A three-dimensional hydrogen-bonded framework in N-(3-nitro­phenyl)­phthal­imide, and hydrogen-bonded chains of rings in N-(3,5-di­nitro­phenyl)­phthal­imide, linked into sheets by dipolar interactions

Molecules of N-(3-nitro­phenyl)­phthal­imide, C₁₄H₈N₂O₄, are linked into a three-dimensional framework by four distinct C—H...O hydrogen bonds [H...O = 2.35–2.58 Å, C...O = 3.105 (5)–3.432 (5) Å and C—H...O = 128–167°]. Molecules of N-(3,5-di­nitro­phenyl)­phthal­imide, C₁₄H₇N₃O₆, lie across twofold rotation axes in space group P2/n and are linked by a single C—H...O hydrogen bond [H...O = 2.58 Å, C...O = 3.410 (2) Å and C—H...O = 147°] into chains of rings. These chains are weakly linked into sheets by intermolecular interactions involving short dipolar O...N and O...C contacts.

S1. Comment

We recently described (Low et al., 2000) the supramolecular structure of N-(2-nitrophenylthio)phthalimide, basing our analysis on the structure determination of Iwasaki & Masuko (1986). In the present paper, we report on the molecular and supramolecular structure of two related compounds, viz. N-(3-nitrophenyl)phthalimide, (I), and N-(3,5-dinitrophenyl)phthalimide, (II).

The molecules of (I) (Fig. 1) are linked by a series of C—H···O hydrogen bonds, thus forming a continuous three-dimensional framework. However, C—H···π(arene) hydrogen bonds and aromatic π–π stacking interactions are both absent. The framework formation is most readily analysed in terms of the simple one-dimensional substructures generated by the individual hydrogen bonds. The amide O atoms are more active as hydrogen-bond acceptors than the nitro O atoms.

Atom C16 in the molecule at (x, y, z) acts as a hydrogen-bond donor to amide atom O1 in the molecule at (1 + x, y, z), so generating by translation a C(6) chain running parallel to the [100] direction, while atom C7 in the molecule at (x, y, z) acts as a donor to nitro atom O132 in the molecule at (0.5 + x, 1 − y, 0.5 + z), so producing a C(10) chain running parallel to [101] and generated by the glide plane at y = 0.5. The combination of the [100] and [101] chains generates a sheet parallel to (010), built from a single type of R⁴₄(29) ring (Fig. 2). At the same time, atom C4 at (x, y, z) acts as a hydrogen-bond donor to amide atom O2 in the molecule at (−1 + x, 1 + y, z), so generating by translation a second C(6) chain, this time running parallel to the [1–10] direction (Fig. 3), and these [1–10] chains suffice to link together all of the (010) sheets. The linking of the sheets is reinforced by the final, rather weak, C—H···O hydrogen bond, in which atom C12 at (x, y, z) acts as a donor to amide atom O1 in the molecule at (x, −1 + y, z), producing, again by translation, yet another C(6) chain, this time running parallel to [010].

Molecules of (II) (Fig. 4) lie across twofold rotation axes in space group P2/n. A single C—H···O hydrogen bond links the molecules into a rather elegant chain of rings. C—H···π(arene) hydrogen bonds are absent, as are aromatic π–π stacking interactions, so the hydrogen-bonded structure of (II) is only one-dimensional.

Atom C12 at (x, y, z) is part of the molecule lying across the twofold axis along (1/4, y, 3/4). This atom acts as a hydrogen-bond donor to amide atom O1 at (−0.5 − x, y, 1.5 − z), which is part of the molecule lying across the twofold axis along (−0.75, y, 3/4). In turn, atom C12 at (−0.5 − x, y, 1.5 − z) acts as a donor to atom O1 at (0.5 − x, y, 1.5 − z), which is part of the reference molecule along (1/4, y, 3/4). In this way, an R²₂(12) ring is formed, lying across the twofold rotation axis along (−0.25, y, 3/4), and propagation of this single hydrogen bond by the twofold axes serves to generate a C(6)[R²₂(12)] chain of rings (Bernstein et al., 1995) running parallel to [100] (Fig. 5). Two such chains, related to one another by the n-glide plane, pass through each unit cell.

