4′-Hydro­xy­bi­phenyl-4-carbo­nitrile

The title compound, C₁₃H₉NO, crystallizes with four mol­ecules in the asymmetric unit. Each of the four crystallographically independent mol­ecules forms a chain parallel to the a axis with symmetry-equivalent mol­ecules. These chains are held together by similar O—H...NC hydrogen bonds, with approximately linear O—H...N angles and significantly bent H...N—C angles. The four different mol­ecules are related by strong elements of pseudosymmetry. To better describe the pseudosymmetry, the structure has been reported in the non-standard space group .

S1. Comment

Many 4,4'-disubstituted biphenyls have similar packing patterns. The dimethyl (Casalone et al., 1969), dichloro (Brock et al., 1978), and dibromo (Kronebusch et al., 1976b; Mohamed et al., 2003) compounds are isomorphous, with the molecules lined up end-to-end with X···X contacts. The bromofluoro (Gleason et al., 1991) compound is the same, with Br···F contacts. The bromocyano (Kronebusch et al., 1976a) and iodocyano (Britton & Gleason, 1991) compounds differ only in that there are X···N interactions. Otherwise the packing is the same. The unit cell for the methylcyano compound (Haase et al., 1992) suggests that this is isomorphous with the bromocyano and iodocyano compounds, but the details of the structure have not been determined. The cyanoethynyl compound (Langley et al., 1998) has a similar arrangement, with molecules forming chains with CCH···N interactions but with different side-to-side packing of the chains. In the dicyano compound (Britton & Young, 2003) the chains are tilted so that there can be antiparallel CN···NC interactions.

The structure of 4-hydroxy-4'-cyanobiphenyl has been determined to see what effect the expected OH···NC interaction has on the packing. An approximately linear molecular packing arrangement, similar to those in the 4,4'-biphenyls, seemed likely, but this would make it difficult to form the approximately linear O—H···NC interactions that appear to be favored in this type of hydrogen bond, as shown in ortho-, meta- and para-hydroxybenzonitrile [Beswick et al. (1996), Britton (2004) and Higashi & Osaki (1977), respectively].

There are four molecules in the asymmetric unit. The anisotropic displacement ellipsoids and atom labelling for molecule A are shown in Fig. 1. The ellipsoids and the labelling are similar for molecules B, C and D. The bond lengths and angles agree among the four molecules within experimental error and are all normal. As is common, the exocyclic angles at the OH-bound C atoms are unequal; the angles cis to the hydroxy H atoms average 123.0 (3)°, and those trans 117.4 (4)°. This difference is presumably due to H···H repulsion. The corresponding angles in 4,4'-biphenyldiol are 122.1 (1) and 117.8 (1)° (Jackisch et al., 1990). The torsion angles in molecules A–D are 31.8 (1), 37.0 (1), 36.4 (1) and 38.2 (1)°, respectively. The central axes of the molecules are bent. Fig. 2 shows molecule A viewed normal to the least-squares plane through atoms N14A, C13A, C1A, C4A, C7A, C10A and O15A; the next molecule in the chain [at (1 + x, y, z)] is also shown. The seven atoms are close to planar, but as can be seen from the figure, the molecule is bowed in the plane. This bowing is such that it tends to bring both the O—H···N and H···NC interactions closer to linearity. In the molecule shown, the angle between the C10A—O15A direction and the C13A—N14A direction is 8.9 (1)°. The other three molecules are similar in arrangement, with corresponding angles of 10.2 (B), 8.6 (C) and 12.2° (D).

In order to simplify the discussion of the pseudosymmetry and to make the molecular chains lie parallel to an axis, the conventional unit cell [a = 10.604 (3) Å, b = 11.826 (3) Å, c = 18.005 (5) Å, α = 103.10 (1)°, β = 100.23 (1)° and γ = 109.80 (1)°] was converted by the matrix 110/112/100 to the cell in C1 reported in the experimental data.

The packing is shown in Figs. 3 and 4, where one asymmetric unit is shown in Fig. 3 and two asymmetic units related by an inversion center at (3/4, 1/4, 1/2) are shown in Fig. 4. The four independent molecules are all aligned approximately parallel to the a axis [the deviations based on the intramolecular N···O directions are 10.2 (1), 10.4 (1), 10.1 (1) and 10.0 (1)° for molecules A, B, C and D, respectively.] The molecules form chains held together by O—H···NC hydrogen bonds. The metric data for these hydogen bonds are given in Table 1, where they are compared with similar bonds in o-, m- and p-hydroxybenzonitrile. The hydrogen bonds in the latter compounds are all almost completely linear for the O—H···NC groups, which is the ideal arrangement for such bonds. In hydroxycyanobiphenyl the bonds are not ideal; while still close to linear at O—H···N, they are bent at H···NC. This is presumably a consequence of the difficulty in forming an efficient packing with the linear arrangement. The bending does not appear to affect the O···N distances significantly.

The packing between chains involves six C—H···N contacts with H···N distances between 2.6 and 2.8 Å, and 37 C—H···C(ring) contacts with H···C distances between 2.8 and 3.1 Å. These contacts are important to the packing but none is remarkably short. This aspect of the packing in biphenyls has been discussed at length by Masunov et al. (1992).

Also evident, particularly in Fig. 4, is the pseudosymmetry relating the four crystallographically independent molecules. Such supersymmetry has been discussed extensively by Zorky and coworkers (see, among others, Zorky, 1996; Belsky et al., 1995; Zorky & Dashevskaya, 1992, 1993). Zorky & Dashevskaya (1992, 1993), in particular, describe an example of Z' = 4 that is close to that reported here.

