Two new polymorphs of 4-(N,N-dimethyl­amino)­benzoic acid

Two new polymorphs of 4-(N,N-dimethyl­amino)­benzoic acid, C₉H₁₁NO₂, resulting from the attempted cocrystallization in ethanol of 4-(N,N-dimethyl­amino)­benzoic acid and a mixture of 3-(N,N-dimethyl­amino)­benzoic acid and 3-(3-pyrid­yl)-2-pyridone producing one polymorph, and a mixture of 3-(N,N-dimethyl­amino)­benzoic acid and 5-meth­oxy-3,3′-bipyridine producing the second polymorph, have been crystallographically characterized. The primary inter­molecular O—H...O hydrogen bonds generate a dimeric acid–acid motif that is present in all three polymorphs.

S1. Comment

It has previously been demonstrated that 4-N,N-dimethylaminobenzoic acid, (1), is capable of forming binary (Sharma et al., 1992, 1993) and ternary (Aakeröy et al., 2001) cocrystals as a result of its propensity for engaging in heteromeric complementary hydrogen-bond interactions with carboxylic acids or carboxamides (Aakeröy et al., 2004), as well as with N-heterocyclic compounds, coupled with a capacity to act as a donor moiety in π-π* charge-transfer donor complexes. With this information in mind, (1) has been used extensively in our laboratory as a cocrystallizing agent, especially since it has also been shown that heterodimers in acid–acid cocrystals, (Hanton et al., 1992; Etter, 1990) gain increased stability as a result of the variation in hydrogen-bond donating/accepting ability of the two different carboxylic acid moieties (Etter & Frankenbach, 1989).

During the course of systematic cocrystallization experiments involving a variety of carboxylic acids [including (1)] and ditopic N-heterocyclic compounds, we obtained two new polymorphs of 4-N,N-dimethylaminobenzoic acid. Views of the molecules in forms (II) and (III), with the atom-numbering schemes, are presented in Fig. 1. Form (I) was previously obtained from water–alcohol mixtures (Vyas et al., 1978) and acetone (Anulewicz et al., 1987).

In (II), near-linear O—H···O hydrogen bonds between adjacent, crystallographically inequivalent carboxylic acid moieties generate the dominating intermolecular interactions and result in well known dimeric acid–acid motifs [O27—H27···O18ⁱⁱ, O···O = 2.602 (3) Å, and O17—H17···O28ⁱ, O···O = 2.609 (3) Å; symmetry codes as in Table 1). Adjacent dimers are positioned with their methyl-substituents `back-to-back', resulting in linear one-dimensional arrangements of dimeric units (Fig. 2).

Form (III) also contains two crystallographically inequivalent molecules; however, symmetry-related molecules form dimers resulting in two distinct chains. The relevant intermolecular O—H···O interactions for the two forms are O17—H17···O18ⁱ [O···O = 2.603 (2) Å] and O27—H27···O28ⁱⁱ [O···O = 2.600 (2) Å]. (The H atoms in each of these two interactions are actually disordered between the two O-atom sites, so that each O atom acts as a donor and an acceptor with roughly equal populations.) Adjacent dimers organize themselves in the same way as the dimers in forms (I) and (II), with relatively short contacts between methyl groups on adjacent dimers within each chain (Fig. 3).

The amine substituent in all three forms is approximately coplanar with the ring to which it is attached (all relevant torsion angles are less than 5°). It has previously been postulated that polymorphic compounds make good cocrystallizing agents (Aakeröy et al., 2003). This statement is supported by, for example, 3,5-dinitrobenzoic acid, a compound that displays several polymorphic forms (Prince et al., 1991; Kanters et al., 1991; Domenicano et al., 1990) and is known to be an excellent cocrystallizing agent (Pedireddi et al., 1998; Bott et al., 2000; Grabowski et al., 2001). In light of the new polymorphs of (1), 4-N,N-dimethylaminobenzoic acid lends further support to the notion that good cocrystallizing agents with appropriate hydrogen-bonding substituents are quite likely to be found amongst polymorphic compounds.

S2. Experimental

Crystals of (II) and (III) were obtained by slow evaporation of 50% aqueous ethanol solutions of 4-N,N-dimethylaminobenzoic acid, 3-N,N-dimethylaminobenzoic acid and 3-(3-pyridyl)-2-pyridone (in 1:1:1 stoichiometry), and of 4-N,N-dimethylaminobenzoic acid, 3-N,N-dimethylaminobenzoic acid and 5-methoxy-3,3'-bipyridine (in 1:1:1 stoichiometry), respectively.

