L-Prolinium picrate and 2-methyl­pyridinium picrate

In the structure of L-prolinium picrate, C₅H₁₀NO₂⁺·C₆H₂N₃O₇⁻, the C^γ atom of the pyrrolidine ring has conformational disorder. Both the major and minor conformers of the pyrrolidine ring adopt conformations inter­mediate between a half-chair and an envelope. Both the cation and anion are packed through chelated three-centred N—H...O hydrogen bonds. The prolinium cation connects two different picrate anions, leading to an infinite chain running along the b axis. In 2-methyl­pyridinium picrate, C₆H₈N⁺·C₆H₂N₃O₇⁻, the cations and anions are packed separately along the a axis and are inter­connected by N—H...O hydrogen bonds. Intra­molecular contacts between phenolate O atoms and adjacent nitro groups are identified in both structures. A graph-set motif of R₁²(6) is observed in both structures.

S1. Comment

Picric acid forms charge-transfer complexes with organic compounds. Crystalline picrates have commonly been used in the preparation of amine derivatives in qualitative organic chemistry (Shriner et al., 1980). The crystal structure elucidation of L-prolinium picrate, (I), and 2-methylpyridinium picrate, (II), was undertaken to study the nature of hydrogen bonding between the molecular ions, involving phenolate O atoms and the protonated N atoms, and the crystal packing in the different environments.

In the structure of (I), the asymmetric part of the unit cell contains a prolinium cation and a picrate anion (Fig. 1). An orthorhombic form of L-prolinium picrate has already been reported (Jin et al., 2003). The backbone conformation angles ψ¹ (O1A—C1—C2—N1) and ψ² (O1B—C1—C2—N1) are cis and trans, respectively. The side-chain conformation angles χ¹ (N1—C2—C3—C4), χ² (C2—C3—C4—C5), χ³ (C4—C5—N1—C2), χ⁴ (C3—C4—C5—N1) and θ (C4—C5—N1—C5) are 8.3, -27.2, -29.6, 34.7 and 13.2, respectively (Prasad & Vijayan, 1993) (Table 1). The C^γ atom (C4) of the pyrolidine ring has conformational disorder, as observed in bis(L-proline) hydrogen perchlorate (Pandiarajan et al., 2002). Atoms C4 and C41 deviate from the plane of which atoms?, whereas atoms N1, C2, C3 and C5 are nearly coplanar. Both major and minor conformers of the pyrrolidine ring adopt conformations intermediate between a half-chair and an envelope (Cremer & Pople, 1975; Nardelli, 1983). The angle between the rings of the anion and cation is 44.4 (2)°.

Both the cation and anion of (I) are packed through chelated three-centred N—H···O hydrogen bonds, as observed in other picrate complexes (Jin et al., 2003; Kai et al., 1994). The prolinium cation connects two different picrate anions, leading to an infinite chain running along the b axis (Fig. 2). Weak three-centred C—H···O hydrogen bonds also stabilize the structure. The prolinium cation forms an infinite chain along the b axis through a C—H···O hydrogen bond (Table 2). The anion and cation form a hydrogen-bonded network with a graph-set motif of R²₁(6) (Etter et al., 1990) (Fig. 2).

We now discuss the crystal structure of (II). The crystal structures of pyridine and pyridine trihydrate (Mootz & Wussow, 1981), pyridine picrate (Talukdar & Chaudhuri, 1976) and pyridinium picrate (Takayanagi et al., 1990) have already been reported. The asymmetric part of the unit cell of (II) contains two 2-methylpyridinium cations and two picrate anions (Fig. 4). The protonation of the N atom of the pyridine ring is confirmed from the values of the C—N bond distances, which agree well with those in pyridinum picrate (Table ? No values were flagged in the CIF for inclusion in a bond table - do you wish to add them?). The angles between the rings of both anions and those of the cations are 74.4 (1) and 79.4 (1)°, and 76.5 (1) and 80.7 (1)° [It is not clear which pairs of rings these are angles between - please clarify]. The pyridine ring is almost normal to the phenyl ring. This fact supports the absence of π bonding in this complex, as observed in p-phenylenediamine picrate and o-phenylenediamine picrate (Takayanagi et al., 1996). Both cations form bifurcated N—H···O hydrogen bonds with inversely related anions, thus forming a graph-set motif of R²₁(6) (Etter et al., 1990) (Fig. 5). This type of bifurcated hydrogen bonding (Table 3) is also observed in the crystal structure of (I).

In the picrate anions of (I) and (II), the bond distances and angles show the deprotonation of the phenolic group, and the geometry is similar to that in other picrate complexes (Takayanagi et al., 1996). The picrate anions are sandwiched between layers of prolinium cations along the c axis in (I) (Fig. 3), whereas in (II), the picrate anions are packed between layers of pyridinium cations (Fig. 5). In the structure of (II), both the anions are arranged nearly parallel to each other, making angles of 9.02 (1) and 11.4 (1)° with the [001] plane. Intramolecular contacts between the phenolate O atoms and adjacent nitro groups are observed in both structures. In compounds (I) and (II), one of the ortho-nitro groups is twisted more from the plane of the ring, while the para-nitro group is nearly planar. In the structure of (II), the angle between the rings of the picrate anions is 20.6 (1)°, and the angle between the rings of the pyridinium cations is 25.1 (1)°.

