organic compounds
(1RS,2RS)-N,N′-Bis(4-nitrophenylmethylene)cyclohexane-1,2-diamine: complex sheets built from C—H⋯O and C—H⋯π(arene) hydrogen bonds
aSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland, bDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and cInstituto de Química, Departamento de Química Inorgânica, Universidade Federal do Rio de Janeiro, 21945-970 Rio de Janeiro, RJ, Brazil
*Correspondence e-mail: cg@st-andrews.ac.uk
The racemic title compound, C20H20N4O4, crystallizes with Z′ = 2 in the P21/c. Each independent molecule exhibits approximate twofold rotation symmetry, but conformational differences between the molecules preclude any higher symmetry. The molecules are linked into complex sheets by a combination of four C—H⋯O hydrogen bonds and two C—H⋯π(arene) hydrogen bonds.
Comment
We have recently reported the structure of R,2R)-N,N′-bis(4-nitrophenylmethylene)cyclohexane-1,2-diamine, (I) (Glidewell et al., 2005). This compound crystallizes with Z′ = 2 in C2, and the independent molecules both exhibit approximate but not crystallographic twofold rotational symmetry. There is a single C—H⋯O hydrogen bond linking the two independent molecules, but there are no other direction-specific interactions in the structure. In this paper, we report the structure of another isomeric form, the racemic 1RS,2RS compound, (II).
(1Compound (II) crystallizes in the centrosymmetric P21/c with Z′ = 2 (Fig. 1). In the selected each of the molecules has the 1R,2R configuration, but the accommodates equal numbers of 1R,2R and 1S,2S enantiomers, as required by the racemic nature of (II). In each of the molecules, the cyclohexane ring adopts a chain conformation, with the pendent substituent units in equatorial positions. Each molecule adopts approximate, but not exact, twofold rotational symmetry, as shown by the leading torsion angles (Table 1), and the differences between corresponding values for the two molecules are sufficient to preclude any additional symmetry. The dihedral angles between the nitro groups containing N14X and N24X (X = A or B) and their adjacent aryl rings are 9.7 (2) and 3.3 (2)° in molecule A, and 16.0 (2) and 12.0 (2)° in molecule B.
The molecules of (II) are linked into complex sheets by a combination of four C—H⋯O hydrogen bonds and two C—H⋯π(arene) hydrogen bonds (Table 2), and the formation of the sheet is best approached in terms of the component sub-structures, each of which depends on a small subset of the hydrogen bonds.
The basic building blocks within the structure of (II) are two centrosymmetric R22(32) dimers, formed by molecules of types A and B, respectively; for the selected the type A dimer is centred at (0, 0, ) and the type B dimer is centred at (, , ). The overall structure can then be envisaged in terms of series of chains which result from the linking of these dimers. There are four such chains, two of which incorporate just one type of dimer, A or B, and the other two of which incorporate both types of dimer, A and B.
Within the A acts as hydrogen-bond donor to nitro atom O15B, and propagation by inversion of this hydrogen bond links the two types of R22(32) dimer into a chain of rings running parallel to the [110] direction (Fig. 2). In addition, aryl atom C27B, which lies in the type B dimer centred at (, , ), acts as hydrogen-bond donor to atom O24A at (x, 1 + y, z), which lies in the type A dimer centred at (0, 1, ), and propagation of this interaction, again by inversion, links the R22(32) dimers into another chain of rings, this time running parallel to the [10] direction (Fig. 3).
aryl atom C22Two further chains are generated by the linking of R22(32) dimers by means of C—H⋯π(arene) hydrogen bonds. These chains differ from those generated by C—H⋯O hydrogen bonds (Figs. 2 and 3) only in that each type of chain involving C—H⋯π(arene) hydrogen bonds is built from just one type of molecule. In the first of these, atom C4A in the type A molecule at (x, y, z), part of the type A dimer centred at (0, 0, ), acts as hydrogen-bond donor, via atom H41A, to the C21A–C26A ring of the type A molecule at (x, 1 + y, z), itself part of the type A dimer centred at (0, 1, ). Hence, a chain of dimers is formed along (0, y, ) (Fig. 4). In the second chain of this type, atom C5B in the molecule at (x, y, z), which is part of the type B dimer centred at (, , ), acts as hydrogen-bond donor, via atom H51B, to the C11B–C16B ring in the type B molecule at (x, 1 + y, z), which forms part of the type B dimer centred at (, , ), so forming a chain of dimers along (, y, ) (Fig. 5).
The combination of the [010], [110] and [10] chains (Figs. 2–5) is sufficient to produce an (001) sheet lying in the domain 0.14 < z < 0.86 and generated by inversion centres at z = . A second such sheet, related to the first by the translational symmetry, is generated by the centres of inversion at z = 1.0. There is one rather weak interaction between molecules in adjacent sheets, an approximately perpendicular nitro–nitro interaction involving type B molecules only. Atom O15B in the type B molecule at (x, y, z), part of the sheet centred at z = , makes a short contact with atom O25B in the type B molecule at (x, − y, + z), part of the sheet centred at z = 1.0, with O15B⋯O25Bi = 2.873 (2) Å, N14B—O15B⋯O25Bi = 86.4 (2)° and O15B⋯O25Bi—N24Bi = 135.9 (3)° [symmetry code: (i) x, − y, + z]. However, there are no significant π–π stacking interactions.
Experimental
A mixture of racemic trans-cyclohexane-1,2-diamine (0.228 g, 2 mmol) and 4-nitrobenzaldehyde (0.604 g, 4 mmol) in MeOH (30 ml) was heated under reflux for 30 min. The solution was then cooled to ambient temperature and the solvent was removed. The resulting solid was recrystallized from aqueous ethanol (1:1 v/v).
Crystal data
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Data collection
Refinement
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The P21/c was uniquely assigned from the All H atoms were located in difference maps and were then treated as riding atoms, with C—H distances of 0.95 (aromatic and –CH=), 0.99 (CH2) or 1.00 Å (aliphatic CH), and with Uiso(H) = 1.2Ueq(C).
Data collection: COLLECT (Hooft, 1999; Nonius, 1997); cell DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).
Supporting information
10.1107/S0108270105024443/sk1864sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S0108270105024443/sk1864Isup2.hkl
A mixture of racemic trans-1,2-diaminocyclohexane (0.228 g, 2 mmol) and 4-nitrobenzaldehyde (0.604 g, 4 mmol) in MeOH (30 ml) was heated under reflux for 30 min. The solution was then cooled to ambient temperature and the solvent was removed. The resulting solid was recrystallized from aqueous ethanol [Solvent ratio?].
The ═), 0.99 (CH2) or 1.00 Å (aliphatic CH), and with Uiso(H) = 1.2Ueq(C).