There are two short intermolecular contacts other than the hydrogen bond, both of which involve a negatively polarized O atom, and either a positively polarized nitro N or a positively polarized carbonyl C atom. The non-bonded contact distances are both significantly less than the sum of the van der Waals radii for C and N atoms (3.20 Å), and for C and O atoms (3.15 Å; Bondi, 1964), and hence both interactions must be regarded as attractive. Their geometry (Fig. 6) resembles that of the perpendicular interaction between pairs of carbonyl groups (Allen et al., 1998). Amide atom O1 at (x, y, z), which lies in the reference molecule along (1/4, y, 3/4), is only 2.810 (3) Å from nitro atom N13 at (−0.5 + x, 1 − y, −0.5 + z), which lies in a molecule across the twofold axis along (−0.25, −y, 1/4); the other amide O atom in the reference molecule, at (0.5 − x, y, 1.5 − z), forms a close contact with atom N13 at (1 − x, 1 − y, 2 − z), which lies in the molecule across the twofold axis along (3/4, −y, 1.25), so producing a chain of edge-fused R²₂(14) rings (Starbuck et al., 1999) along [101]. Nitro atom O31 at (x, y, z) is 2.868 (3) Å from carbonyl atom C1 at (−0.5 + x, 1 − y, 0.5 + z), which lies in a molecule across the twofold axis along (−0.25, −y, 1.25), while atom O131 at (0.5 − x, y, 1.5 − z) forms a close contact with atom C1 at (1 − x, 1 − y, 1 − z), which lies in the molecule across the twofold axis along (3/4, −y, 1/4), so producing another chain of edge-fused R²₂(14) rings, this time along [10–1]. The combined effect of the [101] and [10–1] chains is to link the hydrogen-bonded [100] chains (Fig. 5) into a (010) sheet.

The intramolecular distances in (I) and (II) show no unusual features. The conformations of both molecules are dominated by the twist around the central C—N bond between the phthalimide unit and the nitrated aryl ring. The dihedral angles between the heterocyclic ring and the nitrated ring are 45.5 (2)° in (I) and 77.3 (2)° in (II). The molecular symmetries of (I) and (II) are therefore C₁ and C₂, respectively, so that, in each compound, the molecules are chiral, although the crystals of each contain equal numbers of the two enantiomorphs. The non-planar conformation of (I) is unexpected in view of the very short b axis of the unit cell, while the C—H···O hydrogen bonding in (II) is dependent on the near orthogonality of the rings involved.

It is of interest to compare the supramolecular aggregation in (I) and (II) with that in N-(2-nitrophenyl)phthalimide, (III) [Cambridge Structural Database (CSD; Allen, 2002) refcode COMGUG; Voliotis et al., 1984], although there was no discussion of this in the original report. In (III), pairs of molecules are linked by a single C—H···O hydrogen bond into centrosymmetric R²₂(14) dimers, and these in turn are linked into [100] chains by an aromatic π–π stacking interaction between pairs of aryl rings related by a centre of inversion (Fig. 7). On the other hand, there are no C—H···O hydrogen bonds in the unsubstituted N-phenylphthalimide [CSD refcode ZZZAWJ10; Magomedova et al., 1981)].

S2. Experimental

Equimolar quantities of phthalic anhydride and the appropriate nitroaniline were mixed and then heated on a hotplate, in the absence of solvent, until evolution of water ceased. After cooling the mixtures to ambient temperature, crystallization of the resulting solids from ethanol solutions gave crystals of (I) and (II) suitable for single-crystal X-ray diffraction.

