Hydrogen-bonded sheets in 2-(2-amino­phen­yl)-1H-benzimidazol-3-ium dihydrogen phosphate

The title salt, C₁₃H₁₂N₃⁺·H₂PO₄⁻, contains a nonplanar 2-(2-amino­phenyl)-1H-benzimidazol-3-ium cation and two different dihydrogen phosphate anions, both situated on twofold rotation axes in the space group C2. The anions are linked by O—H...O hydrogen bonds into chains of R₂²(8) rings. The anion chains are linked by the cations, via hydrogen-bonding complementarities and electrostatic inter­actions, giving rise to a sheet structure with alternating rows of organic cations and inorganic anions. Comparison of this structure with that of the pure amine reveals that the two compounds generate characteristically different sheet structures. The anion–anion chain serves as a template for the assembly of the cations, suggesting a possible application in the design of solid-state materials.

S1. Comment

Anions serve as useful building blocks for the formation of self-assembled supramolecular architectures in both organic and inorganic systems (Gale, 2000, 2001). They can assemble in well defined fashions and, by relying on the combined strength of electrostatic and hydrogen-bonding interactions, it is possible to generate reproducible topologies. Partially protonated oxoanions derived from sulfuric and phosphoric acids are two such interesting systems (Braga et al., 2004). We are particularly interested in observing how dihydrogen phosphate would assemble and its role in molecular association. In this context, we report here the preparation and structural characterization of the title salt, 2-(2-aminophenyl)-1H-benzimidazol-3-ium dihydrogen phosphate, (I). Benzimidazolylaniline (BIMD) is a derivative of pharmaceutically useful benzimidazole compounds (Velík et al., 2004, and references therein).

The asymmetric unit of (I) (Fig. 1) comprises one BIMD cation, and one-half of two different dihydrogen phosphate (DPH) anions (P1/O1/O2 and P2/O3/O4) lying across two-fold rotation axes along (0, y, 1/2) and (0, y, 0), respectively. BIMD is non-planar, with the planes of the benzimidazole heterocycle (N1/C2/N3/C3a/C4–C7/C7a) and aniline (N14/C8–C13) making an angle of 38.6 (1)°; the N1—C2—C8—C13 torsion angle is 36.7 (4)°. In DPH, the two P—O distances for the OH groups, as expected, are significantly longer [P1—O2 = 1.561 (2) and P2—O4 = 1.563 (2) Å] than the other two [P1—O1 = 1.5015 (17) and P2—O3 = 1.4996 (17) Å].

In (I), the H₂PO₄^- units are linked by two O—H···O hydrogen bonds (Table 1) to form an R²₂(8) ring (Bernstein et al., 1995). The hydrogen bond involving atom O2 as donor is the more nearly linear of these and has a shorter H···O distance. The R²₂(8) ring motif, extending on either side, gives rise to a chain (Fig. 2). This hydrogen-bonded anionic framework serves as template for the assembly of the cations, resulting in a sheet structure parallel to the bc plane with alternate rows of cations and anions. Due to amine–imine tautomerism, there are two equivalent salt links, N3⁺—H3···O1^- and N1⁺—H1···O3^i- [symmetry code: (i) x, 1 + y, z]. The sheet, apart from the salt bridges, is stabilized by N14—H14A···O1 hydrogen bonds. Intersheet contact is maintained by C11—H11···O4ⁱⁱ [symmetry code: (ii) 1/2 + x, 1/2 + y, 1 + z] and van der Waals interactions. Atom H14B does not participate in any non-bonded interaction scheme. However, this is not an unusual observation in the case of amino groups. The characteristic sheet structure in the present example is mainly the result of the complimentary nature of the molecules, i.e. one with an excess of donors and the other deficient in them, in an attempt to make up this numerical imbalance. Using the idea of hydrogen-bond complementarity, which involves both geometric factors and a suitable balance of the number of hydrogen-bond donors and acceptors, several self-assembled supramolecular architectures have been designed (Aakerby & Schultheiss, 2007, and references therein).