S2. Experimental

Compound (I) was crystallized from an aqueous solution containing L-proline and picric acid in the stoichiometric ratio of 1:1 at room temperature, by the technique of slow evaporation. Similarly, compound (II) was crystallized from an aqueous solution containing pyridoxine and picric acid in the stoichiometric ratio of 1:1 at room temperature by the technique of slow evaporation. Instead of the expected picric acid complex with pyridoxine, crystals of 2-methylpyridinum picrate were obtained.

S3. Refinement

All H atoms were placed in geometrically calculated positions and included in the refinement in the riding-model approximation, with N—H = 0.90 Å and C—H = 0.93–0.98 Å in compound (I), and with N—H = 0.86 Å and C—H = 0.93–0.96 Å and in compound (II). In both compounds, U_iso(H) = 1.2–1.5U_eq(C,N). In compound (I), the C^γ atom (C4) of the pyrolidine ring has conformational disorder, with site-occupancy factors of 0.52 (1) and 0.48 (1). In compound (II), one of the O atoms of the picrate anion is disordered, with occupancy factors of 0.71 (1) and 0.29 (1) for atoms O47 and O471. In compound (I), owing to the absence of atoms heavier than Si, the absolute configuration could not be reliably determined and Friedel pairs were merged.

Computing details

For both compounds, data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXTL/PC (Bruker, 2000); program(s) used to refine structure: SHELXTL/PC; molecular graphics: ORTEP 3 for Windows (Farrugia, 1997), PLATON (Spek, 2003) and Mercury (Version 1.4.1; Macrae et al., 2006); software used to prepare material for publication: SHELXTL/PC.

Figures

	Fig. 1. The molecular structure of compound (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The hydrogen bond is indicated by dashed lines. H atoms not involved in this interaction have been omitted.
	Fig. 2. The infinite chain formed in the crystal structure of (I), connecting two picrate anions with cations, running along the a axis. Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity.
	Fig. 3. A packing diagram of the molecules in the structure of (I), viewed down the b axis. Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity.
	Fig. 4. The molecular structure of title compound (II) with atom numbering scheme and 50% probability displacement ellipsoids. H-bonds are shown as dashed lines.
	Fig. 5. A packing diagram of the molecules in the structure of (II), viewed down the a axis. Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity.

(I) L-prolinium picrate

Crystal data

C5H10NO2^+·C6H2N3O7^−	F(000) = 356
Mr = 344.25	Dx = 1.662 Mg m^−3 Dm = 1.66 Mg m^−3 Dm measured by flotation using a liquid mixture of carbon tetrachloride and bromoform
MonoclinicP21	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: P 2yb	Cell parameters from 25 reflections
a = 10.909 (4) Å	θ = 9.9–14.2°
b = 5.352 (3) Å	µ = 0.15 mm^−1
c = 12.474 (5) Å	T = 293 K
β = 109.142 (5)°	Needle, yellow
V = 688.0 (5) Å^3	0.3 × 0.2 × 0.12 mm
Z = 2

Data collection

Nonius MACH3 sealed tube diffractometer	1590 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.100
Graphite monochromator	θmax = 30.0°, θmin = 2.2°
ω/2θ scans	h = −1→15
Absorption correction: ψ scan (North et al., 1968)	k = −6→7
Tmin = 0.967, Tmax = 0.981	l = −17→16
3719 measured reflections	3 standard reflections every 60 min
2205 independent reflections	intensity decay: none

