Buy article online - an online subscription or single-article purchase is required to access this article.
In the title adduct, C
6H
12N
2·C
7H
8O
2, the orcin and 1,4-diazabicyclo[2.2.2]octane moieties are held together by O—H
N hydrogen bonds. One-dimensional chiral hydrogen-bonded chains are formed along the
b axis. Neighbouring chains are held together principally by van der Waals interactions and are interrelated by translation, resulting in a chiral layer.
Supporting information
CCDC reference: 254953
Equimolar quantites of DABCO and orcin were mixed and dissolved in sufficient water by heating to a temperature where a clear solution resulted. Single crystals of (I) were formed by standing the resulting solution overnight at 293 K.
All H atoms were placed in calculated positions and allowed to ride on their parent atoms at distances of 0.82–0.97 Å, with isotropic displacement parameters 1.2–1.5 times Ueq of the parent atoms. Because of the lack of atoms heavier than O and the short measuring wavelength of Mo radiation, no useful absolute structure parameter can be refined.
Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
5-methyl-1,3-benzenediol (orcin) 1,4-diazabicyclo[2.2.2]octane (1/1)
top
Crystal data top
C6H12N2·C7H8O2 | F(000) = 1024.0 |
Mr = 236.31 | Dx = 1.206 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 346 reflections |
a = 12.2569 (6) Å | θ = 2.4–23.0° |
b = 12.5985 (6) Å | µ = 0.08 mm−1 |
c = 16.8506 (9) Å | T = 293 K |
V = 2602.0 (2) Å3 | Prism, colourless |
Z = 8 | 0.46 × 0.42 × 0.38 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2129 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.025 |
Graphite monochromator | θmax = 25.2°, θmin = 2.0° |
ϕ and ω scans | h = −11→14 |
13862 measured reflections | k = −15→14 |
2645 independent reflections | l = −20→15 |
Refinement top
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)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.157 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.1095P)2 + 0.08P] where P = (Fo2 + 2Fc2)/3 |
2645 reflections | (Δ/σ)max = 0.001 |
307 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
Crystal data top
C6H12N2·C7H8O2 | V = 2602.0 (2) Å3 |
Mr = 236.31 | Z = 8 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 12.2569 (6) Å | µ = 0.08 mm−1 |
b = 12.5985 (6) Å | T = 293 K |
c = 16.8506 (9) Å | 0.46 × 0.42 × 0.38 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2129 reflections with I > 2σ(I) |
13862 measured reflections | Rint = 0.025 |
2645 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.054 | 0 restraints |
