The title compound, C24H12N4·H2O, characterized earlier with limited precision [Rudi, Benayahu, Goldberg & Kashman (1988). Tetrahedron Lett. 29, 6655–6656], was redetermined at ca 110 K in the context of its uniquely interesting metal complexation and crystal packing features. It reveals tight stacking of the flat aromatic molecules, arranged in layered zones parallel to the ab plane of the crystal structure.
Supporting information
CCDC reference: 274631
Key indicators
- Single-crystal X-ray study
- T = 110 K
- Mean (C-C) = 0.003 Å
- R factor = 0.062
- wR factor = 0.166
- Data-to-parameter ratio = 15.1
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ?
PLAT333_ALERT_2_C Large Average Benzene C-C Dist. C12 -C17 1.45 Ang.
PLAT355_ALERT_3_C Long O-H Bond (0.82A) O29 - H29B ... 1.03 Ang.
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 2
H2 O
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
4 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
1 ALERT type 2 Indicator that the structure model may be wrong or deficient
1 ALERT type 3 Indicator that the structure quality may be low
2 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and Mercury (Bruno et al., 2002); software used to prepare material for publication: SHELXL97.
7,8,15,16-tetraazadibenzo[b,n]perylene monohydrate
top
Crystal data top
C24H12N4·H2O | F(000) = 776 |
Mr = 374.39 | Dx = 1.478 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 9.3302 (3) Å | Cell parameters from 3619 reflections |
b = 10.9224 (4) Å | θ = 2.2–27.9° |
c = 16.5491 (7) Å | µ = 0.09 mm−1 |
β = 93.641 (2)° | T = 110 K |
V = 1683.08 (11) Å3 | Prism, yellow |
Z = 4 | 0.25 × 0.20 × 0.10 mm |
Data collection top
Nonius KappaCCD diffractometer | 2456 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.047 |
Graphite monochromator | θmax = 27.9°, θmin = 2.2° |
Detector resolution: 56 microns pixels mm-1 | h = 0→12 |
1° ω scans | k = −14→14 |
12446 measured reflections | l = −21→21 |
3980 independent reflections | |
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)] = 0.062 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.166 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0864P)2 + 0.2186P] where P = (Fo2 + 2Fc2)/3 |
3980 reflections | (Δ/σ)max < 0.001 |
264 parameters | Δρmax = 0.38 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
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 | 1.02429 (17) | 0.23562 (14) | −0.05593 (9) | 0.0261 (4) | |
C2 | 1.1166 (2) | 0.33421 (17) | −0.04428 (11) | 0.0267 (4) | |
C3 | 1.1954 (2) | 0.36771 (18) | −0.11043 (12) | 0.0327 (5) | |
H3 | 1.1824 | 0.3244 | −0.1601 | 0.039* | |