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.169	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.1016P)^2] where P = (Fo^2 + 2Fc^2)/3
2205 reflections	(Δ/σ)max = 0.001
226 parameters	Δρmax = 0.49 e Å^−3
10 restraints	Δρmin = −0.27 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	Occ. (<1)
O1A	0.5965 (3)	0.4460 (5)	0.9635 (2)	0.0504 (7)
O1B	0.4482 (2)	0.2628 (5)	0.8176 (2)	0.0441 (6)
H1B	0.4118	0.3986	0.8119	0.066*
C1	0.5557 (3)	0.2674 (6)	0.9041 (3)	0.0305 (6)
C2	0.6275 (3)	0.0212 (6)	0.9191 (3)	0.0342 (6)
H2	0.5666	−0.1190	0.9064	0.041*
C3	0.7083 (3)	0.0030 (10)	0.8391 (3)	0.0474 (9)	0.52
H3A	0.6755	−0.1281	0.7834	0.057*	0.52
H3B	0.7069	0.1599	0.7999	0.057*	0.52
C4	0.8447 (7)	−0.0576 (19)	0.9166 (7)	0.0455 (17)	0.52
H4A	0.8584	−0.2370	0.9212	0.055*	0.52
H4B	0.9086	0.0178	0.8878	0.055*	0.52
C5	0.8560 (3)	0.0392 (18)	1.0229 (4)	0.0767 (19)	0.52
H5A	0.8803	0.2142	1.0275	0.092*	0.52
H5B	0.9211	−0.0516	1.0821	0.092*	0.52
N1	0.7249 (3)	0.0087 (7)	1.0354 (2)	0.0439 (7)
H1A	0.7196	−0.1393	1.0679	0.053*
H1C	0.7104	0.1312	1.0792	0.053*
C31	0.7083 (3)	0.0030 (10)	0.8391 (3)	0.0474 (9)	0.48
H3C	0.7141	−0.1683	0.8158	0.057*	0.48
H3D	0.6718	0.1059	0.7722	0.057*	0.48
C41	0.8392 (7)	0.100 (2)	0.9115 (7)	0.052 (2)	0.48
H41A	0.9072	0.0239	0.8881	0.062*	0.48
H41B	0.8433	0.2793	0.9033	0.062*	0.48
C51	0.8560 (3)	0.0392 (18)	1.0229 (4)	0.0767 (19)	0.48
H5C	0.9037	0.1707	1.0728	0.092*	0.48
H5D	0.9049	−0.1149	1.0433	0.092*	0.48
O11	0.3453 (2)	0.6864 (5)	0.76837 (19)	0.0387 (6)
O12	0.5313 (2)	0.5462 (7)	0.6679 (2)	0.0537 (8)
O13	0.4166 (3)	0.3670 (6)	0.5124 (3)	0.0625 (8)
O14	0.1507 (3)	1.0047 (9)	0.2598 (2)	0.0617 (9)
O15	0.0693 (3)	1.3017 (9)	0.3313 (3)	0.0742 (11)
O16	0.1150 (3)	1.3073 (6)	0.7175 (3)	0.0636 (9)
O17	0.1876 (3)	0.9980 (7)	0.8269 (2)	0.0541 (8)
N11	0.4326 (2)	0.5253 (6)	0.5860 (3)	0.0380 (6)
N12	0.1304 (3)	1.1055 (7)	0.3397 (3)	0.0453 (8)
N13	0.1659 (2)	1.0970 (6)	0.7365 (3)	0.0393 (7)
C11	0.2968 (3)	0.7829 (6)	0.6720 (3)	0.0287 (6)
C12	0.3281 (3)	0.7069 (6)	0.5727 (3)	0.0318 (6)
C13	0.2725 (3)	0.8005 (7)	0.4665 (3)	0.0347 (7)
H13	0.2942	0.7374	0.4056	0.042*
C14	0.1825 (3)	0.9922 (7)	0.4508 (3)	0.0351 (7)
C15	0.1499 (3)	1.0857 (7)	0.5400 (3)	0.0359 (7)
H15	0.0919	1.2183	0.5289	0.043*
C16	0.2034 (3)	0.9823 (6)	0.6460 (3)	0.0308 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1A	0.0620 (15)	0.0286 (12)	0.0459 (13)	0.0129 (12)	−0.0022 (12)	−0.0044 (11)
O1B	0.0359 (11)	0.0293 (12)	0.0579 (15)	0.0028 (11)	0.0031 (10)	0.0071 (12)
C1	0.0372 (14)	0.0221 (13)	0.0344 (14)	0.0042 (13)	0.0147 (12)	0.0055 (12)
C2	0.0341 (13)	0.0204 (12)	0.0504 (17)	0.0022 (12)	0.0167 (13)	0.0045 (14)
C3	0.0468 (17)	0.056 (2)	0.0407 (17)	0.009 (2)	0.0160 (14)	−0.0078 (19)
C4	0.040 (4)	0.040 (4)	0.059 (5)	0.010 (3)	0.019 (3)	−0.001 (4)
C5	0.0315 (15)	0.142 (6)	0.056 (2)	0.013 (3)	0.0129 (16)	0.005 (4)
N1	0.0476 (14)	0.0489 (18)	0.0407 (14)	0.0229 (16)	0.0222 (12)	0.0195 (15)
C31	0.0468 (17)	0.056 (2)	0.0407 (17)	0.009 (2)	0.0160 (14)	−0.0078 (19)
C41	0.045 (4)	0.056 (6)	0.065 (6)	0.003 (5)	0.032 (4)	0.008 (5)
C51	0.0315 (15)	0.142 (6)	0.056 (2)	0.013 (3)	0.0129 (16)	0.005 (4)
O11	0.0398 (12)	0.0346 (11)	0.0396 (12)	0.0117 (11)	0.0100 (10)	0.0064 (11)
O12	0.0369 (12)	0.065 (2)	0.0578 (15)	0.0196 (14)	0.0135 (11)	0.0124 (16)
O13	0.0572 (16)	0.0412 (14)	0.096 (2)	0.0011 (14)	0.0345 (16)	−0.0226 (17)
O14	0.0555 (15)	0.087 (2)	0.0412 (13)	0.0027 (19)	0.0142 (12)	0.0135 (19)
O15	0.0712 (19)	0.072 (2)	0.074 (2)	0.033 (2)	0.0164 (17)	0.035 (2)
O16	0.0754 (19)	0.0422 (15)	0.073 (2)	0.0232 (16)	0.0235 (17)	−0.0087 (16)
O17	0.0542 (14)	0.069 (2)	0.0382 (13)	0.0208 (17)	0.0136 (11)	−0.0008 (15)
N11	0.0349 (12)	0.0294 (13)	0.0545 (16)	0.0061 (12)	0.0212 (12)	0.0087 (14)
N12	0.0335 (13)	0.0557 (19)	0.0420 (15)	0.0024 (15)	0.0059 (12)	0.0167 (16)
N13	0.0283 (11)	0.0399 (15)	0.0445 (16)	0.0039 (12)	0.0049 (11)	−0.0137 (14)
C11	0.0223 (11)	0.0239 (12)	0.0367 (15)	−0.0014 (11)	0.0052 (11)	−0.0016 (13)
C12	0.0254 (12)	0.0252 (13)	0.0435 (16)	0.0015 (11)	0.0094 (12)	0.0009 (14)
C13	0.0313 (13)	0.0302 (15)	0.0441 (17)	−0.0006 (14)	0.0143 (12)	−0.0007 (15)
C14	0.0285 (12)	0.0366 (16)	0.0368 (14)	−0.0015 (14)	0.0061 (11)	0.0077 (15)
C15	0.0238 (12)	0.0307 (15)	0.0467 (17)	0.0018 (12)	0.0027 (12)	0.0051 (14)
C16	0.0253 (12)	0.0283 (14)	0.0362 (14)	−0.0004 (12)	0.0065 (11)	−0.0054 (13)