S3. Refinement

H atoms were assigned to idealized positions and were allowed to ride, except for the carboxylic acid H atom, whose coordinates were allowed to refine. Heavy atoms were refined with anisotropic displacement parameters. Neither data set was corrected for absorption [the linear absorption coefficients are 0.09 and 0.10 mm⁻¹ for (II) and (III), respectively]. For (III), initial structural models included a single protonation site for the two unique carboxylic acids. Difference electron density maps, as well as the nearly identical C—O bond distances, indicated disorder of the acid H atom across the two O atoms of each acid. To accommodate this disorder, H atoms were placed on the difference peaks and the total occupancy for the two H atoms of each unique acid was constrained to 1. Distance restraints and damping were applied for the initial stages of refinement; these were both relaxed and eventually removed. For both molecules, refinement led to a nearly equal ratio of H-atom populations.

Computing details

For both compounds, data collection: SMART (Bruker, 1999); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. Displacement ellipsoids (50% probability level) and atom-numbering schemes for forms (II) (left) and (III) (right) of 4-N,N-dimethylaminobenzoic acid.
	Fig. 2. A view of adjacent carboxylic dimers in form (II) of (1).
	Fig. 3. A view of the two chains of crystallographically inequivalent dimers in form (III) of (1).

(II) 4-(dimethylamino)benzoic acid

Crystal data

C9H11NO2	F(000) = 352
Mr = 165.19	Dx = 1.320 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 10.3202 (10) Å	Cell parameters from 1626 reflections
b = 7.4068 (8) Å	θ = 2.8–27.7°
c = 11.2845 (11) Å	µ = 0.09 mm^−1
β = 105.505 (5)°	T = 173 K
V = 831.19 (15) Å^3	Plate, colorless
Z = 4	0.35 × 0.30 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer	1280 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.054
Graphite monochromator	θmax = 28.0°, θmin = 1.9°
ϕ and ω scans	h = −13→12
5542 measured reflections	k = −9→9
1982 independent reflections	l = −14→14

