Benz[cd]indol-2(1H)-one at 298 and 100 K

Weakly diffracting crystals of benz[cd]indol-2(1H)-one (naphtho­lactam), C₁₁H₇NO, were unsuitable for data collection by early photographic methods. However, a diffrac­tom­eter data set collected at room temperature in 1989 was solved and refined. The peak scans were broad, and the results indicated disorder or a satellite crystal. Recent data collection (on another crystal from the same sample) with an area detector at 100 K revealed the same disorder, and made it possible to refine two different, more complete, disorder models. Both models assume an occasional 180° rotation of the nearly planar centrosymmetric cis-lactam dimer. The refinements differ, especially in the anisotropic displacement parameters for the -C(=O)-NH- portion of the mol­ecule. Both models at 100 K give a C-N (`amide') bond distance of 1.38 Å, about 0.04 Å longer than the average distance in saturated [gamma]-lactams in the Cambridge Structural Database. Cohesive packing inter­actions between mol­ecules include opposing-dipole dimers; the packing may explain the 10:1 ratio favoring the major-occupancy mol­ecule.

S1. Comment

Naphtholactam, (I), may be used as a starting material in the preparation of anticancer and hypotensive agents; an improved large-scale synthesis of the title compound has been published (Marzoni & Varney, 1997). Deprotonation of (I) yields the lactamate, which has been tested as a ligand with fluorophore properties (Limmert et al., 2003). Nucleoside 2-deoxyribosyltransferase from Trypanosoma brucei was crystallized with a molecule of (I) in the active site (Bosch et al., 2006) in a study of `fragment cocktail soaks'. The Cambridge Structural Database (CSD, Version 5.32; Allen, 2002; Macrae et al., 2008) contains three-dimensional coordinates for 15 derivatives of (I), but no published crystal structure of the unsubstituted compound was found.

Before our investigation began, it was predicted that the –C(═O)—NH– (`amide') bond in (I) would be longer than that in other amides. But what is the distance in `other amides'? The CIF dictionary contains no reference C—N bond length for amides. Clearly, the C—N and C═O bond lengths are changed by distortion of the amide unit away from planarity (Bennett et al., 1990; Wang et al., 1991, and references therein). In this paper, we examine evidence that, in crystal structures, these distances also depend on the intermolecular hydrogen-bonding pattern.

In the crystal structure of (I) presented here, the structural units are pairs of molecules strongly hydrogen0bonded in dimers. The dimers are shown with atom numbering in Figs. 1, 2 and 3. Tables 1, 2 and 3 give bond lengths for the five-membered ring in (Ia), at 298 K, (Ib), at 100 K, and (Ic), with the same data as (Ib) but using a different disorder model.

As in 2-pyrrolidone (or 2-pyrrolidinone, 2-PD, the saturated γ-lactam), the –C(═O)—NH– conformation in (I) is required to be cis, and planar or nearly so (Fig. 4 and Table 4). To estimate the effect of the naphthalene rings on the lactam portion of (I), we may first examine 2-PD and its derivatives.

The length of the cis-amide C—N bond in cyclic lactam crystal structures was found to be nearly independent of ring size, from four- to eight-membered rings (Yang et al., 1987). For five-membered rings, an average value from 41 crystal structures from the CSD [1.335 (13) Å, Table 4] was quoted. The structures surveyed included both dimeric and nondimeric hydrogen bonding in the crystal packing, and all were considered to be planar.

However, in an ab initio study the `amide' C—N and C═O bond lengths for 2-PD were shown to differ for the single molecule, hydrogen-bonded 2-PD dimers and clusters of 2-PD with water molecules (Yekeler et al., 1999). The C—N distance decreased by about 0.02 Å, and the C═O distance increased by about 0.01 Å, if 2-PD formed N—H···O and C═O···H hydrogen bonds with another 2-PD molecule or with water. [Out-of-plane distortions are also accompanied by a smaller change in the C═O than in the C—N bond lengths (Wang et al., (1991).]

The structure of (2-PD)₃.HBr₃ , which was referred to by Yekeler et al. (1999), shows different hydrogen-bonding patterns for the three 2-PD molecules in the asymmetric unit (Table 4). The shortest C—N (1.24 Å) and longest C═O (1.29 Å) are attributed to a C═O···H+···O═C interaction (O···O = 2.45 Å); the structure may be better described in terms of three units, 2-PD, (2-PD)₂.H⁺ and Br₃^- (Boeyens et al., 1986). Ions were excluded from the searches described below.

Table 4 gives the `amide' bond lengths (C—N and C═O) from the ab initio study, from appropriate structures from the CSD and from this work. Fig. 4 shows the models used to search the CSD and some example structures. These examples indicate that, even though there is little or no distortion from planarity, ions and cocrystals may exhibit additional hydrogen bonding that extends the resonance of the –C(═O)—NH– group. The carbonyl O atom may accept two hydrogen bonds, as demonstrated by the structure of 2-PD.H<sub>2</sub>O (Table 4 and Fig. 4). For these reasons, we have averaged the distances for centrosymmetric dimers, nondimers (including `dimers' with no center of symmetry) and cocrystals separately.

As seen in Table 4, more recent crystal structures are, on average, in agreement with the ab initio cyclic dimer value of 1.338 Å (Yekeler et al., 1999). For example, in a low-temperature phase of 2-PD (CSD refcode NILYAI, Fig. 4) the C—N bond length is 1.335 (2) Å. The average C—N and C═O bond lengths for crystal structures of 2-PD derivatives in the CSD are nearly the same for cyclic dimers and for nondimers.

Examination of the structures with unusually long and unusually short amide bonds suggests explanations for variations from the average. An example of an outlier with `long' amide bonds is A2 in Fig. 4 [(5S*)-1-oxo-2-azaspiro[4.4]non-7-ene-7-carboxylate; GASSUP; Yong et al., 2005]. A centrosymmetric amide–amide dimer is formed, but the carbonyl O atom also accepts a C—H···O hydrogen bond and makes contact with a neighboring –C═C– C atom. The amide C—N and C═O distances are 1.355 (2) and 1.256 (2) Å, respectively, each significantly longer than the average distances in Table 4. On average, however, the sum of these two distances is nearly constant. When structures determined at 200 K and below are separated from the overall search results, the average distances for dimers and nondimers are slightly longer, as expected when thermal motion effects are reduced.