Geometric parameters (Å, º)

O1A—C1	1.202 (4)	C41—H41B	0.9700
O1B—C1	1.308 (4)	O11—C11	1.255 (4)
O1B—H1B	0.8200	O12—N11	1.222 (4)
C1—C2	1.513 (4)	O13—N11	1.219 (4)
C2—N1	1.493 (4)	O14—N12	1.215 (5)
C2—C3	1.535 (5)	O15—N12	1.229 (5)
C2—H2	0.9800	O16—N13	1.243 (4)
C3—C4	1.520 (8)	O17—N13	1.197 (4)
C3—H3A	0.9700	N11—C12	1.466 (4)
C3—H3B	0.9700	N12—C14	1.448 (4)
C4—C5	1.392 (9)	N13—C16	1.456 (4)
C4—H4A	0.9700	C11—C16	1.438 (4)
C4—H4B	0.9700	C11—C12	1.447 (4)
C5—N1	1.497 (5)	C12—C13	1.359 (5)
C5—H5A	0.9700	C13—C14	1.388 (5)
C5—H5B	0.9700	C13—H13	0.9300
N1—H1A	0.9000	C14—C15	1.370 (5)
N1—H1C	0.9000	C15—C16	1.375 (4)
C41—H41A	0.9700	C15—H15	0.9300
C1—O1B—H1B	109.5	C2—N1—H1C	110.3
O1A—C1—O1B	125.0 (3)	C5—N1—H1C	110.3
O1A—C1—C2	123.0 (3)	H1A—N1—H1C	108.6
O1B—C1—C2	111.9 (3)	H41A—C41—H41B	108.4
N1—C2—C1	109.5 (3)	O13—N11—O12	124.2 (3)
N1—C2—C3	104.6 (2)	O13—N11—C12	117.5 (3)
C1—C2—C3	111.1 (3)	O12—N11—C12	118.3 (3)
N1—C2—H2	110.5	O14—N12—O15	123.3 (4)
C1—C2—H2	110.5	O14—N12—C14	118.6 (3)
C3—C2—H2	110.5	O15—N12—C14	118.1 (4)
C4—C3—C2	104.6 (4)	O17—N13—O16	121.2 (3)
C4—C3—H3A	110.8	O17—N13—C16	121.6 (3)
C2—C3—H3A	110.8	O16—N13—C16	117.0 (3)
C4—C3—H3B	110.8	O11—C11—C16	124.5 (3)
C2—C3—H3B	110.8	O11—C11—C12	124.1 (3)
H3A—C3—H3B	108.9	C16—C11—C12	111.4 (2)
C5—C4—C3	106.8 (5)	C13—C12—C11	125.2 (3)
C5—C4—H4A	110.4	C13—C12—N11	115.9 (3)
C3—C4—H4A	110.4	C11—C12—N11	118.9 (3)
C5—C4—H4B	110.4	C12—C13—C14	118.6 (3)
C3—C4—H4B	110.4	C12—C13—H13	120.7
H4A—C4—H4B	108.6	C14—C13—H13	120.7
C4—C5—N1	105.6 (5)	C15—C14—C13	121.0 (3)
C4—C5—H5A	110.6	C15—C14—N12	120.0 (3)
N1—C5—H5A	110.6	C13—C14—N12	118.8 (3)
C4—C5—H5B	110.6	C14—C15—C16	119.5 (3)
N1—C5—H5B	110.6	C14—C15—H15	120.2
H5A—C5—H5B	108.7	C16—C15—H15	120.2
C2—N1—C5	107.1 (3)	C15—C16—C11	124.1 (3)
C2—N1—H1A	110.3	C15—C16—N13	115.9 (3)
C5—N1—H1A	110.3	C11—C16—N13	119.8 (3)
O1A—C1—C2—N1	19.1 (5)	N11—C12—C13—C14	−173.3 (3)
O1B—C1—C2—N1	−163.0 (3)	C12—C13—C14—C15	−0.1 (5)
O1A—C1—C2—C3	−95.9 (4)	C12—C13—C14—N12	175.3 (3)
O1B—C1—C2—C3	82.0 (3)	O14—N12—C14—C15	−173.0 (3)
N1—C2—C3—C4	8.2 (6)	O15—N12—C14—C15	8.1 (5)
C1—C2—C3—C4	126.2 (5)	O14—N12—C14—C13	11.5 (5)
C2—C3—C4—C5	−27.1 (8)	O15—N12—C14—C13	−167.4 (3)
C3—C4—C5—N1	34.7 (9)	C13—C14—C15—C16	−2.4 (5)
C1—C2—N1—C5	−107.3 (5)	N12—C14—C15—C16	−177.8 (3)
C3—C2—N1—C5	11.8 (5)	C14—C15—C16—C11	2.1 (5)
C4—C5—N1—C2	−29.5 (8)	C14—C15—C16—N13	178.5 (3)
O11—C11—C12—C13	176.8 (3)	O11—C11—C16—C15	−179.5 (3)
C16—C11—C12—C13	−3.2 (4)	C12—C11—C16—C15	0.6 (4)
O11—C11—C12—N11	−6.9 (5)	O11—C11—C16—N13	4.2 (5)
C16—C11—C12—N11	173.1 (3)	C12—C11—C16—N13	−175.8 (3)
O13—N11—C12—C13	−42.6 (4)	O17—N13—C16—C15	166.8 (3)
O12—N11—C12—C13	135.4 (3)	O16—N13—C16—C15	−16.1 (4)
O13—N11—C12—C11	140.7 (3)	O17—N13—C16—C11	−16.6 (5)
O12—N11—C12—C11	−41.3 (4)	O16—N13—C16—C11	160.5 (3)
C11—C12—C13—C14	3.1 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1B—H1B···O11	0.82	1.71	2.515 (4)	165
N1—H1C···O11^i	0.90	2.20	2.952 (4)	141
N1—H1A···O17^ii	0.90	2.38	3.202 (5)	153
N1—H1C···O17^i	0.90	2.37	3.106 (5)	139