P21/c was uniquely assigned from the All H atoms were located in difference maps and were then treated as riding atoms, with C—H distances of 0.95 (aromatic and –CHData collection: COLLECT (Hooft, 1999; Nonius, 1997); cell
DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).Fig. 1. The (1R,2R) enantiomers of the two independent molecules in compound (II), showing the atom-labelling scheme. (a) The type A molecule. (b) The type B molecule. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. | |
Fig. 2. A stereoview of part of the crystal structure of compound (II), showing the linking of the R22(32) dimers of types A and B into a chain along [110]. For the sake of clarity, H atoms not involved in the motifs shown have been omitted. | |
Fig. 3. A stereoview of part of the crystal structure of compound (II), showing the linking of the R22(32) dimers of types A and B into a chain along [110]. For the sake of clarity, H atoms not involved in the motifs shown have been omitted. | |
Fig. 4. A stereoview of part of the crystal structure of compound (II), showing the linking of R22(32) dimers of type A only into an [010] chain along (0, y, 1/2). For the sake of clarity, H atoms not involved in the motifs shown have been omitted. | |
Fig. 5. A stereoview of part of the crystal structure of compound (II), showing the linking of R22(32) dimers of type B only into an [010] chain along (1/2, y, 1/2). For the sake of clarity, H atoms not involved in the motifs shown have been omitted. |
C20H20N4O4 | F(000) = 1600 |
Mr = 380.40 | Dx = 1.339 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 8633 reflections |
a = 22.4197 (5) Å | θ = 3.1–27.5° |
b = 8.9687 (2) Å | µ = 0.10 mm−1 |
c = 21.2076 (4) Å | T = 120 K |
β = 117.7179 (11)° | Block, yellow |
V = 3774.99 (14) Å3 | 0.40 × 0.40 × 0.20 mm |
Z = 8 |
Bruker Nonius KappaCCD area-detector diffractometer | 8633 independent reflections |
Radiation source: Bruker Nonius FR91 rotating anode | 6275 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.043 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
ϕ and ω scans | h = −29→29 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −10→11 |
Tmin = 0.968, Tmax = 0.981 | l = −27→26 |
43594 measured reflections |
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0599P)2 + 1.1744P] where P = (Fo2 + 2Fc2)/3 |
8633 reflections | (Δ/σ)max < 0.001 |
505 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.29 e Å−3 |
C20H20N4O4 | V = 3774.99 (14) Å3 |
Mr = 380.40 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 22.4197 (5) Å | µ = 0.10 mm−1 |
b = 8.9687 (2) Å | T = 120 K |
c = 21.2076 (4) Å | 0.40 × 0.40 × 0.20 mm |
β = 117.7179 (11)° |
Bruker Nonius KappaCCD area-detector diffractometer | 8633 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 6275 reflections with I > 2σ(I) |
Tmin = 0.968, Tmax = 0.981 | Rint = 0.043 |
43594 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.129 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.37 e Å−3 |
8633 reflections | Δρmin = −0.29 e Å−3 |
505 parameters |
x | y | z | Uiso*/Ueq | ||
C1A | 0.12439 (8) | 0.65843 (17) | 0.57608 (8) | 0.0238 (3) | |
C2A | 0.08905 (8) | 0.64452 (17) | 0.49470 (8) | 0.0228 (3) | |
C3A | 0.10054 (8) | 0.78506 (18) | 0.46075 (8) | 0.0260 (3) | |
C4A | 0.07787 (8) | 0.92517 (18) | 0.48457 (9) | 0.0291 (4) | |
C5A | 0.11318 (9) | 0.93827 (19) | 0.56531 (9) | 0.0305 (4) | |
C6A | 0.10135 (8) | 0.79910 (19) | 0.59924 (8) | 0.0290 (4) | |
N1A | 0.10892 (6) | 0.52650 (15) | 0.60632 (7) | 0.0251 (3) | |
C17A | 0.15854 (8) | 0.45096 (18) | 0.64966 (8) | 0.0248 (3) | |
C11A | 0.15159 (8) | 0.31692 (18) | 0.68609 (8) | 0.0235 (3) | |
C12A | 0.20948 (8) | 0.2404 (2) | 0.73262 (9) | 0.0324 (4) | |
C13A | 0.20560 (9) | 0.1216 (2) | 0.77225 (9) | 0.0330 (4) | |
C14A | 0.14332 (8) | 0.08000 (17) | 0.76412 (8) | 0.0258 (3) | |
C15A | 0.08458 (8) | 0.14839 (18) | 0.71549 (8) | 0.0261 (3) | |
C16A | 0.08913 (8) | 0.26760 (18) | 0.67681 (8) | 0.0255 (3) | |
N14A | 0.13969 (8) | −0.03789 (15) | 0.81064 (7) | 0.0310 (3) | |
O14A | 0.19249 (7) | −0.08221 (15) | 0.85972 (7) | 0.0471 (4) | |