Cocrystals are averaged separately in Table 4 because they generally produce `short' C—N (amide) bonds (and `long' C═O bonds). For 2-PD.H₂O (DIPMUK, Table 4), the C—N bond is significantly shorter [1.319 (3) Å] and the C═O bond longer than average. Each water molecule accepts one and donates two H atoms to hydrogen bonds; see A3 in Fig. 4. (This arrangement was not included in the ab initio study.) Similarly, for gabapentin-lactam–benzoic acid (XOHXAU), the C—N bond is shorter than that in gabapentin-lactam (A1, AWUWOE). In the benzoic acid solvate, the –C(═ O)—NH– O atom is hydrogen-bonded to both solvent and another lactam in a cyclic tetramer, while the pure compound is a cyclic dimer. In a recent example, cocrystals of 2-PD with succinic acid and with fumaric acid have different chain arrangements but similarly short C—N bond lengths of 1.322 (7) and 1.321 (3) Å, respectively (Callear et al., 2009). In all of these cases, additional hydrogen bonding to carbonyl O atoms appears to lengthen the C═O bond and shorten the C—N bond by approximately equal amounts.

Bond lengths also vary for primary amides (Table 4). The examples quoted were chosen from a study of molecule–molecule energies (Gavezzotti, 2010). For an illustration of the effect of intermolecular interactions in trans –C(═O)—N(R)—H amides, we cite a recent study of the crystal structures of two symmetrical pyridine-2-carboxamide derivatives (Munro & Wilson, 2010). Chemically identical but crystallographically unique bonds differ by 0.013 Å, six times the s.u. of the distances (Table 4). The shorter C—N distance is correlated to the longer C═O distance, attributable to stronger intermolecular H···O hydrogen bonds.

For naphtholactam, (I), the values for the C—N bond length (in the major orientation) are 1.37–1.38 Å and the corresponding C═O distances are 1.24–1.23 Å (Tables 1, 2, 3 and 4). For the ten naphtholactam derivatives (excluding cocrystals and helicenes) in the CSD, the values for C—N range from 1.38 to 1.46 Å. Again, longer C—N bonds are accompanied by shorter C═O distances. Only one of these derivatives can form the hydrogen-bonded dimeric structure found here; for QACQOA (B1, Fig. 4 and Table 4), the C—N length is 1.376 (7) Å at 228 K (Wang et al., 1998), in agreement with our 100 K results. Derivatives with N—R have longer C—N bonds. In RAKYUY (B2), a Br atom makes contact with the carbonyl O atom. In DUXXEA (B3), the two molecules in the asymmetric unit have C—N distances of 1.42 (1) and 1.460 (8) Å; the corresponding C═O distances are 1.219 (8) and 1.209 (9) Å. The amide O atom in molecule 1 has three C—H···O close contacts, while that in molecule 2 has only two.

Thus, the C—N bond length in (I) is ~0.04 Å longer than that in 2-PD and its derivatives. The replacement of two single C—C bonds in 2-PD (NILYAI; Goddard et al., 1998) with aromatic C≐C bonds in (I) introduces other changes as well: N1—C2 is shorter (1.41 versus 1.46 Å), C1—C4 is shorter (1.48 versus 1.52 Å) and the five-membered ring is more nearly planar.

The crystal packing for (I), shown in Figs. 5 and 6, is strikingly similar to that in 2-PD (NILYAI). Stacks of centrosymmetric dimers result in a packing coefficient of 0.75 (Gavezzotti, 2003). In the stacks, additional `dimers' are formed (Fig. 6), with opposing dipoles resembling those reported for cyclobutanone and cyclopentanone (Yufit & Howard, 2011). Table 5 gives intermolecular cohesive energy values and distances (Gavezzotti, 2003). Though these are summaries of point-to-point energies, including repulsions between the N and O atoms in the centrosymmetric dimer, they are useful for comparison. It is likely that the dimer was present in the benzene solution that was used to prepare the crystals.

In (I), there are two stacks of dimers related by an n-glide (Fig. 5). If a dimer were rotated by ~180° before insertion in a stack, as is proposed in the disorder model, both the cohesive stacking interactions within the stacks and the cohesive interactions between adjacent stacks would be adversely affected. Thus, the packing may explain the 10:1 ratio favoring the major-occupancy molecule.

Related literature

For related literature, see: Allen (2002); Bennett et al. (1990); Boeyens et al. (1986); Bosch et al. (2006); Callear et al. (2009); Gavezzotti (2003, 2010); Goddard et al. (1998); Grob & Schmid (1950); Limmert et al. (2003); Macrae et al. (2008); Marzoni & Varney (1997); Munro & Wilson (2010); Sheldrick (2008); Wang et al. (1991, 1998); Yang et al. (1987); Yekeler et al. (1999); Yong et al. (2005); Yufit & Howard (2011).

S2. Experimental

The sample was synthesized by Professor Cyril A. Grob (Grob & Schmid, 1950).

S3. Refinement

At room temperature [(Ia)], a peak of 0.59 e^- Å^-3 in the difference map after refinement of the 20 C, H, N and O atoms, close to atom H1N, was assumed to be a second partial O atom (O1A) in the model described above (Fig. 1). Occupancies for the two O atoms refined to 0.921 (4) and 0.079 (4). The C1—O1 distance in Table 1 is for the major orientation. At 100 K [(Ib)] (Fig. 2), a more detailed model for refinement of the disorder was employed, using restraints SIMU, EADP, DFIX, SADI and FLAT (SHELXL97; Sheldrick, 2008) in the O1A, C1A, N1A and H1NA region. The occupancies refined to 0.919 (4) for atoms C1, O1, N1 and H1N, and to 0.081 (4) for atoms C1A, O1A, N1A and H1NA. Restraints were not completely successful, as shown in the selected bond lengths reported in Table 2. In addition, checkCIF reported a Hirshfeld test greater than five times the s.u., as was also true at room temperature. A second model for the 100 K data [(Ic)] (Fig. 3) employed a rigid-body refinement (constructed using the instruction SAME O1A > H11A) for the entire minor-occupancy orientation. Occupancies refined to 0.912 (3) and 0.088 (3). Changes in bond lengths, angles, R and R_w for the major-occupancy molecule were minor (Table 3). Anisotropic displacement parameters were significantly improved; see Fig. 3.

