Four datasets on [2,2]-paracyclophane were collected in-house and at the Advanced Photon Source at two different temperatures for charge density investigation. Global data quality indicators such as high resolution, high I/σ(I) values, low merging R values and high multiplicity were matched for all four datasets. The structural parameters did not show significant differences, but the synchrotron data depicted deficiencies in the topological analysis. In retrospect these deficiencies could be assigned to the low quality of the innermost data, which could have been identified by e.g. merging R values for only these reflections. In the multipole refinement these deficiencies could be monitored using DRK-plot and residual density analysis. In this particular example the differences in the topological parameters were relatively small but significant.
Supporting information
CCDC references: 1036458; 1036459; 1036460; 1036461
For all compounds, data collection: ApexII; cell refinement: SAINT V8.30C; data reduction: SAINT V8.30C. Program(s) used to solve structure: SHELXS in SHELXTL Version 2008/4 for aps1, mo2, aps2. For all compounds, program(s) used to refine structure: Volkov et al., (2006); molecular graphics: Volkov et al., (2006); software used to prepare material for publication: Volkov et al., (2006).
(para) [2,2]-Paracyclophane
top
Crystal data top
C16H16 | F(000) = 224 |
Mr = 208.29 | Dx = 1.278 Mg m−3 |
Tetragonal, P4n2 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.6726 (1) Å | µ = 0.07 mm−1 |
c = 9.1910 (2) Å | T = 15 K |
V = 541.06 (2) Å3 | Block, colorless |
Z = 2 | 0.23 × 0.20 × 0.16 mm |
Data collection top
APEX II CCD diffractometer | 4297 reflections with I > 2σ(I) |
Radiation source: Mo TXS | Rint = 0.021 |
ω scans | θmax = 62.7°, θmin = 3.5° |
Absorption correction: multi-scan SADABS-2014/2,Sheldrick | h = −19→15 |
Tmin = 0.975, Tmax = 1.000 | k = −19→18 |
32293 measured reflections | l = −22→22 |
4407 independent reflections | |
Refinement top
Refinement on F2 | 4389 reflections |
Least-squares matrix: full | 118 parameters |
R[F2 > 2σ(F2)] = 0.013 | 0 restraints |
wR(F2) = 0.032 | w2 = q/[s2(Fo2) + (0.01 P)2 + 0.01 P + 0.00 + 0.00 sin(th)]
where P = (0.3333 Fo2 + 0.6667 Fc2)
q = 1.0 |
S = 2.13 | (Δ/σ)max < 0.001 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C(1) | 0.123242 (15) | 0.633427 (14) | 0.903323 (10) | 0.006 | |
C(2) | 0.250923 (15) | 0.535568 (15) | 0.831235 (12) | 0.007 | |
C(3) | 0.061568 (16) | 0.583716 (15) | 1.053601 (12) | 0.008 | |
C(4) | 0.255107 (15) | 0.529904 (15) | 0.679554 (12) | 0.007 | |
H(2) | 0.32976 | 0.446145 | 0.892893 | 0.008193 (18) | |
H(4) | 0.339203 | 0.440489 | 0.622937 | 0.008169 (18) | |
H(31) | −0.015627 | 0.689588 | 1.098005 | 0.01022 (2) | |
H(32) | 0.168701 | 0.555101 | 1.126859 | 0.01022 (2) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C(1) | 0.00604 (3) | 0.00599 (3) | 0.00614 (2) | −0.00027 (2) | 0.00004 (2) | −0.00009 (2) |