The first hint of the pseudosymmetry can be found if we look at the coordinates of the molecular centers of the four molecules: A at (0.724, 0.127, −0.009); B at (0.606, 0.251, 1/4); C at (0.470, 0.376, 0.491); D at (0.899, 0.502, 3/4). While the x coordinates show no particular relationship, the y coordinates are at, and differ by, approximately integral multiples of b/8, and the z coordinates are at, and differ by, approximately integral multiples of c/4.

There are six kinds of pseudosymmetry elements present: (1) screw axes parallel to b, which relate A←→B and C←→D; (2) screw axes parallel to a, which relate A←→C', B←→D', C←→A', and D←→B'; (3) screw axes perpendicular to the ab plane, which relate A←→D', B←→C', C←→B', and D←→A'; (4) glide planes perpendicular to b, which relate A←→B', B←→A', C←→D', and D←→C'; (5) glide planes perpendicular to a, which relate A←→C and B←→D; (6) glide planes parallel to the ab planes, which relate A←→D and B←→C. The three glide planes, 4, 5 and 6, are related, respectively, to the three screw axes, 1, 2 and 3, by the real inversion center at (3/4, 1/4, 1/2). The pseudo-screw axes are all twofold. The details of the pseudosymmetry elements are included in the CIF in the section _geom_special_details.

It should be emphasized that the pseudosymmetry element directions are only approximately correct. The C-centered triclinic cell was chosen to make the discussion of the pseudo-symmetry simpler, but the α and γ angles differ from 90° and these differences have been ignored. For each of the pairs of molecules, the best overlap has been determined using the program OFIT in SHELXTL, and the r.m.s deviations are given in Table 2, where they are compared with the r.m.s deviations determined from the pseudosymmetry elements described above. As can be seen, the agreement is poorer, as would be expected, but still satisfactory.

The related compound 4-cyano-4'-ethynylbiphenyl (Langley et al., 1998), in which the –OH group has been replaced with –C₂H, also occurs in a triclinic cell with four molecules in the asymmetric unit, and with all the molecules close to parallel to each other and forming chains with their own kind held together by C₂H···NC hydrogen bonds. However, in this case, there are no significant pseudosymmetrical relationships among the molecules.

4-Chloro-2-hydroxybiphenyl (Lehmler et al., 2002), which is less closely related, also has a triclinic unit cell with four molecules in the asymmetric unit. In this case, the four independent molecules form cyclic tetrameric units rather than chains. Again, there are no significant pseudosymmetrical relationships among the molecules.

It is not clear why 4-hydroxy-4'-cyanobiphenyl should show so much pseudosymmetry while the closely related 4-cyano-4'- ethynylbiphenyl, which also has Z' = 4, shows none. Kitaigorodskii (1970) has pointed out that Z' > 1 gives more degrees of freedom and therefore can increase the packing efficiency, but this does not address the question of why some structures show pseudosymmetry and others with the same Z' do not.

S2. Experimental

Recrystallization was carried out from acetone, benzene/acetone, methylene chloride/acetone and carbon tetrachloride/acetone. The first three gave similar crystals; the last gave crystals of a distinctly different platy habit, but all proved to have the same cell dimensions.

S3. Refinement

In order to simplify the discussion of the pseudosymmetry and to make the molecular chains lie parallel to an axis, the conventional unit cell [a = 10.604 (3) Å, b = 11.826 (3) Å, c = 18.005 (5) Å, α = 103.10 (1)°, β = 100.23 (1)° and γ = 109.80 (1)°] was converted by the matrix 110/112/100 to the cell in C1 reported in the experimental data.

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. NCC6H4C6H4OH molecule A. Displacement ellipsoids are shown at the 50% probability level. Molecules B, C and D have similar labelling and ellipsoids.
	Fig. 2. A view of a segment of the chain formed by molecule A, viewed normal to the mean plane through the central backbone of the molecule. A straight line connects the O and N atoms of the left-hand molecule to make the bending more apparent. The bending is such that it pulls both the C—N···H and the N···H—O angles closer to linear.
	Fig. 3. A view along c of the asymmetric unit. The vertical axis is shown from O to a; the horizontal from O to b/2.
	Fig. 4. A view along a of the asymmetric unit shown in Fig. 3, plus the molecules related by a center of symmetry at (3/4, 1/4, 1/2). The vertical axis is shown from O to c; the horizontal axis is shown from O to b/2.

4'-Hydroxybiphenyl-4-carbonitrile

Crystal data

C13H9NO	Z = 16
Mr = 195.21	F(000) = 1632
Triclinic, C1	Dx = 1.305 Mg m^−3
Hall symbol: -C 1	Mo Kα radiation, λ = 0.71073 Å
a = 12.936 (3) Å	Cell parameters from 3725 reflections
b = 33.696 (8) Å	θ = 2.5–27.5°
c = 10.604 (3) Å	µ = 0.08 mm^−1
α = 90.35 (1)°	T = 174 K
β = 120.67 (1)°	Elongated octahedron, colorless
γ = 89.60 (1)°	0.50 × 0.35 × 0.30 mm
V = 3975.5 (17) Å^3

Data collection

Siemens SMART area detector diffractometer	6872 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.025
Graphite monochromator	θmax = 27.0°, θmin = 1.2°
ω scans	h = −16→16
22798 measured reflections	k = −42→42
8628 independent reflections	l = −13→13

