Crystal structure of [1,1′:3′,1′′-ter­phenyl]-2′,3,3′′-tri­carb­oxy­lic acid

Decato, D.A.; Berryman, O.B.

doi:10.1107/S2056989015015029

organic compounds

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Volume 71| Part 9| September 2015| Pages o667-o668

https://doi.org/10.1107/S2056989015015029

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Crystal structure of [1,1′:3′,1′′-terphenyl]-2′,3,3′′-tricarboxylic acid

Daniel A. Decato ^a and Orion B. Berryman ^a ^*

^aDepartment of Chemistry and Biochemistry, University of Montana, 32 Campus Dr., Missoula, Montana 59812, USA
^*Correspondence e-mail: orion.berryman@umontana.edu

Edited by S. V. Lindeman, Marquette University, USA (Received 16 May 2015; accepted 11 August 2015; online 22 August 2015)

The asymmetric unit of the title compound, C₂₁H₁₄O₆, comprises two symmetrically independent molecules that form a locally centrosymmetric hydrogen-bonded dimer, with the planes of the corresponding carboxylic acid groups rotated by 15.8 (1) and 17.5 (1)° relative to those of the adjacent benzene rings. The crystal as a whole, however, exhibits a noncentrosymmetric packing, described by the polar space group Pca2₁. The dimers form layers along the ab plane, being interconnected by hydrogen bonds involving the remaining carboxylic acid groups. The plane of the central carboxylic acid group forms dihedral angles of 62.5 (1) and 63.0 (1)° with those of the adjacent benzene rings and functions as a hydrogen-bond donor and acceptor. As a donor, it interconnects adjacent layers, while as an acceptor it stabilizes the packing within the layers. The `distal' carboxylic acid groups are nearly coplanar with the planes of the adjacent benzene rings, forming dihedral angles of 1.8 (1) and 7.1 (1)°. These groups also form intra- and inter-layer hydrogen bonds, but with `reversed' functionality, as compared with the central carboxylic acid groups.

Keywords: crystal structure; hydrogen bonding; meta-terphenyl.

CCDC reference: 1418223

1. Related literature

For a detailed discussion on local centers of symmetry in the space group Pca2₁, see: Marsh et al. (1998 ). For the synthesis of the starting material 3,3′′-dimethyl-[1,1′:3′,1′′-terphenyl]-2′-carboxylic acid, see: Du et al. (1986 ).

2. Experimental

2.1. Crystal data

C₂₁H₁₄O₆
M_r = 362.32
Orthorhombic, P c a 2₁
a = 23.1735 (9) Å
b = 7.2480 (2) Å
c = 20.3320 (8) Å
V = 3415.0 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 100 K
0.3 × 0.05 × 0.05 mm

2.2. Data collection

Bruker D8 VENTURE DUO diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2012 ) T_min = 0.695, T_max = 0.745
46489 measured reflections
6467 independent reflections
5899 reflections with I > 2σ(I)
R_int = 0.028

2.3. Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.091
S = 1.05
6467 reflections
511 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O3′ⁱ	0.91 (5)	1.79 (5)	2.657 (3)	159 (4)
O4—H4⋯O1ⁱⁱ	0.90 (6)	1.84 (6)	2.689 (3)	156 (5)
O2′—H2′⋯O3ⁱⁱⁱ	0.87 (6)	1.76 (6)	2.628 (3)	171 (5)
O4′—H4′⋯O1′^iv	0.84 (5)	1.90 (5)	2.717 (3)	166 (4)
O6′—H6′⋯O5	0.92 (4)	1.69 (4)	2.593 (3)	168 (4)
O6—H6⋯O5′	1.01 (3)	1.58 (3)	2.581 (3)	172 (6)
Symmetry codes: (i) $[-x+1, -y+2, z-{\script{1\over 2}}]$ ; (ii) x, y-1, z; (iii) $[-x+{\script{3\over 2}}, y+1, z+{\script{1\over 2}}]$ ; (iv) x, y+1, z.

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT; program(s) used to solve structure: SHELXT (Sheldrick, 2015a ); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b ); molecular graphics: OLEX2 (Dolomanov et al., 2009 ); software used to prepare material for publication: OLEX2.

Supporting information

CCDC reference: 1418223

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989015015029/ld2133sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015015029/ld2133Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989015015029/ld2133Isup3.cml

checkCIF report

Experimental top

Synthesis and crystallization top

3,3''-dimethyl-[1,1':3',1''-terphenyl]-2'-carboxylic acid (0.432 g, 1.4 mmol) synthesized according to Du et al. (1986). The starting material was dissolved in 15 ml pyridine and brought to reflux. KMnO₄ (0.50 g, 3.1 mmol) in 1 ml of water was added, and allowed to react for 2 hours. Subsequently, 3 more additions of KMnO₄ (0.25 g, 1.6 mmol) in 1.5 ml of water were added every 2 hours for a total of 4 additions. After six hours, 10 ml of water was added and the reaction was refluxed overnight. The reaction mixture was filtered while hot to remove solid MnO₂. The filtrate was then concentrated under reduced pressure, and treated by 12M HCl. The resulting white precipitate was then filtered and purified via silica gel column chromatograph (50/50 hexanes/ethyl acetate with 0.5% acetic acid) to give of the title compound. (0.366 g Yield 70%) ¹H NMR (DMSO, 400 MHz): δ 7.46 (d, 2H J = 8 Hz), 7.58 (t, 2H, J = 8 Hz), 7.61 (t, 1H, J = 7.2 Hz), 7.68 (d, 2H, J = 8Hz), 7.97 (d, 2H, J = 8 Hz), 8.01 (s, 2H), 13.01 (s, O-H). ¹³C NMR (DMSO, 100 MHz): δ 128.4, 128.7, 129.1, 129.2, 129.3, 130.8, 132.7, 133.9, 138.0, 140.39, 167.0, 169.7. Single crystals suitable for X-ray diffraction were obtained by vapor diffusion of hexane into an ethyl acetate solution of the title compound.

