4-(3,5-Dimethyl-1H-pyrazol-4-yl­methyl)-3,5-dimethyl-1H-pyrazol-2-ium dihydrogen phosphate: a combined X-ray and DFT study

The mol­ecular structure of the title salt, C₁₁H₁₇N₄⁺·H₂PO₄^-, has been determined from single-crystal X-ray analysis and compared with the structure calculated by density functional theory (DFT) at the BLYP level. The crystal packing in the title compound is stabilized primarily by inter­molecular N-H...O, O-H...N and O-H...O hydrogen bonds and [pi]-[pi] stacking inter­actions, and thus a three-dimensional supra­molecular honeycomb network consisting of R₄²(10), R₄⁴(14) and R₄⁴(24) ring motifs is established. The HOMO-LUMO energy gap (1.338 eV; HOMO is the highest occupied molecular orbital and LUMO is the lowest unoccupied molecular orbital) indicates a high chemical reactivity for the title compound.

S1. Comment

Hybrid organic–inorganic adducts are of current interest due to their intriguing architectures and potential applications in crystal engineering (Ma et al., 2009; Almeida Paz et al., 2004). The intermolecular forces between the different components of these hybrid crystals are provided by hydrogen-bonding or other non-covalent and non-ionic interactions (Almarsson & Zaworotko, 2004). Among the various compounds available for studying phosphoric acid–ligand interactions, amines and N-unsubstituted pyrazoles possessing one or more active lone pairs have been frequently used (Turki et al., 2006; Elaoud et al., 2000). The strong N—H···O hydrogen bonds and possible π–π stacking in these hybrid systems facilitate molecular assemblies with one-dimensional chains, two-dimensional layers or three-dimensional frameworks (Turner & Batten, 2008; Oueslati et al., 2006). The recurring structural ensembles in these structures, referred to as synthons (Desiraju, 1995), have been used as building blocks for designing new crystalline materials. Several monophosphate ion–organic ligand hybrid systems also display interesting physical properties, such as ferroelectricity, piezoelectricity and nonlinear optical phenomena (Masse et al., 1993).

The asymmetric unit of (I) consists of a 4-(3,5-dimethyl-1H-pyrazol-4-ylmethyl)-3,5-dimethyl-1H-pyrazol-2-ium (mdmp) cation and a dihydrogen phosphate counteranion (Fig. 1). The molecular conformation of the mdmp cation can be defined in terms of two torsion angles, C2—C3—C10—C5 = -44.3 (5)° and C3—C10—C5—C1 = -57.8 (5)°. The two pyrazole rings (A and B) are essentially planar, with r.m.s. fits of the atomic positions of 0.001 Å for ring A and 0.003 Å for ring B. The twist about the methylene bridge in the mdmp⁺ cation is reflected by the dihedral angle of 82.2 (2)° between the pyrazole rings; the corresponding value in a crystal of mdmp without any phosphate counterion is 81.7 (2)°. The deviation of the A/B dihedral angle in (I) [82.2 (2)°] from that observed in 4,4'-methylenebispyrazole [90.3 (1)°; Monge et al., 1994], in which both the pyrazole rings are unsubstituted, is probably due to non-bonding interactions between the methyl groups and the H atoms of the methylene bridge.

The N—N bond length in the pyrazole ring varies over a wide range, 1.234 (8)–1.385 (4) Å, depending on the substituents at the N atoms (Kettmann & Světlík, 2002). Accordingly, the adjacent C—N distances range from 1.288 (4) to 1.461 (8) Å. The conjugation within the π-electron system of the pyrazole rings in (I) is reflected in the N—N [1.346 (4)–1.349 (4) Å] and C—N [1.341 (4)–1.350 (4) Å] bond lengths (Table 1), which are intermediate between a single and a double bond, and agree with those reported in the literature (Monge et al., 1994; Masse & Tordjman, 1990). The P—O [1.496 (2)–1.523 (2) Å] and P—OH [1.535 (3)–1.565 (2) Å] bond distances in (I) are comparable with the reported values for related phosphates (Oueslati et al., 2006; Turki et al., 2006; Smirani et al., 2004).