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.055	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.119	w = 1/[σ^2(Fo^2) + (0.023P)^2 + 4.96P] where P = (Fo^2 + 2Fc^2)/3
S = 1.12	(Δ/σ)max = 0.014
8628 reflections	Δρmax = 0.20 e Å^−3
558 parameters	Δρmin = −0.16 e Å^−3
0 restraints	Extinction correction: SHELXTL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00031 (6)

Special details

Geometry. The pseudosymmetry operations

A→B screw axis parallel to b x(B) = 1.330 (4) − x(A) y(B) = 0.125 (2) + y(A) z(B) = 0.242 (8) − z(A)

A→C glide plane perpendicular to a x(C) = 1.202 (3) − x(A) + z(A)sin β y(C) = 0.250 (2) + y(A) z(C) = 0.499 (5) + z(A)

A→D glide plane parallel to ab x(D) = 0.168 (6) + x(A) − z(A)sin β y(D) = 0.376 (1) + y(A) z(D) = 0.741 (8) − z(A)

A→B' glide plane perpendicular to b x(B') = 0.170 (4) + x(A) y(B') = 0.375 (2) − y(A) z(B') = 0.758 (8) + z(A)

A→C' screw axis parallel to a x(C') = 0.298 (3) + x(A) −z(A)sin β y(C') = 0.250 (2) − y(A) z(C') = 0.501 (5) − z(A)

A→D' screw axis perpendicular to ab x(D') = 1.332 (5)) − x(A) +z(A)sin β y(D') = 0.124 (1) − y(A) z(D') = 0.259 (8) + z(A)

——————————————————————-

B→A screw axis parallel to b x(A) = 1.330 (4) − x(B) y(A) = −0.125 (2) + y(B) z(A) = 0.242 (8) − z(B)

B→C glide plane parallel to ab x(C) = 0.080 (4) + x(B) − z(B)sin β y(C) = 0.125 (1) + y(B) z(C) = 0.741 (5) − z(B)

B→D glide plane perpendicular to a x(D) = 1.290 (3) − x(B) + z(B)sin β y(D) = 0.251 (1) + y(B) z(D) = 0.500 (3) + z(B)

B→A' glide plane perpendicular to b x(A') = 0.170 (4) + x(B) y(A') = 0.625 (2) − y(B) z(A') = 0.758 (8) + z(B)

B→C' screw axis perpendicular to ab x(C') = 1.420 (4) − x(B) + z(B)sin β y(C') = 0.375 (1) − y(B) z(C') = 0.259 (5) + z(B)

B→D' screw axis parallel to a

x(D') = 0.210 (3) + x(B) − z(B)sin β y(D') = 0.249 (1) − y(B) z(D') = 0.500 (3) − z(B)

——————————————————————-

C→A glide plane perpendicular to a x(A) = 0.773 (2) − x(C) + z(C)sin β y(A) = −0.250 (2) + y(C) z(A) = −0.499 (5) + z(C)

C→B glide plane parallel to ab x(B) = 0.558 (3) + x(C) − z(C)sin β y(B) = −0.125 (1) + y(C) z(B) = 0.741 (5) − z(C)

C→D screw axis parallel to b x(D) = 1.370 (4) − x(C) y(D) = 0.126 (2) + y(C) z(D) = 1.241 (4) − z(C)

C→A' screw axis parallel to a

x(A') = 0.727 (2) + x(C) − z(C)sin β y(A') = 0.750 (2) − y(C) z(A') = 1.499 (5) − z(C)

C→B' screw axis perpendicular to ab x(B') = 0.943 (3) − x(C) + z(C)sin β y(B') = 0.625 (1) − y(C) z(B') = 0.259 (5) + z(C)

C→D' glide plane perpendicular to b x(D') = 0.130 (4) + x(C) y(D') = 0.374 (1) − y(C) z(D') = −0.241 (5) + z(C)

——————————————————————

D→A glide plane parallel to ab x(A) = 0.470 (2) + x(D) − z(D)sin β y(A) = −0.376 (1) + y(D) z(A) = 0.741 (8) − z(D)

D→B glide plane perpendicular to a x(B) = 0.861 (4) − x(D) + z(D)sin β y(B) = −0.251 (1) + y(D) z(B) = −0.500 (3) + z(D)

D→C screw axis parallel to b x(C) = 1.370 (4) − x(D) y(C) = −0.126 (2) + y(D) z(C) = 1.241 (4) − z(D)

D→A' screw axis perpendicular to ab x(A') = 1.030 (2) − x(D) + z(D)sin β y(A') = 0.876 (1) − y(D) z(A') = 0.259 (8) + z(D)

D→B' screw axis parallel to a x(B') = 0.639 (4) + x(D) − z(D)sin β y(B') = 0.751 (1) − y(D) z(B') = 1.500 (3) − z(D)

D→C' glide plane perpendicular to b x(C') = 0.130 (4) + x(D) y(C') = 0.626 (2) − y(D) z(C') = −0.241 (4) + z(D)