C(2) | 0.00600 (3) | 0.00707 (3) | 0.00738 (3) | 0.00102 (2) | −0.00052 (2) | 0.00029 (2) |
C(3) | 0.00914 (4) | 0.00849 (3) | 0.00595 (3) | −0.00218 (3) | 0.00008 (2) | −0.00063 (2) |
C(4) | 0.00601 (3) | 0.00702 (3) | 0.00742 (3) | 0.00106 (2) | 0.00039 (2) | −0.00042 (2) |
Geometric parameters (Å, º) top
C(1)—C(2) | 1.4009 (2) | C(2)—H(2) | 1.0760 (1) |
C(1)—C(3) | 1.5090 (2) | C(3)—H(31) | 1.0850 (1) |
C(1)—C(4)i | 1.4017 (2) | C(3)—H(32) | 1.0850 (1) |
C(2)—C(4) | 1.3952 (1) | C(4)—H(4) | 1.0760 (1) |
| | | |
C(2)—C(1)—C(3) | 121.113 (10) | C(1)—C(3)—H(31) | 109.040 (10) |
C(2)—C(1)—C(4)i | 117.210 (9) | C(1)—C(3)—H(32) | 112.432 (10) |
C(3)—C(1)—C(4)i | 120.368 (10) | H(31)—C(3)—H(32) | 109.368 (9) |
C(1)—C(2)—C(4) | 120.358 (10) | C(1)i—C(4)—C(2) | 120.783 (11) |
C(1)—C(2)—H(2) | 119.064 (10) | C(1)i—C(4)—H(4) | 117.539 (10) |
C(4)—C(2)—H(2) | 119.570 (11) | C(2)—C(4)—H(4) | 121.125 (11) |
Symmetry code: (i) y−1/2, x+1/2, −z+3/2. |
(aps1) [2,2]-Paracyclophane
top
Crystal data top
C16H16 | F(000) = 224 |
Mr = 208.29 | Dx = 1.282 Mg m−3 |
Tetragonal, P4n2 | Synchrotron radiation, λ = 0.3936 Å |
a = 7.6619 (1) Å | µ = 0.07 mm−1 |
c = 9.1830 (2) Å | T = 15 K |
V = 539.09 (2) Å3 | Block, colorless |
Z = 2 | 0.12 × 0.11 × 0.10 mm |
Data collection top
ApexII CCD diffractometer | 4303 reflections with I > 2σ(I) |
Radiation source: 15-ID-B,APS | Rint = 0.056 |
phi scans | θmax = 29.4°, θmin = 1.9° |
Absorption correction: multi-scan SADABS-2014/2,Sheldrick | h = −14→19 |
Tmin = 0.936, Tmax = 1.000 | k = −14→18 |
41593 measured reflections | l = −22→22 |
4407 independent reflections | |
Refinement top
Refinement on F2 | 4388 reflections |
Least-squares matrix: full | 118 parameters |
R[F2 > 2σ(F2)] = 0.017 | 0 restraints |
wR(F2) = 0.035 | w2 = q/[s2(Fo2) + (0.01 P)2 + 0.00 P + 0.00 + 0.00 sin(th)]
where P = (0.3333 Fo2 + 0.6667 Fc2)
q = 1.0 |
S = 1.36 | (Δ/σ)max < 0.001 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C(1) | 0.123238 (14) | 0.633459 (13) | 0.903296 (9) | 0.006 | |
C(2) | 0.250865 (13) | 0.535576 (14) | 0.831254 (11) | 0.007 | |
C(3) | 0.061543 (15) | 0.583712 (15) | 1.053621 (10) | 0.008 | |
C(4) | 0.255142 (13) | 0.529920 (14) | 0.679587 (11) | 0.007 | |
H(2) | 0.326973 | 0.442252 | 0.891537 | 0.008122 (18) | |
H(4) | 0.342341 | 0.440429 | 0.626098 | 0.008119 (17) | |
H(31) | −0.015446 | 0.686262 | 1.103749 | 0.01013 (2) | |
H(32) | 0.172274 | 0.554779 | 1.123202 | 0.01013 (2) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C(1) | 0.00596 (3) | 0.00588 (3) | 0.00599 (2) | −0.00034 (2) | 0.000035 (18) | −0.000110 (18) |
C(2) | 0.00590 (3) | 0.00688 (3) | 0.00717 (2) | 0.00098 (2) | −0.000495 (18) | 0.000362 (19) |
C(3) | 0.00896 (3) | 0.00827 (3) | 0.00570 (2) | −0.00212 (3) | 0.00007 (2) | −0.00060 (2) |
C(4) | 0.00585 (3) | 0.00689 (3) | 0.00727 (2) | 0.00102 (2) | 0.000398 (19) | −0.00045 (2) |