Computing details

Data collection: UCLA Crystallographic Package (Strouse, 1994) for Ia298K; APEX2 (Bruker, 2005) for Ib100K, Ic100K. Cell refinement: UCLA Crystallographic Package (Strouse, 1994) for Ia298K; SAINT (Bruker, 2005) for Ib100K, Ic100K. Data reduction: UCLA Crystallographic Package (Strouse, 1994) for Ia298K; SAINT (Bruker, 2005) for Ib100K, Ic100K. Program(s) used to solve structure: SHELXS90 (Sheldrick, 2008) for Ia298K; SHELXS97 (Sheldrick, 2008) for Ib100K, Ic100K. For all compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The structure of (Ia) at 298 K. The molecule at (x, y, z) is shown on the right, including the minor-occupancy atom O1A. Its hydrogen-bonded partner at (-x, -y, -z + 1) (denoted `ii') is shown on the left (major-occupancy atoms only N1^ii, C1^ii etc.). The occupancies for atoms O1 [0.921 (4)] and O1A [0.079 (4)] were refined and the occupancies for all other atoms are 1.0. Hirshfeld test for N1—C1 = 0.0090 Å^2 (Hirshfeld, 1976). The O1···N1^ii (O1^ii···N1) distance is 2.866 Å. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The structure of (Ib) at 100 K. The molecule at (x, y, z) is shown on the right, including the minor-occupancy atoms N1A, C1A, O1A and H1NA. Its hydrogen-bonded partner at (-x, -y, -z + 1) (denoted `ii') is shown on the left (major-occupancy atoms only N1^ii, C1^ii etc.). Hirshfeld test for N1—C2 = 0.0057 Å^2 (Hirshfeld, 1976). The O1···N1^ii (O1^ii···N1) distance is 2.845 Å. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 3. The structure of (Ic) at 100 K. The molecule at (x, y, z) is shown on the right, including the minor-occupancy molecule refined as a rigid body (atoms O1A–C11A, with isotropic U^ij). Its hydrogen-bonded partner at (-x, -y, -z + 1) (denoted `ii') is shown on the left (major-occupancy atoms only). Hirshfeld test for N1—C2 = 0.0035 Å^2 (Hirshfeld, 1976). The O1···N1^ii (O1^ii···N1) distance is 2.840 Å. Note that atoms C3 and C3A are at nearly the same position in the two orientations. H atoms for the minor-occupancy molecule have been omitted (except for H1NA).
	Fig. 4. Capped-stick representations for the two searches in the CSD (see Table 4) (MercuryCSD; Macrae et al., 2008). Search A: 2-PD derivatives, with C atomss designated T required to be bonded to four atoms and R = H. Examples: A1: 2-azaspiro[4.5]decan-3-one; A2: (5S*)-1-oxo-2-azaspiro[4.4]non-7-ene-7-carboxylate; A3: 2-pyrrolidinone monohydrate. [Symmetry codes: (i) x, y, z; (ii) x, y, z - 1; (iii) x, -y + 1/2, z - 1/2.] Search B: naphtholactam derivatives, any singly-bonded substituent for R, no cocrystals. Examples: B1: 7-amino-6,8-bis(4-methoxyphenyl)benz[cd]indol-2(1H)-one; B2: 6-(4-bromophenyl)-1-methylbenz[cd]indol-2-one; B3: S-benzyl 2-oxobenzo[cd]indole-1(2H)-carbothioate.
	Fig. 5. The crystal packing for the major-occupancy molecule at 100 K, spacefilling style, colored according to symmetry operation (MercuryCSD; Macrae et al., 2008). The b axis is vertical in this view. Hydrogen-bonded pairs of molecules related by centers of symmetry form adjacent stacks. The stacks related by the n-glide (purple and green in the electronic version of the journal) form an angle of 56° to the (x, y, z) and (-x, -y, -z) (gray and yellow) stacks. [Symmetry codes: (i) x, y, z; (ii) -x, -y, -z + 1; (iii) x, y + 1, z; (iv) -x, -y + 1, -z + 1; (v) x, y - 1, z; (vi) -x, -y - 1, -z + 1; (vii) -x + 1/2, y + 1/2, -z + 1/2; (viii) x + 1/2, -y + 1/2, z - 1/2; (ix) -x + 1/2, y - 1/2, -z + 1/2; (x) x + 1/2, -y - 1/2, z - 1/2; (xi) x + 1, y + 1, z; (xii) -x + 1, -y + 1, -z + 1.] The center of symmetry between (i) and (ii) is at (0, 0, 1/2), and that between (vii) and (viii) is at (1/2, 1/2, 0).
	Fig. 6. The `dimer' of opposing dipoles formed by the stacking interaction between molecules at (x, y, z) [symmetry code (i)] and (-x, -y + 1, -z + 1) [symmetry code (iv)]. The distance from N1^i to C3^iv is 3.63 Å. Dipole directions are shown by arrows; the dipole charge is 1.19 (Gavezzotti, 2003). See also Fig. 5.
	Fig. 7. The packing of (I) (principal conformer), in ball-and-stick style, showing 2 × 2 × 1 unit cells. The van der Waals surfaces of the hydrogen-bonded atoms in the centrosymmetric dimer at 0,0,1/2 are highlighted.

(Ia298K) Benz[cd]indol-2(1H)-one

Crystal data

C11H7NO	F(000) = 352
Mr = 169.18	Dx = 1.355 Mg m^−3
Monoclinic, P21/n	Melting point = 448–450 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 9.251 (3) Å	Cell parameters from 19 reflections
b = 6.7748 (17) Å	θ = 4.8–10.2°
c = 13.256 (4) Å	µ = 0.09 mm^−1
β = 93.196 (8)°	T = 298 K
V = 829.5 (4) Å^3	Cut plate, yellow
Z = 4	0.35 × 0.25 × 0.10 mm

Data collection

Modified Hubers diffractometer	Rint = 0.000
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 2.6°
Graphite monochromator	h = 0→11
θ/2θ scans	k = 0→8
1462 measured reflections	l = −15→15
1462 independent reflections	3 standard reflections every 97 reflections
992 reflections with I > 2σ(I)	intensity decay: 0.4%

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.133	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0523P)^2 + 0.0789P] where P = (Fo^2 + 2Fc^2)/3
1462 reflections	(Δ/σ)max < 0.001
128 parameters	Δρmax = 0.19 e Å^−3
0 restraints	Δρmin = −0.14 e Å^−3

Special details

Experimental. The alternate space group setting P 21/n was chosen because the cell angle beta is close to 90 degrees.