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

	x	y	z	Uiso*/Ueq
C1A	0.98745 (17)	0.12082 (6)	0.0517 (2)	0.0366 (4)
C2A	0.94088 (19)	0.08990 (6)	0.0936 (2)	0.0447 (5)
H2A	0.9881	0.0669	0.1388	0.054*
C3A	0.82539 (18)	0.09281 (6)	0.0692 (2)	0.0411 (5)
H3A	0.7943	0.0717	0.0988	0.049*
C4A	0.75349 (16)	0.12605 (5)	0.0022 (2)	0.0310 (4)
C5A	0.80250 (17)	0.15683 (5)	−0.0392 (2)	0.0350 (4)
H5A	0.7552	0.1797	−0.0854	0.042*
C6A	0.91787 (18)	0.15447 (6)	−0.0143 (2)	0.0383 (4)
H6A	0.9498	0.1758	−0.0420	0.046*
C7A	0.62863 (16)	0.12885 (5)	−0.0268 (2)	0.0308 (4)
C8A	0.59531 (17)	0.11127 (5)	0.0666 (2)	0.0320 (4)
H8A	0.6539	0.0971	0.1502	0.038*
C9A	0.47871 (17)	0.11411 (5)	0.0399 (2)	0.0334 (4)
H9A	0.4581	0.1020	0.1049	0.040*
C10A	0.39205 (16)	0.13470 (5)	−0.0823 (2)	0.0336 (4)
C11A	0.42366 (17)	0.15250 (6)	−0.1756 (2)	0.0360 (4)
H11A	0.3650	0.1667	−0.2589	0.043*
C12A	0.53984 (17)	0.14960 (5)	−0.1480 (2)	0.0344 (4)
H12A	0.5600	0.1620	−0.2128	0.041*
C13A	1.10525 (19)	0.11767 (6)	0.0696 (2)	0.0422 (5)
N14A	1.19775 (17)	0.11542 (6)	0.0797 (2)	0.0544 (5)
O15A	0.27569 (13)	0.13834 (5)	−0.11598 (17)	0.0448 (4)
H15A	0.258 (3)	0.1273 (9)	−0.053 (3)	0.080 (10)*
C1B	0.34477 (17)	0.24397 (6)	0.1938 (2)	0.0357 (4)
C2B	0.39675 (18)	0.21186 (6)	0.1629 (2)	0.0374 (4)
H2B	0.3544	0.1876	0.1287	0.045*
C3B	0.51035 (17)	0.21554 (6)	0.1823 (2)	0.0342 (4)
H3B	0.5450	0.1937	0.1598	0.041*
C4B	0.57512 (16)	0.25072 (5)	0.23438 (19)	0.0298 (4)
C5B	0.52048 (17)	0.28283 (6)	0.2635 (2)	0.0350 (4)
H5B	0.5629	0.3071	0.2979	0.042*
C6B	0.40679 (18)	0.27986 (6)	0.2432 (2)	0.0383 (4)
H6B	0.3709	0.3019	0.2626	0.046*
C7B	0.69957 (16)	0.25411 (5)	0.2629 (2)	0.0301 (4)
C8B	0.73681 (18)	0.23553 (5)	0.1745 (2)	0.0346 (4)
H8B	0.6810	0.2201	0.0929	0.042*
C9B	0.85427 (18)	0.23923 (6)	0.2039 (2)	0.0359 (4)
H9B	0.8774	0.2270	0.1411	0.043*
C10B	0.93750 (17)	0.26085 (5)	0.3250 (2)	0.0345 (4)
C11B	0.90259 (18)	0.27900 (5)	0.4155 (2)	0.0356 (4)
H11B	0.9593	0.2937	0.4989	0.043*
C12B	0.78543 (17)	0.27570 (5)	0.3841 (2)	0.0334 (4)
H12B	0.7625	0.2884	0.4463	0.040*
C13B	0.22787 (19)	0.24024 (6)	0.1782 (2)	0.0412 (5)
N14B	0.13566 (17)	0.23775 (6)	0.1682 (2)	0.0517 (5)
O15B	1.05447 (13)	0.26516 (5)	0.36076 (18)	0.0464 (4)
H15B	1.070 (3)	0.2544 (9)	0.292 (3)	0.082 (10)*
C1C	0.25715 (17)	0.36860 (6)	0.5480 (2)	0.0362 (4)
C2C	0.33740 (19)	0.33700 (6)	0.5826 (2)	0.0435 (5)
H2C	0.3262	0.3131	0.6211	0.052*
C3C	0.43298 (19)	0.34073 (6)	0.5603 (2)	0.0408 (5)
H3C	0.4881	0.3193	0.5855	0.049*
C4C	0.45071 (17)	0.37520 (5)	0.5019 (2)	0.0334 (4)
C5C	0.36890 (18)	0.40654 (6)	0.4672 (2)	0.0374 (4)
H5C	0.3792	0.4303	0.4271	0.045*
C6C	0.27332 (18)	0.40338 (6)	0.4904 (2)	0.0385 (5)
H6C	0.2189	0.4249	0.4671	0.046*
C7C	0.55200 (17)	0.37875 (5)	0.4750 (2)	0.0320 (4)
C8C	0.66464 (17)	0.36213 (6)	0.5691 (2)	0.0353 (4)
H8C	0.6772	0.3480	0.6530	0.042*
C9C	0.75901 (18)	0.36586 (6)	0.5428 (2)	0.0365 (4)
H9C	0.8353	0.3545	0.6088	0.044*
C10C	0.74152 (17)	0.38616 (6)	0.4201 (2)	0.0357 (4)
