Packing polymorphism in the crystal structure of 4,5-dimeth-oxy-2-nitro-benzyl acetate.

The title compound, C11H13NO6, shows two polymorphs, orange and yellow forms, both of which crystallize in the space group P21/c. The mol-ecular structures in the two polymorphs are essentially similar and adopt a planar structure, the maximum deviations for the non-H atoms being 0.1836 (13) and 0.1276 (13) Å, respectively, for the orange and yellow forms. In the orange crystal, mol-ecules are linked by an inter-molecular C-H⋯O inter-action into a helical chain along the b-axis direction. The chains are stacked along the c axis through a π-π inter-action [centroid-centroid distance = 3.6087 (11) Å], forming a layer parallel to the bc plane. In the yellow crystal, mol-ecules are connected through C-H⋯O inter-actions into a sheet structure parallel to (-302). No significant π-π inter-action is observed. The unit-cell volume of the orange crystal is larger than that of the yellow one, and this accounts for the predominant growth of the yellow crystal.

Chemical context

Polymorphism is of inter­est in crystallization, phase transition, material synthesis and the pharmaceutical industry because differences in the crystal packing and/or conformation of compounds with the same formula can change the chemical and physical properties, including solubility, bioavailability and so forth (Moulton & Zaworotko, 2001 ▸; Matsuo & Matsuoka, 2007 ▸; Yu, 2010 ▸). We have been investigating silane coupling agents and thiols with distal functional groups protected by photolabile 2-nitro­benzyl groups (Edagawa et al., 2012 ▸). During the course of photoremoval studies of these materials, we found that the simple ester, 4,5-dimeth­oxy-2-nitro­benzyl acetate, which releases acetic acid on photo-irradiation, forms two different types of crystals, orange rods and yellow needles. Here, we report the crystal structures of these two polymorphs of the title compound.

Structural commentary

The mol­ecular structures of the two crystals are approximately planar and almost identical, as shown in Fig. 1 ▸. The C2—C1—C7—O3, C9—C8—O3—C7, C5—C4—O5—C10 and C4—C5—O6—C11 torsion angles in the two crystals are approximately 180°. The dihedral angles between the benzene ring (C1–C6) and the nitro group (O1/N1/O2) are 9.54 (11) and 4.15 (7)° for the orange and yellow polymorphs, respectively.

Figure 1

The mol­ecular structures of the title compound polymorphs, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

Supra­molecular features

Although the two crystals crystallize in the same space group (P21/c) with Z′ = 1, their packing modes are different. In the orange crystal, the mol­ecules are connected by an inter­molecular C—H⋯O inter­action [C11—H11B⋯O4i; symmetry code: (i) 1 − x, − + y,  − z; Table 1 ▸] between the meth­oxy group and the carbonyl group, forming a helical chain along the b axis as shown in Fig. 2 ▸, left. In addition, a π–π inter­action between the benzene rings with a centroid–centroid distance of 3.6087 (11) Å links the chains to be stacked along the c axis. In the yellow crystal, the mol­ecules located in the plane perpendicular to the ac plane are connected by C—H⋯O inter­actions (Table 2 ▸) between meth­oxy groups [C10—H10B⋯O6ii; symmetry code: (ii) 1 − x, 1 − y, 2 − z] and between acetyl groups [C9—H9B⋯O4iii; symmetry code: (iii) −x, − + y,  − z], forming a sheet structure parallel to (02) (Fig. 2 ▸, right).

Table 1

Hydrogen-bond geometry (Å, °) for orange

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11B⋯O4i	0.98	2.50	3.369 (2)	147

Symmetry code: (i) .

Figure 2

Inter­molecular C—H⋯O (black dashed lines) and π–π (red dashed lines) inter­actions in the orange crystal (left), and inter­molecular C—H⋯O inter­actions (black dashed lines) between meth­oxy groups and between acetyl groups in the yellow crystal (right). [Symmetry codes: (i) 1 − x, − + y,  − z; (ii) 1 − x, 1 − y, 2 − z; (iii) −x, − + y,  − z.]