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.132	H atoms treated by a mixture of independent and constrained refinement
S = 0.96	w = 1/[σ^2(Fo^2) + (0.080P)^2] where P = (Fo^2 + 2Fc^2)/3
1982 reflections	(Δ/σ)max < 0.001
223 parameters	Δρmax = 0.20 e Å^−3
1 restraint	Δρmin = −0.23 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
C11	0.2966 (3)	0.5022 (4)	0.0268 (3)	0.0253 (7)
C12	0.3923 (3)	0.4249 (4)	−0.0231 (3)	0.0261 (7)
H12	0.3643	0.3676	−0.1011	0.031*
C13	0.5262 (3)	0.4293 (4)	0.0372 (3)	0.0279 (7)
H13	0.5896	0.3752	0.0006	0.034*
C14	0.5707 (3)	0.5122 (4)	0.1520 (3)	0.0239 (6)
N14	0.7052 (2)	0.5170 (4)	0.2123 (2)	0.0312 (6)
C18	0.8051 (3)	0.4624 (5)	0.1514 (3)	0.0428 (10)
H18A	0.8939	0.4614	0.2109	0.064*
H18B	0.8056	0.5477	0.0851	0.064*
H18C	0.7839	0.3412	0.1169	0.064*
C19	0.7511 (3)	0.6152 (5)	0.3256 (3)	0.0392 (9)
H19A	0.8431	0.5783	0.3674	0.059*
H19B	0.6920	0.5895	0.3786	0.059*
H19C	0.7494	0.7449	0.3082	0.059*
C15	0.4749 (3)	0.5900 (4)	0.2034 (3)	0.0284 (7)
H15	0.5024	0.6474	0.2814	0.034*
C16	0.3407 (3)	0.5836 (4)	0.1410 (3)	0.0268 (7)
H16	0.2766	0.6363	0.1772	0.032*
C17	0.1552 (3)	0.4974 (5)	−0.0418 (3)	0.0296 (7)
O17	0.0727 (2)	0.5754 (4)	0.0117 (2)	0.0415 (7)
H17	−0.009 (4)	0.572 (6)	−0.036 (3)	0.050*
O18	0.1170 (2)	0.4278 (4)	−0.1451 (2)	0.0387 (6)
C21	0.6483 (3)	0.5130 (5)	0.6993 (3)	0.0256 (7)
C22	0.5555 (3)	0.6052 (4)	0.7452 (3)	0.0285 (7)
H22	0.5850	0.6677	0.8212	0.034*
C23	0.4214 (3)	0.6080 (4)	0.6829 (3)	0.0278 (7)
H23	0.3601	0.6732	0.7163	0.033*
C24	0.3731 (3)	0.5164 (4)	0.5708 (3)	0.0271 (7)
N24	0.2399 (2)	0.5198 (4)	0.5099 (2)	0.0352 (7)
C28	0.1441 (4)	0.6098 (6)	0.5613 (4)	0.0482 (10)
H28A	0.0532	0.5897	0.5083	0.072*
H28B	0.1633	0.7396	0.5671	0.072*
H28C	0.1506	0.5615	0.6435	0.072*
C29	0.1884 (4)	0.4253 (6)	0.3957 (3)	0.0463 (10)
H29A	0.0954	0.4629	0.3582	0.069*
H29B	0.1910	0.2950	0.4112	0.069*
H29C	0.2438	0.4536	0.3398	0.069*
C25	0.4678 (3)	0.4233 (5)	0.5255 (3)	0.0275 (7)
H25	0.4387	0.3599	0.4499	0.033*
C26	0.6013 (3)	0.4215 (4)	0.5876 (3)	0.0269 (7)
H26	0.6630	0.3571	0.5543	0.032*