C4 | 1.2914 (2) | 0.4631 (2) | −0.10321 (13) | 0.0391 (5) | |
H4 | 1.3455 | 0.4849 | −0.1478 | 0.047* | |
C5 | 1.3097 (2) | 0.52830 (19) | −0.03054 (13) | 0.0381 (5) | |
H5 | 1.3756 | 0.5946 | −0.0264 | 0.046* | |
C6 | 1.2338 (2) | 0.49787 (18) | 0.03486 (12) | 0.0323 (5) | |
H6 | 1.2469 | 0.5434 | 0.0837 | 0.039* | |
C7 | 1.1361 (2) | 0.39868 (17) | 0.02974 (11) | 0.0272 (4) | |
C8 | 1.0576 (2) | 0.35711 (17) | 0.09702 (11) | 0.0272 (4) | |
C9 | 1.0672 (2) | 0.40929 (18) | 0.17455 (11) | 0.0312 (5) | |
H9 | 1.1241 | 0.4803 | 0.1852 | 0.037* | |
C10 | 0.9936 (2) | 0.35681 (18) | 0.23513 (11) | 0.0321 (5) | |
H10 | 1.0052 | 0.3913 | 0.2878 | 0.039* | |
N11 | 0.90543 (18) | 0.25875 (15) | 0.22398 (9) | 0.0310 (4) | |
C12 | 0.8915 (2) | 0.21056 (17) | 0.14996 (11) | 0.0265 (4) | |
C13 | 0.9665 (2) | 0.25481 (16) | 0.08450 (11) | 0.0247 (4) | |
C14 | 0.95302 (19) | 0.19878 (16) | 0.00541 (11) | 0.0241 (4) | |
C15 | 0.85387 (19) | 0.09319 (16) | −0.00765 (10) | 0.0233 (4) | |
C16 | 0.77689 (19) | 0.04980 (16) | 0.05938 (10) | 0.0238 (4) | |
C17 | 0.7922 (2) | 0.10607 (17) | 0.13658 (10) | 0.0248 (4) | |
N18 | 0.71707 (17) | 0.07030 (14) | 0.19859 (9) | 0.0280 (4) | |
C19 | 0.6260 (2) | −0.02488 (17) | 0.18552 (11) | 0.0306 (5) | |
H19 | 0.5728 | −0.0511 | 0.2295 | 0.037* | |
C20 | 0.6047 (2) | −0.08655 (17) | 0.11355 (11) | 0.0290 (4) | |
H20 | 0.5395 | −0.1534 | 0.1086 | 0.035* | |
C21 | 0.6811 (2) | −0.04892 (16) | 0.04720 (11) | 0.0252 (4) | |
C22 | 0.6642 (2) | −0.10200 (17) | −0.03265 (11) | 0.0254 (4) | |
C23 | 0.5692 (2) | −0.19916 (17) | −0.05316 (12) | 0.0300 (4) | |
H23 | 0.5149 | −0.2351 | −0.0127 | 0.036* | |
C24 | 0.5546 (2) | −0.24209 (18) | −0.13122 (12) | 0.0333 (5) | |
H24 | 0.4893 | −0.3068 | −0.1444 | 0.040* | |
C25 | 0.6351 (2) | −0.19149 (18) | −0.19170 (12) | 0.0323 (5) | |
H25 | 0.6241 | −0.2219 | −0.2455 | 0.039* | |
C26 | 0.7300 (2) | −0.09772 (17) | −0.17310 (11) | 0.0294 (5) | |
H26 | 0.7853 | −0.0640 | −0.2139 | 0.035* | |
C27 | 0.7453 (2) | −0.05174 (16) | −0.09359 (11) | 0.0252 (4) | |
N28 | 0.83945 (17) | 0.04582 (14) | −0.08044 (9) | 0.0261 (4) | |
O29 | 0.66165 (17) | 0.26434 (14) | −0.16238 (9) | 0.0439 (4) | |
H29A | 0.6930 | 0.3042 | −0.2092 | 0.071 (8)* | |
H29B | 0.7372 | 0.1969 | −0.1502 | 0.148 (16)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0260 (9) | 0.0266 (8) | 0.0257 (8) | −0.0007 (7) | 0.0022 (6) | 0.0016 (7) |
C2 | 0.0262 (10) | 0.0266 (10) | 0.0270 (10) | −0.0001 (8) | −0.0004 (8) | 0.0010 (8) |
C3 | 0.0382 (12) | 0.0323 (11) | 0.0279 (10) | −0.0046 (9) | 0.0036 (9) | −0.0001 (9) |
C4 | 0.0410 (13) | 0.0420 (12) | 0.0349 (11) | −0.0102 (10) | 0.0065 (9) | 0.0041 (10) |