S3. Refinement

Compounds (I) and (II) are both monoclinic, and the systematic absences permitted Pn and P2/n as possible space groups for each compound. The unit-cell volumes for both were consistent with Z = 2, and hence the space group Pn, with Z' = 1, was selected for (I) and P2/n, with Z' = 1/2, was selected for (II). These choices were confirmed by the subsequent analyses. All H atoms were treated as riding, with C—H distances of 0.95 Å. In the absence of significant anomalous scattering, the Flack (1983) parameter for (I), value 1(2), was inconclusive (Flack & Bernardinelli, 2000), and the Friedel equivalents were therefore merged prior to the final refinement; the orientation of the structure with respect to the polar axes could not be established.

Computing details

For both compounds, data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. The molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Part of the crystal structure of (I), showing the intersection of the [100] and [101] chains to form a sheet of R^44(29) rings. Atoms marked with an asterisk (*), a hash (#), a dollar sign (), an ampersand (&) or an at sign (@) are at the symmetry positions (1 + x, y, z), (0.5 + x, 1 − y, 0.5 + z), (1 + x, y, 1 + z), (1.5 + x, 1 − y, 0.5 + z) and (2 + x, y, 1 + z), respectively.
	Fig. 3. Part of the crystal structure of (I), showing the formation of a C(6) chain along [1–10]. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (−1 + x, 1 + y, z) and (1 + x, −1 + y, z), respectively.
	Fig. 4. The molecule of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. Atoms marked 'A' are at the symmetry position (0.5 − x, y, 1.5 − z).
	Fig. 5. A stereoview of part of the crystal structure of (II), showing the formation of a hydrogen-bonded chain of rings parallel to [100].
	Fig. 6. A stereoview of part of the crystal structure of (II), showing the weak non-bonded C···N and C···O interactions (dashed lines) that link the [100] chains.
	Fig. 7. Part of the crystal structure of COMGUG (Voliotis et al., 1984), showing the linking of hydrogen-bonded R^22(14) dimers into a π-stacked chain along [100]; the coordinates and the atom labels are those used in the original report. Atoms marked with an asterisk (*), a hash (#) or a dollar sign () are at the symmetry positions (1 − x, 1 − y, 1 − z), (-x, 1 − y, 1 − z) and (−1 + x, y, z), respectively.

(I) N-(3-Nitrophenyl)phthalimide

Crystal data

C14H8N2O4	F(000) = 276
Mr = 268.22	Dx = 1.536 Mg m^−3
Monoclinic, Pn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P -2yac	Cell parameters from 1286 reflections
a = 6.6650 (5) Å	θ = 3.1–27.4°
b = 3.6962 (3) Å	µ = 0.12 mm^−1
c = 23.639 (2) Å	T = 120 K
β = 95.208 (3)°	Plate, colourless
V = 579.95 (8) Å^3	0.20 × 0.10 × 0.03 mm
Z = 2

Data collection

Nonius KappaCCD diffractometer	1286 independent reflections
Radiation source: rotating anode	871 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.096
ϕ scans, and ω scans with κ offsets	θmax = 27.4°, θmin = 3.1°
Absorption correction: multi-scan (DENZO–SMN; Otwinowski & Minor, 1997)	h = −8→8
Tmin = 0.972, Tmax = 0.997	k = −4→4
4904 measured reflections	l = −30→30

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.116	H-atom parameters constrained
S = 0.88	w = 1/[σ^2(Fo^2) + (0.0687P)^2] where P = (Fo^2 + 2Fc^2)/3
1286 reflections	(Δ/σ)max < 0.001
181 parameters	Δρmax = 0.27 e Å^−3
2 restraints	Δρmin = −0.31 e Å^−3