C27	0.7889 (3)	0.5108 (5)	0.7685 (3)	0.0274 (7)
O27	0.8695 (2)	0.4166 (4)	0.7200 (2)	0.0395 (6)
H27	0.950 (4)	0.419 (6)	0.759 (3)	0.047*
O28	0.8294 (2)	0.5906 (4)	0.8664 (2)	0.0402 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C11	0.0280 (15)	0.0232 (14)	0.0247 (16)	−0.0003 (15)	0.0071 (12)	0.0009 (16)
C12	0.0313 (17)	0.0245 (15)	0.0205 (16)	−0.0019 (14)	0.0036 (13)	−0.0009 (15)
C13	0.0327 (17)	0.0235 (15)	0.0289 (18)	0.0065 (14)	0.0106 (14)	0.0027 (16)
C14	0.0257 (15)	0.0205 (13)	0.0256 (16)	−0.0005 (15)	0.0073 (13)	0.0025 (15)
N14	0.0292 (14)	0.0321 (14)	0.0298 (15)	0.0026 (14)	0.0038 (11)	−0.0018 (15)
C18	0.0353 (19)	0.052 (2)	0.039 (2)	0.0039 (16)	0.0078 (16)	−0.0084 (18)
C19	0.0310 (18)	0.048 (2)	0.034 (2)	0.0049 (16)	0.0000 (15)	−0.0029 (18)
C15	0.0361 (18)	0.0279 (16)	0.0216 (17)	−0.0005 (15)	0.0086 (14)	−0.0037 (16)
C16	0.0280 (16)	0.0284 (15)	0.0265 (17)	−0.0003 (14)	0.0115 (13)	−0.0021 (16)
C17	0.0314 (16)	0.0304 (16)	0.0290 (18)	−0.0023 (15)	0.0112 (14)	−0.0024 (16)
O17	0.0271 (12)	0.0585 (16)	0.0386 (15)	0.0032 (12)	0.0084 (11)	−0.0106 (13)
O18	0.0315 (13)	0.0491 (14)	0.0344 (14)	0.0015 (11)	0.0069 (11)	−0.0107 (12)
C21	0.0274 (15)	0.0252 (15)	0.0246 (16)	−0.0009 (16)	0.0079 (13)	0.0044 (17)
C22	0.0363 (19)	0.0264 (17)	0.0244 (18)	0.0007 (15)	0.0108 (15)	−0.0018 (15)
C23	0.0301 (17)	0.0278 (17)	0.0269 (18)	0.0009 (14)	0.0099 (14)	−0.0008 (16)
C24	0.0304 (17)	0.0241 (15)	0.0255 (17)	−0.0032 (17)	0.0052 (14)	0.0038 (17)
N24	0.0293 (14)	0.0442 (17)	0.0297 (16)	0.0025 (15)	0.0035 (12)	−0.0045 (16)
C28	0.0319 (18)	0.059 (3)	0.049 (2)	0.0035 (18)	0.0036 (17)	−0.007 (2)
C29	0.0352 (19)	0.061 (2)	0.040 (2)	−0.006 (2)	0.0053 (17)	−0.015 (2)
C25	0.0315 (17)	0.0287 (16)	0.0217 (17)	−0.0038 (15)	0.0060 (13)	−0.0002 (16)
C26	0.0296 (17)	0.0287 (16)	0.0231 (17)	0.0006 (15)	0.0083 (14)	−0.0018 (17)
C27	0.0312 (16)	0.0237 (14)	0.0275 (18)	−0.0003 (15)	0.0084 (14)	−0.0008 (16)
O27	0.0279 (12)	0.0499 (14)	0.0388 (15)	0.0055 (12)	0.0057 (11)	−0.0122 (13)
O28	0.0308 (13)	0.0504 (15)	0.0355 (15)	0.0069 (12)	0.0022 (11)	−0.0102 (13)