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. Data were collected in 1989; negative intensities were set to zero. F and σ(F) were input, and F² and σ(F²) were calculated by SHELXL97. When refinement was complete, a residual peak of about 0.59 suggested disorder. The disorder model assumes this peak is due to an occasional rotation of the H-bonded pair of molecules; O1 (major) and O1A (minor) have occupancies which refined to 0.921 (4) and 0.079 (4). The positions of C1, N1 and H1N are not corrected for the partial occupancies assumed. For this reason H1N appears to be connected to two atoms (N1 and O1A) and C1 has a short intermolecular contact (C1···O1A, 2.64). Hirshfeld test differences greater than 5 s.u. (N1—C1, C7—C8) show that displacement parameters are affected by the disorder. 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 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	Occ. (<1)
C1	0.1261 (2)	0.2398 (3)	0.48386 (16)	0.0562 (6)
N1	0.0140 (2)	0.2077 (3)	0.41424 (13)	0.0628 (5)
H1N	−0.0409	0.1052	0.4135	0.075*
O1	0.16442 (18)	0.1308 (2)	0.55565 (12)	0.0664 (6)	0.921 (4)
O1A	−0.1084 (19)	0.056 (3)	0.3873 (15)	0.072 (8)	0.079 (4)
C2	−0.0007 (2)	0.3644 (3)	0.34337 (15)	0.0561 (6)
C3	0.1094 (2)	0.4996 (3)	0.37131 (15)	0.0500 (5)
C4	0.1920 (2)	0.4308 (3)	0.45642 (15)	0.0542 (6)
C5	0.3055 (3)	0.5417 (4)	0.49434 (17)	0.0660 (7)
H5	0.3619	0.5006	0.5507	0.079*
C6	0.3341 (3)	0.7198 (4)	0.44545 (18)	0.0724 (7)
H6	0.4118	0.7963	0.4701	0.087*
C7	0.2517 (3)	0.7865 (4)	0.36223 (17)	0.0690 (7)
H7	0.2744	0.9064	0.3328	0.083*
C8	0.1340 (2)	0.6757 (3)	0.32145 (15)	0.0557 (6)
C9	0.0365 (3)	0.7161 (4)	0.23668 (16)	0.0677 (7)
H9	0.0453	0.8321	0.2000	0.081*
C10	−0.0698 (3)	0.5836 (4)	0.20974 (17)	0.0735 (7)
H10	−0.1314	0.6126	0.1539	0.088*
C11	−0.0918 (2)	0.4040 (4)	0.26195 (17)	0.0665 (7)
H11	−0.1655	0.3172	0.2413	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0574 (12)	0.0589 (13)	0.0524 (12)	0.0084 (11)	0.0048 (10)	0.0032 (11)
N1	0.0677 (12)	0.0587 (11)	0.0623 (11)	−0.0041 (9)	0.0064 (9)	0.0084 (9)
O1	0.0720 (12)	0.0647 (11)	0.0614 (11)	0.0026 (9)	−0.0080 (8)	0.0154 (9)
O1A	0.045 (11)	0.097 (16)	0.073 (14)	−0.037 (10)	−0.001 (9)	0.000 (11)
C2	0.0514 (12)	0.0656 (13)	0.0518 (12)	0.0040 (11)	0.0083 (10)	0.0019 (11)
C3	0.0506 (12)	0.0564 (12)	0.0439 (11)	0.0052 (10)	0.0091 (9)	0.0007 (10)
C4	0.0526 (12)	0.0616 (13)	0.0492 (12)	0.0055 (10)	0.0097 (10)	0.0001 (10)
C5	0.0624 (14)	0.0850 (17)	0.0505 (13)	0.0015 (13)	0.0010 (11)	−0.0070 (12)
C6	0.0720 (16)	0.0800 (17)	0.0660 (15)	−0.0172 (14)	0.0106 (13)	−0.0138 (14)
C7	0.0820 (17)	0.0633 (15)	0.0639 (15)	−0.0074 (13)	0.0250 (13)	−0.0017 (12)
C8	0.0594 (13)	0.0569 (13)	0.0525 (12)	0.0024 (10)	0.0176 (10)	0.0021 (11)
C9	0.0744 (15)	0.0727 (15)	0.0571 (14)	0.0128 (13)	0.0137 (12)	0.0191 (12)
C10	0.0645 (15)	0.101 (2)	0.0549 (14)	0.0141 (15)	0.0017 (12)	0.0128 (13)
C11	0.0557 (13)	0.0849 (17)	0.0588 (14)	−0.0005 (12)	0.0021 (11)	0.0031 (12)

Geometric parameters (Å, º)

C1—O1	1.241 (2)	C5—H5	0.9300
C1—N1	1.367 (3)	C6—C7	1.381 (3)
C1—C4	1.484 (3)	C6—H6	0.9300
N1—C2	1.419 (3)	C7—C8	1.405 (3)
N1—H1N	0.8600	C7—H7	0.9300
C2—C11	1.359 (3)	C8—C9	1.428 (3)
C2—C3	1.404 (3)	C9—C10	1.363 (3)
C3—C8	1.389 (3)	C9—H9	0.9300
C3—C4	1.406 (3)	C10—C11	1.420 (3)
C4—C5	1.364 (3)	C10—H10	0.9300
C5—C6	1.402 (3)	C11—H11	0.9300
O1—C1—N1	126.6 (2)	C7—C6—C5	122.7 (2)
O1—C1—C4	127.1 (2)	C7—C6—H6	118.6
N1—C1—C4	106.25 (18)	C5—C6—H6	118.6
C1—N1—C2	111.65 (18)	C6—C7—C8	120.9 (2)
C1—N1—H1N	124.2	C6—C7—H7	119.6
C2—N1—H1N	124.2	C8—C7—H7	119.6
C11—C2—C3	119.3 (2)	C3—C8—C7	114.8 (2)
C11—C2—N1	134.9 (2)	C3—C8—C9	115.2 (2)
C3—C2—N1	105.80 (18)	C7—C8—C9	130.0 (2)
C8—C3—C2	124.8 (2)	C10—C9—C8	119.7 (2)
C8—C3—C4	124.8 (2)	C10—C9—H9	120.2
C2—C3—C4	110.43 (19)	C8—C9—H9	120.2
C5—C4—C3	119.1 (2)	C9—C10—C11	123.9 (2)
C5—C4—C1	135.1 (2)	C9—C10—H10	118.1
C3—C4—C1	105.86 (19)	C11—C10—H10	118.1
C4—C5—C6	117.7 (2)	C2—C11—C10	117.2 (2)
C4—C5—H5	121.1	C2—C11—H11	121.4
C6—C5—H5	121.1	C10—C11—H11	121.4
O1—C1—N1—C2	179.1 (2)	C3—C4—C5—C6	−0.3 (3)
C4—C1—N1—C2	−0.8 (2)	C1—C4—C5—C6	−179.9 (2)
C1—N1—C2—C11	−179.8 (2)	C4—C5—C6—C7	0.7 (3)
C1—N1—C2—C3	0.2 (2)	C5—C6—C7—C8	−0.6 (4)
C11—C2—C3—C8	0.0 (3)	C2—C3—C8—C7	−179.22 (19)
N1—C2—C3—C8	179.96 (18)	C4—C3—C8—C7	0.2 (3)
C11—C2—C3—C4	−179.52 (19)	C2—C3—C8—C9	0.6 (3)
N1—C2—C3—C4	0.5 (2)	C4—C3—C8—C9	−179.97 (19)
C8—C3—C4—C5	−0.1 (3)	C6—C7—C8—C3	0.2 (3)
C2—C3—C4—C5	179.34 (19)	C6—C7—C8—C9	−179.6 (2)
C8—C3—C4—C1	179.59 (18)	C3—C8—C9—C10	−0.9 (3)
C2—C3—C4—C1	−0.9 (2)	C7—C8—C9—C10	178.9 (2)
O1—C1—C4—C5	0.8 (4)	C8—C9—C10—C11	0.6 (4)
N1—C1—C4—C5	−179.3 (2)	C3—C2—C11—C10	−0.3 (3)
O1—C1—C4—C3	−178.8 (2)	N1—C2—C11—C10	179.7 (2)
N1—C1—C4—C3	1.0 (2)	C9—C10—C11—C2	0.0 (4)

