Supporting information
CCDC references: 131753; 131754
For both compounds, data collection: EXPRESS-CAD4 (Enraf Nonius 1992) software; cell refinement: CAD4 (Enraf Nonius 1988) software <CELDIM> routine; data reduction: HELENA (Spek, 1994). Program(s) used to solve structure: SHELXS86 (Sheldrick, 1985, 1990) for DIAZA1; SHELXS86 (Sheldrick, 1990) for DIAZA2. Program(s) used to refine structure: SHELX76 (Sheldrick, 1976) for DIAZA1; SHELXL93 (Sheldrick, 1993) for DIAZA2. For both compounds, molecular graphics: PLATON93 (Spek, 1982, 1990) & ORTEP (Johnson, 1965), PLUTON93 (Spek 1991); software used to prepare material for publication: PLATON93 (Spek 1982, 1990).
C16H12N2 | F(000) = 244 |
Mr = 232.29 | Dx = 1.377 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54184 Å |
Hall symbol: -P 2ybc | Cell parameters from 18 reflections |
a = 4.0246 (5) Å | θ = 11–42° |
b = 15.5147 (5) Å | µ = 0.60 mm−1 |
c = 9.1453 (9) Å | T = 295 K |
β = 101.23 (1)° | Needle, colourless |
V = 560.1 (1) Å3 | 0.3 × 0.04 × 0.04 mm |
Z = 2 |
Enraf-Nonius CAD4 diffractometer | Rint = 0.036 |
Radiation source: fine-focused sealed tube | θmax = 74.2°, θmin = 5.7° |
Graphite monochromator | h = −5→0 |
ω/2θ scans | k = −19→0 |
1297 measured reflections | l = −11→11 |
1135 independent reflections | 3 standard reflections every 41 reflections |
425 reflections with I > 2σ(I) |
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)] = 0.043 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.427 | All H-atom parameters refined |
S = 0.63 | Calculated w = 1/[σ2(Fo2) + (0.1673P)2 + 0.5865P] where P = (Fo2 + 2Fc2)/3 |
660 reflections | (Δ/σ)max = −0.031 |
106 parameters | Δρmax = 0.14 e Å−3 |
0 restraints | Δρmin = −0.15 e Å−3 |
C16H12N2 | V = 560.1 (1) Å3 |
Mr = 232.29 | Z = 2 |
Monoclinic, P21/c | Cu Kα radiation |
a = 4.0246 (5) Å | µ = 0.60 mm−1 |
b = 15.5147 (5) Å | T = 295 K |
c = 9.1453 (9) Å | 0.3 × 0.04 × 0.04 mm |
β = 101.23 (1)° |
Enraf-Nonius CAD4 diffractometer | 425 reflections with I > 2σ(I) |
1297 measured reflections | Rint = 0.036 |
1135 independent reflections | 3 standard reflections every 41 reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.427 | All H-atom parameters refined |
S = 0.63 | Δρmax = 0.14 e Å−3 |
660 reflections | Δρmin = −0.15 e Å−3 |
106 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 on F2 for ALL reflections except for 475 with very negative F2 or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating R-factor-obs 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 | ||
N4 | 0.1676 (8) | 0.35583 (19) | 0.1291 (3) | 0.0470 (11) | |
C1 | 0.4509 (10) | 0.6138 (3) | 0.2271 (4) | 0.0500 (17) | |
C2 | 0.5860 (11) | 0.5469 (3) | 0.3198 (4) | 0.0536 (16) | |
C3 | 0.4908 (11) | 0.4623 (3) | 0.2872 (4) | 0.0530 (17) | |
C5 | −0.0548 (10) | 0.3387 (2) | 0.0075 (4) | 0.0454 (14) | |
C11 | 0.1207 (9) | 0.5102 (3) | 0.0649 (3) | 0.0395 (12) | |
C31 | 0.2587 (10) | 0.4415 (3) | 0.1597 (4) | 0.0444 (12) | |