wR(F2) = 0.157 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.23 e Å−3 |
2645 reflections | Δρmin = −0.27 e Å−3 |
307 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.35392 (19) | 0.96077 (19) | 0.89770 (15) | 0.0491 (6) | |
N2 | 0.15548 (18) | 1.02328 (19) | 0.90321 (15) | 0.0505 (6) | |
C1 | 0.3493 (2) | 1.0765 (2) | 0.8976 (2) | 0.0600 (8) | |
H1A | 0.3846 | 1.1036 | 0.8502 | 0.072* | |
H1B | 0.3880 | 1.1039 | 0.9434 | 0.072* | |
C2 | 0.2297 (2) | 1.1140 (2) | 0.8999 (2) | 0.0576 (8) | |
H2A | 0.2185 | 1.1587 | 0.9460 | 0.069* | |
H2B | 0.2142 | 1.1559 | 0.8529 | 0.069* | |
C3 | 0.3012 (2) | 0.9225 (2) | 0.97123 (17) | 0.0570 (8) | |
H3A | 0.3403 | 0.9496 | 1.0170 | 0.068* | |
H3B | 0.3040 | 0.8456 | 0.9729 | 0.068* | |
C4 | 0.1823 (2) | 0.9594 (2) | 0.97427 (19) | 0.0573 (8) | |
H4A | 0.1345 | 0.8982 | 0.9769 | 0.069* | |
H4B | 0.1706 | 1.0017 | 1.0216 | 0.069* | |
C5 | 0.2942 (2) | 0.9217 (2) | 0.82898 (19) | 0.0577 (8) | |
H5A | 0.2979 | 0.8448 | 0.8275 | 0.069* | |
H5B | 0.3275 | 0.9488 | 0.7809 | 0.069* | |
C6 | 0.1739 (2) | 0.9569 (2) | 0.8325 (2) | 0.0608 (8) | |
H6A | 0.1558 | 0.9969 | 0.7851 | 0.073* | |
H6B | 0.1270 | 0.8950 | 0.8346 | 0.073* | |
N3 | 0.35698 (19) | 0.54541 (18) | 0.84590 (16) | 0.0494 (6) | |
N4 | 0.15835 (19) | 0.48274 (19) | 0.85339 (14) | 0.0495 (6) | |
C7 | 0.3516 (2) | 0.4295 (2) | 0.8488 (2) | 0.0621 (8) | |
H7A | 0.3914 | 0.4040 | 0.8947 | 0.075* | |
H7B | 0.3857 | 0.4002 | 0.8017 | 0.075* | |
C8 | 0.2329 (2) | 0.3924 (2) | 0.8535 (2) | 0.0611 (9) | |
H8A | 0.2169 | 0.3469 | 0.8085 | 0.073* | |
H8B | 0.2224 | 0.3514 | 0.9015 | 0.073* | |
C9 | 0.3046 (2) | 0.5863 (3) | 0.91765 (19) | 0.0620 (8) | |
H9A | 0.3085 | 0.6632 | 0.9179 | 0.074* | |
H9B | 0.3431 | 0.5603 | 0.9640 | 0.074* | |
C10 | 0.1844 (2) | 0.5511 (3) | 0.92158 (19) | 0.0610 (8) | |
H10A | 0.1715 | 0.5126 | 0.9705 | 0.073* | |
H10B | 0.1374 | 0.6130 | 0.9212 | 0.073* | |
C11 | 0.2956 (2) | 0.5814 (2) | 0.77530 (18) | 0.0563 (8) | |
H11A | 0.3293 | 0.5532 | 0.7277 | 0.068* | |
H11B | 0.2976 | 0.6583 | 0.7722 | 0.068* | |
C12 | 0.1769 (2) | 0.5438 (2) | 0.78034 (19) | 0.0574 (8) | |
H12A | 0.1286 | 0.6048 | 0.7794 | 0.069* | |
H12B | 0.1602 | 0.4999 | 0.7347 | 0.069* | |
O1 | 0.57360 (16) | 0.94161 (16) | 0.89557 (16) | 0.0635 (7) | |
H1 | 0.5072 | 0.9335 | 0.8943 | 0.095* | |
O2 | 0.57432 (16) | 0.56999 (15) | 0.82461 (16) | 0.0681 (7) | |
H2 | 0.5080 | 0.5773 | 0.8276 | 0.102* | |
C13 | 0.6235 (2) | 0.8483 (2) | 0.87842 (16) | 0.0429 (7) | |
C14 | 0.5672 (2) | 0.7558 (2) | 0.85998 (17) | 0.0453 (7) | |
H14 | 0.4913 | 0.7554 | 0.8601 | 0.054* | |