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

(II) 2-methylpyridinium picrate

Crystal data

C6H8N^+·C6H2N3O7^−	Z = 4
Mr = 322.24	F(000) = 664
TriclinicP1	Dx = 1.575 Mg m^−3 Dm = 1.57 Mg m^−3 Dm measured by flotation using a liquid mixture of xylene and carbon tetrachloride
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71069 Å
a = 8.211 (3) Å	Cell parameters from 25 reflections
b = 11.806 (4) Å	θ = 10.5–14.0°
c = 14.388 (4) Å	µ = 0.13 mm^−1
α = 85.428 (5)°	T = 293 K
β = 82.863 (5)°	Block, yellow
γ = 79.726 (4)°	0.25 × 0.2 × 0.15 mm
V = 1359.4 (8) Å^3

Data collection

Nonius MACH3 sealed tube diffractometer	3255 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.015
Graphite monochromator	θmax = 25.0°, θmin = 2.2°
ω/2θ scans	h = −1→9
Absorption correction: ψ scan (North et al., 1968)	k = −13→14
Tmin = 0.970, Tmax = 0.980	l = −17→17
5848 measured reflections	3 standard reflections every 60 min
4762 independent reflections	intensity decay: none

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.124	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0564P)^2 + 0.5564P] where P = (Fo^2 + 2Fc^2)/3
4762 reflections	(Δ/σ)max < 0.001
426 parameters	Δρmax = 0.32 e Å^−3
3 restraints	Δρmin = −0.27 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	Occ. (<1)
N11	0.0555 (2)	0.16222 (16)	0.47838 (15)	0.0456 (5)
H11	−0.0174	0.2122	0.4526	0.055*
C12	0.0662 (3)	0.1673 (2)	0.5690 (2)	0.0525 (6)
H12	−0.0034	0.2248	0.6024	0.063*
C13	0.1770 (4)	0.0900 (2)	0.6135 (2)	0.0617 (7)
H13	0.1856	0.0944	0.6769	0.074*
C14	0.2757 (4)	0.0056 (2)	0.5634 (3)	0.0673 (8)
H14	0.3510	−0.0496	0.5929	0.081*
C15	0.2646 (3)	0.0018 (2)	0.4707 (2)	0.0637 (8)
H15	0.3327	−0.0561	0.4370	0.076*
C16	0.1523 (3)	0.0835 (2)	0.42510 (19)	0.0495 (6)
C17	0.1331 (5)	0.0904 (3)	0.3243 (2)	0.0834 (10)
H17A	0.0179	0.1151	0.3156	0.125*
H17B	0.1713	0.0159	0.2997	0.125*
H17C	0.1977	0.1447	0.2919	0.125*
N21	0.5579 (2)	0.15320 (15)	0.02808 (15)	0.0448 (5)
H21	0.4770	0.1973	0.0580	0.054*
C22	0.5970 (3)	0.1786 (2)	−0.06285 (19)	0.0509 (6)
H22	0.5380	0.2436	−0.0919	0.061*
C23	0.7219 (3)	0.1108 (2)	−0.1136 (2)	0.0557 (7)
H23	0.7509	0.1289	−0.1769	0.067*
C24	0.8044 (3)	0.0144 (2)	−0.0686 (2)	0.0601 (7)
H24	0.8885	−0.0348	−0.1020	0.072*
C25	0.7638 (3)	−0.0094 (2)	0.0244 (2)	0.0551 (7)
H25	0.8208	−0.0745	0.0542	0.066*
C26	0.6387 (3)	0.06220 (19)	0.07506 (18)	0.0451 (6)
C27	0.5891 (4)	0.0470 (3)	0.1772 (2)	0.0691 (8)
H27A	0.6613	0.0801	0.2107	0.104*
H27B	0.5977	−0.0337	0.1952	0.104*
H27C	0.4762	0.0848	0.1918	0.104*
O31	0.26158 (19)	0.26093 (13)	0.10363 (13)	0.0509 (4)
O32	−0.0606 (3)	0.24090 (17)	0.03931 (16)	0.0750 (6)
O33	−0.1624 (4)	0.2549 (2)	0.18142 (17)	0.1059 (9)