Refinement top

All H atoms were located in difference Fourier maps but finally their positions were determined geometrically, except for the carboxy H atoms that were refined with isotropic thermal parameters. The O6—H6 bond length in the carboxylic acid dimer was restrained at the distance from the corresponding residual electron density peak to the oxygen (0.996 (2)Å) . This was done due to unreasonable lengthening (> 1.4 Å) of the H—O bond during the refinement. All other H atoms were refined using a riding model with fixed isotropic displacement parameters [Uiso(H) = 1.2Ueq(C) for the C(H) groups]. Additional crystal data, data collection and structure refinement details are summarized in Table 1.

Results and discussion top

Related literature top

For a detailed discussion on local centers of symmetry in the space group Pca2₁, see: Marsh et al. (1998). For the synthesis of the starting material 3,3''-dimethyl-[1,1':3',1''-terphenyl]-2'-carboxylic acid, see: Du et al. (1986).

Structure description top

Synthesis and crystallization top

Refinement details top

Computing details top

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top

	Fig. 1. : The asymmetric unit of the title compound, with displacement elipsoids drawn at 50% probability level. Hydrogen atoms presented by spheres of an arbitrary radius. Intra-dimer hydrogen bonds are represented by dotted lines.
	Fig. 2. : Packing view along b axis. Hydrogen bonds are represented by dotted lines.

[1,1':3',1''-Terphenyl]-2',3,3''-tricarboxylic acid top

Crystal data top

C₂₁H₁₄O₆	D_x = 1.409 Mg m⁻³
M_r = 362.32	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pca2₁	Cell parameters from 9141 reflections
a = 23.1735 (9) Å	θ = 3.1–25.7°
b = 7.2480 (2) Å	µ = 0.10 mm⁻¹
c = 20.3320 (8) Å	T = 100 K
V = 3415.0 (2) Å³	Needle, clear
Z = 8	0.3 × 0.05 × 0.05 mm
F(000) = 1504

Data collection top

Bruker D8 VENTURE DUO diffractometer	6467 independent reflections
Radiation source: sealed tube, fine-focus	5899 reflections with I > 2σ(I)
TRIUMPH graphite monochromator	R_int = 0.028
Detector resolution: 10.5 pixels mm^-1	θ_max = 25.7°, θ_min = 3.0°
ω and φ scans	h = −28→28
Absorption correction: multi-scan (SADABS; Bruker, 2012)	k = −7→8
T_min = 0.695, T_max = 0.745	l = −24→24
46489 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.037	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.091	w = 1/[σ²(F_o²) + (0.0518P)² + 1.0855P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
6467 reflections	Δρ_max = 0.27 e Å⁻³
511 parameters	Δρ_min = −0.17 e Å⁻³
2 restraints

Crystal data top

C₂₁H₁₄O₆	V = 3415.0 (2) Å³
M_r = 362.32	Z = 8
Orthorhombic, Pca2₁	Mo Kα radiation
a = 23.1735 (9) Å	µ = 0.10 mm⁻¹
b = 7.2480 (2) Å	T = 100 K
c = 20.3320 (8) Å	0.3 × 0.05 × 0.05 mm

Data collection top

Bruker D8 VENTURE DUO diffractometer	6467 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2012)	5899 reflections with I > 2σ(I)
T_min = 0.695, T_max = 0.745	R_int = 0.028
46489 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	2 restraints
wR(F²) = 0.091	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.27 e Å⁻³
6467 reflections	Δρ_min = −0.17 e Å⁻³
511 parameters