O15A | 0.08384 (7) | −0.08285 (13) | 0.79903 (6) | 0.0378 (3) | |
N2A | 0.11647 (6) | 0.51612 (14) | 0.47447 (7) | 0.0239 (3) | |
C27A | 0.07493 (8) | 0.42526 (17) | 0.43048 (8) | 0.0242 (3) | |
C21A | 0.09677 (8) | 0.29509 (18) | 0.40343 (8) | 0.0244 (3) | |
C22A | 0.16417 (8) | 0.25086 (18) | 0.43447 (9) | 0.0279 (4) | |
C23A | 0.18415 (8) | 0.13115 (18) | 0.40749 (9) | 0.0305 (4) | |
C24A | 0.13515 (8) | 0.05873 (18) | 0.34797 (9) | 0.0273 (4) | |
C25A | 0.06827 (8) | 0.09872 (18) | 0.31657 (8) | 0.0284 (4) | |
C26A | 0.04881 (8) | 0.21691 (18) | 0.34490 (8) | 0.0272 (3) | |
N24A | 0.15571 (8) | −0.06346 (16) | 0.31586 (9) | 0.0364 (4) | |
O24A | 0.21514 (7) | −0.10102 (16) | 0.34537 (9) | 0.0590 (4) | |
O25A | 0.11288 (8) | −0.12053 (15) | 0.26099 (7) | 0.0473 (4) | |
C1B | 0.40661 (8) | 1.14498 (17) | 0.48900 (8) | 0.0223 (3) | |
C2B | 0.37930 (8) | 1.16469 (17) | 0.40844 (8) | 0.0233 (3) | |
C3B | 0.40644 (8) | 1.30649 (19) | 0.39150 (8) | 0.0287 (4) | |
C4B | 0.39238 (8) | 1.44351 (18) | 0.42503 (8) | 0.0288 (4) | |
C5B | 0.42068 (8) | 1.42341 (18) | 0.50497 (8) | 0.0267 (3) | |
C6B | 0.39173 (8) | 1.28348 (18) | 0.52136 (8) | 0.0253 (3) | |
N1B | 0.37422 (6) | 1.01572 (14) | 0.50188 (6) | 0.0236 (3) | |
C17B | 0.41195 (8) | 0.92504 (17) | 0.54935 (8) | 0.0245 (3) | |
C11B | 0.38543 (8) | 0.79367 (17) | 0.56999 (8) | 0.0240 (3) | |
C12B | 0.42774 (8) | 0.72089 (18) | 0.63335 (8) | 0.0261 (3) | |
C13B | 0.40450 (8) | 0.60050 (18) | 0.65666 (8) | 0.0262 (3) | |
C14B | 0.33964 (8) | 0.55215 (17) | 0.61478 (8) | 0.0251 (3) | |
C15B | 0.29633 (8) | 0.61897 (18) | 0.55044 (8) | 0.0264 (3) | |
C16B | 0.31980 (8) | 0.74171 (18) | 0.52884 (8) | 0.0264 (3) | |
N14B | 0.31482 (7) | 0.42484 (15) | 0.64020 (7) | 0.0290 (3) | |
O14B | 0.34670 (7) | 0.38938 (14) | 0.70303 (6) | 0.0426 (3) | |
O15B | 0.26294 (6) | 0.36263 (13) | 0.59769 (7) | 0.0354 (3) | |
N2B | 0.39917 (6) | 1.03448 (15) | 0.38062 (7) | 0.0253 (3) | |
C27B | 0.35191 (8) | 0.95079 (18) | 0.33889 (8) | 0.0253 (3) | |
C21B | 0.36323 (8) | 0.81585 (18) | 0.30588 (8) | 0.0240 (3) | |
C22B | 0.42762 (8) | 0.76914 (18) | 0.32069 (8) | 0.0252 (3) | |
C23B | 0.43645 (8) | 0.64767 (18) | 0.28605 (8) | 0.0259 (3) | |
C24B | 0.37982 (8) | 0.57521 (17) | 0.23515 (8) | 0.0239 (3) | |
C25B | 0.31539 (8) | 0.61660 (19) | 0.22036 (9) | 0.0296 (4) | |
C26B | 0.30758 (8) | 0.73661 (19) | 0.25688 (9) | 0.0305 (4) | |
N24B | 0.38834 (7) | 0.45423 (15) | 0.19303 (7) | 0.0286 (3) | |
O24B | 0.44525 (6) | 0.40587 (15) | 0.21158 (7) | 0.0443 (3) | |
O25B | 0.33848 (6) | 0.41029 (14) | 0.14043 (6) | 0.0373 (3) | |
H1A | 0.1742 | 0.6637 | 0.5937 | 0.029* | |
H2A | 0.0396 | 0.6299 | 0.4772 | 0.027* | |
H31A | 0.1490 | 0.7936 | 0.4742 | 0.031* | |
H32A | 0.0752 | 0.7765 | 0.4082 | 0.031* | |
H41A | 0.0882 | 1.0141 | 0.4637 | 0.035* | |
H42A | 0.0285 | 0.9215 | 0.4669 | 0.035* | |
H51A | 0.0959 | 1.0268 | 0.5796 | 0.037* | |
H52A | 0.1621 | 0.9520 | 0.5826 | 0.037* | |
H61A | 0.0528 | 0.7907 | 0.5854 | 0.035* | |
H62A | 0.1263 | 0.8083 | 0.6517 | 0.035* | |
H17A | 0.2025 | 0.4818 | 0.6593 | 0.030* | |
H12A | 0.2520 | 0.2699 | 0.7372 | 0.039* | |
H13A | 0.2451 | 0.0698 | 0.8044 | 0.040* | |
H15A | 0.0420 | 0.1140 | 0.7088 | 0.031* | |
H16A | 0.0493 | 0.3165 | 0.6435 | 0.031* | |
H27A | 0.0281 | 0.4409 | 0.4142 | 0.029* | |
H22A | 0.1967 | 0.3035 | 0.4746 | 0.033* | |
H23A | 0.2298 | 0.0996 | 0.4290 | 0.037* | |
H25A | 0.0360 | 0.0462 | 0.2762 | 0.034* | |
H26A | 0.0027 | 0.2448 | 0.3244 | 0.033* | |
H1B | 0.4564 | 1.1284 | 0.5117 | 0.027* | |
H2B | 0.3290 | 1.1702 | 0.3853 | 0.028* | |
H31B | 0.3853 | 1.3199 | 0.3392 | 0.034* | |
H32B | 0.4557 | 1.2965 | 0.4094 | 0.034* | |
H41B | 0.4131 | 1.5323 | 0.4154 | 0.035* | |
H42B | 0.3432 | 1.4603 | 0.4033 | 0.035* | |
H51B | 0.4093 | 1.5116 | 0.5254 | 0.032* | |
H52B | 0.4704 | 1.4153 | 0.5273 | 0.032* | |
H61B | 0.3424 | 1.2949 | 0.5020 | 0.030* | |
H62B | 0.4115 | 1.2709 | 0.5736 | 0.030* | |
H17B | 0.4592 | 0.9422 | 0.5726 | 0.029* | |
H12B | 0.4728 | 0.7541 | 0.6608 | 0.031* | |
H13B | 0.4327 | 0.5526 | 0.7005 | 0.031* | |
H15B | 0.2521 | 0.5818 | 0.5222 | 0.032* | |