Geometric parameters (Å, º)

C11—C16	1.384 (4)	C21—C22	1.385 (4)
C11—C12	1.385 (4)	C21—C26	1.399 (4)
C11—C17	1.459 (4)	C21—C27	1.453 (4)
C12—C13	1.368 (4)	C22—C23	1.375 (5)
C12—H12	0.9500	C22—H22	0.9500
C13—C14	1.395 (4)	C23—C24	1.404 (4)
C13—H13	0.9500	C23—H23	0.9500
C14—N14	1.373 (4)	C24—N24	1.363 (4)
C14—C15	1.397 (4)	C24—C25	1.400 (4)
N14—C19	1.438 (4)	N24—C28	1.437 (4)
N14—C18	1.442 (4)	N24—C29	1.437 (4)
C18—H18A	0.9800	C28—H28A	0.9800
C18—H18B	0.9800	C28—H28B	0.9800
C18—H18C	0.9800	C28—H28C	0.9800
C19—H19A	0.9800	C29—H29A	0.9800
C19—H19B	0.9800	C29—H29B	0.9800
C19—H19C	0.9800	C29—H29C	0.9800
C15—C16	1.377 (4)	C25—C26	1.368 (4)
C15—H15	0.9500	C25—H25	0.9500
C16—H16	0.9500	C26—H26	0.9500
C17—O18	1.238 (4)	C27—O28	1.224 (4)
C17—O17	1.303 (4)	C27—O27	1.312 (4)
O17—H17	0.87 (4)	O27—H27	0.83 (4)
C16—C11—C12	117.8 (3)	C22—C21—C26	117.9 (3)
C16—C11—C17	122.5 (3)	C22—C21—C27	119.7 (3)
C12—C11—C17	119.7 (3)	C26—C21—C27	122.3 (3)
C13—C12—C11	121.5 (3)	C23—C22—C21	121.2 (3)
C13—C12—H12	119.2	C23—C22—H22	119.4
C11—C12—H12	119.2	C21—C22—H22	119.4
C12—C13—C14	120.7 (3)	C22—C23—C24	121.3 (3)
C12—C13—H13	119.7	C22—C23—H23	119.4
C14—C13—H13	119.7	C24—C23—H23	119.4
N14—C14—C13	120.6 (3)	N24—C24—C25	122.2 (3)
N14—C14—C15	121.1 (3)	N24—C24—C23	120.8 (3)
C13—C14—C15	118.2 (3)	C25—C24—C23	117.0 (3)
C14—N14—C19	120.2 (3)	C24—N24—C28	121.0 (3)
C14—N14—C18	120.9 (3)	C24—N24—C29	121.7 (3)
C19—N14—C18	117.3 (3)	C28—N24—C29	117.3 (3)
N14—C18—H18A	109.5	N24—C28—H28A	109.5
N14—C18—H18B	109.5	N24—C28—H28B	109.5
H18A—C18—H18B	109.5	H28A—C28—H28B	109.5
N14—C18—H18C	109.5	N24—C28—H28C	109.5
H18A—C18—H18C	109.5	H28A—C28—H28C	109.5
H18B—C18—H18C	109.5	H28B—C28—H28C	109.5
N14—C19—H19A	109.5	N24—C29—H29A	109.5
N14—C19—H19B	109.5	N24—C29—H29B	109.5
H19A—C19—H19B	109.5	H29A—C29—H29B	109.5
N14—C19—H19C	109.5	N24—C29—H29C	109.5
H19A—C19—H19C	109.5	H29A—C29—H29C	109.5
H19B—C19—H19C	109.5	H29B—C29—H29C	109.5
C16—C15—C14	120.0 (3)	C26—C25—C24	121.6 (3)
C16—C15—H15	120.0	C26—C25—H25	119.2
C14—C15—H15	120.0	C24—C25—H25	119.2
C15—C16—C11	121.7 (3)	C25—C26—C21	121.0 (3)
C15—C16—H16	119.1	C25—C26—H26	119.5
C11—C16—H16	119.1	C21—C26—H26	119.5
O18—C17—O17	122.5 (3)	O28—C27—O27	122.2 (3)
O18—C17—C11	122.1 (3)	O28—C27—C21	122.0 (3)
O17—C17—C11	115.3 (3)	O27—C27—C21	115.8 (3)
C17—O17—H17	110 (3)	C27—O27—H27	115 (3)
C16—C11—C12—C13	−0.5 (5)	C26—C21—C22—C23	−0.4 (5)
C17—C11—C12—C13	178.9 (3)	C27—C21—C22—C23	−179.1 (3)
C11—C12—C13—C14	0.1 (5)	C21—C22—C23—C24	0.5 (5)
C12—C13—C14—N14	−179.8 (3)	C22—C23—C24—N24	179.9 (3)
C12—C13—C14—C15	0.2 (5)	C22—C23—C24—C25	−0.3 (5)
C13—C14—N14—C19	175.0 (3)	C25—C24—N24—C28	177.2 (4)
C15—C14—N14—C19	−5.0 (5)	C23—C24—N24—C28	−3.0 (5)
C13—C14—N14—C18	9.8 (5)	C25—C24—N24—C29	0.9 (5)
C15—C14—N14—C18	−170.2 (3)	C23—C24—N24—C29	−179.4 (3)
N14—C14—C15—C16	180.0 (3)	N24—C24—C25—C26	179.8 (3)
C13—C14—C15—C16	0.0 (5)	C23—C24—C25—C26	0.1 (5)
C14—C15—C16—C11	−0.4 (5)	C24—C25—C26—C21	0.0 (5)
C12—C11—C16—C15	0.6 (5)	C22—C21—C26—C25	0.1 (5)
C17—C11—C16—C15	−178.7 (3)	C27—C21—C26—C25	178.8 (3)
C16—C11—C17—O18	178.4 (3)	C22—C21—C27—O28	−1.1 (5)
C12—C11—C17—O18	−0.9 (5)	C26—C21—C27—O28	−179.8 (3)
C16—C11—C17—O17	0.1 (5)	C22—C21—C27—O27	178.3 (3)
C12—C11—C17—O17	−179.2 (3)	C26—C21—C27—O27	−0.3 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O17—H17···O28^i	0.87 (4)	1.74 (4)	2.609 (3)	174 (4)
O27—H27···O18^ii	0.83 (4)	1.78 (4)	2.602 (3)	175 (4)