Table 2

Hydrogen-bond geometry (Å, °) for yellow

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9B⋯O4iii	0.98	2.40	3.375 (2)	174
C10—H10B⋯O6ii	0.98	2.51	3.472 (2)	169

Symmetry codes: (ii) ; (iii) .

In the orange crystal, the mol­ecules are stacked in columnar structures via π–π inter­actions along the c axis (Fig. 3 ▸, left). In contrast, no π–π inter­actions are observed in the yellow crystal. The mol­ecules are therefore terraced along the diagonal line of the a and c axes as shown in Fig. 3 ▸, right. As a result of these packing differences, the volume of the unit cell of the orange crystal is larger than that of the yellow one, i.e., the orange crystal contains slightly more void space than the yellow one. This would account for the predominant growth of the yellow crystals.

Figure 3

Side views of space-filling models of mol­ecular packing of the orange (left) and yellow (right) crystals.

Synthesis and crystallization

4,5-Dimeth­oxy-2-nitro­benzyl alcohol (0.714 g, 3.35 mmol), acetic anhydride (0.63 ml, 6.66 mmol), Et3N (1 ml) and CH2Cl2 (20 ml) were placed in a 100 mL flask, and the mixture was stirred at ambient temperature overnight. The mixture was extracted with CH2Cl2 (20 ml × 3), washed with brine, dried over MgSO4, and evaporated to give a yellow solid (0.773 g, 90% yield). The solid was crystallized by slow evaporation from a mixed solution of ethyl acetate and hexane (1:1). Orange crystals were occasionally obtained in small amounts, but the yellow crystals grew predominantly.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. All H atoms were located geometrically and refined using a riding model, with C—H = 0.99 Å and U iso(H) = 1.2U eq(C) for methyl­ene H atoms, C—H = 0.95 Å and U iso(H) = 1.2U eq(C) for aromatic H atoms, and C—H = 0.98 Å and U iso(H) = 1.5U eq(C) for methyl H atoms.

Table 3

Experimental details

	orange	yellow
Crystal data
Chemical formula	C11H13NO6	C11H13NO6
M r	255.22	255.22
Crystal system, space group	Monoclinic, P21/c	Monoclinic, P21/c
Temperature (K)	93	93
a, b, c (Å)	8.8751 (13), 19.555 (2), 6.8688 (9)	10.476 (3), 10.714 (3), 10.266 (3)
β (°)	106.298 (6)	105.077 (10)
V (Å3)	1144.2 (3)	1112.6 (6)
Z	4	4
Radiation type	Mo Kα	Mo Kα
μ (mm−1)	0.12	0.13
Crystal size (mm)	0.45 × 0.42 × 0.39	0.56 × 0.54 × 0.25
Data collection
Diffractometer	Rigaku Mercury375R	Rigaku Mercury375R
Absorption correction	Multi-scan (REQAB; Rigaku, 1998 ▸)	Multi-scan (REQAB; Rigaku, 1998 ▸)
T min, T max	0.960, 0.970	0.797, 0.970
No. of measured, independent and observed [I > 2σ(I)] reflections	11495, 2612, 2098	9498, 2058, 1769
R int	0.047	0.033
(sin θ/λ)max (Å−1)	0.649	0.606
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.051, 0.132, 1.11	0.049, 0.130, 1.13
No. of reflections	2612	2058
No. of parameters	166	166
H-atom treatment	H-atom parameters not refined	H-atom parameters not refined
Δρmax, Δρmin (e Å−3)	0.39, −0.30	0.38, −0.35

Computer programs: CrystalClear-SM Expert (Rigaku, 2011 ▸), SIR2004 (Burla et al., 2005 ▸), SHELXL97 (Sheldrick, 2008 ▸), Mercury (Macrae et al., 2008 ▸), Yadokari-XG (Wakita, 2001 ▸).