Special details top

Experimental. SADABS-2012/1 (Bruker,2012) was used for absorption correction. wR2(int) was 0.0509 before and 0.0455 after correction. The Ratio of minimum to maximum transmission is 0.9326. The λ/2 correction factor is 0.0015.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.96578 (9)	0.7615 (3)	0.28358 (11)	0.0228 (5)
O2	0.89715 (9)	0.5814 (3)	0.32756 (11)	0.0244 (5)
H2	0.8852 (17)	0.572 (5)	0.285 (2)	0.042 (11)*
O3	1.10167 (9)	0.0388 (3)	0.28278 (11)	0.0303 (5)
O4	1.01069 (10)	0.0942 (3)	0.31188 (12)	0.0306 (5)
H4	1.006 (2)	−0.025 (8)	0.301 (3)	0.085 (18)*
O5	0.65152 (9)	0.9096 (3)	0.43665 (11)	0.0258 (5)
O6	0.70682 (9)	0.7133 (3)	0.49305 (12)	0.0285 (5)
C1	0.95397 (12)	0.7560 (4)	0.40061 (15)	0.0188 (6)
C2	1.00836 (13)	0.7148 (4)	0.42736 (15)	0.0200 (6)
C3	1.02024 (14)	0.7721 (4)	0.49135 (16)	0.0214 (7)
H3	1.0572	0.7495	0.5098	0.026*
C4	0.97881 (14)	0.8613 (4)	0.52817 (16)	0.0235 (7)
H4A	0.9872	0.8968	0.5721	0.028*
C5	0.92531 (13)	0.8995 (4)	0.50187 (15)	0.0228 (7)
H5	0.8969	0.9586	0.5282	0.027*
C6	0.91246 (13)	0.8522 (4)	0.43706 (15)	0.0197 (6)
C7	1.05206 (13)	0.6053 (4)	0.38977 (15)	0.0188 (6)
C8	1.03776 (13)	0.4318 (4)	0.36459 (15)	0.0201 (7)
H8	0.9999	0.3841	0.3704	0.024*
C9	1.07890 (13)	0.3293 (4)	0.33113 (14)	0.0178 (6)
C10	1.13447 (14)	0.3978 (4)	0.32208 (16)	0.0239 (7)
H10	1.1625	0.3272	0.2991	0.029*
C11	1.14841 (13)	0.5694 (4)	0.34687 (16)	0.0251 (7)
H11	1.1861	0.6178	0.3404	0.030*
C12	1.10790 (13)	0.6712 (4)	0.38102 (15)	0.0221 (6)
H12	1.1183	0.7878	0.3988	0.026*
C13	0.85570 (13)	0.9045 (4)	0.40774 (15)	0.0203 (6)
C14	0.80514 (13)	0.8518 (4)	0.43914 (15)	0.0212 (7)
H14	0.8072	0.7839	0.4790	0.025*
C15	0.75168 (13)	0.8969 (4)	0.41302 (16)	0.0205 (6)
C16	0.74787 (13)	0.9963 (4)	0.35433 (16)	0.0226 (7)
H16	0.7113	1.0245	0.3357	0.027*
C17	0.79797 (13)	1.0528 (4)	0.32379 (16)	0.0243 (7)
H17	0.7959	1.1237	0.2846	0.029*
C18	0.85140 (13)	1.0069 (4)	0.34989 (16)	0.0233 (7)
H18	0.8855	1.0459	0.3280	0.028*
C19	0.94049 (13)	0.7010 (4)	0.33133 (15)	0.0199 (6)
C20	1.06555 (13)	0.1399 (4)	0.30611 (14)	0.0209 (6)
C21	0.69880 (13)	0.8403 (4)	0.44841 (16)	0.0220 (6)
O1'	0.29732 (9)	0.7389 (3)	0.70997 (10)	0.0213 (5)
O2'	0.36530 (10)	0.9209 (3)	0.66648 (12)	0.0265 (5)
H2'	0.376 (2)	0.949 (7)	0.706 (3)	0.070 (15)*
O3'	0.16368 (9)	1.4521 (3)	0.71744 (11)	0.0247 (5)
O4'	0.25240 (10)	1.4042 (3)	0.67837 (12)	0.0282 (5)
H4'	0.2621 (18)	1.507 (7)	0.693 (2)	0.054 (13)*
O5'	0.61435 (9)	0.6032 (3)	0.55199 (11)	0.0247 (5)
O6'	0.55852 (10)	0.7980 (3)	0.49534 (11)	0.0271 (5)
C1'	0.31076 (12)	0.7424 (4)	0.59342 (15)	0.0191 (6)
C2'	0.25613 (13)	0.7813 (4)	0.56681 (15)	0.0193 (6)
C3'	0.24393 (13)	0.7237 (4)	0.50299 (16)	0.0216 (7)
H3'	0.2067	0.7449	0.4850	0.026*
C4'	0.28570 (14)	0.6353 (4)	0.46537 (16)	0.0245 (7)
