.0072 (12) | −0.0022 (12) | −0.0017 (11) |
C3B | 0.0494 (17) | 0.0386 (14) | 0.0226 (14) | −0.0030 (12) | 0.0009 (12) | 0.0021 (11) |
N4B | 0.0393 (13) | 0.0449 (13) | 0.0333 (12) | −0.0026 (10) | −0.0026 (10) | −0.0029 (10) |
C5B | 0.0430 (16) | 0.0342 (13) | 0.0387 (16) | 0.0004 (12) | 0.0097 (13) | −0.0029 (13) |
C6B | 0.0602 (19) | 0.0403 (17) | 0.0292 (16) | 0.0041 (14) | 0.0063 (16) | −0.0045 (13) |
C7B | 0.0421 (17) | 0.0393 (18) | 0.0500 (19) | 0.0028 (14) | −0.0005 (13) | 0.0011 (15) |
N1A—C2A | 1.328 (3) | N1B—C2B | 1.332 (3) |
N1A—C6A | 1.342 (4) | N1B—C6B | 1.339 (4) |
C2A—C3A | 1.384 (4) | C2B—C3B | 1.391 (4) |
C2A—C7A | 1.492 (4) | C2B—C7B | 1.492 (4) |
C3A—N4A | 1.329 (4) | C3B—N4B | 1.332 (4) |
N4A—C5A | 1.342 (3) | N4B—C5B | 1.335 (4) |
C5A—C6A | 1.368 (4) | C5B—C6B | 1.385 (4) |
C2A—N1A—C6A | 116.6 (2) | C2B—N1B—C6B | 116.3 (2) |
N1A—C2A—C3A | 120.1 (2) | N1B—C2B—C3B | 120.5 (2) |
N1A—C2A—C7A | 118.2 (2) | N1B—C2B—C7B | 117.9 (2) |
C3A—C2A—C7A | 121.7 (2) | C3B—C2B—C7B | 121.5 (2) |
N4A—C3A—C2A | 124.0 (2) | N4B—C3B—C2B | 123.5 (3) |
C3A—N4A—C5A | 115.1 (2) | C3B—N4B—C5B | 115.6 (2) |
N4A—C5A—C6A | 121.6 (3) | N4B—C5B—C6B | 121.4 (3) |
N1A—C6A—C5A | 122.5 (2) | N1B—C6B—C5B | 122.7 (3) |