Crystal structure: contains datablock(s) orange, yellow, global. DOI: 10.1107/S2056989015006714/is5391sup1.cif

Structure factors: contains datablock(s) orange. DOI: 10.1107/S2056989015006714/is5391orangesup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015006714/is5391orangesup4.cdx

Structure factors: contains datablock(s) yellow. DOI: 10.1107/S2056989015006714/is5391yellowsup3.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015006714/is5391yellowsup5.cdx

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015006714/is5391orangesup6.cml

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015006714/is5391yellowsup7.cml

CCDC references: 967703, 967704

Additional supporting information: crystallographic information; 3D view; checkCIF report

C11H13NO6	F(000) = 536
Mr = 255.22	Dx = 1.48 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybc	Cell parameters from 2655 reflections
a = 8.8751 (13) Å	θ = 3.1–27.5°
b = 19.555 (2) Å	µ = 0.12 mm−1
c = 6.8688 (9) Å	T = 93 K
β = 106.298 (6)°	Platelet, orange
V = 1144.2 (3) Å3	0.45 × 0.42 × 0.39 mm
Z = 4

Rigaku Mercury375R (2x2 bin mode) diffractometer	2612 independent reflections
Radiation source: fine-focus sealed tube	2098 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.047
Detector resolution: 13.6612 pixels mm-1	θmax = 27.5°, θmin = 3.2°
profile data from ω–scans	h = −11→11
Absorption correction: multi-scan (REQAB; Rigaku, 1998)	k = −25→25
Tmin = 0.960, Tmax = 0.970	l = −8→8
11495 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.132	H-atom parameters not refined
S = 1.11	w = 1/[σ2(Fo2) + (0.0597P)2 + 0.5862P] where P = (Fo2 + 2Fc2)/3
2612 reflections	(Δ/σ)max < 0.001
166 parameters	Δρmax = 0.39 e Å−3
0 restraints	Δρmin = −0.30 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.19328 (19)	0.29434 (8)	0.7664 (2)	0.0124 (3)
C2	0.04911 (19)	0.26435 (9)	0.7614 (3)	0.0139 (3)
C3	0.02606 (19)	0.19342 (8)	0.7577 (3)	0.0140 (3)
H3	−0.0739	0.1752	0.7541	0.017*
C4	0.1487 (2)	0.15013 (8)	0.7593 (3)	0.0139 (3)
C5	0.29755 (19)	0.17865 (8)	0.7678 (2)	0.0125 (3)
C6	0.31701 (19)	0.24911 (8)	0.7700 (2)	0.0128 (3)
H6	0.4171	0.2673	0.7740	0.015*
C7	0.22141 (19)	0.37064 (8)	0.7674 (3)	0.0138 (3)
H7A	0.1502	0.3919	0.6450	0.017*
H7B	0.2010	0.3916	0.8887	0.017*
C8	0.4225 (2)	0.44786 (9)	0.7575 (3)	0.0155 (4)
C9	0.5882 (2)	0.45412 (9)	0.7490 (3)	0.0218 (4)
H9A	0.5938	0.4425	0.6124	0.033*
H9B	0.6550	0.4227	0.8475	0.033*
H9C	0.6247	0.5012	0.7816	0.033*
C10	−0.0084 (2)	0.05009 (9)	0.7387 (3)	0.0200 (4)
H10A	−0.0436	0.0632	0.8565	0.030*
H10B	0.0007	0.0002	0.7344	0.030*
H10C	−0.0848	0.0660	0.6144	0.030*
C11	0.5657 (2)	0.15867 (9)	0.7809 (3)	0.0187 (4)
H11A	0.5598	0.1883	0.6639	0.028*
H11B	0.6370	0.1205	0.7803	0.028*
H11C	0.6051	0.1850	0.9063	0.028*
N1	−0.08677 (17)	0.30611 (7)	0.7608 (2)	0.0154 (3)
O1	−0.08009 (15)	0.36827 (7)	0.7379 (2)	0.0252 (3)
O2	−0.20491 (15)	0.27751 (7)	0.7846 (2)	0.0236 (3)
O3	0.38271 (14)	0.38139 (6)	0.7701 (2)	0.0154 (3)
O4	0.33181 (16)	0.49408 (7)	0.7520 (2)	0.0257 (3)
O5	0.14161 (14)	0.08062 (6)	0.7543 (2)	0.0176 (3)
O6	0.41110 (14)	0.13243 (6)	0.7695 (2)	0.0164 (3)