C11C	0.63037 (18)	0.40299 (6)	0.3251 (2)	0.0378 (4)
H11C	0.6182	0.4170	0.2410	0.045*
C12C	0.53746 (18)	0.39950 (5)	0.3524 (2)	0.0355 (4)
H12C	0.4620	0.4114	0.2869	0.043*
C13C	0.15359 (19)	0.36513 (6)	0.5643 (2)	0.0412 (5)
N14C	0.06959 (17)	0.36321 (6)	0.5746 (2)	0.0514 (5)
O15C	0.83044 (14)	0.39063 (5)	0.38768 (18)	0.0475 (4)
H15C	0.900 (2)	0.3789 (8)	0.457 (3)	0.072 (9)*
C1D	1.11473 (18)	0.49599 (6)	0.6949 (2)	0.0392 (5)
C2D	1.03733 (19)	0.46372 (6)	0.6595 (2)	0.0422 (5)
H2D	1.0521	0.4398	0.6231	0.051*
C3D	0.93916 (18)	0.46674 (6)	0.6778 (2)	0.0391 (5)
H3D	0.8862	0.4448	0.6523	0.047*
C4D	0.91615 (17)	0.50113 (5)	0.7327 (2)	0.0340 (4)
C5D	0.99403 (18)	0.53363 (6)	0.7654 (2)	0.0384 (5)
H5D	0.9789	0.5576	0.8010	0.046*
C6D	1.09171 (18)	0.53120 (6)	0.7465 (2)	0.0407 (5)
H6D	1.1431	0.5534	0.7685	0.049*
C7D	0.81565 (17)	0.50391 (5)	0.7615 (2)	0.0341 (4)
C8D	0.70321 (18)	0.48708 (6)	0.6693 (2)	0.0383 (4)
H8D	0.6897	0.4727	0.5849	0.046*
C9D	0.61057 (18)	0.49103 (6)	0.6988 (2)	0.0421 (5)
H9D	0.5342	0.4797	0.6343	0.050*
C10D	0.62971 (19)	0.51157 (6)	0.8228 (2)	0.0402 (5)
C11D	0.74151 (19)	0.52809 (6)	0.9170 (2)	0.0416 (5)
H11D	0.7551	0.5420	1.0023	0.050*
C12D	0.83264 (18)	0.52422 (6)	0.8864 (2)	0.0396 (5)
H12D	0.9088	0.5356	0.9516	0.047*
C13D	1.2198 (2)	0.49270 (7)	0.6818 (2)	0.0461 (5)
N14D	1.30501 (19)	0.49029 (6)	0.6741 (2)	0.0592 (5)
O15D	0.54339 (16)	0.51658 (5)	0.8601 (2)	0.0536 (4)
H15D	0.471 (2)	0.5073 (7)	0.784 (3)	0.058 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1A	0.0357 (10)	0.0432 (11)	0.0328 (10)	−0.0024 (8)	0.0189 (9)	−0.0040 (8)
C2A	0.0409 (12)	0.0405 (12)	0.0521 (13)	0.0063 (9)	0.0233 (10)	0.0112 (10)
C3A	0.0393 (11)	0.0358 (11)	0.0481 (12)	0.0008 (9)	0.0221 (10)	0.0112 (9)
C4A	0.0353 (10)	0.0283 (9)	0.0290 (9)	−0.0036 (7)	0.0160 (8)	−0.0011 (7)
C5A	0.0408 (11)	0.0282 (10)	0.0359 (10)	0.0000 (8)	0.0195 (9)	0.0033 (8)
C6A	0.0441 (12)	0.0361 (11)	0.0406 (11)	−0.0055 (9)	0.0259 (10)	0.0011 (8)
C7A	0.0338 (10)	0.0244 (9)	0.0315 (9)	−0.0034 (7)	0.0148 (8)	−0.0030 (7)
C8A	0.0355 (10)	0.0275 (9)	0.0291 (9)	−0.0017 (7)	0.0135 (8)	0.0011 (7)
C9A	0.0392 (10)	0.0293 (9)	0.0336 (10)	−0.0056 (8)	0.0198 (9)	−0.0035 (8)
C10A	0.0319 (10)	0.0306 (10)	0.0347 (10)	−0.0019 (8)	0.0145 (8)	−0.0077 (8)
C11A	0.0375 (11)	0.0333 (10)	0.0311 (10)	0.0031 (8)	0.0131 (8)	0.0021 (8)
C12A	0.0404 (11)	0.0298 (10)	0.0322 (10)	−0.0016 (8)	0.0179 (9)	0.0026 (8)
C13A	0.0416 (12)	0.0488 (12)	0.0371 (11)	−0.0026 (9)	0.0208 (9)	−0.0047 (9)
N14A	0.0443 (11)	0.0699 (14)	0.0553 (12)	−0.0017 (9)	0.0300 (10)	−0.0078 (10)
O15A	0.0351 (8)	0.0503 (9)	0.0484 (9)	0.0033 (6)	0.0209 (7)	−0.0002 (7)
C1B	0.0341 (10)	0.0423 (11)	0.0310 (10)	0.0018 (8)	0.0168 (8)	0.0053 (8)
C2B	0.0400 (11)	0.0349 (10)	0.0356 (10)	−0.0060 (8)	0.0180 (9)	−0.0033 (8)
C3B	0.0394 (11)	0.0298 (10)	0.0338 (10)	0.0014 (8)	0.0189 (9)	−0.0016 (8)
C4B	0.0369 (10)	0.0288 (9)	0.0236 (9)	0.0013 (7)	0.0152 (8)	0.0034 (7)
C5B	0.0403 (11)	0.0275 (9)	0.0386 (11)	−0.0006 (8)	0.0211 (9)	−0.0007 (8)