H4'A	0.2771	0.5986	0.4216	0.029*
C5'	0.33996 (13)	0.6003 (4)	0.49149 (16)	0.0214 (6)
H5'	0.3685	0.5418	0.4652	0.026*
C6'	0.35278 (13)	0.6504 (4)	0.55605 (15)	0.0198 (6)
C7'	0.21240 (13)	0.8890 (4)	0.60456 (16)	0.0209 (7)
C8'	0.22618 (12)	1.0626 (4)	0.63010 (14)	0.0183 (6)
H8'	0.2640	1.1105	0.6247	0.022*
C9'	0.18463 (13)	1.1658 (4)	0.66341 (15)	0.0198 (6)
C10'	0.12932 (13)	1.0961 (4)	0.67205 (15)	0.0212 (6)
H10'	0.1011	1.1663	0.6949	0.025*
C11'	0.11546 (13)	0.9241 (4)	0.64717 (17)	0.0242 (7)
H11'	0.0777	0.8760	0.6532	0.029*
C12'	0.15643 (13)	0.8211 (4)	0.61342 (16)	0.0228 (7)
H12'	0.1464	0.7036	0.5962	0.027*
C13'	0.41042 (13)	0.6027 (4)	0.58405 (15)	0.0198 (6)
C14'	0.46007 (13)	0.6550 (4)	0.55043 (15)	0.0192 (6)
H14'	0.4569	0.7180	0.5096	0.023*
C15'	0.51443 (13)	0.6154 (4)	0.57626 (15)	0.0199 (6)
C16'	0.51981 (13)	0.5223 (4)	0.63543 (15)	0.0231 (7)
H16'	0.5569	0.4950	0.6528	0.028*
C17'	0.47048 (13)	0.4694 (4)	0.66912 (16)	0.0252 (7)
H17'	0.4738	0.4067	0.7100	0.030*
C18'	0.41620 (13)	0.5075 (4)	0.64352 (16)	0.0252 (7)
H18'	0.3827	0.4685	0.6666	0.030*
C19'	0.32344 (12)	0.7990 (4)	0.66247 (15)	0.0183 (6)
C20'	0.19858 (13)	1.3529 (4)	0.68902 (15)	0.0210 (6)
C21'	0.56704 (13)	0.6716 (4)	0.53989 (14)	0.0197 (6)
H6'	0.5939 (17)	0.824 (6)	0.477 (2)	0.045 (12)*
H6	0.6693 (16)	0.681 (8)	0.515 (3)	0.098 (19)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0208 (11)	0.0242 (11)	0.0235 (11)	0.0006 (8)	−0.0009 (9)	−0.0026 (9)
O2	0.0228 (12)	0.0250 (11)	0.0255 (13)	−0.0031 (9)	−0.0048 (10)	−0.0020 (9)
O3	0.0304 (12)	0.0302 (12)	0.0304 (13)	0.0075 (10)	0.0024 (10)	−0.0070 (10)
O4	0.0275 (13)	0.0232 (12)	0.0411 (14)	−0.0028 (10)	0.0041 (10)	−0.0084 (10)
O5	0.0209 (11)	0.0256 (11)	0.0309 (12)	0.0030 (9)	0.0016 (9)	0.0029 (10)
O6	0.0221 (12)	0.0292 (12)	0.0341 (13)	0.0023 (10)	0.0037 (11)	0.0100 (11)
C1	0.0199 (15)	0.0150 (14)	0.0215 (15)	−0.0009 (11)	−0.0003 (12)	0.0006 (11)
C2	0.0192 (15)	0.0149 (13)	0.0259 (16)	−0.0022 (11)	−0.0009 (12)	0.0019 (12)
C3	0.0224 (16)	0.0195 (15)	0.0225 (17)	−0.0004 (12)	−0.0040 (14)	0.0022 (13)
C4	0.0287 (18)	0.0191 (15)	0.0228 (16)	0.0006 (13)	−0.0033 (13)	−0.0010 (12)
C5	0.0252 (17)	0.0213 (15)	0.0218 (16)	−0.0007 (12)	0.0047 (13)	−0.0016 (13)
C6	0.0207 (15)	0.0149 (14)	0.0236 (15)	−0.0017 (12)	0.0019 (13)	0.0017 (12)
C7	0.0217 (16)	0.0163 (14)	0.0183 (15)	0.0021 (12)	−0.0029 (12)	0.0022 (12)
C8	0.0181 (15)	0.0199 (15)	0.0222 (16)	0.0020 (12)	−0.0025 (12)	0.0011 (12)
C9	0.0166 (15)	0.0189 (14)	0.0178 (14)	0.0028 (11)	−0.0020 (12)	0.0042 (11)
C10	0.0211 (17)	0.0269 (16)	0.0235 (16)	0.0045 (13)	−0.0009 (13)	0.0041 (13)
C11	0.0166 (16)	0.0287 (17)	0.0299 (18)	−0.0010 (12)	−0.0020 (13)	0.0061 (14)
C12	0.0203 (16)	0.0222 (15)	0.0237 (16)	−0.0014 (12)	−0.0056 (13)	0.0025 (12)