	U11	U22	U33	U12	U13	U23
C1	0.0128 (8)	0.0155 (8)	0.0088 (8)	0.0001 (6)	0.0027 (6)	0.0011 (6)
C2	0.0112 (8)	0.0174 (8)	0.0137 (8)	0.0022 (6)	0.0046 (6)	0.0009 (6)
C3	0.0121 (8)	0.0174 (8)	0.0127 (8)	−0.0021 (6)	0.0037 (6)	0.0004 (6)
C4	0.0147 (8)	0.0137 (8)	0.0133 (8)	−0.0031 (6)	0.0040 (6)	0.0003 (6)
C5	0.0134 (8)	0.0152 (8)	0.0095 (8)	0.0014 (6)	0.0041 (6)	−0.0001 (6)
C6	0.0113 (8)	0.0160 (8)	0.0117 (8)	−0.0008 (6)	0.0043 (6)	−0.0002 (6)
C7	0.0105 (8)	0.0147 (8)	0.0177 (9)	−0.0003 (6)	0.0065 (6)	0.0002 (6)
C8	0.0161 (8)	0.0149 (8)	0.0164 (9)	−0.0025 (6)	0.0063 (7)	−0.0006 (6)
C9	0.0140 (8)	0.0182 (9)	0.0347 (11)	−0.0021 (7)	0.0094 (8)	−0.0009 (8)
C10	0.0173 (9)	0.0163 (8)	0.0271 (10)	−0.0074 (7)	0.0075 (7)	−0.0016 (7)
C11	0.0120 (8)	0.0170 (8)	0.0277 (10)	−0.0006 (6)	0.0065 (7)	−0.0011 (7)
N1	0.0113 (7)	0.0171 (7)	0.0177 (8)	−0.0005 (5)	0.0041 (6)	−0.0007 (5)
O1	0.0179 (7)	0.0159 (6)	0.0437 (9)	0.0031 (5)	0.0119 (6)	0.0037 (6)
O2	0.0133 (6)	0.0236 (7)	0.0364 (8)	−0.0016 (5)	0.0111 (6)	0.0010 (6)
O3	0.0114 (6)	0.0131 (6)	0.0227 (7)	−0.0011 (4)	0.0063 (5)	0.0000 (5)
O4	0.0203 (7)	0.0141 (6)	0.0461 (9)	0.0008 (5)	0.0147 (6)	0.0018 (6)
O5	0.0160 (6)	0.0120 (6)	0.0264 (7)	−0.0022 (5)	0.0085 (5)	−0.0001 (5)
O6	0.0124 (6)	0.0137 (6)	0.0244 (7)	0.0013 (5)	0.0071 (5)	0.0005 (5)