C6B	0.0434 (11)	0.0344 (10)	0.0402 (11)	0.0060 (8)	0.0236 (9)	0.0020 (8)
C7B	0.0365 (10)	0.0237 (9)	0.0305 (9)	0.0023 (7)	0.0174 (8)	0.0049 (7)
C8B	0.0415 (11)	0.0291 (9)	0.0331 (10)	0.0012 (8)	0.0189 (9)	0.0001 (8)
C9B	0.0440 (11)	0.0327 (10)	0.0373 (10)	0.0077 (8)	0.0253 (9)	0.0037 (8)
C10B	0.0363 (10)	0.0299 (10)	0.0387 (11)	0.0048 (8)	0.0201 (9)	0.0112 (8)
C11B	0.0398 (11)	0.0303 (10)	0.0349 (10)	−0.0034 (8)	0.0177 (9)	0.0016 (8)
C12B	0.0415 (11)	0.0293 (9)	0.0338 (10)	−0.0013 (8)	0.0225 (9)	−0.0016 (8)
C13B	0.0424 (12)	0.0468 (12)	0.0362 (11)	0.0012 (9)	0.0214 (9)	0.0052 (9)
N14B	0.0456 (11)	0.0622 (13)	0.0556 (12)	0.0006 (9)	0.0319 (10)	0.0094 (10)
O15B	0.0388 (8)	0.0493 (9)	0.0558 (10)	0.0033 (7)	0.0276 (8)	0.0082 (7)
C1C	0.0354 (10)	0.0372 (11)	0.0319 (10)	−0.0002 (8)	0.0143 (8)	−0.0019 (8)
C2C	0.0508 (13)	0.0361 (11)	0.0465 (12)	0.0063 (9)	0.0268 (10)	0.0115 (9)
C3C	0.0461 (12)	0.0348 (11)	0.0436 (11)	0.0125 (9)	0.0245 (10)	0.0107 (9)
C4C	0.0368 (10)	0.0302 (10)	0.0282 (9)	0.0024 (8)	0.0131 (8)	−0.0003 (7)
C5C	0.0411 (11)	0.0271 (10)	0.0406 (11)	0.0015 (8)	0.0183 (9)	0.0025 (8)
C6C	0.0364 (11)	0.0312 (10)	0.0415 (11)	0.0043 (8)	0.0152 (9)	−0.0001 (8)
C7C	0.0370 (10)	0.0270 (9)	0.0287 (9)	0.0002 (7)	0.0143 (8)	−0.0027 (7)
C8C	0.0411 (11)	0.0323 (10)	0.0285 (9)	0.0029 (8)	0.0149 (8)	0.0020 (8)
C9C	0.0352 (10)	0.0334 (10)	0.0340 (10)	0.0033 (8)	0.0125 (8)	0.0001 (8)
C10C	0.0373 (11)	0.0316 (10)	0.0375 (11)	−0.0058 (8)	0.0187 (9)	−0.0053 (8)
C11C	0.0438 (11)	0.0335 (10)	0.0328 (10)	−0.0025 (8)	0.0171 (9)	0.0018 (8)
C12C	0.0379 (10)	0.0291 (10)	0.0334 (10)	0.0023 (8)	0.0137 (8)	0.0032 (8)
C13C	0.0417 (12)	0.0370 (11)	0.0405 (11)	−0.0012 (9)	0.0178 (10)	−0.0021 (9)
N14C	0.0429 (11)	0.0485 (11)	0.0644 (13)	−0.0035 (8)	0.0284 (10)	−0.0051 (9)
O15C	0.0429 (9)	0.0526 (9)	0.0499 (9)	−0.0024 (7)	0.0257 (8)	0.0030 (7)
C1D	0.0397 (11)	0.0404 (11)	0.0342 (10)	−0.0015 (9)	0.0164 (9)	0.0006 (8)
C2D	0.0482 (12)	0.0343 (11)	0.0419 (12)	−0.0014 (9)	0.0213 (10)	−0.0039 (9)
C3D	0.0450 (12)	0.0286 (10)	0.0392 (11)	−0.0054 (8)	0.0183 (9)	−0.0020 (8)
C4D	0.0356 (10)	0.0288 (9)	0.0284 (9)	0.0002 (8)	0.0096 (8)	0.0029 (7)
C5D	0.0421 (11)	0.0287 (10)	0.0394 (11)	−0.0024 (8)	0.0170 (9)	−0.0033 (8)
C6D	0.0423 (11)	0.0354 (11)	0.0392 (11)	−0.0082 (9)	0.0170 (9)	−0.0017 (8)
C7D	0.0369 (10)	0.0253 (9)	0.0335 (10)	0.0007 (8)	0.0132 (8)	0.0053 (7)
C8D	0.0425 (11)	0.0320 (10)	0.0345 (10)	−0.0049 (8)	0.0151 (9)	0.0033 (8)
C9D	0.0374 (11)	0.0369 (11)	0.0421 (12)	−0.0046 (9)	0.0130 (9)	0.0075 (9)
C10D	0.0420 (11)	0.0330 (10)	0.0469 (12)	0.0067 (8)	0.0236 (10)	0.0150 (9)
C11D	0.0477 (12)	0.0359 (11)	0.0389 (11)	0.0055 (9)	0.0204 (10)	0.0034 (9)
C12D	0.0387 (11)	0.0328 (10)	0.0391 (11)	0.0003 (8)	0.0139 (9)	0.0004 (8)
C13D	0.0477 (13)	0.0460 (13)	0.0431 (12)	−0.0033 (10)	0.0220 (10)	−0.0014 (10)
N14D	0.0547 (13)	0.0660 (14)	0.0639 (14)	−0.0049 (10)	0.0353 (11)	−0.0072 (11)
O15D	0.0501 (10)	0.0534 (10)	0.0644 (11)	0.0050 (8)	0.0342 (9)	0.0120 (8)