Symmetry codes: (i) x−1, y, z−1; (ii) x+1, y, z+1.

(III) 4-(dimethylamino)benzoic acid

Crystal data

C9H11NO2	Z = 4
Mr = 165.19	F(000) = 352
Triclinic, P1	Dx = 1.337 Mg m^−3
a = 9.6507 (11) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.8918 (11) Å	Cell parameters from 1288 reflections
c = 10.0082 (10) Å	θ = 2.2–26.8°
α = 76.118 (6)°	µ = 0.10 mm^−1
β = 67.655 (7)°	T = 173 K
γ = 69.334 (9)°	Plate, colorless
V = 820.61 (15) Å^3	0.30 × 0.20 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer	1717 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.059
Graphite monochromator	θmax = 27.5°, θmin = 2.2°
ϕ and ω scans	h = −11→12
5655 measured reflections	k = −12→12
3506 independent reflections	l = −12→12

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.142	H atoms treated by a mixture of independent and constrained refinement
S = 0.85	w = 1/[σ^2(Fo^2) + (0.07P)^2] where P = (Fo^2 + 2Fc^2)/3
3506 reflections	(Δ/σ)max < 0.001
235 parameters	Δρmax = 0.21 e Å^−3
0 restraints	Δρmin = −0.28 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. X-ray data were collected on a Bruker SMART 1000 four-circle CCD diffractometer using a fine-focus molybdenum Ka tube. Data were collected using SMART (1997). Initial cell constants were found by small widely separated "matrix" runs. Preliminary Laué symmetry was determined from axial images. For both structures, an entire hemisphere of reciprocal space was collected. Scan speed and scan width were chosen based on scattering power and peak rocking curves. Data were collected at −100 °C, using 0.25° scan width. Unit cell constants and orientation matrix were improved by least-squares refinement of reflections "thresholded" from the entire dataset. Integration was performed with SAINT (1997), using this improved unit cell as a starting point. Precise unit cell constants were calculated in SAINT from the final merged dataset. Lorenz and polarization corrections were applied. Laué symmetry, space group, and unit-cell contents were found with XPREP. Friedel opposites were merged for the noncentrosymmetric II. Data were reduced with SHELXTL (1997). The structures were solved in all cases by direct methods. 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	Occ. (<1)
C11	0.3291 (2)	0.3217 (2)	0.8360 (2)	0.0278 (5)
C12	0.3661 (2)	0.3508 (2)	0.6857 (2)	0.0302 (5)
H12	0.4352	0.2755	0.6274	0.036*
C13	0.3056 (2)	0.4851 (2)	0.6196 (2)	0.0299 (5)
H13	0.3330	0.5017	0.5166	0.036*
C14	0.2033 (2)	0.5985 (2)	0.7027 (2)	0.0280 (5)
N14	0.1411 (2)	0.73427 (19)	0.63953 (19)	0.0369 (5)
C18	0.0449 (3)	0.8517 (2)	0.7270 (3)	0.0463 (6)
H18A	0.1030	0.8643	0.7826	0.069*
H18B	−0.0508	0.8285	0.7943	0.069*
H18C	0.0171	0.9419	0.6635	0.069*
C19	0.1843 (3)	0.7676 (2)	0.4839 (2)	0.0423 (6)
H19A	0.1215	0.8660	0.4587	0.063*
H19B	0.1653	0.6973	0.4437	0.063*
H19C	0.2956	0.7623	0.4432	0.063*
C15	0.1645 (2)	0.5684 (2)	0.8542 (2)	0.0303 (5)
H15	0.0941	0.6426	0.9134	0.036*
C16	0.2272 (2)	0.4326 (2)	0.9183 (2)	0.0299 (5)
H16	0.1999	0.4147	1.0213	0.036*
C17	0.4002 (2)	0.1799 (2)	0.9055 (2)	0.0317 (5)
O17	0.49830 (19)	0.08182 (17)	0.82613 (17)	0.0435 (4)