As often observed in this kind of system, the two components of (I), i.e. the mdmp⁺ and H₂PO₄^- ions, are connected through a network of hydrogen bonds and aromatic π–π stacking, in which both pyrazole rings participate (Table 2). It is convenient to consider the substructures generated by different kinds of hydrogen bond acting individually, and then a combination of substructures to build a supramolecular assembly.

Centrosymmetrically related phosphate tetrahedra are connected through pairs of O3—H(O3)···O1 hydrogen bonds, which according to graph-set notation (Bernstein et al., 1995) can be described as an R₂²(8) ring centred at (1/2, 0, 1/2). Intermolecular N1—H(N1)···O1(x, 1 + y, 1 + z) and N2—H(N2)···O2(x, y, z) hydrogen bonds link the mdmp⁺ cation and phosphate anion into a polymeric C(13) chain propagating along the [001] direction, as shown in Fig. 2. Similarly, another C(13) chain running along the [010] direction is formed by intermolecular N3—H(N3)···O2(1 - x, -y, -z) and O4—H(O4)···N4(-x, 1 - y, -z) hydrogen bonds. The interactions mentioned above generate two types of supramolecular arrangement. In the first, two phosphate anions at (x, y, z) and (1 - x, -y, -z), together with the pyrazole B rings of mdmp⁺ cations at (1 - x, -y, -z) and (x, y, z), give rise to the formation of a cyclic R₄⁴(10) synthon having its symmetry centre at (1/2, 0, 0) (Fig. 3). The second R₄⁴(14) synthon (Fig. 3) is formed by two H₂PO₄^- anions at (x, y, z) and (-x, -y, -1 - z) and two pyrazole A rings of cations at (-x, 1 - y, -z) and (x, y - 1, z - 1), with a symmetry centre at (0, 0, -1/2). Propagation of the R₄⁴(10) and R₄⁴(14) rings through lattice translations generates an R₄⁴(24) synthon centred at (0, 1/2, 0), which in combination with other R₄⁴(X) rings forms a three-dimensional molecular framework. Viewed down (111), the three-dimensional network appears as a honeycomb structure with fused R₄⁴(X) rings (Fig. 3).

The molecular packing in (I) facilitates π–π interactions. The pyrazole B rings of centrosymmetrically related mdmp⁺ cations form a π–π stacking interaction across the inversion centre at (0, 0, 0); the interplanar spacing and centroid separation are 3.447 and 3.474 (3) Å, respectively, corresponding to a centroid offset of 0.432 Å. Similarly, the pyrazole A rings in the cations at (x, y, z) and (-x, 1 - y, 1 - z) form a second π–π stacking interaction across the inversion centre at (0, 1/2, 1/2), where the interplanar spacing and centroid separation are 3.586 and 4.462 (3) Å, respectively, corresponding to a centroid offset of 2.656 Å.

Solid-state density functional theory (DFT) calculations of (I) have been performed using the DMOL³ code (Delly, 1996, 1998) in the framework of a generalized-gradient approximation (GGA) (Perdew et al., 1996). The starting atomic coordinates were taken from the final X-ray refinement cycle. The geometry of the system was fully optimized using the hybrid exchange-correlation function BLYP (Becke, 1988; Lee et al., 1988) and a double numeric plus polarization (DNP) basis set. The cell parameters were kept fixed during the DFT calculations. No constraints were applied to bond lengths, bond angles or dihedral angles during the calculations, and all atoms were free to optimize.