H16B | 0.2909 | 0.7909 | 0.4856 | 0.032* | |
H27B | 0.3070 | 0.9758 | 0.3283 | 0.030* | |
H22B | 0.4658 | 0.8214 | 0.3550 | 0.030* | |
H23B | 0.4804 | 0.6143 | 0.2968 | 0.031* | |
H25B | 0.2773 | 0.5641 | 0.1860 | 0.036* | |
H26B | 0.2637 | 0.7652 | 0.2484 | 0.037* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1A | 0.0252 (8) | 0.0229 (8) | 0.0249 (8) | 0.0012 (6) | 0.0130 (7) | 0.0035 (6) |
C2A | 0.0235 (8) | 0.0213 (8) | 0.0252 (8) | 0.0034 (6) | 0.0125 (6) | 0.0021 (6) |
C3A | 0.0302 (8) | 0.0256 (9) | 0.0258 (8) | 0.0048 (7) | 0.0160 (7) | 0.0046 (7) |
C4A | 0.0332 (9) | 0.0228 (9) | 0.0341 (9) | 0.0041 (7) | 0.0180 (7) | 0.0052 (7) |
C5A | 0.0363 (9) | 0.0227 (9) | 0.0352 (9) | 0.0018 (7) | 0.0189 (8) | −0.0023 (7) |
C6A | 0.0359 (9) | 0.0283 (9) | 0.0252 (8) | 0.0020 (7) | 0.0163 (7) | −0.0008 (7) |
N1A | 0.0290 (7) | 0.0258 (7) | 0.0223 (6) | 0.0020 (6) | 0.0134 (6) | 0.0030 (6) |
C17A | 0.0265 (8) | 0.0270 (9) | 0.0233 (8) | 0.0009 (6) | 0.0136 (7) | 0.0001 (6) |
C11A | 0.0285 (8) | 0.0232 (8) | 0.0194 (7) | 0.0021 (6) | 0.0118 (6) | −0.0014 (6) |
C12A | 0.0267 (8) | 0.0337 (10) | 0.0337 (9) | 0.0033 (7) | 0.0115 (7) | 0.0055 (7) |
C13A | 0.0302 (9) | 0.0312 (10) | 0.0308 (9) | 0.0079 (7) | 0.0084 (7) | 0.0076 (7) |
C14A | 0.0372 (9) | 0.0188 (8) | 0.0201 (7) | 0.0031 (7) | 0.0121 (7) | 0.0000 (6) |
C15A | 0.0279 (8) | 0.0249 (9) | 0.0252 (8) | −0.0009 (7) | 0.0121 (7) | −0.0002 (7) |
C16A | 0.0272 (8) | 0.0263 (9) | 0.0207 (7) | 0.0037 (7) | 0.0092 (6) | 0.0033 (6) |
N14A | 0.0449 (9) | 0.0211 (7) | 0.0260 (7) | 0.0046 (6) | 0.0156 (7) | 0.0019 (6) |
O14A | 0.0520 (8) | 0.0424 (8) | 0.0379 (7) | 0.0137 (7) | 0.0134 (7) | 0.0189 (6) |
O15A | 0.0517 (8) | 0.0291 (7) | 0.0339 (6) | −0.0054 (6) | 0.0210 (6) | 0.0021 (5) |
N2A | 0.0285 (7) | 0.0214 (7) | 0.0241 (6) | 0.0024 (5) | 0.0141 (6) | 0.0025 (5) |
C27A | 0.0260 (8) | 0.0241 (8) | 0.0246 (8) | 0.0014 (6) | 0.0135 (7) | 0.0042 (6) |
C21A | 0.0308 (8) | 0.0209 (8) | 0.0271 (8) | −0.0012 (6) | 0.0181 (7) | 0.0033 (6) |
C22A | 0.0298 (9) | 0.0238 (9) | 0.0311 (8) | −0.0040 (7) | 0.0149 (7) | −0.0024 (7) |
C23A | 0.0297 (9) | 0.0248 (9) | 0.0433 (10) | −0.0026 (7) | 0.0222 (8) | −0.0021 (7) |
C24A | 0.0394 (9) | 0.0191 (8) | 0.0352 (9) | −0.0060 (7) | 0.0273 (8) | −0.0028 (7) |
C25A | 0.0362 (9) | 0.0259 (9) | 0.0257 (8) | −0.0076 (7) | 0.0167 (7) | −0.0011 (7) |
C26A | 0.0290 (8) | 0.0270 (9) | 0.0271 (8) | −0.0017 (7) | 0.0142 (7) | 0.0036 (7) |
N24A | 0.0518 (10) | 0.0235 (8) | 0.0520 (10) | −0.0100 (7) | 0.0393 (8) | −0.0063 (7) |
O24A | 0.0492 (9) | 0.0436 (9) | 0.1044 (13) | −0.0092 (7) | 0.0527 (9) | −0.0286 (8) |
O25A | 0.0752 (10) | 0.0316 (7) | 0.0406 (7) | −0.0065 (7) | 0.0315 (8) | −0.0111 (6) |
C1B | 0.0227 (7) | 0.0229 (8) | 0.0228 (7) | −0.0018 (6) | 0.0117 (6) | −0.0008 (6) |
C2B | 0.0242 (8) | 0.0233 (8) | 0.0228 (7) | −0.0014 (6) | 0.0113 (6) | −0.0028 (6) |
C3B | 0.0320 (9) | 0.0311 (9) | 0.0245 (8) | −0.0033 (7) | 0.0145 (7) | 0.0025 (7) |
C4B | 0.0278 (8) | 0.0235 (9) | 0.0330 (9) | −0.0032 (7) | 0.0125 (7) | 0.0024 (7) |
C5B | 0.0282 (8) | 0.0227 (8) | 0.0301 (8) | −0.0035 (6) | 0.0143 (7) | −0.0048 (7) |
C6B | 0.0284 (8) | 0.0254 (9) | 0.0252 (8) | −0.0022 (6) | 0.0150 (7) | −0.0025 (7) |
N1B | 0.0288 (7) | 0.0211 (7) | 0.0239 (6) | −0.0028 (5) | 0.0148 (6) | −0.0022 (5) |
C17B | 0.0270 (8) | 0.0237 (8) | 0.0244 (8) | −0.0013 (6) | 0.0134 (7) | −0.0043 (6) |
C11B | 0.0316 (8) | 0.0189 (8) | 0.0262 (8) | 0.0018 (6) | 0.0174 (7) | −0.0024 (6) |
C12B | 0.0279 (8) | 0.0258 (9) | 0.0248 (8) | 0.0004 (7) | 0.0124 (7) | −0.0042 (7) |
C13B | 0.0345 (9) | 0.0238 (8) | 0.0205 (7) | 0.0075 (7) | 0.0128 (7) | 0.0007 (6) |
C14B | 0.0350 (9) | 0.0184 (8) | 0.0298 (8) | 0.0014 (6) | 0.0216 (7) | −0.0019 (6) |
C15B | 0.0256 (8) | 0.0241 (8) | 0.0301 (8) | 0.0008 (6) | 0.0134 (7) | −0.0033 (7) |
C16B | 0.0290 (8) | 0.0236 (8) | 0.0258 (8) | 0.0048 (6) | 0.0122 (7) | 0.0024 (7) |
N14B | 0.0395 (8) | 0.0221 (7) | 0.0309 (8) | 0.0009 (6) | 0.0209 (7) | −0.0009 (6) |
O14B | 0.0682 (9) | 0.0338 (7) | 0.0255 (6) | −0.0094 (6) | 0.0216 (6) | 0.0005 (5) |