The structure of the desalted compound, namely 2-(1H-benzimidazol-2-yl)aniline, (II), in space group Pbca has been reported previously (Das et al., 2003; Shylaja et al., 2008). It is interesting to compare the packing of salt (I) with its pure derivative, (II), primarily because (II) is deficient in acceptors while (I) has an excess of them. The packing in (II) is characterized by BIMD molecules forming a sheet structure in the ab plane. BIMD molecules are arranged into a linear chain via intermolecular N—H···N hydrogen bonds along the b axis. These chains are linked into sheets by N—H···π and C—H···π interactions (shown in Supplementary Fig. 3). In view of the inadequate number of acceptors, the energetically next favourable π-acceptors are utilized to fulfil this imbalance and maximize lattice interactions. The hierarchical choice of intermolecular interactions is a phenomenological rule governing supramolecular assembly.

A search of the Cambridge Structural Database (CSD, Version 5.28; Allen, 2002) revealed 27 examples of hydrogen-bonded DPH, forming R²₂(8) rings and extending into infinite linear chains (CSD refcodes: ACUXIG, BIDPEJ, CLQUON01, CPAIMZ, DASNUH, DAYHOB, DUNHID, EDUQUP, EJEGAB, FAXGUH, FEDMIL, FIJHEL, GEXXAI, GOLTOQ, IDAPE101, ISUZIF, LELXIJ, MATKAT, MPHAZP, NELVUV, PAMRAX, PROCPH, REZNEP, SASBIX, SEGGER, SODCUJ and XAPRUC). FAXGUH and IDAPE101 are examples of metal-coordinated DPH. HAHGED [Not in list above?] is another example containing extended nonlinear chains of R²₂(8) type, forming a honeycomb structure (Braga et al., 2004). Some interesting packings have been observed. The oxoanion–oxoanion one-dimensional motif in NELVUV gives rise to a sheath-like structure of cations around it (Light et al., 2001). In LELXIJ, the linear DPH chains form a hydrated layer structure, resulting in alternating cationic and anionic layers (Braga et al., 1999) The oligomeric assembly of DPH observed in (I) serves as an interesting example of a template-assembled supramolecular architecture.

S2. Experimental

Initially, compound (II) was synthesized by the standard phosphoric acid cyclization, i.e. the Phillips method (Phillips, 1928a,b), by heating equimolar quantities of technical grade 1,2 phenylenediamine and 2-aminobenzoic acid (anthranilic acid) in polyphosphoric acid for 4 h at about 473 K [yield 60%; m.p. 484 (1) K]. Compound (I) was prepared from (II) by dissolving it in ethanol and adding dropwise an equimolar quantity of 85% syrupy orthophosphoric acid. The resulting grey precipitate was filtered off, washed with water and dried at 323–333 K in an oven [yield 86%; m.p. 545 (1) K]. Compound (I) was crystallized from a mixture of methanol and water (70:30 v/v) by slow evaporation; colourless crystals appeared within a week.

The second-harmonic generation (SHG) efficiency of (I) was measured relative to potassium dihydrogen phosphate (KDP) by a standard powder technique (Kurtz & Perry, 1968) using a Nd:YAG laser (λ = 1064 nm, 8 ns pulse and 3.4 mJ P^-1 [P is the poise, a unit of viscosity. Should it be `per pulse'?]). The compound exhibits a weak activity of 0.15 times that of KDP.

As the CSD search was quite time-consuming it was carried out in stages. Firstly, a sub-database of 132 structures containing dimeric DPH units was created. The final search for infinitely extended chains was then carried out using this sub-database, yielding 27 hits.

S3. Refinement

H atoms attached to N and O atoms were refined isotropically, with N—H and O—H distances restrained in the ranges 0.88 (1)–0.89 (1) and 0.81 (1)–0.82 (1) Å, respectively, and with U_iso(H) = 1.5U_eq(N,O). H atoms attached to aromatic C atoms were positioned geometrically, with C_ar—H distances of 0.93 Å, and refined as riding on their parent atoms, with U_iso(H) = 1.2U_eq(C). The correct absolute structure was established by the anomalous dispersion effect of the P atoms (1224 Bijvoet pairs), as described by the Flack parameter value of 0.02 (10) (Flack, 1983; Flack & Bernardinelli, 1999). In the refined structure, compound (I) contains an intramolecular N14—H14A···N3 short contact, as also observed in (II).

Computing details

Data collection: SMART (Bruker, 2003); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus (Bruker, 2003); program(s) used to solve structure: SHELXTL (Bruker, 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2003).