O34	−0.2623 (2)	0.70981 (16)	0.14801 (16)	0.0689 (6)
O35	−0.0467 (2)	0.77191 (15)	0.18087 (14)	0.0626 (5)
O36	0.4826 (2)	0.53746 (15)	0.14666 (14)	0.0609 (5)
O37	0.5224 (2)	0.38072 (16)	0.07610 (17)	0.0736 (6)
N31	−0.0786 (2)	0.28612 (17)	0.11263 (17)	0.0482 (5)
N32	−0.1139 (3)	0.69502 (17)	0.15822 (15)	0.0472 (5)
N33	0.4295 (2)	0.45950 (17)	0.11523 (14)	0.0448 (5)
C31	0.1830 (3)	0.36127 (18)	0.11291 (16)	0.0385 (5)
C32	0.0035 (3)	0.38540 (18)	0.11985 (16)	0.0378 (5)
C33	−0.0943 (3)	0.48951 (19)	0.13400 (16)	0.0407 (5)
H33	−0.2097	0.4983	0.1373	0.049*
C34	−0.0160 (3)	0.58273 (18)	0.14340 (16)	0.0400 (5)
C35	0.1546 (3)	0.56928 (19)	0.13908 (16)	0.0400 (5)
H35	0.2047	0.6319	0.1473	0.048*
C36	0.2512 (3)	0.46385 (18)	0.12263 (16)	0.0376 (5)
O41	−0.2188 (2)	0.28144 (13)	0.41520 (13)	0.0549 (5)
O42	−0.6001 (4)	0.2878 (2)	0.31333 (18)	0.1024 (9)
O43	−0.5605 (3)	0.24710 (17)	0.45615 (17)	0.0802 (7)
O44	−0.7095 (2)	0.72988 (16)	0.32174 (16)	0.0715 (6)
O45	−0.4888 (2)	0.80333 (14)	0.32766 (14)	0.0625 (5)
O46	0.0213 (2)	0.56425 (17)	0.3695 (2)	0.0883 (8)
O47	0.0416 (6)	0.3939 (4)	0.4240 (3)	0.0793 (14)	0.71
O471	0.0475 (12)	0.3818 (8)	0.3708 (6)	0.058 (2)	0.29
N41	−0.5474 (2)	0.30597 (17)	0.38478 (17)	0.0500 (5)
N42	−0.5624 (3)	0.72029 (17)	0.33411 (15)	0.0487 (5)
N43	−0.0402 (2)	0.47909 (17)	0.38919 (15)	0.0499 (5)
C41	−0.2903 (3)	0.38214 (18)	0.39647 (16)	0.0384 (5)
C42	−0.4640 (3)	0.40615 (18)	0.38166 (16)	0.0377 (5)
C43	−0.5534 (3)	0.51179 (19)	0.36168 (16)	0.0405 (5)
H43	−0.6651	0.5206	0.3522	0.049*
C44	−0.4718 (3)	0.60678 (18)	0.35587 (16)	0.0398 (5)
C45	−0.3061 (3)	0.59369 (18)	0.36621 (16)	0.0405 (5)
H45	−0.2537	0.6579	0.3608	0.049*
C46	−0.2166 (3)	0.48558 (18)	0.38464 (16)	0.0389 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N11	0.0345 (11)	0.0340 (10)	0.0670 (14)	−0.0017 (8)	−0.0094 (9)	0.0011 (9)
C12	0.0461 (15)	0.0418 (14)	0.0685 (18)	−0.0048 (12)	−0.0005 (12)	−0.0117 (12)
C13	0.0624 (18)	0.0546 (16)	0.0719 (19)	−0.0135 (14)	−0.0211 (15)	0.0028 (14)
C14	0.0538 (17)	0.0448 (15)	0.103 (3)	−0.0008 (13)	−0.0277 (17)	0.0061 (16)
C15	0.0442 (16)	0.0369 (14)	0.106 (3)	0.0022 (12)	0.0056 (15)	−0.0197 (14)
C16	0.0427 (14)	0.0407 (13)	0.0663 (17)	−0.0139 (11)	0.0033 (12)	−0.0096 (12)
C17	0.094 (3)	0.093 (2)	0.071 (2)	−0.040 (2)	0.0044 (18)	−0.0146 (17)
N21	0.0339 (10)	0.0341 (10)	0.0650 (14)	−0.0004 (8)	−0.0059 (9)	−0.0066 (9)
C22	0.0486 (15)	0.0397 (13)	0.0650 (17)	−0.0039 (11)	−0.0191 (13)	0.0042 (12)
C23	0.0591 (17)	0.0494 (15)	0.0593 (16)	−0.0105 (13)	−0.0052 (13)	−0.0071 (12)
C24	0.0523 (16)	0.0470 (15)	0.078 (2)	−0.0003 (13)	0.0013 (14)	−0.0159 (14)
C25	0.0461 (15)	0.0324 (12)	0.085 (2)	0.0053 (11)	−0.0183 (14)	−0.0011 (12)