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

	x	y	z	Uiso*/Ueq
N1	0.7445 (5)	0.8585 (9)	0.20877 (15)	0.0279 (8)
C1	0.5599 (6)	1.0114 (11)	0.22174 (19)	0.0266 (10)
O1	0.4373 (4)	1.1439 (8)	0.18681 (12)	0.0306 (7)
C2	0.8600 (6)	0.7387 (11)	0.25848 (19)	0.0290 (10)
O2	1.0213 (4)	0.5878 (8)	0.25924 (13)	0.0359 (7)
C3	0.5602 (6)	0.9848 (11)	0.28435 (19)	0.0283 (10)
C4	0.4130 (6)	1.0903 (11)	0.3188 (2)	0.0297 (10)
C5	0.4544 (7)	1.0324 (11)	0.3768 (2)	0.0358 (11)
C6	0.6376 (7)	0.8856 (12)	0.3991 (2)	0.0365 (11)
C7	0.7843 (6)	0.7810 (11)	0.36369 (19)	0.0327 (10)
C8	0.7405 (6)	0.8316 (10)	0.30614 (18)	0.0270 (9)
C11	0.8064 (6)	0.8257 (11)	0.15264 (17)	0.0288 (10)
C12	0.6746 (6)	0.6874 (10)	0.10976 (18)	0.0255 (9)
C13	0.7409 (6)	0.6553 (10)	0.05634 (19)	0.0281 (10)
C14	0.9339 (6)	0.7516 (12)	0.0448 (2)	0.0303 (10)
C15	1.0634 (6)	0.8910 (12)	0.08854 (18)	0.0312 (10)
C16	1.0007 (6)	0.9310 (11)	0.14216 (19)	0.0287 (10)
N13	0.6026 (5)	0.5020 (10)	0.01052 (16)	0.0325 (9)
O131	0.4289 (4)	0.4367 (11)	0.02037 (13)	0.0487 (9)
O132	0.6673 (5)	0.4450 (11)	−0.03559 (14)	0.0500 (9)
H4	0.2901	1.1969	0.3035	0.036*
H5	0.3559	1.0941	0.4018	0.043*
H6	0.6631	0.8562	0.4390	0.044*
H7	0.9088	0.6794	0.3787	0.039*
H12	0.5421	0.6163	0.1168	0.031*
H14	0.9764	0.7226	0.0078	0.036*
H15	1.1963	0.9595	0.0815	0.037*
H16	1.0894	1.0300	0.1719	0.034*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0226 (18)	0.0291 (19)	0.031 (2)	0.0000 (15)	−0.0009 (15)	−0.0009 (16)
C1	0.022 (2)	0.0186 (19)	0.039 (3)	−0.0068 (18)	0.0041 (19)	0.0017 (17)
O1	0.0208 (14)	0.0365 (17)	0.0340 (17)	0.0013 (13)	−0.0009 (13)	0.0025 (14)
C2	0.026 (2)	0.023 (2)	0.038 (3)	−0.0040 (19)	0.0001 (18)	−0.0035 (19)
O2	0.0290 (17)	0.0361 (16)	0.0418 (19)	0.0078 (14)	−0.0015 (13)	−0.0009 (15)
C3	0.026 (2)	0.023 (2)	0.036 (2)	−0.0039 (18)	0.0007 (18)	0.0017 (17)
C4	0.027 (2)	0.023 (2)	0.038 (3)	0.0013 (18)	−0.0022 (19)	0.0004 (19)
C5	0.035 (3)	0.035 (2)	0.037 (3)	−0.002 (2)	0.005 (2)	−0.001 (2)
C6	0.041 (2)	0.036 (2)	0.032 (3)	0.001 (2)	−0.001 (2)	0.002 (2)
C7	0.033 (2)	0.027 (2)	0.037 (3)	0.003 (2)	−0.002 (2)	0.0003 (19)
C8	0.025 (2)	0.0208 (19)	0.034 (2)	−0.0052 (18)	−0.0005 (18)	0.0005 (18)
C11	0.027 (2)	0.029 (2)	0.029 (3)	0.0054 (19)	−0.0028 (18)	0.0016 (18)
C12	0.0183 (18)	0.0214 (19)	0.037 (3)	0.0011 (17)	0.0016 (17)	0.0048 (17)
C13	0.029 (2)	0.024 (2)	0.030 (2)	−0.0037 (18)	−0.0030 (19)	−0.0008 (18)
C14	0.026 (2)	0.033 (2)	0.033 (3)	0.0007 (19)	0.0044 (18)	0.0035 (19)
C15	0.0204 (19)	0.033 (2)	0.041 (3)	−0.0007 (18)	0.0064 (19)	0.0023 (19)
C16	0.023 (2)	0.025 (2)	0.038 (3)	0.0017 (18)	−0.0011 (19)	−0.0022 (18)
N13	0.032 (2)	0.035 (2)	0.030 (2)	−0.0021 (17)	0.0000 (16)	0.0010 (16)
O131	0.0306 (18)	0.076 (3)	0.039 (2)	−0.0156 (17)	0.0007 (15)	−0.0113 (16)
O132	0.0463 (19)	0.073 (2)	0.031 (2)	−0.0117 (18)	0.0042 (16)	−0.0090 (17)