C15 | 0.6241 (2) | 0.6642 (2) | 0.84145 (17) | 0.0450 (7) | |
C16 | 0.7375 (2) | 0.6648 (2) | 0.84002 (18) | 0.0477 (7) | |
H16 | 0.7755 | 0.6035 | 0.8265 | 0.057* | |
C17 | 0.7937 (2) | 0.7569 (2) | 0.85878 (17) | 0.0452 (7) | |
C18 | 0.7373 (2) | 0.8482 (2) | 0.87774 (18) | 0.0467 (7) | |
H18 | 0.7753 | 0.9099 | 0.8901 | 0.056* | |
C19 | 0.9172 (3) | 0.7574 (2) | 0.8584 (2) | 0.0721 (12) | |
H19A | 0.9431 | 0.8266 | 0.8730 | 0.108* | |
H19B | 0.9431 | 0.7399 | 0.8063 | 0.108* | |
H19C | 0.9438 | 0.7060 | 0.8958 | 0.108* | |
O3 | 0.94242 (16) | 0.44160 (16) | 0.85138 (16) | 0.0685 (7) | |
H3 | 1.0089 | 0.4345 | 0.8523 | 0.103* | |
O4 | 0.94221 (17) | 0.06990 (16) | 0.92750 (16) | 0.0719 (7) | |
H4 | 1.0087 | 0.0764 | 0.9250 | 0.108* | |
C20 | 0.8941 (2) | 0.3474 (2) | 0.86996 (16) | 0.0432 (6) | |
C21 | 0.7802 (2) | 0.3470 (2) | 0.87098 (17) | 0.0453 (7) | |
H21 | 0.7421 | 0.4085 | 0.8582 | 0.054* | |
C22 | 0.7241 (2) | 0.2566 (2) | 0.89075 (17) | 0.0448 (7) | |
C23 | 0.7804 (2) | 0.1653 (2) | 0.91022 (18) | 0.0482 (7) | |
H23 | 0.7424 | 0.1043 | 0.9244 | 0.058* | |
C24 | 0.8937 (2) | 0.1643 (2) | 0.90865 (18) | 0.0466 (7) | |
C25 | 0.9511 (2) | 0.2553 (2) | 0.88899 (17) | 0.0453 (7) | |
H25 | 1.0270 | 0.2549 | 0.8885 | 0.054* | |
C26 | 0.6006 (3) | 0.2572 (3) | 0.8901 (2) | 0.0664 (10) | |
H26A | 0.5749 | 0.3265 | 0.8757 | 0.100* | |
H26B | 0.5739 | 0.2393 | 0.9420 | 0.100* | |
H26C | 0.5746 | 0.2061 | 0.8523 | 0.100* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0362 (12) | 0.0518 (13) | 0.0591 (15) | 0.0082 (10) | −0.0013 (11) | −0.0028 (11) |
N2 | 0.0365 (12) | 0.0533 (13) | 0.0615 (14) | 0.0050 (11) | 0.0012 (11) | 0.0055 (12) |
C1 | 0.0456 (17) | 0.0526 (16) | 0.082 (2) | −0.0102 (14) | 0.0029 (16) | −0.0071 (17) |
C2 | 0.0573 (18) | 0.0402 (15) | 0.075 (2) | 0.0086 (13) | 0.0062 (16) | 0.0042 (15) |
C3 | 0.0573 (18) | 0.0576 (17) | 0.0561 (17) | 0.0127 (15) | −0.0036 (14) | 0.0041 (15) |
C4 | 0.0470 (16) | 0.0638 (18) | 0.0611 (18) | 0.0024 (15) | 0.0064 (14) | 0.0107 (15) |
C5 | 0.0533 (17) | 0.0558 (16) | 0.0638 (19) | 0.0006 (15) | 0.0013 (15) | −0.0100 (16) |
C6 | 0.0485 (17) | 0.0697 (18) | 0.0642 (19) | −0.0071 (15) | −0.0099 (15) | −0.0034 (16) |
N3 | 0.0369 (12) | 0.0495 (13) | 0.0619 (15) | −0.0079 (10) | 0.0008 (11) | −0.0025 (11) |
N4 | 0.0376 (12) | 0.0534 (13) | 0.0575 (14) | −0.0095 (11) | 0.0002 (11) | 0.0031 (12) |
C7 | 0.0483 (17) | 0.0528 (17) | 0.085 (2) | 0.0099 (14) | −0.0013 (17) | −0.0016 (17) |
C8 | 0.0576 (19) | 0.0468 (16) | 0.079 (2) | −0.0078 (14) | −0.0040 (17) | 0.0079 (16) |