C13	0.0201 (15)	0.0173 (14)	0.0234 (16)	0.0029 (12)	0.0012 (13)	−0.0033 (12)
C14	0.0255 (17)	0.0171 (14)	0.0211 (16)	0.0024 (12)	−0.0009 (13)	−0.0009 (12)
C15	0.0206 (15)	0.0158 (13)	0.0250 (16)	0.0026 (12)	−0.0001 (12)	−0.0050 (12)
C16	0.0206 (15)	0.0211 (15)	0.0262 (17)	0.0044 (13)	−0.0033 (13)	−0.0026 (13)
C17	0.0252 (17)	0.0252 (15)	0.0225 (17)	0.0048 (13)	0.0026 (13)	−0.0007 (13)
C18	0.0238 (16)	0.0227 (15)	0.0234 (17)	0.0021 (14)	0.0065 (12)	0.0007 (13)
C19	0.0173 (15)	0.0159 (14)	0.0264 (16)	0.0051 (12)	−0.0016 (13)	−0.0044 (12)
C20	0.0226 (17)	0.0248 (15)	0.0153 (14)	0.0081 (13)	−0.0009 (12)	0.0002 (12)
C21	0.0227 (17)	0.0170 (14)	0.0261 (16)	0.0037 (12)	−0.0006 (13)	−0.0049 (12)
O1'	0.0212 (11)	0.0221 (11)	0.0207 (11)	−0.0001 (8)	0.0011 (9)	−0.0013 (9)
O2'	0.0268 (12)	0.0283 (11)	0.0244 (12)	−0.0108 (9)	−0.0009 (10)	−0.0065 (10)
O3'	0.0237 (11)	0.0205 (11)	0.0301 (12)	0.0016 (9)	0.0070 (10)	−0.0003 (9)
O4'	0.0217 (11)	0.0201 (11)	0.0428 (15)	−0.0052 (9)	0.0083 (10)	−0.0080 (11)
O5'	0.0205 (12)	0.0258 (11)	0.0277 (12)	0.0002 (9)	0.0022 (9)	0.0023 (10)
O6'	0.0232 (12)	0.0300 (12)	0.0280 (12)	0.0029 (9)	0.0047 (10)	0.0076 (10)
C1'	0.0191 (15)	0.0141 (13)	0.0241 (16)	−0.0039 (11)	−0.0004 (13)	0.0006 (12)
C2'	0.0209 (16)	0.0136 (13)	0.0233 (16)	−0.0028 (11)	−0.0002 (12)	0.0020 (12)
C3'	0.0221 (16)	0.0162 (14)	0.0264 (17)	−0.0011 (12)	−0.0064 (13)	0.0002 (12)
C4'	0.0330 (18)	0.0204 (16)	0.0201 (15)	−0.0046 (13)	−0.0039 (13)	−0.0020 (12)
C5'	0.0235 (17)	0.0177 (14)	0.0229 (15)	−0.0012 (12)	0.0020 (13)	−0.0020 (12)
C6'	0.0204 (16)	0.0157 (13)	0.0234 (15)	−0.0037 (11)	0.0000 (12)	−0.0017 (12)
C7'	0.0201 (16)	0.0197 (14)	0.0227 (16)	−0.0001 (12)	−0.0060 (13)	0.0049 (12)
C8'	0.0140 (15)	0.0198 (15)	0.0212 (16)	−0.0025 (11)	−0.0027 (12)	0.0031 (12)
C9'	0.0228 (15)	0.0182 (14)	0.0185 (14)	−0.0001 (12)	−0.0024 (13)	0.0029 (12)
C10'	0.0171 (15)	0.0237 (15)	0.0227 (15)	0.0025 (12)	0.0018 (13)	0.0025 (12)
C11'	0.0151 (16)	0.0265 (16)	0.0309 (18)	−0.0040 (12)	−0.0045 (13)	0.0029 (14)
C12'	0.0203 (16)	0.0181 (14)	0.0301 (17)	−0.0029 (12)	−0.0057 (13)	−0.0005 (12)
C13'	0.0217 (15)	0.0152 (13)	0.0226 (16)	−0.0012 (12)	0.0011 (12)	−0.0024 (12)
C14'	0.0240 (16)	0.0155 (13)	0.0180 (14)	0.0003 (11)	0.0029 (12)	−0.0023 (12)
C15'	0.0245 (16)	0.0146 (14)	0.0205 (15)	0.0011 (12)	0.0003 (12)	−0.0041 (12)
C16'	0.0241 (16)	0.0230 (15)	0.0221 (16)	0.0028 (13)	−0.0014 (12)	−0.0017 (12)
C17'	0.0275 (17)	0.0275 (16)	0.0207 (16)	0.0011 (13)	−0.0002 (13)	0.0040 (14)
C18'	0.0226 (16)	0.0256 (16)	0.0272 (18)	0.0000 (14)	0.0057 (13)	0.0026 (14)
C19'	0.0151 (14)	0.0174 (13)	0.0223 (15)	0.0017 (11)	−0.0002 (13)	−0.0004 (12)
C20'	0.0211 (16)	0.0202 (14)	0.0217 (15)	−0.0021 (13)	0.0026 (13)	0.0052 (12)
C21'	0.0224 (16)	0.0167 (13)	0.0198 (15)	−0.0017 (12)	−0.0019 (12)	−0.0023 (12)