Geometric parameters (Å, º) top
C(1)—C(2) | 1.3987 (2) | C(2)—H(2) | 1.0760 (1) |
C(1)—C(3) | 1.5081 (1) | C(3)—H(31) | 1.0850 (1) |
C(1)—C(4)i | 1.3999 (2) | C(3)—H(32) | 1.0850 (1) |
C(2)—C(4) | 1.3938 (1) | C(4)—H(4) | 1.0760 (1) |
| | | |
C(2)—C(1)—C(3) | 121.102 (9) | C(1)—C(3)—H(31) | 112.070 (9) |
C(2)—C(1)—C(4)i | 117.195 (8) | C(1)—C(3)—H(32) | 110.219 (9) |
C(3)—C(1)—C(4)i | 120.391 (9) | H(31)—C(3)—H(32) | 108.858 (8) |
C(1)—C(2)—C(4) | 120.380 (9) | C(1)i—C(4)—C(2) | 120.780 (9) |
C(1)—C(2)—H(2) | 119.463 (9) | C(1)i—C(4)—H(4) | 119.393 (9) |
C(4)—C(2)—H(2) | 118.730 (10) | C(2)—C(4)—H(4) | 119.377 (10) |
Symmetry code: (i) y−1/2, x+1/2, −z+3/2. |
(mo2) [2,2]-Paracyclophane
top
Crystal data top
C16H16 | F(000) = 224 |
Mr = 208.29 | Dx = 1.278 Mg m−3 |
Tetragonal, P4n2 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.6761 (1) Å | µ = 0.07 mm−1 |
c = 9.1966 (2) Å | T = 35 K |
V = 541.89 (2) Å3 | Block, colorless |
Z = 2 | 0.23 × 0.20 × 0.16 mm |
Data collection top
APEX II CCD diffractometer | 3763 reflections with I > 2σ(I) |
Radiation source: Mo TXS | Rint = 0.017 |
ω scans | θmax = 57.9°, θmin = 3.5° |
Absorption correction: multi-scan SADABS-2014/2,Sheldrick | h = −18→17 |
Tmin = 0.975, Tmax = 1.000 | k = −18→17 |
34569 measured reflections | l = −21→19 |
3834 independent reflections | |
Refinement top
Refinement on F2 | 3822 reflections |
Least-squares matrix: full | 118 parameters |
R[F2 > 2σ(F2)] = 0.012 | 0 restraints |
wR(F2) = 0.027 | w2 = q/[s2(Fo2) + (0.01 P)2 + 0.01 P + 0.00 + 0.00 sin(th)]
where P = (0.3333 Fo2 + 0.6667 Fc2)
q = 1.0 |
S = 2.78 | (Δ/σ)max < 0.001 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C(1) | 0.123525 (14) | 0.633022 (14) | 0.903242 (11) | 0.008 | |
C(2) | 0.250907 (14) | 0.535369 (15) | 0.830826 (12) | 0.009 | |
C(3) | 0.062172 (16) | 0.583105 (16) | 1.053466 (12) | 0.011 | |
C(4) | 0.254854 (14) | 0.530090 (14) | 0.679214 (12) | 0.009 | |
H(2) | 0.328875 | 0.444553 | 0.891721 | 0.01056 (2) | |
H(4) | 0.339671 | 0.441257 | 0.622827 | 0.01054 (2) | |
H(31) | −0.015176 | 0.688054 | 1.099047 | 0.01315 (3) | |
H(32) | 0.16878 | 0.552875 | 1.126708 | 0.01315 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C(1) | 0.00781 (3) | 0.00781 (3) | 0.00852 (3) | −0.00069 (2) | −0.00012 (2) | −0.00024 (2) |
C(2) | 0.00743 (3) | 0.00872 (3) | 0.01042 (3) | 0.00106 (2) | −0.00084 (2) | 0.00044 (2) |
C(3) | 0.01232 (4) | 0.01174 (4) | 0.00823 (3) | −0.00343 (3) | 0.00007 (3) | −0.00093 (3) |
C(4) | 0.00732 (3) | 0.00875 (3) | 0.01054 (3) | 0.00112 (2) | 0.00071 (2) | −0.00068 (2) |
Geometric parameters (Å, º) top
C(1)—C(2) | 1.4005 (2) | C(2)—H(2) | 1.0760 (1) |
C(1)—C(3) | 1.5091 (2) | C(3)—H(31) | 1.0850 (1) |
C(1)—C(4)i | 1.4014 (2) | C(3)—H(32) | 1.0850 (1) |
C(2)—C(4) | 1.3952 (1) | C(4)—H(4) | 1.0760 (1) |
| | | |
C(2)—C(1)—C(3) | 121.153 (11) | C(1)—C(3)—H(31) | 109.631 (10) |
