π–π stacking in 7,8,15,16-tetra­aza­dibenzo­[b,n]­peryl­ene monohydrate at 110 K

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.

Key indicators

• Single-crystal X-ray study
• T = 110 K
• Mean [sigma](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

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Computing details

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

Crystal data

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) Å^3	Prism, yellow
Z = 4	0.25 × 0.20 × 0.10 mm

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.166	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0864P)^2 + 0.2186P] where P = (Fo^2 + 2Fc^2)/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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

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···N18^i	0.95	2.07	2.996 (2)	163

Symmetry code: (i) x, −y+1/2, z−1/2.