O15B | 0.0320 (7) | 0.0281 (7) | 0.0446 (7) | −0.0025 (5) | 0.0165 (6) | 0.0030 (5) |
N2B | 0.0293 (7) | 0.0266 (7) | 0.0222 (6) | −0.0007 (6) | 0.0137 (6) | −0.0014 (5) |
C27B | 0.0266 (8) | 0.0254 (9) | 0.0260 (8) | −0.0008 (6) | 0.0140 (7) | −0.0007 (7) |
C21B | 0.0288 (8) | 0.0232 (8) | 0.0217 (7) | −0.0026 (6) | 0.0133 (7) | 0.0012 (6) |
C22B | 0.0263 (8) | 0.0277 (9) | 0.0195 (7) | −0.0031 (6) | 0.0088 (6) | −0.0018 (6) |
C23B | 0.0249 (8) | 0.0290 (9) | 0.0235 (8) | 0.0012 (6) | 0.0111 (7) | −0.0009 (7) |
C24B | 0.0325 (8) | 0.0195 (8) | 0.0218 (7) | −0.0017 (6) | 0.0144 (7) | 0.0004 (6) |
C25B | 0.0266 (8) | 0.0275 (9) | 0.0301 (8) | −0.0067 (7) | 0.0093 (7) | −0.0059 (7) |
C26B | 0.0256 (8) | 0.0278 (9) | 0.0378 (9) | −0.0025 (7) | 0.0146 (7) | −0.0049 (7) |
N24B | 0.0357 (8) | 0.0245 (7) | 0.0274 (7) | −0.0043 (6) | 0.0161 (6) | −0.0032 (6) |
O24B | 0.0364 (7) | 0.0466 (8) | 0.0480 (8) | 0.0046 (6) | 0.0181 (6) | −0.0164 (6) |
O25B | 0.0425 (7) | 0.0322 (7) | 0.0328 (6) | −0.0099 (6) | 0.0138 (6) | −0.0108 (5) |
C1A—N1A | 1.4623 (19) | C1B—N1B | 1.4596 (19) |
C1A—C6A | 1.528 (2) | C1B—C6B | 1.529 (2) |
C1A—C2A | 1.533 (2) | C1B—C2B | 1.534 (2) |
C1A—H1A | 1.00 | C1B—H1B | 1.00 |
C2A—N2A | 1.4606 (19) | C2B—N2B | 1.468 (2) |
C2A—C3A | 1.532 (2) | C2B—C3B | 1.523 (2) |
C2A—H2A | 1.00 | C2B—H2B | 1.00 |
C3A—C4A | 1.527 (2) | C3B—C4B | 1.524 (2) |
C3A—H31A | 0.99 | C3B—H31B | 0.99 |
C3A—H32A | 0.99 | C3B—H32B | 0.99 |
C4A—C5A | 1.520 (2) | C4B—C5B | 1.519 (2) |
C4A—H41A | 0.99 | C4B—H41B | 0.99 |
C4A—H42A | 0.99 | C4B—H42B | 0.99 |
C5A—C6A | 1.524 (2) | C5B—C6B | 1.525 (2) |
C5A—H51A | 0.99 | C5B—H51B | 0.99 |
C5A—H52A | 0.99 | C5B—H52B | 0.99 |
C6A—H61A | 0.99 | C6B—H61B | 0.99 |
C6A—H62A | 0.99 | C6B—H62B | 0.99 |
N1A—C17A | 1.261 (2) | N1B—C17B | 1.264 (2) |
C17A—C11A | 1.476 (2) | C17B—C11B | 1.475 (2) |
C17A—H17A | 0.95 | C17B—H17B | 0.95 |
C11A—C12A | 1.392 (2) | C11B—C12B | 1.395 (2) |
C11A—C16A | 1.392 (2) | C11B—C16B | 1.396 (2) |
C12A—C13A | 1.385 (2) | C12B—C13B | 1.386 (2) |
C12A—H12A | 0.95 | C12B—H12B | 0.95 |
C13A—C14A | 1.376 (2) | C13B—C14B | 1.375 (2) |
C13A—H13A | 0.95 | C13B—H13B | 0.95 |
C14A—C15A | 1.382 (2) | C14B—C15B | 1.390 (2) |
C14A—N14A | 1.474 (2) | C14B—N14B | 1.478 (2) |
C15A—C16A | 1.380 (2) | C15B—C16B | 1.387 (2) |
C15A—H15A | 0.95 | C15B—H15B | 0.95 |
C16A—H16A | 0.95 | C16B—H16B | 0.95 |
N14A—O14A | 1.2233 (18) | N14B—O14B | 1.2253 (18) |
N14A—O15A | 1.2266 (18) | N14B—O15B | 1.2254 (18) |
N2A—C27A | 1.262 (2) | N2B—C27B | 1.264 (2) |
C27A—C21A | 1.481 (2) | C27B—C21B | 1.478 (2) |
C27A—H27A | 0.95 | C27B—H27B | 0.95 |
C21A—C26A | 1.395 (2) | C21B—C26B | 1.391 (2) |
C21A—C22A | 1.396 (2) | C21B—C22B | 1.391 (2) |
C22A—C23A | 1.385 (2) | C22B—C23B | 1.379 (2) |
C22A—H22A | 0.95 | C22B—H22B | 0.95 |
C23A—C24A | 1.390 (2) | C23B—C24B | 1.387 (2) |
C23A—H23A | 0.95 | C23B—H23B | 0.95 |
C24A—C25A | 1.375 (2) | C24B—C25B | 1.379 (2) |
C24A—N24A | 1.473 (2) | C24B—N24B | 1.473 (2) |
C25A—C26A | 1.385 (2) | C25B—C26B | 1.384 (2) |
C25A—H25A | 0.95 | C25B—H25B | 0.95 |
C26A—H26A | 0.95 | C26B—H26B | 0.95 |
N24A—O25A | 1.2243 (19) | N24B—O25B | 1.2205 (17) |
N24A—O24A | 1.227 (2) | N24B—O24B | 1.2262 (18) |
N1A—C1A—C6A | 110.03 (12) | N1B—C1B—C6B | 109.25 (11) |
N1A—C1A—C2A | 108.91 (12) | N1B—C1B—C2B | 108.93 (12) |
C6A—C1A—C2A | 110.74 (12) | C6B—C1B—C2B | 110.42 (12) |
N1A—C1A—H1A | 109.0 | N1B—C1B—H1B | 109.4 |
C6A—C1A—H1A | 109.0 | C6B—C1B—H1B | 109.4 |
C2A—C1A—H1A | 109.0 | C2B—C1B—H1B | 109.4 |
N2A—C2A—C3A | 108.96 (11) | N2B—C2B—C3B | 109.89 (12) |
N2A—C2A—C1A | 109.10 (12) | N2B—C2B—C1B | 108.51 (12) |
C3A—C2A—C1A | 110.52 (13) | C3B—C2B—C1B | 111.26 (12) |
N2A—C2A—H2A | 109.4 | N2B—C2B—H2B | 109.0 |
C3A—C2A—H2A | 109.4 | C3B—C2B—H2B | 109.0 |
C1A—C2A—H2A | 109.4 | C1B—C2B—H2B | 109.0 |
C4A—C3A—C2A | 111.53 (12) | C2B—C3B—C4B | 111.79 (12) |
C4A—C3A—H31A | 109.3 | C2B—C3B—H31B | 109.3 |
C2A—C3A—H31A | 109.3 | C4B—C3B—H31B | 109.3 |
C4A—C3A—H32A | 109.3 | C2B—C3B—H32B | 109.3 |
C2A—C3A—H32A | 109.3 | C4B—C3B—H32B | 109.3 |
H31A—C3A—H32A | 108.0 | H31B—C3B—H32B | 107.9 |
C5A—C4A—C3A | 110.92 (13) | C5B—C4B—C3B | 110.81 (13) |