Geometric parameters (Å, º) top

O1—C19	1.216 (4)	O1'—C19'	1.220 (4)
O2—H2	0.91 (5)	O2'—H2'	0.87 (6)
O2—C19	1.329 (4)	O2'—C19'	1.314 (4)
O3—C20	1.209 (4)	O3'—C20'	1.227 (4)
O4—H4	0.90 (6)	O4'—H4'	0.84 (5)
O4—C20	1.319 (4)	O4'—C20'	1.319 (4)
O5—C21	1.229 (4)	O5'—C21'	1.228 (4)
O6—C21	1.306 (4)	O6'—C21'	1.303 (4)
O6—H6	1.01 (3)	O6'—H6'	0.92 (4)
C1—C2	1.405 (4)	C1'—C2'	1.405 (4)
C1—C6	1.400 (4)	C1'—C6'	1.404 (4)
C1—C19	1.497 (4)	C1'—C19'	1.492 (4)
C2—C3	1.393 (5)	C2'—C3'	1.392 (4)
C2—C7	1.496 (4)	C2'—C7'	1.491 (4)
C3—H3	0.9500	C3'—H3'	0.9500
C3—C4	1.378 (4)	C3'—C4'	1.390 (4)
C4—H4A	0.9500	C4'—H4'A	0.9500
C4—C5	1.378 (4)	C4'—C5'	1.388 (4)
C5—H5	0.9500	C5'—H5'	0.9500
C5—C6	1.394 (5)	C5'—C6'	1.394 (4)
C6—C13	1.493 (4)	C6'—C13'	1.493 (4)
C7—C8	1.398 (4)	C7'—C8'	1.398 (4)
C7—C12	1.391 (4)	C7'—C12'	1.399 (4)
C8—H8	0.9500	C8'—H8'	0.9500
C8—C9	1.387 (4)	C8'—C9'	1.395 (4)
C9—C10	1.393 (4)	C9'—C10'	1.389 (4)
C9—C20	1.496 (4)	C9'—C20'	1.488 (4)
C10—H10	0.9500	C10'—H10'	0.9500
C10—C11	1.380 (5)	C10'—C11'	1.384 (4)
C11—H11	0.9500	C11'—H11'	0.9500
C11—C12	1.381 (5)	C11'—C12'	1.389 (5)
C12—H12	0.9500	C12'—H12'	0.9500
C13—C14	1.388 (4)	C13'—C14'	1.391 (4)
C13—C18	1.394 (5)	C13'—C18'	1.399 (4)
C14—H14	0.9500	C14'—H14'	0.9500
C14—C15	1.387 (4)	C14'—C15'	1.394 (4)
C15—C16	1.397 (5)	C15'—C16'	1.385 (4)
C15—C21	1.479 (5)	C15'—C21'	1.483 (4)
C16—H16	0.9500	C16'—H16'	0.9500
C16—C17	1.379 (5)	C16'—C17'	1.387 (4)
C17—H17	0.9500	C17'—H17'	0.9500
C17—C18	1.387 (4)	C17'—C18'	1.389 (4)
C18—H18	0.9500	C18'—H18'	0.9500

C19—O2—H2	110 (3)	C19'—O2'—H2'	115 (3)
C20—O4—H4	109 (3)	C20'—O4'—H4'	117 (3)
C21—O6—H6	111 (3)	C21'—O6'—H6'	107 (3)
C2—C1—C19	119.7 (3)	C2'—C1'—C19'	119.0 (3)
C6—C1—C2	121.1 (3)	C6'—C1'—C2'	120.8 (3)
C6—C1—C19	119.2 (3)	C6'—C1'—C19'	120.2 (3)
C1—C2—C7	121.5 (3)	C1'—C2'—C7'	121.3 (3)
C3—C2—C1	118.4 (3)	C3'—C2'—C1'	118.8 (3)
C3—C2—C7	120.1 (3)	C3'—C2'—C7'	119.9 (3)
C2—C3—H3	119.7	C2'—C3'—H3'	119.7
C4—C3—C2	120.6 (3)	C4'—C3'—C2'	120.7 (3)
C4—C3—H3	119.7	C4'—C3'—H3'	119.7
C3—C4—H4A	119.7	C3'—C4'—H4'A	119.9
C5—C4—C3	120.7 (3)	C5'—C4'—C3'	120.3 (3)
C5—C4—H4A	119.7	C5'—C4'—H4'A	119.9
C4—C5—H5	119.7	C4'—C5'—H5'	119.8
C4—C5—C6	120.6 (3)	C4'—C5'—C6'	120.4 (3)
C6—C5—H5	119.7	C6'—C5'—H5'	119.8
C1—C6—C13	121.3 (3)	C1'—C6'—C13'	121.6 (3)
C5—C6—C1	118.4 (3)	C5'—C6'—C1'	119.1 (3)
C5—C6—C13	120.2 (3)	C5'—C6'—C13'	119.3 (3)
C8—C7—C2	120.2 (3)	C8'—C7'—C2'	120.5 (3)
C12—C7—C2	120.9 (3)	C8'—C7'—C12'	118.7 (3)
C12—C7—C8	118.9 (3)	C12'—C7'—C2'	120.8 (3)
C7—C8—H8	120.0	C7'—C8'—H8'	119.8
C9—C8—C7	119.9 (3)	C9'—C8'—C7'	120.4 (3)
C9—C8—H8	120.0	C9'—C8'—H8'	119.8
C8—C9—C10	120.6 (3)	C8'—C9'—C20'	120.6 (3)
C8—C9—C20	121.1 (3)	C10'—C9'—C8'	120.2 (3)
C10—C9—C20	118.3 (3)	C10'—C9'—C20'	119.2 (3)
C9—C10—H10	120.3	C9'—C10'—H10'	120.1
C11—C10—C9	119.3 (3)	C11'—C10'—C9'	119.7 (3)
C11—C10—H10	120.3	C11'—C10'—H10'	120.1
C10—C11—H11	119.8	C10'—C11'—H11'	119.8
C10—C11—C12	120.4 (3)	C10'—C11'—C12'	120.4 (3)
C12—C11—H11	119.8	C12'—C11'—H11'	119.8
C7—C12—H12	119.5	C7'—C12'—H12'	119.7
C11—C12—C7	120.9 (3)	C11'—C12'—C7'	120.6 (3)
C11—C12—H12	119.5	C11'—C12'—H12'	119.7
C14—C13—C6	119.3 (3)	C14'—C13'—C6'	119.3 (3)
C14—C13—C18	118.3 (3)	C14'—C13'—C18'	118.7 (3)
C18—C13—C6	122.3 (3)	C18'—C13'—C6'	122.0 (3)
C13—C14—H14	119.6	C13'—C14'—H14'	119.8
C15—C14—C13	120.9 (3)	C13'—C14'—C15'	120.4 (3)
C15—C14—H14	119.6	C15'—C14'—H14'	119.8
C14—C15—C16	120.3 (3)	C14'—C15'—C21'	119.9 (3)
C14—C15—C21	119.2 (3)	C16'—C15'—C14'	120.6 (3)
C16—C15—C21	120.4 (3)	C16'—C15'—C21'	119.5 (3)
C15—C16—H16	120.5	C15'—C16'—H16'	120.3
C17—C16—C15	119.0 (3)	C15'—C16'—C17'	119.3 (3)
C17—C16—H16	120.5	C17'—C16'—H16'	120.3
C16—C17—H17	119.7	C16'—C17'—H17'	119.8
C16—C17—C18	120.5 (3)	C16'—C17'—C18'	120.4 (3)
C18—C17—H17	119.7	C18'—C17'—H17'	119.8
C13—C18—H18	119.5	C13'—C18'—H18'	119.7
C17—C18—C13	120.9 (3)	C17'—C18'—C13'	120.6 (3)
C17—C18—H18	119.5	C17'—C18'—H18'	119.7
O1—C19—O2	123.6 (3)	O1'—C19'—O2'	123.8 (3)
O1—C19—C1	123.7 (3)	O1'—C19'—C1'	123.3 (3)
O2—C19—C1	112.7 (3)	O2'—C19'—C1'	112.9 (3)
O3—C20—O4	123.3 (3)	O3'—C20'—O4'	122.4 (3)
O3—C20—C9	123.1 (3)	O3'—C20'—C9'	123.8 (3)
O4—C20—C9	113.6 (2)	O4'—C20'—C9'	113.9 (3)
O5—C21—O6	123.4 (3)	O5'—C21'—O6'	123.9 (3)
O5—C21—C15	122.1 (3)	O5'—C21'—C15'	121.5 (3)
O6—C21—C15	114.6 (3)	O6'—C21'—C15'	114.5 (3)