C5 | 0.0371 (13) | 0.0357 (12) | 0.0413 (12) | −0.0121 (9) | 0.0003 (9) | 0.0014 (10) |
C6 | 0.0347 (12) | 0.0290 (10) | 0.0328 (10) | −0.0020 (9) | −0.0014 (9) | −0.0035 (9) |
C7 | 0.0260 (10) | 0.0256 (10) | 0.0295 (10) | 0.0005 (8) | −0.0015 (8) | 0.0008 (8) |
C8 | 0.0285 (11) | 0.0276 (10) | 0.0250 (10) | 0.0029 (8) | −0.0013 (8) | −0.0010 (8) |
C9 | 0.0322 (11) | 0.0295 (10) | 0.0313 (10) | −0.0014 (9) | −0.0026 (8) | −0.0034 (8) |
C10 | 0.0354 (12) | 0.0352 (11) | 0.0256 (10) | 0.0004 (9) | 0.0007 (8) | −0.0067 (9) |
N11 | 0.0352 (10) | 0.0350 (9) | 0.0226 (8) | 0.0010 (7) | 0.0010 (7) | −0.0030 (7) |
C12 | 0.0275 (10) | 0.0269 (10) | 0.0250 (9) | 0.0038 (8) | 0.0012 (8) | 0.0001 (8) |
C13 | 0.0242 (10) | 0.0262 (10) | 0.0234 (9) | 0.0025 (8) | −0.0006 (7) | 0.0011 (8) |
C14 | 0.0249 (10) | 0.0231 (9) | 0.0240 (9) | 0.0024 (7) | −0.0006 (7) | 0.0002 (8) |
C15 | 0.0230 (10) | 0.0245 (9) | 0.0225 (9) | 0.0006 (8) | 0.0014 (7) | 0.0005 (8) |
C16 | 0.0240 (10) | 0.0238 (9) | 0.0234 (9) | 0.0031 (7) | 0.0010 (7) | 0.0009 (8) |
C17 | 0.0270 (10) | 0.0255 (9) | 0.0218 (9) | 0.0037 (8) | 0.0021 (7) | 0.0034 (8) |
N18 | 0.0313 (9) | 0.0291 (9) | 0.0238 (8) | 0.0022 (7) | 0.0031 (7) | 0.0032 (7) |
C19 | 0.0339 (11) | 0.0310 (10) | 0.0274 (10) | 0.0034 (9) | 0.0057 (8) | 0.0067 (8) |
C20 | 0.0295 (11) | 0.0271 (10) | 0.0304 (10) | −0.0001 (8) | 0.0027 (8) | 0.0034 (8) |
C21 | 0.0281 (10) | 0.0227 (9) | 0.0246 (9) | 0.0041 (8) | 0.0011 (7) | 0.0033 (8) |
C22 | 0.0248 (10) | 0.0241 (9) | 0.0272 (9) | 0.0022 (8) | 0.0012 (8) | 0.0008 (8) |
C23 | 0.0321 (11) | 0.0266 (10) | 0.0312 (10) | −0.0016 (8) | 0.0021 (8) | 0.0018 (8) |
C24 | 0.0363 (12) | 0.0266 (10) | 0.0367 (11) | −0.0056 (9) | 0.0001 (9) | −0.0010 (9) |
C25 | 0.0360 (12) | 0.0308 (11) | 0.0297 (10) | −0.0003 (9) | −0.0019 (8) | −0.0063 (9) |
C26 | 0.0323 (11) | 0.0309 (10) | 0.0254 (9) | 0.0003 (9) | 0.0043 (8) | −0.0013 (8) |
C27 | 0.0250 (10) | 0.0241 (9) | 0.0266 (9) | 0.0009 (8) | 0.0024 (7) | −0.0001 (8) |
N28 | 0.0267 (9) | 0.0269 (8) | 0.0247 (8) | −0.0010 (7) | 0.0017 (6) | −0.0021 (7) |
O29 | 0.0459 (10) | 0.0463 (9) | 0.0407 (9) | −0.0004 (8) | 0.0126 (7) | 0.0101 (7) |
Geometric parameters (Å, º) top
N1—C14 | 1.311 (2) | C15—N28 | 1.310 (2) |
N1—C2 | 1.385 (2) | C15—C16 | 1.439 (2) |
C2—C3 | 1.406 (3) | C16—C21 | 1.407 (3) |
C2—C7 | 1.415 (3) | C16—C17 | 1.417 (2) |
C3—C4 | 1.374 (3) | C17—N18 | 1.337 (2) |
C3—H3 | 0.9500 | N18—C19 | 1.351 (2) |
C4—C5 | 1.399 (3) | C19—C20 | 1.372 (3) |
C4—H4 | 0.9500 | C19—H19 | 0.9500 |
C5—C6 | 1.371 (3) | C20—C21 | 1.408 (3) |
C5—H5 | 0.9500 | C20—H20 | 0.9500 |
C6—C7 | 1.415 (3) | C21—C22 | 1.443 (2) |