H17	0.549 (5)	0.006 (7)	0.883 (5)	0.052*	0.57 (5)
O18	0.36301 (19)	0.16002 (18)	1.04317 (17)	0.0432 (4)
H18	0.419 (7)	0.090 (10)	1.080 (8)	0.052*	0.43 (5)
C21	0.8391 (2)	0.3220 (2)	0.8316 (2)	0.0276 (5)
C22	0.6787 (2)	0.3752 (2)	0.8573 (2)	0.0307 (5)
H22A	0.6138	0.3158	0.9174	0.037*
C23	0.6117 (2)	0.5109 (2)	0.7980 (2)	0.0315 (5)
H23A	0.5016	0.5438	0.8172	0.038*
C24	0.7030 (2)	0.6022 (2)	0.7094 (2)	0.0281 (5)
N24	0.63636 (19)	0.73817 (19)	0.65204 (19)	0.0351 (5)
C28	0.4685 (2)	0.7994 (2)	0.6941 (3)	0.0441 (6)
H28A	0.4424	0.9005	0.6489	0.066*
H28B	0.4246	0.7966	0.8003	0.066*
H28C	0.4243	0.7427	0.6619	0.066*
C29A	0.7306 (3)	0.8344 (2)	0.5672 (3)	0.0469 (6)
H29A	0.6635	0.9275	0.5359	0.070*
H29B	0.8101	0.7899	0.4815	0.070*
H29C	0.7822	0.8511	0.6267	0.070*
C25	0.8649 (2)	0.5474 (2)	0.6821 (2)	0.0309 (5)
H25A	0.9305	0.6056	0.6205	0.037*
C26	0.9302 (2)	0.4117 (2)	0.7424 (2)	0.0300 (5)
H26A	1.0404	0.3780	0.7230	0.036*
C27	0.9090 (2)	0.1808 (2)	0.8992 (2)	0.0310 (5)
O27	0.82245 (17)	0.10064 (17)	0.97916 (17)	0.0413 (4)
H27	0.872 (6)	0.018 (7)	1.023 (6)	0.050*	0.55 (5)
O28	1.05549 (17)	0.14058 (17)	0.87839 (19)	0.0420 (4)
H28	1.096 (7)	0.066 (9)	0.927 (7)	0.050*	0.45 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C11	0.0244 (10)	0.0293 (12)	0.0299 (12)	−0.0092 (9)	−0.0054 (9)	−0.0078 (10)
C12	0.0246 (10)	0.0323 (12)	0.0306 (12)	−0.0063 (9)	−0.0031 (9)	−0.0116 (10)
C13	0.0284 (10)	0.0369 (13)	0.0244 (11)	−0.0119 (10)	−0.0045 (9)	−0.0070 (9)
C14	0.0257 (10)	0.0271 (12)	0.0326 (12)	−0.0091 (9)	−0.0090 (9)	−0.0050 (10)
N14	0.0468 (11)	0.0314 (11)	0.0310 (10)	−0.0069 (9)	−0.0139 (9)	−0.0062 (9)
C18	0.0576 (15)	0.0319 (13)	0.0438 (14)	0.0022 (11)	−0.0214 (12)	−0.0095 (11)
C19	0.0419 (13)	0.0391 (14)	0.0383 (14)	−0.0068 (11)	−0.0130 (11)	0.0010 (11)
C15	0.0292 (11)	0.0315 (12)	0.0309 (12)	−0.0077 (9)	−0.0076 (9)	−0.0104 (10)
C16	0.0307 (11)	0.0340 (12)	0.0240 (11)	−0.0106 (10)	−0.0042 (9)	−0.0077 (9)
C17	0.0298 (11)	0.0316 (13)	0.0308 (12)	−0.0093 (10)	−0.0036 (10)	−0.0082 (10)
O17	0.0473 (10)	0.0303 (9)	0.0385 (10)	0.0018 (8)	−0.0077 (8)	−0.0092 (8)
O18	0.0522 (10)	0.0351 (10)	0.0312 (10)	−0.0040 (8)	−0.0102 (8)	−0.0032 (7)
C21	0.0283 (11)	0.0304 (12)	0.0240 (11)	−0.0087 (9)	−0.0044 (9)	−0.0096 (9)
C22	0.0275 (11)	0.0359 (13)	0.0271 (11)	−0.0117 (10)	−0.0028 (9)	−0.0076 (10)
C23	0.0275 (10)	0.0389 (13)	0.0275 (11)	−0.0121 (10)	−0.0064 (9)	−0.0036 (10)
C24	0.0296 (11)	0.0325 (12)	0.0218 (11)	−0.0104 (9)	−0.0044 (9)	−0.0069 (9)
N24	0.0305 (10)	0.0345 (11)	0.0360 (11)	−0.0099 (8)	−0.0082 (8)	−0.0004 (9)
C28	0.0337 (12)	0.0408 (14)	0.0491 (15)	−0.0061 (11)	−0.0118 (11)	−0.0001 (12)
C29A	0.0443 (13)	0.0359 (14)	0.0510 (15)	−0.0144 (11)	−0.0099 (12)	0.0066 (12)
C25	0.0308 (11)	0.0338 (12)	0.0281 (12)	−0.0125 (10)	−0.0055 (9)	−0.0061 (10)
C26	0.0244 (10)	0.0326 (12)	0.0305 (12)	−0.0089 (9)	−0.0022 (9)	−0.0099 (10)
C27	0.0316 (11)	0.0325 (13)	0.0285 (11)	−0.0108 (10)	−0.0033 (9)	−0.0118 (10)
O27	0.0389 (9)	0.0334 (10)	0.0418 (10)	−0.0114 (8)	−0.0050 (8)	0.0007 (8)
O28	0.0310 (9)	0.0343 (10)	0.0547 (11)	−0.0052 (7)	−0.0132 (8)	−0.0027 (8)