C1—C2—C3—C4	2.2 (4)	C1'—C2'—C3'—C4'	−2.3 (4)
C1—C2—C7—C8	−54.7 (4)	C1'—C2'—C7'—C8'	54.2 (4)
C1—C2—C7—C12	127.4 (3)	C1'—C2'—C7'—C12'	−127.7 (3)
C1—C6—C13—C14	125.4 (3)	C1'—C6'—C13'—C14'	−127.7 (3)
C1—C6—C13—C18	−55.3 (4)	C1'—C6'—C13'—C18'	52.0 (4)
C2—C1—C6—C5	−2.8 (4)	C2'—C1'—C6'—C5'	1.0 (4)
C2—C1—C6—C13	176.9 (3)	C2'—C1'—C6'—C13'	−178.1 (3)
C2—C1—C19—O1	−63.6 (4)	C2'—C1'—C19'—O1'	62.6 (4)
C2—C1—C19—O2	117.5 (3)	C2'—C1'—C19'—O2'	−117.0 (3)
C2—C3—C4—C5	−1.6 (5)	C2'—C3'—C4'—C5'	1.2 (4)
C2—C7—C8—C9	−178.5 (3)	C2'—C7'—C8'—C9'	177.8 (3)
C2—C7—C12—C11	179.4 (3)	C2'—C7'—C12'—C11'	−178.3 (3)
C3—C2—C7—C8	122.8 (3)	C3'—C2'—C7'—C8'	−123.3 (3)
C3—C2—C7—C12	−55.2 (4)	C3'—C2'—C7'—C12'	54.8 (4)
C3—C4—C5—C6	−1.4 (5)	C3'—C4'—C5'—C6'	1.1 (4)
C4—C5—C6—C1	3.5 (4)	C4'—C5'—C6'—C1'	−2.2 (4)
C4—C5—C6—C13	−176.2 (3)	C4'—C5'—C6'—C13'	176.9 (3)
C5—C6—C13—C14	−54.9 (4)	C5'—C6'—C13'—C14'	53.2 (4)
C5—C6—C13—C18	124.4 (3)	C5'—C6'—C13'—C18'	−127.1 (3)
C6—C1—C2—C3	0.0 (4)	C6'—C1'—C2'—C3'	1.2 (4)
C6—C1—C2—C7	177.4 (3)	C6'—C1'—C2'—C7'	−176.3 (3)
C6—C1—C19—O1	114.7 (3)	C6'—C1'—C19'—O1'	−116.9 (3)
C6—C1—C19—O2	−64.1 (3)	C6'—C1'—C19'—O2'	63.6 (4)
C6—C13—C14—C15	−179.5 (3)	C6'—C13'—C14'—C15'	178.7 (3)
C6—C13—C18—C17	179.8 (3)	C6'—C13'—C18'—C17'	−178.3 (3)
C7—C2—C3—C4	−175.3 (3)	C7'—C2'—C3'—C4'	175.2 (3)
C7—C8—C9—C10	−0.2 (4)	C7'—C8'—C9'—C10'	0.6 (4)
C7—C8—C9—C20	177.4 (3)	C7'—C8'—C9'—C20'	−178.2 (3)
C8—C7—C12—C11	1.4 (4)	C8'—C7'—C12'—C11'	−0.2 (5)
C8—C9—C10—C11	0.1 (4)	C8'—C9'—C10'—C11'	−0.3 (4)
C8—C9—C20—O3	−172.2 (3)	C8'—C9'—C20'—O3'	178.4 (3)
C8—C9—C20—O4	7.9 (4)	C8'—C9'—C20'—O4'	−1.5 (4)
C9—C10—C11—C12	0.8 (5)	C9'—C10'—C11'—C12'	−0.3 (5)
C10—C9—C20—O3	5.5 (4)	C10'—C9'—C20'—O3'	−0.5 (5)
C10—C9—C20—O4	−174.4 (3)	C10'—C9'—C20'—O4'	179.6 (3)
C10—C11—C12—C7	−1.5 (5)	C10'—C11'—C12'—C7'	0.5 (5)
C12—C7—C8—C9	−0.5 (4)	C12'—C7'—C8'—C9'	−0.3 (4)
C13—C14—C15—C16	0.1 (4)	C13'—C14'—C15'—C16'	0.5 (4)
C13—C14—C15—C21	−179.2 (3)	C13'—C14'—C15'—C21'	179.9 (3)
C14—C13—C18—C17	−0.9 (4)	C14'—C13'—C18'—C17'	1.4 (4)
C14—C15—C16—C17	−1.7 (4)	C14'—C15'—C16'—C17'	−0.4 (4)
C14—C15—C21—O5	163.2 (3)	C14'—C15'—C21'—O5'	−162.4 (3)
C14—C15—C21—O6	−16.1 (4)	C14'—C15'—C21'—O6'	18.1 (4)
C15—C16—C17—C18	1.9 (5)	C15'—C16'—C17'—C18'	0.7 (5)
C16—C15—C21—O5	−16.1 (4)	C16'—C15'—C21'—O5'	17.0 (4)
C16—C15—C21—O6	164.5 (3)	C16'—C15'—C21'—O6'	−162.6 (3)
C16—C17—C18—C13	−0.6 (5)	C16'—C17'—C18'—C13'	−1.2 (5)
C18—C13—C14—C15	1.1 (4)	C18'—C13'—C14'—C15'	−1.0 (4)
C19—C1—C2—C3	178.3 (3)	C19'—C1'—C2'—C3'	−178.2 (3)
C19—C1—C2—C7	−4.2 (4)	C19'—C1'—C2'—C7'	4.3 (4)
C19—C1—C6—C5	178.9 (3)	C19'—C1'—C6'—C5'	−179.5 (3)
C19—C1—C6—C13	−1.4 (4)	C19'—C1'—C6'—C13'	1.3 (4)
C20—C9—C10—C11	−177.6 (3)	C20'—C9'—C10'—C11'	178.6 (3)
C21—C15—C16—C17	177.7 (3)	C21'—C15'—C16'—C17'	−179.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3′ⁱ	0.91 (5)	1.79 (5)	2.657 (3)	159 (4)
O4—H4···O1ⁱⁱ	0.90 (6)	1.84 (6)	2.689 (3)	156 (5)
O2′—H2′···O3ⁱⁱⁱ	0.87 (6)	1.76 (6)	2.628 (3)	171 (5)
O4′—H4′···O1′^iv	0.84 (5)	1.90 (5)	2.717 (3)	166 (4)
O6′—H6′···O5	0.92 (4)	1.69 (4)	2.593 (3)	168 (4)
O6—H6···O5′	1.01 (3)	1.58 (3)	2.581 (3)	172 (6)