Geometric parameters (Å, º)

N1—C1	1.413 (5)	C7—C8	1.378 (6)
N1—C2	1.416 (5)	C7—H7	0.95
N1—C11	1.430 (5)	C11—C12	1.378 (5)
C1—O1	1.211 (5)	C11—C16	1.396 (6)
C1—C3	1.483 (6)	C12—C13	1.380 (6)
C2—O2	1.210 (5)	C12—H12	0.95
C2—C8	1.478 (6)	C13—C14	1.385 (6)
C3—C8	1.385 (6)	C13—N13	1.471 (5)
C3—C4	1.386 (6)	C14—C15	1.385 (6)
C4—C5	1.391 (7)	C14—H14	0.95
C4—H4	0.95	C15—C16	1.378 (6)
C5—C6	1.395 (6)	C15—H15	0.95
C5—H5	0.95	C16—H16	0.95
C6—C7	1.398 (6)	N13—O131	1.226 (4)
C6—H6	0.95	N13—O132	1.226 (5)
C1—N1—C2	111.3 (3)	C7—C8—C3	121.4 (4)
C1—N1—C11	124.5 (3)	C7—C8—C2	129.8 (4)
C2—N1—C11	124.2 (3)	C3—C8—C2	108.7 (4)
O1—C1—N1	124.1 (4)	C12—C11—C16	120.8 (4)
O1—C1—C3	130.3 (4)	C12—C11—N1	119.7 (4)
N1—C1—C3	105.5 (3)	C16—C11—N1	119.4 (4)
O2—C2—N1	124.9 (4)	C11—C12—C13	118.0 (4)
O2—C2—C8	129.5 (4)	C11—C12—H12	121.0
N1—C2—C8	105.7 (3)	C13—C12—H12	121.0
C8—C3—C4	122.2 (4)	C12—C13—C14	122.5 (4)
C8—C3—C1	108.7 (4)	C12—C13—N13	118.4 (4)
C4—C3—C1	129.1 (4)	C14—C13—N13	119.0 (4)
C3—C4—C5	116.6 (4)	C15—C14—C13	118.4 (4)
C3—C4—H4	121.7	C15—C14—H14	120.8
C5—C4—H4	121.7	C13—C14—H14	120.8
C4—C5—C6	121.4 (4)	C16—C15—C14	120.4 (4)
C4—C5—H5	119.3	C16—C15—H15	119.8
C6—C5—H5	119.3	C14—C15—H15	119.8
C5—C6—C7	121.2 (4)	C15—C16—C11	119.8 (4)
C5—C6—H6	119.4	C15—C16—H16	120.1
C7—C6—H6	119.4	C11—C16—H16	120.1
C8—C7—C6	117.2 (4)	O131—N13—O132	123.3 (4)
C8—C7—H7	121.4	O131—N13—C13	118.4 (4)
C6—C7—H7	121.4	O132—N13—C13	118.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O2^i	0.95	2.46	3.393 (5)	167
C7—H7···O132^ii	0.95	2.58	3.432 (5)	150
C12—H12···O1^iii	0.95	2.55	3.221 (5)	128
C16—H16···O1^iv	0.95	2.35	3.105 (5)	136