Geometric parameters (Å, º)

C1A—C2A	1.391 (3)	C1C—C6C	1.390 (3)
C1A—C6A	1.392 (3)	C1C—C2C	1.395 (3)
C1A—C13A	1.439 (3)	C1C—C13C	1.441 (3)
C2A—C3A	1.383 (3)	C2C—C3C	1.378 (3)
C2A—H2A	0.9500	C2C—H2C	0.9500
C3A—C4A	1.395 (3)	C3C—C4C	1.394 (3)
C3A—H3A	0.9500	C3C—H3C	0.9500
C4A—C5A	1.403 (2)	C4C—C5C	1.401 (3)
C4A—C7A	1.485 (3)	C4C—C7C	1.482 (3)
C5A—C6A	1.378 (3)	C5C—C6C	1.383 (3)
C5A—H5A	0.9500	C5C—H5C	0.9500
C6A—H6A	0.9500	C6C—H6C	0.9500
C7A—C12A	1.398 (3)	C7C—C8C	1.395 (3)
C7A—C8A	1.402 (3)	C7C—C12C	1.405 (3)
C8A—C9A	1.388 (3)	C8C—C9C	1.391 (3)
C8A—H8A	0.9500	C8C—H8C	0.9500
C9A—C10A	1.391 (3)	C9C—C10C	1.386 (3)
C9A—H9A	0.9500	C9C—H9C	0.9500
C10A—O15A	1.363 (2)	C10C—O15C	1.368 (2)
C10A—C11A	1.389 (3)	C10C—C11C	1.386 (3)
C11A—C12A	1.379 (3)	C11C—C12C	1.378 (3)
C11A—H11A	0.9500	C11C—H11C	0.9500
C12A—H12A	0.9500	C12C—H12C	0.9500
C13A—N14A	1.148 (3)	C13C—N14C	1.148 (3)
O15A—H15A	0.89 (3)	O15C—H15C	0.91 (3)
C1B—C2B	1.393 (3)	C1D—C2D	1.397 (3)
C1B—C6B	1.399 (3)	C1D—C6D	1.396 (3)
C1B—C13B	1.441 (3)	C1D—C13D	1.439 (3)
C2B—C3B	1.382 (3)	C2D—C3D	1.382 (3)
C2B—H2B	0.9500	C2D—H2D	0.9500
C3B—C4B	1.395 (3)	C3D—C4D	1.391 (3)
C3B—H3B	0.9500	C3D—H3D	0.9500
C4B—C5B	1.405 (3)	C4D—C5D	1.410 (3)
C4B—C7B	1.484 (3)	C4D—C7D	1.481 (3)
C5B—C6B	1.378 (3)	C5D—C6D	1.378 (3)
C5B—H5B	0.9500	C5D—H5D	0.9500
C6B—H6B	0.9500	C6D—H6D	0.9500
C7B—C8B	1.397 (3)	C7D—C8D	1.396 (3)
C7B—C12B	1.399 (3)	C7D—C12D	1.402 (3)
C8B—C9B	1.393 (3)	C8D—C9D	1.390 (3)
C8B—H8B	0.9500	C8D—H8D	0.9500
C9B—C10B	1.388 (3)	C9D—C10D	1.388 (3)
C9B—H9B	0.9500	C9D—H9D	0.9500
C10B—O15B	1.368 (2)	C10D—O15D	1.371 (3)
C10B—C11B	1.390 (3)	C10D—C11D	1.389 (3)
C11B—C12B	1.381 (3)	C11D—C12D	1.378 (3)
C11B—H11B	0.9500	C11D—H11D	0.9500
C12B—H12B	0.9500	C12D—H12D	0.9500
C13B—N14B	1.146 (3)	C13D—N14D	1.148 (3)
O15B—H15B	0.92 (3)	O15D—H15D	0.92 (3)
C2A—C1A—C6A	119.95 (18)	C6C—C1C—C2C	120.02 (19)
C2A—C1A—C13A	120.62 (19)	C6C—C1C—C13C	119.01 (18)
C6A—C1A—C13A	119.37 (18)	C2C—C1C—C13C	120.90 (19)
C3A—C2A—C1A	119.63 (19)	C3C—C2C—C1C	119.49 (19)
C3A—C2A—H2A	120.2	C3C—C2C—H2C	120.3
C1A—C2A—H2A	120.2	C1C—C2C—H2C	120.3
C2A—C3A—C4A	121.53 (18)	C2C—C3C—C4C	121.58 (18)
C2A—C3A—H3A	119.2	C2C—C3C—H3C	119.2
C4A—C3A—H3A	119.2	C4C—C3C—H3C	119.2
C3A—C4A—C5A	117.75 (17)	C3C—C4C—C5C	118.11 (18)
C3A—C4A—C7A	121.56 (17)	C3C—C4C—C7C	121.42 (17)
C5A—C4A—C7A	120.68 (17)	C5C—C4C—C7C	120.46 (17)
C6A—C5A—C4A	121.31 (18)	C6C—C5C—C4C	120.93 (18)
C6A—C5A—H5A	119.3	C6C—C5C—H5C	119.5
C4A—C5A—H5A	119.3	C4C—C5C—H5C	119.5
C5A—C6A—C1A	119.83 (18)	C5C—C6C—C1C	119.87 (18)
C5A—C6A—H6A	120.1	C5C—C6C—H6C	120.1
C1A—C6A—H6A	120.1	C1C—C6C—H6C	120.1