C1—C2	1.399 (2)	C8—O3	1.356 (2)
C1—C6	1.405 (2)	C8—C9	1.494 (2)
C1—C7	1.512 (2)	C9—H9A	0.9800
C2—C3	1.401 (2)	C9—H9B	0.9800
C2—N1	1.456 (2)	C9—H9C	0.9800
C3—C4	1.377 (2)	C10—O5	1.436 (2)
C3—H3	0.9500	C10—H10A	0.9800
C4—O5	1.361 (2)	C10—H10B	0.9800
C4—C5	1.420 (2)	C10—H10C	0.9800
C5—O6	1.351 (2)	C11—O6	1.446 (2)
C5—C6	1.388 (2)	C11—H11A	0.9800
C6—H6	0.9500	C11—H11B	0.9800
C7—O3	1.4419 (19)	C11—H11C	0.9800
C7—H7A	0.9900	N1—O1	1.229 (2)
C7—H7B	0.9900	N1—O2	1.2390 (19)
C8—O4	1.204 (2)
C2—C1—C6	116.20 (15)	O3—C8—C9	110.96 (15)
C2—C1—C7	124.21 (15)	C8—C9—H9A	109.5
C6—C1—C7	119.59 (15)	C8—C9—H9B	109.5
C1—C2—C3	122.90 (15)	H9A—C9—H9B	109.5
C1—C2—N1	121.08 (15)	C8—C9—H9C	109.5
C3—C2—N1	116.02 (15)	H9A—C9—H9C	109.5
C4—C3—C2	119.83 (15)	H9B—C9—H9C	109.5
C4—C3—H3	120.1	O5—C10—H10A	109.5
C2—C3—H3	120.1	O5—C10—H10B	109.5
O5—C4—C3	125.67 (15)	H10A—C10—H10B	109.5
O5—C4—C5	115.43 (15)	O5—C10—H10C	109.5
C3—C4—C5	118.90 (15)	H10A—C10—H10C	109.5
O6—C5—C6	125.00 (15)	H10B—C10—H10C	109.5
O6—C5—C4	114.87 (15)	O6—C11—H11A	109.5
C6—C5—C4	120.12 (15)	O6—C11—H11B	109.5
C5—C6—C1	122.03 (15)	H11A—C11—H11B	109.5
C5—C6—H6	119.0	O6—C11—H11C	109.5
C1—C6—H6	119.0	H11A—C11—H11C	109.5
O3—C7—C1	107.82 (13)	H11B—C11—H11C	109.5
O3—C7—H7A	110.1	O1—N1—O2	122.43 (15)
C1—C7—H7A	110.1	O1—N1—C2	119.04 (14)
O3—C7—H7B	110.1	O2—N1—C2	118.53 (14)
C1—C7—H7B	110.1	C8—O3—C7	114.47 (13)
H7A—C7—H7B	108.5	C4—O5—C10	116.93 (13)
O4—C8—O3	122.58 (16)	C5—O6—C11	117.20 (13)
O4—C8—C9	126.45 (16)
C6—C1—C2—C3	−0.7 (2)	C7—C1—C6—C5	−179.55 (15)
C7—C1—C2—C3	179.08 (16)	C2—C1—C7—O3	−179.18 (15)
C6—C1—C2—N1	178.95 (15)	C6—C1—C7—O3	0.6 (2)
C7—C1—C2—N1	−1.2 (3)	C1—C2—N1—O1	9.5 (2)
C1—C2—C3—C4	0.1 (3)	C3—C2—N1—O1	−170.83 (16)
N1—C2—C3—C4	−179.59 (15)	C1—C2—N1—O2	−170.13 (16)
C2—C3—C4—O5	−179.39 (16)	C3—C2—N1—O2	9.6 (2)
C2—C3—C4—C5	1.0 (2)	O4—C8—O3—C7	2.5 (2)
O5—C4—C5—O6	0.1 (2)	C9—C8—O3—C7	−176.69 (15)
C3—C4—C5—O6	179.78 (15)	C1—C7—O3—C8	175.79 (14)
O5—C4—C5—C6	178.91 (14)	C3—C4—O5—C10	2.4 (3)
C3—C4—C5—C6	−1.4 (2)	C5—C4—O5—C10	−177.96 (15)
O6—C5—C6—C1	179.47 (15)	C6—C5—O6—C11	2.1 (2)
C4—C5—C6—C1	0.8 (2)	C4—C5—O6—C11	−179.17 (15)
C2—C1—C6—C5	0.3 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11B···O4i	0.98	2.50	3.369 (2)	147