Geometric parameters (Å, º)

C11—C16	1.380 (3)	C21—C22	1.388 (3)
C11—C12	1.389 (3)	C21—C26	1.390 (3)
C11—C17	1.462 (3)	C21—C27	1.447 (3)
C12—C13	1.366 (3)	C22—C23	1.367 (3)
C12—H12	0.9500	C22—H22A	0.9500
C13—C14	1.402 (3)	C23—C24	1.401 (3)
C13—H13	0.9500	C23—H23A	0.9500
C14—N14	1.370 (3)	C24—N24	1.361 (3)
C14—C15	1.400 (3)	C24—C25	1.399 (3)
N14—C19	1.437 (3)	N24—C28	1.442 (2)
N14—C18	1.445 (2)	N24—C29A	1.446 (2)
C18—H18A	0.9800	C28—H28A	0.9800
C18—H18B	0.9800	C28—H28B	0.9800
C18—H18C	0.9800	C28—H28C	0.9800
C19—H19A	0.9800	C29A—H29A	0.9800
C19—H19B	0.9800	C29A—H29B	0.9800
C19—H19C	0.9800	C29A—H29C	0.9800
C15—C16	1.375 (3)	C25—C26	1.367 (3)
C15—H15	0.9500	C25—H25A	0.9500
C16—H16	0.9500	C26—H26A	0.9500
C17—O18	1.269 (2)	C27—O28	1.273 (2)
C17—O17	1.272 (2)	C27—O27	1.273 (2)
O17—H17	0.93 (6)	O27—H27	0.89 (7)
O18—H18	0.83 (9)	O28—H28	0.84 (9)
C16—C11—C12	118.02 (19)	C22—C21—C26	117.6 (2)
C16—C11—C17	120.61 (18)	C22—C21—C27	121.51 (18)
C12—C11—C17	121.32 (18)	C26—C21—C27	120.89 (18)
C13—C12—C11	121.65 (19)	C23—C22—C21	121.59 (19)
C13—C12—H12	119.2	C23—C22—H22A	119.2
C11—C12—H12	119.2	C21—C22—H22A	119.2
C12—C13—C14	120.54 (19)	C22—C23—C24	120.99 (18)
C12—C13—H13	119.7	C22—C23—H23A	119.5
C14—C13—H13	119.7	C24—C23—H23A	119.5
N14—C14—C15	120.41 (19)	N24—C24—C25	121.68 (19)
N14—C14—C13	121.88 (19)	N24—C24—C23	121.09 (18)
C15—C14—C13	117.71 (19)	C25—C24—C23	117.23 (19)
C14—N14—C19	120.82 (18)	C24—N24—C28	121.02 (18)
C14—N14—C18	120.61 (18)	C24—N24—C29A	120.62 (17)
C19—N14—C18	118.20 (18)	C28—N24—C29A	117.52 (18)
N14—C18—H18A	109.5	N24—C28—H28A	109.5
N14—C18—H18B	109.5	N24—C28—H28B	109.5
H18A—C18—H18B	109.5	H28A—C28—H28B	109.5
N14—C18—H18C	109.5	N24—C28—H28C	109.5
H18A—C18—H18C	109.5	H28A—C28—H28C	109.5
H18B—C18—H18C	109.5	H28B—C28—H28C	109.5
N14—C19—H19A	109.5	N24—C29A—H29A	109.5
N14—C19—H19B	109.5	N24—C29A—H29B	109.5
H19A—C19—H19B	109.5	H29A—C29A—H29B	109.5
N14—C19—H19C	109.5	N24—C29A—H29C	109.5
H19A—C19—H19C	109.5	H29A—C29A—H29C	109.5
H19B—C19—H19C	109.5	H29B—C29A—H29C	109.5
C16—C15—C14	120.73 (19)	C26—C25—C24	121.17 (19)
C16—C15—H15	119.6	C26—C25—H25A	119.4
C14—C15—H15	119.6	C24—C25—H25A	119.4
C15—C16—C11	121.34 (19)	C25—C26—C21	121.44 (19)
C15—C16—H16	119.3	C25—C26—H26A	119.3
C11—C16—H16	119.3	C21—C26—H26A	119.3
O18—C17—O17	122.4 (2)	O28—C27—O27	121.7 (2)
O18—C17—C11	118.54 (19)	O28—C27—C21	118.98 (19)
O17—C17—C11	119.06 (19)	O27—C27—C21	119.33 (19)
C17—O17—H17	109 (3)	C27—O27—H27	115 (3)
C17—O18—H18	118 (4)	C27—O28—H28	120 (4)
C16—C11—C12—C13	0.6 (3)	C26—C21—C22—C23	−0.3 (3)
C17—C11—C12—C13	−176.99 (18)	C27—C21—C22—C23	177.40 (18)
C11—C12—C13—C14	0.0 (3)	C21—C22—C23—C24	−0.4 (3)
C12—C13—C14—N14	179.80 (18)	C22—C23—C24—N24	−179.02 (19)
C12—C13—C14—C15	−0.8 (3)	C22—C23—C24—C25	1.2 (3)
C15—C14—N14—C19	177.86 (17)	C25—C24—N24—C28	−172.88 (19)
C13—C14—N14—C19	−2.8 (3)	C23—C24—N24—C28	7.4 (3)
C15—C14—N14—C18	5.1 (3)	C25—C24—N24—C29A	−3.7 (3)
C13—C14—N14—C18	−175.61 (18)	C23—C24—N24—C29A	176.62 (18)
N14—C14—C15—C16	−179.58 (18)	N24—C24—C25—C26	178.78 (18)
C13—C14—C15—C16	1.1 (3)	C23—C24—C25—C26	−1.5 (3)
C14—C15—C16—C11	−0.5 (3)	C24—C25—C26—C21	0.9 (3)
C12—C11—C16—C15	−0.4 (3)	C22—C21—C26—C25	0.1 (3)
C17—C11—C16—C15	177.22 (18)	C27—C21—C26—C25	−177.66 (18)
C16—C11—C17—O18	1.8 (3)	C22—C21—C27—O28	−176.16 (18)
C12—C11—C17—O18	179.34 (18)	C26—C21—C27—O28	1.5 (3)
C16—C11—C17—O17	−177.27 (18)	C22—C21—C27—O27	3.0 (3)
C12—C11—C17—O17	0.2 (3)	C26—C21—C27—O27	−179.34 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O17—H17···O18^i	0.93 (6)	1.70 (7)	2.607 (2)	164 (4)
O18—H18···O17^i	0.83 (9)	1.80 (9)	2.607 (2)	166 (7)
O27—H27···O28^ii	0.89 (7)	1.71 (7)	2.603 (2)	173 (5)
O28—H28···O27^ii	0.84 (9)	1.77 (9)	2.603 (2)	175 (6)

Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x+2, −y, −z+2.