Figures

	Fig. 1. A view of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. Dashed lines represent hydrogen bonds. [Symmetry codes (i): -x, y, 1 - z; (ii) -x, y, -z.]
	Fig. 2. The hydrogen-bonded sheet structure of (I) in the bc plane, formed by alternating rows of organic cations and inorganic anions. Only relevant H atoms are shown. [Symmetry code: (i) x, 1 + y, z.]

2-(2-aminophenyl)-1H-benzimidazol-3-ium dihydrogen phosphate

Crystal data

C13H12N3^+·H2O4P^−	F(000) = 640
Mr = 307.24	Dx = 1.531 Mg m^−3
Monoclinic, C2	Melting point: 534(2) K
Hall symbol: C 2y	Mo Kα radiation, λ = 0.71073 Å
a = 18.3700 (11) Å	Cell parameters from 929 reflections
b = 10.0050 (13) Å	θ = 2.4–25.7°
c = 7.9145 (14) Å	µ = 0.23 mm^−1
β = 113.575 (2)°	T = 295 K
V = 1333.2 (3) Å^3	Block, colourless
Z = 4	0.33 × 0.28 × 0.22 mm

Data collection

Bruker SMART CCD area-detector diffractometer	2612 independent reflections
Radiation source: fine-focus sealed tube	2374 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
ϕ and ω scans	θmax = 26.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −22→22
Tmin = 0.91, Tmax = 0.96	k = −12→12
6829 measured reflections	l = −9→9

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.090	w = 1/[σ^2(Fo^2) + (0.0476P)^2 + 0.3082P] where P = (Fo^2 + 2Fc^2)/3
S = 1.11	(Δ/σ)max < 0.001
2612 reflections	Δρmax = 0.32 e Å^−3
209 parameters	Δρmin = −0.18 e Å^−3
7 restraints	Absolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.02 (10)

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.

Weighted least-squares planes through the starred atoms (Nardelli, Musatti, Domiano & Andreetti Ric.Sci.(1965),15(II—A),807). Equation of the plane: m1*X+m2*Y+m3*Z=d

Plane 1 m1 = 0.62947(0.00047) m2 = -0.26366(0.00089) m3 = -0.73093(0.00040) D = -3.46050(0.00518) Atom d s d/s (d/s)**2 N1 * -0.0076 0.0022 - 3.449 11.898 C2 * -0.0083 0.0029 - 2.894 8.373 N3 * 0.0107 0.0022 4.899 24.005 C3a * 0.0072 0.0026 2.756 7.593 C4 * -0.0068 0.0028 - 2.404 5.779 C5 * -0.0165 0.0031 - 5.300 28.092 C6 * 0.0068 0.0030 2.284 5.216 C7 * 0.0137 0.0029 4.783 22.878 C7a * -0.0040 0.0025 - 1.597 2.551 C8 - 0.0301 0.0025 - 11.890 141.371 C9 0.7029 0.0029 244.988 60019.324 C13 - 0.7899 0.0029 - 276.312 76348.516 N14 1.5113 0.0032 468.881 219849.781 ============ Sum((d/s)**2) for starred atoms 116.385 Chi-squared at 95% for 6 degrees of freedom: 12.60 The group of atoms deviates significantly from planarity

Plane 2 m1 = 0.60730(0.00098) m2 = 0.39628(0.00083) m3 = -0.68858(0.00077) D = 0.67513(0.00605) Atom d s d/s (d/s)**2 C8 * -0.0075 0.0026 - 2.956 8.736 C9 * -0.0194 0.0029 - 6.765 45.770 C10 * -0.0044 0.0033 - 1.353 1.831 C11 * 0.0018 0.0034 0.537 0.288 C12 * 0.0057 0.0032 1.775 3.151 C13 * 0.0086 0.0029 2.993 8.960 N14 * 0.0221 0.0032 6.931 48.038 N1 0.7257 0.0022 330.007 108904.555 C2 0.0242 0.0029 8.342 69.597 N3 - 0.6138 0.0022 - 283.960 80633.555 ============ Sum((d/s)**2) for starred atoms 116.774 Chi-squared at 95% for 4 degrees of freedom: 9.49 The group of atoms deviates significantly from planarity

Dihedral angles formed by LSQ-planes Plane - plane angle (s.u.) angle (s.u.) 1 2 38.64 (0.06) 141.36 (0.06)