C6—H6 | 0.9500 | C22—C27 | 1.410 (3) |
C7—C8 | 1.444 (3) | C22—C23 | 1.410 (3) |
C8—C9 | 1.402 (3) | C23—C24 | 1.373 (3) |
C8—C13 | 1.412 (3) | C23—H23 | 0.9500 |
C9—C10 | 1.376 (3) | C24—C25 | 1.402 (3) |
C9—H9 | 0.9500 | C24—H24 | 0.9500 |
C10—N11 | 1.356 (3) | C25—C26 | 1.376 (3) |
C10—H10 | 0.9500 | C25—H25 | 0.9500 |
N11—C12 | 1.332 (2) | C26—C27 | 1.407 (3) |
C12—C13 | 1.411 (3) | C26—H26 | 0.9500 |
C12—C17 | 1.478 (3) | C27—N28 | 1.389 (2) |
C13—C14 | 1.443 (2) | O29—H29A | 0.9515 |
C14—C15 | 1.486 (2) | O29—H29B | 1.0306 |
| | | |
C14—N1—C2 | 118.18 (16) | N28—C15—C14 | 117.84 (16) |
N1—C2—C3 | 116.46 (17) | C16—C15—C14 | 118.68 (15) |
N1—C2—C7 | 123.53 (17) | C21—C16—C17 | 119.23 (16) |
C3—C2—C7 | 120.00 (18) | C21—C16—C15 | 119.05 (16) |
C4—C3—C2 | 120.00 (19) | C17—C16—C15 | 121.70 (17) |
C4—C3—H3 | 120.0 | N18—C17—C16 | 122.52 (17) |
C2—C3—H3 | 120.0 | N18—C17—C12 | 117.71 (16) |
C3—C4—C5 | 120.26 (19) | C16—C17—C12 | 119.75 (16) |
C3—C4—H4 | 119.9 | C17—N18—C19 | 117.18 (16) |
C5—C4—H4 | 119.9 | N18—C19—C20 | 124.88 (18) |
C6—C5—C4 | 120.96 (19) | N18—C19—H19 | 117.6 |
C6—C5—H5 | 119.5 | C20—C19—H19 | 117.6 |
C4—C5—H5 | 119.5 | C19—C20—C21 | 118.74 (18) |
C5—C6—C7 | 120.08 (19) | C19—C20—H20 | 120.6 |
C5—C6—H6 | 120.0 | C21—C20—H20 | 120.6 |
C7—C6—H6 | 120.0 | C16—C21—C20 | 117.44 (17) |
C2—C7—C6 | 118.67 (17) | C16—C21—C22 | 118.08 (16) |
C2—C7—C8 | 117.88 (17) | C20—C21—C22 | 124.45 (17) |
C6—C7—C8 | 123.42 (17) | C27—C22—C23 | 118.58 (16) |
C9—C8—C13 | 117.34 (17) | C27—C22—C21 | 117.80 (17) |
C9—C8—C7 | 124.88 (18) | C23—C22—C21 | 123.61 (17) |
C13—C8—C7 | 117.77 (16) | C24—C23—C22 | 120.45 (18) |
C10—C9—C8 | 119.46 (19) | C24—C23—H23 | 119.8 |
C10—C9—H9 | 120.3 | C22—C23—H23 | 119.8 |
C8—C9—H9 | 120.3 | C23—C24—C25 | 120.77 (19) |
N11—C10—C9 | 123.82 (18) | C23—C24—H24 | 119.6 |
N11—C10—H10 | 118.1 | C25—C24—H24 | 119.6 |
C9—C10—H10 | 118.1 | C26—C25—C24 | 119.99 (18) |
C12—N11—C10 | 117.39 (17) | C26—C25—H25 | 120.0 |
N11—C12—C13 | 123.13 (18) | C24—C25—H25 | 120.0 |
N11—C12—C17 | 117.79 (17) | C25—C26—C27 | 120.01 (18) |
C13—C12—C17 | 119.07 (16) | C25—C26—H26 | 120.0 |
C12—C13—C8 | 118.78 (16) | C27—C26—H26 | 120.0 |
C12—C13—C14 | 122.15 (17) | N28—C27—C26 | 116.45 (16) |
C8—C13—C14 | 119.06 (17) | N28—C27—C22 | 123.32 (16) |
N1—C14—C13 | 123.55 (17) | C26—C27—C22 | 120.20 (17) |
N1—C14—C15 | 117.85 (16) | C15—N28—C27 | 118.29 (16) |
C13—C14—C15 | 118.60 (16) | H29A—O29—H29B | 104.1 |
N28—C15—C16 | 123.47 (17) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O29—H29B···N28 | 1.03 | 2.20 | 3.162 (2) | 155 |
O29—H29A···N18i | 0.95 | 2.07 | 2.996 (2) | 163 |
Symmetry code: (i) x, −y+1/2, z−1/2. |