A superposition of molecular conformations of (I), as established by the X-ray study and quantum mechanical calculations, shows good agreement (Fig. 4); the r.m.s. deviation between the coordinates obtained by geometry optimization and X-ray structure analysis is 0.025 Å. The net charges of atoms and dipoles, and the molecular orbital energy of (I) calculated at the BLYP level are listed in Table 3. The O and N atoms in (I) bear negative charges, while atom P1 bears a positive charge. The C atoms of the pyrazole rings with methyl substituents (C1, C2, C4 and C6) bear positive charges, while the bridging C (C10) and methyl C (C7, C8, C9 and C11) atoms bear negative charges. The bridge-head C atoms of ring A (C3) and ring B (C5) are almost neutral. The orbital energy level analysis for (I) at the BLYP level shows E_HOMO (highest occupied molecular orbital) and E_LUMO (lowest unoccupied molecular orbital) values of -3.791 and -2.453 eV, respectively. The HOMO–LUMO energy separation has been used as a simple indicator of kinetic stability (Aihara, 1999; Kim et al., 2005). The small HOMO–LUMO gap in (I) (1.338 eV) probably indicates a high chemical reactivity for the title compound. The charge densities for the HOMO and LUMO are shown in Fig. 5.

S2. Experimental

A suspension containing 3,5-dimethylpyrazole (0.192 g, 0.02 mmol) and H₃PO₄ (0.49 g, 5 mmol) in distilled water (30 ml) was stirred thoroughly for 30 min at ambient temperature. The suspension was transferred into a Teflon jacket in a stainless steel pressure vessel and kept in an oven at 433 K for 3 d under autogeneous pressure. The solution was then slowly cooled to ambient temperature to yield light-brown crystals of (I) suitable for X-ray diffraction analysis.

S3. Refinement

All H atoms were located in difference Fourier maps and treated as riding, with C—H = 0.96–0.97, N—H = 0.86 and O—H = 0.82 Å [Please check added text] and with U_iso(H) = 1.2U_eq(C,N) or 1.5U_eq(O). The isotropic displacement parameters for methyl H atoms were refined. The best crystal available was a thin plate (0.35 × 0.23 × 0.02 mm), which diffracted weakly at higher angles, so data collection was terminated at θ = 24.2°. Despite this, the title structure was refined using 99% of the possible data, which is considered adequate to give a precise structure.

Computing details

Data collection: APEX2 (Bruker, 2007); cell refinement: APEX2 (Bruker, 2007) and SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007) and XPREP (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997), DIAMOND (Brandenburg, 1999) and Mercury (Macrae et al., 2006); software used to prepare material for publication: PLATON (Spek, 2009).

Figures

	Fig. 1. A view of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. The dotted line indicates the N—H···O hydrogen bond. [Please check added text]
	Fig. 2. The network of hydrogen bonds forming a C(13) chain running along the [001] direction. H atoms not participating in this hydrogen-bond chain have been omitted for clarity. [Symmetry code: (i) x, 1 + y, 1 + z.]
	Fig. 3. Part of the crystal structure of (I), showing the combination of R4^4(10) (denoted a) and R4^4(14) (denoted b) rings fused alternately, producing R4^4(24) (denoted c) synthons, organized in a honeycomb type three-dimensional supramolecular hydrogen-bonded network. H atoms have been omitted for clarity.
	Fig. 4. Superposition of crystal packing diagrams of (I) obtained from the X-ray analysis (blue lines) and solid-state DFT calculation (red lines). [Colour will not be available in the printed journal - please use another means of distinguishing them]
	Fig. 5. Charge density of the HOMO orbital for (I) (top) and that of the LUMO orbital (bottom), both calculated by DFT.

4-(3,5-dimethyl-1H-pyrazol-4-ylmethyl)-3,5-dimethyl-1H- pyrazol-2-ium dihydrogen phosphate

Crystal data

C11H17N4^+·H2O4P^−	Z = 2
Mr = 302.27	F(000) = 320
Triclinic, P1	Dx = 1.421 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.649 (4) Å	Cell parameters from 1408 reflections
b = 10.504 (2) Å	θ = 2.3–24.2°
c = 10.538 (2) Å	µ = 0.21 mm^−1
α = 117.624 (3)°	T = 298 K
β = 104.576 (4)°	Flake, brown
γ = 94.663 (4)°	0.35 × 0.23 × 0.02 mm
V = 706.4 (5) Å^3

Data collection

Bruker APEXII Kappa CCD area-detector diffractometer	2239 independent reflections
Radiation source: fine-focus sealed tube	1536 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
ω and ϕ scans	θmax = 24.2°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −8→8
Tmin = 0.933, Tmax = 0.986	k = −12→12
4686 measured reflections	l = −12→12