C51 | −0.2135 (10) | 0.4036 (2) | −0.0975 (4) | 0.0435 (12) | |
C53 | −0.1415 (15) | 0.2452 (3) | −0.0233 (6) | 0.062 (2) | |
H1 | 0.511 (11) | 0.675 (3) | 0.248 (5) | 0.067 (13)* | |
H2 | 0.756 (11) | 0.559 (3) | 0.412 (5) | 0.069 (13)* | |
H3 | 0.613 (10) | 0.421 (3) | 0.352 (4) | 0.057 (13)* | |
H531 | −0.055 (11) | 0.226 (3) | −0.116 (5) | 0.073 (15)* | |
H532 | −0.394 (14) | 0.237 (3) | −0.039 (6) | 0.103 (19)* | |
H533 | −0.024 (13) | 0.214 (3) | 0.062 (5) | 0.089 (17)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N4 | 0.050 (2) | 0.0373 (18) | 0.055 (2) | 0.0011 (17) | 0.0137 (17) | 0.0012 (17) |
C1 | 0.050 (3) | 0.045 (3) | 0.056 (3) | −0.002 (2) | 0.013 (2) | 0.000 (2) |
C2 | 0.058 (3) | 0.056 (3) | 0.046 (2) | 0.001 (2) | 0.008 (2) | 0.003 (2) |
C3 | 0.060 (3) | 0.048 (3) | 0.051 (3) | 0.009 (2) | 0.011 (2) | 0.010 (2) |
C5 | 0.051 (2) | 0.033 (2) | 0.055 (3) | 0.0051 (18) | 0.017 (2) | 0.0039 (19) |
C11 | 0.044 (2) | 0.035 (2) | 0.043 (2) | 0.0039 (17) | 0.0174 (18) | 0.0000 (17) |
C31 | 0.046 (2) | 0.042 (2) | 0.048 (2) | 0.001 (2) | 0.0163 (18) | 0.002 (2) |
C51 | 0.048 (2) | 0.037 (2) | 0.049 (2) | 0.0013 (18) | 0.0178 (19) | 0.0022 (18) |
C53 | 0.070 (4) | 0.038 (3) | 0.080 (4) | 0.002 (2) | 0.016 (3) | 0.007 (3) |
N4—C5 | 1.312 (5) | C11—C11i | 1.416 (4) |
N4—C31 | 1.393 (5) | C11—C51i | 1.405 (6) |
C1—C2 | 1.383 (6) | C1—H1 | 0.99 (5) |
C1—C51i | 1.396 (5) | C2—H2 | 0.99 (5) |
C2—C3 | 1.383 (7) | C3—H3 | 0.94 (4) |
C3—C31 | 1.383 (5) | C53—H531 | 1.02 (5) |
C5—C51 | 1.451 (5) | C53—H532 | 1.01 (6) |
C5—C53 | 1.506 (6) | C53—H533 | 0.96 (5) |
C11—C31 | 1.417 (6) | ||
C5—N4—C31 | 118.2 (3) | C5—C51—C11i | 117.1 (3) |
C2—C1—C51i | 119.8 (4) | C1i—C51—C11i | 118.3 (3) |
C1—C2—C3 | 121.4 (4) | C2—C1—H1 | 123 (3) |
C2—C3—C31 | 121.1 (4) | C51i—C1—H1 | 117 (3) |
N4—C5—C51 | 124.1 (3) | C1—C2—H2 | 120 (3) |
N4—C5—C53 | 116.7 (3) | C3—C2—H2 | 119 (3) |
C51—C5—C53 | 119.3 (4) | C2—C3—H3 | 115 (3) |
C11i—C11—C31 | 117.9 (4) | C31—C3—H3 | 124 (3) |
C31—C11—C51i | 122.0 (3) | C5—C53—H531 | 109 (3) |
C11i—C11—C51i | 120.1 (4) | C5—C53—H532 | 110 (3) |
N4—C31—C3 | 120.0 (4) | C5—C53—H533 | 106 (3) |
N4—C31—C11 | 122.6 (3) | H531—C53—H532 | 110 (4) |
C3—C31—C11 | 117.4 (4) | H531—C53—H533 | 109 (4) |
C1i—C51—C5 | 124.6 (3) | H532—C53—H533 | 112 (4) |
C31—N4—C5—C53 | 178.8 (4) | N4—C5—C51—C11i | −0.2 (6) |
C5—N4—C31—C11 | 0.0 (19) | N4—C5—C51—C1i | −179.9 (5) |
C5—N4—C31—C3 | 179.6 (4) | C51i—C11—C31—N4 | 179.7 (4) |
C31—N4—C5—C51 | −0.2 (6) | C11i—C11—C31—N4 | 0.5 (5) |
C51i—C1—C2—C3 | −0.1 (6) | C11i—C11—C31—C3 | −179.1 (4) |
C2—C1—C51i—C5i | 179.8 (4) | C31—C11—C11i—C31i | −180 (2) |
C2—C1—C51i—C11 | −0.4 (6) | C51i—C11—C11i—C51 | −180.0 (16) |
C1—C2—C3—C31 | 0.6 (6) | C31—C11—C51i—C1 | 0.4 (6) |
C2—C3—C31—N4 | 179.8 (4) | C31—C11—C51i—C5i | −179.8 (3) |
C2—C3—C31—C11 | −0.5 (6) | C11i—C11—C51i—C1 | 179.6 (4) |
C53—C5—C51—C1i | 1.2 (6) | C51i—C11—C31—C3 | 0.0 (12) |