C12A—C7A—C8A	117.37 (17)	C8C—C7C—C12C	117.41 (18)
C12A—C7A—C4A	121.05 (17)	C8C—C7C—C4C	122.05 (17)
C8A—C7A—C4A	121.58 (16)	C12C—C7C—C4C	120.54 (17)
C9A—C8A—C7A	121.52 (17)	C9C—C8C—C7C	121.39 (18)
C9A—C8A—H8A	119.2	C9C—C8C—H8C	119.3
C7A—C8A—H8A	119.2	C7C—C8C—H8C	119.3
C8A—C9A—C10A	119.77 (18)	C10C—C9C—C8C	119.84 (18)
C8A—C9A—H9A	120.1	C10C—C9C—H9C	120.1
C10A—C9A—H9A	120.1	C8C—C9C—H9C	120.1
O15A—C10A—C11A	117.64 (18)	O15C—C10C—C11C	117.57 (18)
O15A—C10A—C9A	122.88 (18)	O15C—C10C—C9C	122.63 (18)
C11A—C10A—C9A	119.48 (18)	C11C—C10C—C9C	119.80 (18)
C12A—C11A—C10A	120.34 (18)	C12C—C11C—C10C	120.13 (18)
C12A—C11A—H11A	119.8	C12C—C11C—H11C	119.9
C10A—C11A—H11A	119.8	C10C—C11C—H11C	119.9
C11A—C12A—C7A	121.52 (18)	C11C—C12C—C7C	121.42 (18)
C11A—C12A—H12A	119.2	C11C—C12C—H12C	119.3
C7A—C12A—H12A	119.2	C7C—C12C—H12C	119.3
N14A—C13A—C1A	178.0 (2)	N14C—C13C—C1C	178.1 (2)
C10A—O15A—H15A	116.3 (19)	C10C—O15C—H15C	110.6 (17)
C2B—C1B—C6B	120.23 (18)	C2D—C1D—C6D	119.97 (19)
C2B—C1B—C13B	120.31 (19)	C2D—C1D—C13D	120.14 (19)
C6B—C1B—C13B	119.45 (18)	C6D—C1D—C13D	119.86 (19)
C3B—C2B—C1B	119.64 (18)	C3D—C2D—C1D	119.61 (19)
C3B—C2B—H2B	120.2	C3D—C2D—H2D	120.2
C1B—C2B—H2B	120.2	C1D—C2D—H2D	120.2
C2B—C3B—C4B	121.28 (18)	C2D—C3D—C4D	121.47 (19)
C2B—C3B—H3B	119.4	C2D—C3D—H3D	119.3
C4B—C3B—H3B	119.4	C4D—C3D—H3D	119.3
C3B—C4B—C5B	118.08 (17)	C3D—C4D—C5D	118.10 (19)
C3B—C4B—C7B	121.45 (16)	C3D—C4D—C7D	122.03 (17)
C5B—C4B—C7B	120.44 (16)	C5D—C4D—C7D	119.84 (17)
C6B—C5B—C4B	121.45 (18)	C6D—C5D—C4D	121.09 (18)
C6B—C5B—H5B	119.3	C6D—C5D—H5D	119.5
C4B—C5B—H5B	119.3	C4D—C5D—H5D	119.5
C5B—C6B—C1B	119.30 (18)	C5D—C6D—C1D	119.72 (19)
C5B—C6B—H6B	120.4	C5D—C6D—H6D	120.1
C1B—C6B—H6B	120.3	C1D—C6D—H6D	120.1
C8B—C7B—C12B	117.50 (17)	C8D—C7D—C12D	117.72 (19)
C8B—C7B—C4B	122.42 (17)	C8D—C7D—C4D	122.90 (18)
C12B—C7B—C4B	120.06 (16)	C12D—C7D—C4D	119.38 (17)
C9B—C8B—C7B	121.18 (18)	C9D—C8D—C7D	121.06 (19)
C9B—C8B—H8B	119.4	C9D—C8D—H8D	119.5
C7B—C8B—H8B	119.4	C7D—C8D—H8D	119.5
C10B—C9B—C8B	120.00 (18)	C8D—C9D—C10D	119.95 (19)
C10B—C9B—H9B	120.0	C8D—C9D—H9D	120.0
C8B—C9B—H9B	120.0	C10D—C9D—H9D	120.0
O15B—C10B—C9B	122.80 (18)	O15D—C10D—C11D	116.6 (2)
O15B—C10B—C11B	117.58 (18)	O15D—C10D—C9D	123.5 (2)
C9B—C10B—C11B	119.62 (18)	C11D—C10D—C9D	119.85 (19)
C12B—C11B—C10B	119.93 (18)	C12D—C11D—C10D	119.8 (2)
C12B—C11B—H11B	120.0	C12D—C11D—H11D	120.1
C10B—C11B—H11B	120.0	C10D—C11D—H11D	120.1
C11B—C12B—C7B	121.75 (17)	C11D—C12D—C7D	121.60 (19)
C11B—C12B—H12B	119.1	C11D—C12D—H12D	119.2
C7B—C12B—H12B	119.1	C7D—C12D—H12D	119.2
N14B—C13B—C1B	178.6 (3)	N14D—C13D—C1D	178.7 (3)
C10B—O15B—H15B	113.0 (18)	C10D—O15D—H15D	108.8 (15)