C(2)—C(1)—C(4)i | 117.204 (9) | C(1)—C(3)—H(32) | 112.785 (10) |
C(3)—C(1)—C(4)i | 120.338 (11) | H(31)—C(3)—H(32) | 109.370 (10) |
C(1)—C(2)—C(4) | 120.392 (10) | C(1)i—C(4)—C(2) | 120.756 (10) |
C(1)—C(2)—H(2) | 119.182 (10) | C(1)i—C(4)—H(4) | 117.861 (10) |
C(4)—C(2)—H(2) | 119.290 (11) | C(2)—C(4)—H(4) | 120.875 (11) |
Symmetry code: (i) y−1/2, x+1/2, −z+3/2. |
(aps2) [2,2]-Paracyclophane
top
Crystal data top
C16H16 | F(000) = 224 |
Mr = 208.29 | Dx = 1.282 Mg m−3 |
Tetragonal, P4n2 | Synchrotron radiation, λ = 0.3936 Å |
a = 7.6648 (1) Å | µ = 0.07 mm−1 |
c = 9.1858 (2) Å | T = 35 K |
V = 539.66 (2) Å3 | Block, colorless |
Z = 2 | 0.12 × 0.11 × 0.10 mm |
Data collection top
ApexII CCD diffractometer | 3418 reflections with I > 2σ(I) |
Radiation source: 15-ID-B, APS | Rint = 0.043 |
phi scans | θmax = 27.2°, θmin = 1.9° |
Absorption correction: multi-scan SADABS-2014/2,Sheldrick | h = −17→13 |
Tmin = 0.924, Tmax = 1.000 | k = −11→17 |
29629 measured reflections | l = −21→15 |
3544 independent reflections | |
Refinement top
Refinement on F2 | 3525 reflections |
Least-squares matrix: full | 118 parameters |
R[F2 > 2σ(F2)] = 0.016 | 0 restraints |
wR(F2) = 0.035 | w2 = q/[s2(Fo2) + (0.02 P)2 + 0.00 P + 0.00 + 0.00 sin(th)]
where P = (0.3333 Fo2 + 0.6667 Fc2)
q = 1.0 |
S = 1.80 | (Δ/σ)max < 0.001 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C(1) | 0.123500 (16) | 0.633105 (16) | 0.903241 (11) | 0.008 | |
C(2) | 0.250905 (16) | 0.535411 (17) | 0.830887 (14) | 0.009 | |
C(3) | 0.062107 (19) | 0.583167 (18) | 1.053483 (12) | 0.011 | |
C(4) | 0.254879 (16) | 0.530092 (16) | 0.679265 (14) | 0.009 | |
H(2) | 0.322821 | 0.43991 | 0.892288 | 0.01074 (2) | |
H(4) | 0.34141 | 0.443434 | 0.622 | 0.01072 (2) | |
H(31) | 0.168969 | 0.550253 | 1.125917 | 0.01336 (3) | |
H(32) | −0.015825 | 0.686984 | 1.100587 | 0.01336 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C(1) | 0.00784 (4) | 0.00787 (4) | 0.00858 (3) | −0.00067 (3) | −0.00004 (3) | −0.00025 (3) |
C(2) | 0.00751 (4) | 0.00880 (4) | 0.01033 (4) | 0.00105 (3) | −0.00085 (3) | 0.00045 (3) |
C(3) | 0.01230 (4) | 0.01167 (4) | 0.00828 (3) | −0.00328 (3) | 0.00008 (3) | −0.00095 (3) |
C(4) | 0.00740 (4) | 0.00876 (4) | 0.01055 (4) | 0.00107 (3) | 0.00071 (3) | −0.00065 (3) |
Geometric parameters (Å, º) top
C(1)—C(2) | 1.3986 (2) | C(2)—H(2) | 1.0760 (1) |
C(1)—C(3) | 1.5075 (2) | C(3)—H(31) | 1.0850 (1) |
C(1)—C(4)i | 1.3993 (2) | C(3)—H(32) | 1.0850 (2) |
C(2)—C(4) | 1.3937 (2) | C(4)—H(4) | 1.0760 (1) |
| | | |
C(2)—C(1)—C(3) | 121.135 (12) | C(1)—C(3)—H(31) | 112.631 (11) |
C(2)—C(1)—C(4)i | 117.192 (9) | C(1)—C(3)—H(32) | 110.531 (12) |
C(3)—C(1)—C(4)i | 120.363 (12) | H(31)—C(3)—H(32) | 109.973 (10) |
C(1)—C(2)—C(4) | 120.386 (11) | C(1)i—C(4)—C(2) | 120.777 (11) |
C(1)—C(2)—H(2) | 118.218 (11) | C(1)i—C(4)—H(4) | 117.529 (11) |
C(4)—C(2)—H(2) | 119.520 (12) | C(2)—C(4)—H(4) | 121.337 (12) |
Symmetry code: (i) y−1/2, x+1/2, −z+3/2. |