C9 | 0.0566 (19) | 0.0627 (18) | 0.067 (2) | −0.0086 (16) | −0.0027 (16) | −0.0097 (17) |
C10 | 0.0558 (19) | 0.0679 (19) | 0.0593 (19) | −0.0003 (16) | 0.0107 (15) | −0.0039 (15) |
C11 | 0.0562 (18) | 0.0573 (17) | 0.0555 (17) | −0.0083 (15) | 0.0027 (14) | 0.0104 (15) |
C12 | 0.0457 (15) | 0.0659 (18) | 0.0605 (18) | 0.0022 (15) | −0.0032 (14) | 0.0085 (14) |
O1 | 0.0355 (10) | 0.0504 (12) | 0.1047 (19) | 0.0060 (9) | −0.0029 (11) | −0.0166 (12) |
O2 | 0.0389 (11) | 0.0505 (12) | 0.115 (2) | −0.0082 (9) | 0.0092 (12) | −0.0198 (13) |
C13 | 0.0291 (13) | 0.0475 (15) | 0.0521 (16) | 0.0043 (11) | −0.0021 (11) | −0.0009 (13) |
C14 | 0.0240 (12) | 0.0520 (16) | 0.060 (2) | −0.0012 (11) | 0.0016 (12) | −0.0015 (14) |
C15 | 0.0299 (13) | 0.0468 (15) | 0.0581 (17) | −0.0047 (11) | 0.0050 (12) | −0.0009 (14) |
C16 | 0.0362 (14) | 0.0420 (14) | 0.0649 (18) | 0.0039 (11) | 0.0074 (13) | 0.0006 (14) |
C17 | 0.0289 (13) | 0.0521 (15) | 0.0544 (18) | −0.0009 (11) | 0.0029 (12) | 0.0084 (14) |
C18 | 0.0344 (14) | 0.0458 (15) | 0.0600 (17) | −0.0054 (12) | −0.0014 (12) | −0.0002 (13) |
C19 | 0.0284 (14) | 0.071 (2) | 0.117 (3) | 0.0004 (14) | 0.0065 (17) | 0.004 (2) |
O3 | 0.0337 (11) | 0.0549 (12) | 0.117 (2) | −0.0070 (10) | −0.0063 (12) | 0.0267 (13) |
O4 | 0.0380 (11) | 0.0519 (12) | 0.126 (2) | 0.0077 (10) | 0.0113 (12) | 0.0248 (14) |
C20 | 0.0312 (13) | 0.0477 (15) | 0.0506 (16) | −0.0053 (11) | −0.0018 (11) | 0.0021 (12) |
C21 | 0.0311 (13) | 0.0466 (14) | 0.0582 (17) | 0.0037 (12) | −0.0030 (12) | 0.0001 (13) |
C22 | 0.0302 (14) | 0.0496 (15) | 0.0544 (18) | 0.0001 (11) | −0.0001 (12) | −0.0113 (14) |
C23 | 0.0350 (14) | 0.0430 (14) | 0.0665 (19) | −0.0032 (12) | 0.0077 (13) | −0.0027 (14) |
C24 | 0.0333 (14) | 0.0439 (14) | 0.0627 (18) | 0.0038 (11) | 0.0042 (12) | 0.0023 (14) |
C25 | 0.0208 (12) | 0.0533 (16) | 0.0619 (19) | 0.0002 (11) | −0.0011 (11) | 0.0046 (14) |
C26 | 0.0295 (15) | 0.072 (2) | 0.097 (3) | 0.0004 (14) | 0.0050 (16) | −0.004 (2) |
Geometric parameters (Å, º) top
N1—C5 | 1.456 (4) | C11—H11A | 0.9700 |
N1—C1 | 1.459 (4) | C11—H11B | 0.9700 |
N1—C3 | 1.478 (4) | C12—H12A | 0.9700 |
N2—C2 | 1.462 (4) | C12—H12B | 0.9700 |
N2—C6 | 1.473 (4) | O1—C13 | 1.357 (3) |
N2—C4 | 1.479 (4) | O1—H1 | 0.8200 |
C1—C2 | 1.540 (4) | O2—C15 | 1.364 (3) |
C1—H1A | 0.9700 | O2—H2 | 0.8200 |
C1—H1B | 0.9700 | C13—C14 | 1.390 (4) |
C2—H2A | 0.9700 | C13—C18 | 1.396 (3) |
C2—H2B | 0.9700 | C14—C15 | 1.384 (4) |
C3—C4 | 1.531 (4) | C14—H14 | 0.9300 |
C3—H3A | 0.9700 | C15—C16 | 1.390 (3) |
C3—H3B | 0.9700 | C16—C17 | 1.386 (4) |
C4—H4A | 0.9700 | C16—H16 | 0.9300 |