C11H13NO6	F(000) = 536
Mr = 255.22	Dx = 1.52 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybc	Cell parameters from 2424 reflections
a = 10.476 (3) Å	θ = 3.1–27.5°
b = 10.714 (3) Å	µ = 0.13 mm−1
c = 10.266 (3) Å	T = 93 K
β = 105.077 (10)°	Neecle, yellow
V = 1112.6 (6) Å3	0.56 × 0.54 × 0.25 mm
Z = 4

Rigaku Mercury375R (2x2 bin mode) diffractometer	2058 independent reflections
Radiation source: fine-focus sealed tube	1769 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
Detector resolution: 13.6612 pixels mm-1	θmax = 25.5°, θmin = 3.1°
profile data from ω–scan	h = −12→12
Absorption correction: multi-scan (REQAB; Rigaku, 1998)	k = −12→12
Tmin = 0.797, Tmax = 0.970	l = −12→12
9498 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.130	H-atom parameters not refined
S = 1.13	w = 1/[σ2(Fo2) + (0.0689P)2 + 0.4454P] where P = (Fo2 + 2Fc2)/3
2058 reflections	(Δ/σ)max < 0.001
166 parameters	Δρmax = 0.38 e Å−3
0 restraints	Δρmin = −0.35 e Å−3

Experimental. Rigaku (1998). REQAB. Rigaku Corporation, Tokyo, Japan.

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.

	x	y	z	Uiso*/Ueq
C1	0.22297 (15)	0.82305 (16)	0.58154 (16)	0.0158 (4)
C2	0.29963 (16)	0.88543 (15)	0.69423 (17)	0.0154 (4)
C3	0.37895 (16)	0.82230 (16)	0.80564 (16)	0.0168 (4)
H3	0.4307	0.8681	0.8801	0.020*
C4	0.38181 (16)	0.69396 (16)	0.80717 (16)	0.0167 (4)
C5	0.30317 (15)	0.62775 (16)	0.69555 (17)	0.0154 (4)
C6	0.22676 (16)	0.69258 (16)	0.58567 (16)	0.0158 (4)
H6	0.1754	0.6469	0.5109	0.019*
C7	0.13844 (16)	0.88840 (15)	0.45857 (17)	0.0166 (4)
H7A	0.0754	0.9456	0.4852	0.020*
H7B	0.1948	0.9379	0.4140	0.020*
C8	−0.01205 (16)	0.83679 (16)	0.25084 (16)	0.0175 (4)
C9	−0.08377 (18)	0.73342 (16)	0.16403 (18)	0.0216 (4)
H9A	−0.1781	0.7378	0.1603	0.032*
H9B	−0.0481	0.6529	0.2022	0.032*
H9C	−0.0721	0.7418	0.0728	0.032*
C10	0.53711 (16)	0.68572 (16)	1.02246 (16)	0.0186 (4)
H10A	0.6026	0.7354	0.9923	0.028*
H10B	0.5826	0.6245	1.0895	0.028*
H10C	0.4834	0.7409	1.0630	0.028*
C11	0.22990 (18)	0.43083 (16)	0.59702 (17)	0.0211 (4)
H11A	0.1368	0.4538	0.5832	0.032*
H11B	0.2410	0.3417	0.6185	0.032*
H11C	0.2574	0.4480	0.5146	0.032*
O1	0.23683 (12)	1.08224 (11)	0.60592 (12)	0.0219 (3)
O2	0.36433 (12)	1.07109 (11)	0.80903 (12)	0.0228 (3)
O3	0.06713 (11)	0.79354 (11)	0.36698 (12)	0.0186 (3)
O4	−0.02320 (12)	0.94638 (11)	0.22241 (12)	0.0229 (3)
O5	0.45330 (11)	0.62196 (11)	0.90924 (12)	0.0183 (3)
O6	0.30975 (12)	0.50251 (11)	0.70663 (12)	0.0187 (3)
N1	0.30069 (14)	1.02142 (14)	0.70366 (14)	0.0175 (3)