(Ib100K) Benz[cd]indol-2(1H)-one

Crystal data

C11H7NO	F(000) = 352
Mr = 169.18	Dx = 1.407 Mg m^−3
Monoclinic, P21/n	Melting point = 448–450 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 9.0551 (19) Å	Cell parameters from 6093 reflections
b = 6.7287 (14) Å	θ = 4.0–28.3°
c = 13.120 (3) Å	µ = 0.09 mm^−1
β = 92.600 (2)°	T = 100 K
V = 798.5 (3) Å^3	Platelet, yellow
Z = 4	0.20 × 0.10 × 0.05 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	1969 independent reflections
Radiation source: fine-focus sealed tube	1700 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.079
ϕ and ω scans	θmax = 28.3°, θmin = 3.8°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −12→11
Tmin = 0.982, Tmax = 0.995	k = −8→8
9032 measured reflections	l = −17→17

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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.180	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.1056P)^2 + 0.3049P] where P = (Fo^2 + 2Fc^2)/3
1969 reflections	(Δ/σ)max < 0.001
135 parameters	Δρmax = 0.48 e Å^−3
14 restraints	Δρmin = −0.31 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 same disorder is found in this crystal as in a larger crystal at room temperature. Atoms C1, O1, N1 and H1N and the atoms C1A, O1A, N1A and H1NA (related by an approximate twofold rotation) are refined with restraints to occupancies of 0.919 (4) and 0.081 (4), respectively. Restraints in the final cycles are shown in the iucr_refine_instructions_details section below. The restraints are inadequate to define the minor-occupancy molecule, for example, the C1A—O1A distance is 1.31 (C1—O1 is 1.230) and N1A—C1A is 1.34 (N1—C1 is 1.375). Also the Hirshfeld test difference for N1—C2 is 5.2 s.u., indicating poor refinement of displacement parameters in the major-occupancy molecule (C2···C1A is not a bonded distance). 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	Occ. (<1)
O1	0.16662 (14)	0.13056 (19)	0.55699 (10)	0.0234 (4)	0.919 (4)
C1	0.1282 (4)	0.2405 (5)	0.4857 (3)	0.0227 (4)	0.919 (4)
N1	0.0148 (3)	0.2082 (3)	0.41439 (19)	0.0236 (4)	0.919 (4)
H1N	−0.0416	0.1016	0.4129	0.028*	0.919 (4)
O1A	−0.1009 (16)	0.066 (2)	0.3875 (12)	0.033 (5)	0.081 (4)
C1A	0.003 (3)	0.196 (3)	0.411 (2)	0.0236 (4)	0.081 (4)
N1A	0.117 (4)	0.244 (4)	0.475 (3)	0.0227 (4)	0.081 (4)
H1NA	0.1454	0.1646	0.5257	0.027*	0.081 (4)
C2	−0.00089 (18)	0.3660 (3)	0.34374 (13)	0.0228 (4)
C3	0.11037 (17)	0.5037 (2)	0.37205 (12)	0.0195 (4)
C4	0.19355 (19)	0.4341 (2)	0.45724 (12)	0.0216 (4)
C5	0.3099 (2)	0.5471 (3)	0.49643 (13)	0.0264 (4)
H5	0.3681	0.5051	0.5546	0.032*
C6	0.3389 (2)	0.7278 (3)	0.44640 (13)	0.0284 (4)
H6	0.4197	0.8065	0.4714	0.034*
C7	0.2554 (2)	0.7952 (3)	0.36300 (13)	0.0256 (4)
H7	0.2787	0.9191	0.3329	0.031*
C8	0.13541 (18)	0.6820 (2)	0.32180 (12)	0.0213 (4)
C9	0.0365 (2)	0.7238 (3)	0.23605 (13)	0.0265 (4)
H9	0.0456	0.8436	0.1986	0.032*
C10	−0.0720 (2)	0.5880 (3)	0.20861 (13)	0.0287 (4)
H10	−0.1360	0.6174	0.1512	0.034*
C11	−0.09397 (19)	0.4049 (3)	0.26171 (13)	0.0273 (4)
H11	−0.1701	0.3147	0.2406	0.033*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0239 (7)	0.0236 (7)	0.0227 (7)	0.0008 (5)	0.0018 (5)	0.0046 (5)
C1	0.0241 (11)	0.0221 (8)	0.0227 (11)	0.0036 (6)	0.0096 (7)	0.0017 (7)
N1	0.0251 (9)	0.0209 (8)	0.0254 (7)	−0.0018 (5)	0.0079 (6)	0.0031 (6)
O1A	0.030 (9)	0.034 (9)	0.034 (9)	0.000 (7)	−0.002 (7)	0.021 (7)
C1A	0.0251 (9)	0.0209 (8)	0.0254 (7)	−0.0018 (5)	0.0079 (6)	0.0031 (6)
N1A	0.0241 (11)	0.0221 (8)	0.0227 (11)	0.0036 (6)	0.0096 (7)	0.0017 (7)
C2	0.0198 (8)	0.0252 (8)	0.0243 (8)	0.0004 (6)	0.0103 (6)	−0.0007 (6)
C3	0.0178 (8)	0.0216 (8)	0.0198 (7)	0.0021 (5)	0.0081 (6)	−0.0007 (6)
C4	0.0232 (8)	0.0232 (8)	0.0191 (7)	0.0047 (6)	0.0091 (6)	0.0010 (6)
C5	0.0246 (9)	0.0355 (10)	0.0195 (7)	0.0038 (7)	0.0043 (6)	−0.0033 (6)
C6	0.0255 (9)	0.0333 (10)	0.0270 (8)	−0.0059 (7)	0.0085 (7)	−0.0081 (7)
C7	0.0276 (9)	0.0238 (8)	0.0265 (8)	−0.0027 (6)	0.0127 (7)	−0.0011 (6)
C8	0.0212 (8)	0.0231 (8)	0.0204 (7)	0.0025 (6)	0.0108 (6)	0.0010 (6)
C9	0.0274 (9)	0.0297 (9)	0.0232 (8)	0.0067 (7)	0.0101 (7)	0.0071 (7)
C10	0.0225 (9)	0.0416 (11)	0.0226 (8)	0.0074 (7)	0.0055 (6)	0.0047 (7)
C11	0.0193 (8)	0.0365 (10)	0.0266 (8)	−0.0015 (6)	0.0063 (6)	−0.0014 (7)