C4—H4B | 0.9700 | C17—C18 | 1.379 (4) |
C5—C6 | 1.540 (4) | C17—C19 | 1.515 (4) |
C5—H5A | 0.9700 | C18—H18 | 0.9300 |
C5—H5B | 0.9700 | C19—H19A | 0.9600 |
C6—H6A | 0.9700 | C19—H19B | 0.9600 |
C6—H6B | 0.9700 | C19—H19C | 0.9600 |
N3—C7 | 1.462 (4) | O3—C20 | 1.363 (3) |
N3—C9 | 1.463 (4) | O3—H3 | 0.8200 |
N3—C11 | 1.479 (4) | O4—C24 | 1.367 (3) |
N4—C8 | 1.459 (4) | O4—H4 | 0.8200 |
N4—C12 | 1.469 (4) | C20—C25 | 1.392 (4) |
N4—C10 | 1.471 (4) | C20—C21 | 1.396 (3) |
C7—C8 | 1.530 (4) | C21—C22 | 1.371 (4) |
C7—H7A | 0.9700 | C21—H21 | 0.9300 |
C7—H7B | 0.9700 | C22—C23 | 1.382 (4) |
C8—H8A | 0.9700 | C22—C26 | 1.514 (4) |
C8—H8B | 0.9700 | C23—C24 | 1.388 (4) |
C9—C10 | 1.540 (4) | C23—H23 | 0.9300 |
C9—H9A | 0.9700 | C24—C25 | 1.386 (4) |
C9—H9B | 0.9700 | C25—H25 | 0.9300 |
C10—H10A | 0.9700 | C26—H26A | 0.9600 |
C10—H10B | 0.9700 | C26—H26B | 0.9600 |
C11—C12 | 1.532 (4) | C26—H26C | 0.9600 |
| | | |
C5—N1—C1 | 108.5 (3) | C9—C10—H10A | 109.7 |
C5—N1—C3 | 109.7 (2) | N4—C10—H10B | 109.7 |
C1—N1—C3 | 108.1 (3) | C9—C10—H10B | 109.7 |
C2—N2—C6 | 108.5 (2) | H10A—C10—H10B | 108.2 |
C2—N2—C4 | 108.5 (2) | N3—C11—C12 | 110.1 (2) |
C6—N2—C4 | 108.2 (2) | N3—C11—H11A | 109.6 |
N1—C1—C2 | 110.1 (2) | C12—C11—H11A | 109.6 |
N1—C1—H1A | 109.6 | N3—C11—H11B | 109.6 |
C2—C1—H1A | 109.6 | C12—C11—H11B | 109.6 |
N1—C1—H1B | 109.6 | H11A—C11—H11B | 108.2 |
C2—C1—H1B | 109.6 | N4—C12—C11 | 110.8 (2) |
H1A—C1—H1B | 108.2 | N4—C12—H12A | 109.5 |
N2—C2—C1 | 110.7 (2) | C11—C12—H12A | 109.5 |
N2—C2—H2A | 109.5 | N4—C12—H12B | 109.5 |
C1—C2—H2A | 109.5 | C11—C12—H12B | 109.5 |
N2—C2—H2B | 109.5 | H12A—C12—H12B | 108.1 |
C1—C2—H2B | 109.5 | C13—O1—H1 | 109.5 |
H2A—C2—H2B | 108.1 | C15—O2—H2 | 109.5 |
N1—C3—C4 | 110.2 (2) | O1—C13—C14 | 123.4 (2) |
N1—C3—H3A | 109.6 | O1—C13—C18 | 117.0 (2) |
C4—C3—H3A | 109.6 | C14—C13—C18 | 119.6 (3) |
N1—C3—H3B | 109.6 | C15—C14—C13 | 119.9 (2) |
C4—C3—H3B | 109.6 | C15—C14—H14 | 120.0 |
H3A—C3—H3B | 108.1 | C13—C14—H14 | 120.0 |
N2—C4—C3 | 110.5 (2) | O2—C15—C14 | 123.1 (2) |
N2—C4—H4A | 109.6 | O2—C15—C16 | 116.6 (2) |
C3—C4—H4A | 109.6 | C14—C15—C16 | 120.2 (3) |
N2—C4—H4B | 109.6 | C17—C16—C15 | 119.9 (3) |
C3—C4—H4B | 109.6 | C17—C16—H16 | 120.1 |
H4A—C4—H4B | 108.1 | C15—C16—H16 | 120.1 |
N1—C5—C6 | 110.7 (2) | C18—C17—C16 | 120.1 (2) |
N1—C5—H5A | 109.5 | C18—C17—C19 | 119.9 (3) |
C6—C5—H5A | 109.5 | C16—C17—C19 | 120.0 (3) |
N1—C5—H5B | 109.5 | C17—C18—C13 | 120.2 (3) |
C6—C5—H5B | 109.5 | C17—C18—H18 | 119.9 |
H5A—C5—H5B | 108.1 | C13—C18—H18 | 119.9 |
N2—C6—C5 | 110.0 (2) | C17—C19—H19A | 109.5 |
N2—C6—H6A | 109.7 | C17—C19—H19B | 109.5 |