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
P1	0.0000	0.18197 (8)	0.5000	0.0298 (2)
P2	0.0000	0.05644 (8)	0.0000	0.0282 (2)
O1	−0.03639 (11)	0.26119 (16)	0.3249 (2)	0.0352 (4)
O2	0.06749 (13)	0.0893 (2)	0.4951 (3)	0.0566 (7)
H2O	0.060 (2)	0.049 (4)	0.401 (3)	0.085*
O3	0.03355 (11)	−0.02401 (16)	0.1742 (2)	0.0369 (5)
O4	−0.06809 (12)	0.1499 (2)	0.0005 (3)	0.0510 (6)
H4O	−0.063 (2)	0.171 (4)	0.104 (2)	0.077*
N1	−0.02780 (12)	0.7261 (2)	0.1688 (3)	0.0331 (5)
H1	−0.0022 (15)	0.8015 (17)	0.182 (4)	0.040*
N3	−0.04513 (12)	0.5167 (2)	0.2145 (3)	0.0326 (5)
H3	−0.0402 (16)	0.4372 (15)	0.264 (3)	0.039*
N14	0.11603 (15)	0.3903 (3)	0.3100 (5)	0.0596 (7)
H14A	0.0658 (9)	0.375 (4)	0.240 (5)	0.089*
H14B	0.1521 (18)	0.328 (3)	0.365 (5)	0.089*
C2	0.00674 (16)	0.6167 (3)	0.2632 (4)	0.0304 (5)
C3a	−0.11729 (14)	0.5624 (3)	0.0841 (3)	0.0325 (5)
C4	−0.18945 (15)	0.4994 (3)	−0.0056 (4)	0.0419 (6)
H4	−0.1969	0.4100	0.0153	0.050*
C5	−0.24971 (17)	0.5760 (3)	−0.1275 (4)	0.0447 (7)
H5	−0.2995	0.5378	−0.1895	0.054*
C6	−0.23815 (16)	0.7087 (3)	−0.1603 (4)	0.0445 (7)
H6	−0.2802	0.7564	−0.2459	0.053*
C7	−0.16685 (16)	0.7722 (3)	−0.0712 (4)	0.0429 (6)
H7	−0.1596	0.8613	−0.0940	0.051*
C7a	−0.10589 (14)	0.6963 (3)	0.0553 (3)	0.0322 (5)
C8	0.08968 (14)	0.6125 (3)	0.3992 (3)	0.0329 (5)
C9	0.13909 (15)	0.5017 (3)	0.4171 (4)	0.0376 (6)
C10	0.21806 (17)	0.5107 (3)	0.5474 (4)	0.0494 (7)
H10	0.2525	0.4394	0.5613	0.059*
C11	0.24504 (18)	0.6218 (4)	0.6537 (4)	0.0558 (9)
H11	0.2974	0.6248	0.7396	0.067*
C12	0.19614 (18)	0.7295 (4)	0.6361 (4)	0.0536 (8)
H12	0.2152	0.8047	0.7098	0.064*
C13	0.11930 (16)	0.7255 (3)	0.5094 (4)	0.0416 (6)
H13	0.0863	0.7988	0.4964	0.050*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0370 (5)	0.0224 (4)	0.0240 (4)	0.000	0.0061 (4)	0.000
P2	0.0346 (5)	0.0214 (4)	0.0243 (4)	0.000	0.0071 (4)	0.000
O1	0.0473 (11)	0.0257 (9)	0.0286 (9)	0.0040 (8)	0.0111 (8)	0.0058 (8)
O2	0.0638 (13)	0.0614 (16)	0.0302 (11)	0.0307 (12)	0.0038 (10)	−0.0067 (10)
O3	0.0524 (12)	0.0242 (9)	0.0291 (10)	0.0014 (8)	0.0111 (9)	0.0011 (8)
O4	0.0522 (11)	0.0583 (15)	0.0306 (10)	0.0217 (11)	0.0039 (9)	−0.0053 (10)
N1	0.0332 (11)	0.0234 (11)	0.0399 (11)	−0.0017 (9)	0.0116 (9)	0.0044 (9)
N3	0.0339 (11)	0.0279 (11)	0.0311 (11)	−0.0011 (9)	0.0079 (9)	0.0046 (9)
N14	0.0471 (15)	0.0436 (15)	0.087 (2)	−0.0017 (13)	0.0257 (15)	−0.0115 (15)
C2	0.0347 (12)	0.0272 (11)	0.0296 (12)	0.0006 (10)	0.0131 (10)	0.0024 (10)
C3a	0.0347 (12)	0.0313 (12)	0.0307 (13)	−0.0004 (11)	0.0122 (10)	0.0006 (11)
C4	0.0428 (15)	0.0376 (14)	0.0438 (16)	−0.0077 (12)	0.0157 (13)	−0.0046 (13)
C5	0.0330 (13)	0.0488 (18)	0.0432 (16)	−0.0015 (12)	0.0057 (12)	−0.0083 (13)
C6	0.0374 (15)	0.0511 (19)	0.0380 (14)	0.0089 (13)	0.0078 (12)	0.0026 (14)
C7	0.0447 (16)	0.0364 (14)	0.0450 (15)	0.0081 (12)	0.0153 (13)	0.0093 (13)
C7a	0.0338 (13)	0.0307 (13)	0.0318 (13)	0.0029 (11)	0.0128 (10)	0.0029 (11)
C8	0.0344 (13)	0.0307 (12)	0.0320 (13)	−0.0015 (11)	0.0116 (10)	0.0047 (12)
C9	0.0371 (14)	0.0349 (13)	0.0438 (15)	0.0002 (12)	0.0193 (12)	0.0065 (12)
C10	0.0371 (15)	0.0525 (18)	0.0569 (18)	0.0071 (14)	0.0171 (14)	0.0176 (16)
C11	0.0388 (15)	0.075 (2)	0.0427 (17)	−0.0114 (18)	0.0049 (13)	0.0146 (18)
C12	0.0559 (18)	0.0568 (19)	0.0409 (16)	−0.0209 (16)	0.0117 (14)	−0.0064 (14)
C13	0.0456 (15)	0.0360 (14)	0.0400 (15)	−0.0036 (12)	0.0138 (12)	0.0016 (12)