Geometric parameters (Å, º)

O1—C1	1.230 (3)	C4—C5	1.380 (3)
C1—N1	1.375 (3)	C5—C6	1.412 (3)
C1—C4	1.485 (3)	C5—H5	0.9500
N1—C2	1.412 (3)	C6—C7	1.378 (3)
N1—H1N	0.8800	C6—H6	0.9500
O1A—C1A	1.313 (15)	C7—C8	1.414 (2)
C1A—N1A	1.339 (16)	C7—H7	0.9500
C1A—C2	1.445 (18)	C8—C9	1.434 (2)
N1A—C4	1.481 (11)	C9—C10	1.377 (3)
N1A—H1NA	0.8800	C9—H9	0.9500
C2—C11	1.362 (3)	C10—C11	1.433 (3)
C2—C3	1.406 (2)	C10—H10	0.9500
C3—C8	1.393 (2)	C11—H11	0.9500
C3—C4	1.400 (2)
O1—C1—N1	126.8 (2)	C5—C4—C1	134.08 (17)
O1—C1—C4	128.1 (2)	C3—C4—C1	106.75 (17)
N1—C1—C4	105.14 (18)	C4—C5—C6	117.13 (16)
C1—N1—C2	112.18 (18)	C4—C5—H5	121.4
C1—N1—H1N	123.9	C6—C5—H5	121.4
C2—N1—H1N	123.9	C7—C6—C5	123.09 (17)
O1A—C1A—N1A	146.2 (17)	C7—C6—H6	118.5
O1A—C1A—C2	112.8 (15)	C5—C6—H6	118.5
N1A—C1A—C2	101.0 (10)	C6—C7—C8	120.68 (16)
C1A—N1A—C4	117.4 (12)	C6—C7—H7	119.7
C1A—N1A—H1NA	121.3	C8—C7—H7	119.7
C4—N1A—H1NA	121.3	C3—C8—C7	114.96 (16)
C11—C2—C3	119.49 (16)	C3—C8—C9	115.51 (16)
C11—C2—N1	134.69 (17)	C7—C8—C9	129.53 (16)
C3—C2—N1	105.81 (16)	C10—C9—C8	119.22 (16)
C11—C2—C1A	129.2 (7)	C10—C9—H9	120.4
C3—C2—C1A	111.3 (7)	C8—C9—H9	120.4
C8—C3—C4	124.95 (16)	C9—C10—C11	123.78 (16)
C8—C3—C2	124.94 (16)	C9—C10—H10	118.1
C4—C3—C2	110.10 (15)	C11—C10—H10	118.1
C5—C4—C3	119.17 (16)	C2—C11—C10	117.05 (17)
C5—C4—N1A	140.6 (6)	C2—C11—H11	121.5
C3—C4—N1A	100.2 (6)	C10—C11—H11	121.5

(Ic100K) Benz[cd]indol-2(1H)-one

Crystal data

C11H7NO	F(000) = 352
Mr = 169.18	Dx = 1.407 Mg m^−3
Monoclinic, P21/n	Melting point = 448–450 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 9.0551 (19) Å	Cell parameters from 6093 reflections
b = 6.7287 (14) Å	θ = 4.0–28.3°
c = 13.120 (3) Å	µ = 0.09 mm^−1
β = 92.600 (2)°	T = 100 K
V = 798.5 (3) Å^3	Platelet, yellow
Z = 4	0.20 × 0.10 × 0.05 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	1969 independent reflections
Radiation source: fine-focus sealed tube	1700 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.079
ϕ and ω scans	θmax = 28.3°, θmin = 3.8°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −12→11
Tmin = 0.982, Tmax = 0.995	k = −8→8
9032 measured reflections	l = −17→17

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.164	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.1076P)^2 + 0.0449P] where P = (Fo^2 + 2Fc^2)/3
1969 reflections	(Δ/σ)max = 0.002
138 parameters	Δρmax = 0.45 e Å^−3
0 restraints	Δρmin = −0.27 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. After refinement of a disorder model with four minor-occupancy atoms (data_Ib), with 135 parameters and 14 restraints, resulting in R = 0.0651 and wR = 0.1725, Hirshfeld (Hirshfeld, 1976) tests of the ADPs for the major conformer were poor. A rigid-body refinement was tried, first with six minor-occupancy atoms and finally with the entire minor molecule. The rigid body was constructed using SAME O1A > H11A at the beginning of the atom list. In the final cycles the major conformer and occupancy were fully refined, while AFIX 6 was used for the minor conformer, with isotropic U values. The result presented here (138 parameters, 0 restraints) gave improved Hirshfeld tests, a reduced R and wR, and a slightly reduced major-occupancy factor [0.912 (3) versus 0.919 (4)].