C5—C6—H6A | 109.7 | H19A—C19—H19B | 109.5 |
N2—C6—H6B | 109.7 | C17—C19—H19C | 109.5 |
C5—C6—H6B | 109.7 | H19A—C19—H19C | 109.5 |
H6A—C6—H6B | 108.2 | H19B—C19—H19C | 109.5 |
C7—N3—C9 | 107.7 (3) | C20—O3—H3 | 109.5 |
C7—N3—C11 | 108.1 (3) | C24—O4—H4 | 109.5 |
C9—N3—C11 | 109.5 (2) | O3—C20—C25 | 124.1 (2) |
C8—N4—C12 | 108.2 (2) | O3—C20—C21 | 116.1 (3) |
C8—N4—C10 | 108.7 (2) | C25—C20—C21 | 119.8 (3) |
C12—N4—C10 | 108.3 (2) | C22—C21—C20 | 120.5 (3) |
N3—C7—C8 | 110.5 (2) | C22—C21—H21 | 119.8 |
N3—C7—H7A | 109.6 | C20—C21—H21 | 119.8 |
C8—C7—H7A | 109.6 | C21—C22—C23 | 119.9 (3) |
N3—C7—H7B | 109.6 | C21—C22—C26 | 119.7 (3) |
C8—C7—H7B | 109.6 | C23—C22—C26 | 120.4 (3) |
H7A—C7—H7B | 108.1 | C22—C23—C24 | 120.2 (3) |
N4—C8—C7 | 110.9 (2) | C22—C23—H23 | 119.9 |
N4—C8—H8A | 109.5 | C24—C23—H23 | 119.9 |
C7—C8—H8A | 109.5 | O4—C24—C25 | 123.6 (2) |
N4—C8—H8B | 109.5 | O4—C24—C23 | 116.0 (3) |
C7—C8—H8B | 109.5 | C25—C24—C23 | 120.3 (3) |
H8A—C8—H8B | 108.0 | C24—C25—C20 | 119.3 (2) |
N3—C9—C10 | 110.7 (2) | C24—C25—H25 | 120.4 |
N3—C9—H9A | 109.5 | C20—C25—H25 | 120.4 |
C10—C9—H9A | 109.5 | C22—C26—H26A | 109.5 |
N3—C9—H9B | 109.5 | C22—C26—H26B | 109.5 |
C10—C9—H9B | 109.5 | H26A—C26—H26B | 109.5 |
H9A—C9—H9B | 108.1 | C22—C26—H26C | 109.5 |
N4—C10—C9 | 110.0 (2) | H26A—C26—H26C | 109.5 |
N4—C10—H10A | 109.7 | H26B—C26—H26C | 109.5 |
| | | |
C5—N1—C1—C2 | 58.6 (3) | C8—N4—C12—C11 | −58.5 (3) |
C3—N1—C1—C2 | −60.3 (3) | C10—N4—C12—C11 | 59.1 (3) |
C6—N2—C2—C1 | −59.3 (3) | N3—C11—C12—N4 | −0.2 (4) |
C4—N2—C2—C1 | 58.0 (3) | O1—C13—C14—C15 | 178.6 (3) |
N1—C1—C2—N2 | 1.2 (4) | C18—C13—C14—C15 | 0.3 (4) |
C5—N1—C3—C4 | −58.2 (3) | C13—C14—C15—O2 | 178.4 (3) |
C1—N1—C3—C4 | 59.9 (3) | C13—C14—C15—C16 | −1.0 (4) |
C2—N2—C4—C3 | −58.3 (3) | O2—C15—C16—C17 | −178.1 (3) |
C6—N2—C4—C3 | 59.3 (3) | C14—C15—C16—C17 | 1.3 (5) |
N1—C3—C4—N2 | −0.5 (4) | C15—C16—C17—C18 | −0.9 (5) |
C1—N1—C5—C6 | −60.5 (3) | C15—C16—C17—C19 | 179.1 (3) |
C3—N1—C5—C6 | 57.3 (3) | C16—C17—C18—C13 | 0.2 (4) |
C2—N2—C6—C5 | 57.4 (3) | C19—C17—C18—C13 | −179.8 (3) |
C4—N2—C6—C5 | −60.1 (3) | O1—C13—C18—C17 | −178.3 (3) |
N1—C5—C6—N2 | 2.0 (4) | C14—C13—C18—C17 | 0.1 (5) |
C9—N3—C7—C8 | 59.1 (4) | O3—C20—C21—C22 | −178.5 (3) |
C11—N3—C7—C8 | −59.2 (4) | C25—C20—C21—C22 | 0.1 (4) |
C12—N4—C8—C7 | 58.6 (3) | C20—C21—C22—C23 | 0.3 (4) |
C10—N4—C8—C7 | −58.8 (3) | C20—C21—C22—C26 | −178.9 (3) |
N3—C7—C8—N4 | 0.3 (4) | C21—C22—C23—C24 | −1.0 (5) |
C7—N3—C9—C10 | −60.4 (3) | C26—C22—C23—C24 | 178.3 (3) |
C11—N3—C9—C10 | 56.9 (3) | C22—C23—C24—O4 | −178.9 (3) |