Geometric parameters (Å, º)

P1—O1^i	1.5015 (17)	C3a—C4	1.380 (4)
P1—O1	1.5015 (17)	C3a—C7a	1.389 (4)
P1—O2^i	1.561 (2)	C4—C5	1.375 (4)
P1—O2	1.561 (2)	C4—H4	0.9300
P2—O3^ii	1.4996 (17)	C5—C6	1.385 (5)
P2—O3	1.4996 (17)	C5—H5	0.9300
P2—O4^ii	1.563 (2)	C6—C7	1.370 (4)
P2—O4	1.563 (2)	C6—H6	0.9300
O2—H2O	0.81 (3)	C7—C7a	1.391 (3)
O4—H4O	0.81 (2)	C7—H7	0.9300
N1—C2	1.334 (3)	C8—C13	1.399 (4)
N1—C7a	1.387 (3)	C8—C9	1.404 (4)
N1—H1	0.87 (2)	C9—C10	1.407 (4)
N3—C2	1.327 (3)	C10—C11	1.362 (5)
N3—C3a	1.392 (3)	C10—H10	0.9300
N3—H3	0.875 (17)	C11—C12	1.374 (5)
N14—C9	1.361 (4)	C11—H11	0.9300
N14—H14A	0.88 (3)	C12—C13	1.366 (4)
N14—H14B	0.89 (3)	C12—H12	0.9300
C2—C8	1.473 (4)	C13—H13	0.9300
O1^i—P1—O1	116.28 (14)	C3a—C4—H4	121.8
O1^i—P1—O2^i	110.82 (10)	C4—C5—C6	121.7 (3)
O1—P1—O2^i	105.76 (10)	C4—C5—H5	119.1
O1^i—P1—O2	105.76 (10)	C6—C5—H5	119.1
O1—P1—O2	110.82 (10)	C7—C6—C5	122.3 (3)
O2^i—P1—O2	107.14 (19)	C7—C6—H6	118.9
O3^ii—P2—O3	115.08 (14)	C5—C6—H6	118.9
O3^ii—P2—O4^ii	110.73 (10)	C6—C7—C7a	116.5 (3)
O3—P2—O4^ii	106.74 (10)	C6—C7—H7	121.7
O3^ii—P2—O4	106.74 (10)	C7a—C7—H7	121.7
O3—P2—O4	110.73 (10)	N1—C7a—C3a	106.6 (2)
O4^ii—P2—O4	106.53 (18)	N1—C7a—C7	132.5 (2)
P1—O2—H2O	118 (3)	C3a—C7a—C7	120.9 (2)
P2—O4—H4O	113 (3)	C13—C8—C9	120.1 (2)
C2—N1—C7a	108.9 (2)	C13—C8—C2	117.6 (2)
C2—N1—H1	122.0 (19)	C9—C8—C2	122.3 (3)
C7a—N1—H1	129.1 (19)	N14—C9—C8	123.8 (3)
C2—N3—C3a	109.2 (2)	N14—C9—C10	118.8 (3)
C2—N3—H3	128.3 (18)	C8—C9—C10	117.3 (3)
C3a—N3—H3	121.9 (18)	C11—C10—C9	121.2 (3)
C9—N14—H14A	121 (3)	C11—C10—H10	119.4
C9—N14—H14B	107 (3)	C9—C10—H10	119.4