C5A—C4A—H41A | 109.5 | C5B—C4B—H41B | 109.5 |
C3A—C4A—H41A | 109.5 | C3B—C4B—H41B | 109.5 |
C5A—C4A—H42A | 109.5 | C5B—C4B—H42B | 109.5 |
C3A—C4A—H42A | 109.5 | C3B—C4B—H42B | 109.5 |
H41A—C4A—H42A | 108.0 | H41B—C4B—H42B | 108.1 |
C4A—C5A—C6A | 110.77 (14) | C4B—C5B—C6B | 110.53 (13) |
C4A—C5A—H51A | 109.5 | C4B—C5B—H51B | 109.5 |
C6A—C5A—H51A | 109.5 | C6B—C5B—H51B | 109.5 |
C4A—C5A—H52A | 109.5 | C4B—C5B—H52B | 109.5 |
C6A—C5A—H52A | 109.5 | C6B—C5B—H52B | 109.5 |
H51A—C5A—H52A | 108.1 | H51B—C5B—H52B | 108.1 |
C5A—C6A—C1A | 111.42 (12) | C5B—C6B—C1B | 111.18 (12) |
C5A—C6A—H61A | 109.3 | C5B—C6B—H61B | 109.4 |
C1A—C6A—H61A | 109.3 | C1B—C6B—H61B | 109.4 |
C5A—C6A—H62A | 109.3 | C5B—C6B—H62B | 109.4 |
C1A—C6A—H62A | 109.3 | C1B—C6B—H62B | 109.4 |
H61A—C6A—H62A | 108.0 | H61B—C6B—H62B | 108.0 |
C17A—N1A—C1A | 116.47 (13) | C17B—N1B—C1B | 116.94 (13) |
N1A—C17A—C11A | 123.16 (14) | N1B—C17B—C11B | 122.50 (14) |
N1A—C17A—H17A | 118.4 | N1B—C17B—H17B | 118.7 |
C11A—C17A—H17A | 118.4 | C11B—C17B—H17B | 118.7 |
C12A—C11A—C16A | 119.23 (15) | C12B—C11B—C16B | 119.52 (15) |
C12A—C11A—C17A | 118.81 (14) | C12B—C11B—C17B | 118.19 (14) |
C16A—C11A—C17A | 121.93 (14) | C16B—C11B—C17B | 122.29 (14) |
C13A—C12A—C11A | 120.56 (15) | C13B—C12B—C11B | 120.54 (15) |
C13A—C12A—H12A | 119.7 | C13B—C12B—H12B | 119.7 |
C11A—C12A—H12A | 119.7 | C11B—C12B—H12B | 119.7 |
C14A—C13A—C12A | 118.62 (15) | C14B—C13B—C12B | 118.38 (14) |
C14A—C13A—H13A | 120.7 | C14B—C13B—H13B | 120.8 |
C12A—C13A—H13A | 120.7 | C12B—C13B—H13B | 120.8 |
C13A—C14A—C15A | 122.15 (15) | C13B—C14B—C15B | 122.99 (15) |
C13A—C14A—N14A | 118.62 (14) | C13B—C14B—N14B | 118.20 (14) |
C15A—C14A—N14A | 119.19 (14) | C15B—C14B—N14B | 118.80 (14) |
C16A—C15A—C14A | 118.63 (15) | C16B—C15B—C14B | 117.87 (15) |
C16A—C15A—H15A | 120.7 | C16B—C15B—H15B | 121.1 |
C14A—C15A—H15A | 120.7 | C14B—C15B—H15B | 121.1 |
C15A—C16A—C11A | 120.64 (15) | C15B—C16B—C11B | 120.66 (14) |
C15A—C16A—H16A | 119.7 | C15B—C16B—H16B | 119.7 |
C11A—C16A—H16A | 119.7 | C11B—C16B—H16B | 119.7 |
O14A—N14A—O15A | 123.88 (14) | O14B—N14B—O15B | 123.77 (14) |
O14A—N14A—C14A | 118.03 (15) | O14B—N14B—C14B | 117.99 (14) |
O15A—N14A—C14A | 118.06 (13) | O15B—N14B—C14B | 118.23 (13) |
C27A—N2A—C2A | 117.35 (13) | C27B—N2B—C2B | 116.21 (13) |
N2A—C27A—C21A | 122.14 (14) | N2B—C27B—C21B | 123.04 (14) |
N2A—C27A—H27A | 118.9 | N2B—C27B—H27B | 118.5 |
C21A—C27A—H27A | 118.9 | C21B—C27B—H27B | 118.5 |
C26A—C21A—C22A | 119.60 (15) | C26B—C21B—C22B | 119.39 (15) |
C26A—C21A—C27A | 118.94 (14) | C26B—C21B—C27B | 118.69 (14) |
C22A—C21A—C27A | 121.45 (14) | C22B—C21B—C27B | 121.89 (14) |
C23A—C22A—C21A | 120.84 (15) | C23B—C22B—C21B | 120.57 (14) |
C23A—C22A—H22A | 119.6 | C23B—C22B—H22B | 119.7 |
C21A—C22A—H22A | 119.6 | C21B—C22B—H22B | 119.7 |
C22A—C23A—C24A | 117.80 (15) | C22B—C23B—C24B | 118.59 (14) |
C22A—C23A—H23A | 121.1 | C22B—C23B—H23B | 120.7 |
C24A—C23A—H23A | 121.1 | C24B—C23B—H23B | 120.7 |
C25A—C24A—C23A | 122.75 (15) | C25B—C24B—C23B | 122.24 (15) |
C25A—C24A—N24A | 118.38 (15) | C25B—C24B—N24B | 118.55 (14) |
C23A—C24A—N24A | 118.84 (15) | C23B—C24B—N24B | 119.15 (14) |
C24A—C25A—C26A | 118.82 (15) | C24B—C25B—C26B | 118.29 (15) |
C24A—C25A—H25A | 120.6 | C24B—C25B—H25B | 120.9 |
C26A—C25A—H25A | 120.6 | C26B—C25B—H25B | 120.9 |
C25A—C26A—C21A | 120.16 (15) | C25B—C26B—C21B | 120.82 (15) |
C25A—C26A—H26A | 119.9 | C25B—C26B—H26B | 119.6 |
C21A—C26A—H26A | 119.9 | C21B—C26B—H26B | 119.6 |
O25A—N24A—O24A | 123.77 (15) | O25B—N24B—O24B | 123.58 (14) |
O25A—N24A—C24A | 118.34 (15) | O25B—N24B—C24B | 118.04 (14) |
O24A—N24A—C24A | 117.88 (15) | O24B—N24B—C24B | 118.35 (13) |
N1A—C1A—C2A—N2A | −63.63 (15) | N1B—C1B—C2B—N2B | −64.28 (15) |
C6A—C1A—C2A—N2A | 175.25 (12) | C6B—C1B—C2B—N2B | 175.74 (12) |
N1A—C1A—C2A—C3A | 176.59 (11) | N1B—C1B—C2B—C3B | 174.69 (12) |
C6A—C1A—C2A—C3A | 55.47 (16) | C6B—C1B—C2B—C3B | 54.71 (16) |
N2A—C2A—C3A—C4A | −175.57 (13) | N2B—C2B—C3B—C4B | −174.97 (13) |
C1A—C2A—C3A—C4A | −55.70 (17) | C1B—C2B—C3B—C4B | −54.75 (17) |
C2A—C3A—C4A—C5A | 56.18 (18) | C2B—C3B—C4B—C5B | 55.73 (17) |