	U11	U22	U33	U12	U13	U23
C1	0.0163 (8)	0.0161 (8)	0.0155 (8)	0.0025 (6)	0.0052 (7)	0.0004 (6)
C2	0.0196 (8)	0.0084 (8)	0.0189 (9)	0.0000 (6)	0.0064 (7)	−0.0011 (6)
C3	0.0179 (8)	0.0159 (8)	0.0154 (8)	−0.0026 (7)	0.0023 (7)	−0.0015 (6)
C4	0.0189 (8)	0.0155 (9)	0.0149 (8)	0.0008 (7)	0.0031 (7)	0.0008 (6)
C5	0.0163 (8)	0.0136 (9)	0.0158 (8)	−0.0006 (6)	0.0033 (7)	−0.0002 (6)
C6	0.0177 (8)	0.0137 (9)	0.0153 (8)	−0.0009 (6)	0.0033 (7)	−0.0023 (6)
C7	0.0193 (8)	0.0115 (8)	0.0163 (8)	−0.0006 (6)	0.0000 (7)	−0.0022 (6)
C8	0.0169 (8)	0.0188 (9)	0.0148 (8)	0.0001 (7)	0.0006 (7)	0.0014 (7)
C9	0.0233 (9)	0.0158 (9)	0.0212 (9)	0.0007 (7)	−0.0025 (7)	0.0003 (7)
C10	0.0199 (8)	0.0181 (9)	0.0144 (8)	−0.0017 (7)	−0.0018 (7)	−0.0009 (7)
C11	0.0278 (9)	0.0134 (9)	0.0188 (9)	−0.0016 (7)	0.0000 (7)	−0.0029 (6)
O1	0.0277 (7)	0.0145 (6)	0.0204 (7)	0.0032 (5)	0.0009 (5)	0.0035 (5)
O2	0.0307 (7)	0.0153 (7)	0.0189 (7)	−0.0016 (5)	−0.0001 (5)	−0.0052 (5)
O3	0.0215 (6)	0.0127 (6)	0.0173 (6)	0.0004 (5)	−0.0027 (5)	−0.0002 (5)
O4	0.0277 (7)	0.0140 (6)	0.0229 (7)	0.0001 (5)	−0.0008 (5)	0.0031 (5)
O5	0.0222 (6)	0.0131 (6)	0.0146 (6)	−0.0007 (5)	−0.0040 (5)	0.0008 (5)
O6	0.0245 (6)	0.0095 (6)	0.0183 (6)	−0.0001 (5)	−0.0013 (5)	−0.0001 (4)
N1	0.0195 (7)	0.0153 (8)	0.0168 (7)	−0.0007 (6)	0.0029 (6)	−0.0007 (6)