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

(II) N-(3,5-Dinitrophenyl)phthalimide

Crystal data

C14H7N3O6	F(000) = 320
Mr = 313.23	Dx = 1.591 Mg m^−3
Monoclinic, P2/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yac	Cell parameters from 1470 reflections
a = 5.0936 (7) Å	θ = 3.2–27.5°
b = 12.6297 (18) Å	µ = 0.13 mm^−1
c = 10.366 (2) Å	T = 120 K
β = 101.335 (6)°	Needle, colourless
V = 653.84 (18) Å^3	0.50 × 0.10 × 0.04 mm
Z = 2

Data collection

Nonius KappaCCD diffractometer	1470 independent reflections
Radiation source: rotating anode	914 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.078
ϕ scans, and ω scans with κ offsets	θmax = 27.5°, θmin = 3.2°
Absorption correction: multi-scan (DENZO–SMN; Otwinowski & Minor, 1997)	h = −6→6
Tmin = 0.933, Tmax = 0.995	k = −16→16
6913 measured reflections	l = −13→13

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) = 0.128	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0655P)^2] where P = (Fo^2 + 2Fc^2)/3
1470 reflections	(Δ/σ)max < 0.001
106 parameters	Δρmax = 0.24 e Å^−3
0 restraints	Δρmin = −0.40 e Å^−3

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

	x	y	z	Uiso*/Ueq
N1	0.2500	0.37629 (17)	0.7500	0.0226 (6)
C1	0.0390 (4)	0.31442 (16)	0.68110 (19)	0.0235 (5)
O1	−0.1659 (3)	0.34953 (10)	0.61631 (14)	0.0274 (4)
C2	0.1267 (4)	0.20282 (15)	0.7077 (2)	0.0245 (5)
C3	−0.0026 (4)	0.10993 (18)	0.6631 (2)	0.0326 (5)
C4	0.1276 (4)	0.01564 (18)	0.7072 (3)	0.0413 (6)
C11	0.2500	0.4893 (2)	0.7500	0.0210 (6)
C12	0.0935 (4)	0.54315 (16)	0.82428 (19)	0.0232 (5)
C13	0.0997 (4)	0.65247 (15)	0.82276 (18)	0.0224 (5)
N13	−0.0639 (3)	0.71134 (14)	0.90124 (16)	0.0269 (4)
O31	−0.2117 (3)	0.66002 (11)	0.95792 (14)	0.0305 (4)
O32	−0.0481 (3)	0.80857 (12)	0.90361 (15)	0.0398 (5)
C14	0.2500	0.7098 (2)	0.7500	0.0238 (6)
H3	−0.1721	0.1102	0.6051	0.039*
H4	0.0459	−0.0500	0.6778	0.050*
H12	−0.0141	0.5060	0.8744	0.028*
H14	0.2500	0.7850	0.7500	0.029*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0237 (13)	0.0198 (13)	0.0236 (14)	0.000	0.0030 (10)	0.000
C1	0.0248 (11)	0.0285 (12)	0.0180 (11)	−0.0014 (8)	0.0060 (8)	−0.0027 (9)
O1	0.0240 (7)	0.0294 (8)	0.0277 (9)	0.0014 (6)	0.0028 (6)	0.0005 (6)
C2	0.0255 (10)	0.0248 (12)	0.0237 (12)	−0.0004 (8)	0.0056 (8)	−0.0008 (9)
C3	0.0299 (12)	0.0313 (13)	0.0353 (13)	−0.0014 (9)	0.0033 (10)	−0.0028 (10)
C4	0.0426 (14)	0.0242 (13)	0.0537 (17)	−0.0043 (10)	0.0013 (11)	−0.0031 (11)
C11	0.0216 (15)	0.0201 (16)	0.0206 (16)	0.000	0.0020 (11)	0.000
C12	0.0211 (11)	0.0287 (12)	0.0186 (11)	−0.0008 (8)	0.0014 (8)	0.0010 (8)
C13	0.0239 (10)	0.0243 (12)	0.0173 (11)	0.0030 (8)	0.0002 (8)	−0.0010 (8)
N13	0.0264 (10)	0.0302 (11)	0.0226 (10)	0.0043 (7)	0.0012 (7)	−0.0017 (8)
O31	0.0240 (8)	0.0400 (10)	0.0287 (9)	−0.0011 (6)	0.0078 (6)	−0.0016 (7)
O32	0.0549 (10)	0.0251 (10)	0.0422 (11)	0.0088 (7)	0.0164 (8)	−0.0008 (7)
C14	0.0228 (15)	0.0228 (16)	0.0234 (16)	0.000	−0.0014 (11)	0.000