C3A—C4A—C5A—C6A | −56.15 (18) | C3B—C4B—C5B—C6B | −56.79 (17) |
C4A—C5A—C6A—C1A | 56.65 (18) | C4B—C5B—C6B—C1B | 57.74 (17) |
N1A—C1A—C6A—C5A | −176.85 (13) | N1B—C1B—C6B—C5B | −176.23 (12) |
C2A—C1A—C6A—C5A | −56.38 (17) | C2B—C1B—C6B—C5B | −56.45 (16) |
C6A—C1A—N1A—C17A | −116.25 (15) | C6B—C1B—N1B—C17B | −105.20 (15) |
C2A—C1A—N1A—C17A | 122.19 (14) | C2B—C1B—N1B—C17B | 134.10 (14) |
C1A—N1A—C17A—C11A | 178.52 (13) | C1B—N1B—C17B—C11B | 177.12 (12) |
N1A—C17A—C11A—C12A | 179.48 (15) | N1B—C17B—C11B—C12B | −164.89 (14) |
N1A—C17A—C11A—C16A | −2.4 (2) | N1B—C17B—C11B—C16B | 14.4 (2) |
C16A—C11A—C12A—C13A | −3.5 (2) | C16B—C11B—C12B—C13B | −1.9 (2) |
C17A—C11A—C12A—C13A | 174.65 (15) | C17B—C11B—C12B—C13B | 177.44 (13) |
C11A—C12A—C13A—C14A | 0.6 (3) | C11B—C12B—C13B—C14B | 2.0 (2) |
C12A—C13A—C14A—C15A | 3.0 (3) | C12B—C13B—C14B—C15B | −0.4 (2) |
C12A—C13A—C14A—N14A | −174.85 (14) | C12B—C13B—C14B—N14B | −179.33 (13) |
C13A—C14A—C15A—C16A | −3.7 (2) | C13B—C14B—C15B—C16B | −1.3 (2) |
N14A—C14A—C15A—C16A | 174.19 (13) | N14B—C14B—C15B—C16B | 177.66 (13) |
C14A—C15A—C16A—C11A | 0.7 (2) | C14B—C15B—C16B—C11B | 1.4 (2) |
C12A—C11A—C16A—C15A | 2.9 (2) | C12B—C11B—C16B—C15B | 0.2 (2) |
C17A—C11A—C16A—C15A | −175.25 (14) | C17B—C11B—C16B—C15B | −179.14 (13) |
C13A—C14A—N14A—O14A | 8.0 (2) | C13B—C14B—N14B—O14B | 15.7 (2) |
C15A—C14A—N14A—O14A | −170.00 (15) | C15B—C14B—N14B—O14B | −163.32 (14) |
C13A—C14A—N14A—O15A | −173.98 (15) | C13B—C14B—N14B—O15B | −165.66 (14) |
C15A—C14A—N14A—O15A | 8.1 (2) | C15B—C14B—N14B—O15B | 15.3 (2) |
C3A—C2A—N2A—C27A | −108.18 (15) | C3B—C2B—N2B—C27B | −124.46 (15) |
C1A—C2A—N2A—C27A | 131.08 (14) | C1B—C2B—N2B—C27B | 113.68 (15) |
C2A—N2A—C27A—C21A | 177.00 (13) | C2B—N2B—C27B—C21B | 179.59 (13) |
N2A—C27A—C21A—C26A | −167.26 (14) | N2B—C27B—C21B—C26B | −175.66 (15) |
N2A—C27A—C21A—C22A | 11.7 (2) | N2B—C27B—C21B—C22B | 2.2 (2) |
C26A—C21A—C22A—C23A | 0.6 (2) | C26B—C21B—C22B—C23B | 1.5 (2) |
C27A—C21A—C22A—C23A | −178.36 (14) | C27B—C21B—C22B—C23B | −176.31 (14) |
C21A—C22A—C23A—C24A | 1.1 (2) | C21B—C22B—C23B—C24B | 1.3 (2) |
C22A—C23A—C24A—C25A | −1.7 (2) | C22B—C23B—C24B—C25B | −2.8 (2) |
C22A—C23A—C24A—N24A | 176.62 (14) | C22B—C23B—C24B—N24B | 174.36 (13) |
C23A—C24A—C25A—C26A | 0.6 (2) | C23B—C24B—C25B—C26B | 1.3 (2) |
N24A—C24A—C25A—C26A | −177.78 (13) | N24B—C24B—C25B—C26B | −175.88 (14) |
C24A—C25A—C26A—C21A | 1.2 (2) | C24B—C25B—C26B—C21B | 1.7 (2) |
C22A—C21A—C26A—C25A | −1.8 (2) | C22B—C21B—C26B—C25B | −3.1 (2) |
C27A—C21A—C26A—C25A | 177.21 (13) | C27B—C21B—C26B—C25B | 174.83 (14) |
C25A—C24A—N24A—O25A | 2.8 (2) | C25B—C24B—N24B—O25B | 10.2 (2) |
C23A—C24A—N24A—O25A | −175.67 (15) | C23B—C24B—N24B—O25B | −167.06 (14) |
C25A—C24A—N24A—O24A | −178.04 (15) | C25B—C24B—N24B—O24B | −171.61 (15) |
C23A—C24A—N24A—O24A | 3.5 (2) | C23B—C24B—N24B—O24B | 11.1 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C22A—H22A···O15B | 0.95 | 2.39 | 3.280 (2) | 157 |
C25A—H25A···O15Ai | 0.95 | 2.43 | 3.144 (2) | 132 |
C13B—H13B···O24Bii | 0.95 | 2.52 | 3.225 (2) | 131 |
C27B—H27B···O24Aiii | 0.95 | 2.35 | 3.167 (2) | 143 |
C4A—H41A···Cg1iii | 0.99 | 2.65 | 3.596 (2) | 159 |
C5B—H51B···Cg2iii | 0.99 | 2.56 | 3.515 (2) | 161 |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | C20H20N4O4 |
Mr | 380.40 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 120 |
a, b, c (Å) | 22.4197 (5), 8.9687 (2), 21.2076 (4) |
β (°) | 117.7179 (11) |
V (Å3) | 3774.99 (14) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.40 × 0.40 × 0.20 |
Data collection | |
Diffractometer | Bruker Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.968, 0.981 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 43594, 8633, 6275 |
Rint | 0.043 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.129, 1.06 |
No. of reflections | 8633 |
No. of parameters | 505 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.37, −0.29 |
Computer programs: COLLECT (Hooft, 1999; Nonius, 1997), DENZO (Otwinowski & Minor, 1997) and COLLECT, DENZO and COLLECT, OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997), OSCAIL and SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).