C1—C2	1.395 (2)	C8—O3	1.345 (2)
C1—C6	1.399 (2)	C8—C9	1.496 (2)
C1—C7	1.512 (2)	C9—H9A	0.9800
C2—C3	1.401 (2)	C9—H9B	0.9800
C2—N1	1.460 (2)	C9—H9C	0.9800
C3—C4	1.375 (3)	C10—O5	1.4344 (19)
C3—H3	0.9500	C10—H10A	0.9800
C4—O5	1.359 (2)	C10—H10B	0.9800
C4—C5	1.416 (2)	C10—H10C	0.9800
C5—O6	1.347 (2)	C11—O6	1.437 (2)
C5—C6	1.388 (2)	C11—H11A	0.9800
C6—H6	0.9500	C11—H11B	0.9800
C7—O3	1.4524 (19)	C11—H11C	0.9800
C7—H7A	0.9900	O1—N1	1.2368 (19)
C7—H7B	0.9900	O2—N1	1.2339 (19)
C8—O4	1.208 (2)
C2—C1—C6	116.61 (15)	O3—C8—C9	111.81 (14)
C2—C1—C7	123.79 (16)	C8—C9—H9A	109.5
C6—C1—C7	119.60 (14)	C8—C9—H9B	109.5
C1—C2—C3	122.48 (16)	H9A—C9—H9B	109.5
C1—C2—N1	121.72 (15)	C8—C9—H9C	109.5
C3—C2—N1	115.79 (15)	H9A—C9—H9C	109.5
C4—C3—C2	119.91 (15)	H9B—C9—H9C	109.5
C4—C3—H3	120.0	O5—C10—H10A	109.5
C2—C3—H3	120.0	O5—C10—H10B	109.5
O5—C4—C3	125.62 (15)	H10A—C10—H10B	109.5
O5—C4—C5	115.33 (15)	O5—C10—H10C	109.5
C3—C4—C5	119.04 (15)	H10A—C10—H10C	109.5
O6—C5—C6	124.98 (15)	H10B—C10—H10C	109.5
O6—C5—C4	115.13 (14)	O6—C11—H11A	109.5
C6—C5—C4	119.89 (16)	O6—C11—H11B	109.5
C5—C6—C1	122.05 (15)	H11A—C11—H11B	109.5
C5—C6—H6	119.0	O6—C11—H11C	109.5
C1—C6—H6	119.0	H11A—C11—H11C	109.5
O3—C7—C1	107.90 (13)	H11B—C11—H11C	109.5
O3—C7—H7A	110.1	C8—O3—C7	115.31 (13)
C1—C7—H7A	110.1	C4—O5—C10	116.94 (13)
O3—C7—H7B	110.1	C5—O6—C11	117.37 (13)
C1—C7—H7B	110.1	O2—N1—O1	122.61 (15)
H7A—C7—H7B	108.4	O2—N1—C2	118.78 (14)
O4—C8—O3	123.19 (15)	O1—N1—C2	118.60 (13)
O4—C8—C9	125.01 (15)
C6—C1—C2—C3	1.2 (2)	C7—C1—C6—C5	179.61 (14)
C7—C1—C2—C3	−178.75 (15)	C2—C1—C7—O3	−176.32 (14)
C6—C1—C2—N1	−178.07 (14)	C6—C1—C7—O3	3.7 (2)
C7—C1—C2—N1	2.0 (2)	O4—C8—O3—C7	0.8 (2)
C1—C2—C3—C4	−0.8 (2)	C9—C8—O3—C7	−178.75 (13)
N1—C2—C3—C4	178.48 (15)	C1—C7—O3—C8	−179.24 (13)
C2—C3—C4—O5	−179.33 (14)	C3—C4—O5—C10	−2.8 (2)
C2—C3—C4—C5	−0.4 (2)	C5—C4—O5—C10	178.28 (13)
O5—C4—C5—O6	0.4 (2)	C6—C5—O6—C11	−1.0 (2)
C3—C4—C5—O6	−178.65 (15)	C4—C5—O6—C11	178.91 (13)
O5—C4—C5—C6	−179.73 (14)	C1—C2—N1—O2	175.79 (14)
C3—C4—C5—C6	1.3 (2)	C3—C2—N1—O2	−3.5 (2)
O6—C5—C6—C1	179.03 (15)	C1—C2—N1—O1	−3.7 (2)
C4—C5—C6—C1	−0.9 (2)	C3—C2—N1—O1	177.02 (14)
C2—C1—C6—C5	−0.3 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9B···O4i	0.98	2.40	3.375 (2)	174
C10—H10B···O6ii	0.98	2.51	3.472 (2)	169