C26	0.0399 (13)	0.0343 (12)	0.0631 (16)	−0.0085 (10)	−0.0114 (11)	−0.0006 (11)
C27	0.075 (2)	0.0675 (19)	0.0670 (19)	−0.0209 (16)	−0.0092 (15)	0.0049 (14)
O31	0.0355 (9)	0.0335 (9)	0.0811 (12)	0.0008 (7)	−0.0040 (8)	−0.0073 (8)
O32	0.0802 (15)	0.0612 (12)	0.0909 (15)	−0.0254 (11)	−0.0022 (12)	−0.0310 (11)
O33	0.137 (2)	0.122 (2)	0.0800 (16)	−0.095 (2)	−0.0008 (15)	0.0086 (14)
O34	0.0368 (11)	0.0501 (11)	0.1154 (17)	0.0070 (8)	−0.0119 (10)	−0.0058 (10)
O35	0.0562 (11)	0.0395 (10)	0.0928 (14)	−0.0023 (9)	−0.0109 (10)	−0.0184 (9)
O36	0.0381 (10)	0.0553 (11)	0.0949 (15)	−0.0128 (8)	−0.0143 (9)	−0.0178 (10)
O37	0.0334 (10)	0.0583 (12)	0.1290 (18)	−0.0033 (9)	0.0053 (10)	−0.0371 (12)
N31	0.0386 (11)	0.0417 (11)	0.0666 (14)	−0.0105 (9)	−0.0124 (10)	0.0012 (11)
N32	0.0384 (12)	0.0376 (11)	0.0624 (13)	0.0008 (9)	−0.0031 (9)	−0.0038 (9)
N33	0.0308 (10)	0.0424 (11)	0.0617 (13)	−0.0056 (9)	−0.0055 (9)	−0.0060 (9)
C31	0.0334 (12)	0.0357 (12)	0.0455 (13)	−0.0034 (10)	−0.0044 (10)	−0.0024 (9)
C32	0.0325 (12)	0.0347 (12)	0.0475 (13)	−0.0082 (9)	−0.0069 (10)	−0.0013 (9)
C33	0.0277 (12)	0.0422 (13)	0.0512 (14)	−0.0035 (10)	−0.0052 (10)	−0.0007 (10)
C34	0.0341 (12)	0.0328 (11)	0.0511 (14)	0.0002 (9)	−0.0049 (10)	−0.0040 (10)
C35	0.0341 (12)	0.0350 (12)	0.0521 (14)	−0.0070 (9)	−0.0068 (10)	−0.0044 (10)
C36	0.0262 (11)	0.0390 (12)	0.0479 (13)	−0.0039 (9)	−0.0066 (9)	−0.0036 (10)
O41	0.0421 (10)	0.0350 (9)	0.0875 (13)	−0.0010 (7)	−0.0201 (9)	0.0048 (8)
O42	0.131 (2)	0.1091 (19)	0.0918 (17)	−0.0722 (18)	−0.0236 (16)	−0.0221 (14)
O43	0.0923 (16)	0.0548 (12)	0.1009 (17)	−0.0361 (12)	−0.0225 (13)	0.0215 (12)
O44	0.0405 (11)	0.0528 (11)	0.1144 (17)	0.0066 (9)	−0.0142 (11)	0.0127 (11)
O45	0.0605 (12)	0.0321 (9)	0.0925 (14)	−0.0063 (9)	−0.0060 (10)	0.0043 (9)
O46	0.0420 (11)	0.0525 (12)	0.174 (2)	−0.0187 (10)	−0.0195 (13)	0.0079 (13)
O47	0.050 (2)	0.053 (2)	0.141 (4)	−0.0125 (16)	−0.048 (3)	0.027 (3)
O471	0.031 (4)	0.055 (5)	0.085 (6)	0.000 (3)	−0.013 (5)	0.001 (5)
N41	0.0405 (12)	0.0391 (11)	0.0729 (15)	−0.0104 (9)	−0.0080 (11)	−0.0080 (11)
N42	0.0432 (12)	0.0367 (11)	0.0616 (13)	0.0016 (9)	−0.0028 (10)	0.0020 (9)
N43	0.0359 (11)	0.0437 (12)	0.0700 (14)	−0.0073 (10)	−0.0100 (10)	0.0044 (10)
C41	0.0365 (12)	0.0336 (12)	0.0448 (13)	−0.0034 (10)	−0.0066 (10)	−0.0023 (9)
C42	0.0354 (12)	0.0312 (11)	0.0476 (13)	−0.0082 (9)	−0.0050 (10)	−0.0027 (9)
C43	0.0313 (12)	0.0401 (12)	0.0494 (14)	−0.0031 (10)	−0.0065 (10)	−0.0029 (10)
C44	0.0376 (13)	0.0316 (11)	0.0479 (13)	−0.0009 (10)	−0.0046 (10)	0.0002 (9)
C45	0.0380 (13)	0.0337 (12)	0.0498 (14)	−0.0086 (10)	−0.0034 (10)	−0.0003 (10)
C46	0.0299 (11)	0.0386 (12)	0.0478 (13)	−0.0053 (10)	−0.0059 (10)	0.0005 (10)