C8—N4—C10—C9 | 57.0 (3) | C22—C23—C24—C25 | 1.2 (5) |
C12—N4—C10—C9 | −60.2 (3) | O4—C24—C25—C20 | 179.4 (3) |
N3—C9—C10—N4 | 2.3 (4) | C23—C24—C25—C20 | −0.7 (4) |
C7—N3—C11—C12 | 59.0 (3) | O3—C20—C25—C24 | 178.6 (3) |
C9—N3—C11—C12 | −58.1 (3) | C21—C20—C25—C24 | 0.1 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N1 | 0.82 | 1.91 | 2.704 (3) | 162 |
O2—H2···N3 | 0.82 | 1.92 | 2.706 (3) | 161 |
O3—H3···N4i | 0.82 | 1.93 | 2.697 (3) | 155 |
O4—H4···N2ii | 0.82 | 1.95 | 2.710 (3) | 153 |
C5—H5B···O2iii | 0.97 | 2.63 | 3.576 (4) | 164 |
C6—H6A···O3iii | 0.97 | 2.69 | 3.417 (4) | 132 |
C10—H10A···O1iv | 0.97 | 2.62 | 3.369 (4) | 134 |
Symmetry codes: (i) x+1, y, z; (ii) x+1, y−1, z; (iii) −x+1, y+1/2, −z+3/2; (iv) x−1/2, −y+3/2, −z+2. |
Experimental details
Crystal data |
Chemical formula | C6H12N2·C7H8O2 |
Mr | 236.31 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 293 |
a, b, c (Å) | 12.2569 (6), 12.5985 (6), 16.8506 (9) |
V (Å3) | 2602.0 (2) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.46 × 0.42 × 0.38 |
|
Data collection |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13862, 2645, 2129 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.599 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.157, 1.06 |
No. of reflections | 2645 |
No. of parameters | 307 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.23, −0.27 |
Selected geometric parameters (Å, º) topN1—C5 | 1.456 (4) | O1—C13 | 1.357 (3) |
N1—C1 | 1.459 (4) | O2—C15 | 1.364 (3) |
N1—C3 | 1.478 (4) | C13—C14 | 1.390 (4) |
N2—C2 | 1.462 (4) | C13—C18 | 1.396 (3) |
N2—C6 | 1.473 (4) | C14—C15 | 1.384 (4) |
N2—C4 | 1.479 (4) | C15—C16 | 1.390 (3) |
C1—C2 | 1.540 (4) | C16—C17 | 1.386 (4) |
C3—C4 | 1.531 (4) | C17—C18 | 1.379 (4) |
C5—C6 | 1.540 (4) | C17—C19 | 1.515 (4) |
| | | |
N1—C1—C2—N2 | 1.2 (4) | N3—C7—C8—N4 | 0.3 (4) |
N1—C3—C4—N2 | −0.5 (4) | N3—C9—C10—N4 | 2.3 (4) |
N1—C5—C6—N2 | 2.0 (4) | N3—C11—C12—N4 | −0.2 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N1 | 0.82 | 1.91 | 2.704 (3) | 162 |
O2—H2···N3 | 0.82 | 1.92 | 2.706 (3) | 161 |
O3—H3···N4i | 0.82 | 1.93 | 2.697 (3) | 155 |
O4—H4···N2ii | 0.82 | 1.95 | 2.710 (3) | 153 |
C5—H5B···O2iii | 0.97 | 2.63 | 3.576 (4) | 164 |
C6—H6A···O3iii | 0.97 | 2.69 | 3.417 (4) | 132 |
C10—H10A···O1iv | 0.97 | 2.62 | 3.369 (4) | 134 |
Symmetry codes: (i) x+1, y, z; (ii) x+1, y−1, z; (iii) −x+1, y+1/2, −z+3/2; (iv) x−1/2, −y+3/2, −z+2. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
If you have already registered and are using a computer listed in your registration details, please email
support@iucr.org for assistance.