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.16659 (11)	0.13084 (14)	0.55695 (7)	0.0241 (3)	0.912 (3)
C1	0.12932 (18)	0.2418 (2)	0.48603 (11)	0.0191 (3)	0.912 (3)
N1	0.01491 (17)	0.20721 (17)	0.41482 (10)	0.0206 (3)	0.912 (3)
H1N	−0.0412	0.1004	0.4135	0.025*	0.912 (3)
C2	0.0001 (2)	0.3649 (2)	0.34490 (18)	0.0205 (4)	0.912 (3)
C3	0.1117 (4)	0.5040 (2)	0.37240 (12)	0.0193 (9)	0.912 (3)
C4	0.1947 (2)	0.4356 (3)	0.45732 (10)	0.0188 (3)	0.912 (3)
C5	0.31064 (16)	0.5485 (3)	0.49643 (10)	0.0223 (3)	0.912 (3)
H5	0.3689	0.5070	0.5546	0.027*	0.912 (3)
C6	0.33907 (17)	0.7301 (3)	0.44569 (11)	0.0242 (4)	0.912 (3)
H6	0.4197	0.8096	0.4703	0.029*	0.912 (3)
C7	0.2541 (2)	0.7967 (2)	0.36159 (16)	0.0232 (4)	0.912 (3)
H7	0.2767	0.9204	0.3310	0.028*	0.912 (3)
C8	0.1346 (3)	0.6821 (2)	0.32122 (18)	0.0195 (6)	0.912 (3)
C9	0.0360 (2)	0.7232 (3)	0.23569 (13)	0.0229 (4)	0.912 (3)
H9	0.0448	0.8430	0.1981	0.027*	0.912 (3)
C10	−0.07256 (17)	0.5859 (3)	0.20847 (10)	0.0248 (4)	0.912 (3)
H10	−0.1366	0.6141	0.1509	0.030*	0.912 (3)
C11	−0.09390 (16)	0.4029 (3)	0.26237 (12)	0.0238 (3)	0.912 (3)
H11	−0.1699	0.3122	0.2417	0.029*	0.912 (3)
O1A	−0.1101 (10)	0.0612 (11)	0.3819 (7)	0.033 (3)*	0.088 (3)
C1A	−0.0268 (8)	0.2094 (10)	0.3908 (6)	0.026 (5)*	0.088 (3)
N1A	0.0866 (9)	0.2198 (11)	0.4589 (6)	0.015 (3)*	0.088 (3)
H1NA	0.1109	0.1239	0.5020	0.018*	0.088 (3)
C2A	0.1620 (8)	0.3990 (11)	0.4543 (6)	0.044 (11)*	0.088 (3)
C3A	0.0935 (9)	0.5004 (10)	0.3694 (6)	0.025 (12)*	0.088 (3)
C4A	−0.0212 (9)	0.3853 (11)	0.3231 (6)	0.034 (9)*	0.088 (3)
C5A	−0.0976 (13)	0.4653 (15)	0.2416 (8)	0.035 (6)*	0.088 (3)
H5A	−0.1770	0.3968	0.2074	0.042*	0.088 (3)
C6A	−0.0526 (16)	0.6548 (17)	0.2109 (9)	0.045 (8)*	0.088 (3)
H6A	−0.1097	0.7184	0.1579	0.053*	0.088 (3)
C7A	0.0653 (16)	0.7523 (14)	0.2511 (9)	0.088 (18)*	0.088 (3)
H7A	0.0915	0.8760	0.2220	0.105*	0.088 (3)
C8A	0.1511 (12)	0.6796 (11)	0.3338 (8)	0.049 (15)*	0.088 (3)
C9A	0.2743 (13)	0.7741 (13)	0.3876 (10)	0.018 (5)*	0.088 (3)
H9A	0.3111	0.9009	0.3697	0.021*	0.088 (3)
C10A	0.3328 (11)	0.6645 (16)	0.4664 (9)	0.022 (4)*	0.088 (3)
H10A	0.4165	0.7182	0.5029	0.027*	0.088 (3)
C11A	0.2815 (10)	0.4804 (15)	0.4988 (8)	0.041 (6)*	0.088 (3)
H11A	0.3327	0.4129	0.5533	0.049*	0.088 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0245 (6)	0.0243 (5)	0.0234 (5)	0.0006 (4)	0.0014 (4)	0.0037 (4)
C1	0.0178 (8)	0.0215 (7)	0.0183 (6)	0.0004 (5)	0.0040 (6)	−0.0011 (5)
N1	0.0188 (7)	0.0226 (6)	0.0206 (6)	−0.0016 (4)	0.0014 (6)	0.0034 (4)
C2	0.0178 (7)	0.0240 (8)	0.0205 (7)	0.0018 (5)	0.0079 (6)	0.0008 (6)
C3	0.0160 (8)	0.0223 (13)	0.0203 (11)	0.0017 (4)	0.0080 (5)	−0.0011 (5)
C4	0.0186 (7)	0.0203 (6)	0.0180 (7)	0.0019 (7)	0.0080 (5)	−0.0001 (5)
C5	0.0223 (7)	0.0262 (8)	0.0188 (6)	−0.0004 (6)	0.0049 (5)	−0.0022 (5)
C6	0.0253 (8)	0.0250 (8)	0.0230 (7)	−0.0063 (5)	0.0080 (6)	−0.0022 (6)
C7	0.0261 (9)	0.0237 (8)	0.0205 (8)	−0.0008 (6)	0.0088 (7)	0.0016 (6)
C8	0.0191 (8)	0.0226 (10)	0.0177 (6)	0.0024 (5)	0.0095 (5)	0.0013 (5)
C9	0.0229 (8)	0.0262 (7)	0.0202 (6)	0.0051 (6)	0.0081 (6)	0.0058 (5)
C10	0.0208 (8)	0.0324 (10)	0.0217 (7)	0.0043 (6)	0.0056 (5)	0.0052 (6)
C11	0.0188 (7)	0.0299 (8)	0.0232 (7)	−0.0011 (5)	0.0055 (5)	0.0028 (7)

Geometric parameters (Å, º)