C2A—C1A—N1A—C17A | 122.19 (14) | C2B—C1B—N1B—C17B | 134.10 (14) |
C1A—N1A—C17A—C11A | 178.52 (13) | C1B—N1B—C17B—C11B | 177.12 (12) |
N1A—C17A—C11A—C12A | 179.48 (15) | N1B—C17B—C11B—C12B | −164.89 (14) |
C13A—C14A—N14A—O14A | 8.0 (2) | C13B—C14B—N14B—O14B | 15.7 (2) |
C1A—C2A—N2A—C27A | 131.08 (14) | C1B—C2B—N2B—C27B | 113.68 (15) |
C2A—N2A—C27A—C21A | 177.00 (13) | C2B—N2B—C27B—C21B | 179.59 (13) |
N2A—C27A—C21A—C26A | −167.26 (14) | N2B—C27B—C21B—C26B | −175.66 (15) |
C23A—C24A—N24A—O24A | 3.5 (2) | C23B—C24B—N24B—O24B | 11.1 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C22A—H22A···O15B | 0.95 | 2.39 | 3.280 (2) | 157 |
C25A—H25A···O15Ai | 0.95 | 2.43 | 3.144 (2) | 132 |
C13B—H13B···O24Bii | 0.95 | 2.52 | 3.225 (2) | 131 |
C27B—H27B···O24Aiii | 0.95 | 2.35 | 3.167 (2) | 143 |
C4A—H41A···Cg1iii | 0.99 | 2.65 | 3.596 (2) | 159 |
C5B—H51B···Cg2iii | 0.99 | 2.56 | 3.515 (2) | 161 |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x, y+1, z. |
Acknowledgements
The X-ray data were collected at the EPSRC X-ray Crystallographic Service, University of Southampton, England; the authors thank the staff for all their help and advice. JLW thanks CNPq and FAPERJ for financial support.
References
Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada. Google Scholar
Glidewell, C., Low, J. N., Skakle, J. M. S. & Wardell, J. L. (2005). Acta Cryst. E61, o1699–o1701. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hooft, R. W. W. (1999). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
McArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland. Google Scholar
Nonius (1997). KappaCCD Server Software. Windows 3.11 Version. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
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Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
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We have recently reported the structure of enantiopure (1R,2R)-N,N'-bis(4-nitrophenylmethylene)-1,2-cyclohexanediamine, (I) (Glidewell et al., 2005). This compound crystallizes with Z' = 2 in space group C2, and the independent molecules both exhibit approximate but not crystallographic twofold rotational symmetry. There is a single C—H···O hydrogen bond linking the two independent molecules, but there are no other direction-specific interactions in the structure. In this paper, we report the structure of another isomeric form, the racemic (1RS,2RS) compound, (II).
Compound (II) crystallizes in the centrosymmetric space group P21/c with Z' = 2 (Fig. 1). In the selected asymmetric unit each of the molecules has the (1R,2R) configuration, but the space group accommodates equal numbers of (1R,2R) and (1S,2S) enantiomers, as required by the racemic nature of (II). In each of the molecules, the cyclohexane ring adopts a chain conformation, with the pendent substituent units in equatorial positions. Each molecule adopts approximate, but not exact, twofold rotational symmetry, as shown by the leading torsion angles (Table 1), and the differences between corresponding values for the two molecules are sufficient to preclude any additional symmetry. The dihedral angles between the nitro groups containing N14X and N24X (X = A or B) and their adjacent aryl rings are 9.7 (2) and 3.3 (2)° in molecule A, and 16.0 (2) and 12.0 (2)° in molecule B.
The molecules of (II) are linked into complex sheets by a combination of four C—H···O hydrogen bonds and two C—H···π(arene) hydrogen bonds (Table 2), and the formation of the sheet is best approached in terms of the component sub-structures, each of which depends on a small sub-set of the hydrogen bonds.
The basic building blocks within the structure of (II) are two centrosymmetric R22(32) dimers, formed by molecules of types A and B respectively; for the selected asymmetric unit, the type A dimer is centred at (0, 0, 1/2) and the type B dimer is centred at (1/2, 1/2, 1/2). The overall structure can then be envisaged in terms of series of chains which result from the linking of these dimers. There are four such chains, two of which incorporate just one type of dimer, A or B, and the other two of which incorporate both types of dimer, A and B.
Within the asymmetric unit, aryl atom C22A acts as hydrogen-bond donor to nitro atom O15B, and propagation by inversion of this hydrogen bond links the two types of R22(32) dimer into a chain of rings running parallel to the [110] direction (Fig. 2). In addition, aryl atom C27B, which lies in the type B dimer centred at (1/2,1/2,1/2), acts as hydrogen-bond donor to atom O24A at (x, 1 + y, z), which lies in the type A dimer centred at (0, 1, 1/2), and propagation of this interaction, again by inversion, links the R22(32) dimers into another chain of rings, this time running parallel to the [110] direction (Fig. 3).
Two further chains are generated by the linking of R22(32) dimers by means of C—H···π(arene) hydrogen bonds. These chains differ from those generated by C—H···O hydrogen bonds (Figs. 2 and 3) only in that each type of chain involving C—H···π(arene) hydrogen bonds is built from just one type of molecule. In the first of these, atom C4A in the type A molecule at (x, y, z), part of the type A dimer centred at (0, 0, 1/2), acts as hydrogen-bond donor, via atom H41A, to the C21A–C26A ring of the type A molecule at (x, 1 + y, z), itself part of the type A dimer centred at (0, 1, 1/2). Hence, a chain of dimers is formed along (0, y, 1/2) (Fig. 4). In the second chain of this type, atom C5B in the molecule at (x, y, z), which is part of the type B dimer centred at (1/2, 1/2, 1/2), acts as hydrogen-bond donor, via atom H51B, to the C11B–C16B ring in the type 2 [type B?] molecule at (x, 1 + y, z), which forms part of the type B dimer centred at (1/2, 3/2, 1/2), so forming a chain of dimers along (1/2, y, 1/2) (Fig. 5).
The combination of the [010], [110] and [110] chains (Figs. 2–5) is sufficient to produce an (001) sheet lying in the domain 0.14 < z < 0.86 and generated by inversion centres at z = 1/2. A second such sheet, related to the first by the translational symmetry, is generated by the centres of inversion at z = 1.0. There is one rather weak interaction between molecules in adjacent sheets, an approximately perpendicular nitro···nitro interaction involving type B molecules only. Atom O15B in the type B molecule at (x, y, z), part of the sheet centred at z = 1/2, makes a short contact with atom O25B in the type B molecule at (x, 1/2 − y, 1/2 + z), part of the sheet centred at z = 1.0, with O15B···O25Bi 2.873 (2) Å, N14B—O15B···O25Bi 86.4 (2)° and O15B···O25Bi—N24Bi 135.9 (3)° [symmetry code: (i) x, 1/2 − y, 1/2 + z]. However, there are no significant π–π stacking interactions.