C53—C5—C51—C11i | −179.1 (4) | C31—C11—C11i—C51 | −0.8 (5) |
Symmetry code: (i) −x, −y+1, −z. |
C16H12N2 | F(000) = 244 |
Mr = 232.29 | Dx = 1.369 Mg m−3 |
Monoclinic, C2/m | Cu Kα radiation, λ = 1.54184 Å |
Hall symbol: -C 2y | Cell parameters from 21 reflections |
a = 12.4968 (3) Å | θ = 10.5–42.6° |
b = 11.4751 (4) Å | µ = 0.60 mm−1 |
c = 3.9615 (3) Å | T = 295 K |
β = 96.80 (1)° | Prism, colourless |
V = 564.09 (5) Å3 | 0.32 × 0.14 × 0.11 mm |
Z = 2 |
Enraf-Nonius CAD4 diffractometer | Rint = 0.043 |
Radiation source: fine-focus sealed tube | θmax = 65.2°, θmin = 5.3° |
Graphite monochromator | h = 0→4 |
ω/2θ scans | k = −9→9 |
1108 measured reflections | l = −9→9 |
508 independent reflections | 3 standard reflections every 44 reflections |
322 reflections with I > 2σ(I) |
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)] = 0.041 | Hydrogen site location: difmap,geom |
wR(F2) = 0.138 | All H-atom parameters refined |
S = 0.90 | Calculated w = 1/[σ2(Fo2) + (0.0966P)2 + 0.0939P] where P = (Fo2 + 2Fc2)/3 |
508 reflections | (Δ/σ)max = 0.005 |
70 parameters | Δρmax = 0.19 e Å−3 |
0 restraints | Δρmin = −0.12 e Å−3 |
15 constraints |
C16H12N2 | V = 564.09 (5) Å3 |
Mr = 232.29 | Z = 2 |
Monoclinic, C2/m | Cu Kα radiation |
a = 12.4968 (3) Å | µ = 0.60 mm−1 |
b = 11.4751 (4) Å | T = 295 K |
c = 3.9615 (3) Å | 0.32 × 0.14 × 0.11 mm |
β = 96.80 (1)° |
Enraf-Nonius CAD4 diffractometer | 322 reflections with I > 2σ(I) |
1108 measured reflections | Rint = 0.043 |
508 independent reflections | 3 standard reflections every 44 reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.138 | All H-atom parameters refined |
S = 0.90 | Δρmax = 0.19 e Å−3 |
508 reflections | Δρmin = −0.12 e Å−3 |
70 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 on F2 for ALL reflections except for 0 with very negative F2 or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating R-factor-obs 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 | Occ. (<1) | |
N4 | 0.0454 (9) | 0.2129 (8) | 0.940 (3) | 0.067 (5) | 0.5 |
C1 | 0.20167 (13) | 0.10471 (15) | 0.7671 (4) | 0.0577 (6) | |
C2 | 0.25315 (17) | 0.00000 | 0.7111 (6) | 0.0574 (8) | 0.5 |
C4 | 0.0510 (9) | 0.2091 (11) | 0.953 (4) | 0.064 (5) | 0.5 |
C11 | 0.05070 (15) | 0.00000 | 0.9407 (5) | 0.0456 (7) | 0.5 |
C21 | 0.3642 (2) | 0.00000 | 0.5974 (9) | 0.0764 (11) | 0.5 |
C51 | 0.10093 (12) | 0.10675 (14) | 0.8818 (4) | 0.0512 (6) | |
H1 | 0.2365 (13) | 0.1769 (19) | 0.727 (5) | 0.075 (5)* | |
H4 | 0.073 (3) | 0.286 (3) | 0.892 (8) | 0.055 (9)* | 0.5 |
H211 | 0.3727 (19) | −0.064 (2) | 0.456 (7) | 0.145 (11)* | |
H212 | 0.422 (3) | 0.00000 | 0.773 (11) | 0.155 (16)* | 0.5 |
U11 | U22 | U33 | U12 | U13 | U23 | |
N4 | 0.105 (12) | 0.034 (4) | 0.060 (6) | 0.009 (4) | 0.003 (4) | −0.003 (3) |
C1 | 0.0543 (11) | 0.0636 (12) | 0.0539 (10) | −0.0104 (8) | 0.0012 (8) | 0.0054 (7) |
C2 | 0.0513 (14) | 0.0742 (16) | 0.0450 (13) | 0.0000 | −0.0009 (10) | 0.0000 |