O1—C1	1.2283 (17)	O1A—C1A	1.25
C1—N1	1.383 (2)	C1A—N1A	1.33
C1—C4	1.488 (3)	C1A—C4A	1.48
N1—C2	1.405 (3)	N1A—C2A	1.39
N1—H1N	0.8800	N1A—H1NA	0.8800
C2—C11	1.371 (3)	C2A—C11A	1.32
C2—C3	1.413 (3)	C2A—C3A	1.42
C3—C4	1.393 (3)	C3A—C8A	1.40
C3—C8	1.394 (2)	C3A—C4A	1.41
C4—C5	1.376 (3)	C4A—C5A	1.36
C5—C6	1.421 (2)	C5A—C6A	1.40
C5—H5	0.9500	C5A—H5A	0.9500
C6—C7	1.390 (3)	C6A—C7A	1.34
C6—H6	0.9500	C6A—H6A	0.9500
C7—C8	1.412 (3)	C7A—C8A	1.39
C7—H7	0.9500	C7A—H7A	0.9500
C8—C9	1.429 (3)	C8A—C9A	1.44
C9—C10	1.384 (3)	C9A—C10A	1.36
C9—H9	0.9500	C9A—H9A	0.9500
C10—C11	1.437 (2)	C10A—C11A	1.40
C10—H10	0.9500	C10A—H10A	0.9500
C11—H11	0.9500	C11A—H11A	0.9500
O1—C1—N1	125.53 (14)	O1A—C1A—N1A	123.2
O1—C1—C4	128.74 (16)	O1A—C1A—C4A	128.1
N1—C1—C4	105.73 (12)	N1A—C1A—C4A	108.3
C1—N1—C2	111.12 (13)	C1A—N1A—C2A	112.5
C1—N1—H1N	124.4	C1A—N1A—H1NA	123.8
C2—N1—H1N	124.4	C2A—N1A—H1NA	123.8
C11—C2—N1	133.96 (15)	C11A—C2A—N1A	137.2
C11—C2—C3	119.32 (18)	C11A—C2A—C3A	117.7
N1—C2—C3	106.7 (2)	N1A—C2A—C3A	104.6
C4—C3—C8	125.6 (3)	C8A—C3A—C4A	127.3
C4—C3—C2	109.82 (18)	C8A—C3A—C2A	121.1
C8—C3—C2	124.5 (3)	C4A—C3A—C2A	111.1
C5—C4—C3	119.35 (18)	C5A—C4A—C3A	117.4
C5—C4—C1	134.05 (13)	C5A—C4A—C1A	139.3
C3—C4—C1	106.59 (19)	C3A—C4A—C1A	103.0
C4—C5—C6	116.85 (13)	C4A—C5A—C6A	116.2
C4—C5—H5	121.6	C4A—C5A—H5A	121.9
C6—C5—H5	121.6	C6A—C5A—H5A	121.9
C7—C6—C5	122.93 (13)	C7A—C6A—C5A	124.7
C7—C6—H6	118.5	C7A—C6A—H6A	117.7
C5—C6—H6	118.5	C5A—C6A—H6A	117.7
C6—C7—C8	120.58 (17)	C6A—C7A—C8A	122.7
C6—C7—H7	119.7	C6A—C7A—H7A	118.7
C8—C7—H7	119.7	C8A—C7A—H7A	118.7
C3—C8—C7	114.7 (3)	C7A—C8A—C3A	111.0
C3—C8—C9	116.3 (2)	C7A—C8A—C9A	128.2
C7—C8—C9	129.03 (17)	C3A—C8A—C9A	120.5
C10—C9—C8	118.98 (13)	C10A—C9A—C8A	113.6
C10—C9—H9	120.5	C10A—C9A—H9A	123.2
C8—C9—H9	120.5	C8A—C9A—H9A	123.2
C9—C10—C11	123.70 (13)	C9A—C10A—C11A	126.2
C9—C10—H10	118.2	C9A—C10A—H10A	116.9
C11—C10—H10	118.2	C11A—C10A—H10A	116.9
C2—C11—C10	117.13 (14)	C2A—C11A—C10A	120.6
C2—C11—H11	121.4	C2A—C11A—H11A	119.7
C10—C11—H11	121.4	C10A—C11A—H11A	119.7
O1—C1—N1—C2	179.08 (12)	O1A—C1A—N1A—C2A	−179.8
C4—C1—N1—C2	−1.40 (14)	C4A—C1A—N1A—C2A	7.5
C1—N1—C2—C11	−179.60 (14)	C1A—N1A—C2A—C11A	−176.1
C1—N1—C2—C3	0.89 (15)	C1A—N1A—C2A—C3A	−4.7
C11—C2—C3—C4	−179.55 (12)	C11A—C2A—C3A—C8A	0.4
N1—C2—C3—C4	0.05 (16)	N1A—C2A—C3A—C8A	−172.9
C11—C2—C3—C8	0.2 (2)	C11A—C2A—C3A—C4A	173.2
N1—C2—C3—C8	179.77 (14)	N1A—C2A—C3A—C4A	−0.1
C8—C3—C4—C5	−0.2 (2)	C8A—C3A—C4A—C5A	−8.5
C2—C3—C4—C5	179.50 (12)	C2A—C3A—C4A—C5A	179.2
C8—C3—C4—C1	179.40 (14)	C8A—C3A—C4A—C1A	176.5
C2—C3—C4—C1	−0.88 (16)	C2A—C3A—C4A—C1A	4.2
O1—C1—C4—C5	0.4 (2)	O1A—C1A—C4A—C5A	7.6
N1—C1—C4—C5	−179.07 (13)	N1A—C1A—C4A—C5A	179.8
O1—C1—C4—C3	−179.12 (14)	O1A—C1A—C4A—C3A	−179.2
N1—C1—C4—C3	1.38 (14)	N1A—C1A—C4A—C3A	−7.0
C3—C4—C5—C6	−0.60 (19)	C3A—C4A—C5A—C6A	0.9
C1—C4—C5—C6	179.90 (13)	C1A—C4A—C5A—C6A	173.4
C4—C5—C6—C7	1.2 (2)	C4A—C5A—C6A—C7A	5.3
C5—C6—C7—C8	−1.0 (2)	C5A—C6A—C7A—C8A	−4.6
C4—C3—C8—C7	0.4 (2)	C6A—C7A—C8A—C3A	−2.3
C2—C3—C8—C7	−179.24 (13)	C6A—C7A—C8A—C9A	−176.1
C4—C3—C8—C9	−179.91 (14)	C4A—C3A—C8A—C7A	9.0
C2—C3—C8—C9	0.4 (2)	C2A—C3A—C8A—C7A	−179.5
C6—C7—C8—C3	0.19 (19)	C4A—C3A—C8A—C9A	−176.7
C6—C7—C8—C9	−179.40 (13)	C2A—C3A—C8A—C9A	−5.1
C3—C8—C9—C10	−0.89 (19)	C7A—C8A—C9A—C10A	178.9
C7—C8—C9—C10	178.70 (13)	C3A—C8A—C9A—C10A	5.7
C8—C9—C10—C11	0.9 (2)	C8A—C9A—C10A—C11A	−2.1
N1—C2—C11—C10	−179.72 (13)	N1A—C2A—C11A—C10A	173.8
C3—C2—C11—C10	−0.26 (19)	C3A—C2A—C11A—C10A	3.3
C9—C10—C11—C2	−0.3 (2)	C9A—C10A—C11A—C2A	−2.5