Chiral crystals can be formed through self-assembly even from achiral molecules (Jacques et al., 1981). It is possible to synthesize substances asymmetrically from such crystals by solid state reactions (Elgavi et al., 1973; Green et al., 1979; Sakamoto, 1997). Furthermore, chiral crystallization is relevant to the origin of chiral compounds in nature (Addadi & Lahav, 1979). The design of chiral crystalline complexes from different achiral molecules (Koshima et al., 1996, 1997, 1998, 1999; Koshima & Honke 1999) is an active field. It has been reported previously that a resorcinol-urea adduct crystallizes in a chiral space group, P212121 (Pickering & Small, 1982). In our case, the chiral crystal of the title adduct, (I), was synthesized from two achiral compounds, 5-methylresorcinol (orcin) and 1,4-diazabicyclo[2.2.2]octane (DABCO). Here, the structure and the chirality of (I) are discussed. \sch
There are two crystallographically independent molecules each of DABCO and orcin in the unit cell of (I) (Fig. 1). In the structure of (I), the orcin and DABCO moieties are linked by O1—H1···N1, O2—H2···N3, O3—H3···N4i and O4—H4···N2ii hydrogen bonds (Fig. 2 and Table 2; symmetry codes as in Table 2).
The resorcinol hydroxy group may be arranged in one of the ways depicted in Scheme 2. In (I), the orcin hydroxy groups assume the first motif, which is in contrast with the third motif observed in the resorcinol-urea (1/1) adduct (Pickering & Small, 1982) and the second motif observed in the resorcinol-isonicotinamide (1/2) adduct (Vishweshwar et al., 2003). The orcin molecules are pseudo-C2 symmetrically related.
As shown in Fig. 2, one-dimensional chiral hydrogen-bonded chains are formed along the b axis, with the screw-pitch equal to the length of the b axis. The chain can be described in graph-set notation (Etter, 1990; Grell et al., 2000) as C44(22). Neighbouring chains in the (001) plane are associated with each other principally by van der Waals interactions and are interrelated by translation, thus resulting in a chiral layer. There are four kinds of chiral layer in the crystal of (I). C—H···O hydrogen bonds (Table 2) play an important role in stabilizing the chiral structure. Neighbouring chiral layers are related to each other via C5—H5B···O2iii, C6—H6A···O3iii and C10—H10A···O1iv hydrogen bonds (symmetry codes as in Table 2?).
There are four C—H···π interactions in the crystal, namely C8—H8Aiii···π(C13/C15/C17) (3.30 Å), C7—H7Biii···π(C13/C15/C17) (3.36 Å), C1—H1B(x + 1/2, 3/2 − y, 2 − z)···π(C20/C22/C24) (3.37 Å) and C2—H2A(x + 1/2, 3/2 − y, 2 − z)···π(C20/C22/C24) (3.30 Å), where the values in parentheses indicate the distances between the H atom and the centroid of the phenyl ring. As a result of the balance of C—H···O and C—H···π interactions, the two orcin molecules that are bridged by a DABCO molecule are fixed in a dihedral angle of 30.8 (3)°.
DABCO may assume one of four conformations, namely ordered and non-distorted, ordered and distorted, disordered and non-distorted, or disordered and distorted (Nimmo & Lucas, 1976). The disordered conformations are frequently observed, such as in DABCO-biphenol (1/1) (Ferguson et al., 1998), DABCO-perchloric acid (1/1) (Katrusiak, 2000) and DABCO-maleic acid (1/2) (Sun & Jin, 2002). In (I), both of the DABCO molecules are ordered, and they are almost non-distorted, as indicated by N—C—C—N torsion angles with mean values of 1.2 (4) and 0.9 (4)°, respectively, for N1/N2 and N3/N4.