Geometric parameters (Å, º)

N11—C12	1.324 (3)	O35—N32	1.227 (3)
N11—C16	1.335 (3)	O36—N33	1.225 (2)
N11—H11	0.8600	O37—N33	1.219 (2)
C12—C13	1.350 (4)	N31—C32	1.469 (3)
C12—H12	0.9300	N32—C34	1.439 (3)
C13—C14	1.361 (4)	N33—C36	1.447 (3)
C13—H13	0.9300	C31—C32	1.442 (3)
C14—C15	1.353 (4)	C31—C36	1.445 (3)
C14—H14	0.9300	C32—C33	1.358 (3)
C15—C16	1.394 (4)	C33—C34	1.393 (3)
C15—H15	0.9300	C33—H33	0.9300
C16—C17	1.472 (4)	C34—C35	1.376 (3)
C17—H17A	0.9600	C35—C36	1.372 (3)
C17—H17B	0.9600	C35—H35	0.9300
C17—H17C	0.9600	O41—C41	1.253 (3)
N21—C22	1.331 (3)	O42—N41	1.212 (3)
N21—C26	1.339 (3)	O43—N41	1.198 (3)
N21—H21	0.8600	O44—N42	1.227 (3)
C22—C23	1.357 (4)	O45—N42	1.232 (3)
C22—H22	0.9300	O46—N43	1.202 (3)
C23—C24	1.374 (4)	O47—O471	0.784 (8)
C23—H23	0.9300	O47—N43	1.214 (4)
C24—C25	1.357 (4)	O471—N43	1.271 (9)
C24—H24	0.9300	N41—C42	1.463 (3)
C25—C26	1.379 (4)	N42—C44	1.443 (3)
C25—H25	0.9300	N43—C46	1.447 (3)
C26—C27	1.480 (4)	C41—C42	1.443 (3)
C27—H27A	0.9600	C41—C46	1.446 (3)
C27—H27B	0.9600	C42—C43	1.359 (3)
C27—H27C	0.9600	C43—C44	1.398 (3)
O31—C31	1.252 (3)	C43—H43	0.9300
O32—N31	1.201 (3)	C44—C45	1.367 (3)
O33—N31	1.205 (3)	C45—C46	1.378 (3)
O34—N32	1.226 (3)	C45—H45	0.9300
C12—N11—C16	123.3 (2)	O37—N33—O36	121.85 (19)
C12—N11—H11	118.3	O37—N33—C36	119.61 (19)
C16—N11—H11	118.3	O36—N33—C36	118.51 (19)
N11—C12—C13	120.9 (2)	O31—C31—C32	121.3 (2)
N11—C12—H12	119.6	O31—C31—C36	127.2 (2)
C13—C12—H12	119.6	C32—C31—C36	111.43 (19)
C12—C13—C14	118.5 (3)	C33—C32—C31	126.2 (2)
C12—C13—H13	120.7	C33—C32—N31	118.0 (2)
C14—C13—H13	120.7	C31—C32—N31	115.80 (19)
C15—C14—C13	120.1 (3)	C32—C33—C34	117.7 (2)
C15—C14—H14	120.0	C32—C33—H33	121.1
C13—C14—H14	120.0	C34—C33—H33	121.1
C14—C15—C16	120.9 (2)	C35—C34—C33	121.0 (2)
C14—C15—H15	119.6	C35—C34—N32	119.0 (2)
C16—C15—H15	119.6	C33—C34—N32	120.0 (2)
N11—C16—C15	116.3 (2)	C36—C35—C34	120.3 (2)
N11—C16—C17	118.0 (3)	C36—C35—H35	119.9
C15—C16—C17	125.7 (3)	C34—C35—H35	119.9
C16—C17—H17A	109.5	C35—C36—C31	123.3 (2)
C16—C17—H17B	109.5	C35—C36—N33	116.17 (19)
H17A—C17—H17B	109.5	C31—C36—N33	120.50 (19)
C16—C17—H17C	109.5	O471—O47—N43	75.6 (8)
H17A—C17—H17C	109.5	O47—O471—N43	67.7 (8)
H17B—C17—H17C	109.5	O43—N41—O42	123.7 (2)
C22—N21—C26	123.1 (2)	O43—N41—C42	119.5 (2)
C22—N21—H21	118.5	O42—N41—C42	116.9 (2)
C26—N21—H21	118.5	O44—N42—O45	122.7 (2)
N21—C22—C23	120.8 (2)	O44—N42—C44	118.5 (2)
N21—C22—H22	119.6	O45—N42—C44	118.9 (2)
C23—C22—H22	119.6	O46—N43—O47	119.3 (3)
C22—C23—C24	117.9 (3)	O46—N43—O471	118.5 (5)
C22—C23—H23	121.0	O47—N43—O471	36.7 (4)
C24—C23—H23	121.0	O46—N43—C46	119.2 (2)
C25—C24—C23	120.4 (2)	O47—N43—C46	120.9 (3)
C25—C24—H24	119.8	O471—N43—C46	114.5 (5)
C23—C24—H24	119.8	O41—C41—C42	121.2 (2)
C24—C25—C26	120.7 (2)	O41—C41—C46	127.1 (2)
C24—C25—H25	119.7	C42—C41—C46	111.68 (18)
C26—C25—H25	119.7	C43—C42—C41	125.9 (2)
N21—C26—C25	117.1 (2)	C43—C42—N41	117.9 (2)
N21—C26—C27	117.8 (2)	C41—C42—N41	116.10 (19)
C25—C26—C27	125.1 (2)	C42—C43—C44	117.7 (2)
C26—C27—H27A	109.5	C42—C43—H43	121.2
C26—C27—H27B	109.5	C44—C43—H43	121.2
H27A—C27—H27B	109.5	C45—C44—C43	121.3 (2)
C26—C27—H27C	109.5	C45—C44—N42	119.4 (2)
H27A—C27—H27C	109.5	C43—C44—N42	119.3 (2)
H27B—C27—H27C	109.5	C44—C45—C46	120.2 (2)
O32—N31—O33	123.4 (2)	C44—C45—H45	119.9
O32—N31—C32	119.1 (2)	C46—C45—H45	119.9
O33—N31—C32	117.5 (2)	C45—C46—C41	123.1 (2)
O34—N32—O35	122.5 (2)	C45—C46—N43	116.4 (2)
O34—N32—C34	118.3 (2)	C41—C46—N43	120.46 (19)
O35—N32—C34	119.2 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···O41	0.86	1.83	2.656 (3)	160
N11—H11···O47	0.86	2.28	2.771 (5)	117
N11—H11···O471	0.86	2.35	2.906 (11)	123
N21—H21···O31	0.86	1.85	2.680 (3)	160
N21—H21···O37	0.86	2.30	2.783 (3)	116