Geometric parameters (Å, º)

N1—C1	1.405 (2)	C11—C12	1.390 (2)
N1—C1^i	1.405 (2)	C11—C12^i	1.390 (2)
N1—C11	1.428 (3)	C12—C13	1.381 (3)
C1—O1	1.209 (2)	C12—H12	0.95
C1—C2	1.488 (3)	C13—C14	1.381 (2)
C2—C3	1.380 (3)	C13—N13	1.475 (2)
C2—C2^i	1.383 (4)	N13—O31	1.227 (2)
C3—C4	1.396 (3)	N13—O32	1.231 (2)
C3—H3	0.95	C14—C13^i	1.381 (2)
C4—C4^i	1.381 (5)	C14—H14	0.95
C4—H4	0.95
C1—N1—C1^i	112.4 (2)	C12—C11—C12^i	121.4 (2)
C1—N1—C11	123.79 (11)	C12—C11—N1	119.28 (12)
C1^i—N1—C11	123.79 (11)	C12^i—C11—N1	119.28 (12)
O1—C1—N1	124.68 (19)	C13—C12—C11	117.76 (18)
O1—C1—C2	130.20 (18)	C13—C12—H12	121.1
N1—C1—C2	105.12 (16)	C11—C12—H12	121.1
C3—C2—C2^i	121.77 (12)	C14—C13—C12	123.16 (19)
C3—C2—C1	129.58 (18)	C14—C13—N13	118.09 (18)
C2^i—C2—C1	108.64 (10)	C12—C13—N13	118.75 (17)
C2—C3—C4	116.8 (2)	O31—N13—O32	124.15 (16)
C2—C3—H3	121.6	O31—N13—C13	117.65 (17)
C4—C3—H3	121.6	O32—N13—C13	118.18 (16)
C4^i—C4—C3	121.42 (13)	C13—C14—C13^i	116.7 (3)
C4^i—C4—H4	119.3	C13—C14—H14	121.6
C3—C4—H4	119.3	C13^i—C14—H14	121.6
C1^i—N1—C1—O1	178.9 (2)	C1—N1—C11—C12^i	−104.63 (13)
C11—N1—C1—O1	−1.1 (2)	C1^i—N1—C11—C12^i	75.37 (13)
C1^i—N1—C1—C2	−0.76 (9)	C12^i—C11—C12—C13	−0.44 (12)
C11—N1—C1—C2	179.24 (9)	N1—C11—C12—C13	179.56 (12)
O1—C1—C2—C3	1.2 (3)	C11—C12—C13—C14	0.9 (3)
N1—C1—C2—C3	−179.21 (19)	C11—C12—C13—N13	−179.76 (13)
O1—C1—C2—C2^i	−177.5 (2)	C14—C13—N13—O31	174.82 (14)
N1—C1—C2—C2^i	2.1 (2)	C12—C13—N13—O31	−4.5 (2)
C2^i—C2—C3—C4	−0.1 (4)	C14—C13—N13—O32	−3.7 (2)
C1—C2—C3—C4	−178.6 (2)	C12—C13—N13—O32	176.95 (17)
C2—C3—C4—C4^i	0.8 (4)	C12—C13—C14—C13^i	−0.48 (13)
C1—N1—C11—C12	75.37 (13)	N13—C13—C14—C13^i	−179.79 (18)
C1^i—N1—C11—C12	−104.63 (13)

Symmetry code: (i) −x+1/2, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···O1^ii	0.95	2.58	3.410 (2)	147

Symmetry code: (ii) −x−1/2, y, −z+3/2.