Symmetry codes: (i) −x+1, −y+2, z−1/2; (ii) x, y−1, z; (iii) −x+3/2, y+1, z+1/2; (iv) x, y+1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3'ⁱ	0.91 (5)	1.79 (5)	2.657 (3)	159 (4)
O4—H4···O1ⁱⁱ	0.90 (6)	1.84 (6)	2.689 (3)	156 (5)
O2'—H2'···O3ⁱⁱⁱ	0.87 (6)	1.76 (6)	2.628 (3)	171 (5)
O4'—H4'···O1'^iv	0.84 (5)	1.90 (5)	2.717 (3)	166 (4)
O6'—H6'···O5	0.92 (4)	1.69 (4)	2.593 (3)	168 (4)
O6—H6···O5'	1.01 (3)	1.58 (3)	2.581 (3)	172 (6)

Symmetry codes: (i) −x+1, −y+2, z−1/2; (ii) x, y−1, z; (iii) −x+3/2, y+1, z+1/2; (iv) x, y+1, z.

Acknowledgements

This work was supported by grants from the National Science Foundation (NSF)–MRI (CHE-1337908) and the National Institutes of Health (CoBRE NIGMS P20GM103546). The University of Montana and the Center for Biomolecular Structure and Dynamics are aknowledged for their support of the University of Montana X-ray diffraction core facility.

References

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