C4 | 0.045 (8) | 0.067 (8) | 0.083 (8) | −0.015 (5) | 0.014 (4) | 0.013 (5) |
C11 | 0.0475 (12) | 0.0466 (12) | 0.0404 (11) | 0.0000 | −0.0044 (9) | 0.0000 |
C21 | 0.0547 (17) | 0.105 (2) | 0.0714 (19) | 0.0000 | 0.0157 (14) | 0.0000 |
C51 | 0.0509 (10) | 0.0516 (11) | 0.0492 (10) | −0.0019 (7) | −0.0015 (7) | 0.0013 (6) |
N4—C51 | 1.434 (10) | C11—C51 | 1.4084 (18) |
N4—H4 | 0.94 (4) | C11—C11i | 1.403 (3) |
C1—C51 | 1.388 (2) | C1—H1 | 0.96 (2) |
C1—C2 | 1.393 (2) | C4—H4 | 0.96 (4) |
C2—C21 | 1.509 (3) | C21—H211 | 0.94 (2) |
C4—C51 | 1.375 (13) | C21—H212 | 0.94 (4) |
C51—N4—H4 | 122 (2) | C4—C51—C11 | 119.1 (5) |
C2—C1—C51 | 121.36 (16) | C1—C51—C4 | 122.2 (5) |
C1—C2—C21 | 120.39 (10) | C2—C1—H1 | 119.5 (11) |
C1—C2—C1ii | 119.20 (18) | C51—C1—H1 | 119.2 (11) |
C1ii—C2—C21 | 120.39 (10) | C51—C4—H4 | 126 (2) |
C11i—C11—C51 | 119.57 (9) | C2—C21—H211 | 110.6 (15) |
C51—C11—C51ii | 120.86 (16) | C2—C21—H212 | 116 (2) |
C11i—C11—C51ii | 119.57 (9) | C2—C21—H211ii | 110.6 (15) |
N4—C51—C4 | 2.9 (8) | H211—C21—H212 | 108 (2) |
N4—C51—C11 | 118.6 (4) | H211—C21—H211ii | 103 (2) |
N4—C51—C1 | 122.8 (5) | H211ii—C21—H212 | 108 (2) |
C1—C51—C11 | 118.60 (15) | ||
C51—C1—C2—C21 | −178.0 (2) | C11i—C11—C51—C4 | 2.2 (8) |
C2—C1—C51—C4 | 177.0 (8) | C51ii—C11—C51—C1 | −0.6 (3) |
C51—C1—C2—C1ii | 0.9 (3) | C51ii—C11—C51—C4 | −177.9 (7) |
C2—C1—C51—N4 | −179.6 (6) | C51ii—C11—C51—N4 | 178.9 (5) |
C2—C1—C51—C11 | −0.2 (3) | C11i—C11—C51—N4 | −1.1 (6) |
C11i—C11—C51—C1 | 179.48 (16) |
Symmetry codes: (i) −x, y, −z+2; (ii) −x+1/2, y+1/2, −z. |
Experimental details
(DIAZA1) | (DIAZA2) | |
Crystal data | ||
Chemical formula | C16H12N2 | C16H12N2 |
Mr | 232.29 | 232.29 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, C2/m |
Temperature (K) | 295 | 295 |
a, b, c (Å) | 4.0246 (5), 15.5147 (5), 9.1453 (9) | 12.4968 (3), 11.4751 (4), 3.9615 (3) |
β (°) | 101.23 (1) | 96.80 (1) |
V (Å3) | 560.1 (1) | 564.09 (5) |
Z | 2 | 2 |
Radiation type | Cu Kα | Cu Kα |
µ (mm−1) | 0.60 | 0.60 |
Crystal size (mm) | 0.3 × 0.04 × 0.04 | 0.32 × 0.14 × 0.11 |
Data collection | ||
Diffractometer | Enraf-Nonius CAD4 diffractometer | Enraf-Nonius CAD4 diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1297, 1135, 425 | 1108, 508, 322 |
Rint | 0.036 | 0.043 |
(sin θ/λ)max (Å−1) | 0.624 | 0.589 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.427, 0.63 | 0.041, 0.138, 0.90 |
No. of reflections | 660 | 508 |
No. of parameters | 106 | 70 |
H-atom treatment | All H-atom parameters refined | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.14, −0.15 | 0.19, −0.12 |
Computer programs: EXPRESS-CAD4 (Enraf Nonius 1992) software, CAD4 (Enraf Nonius 1988) software <CELDIM> routine, HELENA (Spek, 1994), SHELXS86 (Sheldrick, 1985, 1990), SHELXS86 (Sheldrick, 1990), SHELX76 (Sheldrick, 1976), SHELXL93 (Sheldrick, 1993), PLATON93 (Spek, 1982, 1990) & ORTEP (Johnson, 1965), PLUTON93 (Spek 1991), PLATON93 (Spek 1982, 1990).