H14A—N14—H14B	125 (4)	C10—C11—C12	121.0 (3)
N3—C2—N1	109.3 (2)	C10—C11—H11	119.5
N3—C2—C8	127.1 (3)	C12—C11—H11	119.5
N1—C2—C8	123.6 (3)	C13—C12—C11	119.6 (3)
C4—C3a—C7a	122.2 (3)	C13—C12—H12	120.2
C4—C3a—N3	131.7 (3)	C11—C12—H12	120.2
C7a—C3a—N3	106.1 (2)	C12—C13—C8	120.7 (3)
C5—C4—C3a	116.4 (3)	C12—C13—H13	119.6
C5—C4—H4	121.8	C8—C13—H13	119.6
C3a—N3—C2—N1	−0.7 (3)	C6—C7—C7a—N1	−179.8 (3)
C3a—N3—C2—C8	179.1 (3)	C6—C7—C7a—C3a	1.7 (4)
C7a—N1—C2—N3	0.7 (3)	N3—C2—C8—C13	−143.1 (3)
C7a—N1—C2—C8	−179.2 (2)	N1—C2—C8—C13	36.7 (4)
C2—N3—C3a—C4	−178.4 (3)	N3—C2—C8—C9	38.5 (4)
C2—N3—C3a—C7a	0.5 (3)	N1—C2—C8—C9	−141.7 (3)
C7a—C3a—C4—C5	0.8 (4)	C13—C8—C9—N14	−177.1 (3)
N3—C3a—C4—C5	179.5 (3)	C2—C8—C9—N14	1.3 (4)
C3a—C4—C5—C6	0.9 (4)	C13—C8—C9—C10	−0.5 (4)
C4—C5—C6—C7	−1.3 (5)	C2—C8—C9—C10	177.9 (2)
C5—C6—C7—C7a	0.0 (4)	N14—C9—C10—C11	177.7 (3)
C2—N1—C7a—C3a	−0.4 (3)	C8—C9—C10—C11	0.9 (4)
C2—N1—C7a—C7	−179.1 (3)	C9—C10—C11—C12	−0.6 (5)
C4—C3a—C7a—N1	179.0 (2)	C10—C11—C12—C13	−0.3 (5)
N3—C3a—C7a—N1	0.0 (3)	C11—C12—C13—C8	0.7 (4)
C4—C3a—C7a—C7	−2.1 (4)	C9—C8—C13—C12	−0.4 (4)
N3—C3a—C7a—C7	178.9 (2)	C2—C8—C13—C12	−178.8 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···O3	0.81 (3)	1.82 (3)	2.619 (3)	172 (4)
O4—H4O···O1	0.81 (2)	1.85 (2)	2.641 (3)	163 (4)
N1—H1···O3^iii	0.87 (2)	1.88 (2)	2.736 (3)	169 (3)
N3—H3···O1	0.88 (2)	1.82 (2)	2.686 (3)	170 (2)
N14—H14A···O1	0.88 (3)	2.51 (3)	3.128 (4)	128 (3)
C11—H11···O4^iv	0.93	2.52	3.444 (4)	172
N14—H14A···N3	0.88 (3)	2.44 (3)	3.022 (4)	125 (3)

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