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) = 0.136	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0706P)^2 + 0.0452P] where P = (Fo^2 + 2Fc^2)/3
2239 reflections	(Δ/σ)max = 0.017
189 parameters	Δρmax = 0.20 e Å^−3
0 restraints	Δρmin = −0.38 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
P1	0.39358 (13)	0.05811 (10)	−0.31027 (10)	0.0380 (3)
O1	0.3604 (3)	−0.0879 (2)	−0.4499 (3)	0.0489 (7)
O2	0.4609 (3)	0.0548 (3)	−0.1632 (2)	0.0494 (7)
O3	0.5414 (4)	0.1740 (3)	−0.3051 (3)	0.0508 (7)
H3A	0.5581	0.1402	−0.3874	0.076*
O4	0.2154 (4)	0.1154 (3)	−0.3088 (4)	0.0644 (8)
H4	0.2244	0.1867	−0.3215	0.097*
N1	0.0607 (4)	0.6786 (3)	0.3971 (3)	0.0440 (8)
H1	0.1403	0.7620	0.4517	0.053*
N2	0.2495 (4)	0.1435 (3)	0.0302 (3)	0.0435 (8)
H2	0.3054	0.1305	−0.0347	0.052*
N3	0.2854 (4)	0.0944 (3)	0.1294 (3)	0.0403 (7)
H3	0.3682	0.0459	0.1390	0.048*
N4	−0.1193 (4)	0.6618 (3)	0.3240 (3)	0.0415 (7)
C1	0.1130 (5)	0.2159 (4)	0.0482 (4)	0.0415 (9)
C2	0.0441 (7)	0.2893 (5)	−0.0399 (5)	0.0702 (13)
H2A	0.1072	0.3917	0.0169	0.123 (6)*
H2B	−0.0869	0.2810	−0.0587	0.123 (6)*
H2C	0.0677	0.2425	−0.1347	0.123 (6)*
C3	0.1765 (6)	0.1002 (5)	0.3339 (4)	0.0576 (11)
H3B	0.2521	0.0304	0.3280	0.123 (6)*
H3C	0.0531	0.0590	0.3226	0.123 (6)*
H3D	0.2286	0.1893	0.4304	0.123 (6)*
C4	0.1696 (5)	0.1342 (4)	0.2109 (4)	0.0372 (8)
C5	0.0586 (5)	0.2114 (3)	0.1613 (4)	0.0355 (8)
C6	−0.0901 (5)	0.2780 (4)	0.2208 (4)	0.0439 (9)
H6A	−0.0971	0.2583	0.3009	0.053*
H6B	−0.2085	0.2293	0.1398	0.053*
C7	−0.0611 (4)	0.4416 (3)	0.2815 (4)	0.0339 (8)
C8	−0.1938 (5)	0.5165 (4)	0.2529 (4)	0.0370 (8)
C9	−0.3950 (5)	0.4581 (4)	0.1581 (4)	0.0592 (11)
H9A	−0.4536	0.5391	0.1735	0.123 (6)*
H9B	−0.4545	0.3966	0.1870	0.123 (6)*
H9C	−0.4059	0.4011	0.0530	0.123 (6)*
C10	0.1002 (5)	0.5482 (4)	0.3742 (4)	0.0366 (8)
C11	0.2918 (5)	0.5410 (4)	0.4450 (4)	0.0567 (11)
H11A	0.3556	0.5111	0.3717	0.123 (6)*
H11B	0.2849	0.4708	0.4788	0.123 (6)*
H11C	0.3582	0.6366	0.5299	0.123 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0406 (6)	0.0362 (5)	0.0415 (5)	0.0136 (4)	0.0207 (4)	0.0186 (4)
O1	0.0562 (17)	0.0381 (14)	0.0461 (14)	0.0019 (12)	0.0256 (12)	0.0131 (12)
O2	0.0602 (17)	0.0654 (17)	0.0408 (14)	0.0311 (14)	0.0271 (12)	0.0329 (13)
O3	0.0596 (17)	0.0401 (14)	0.0474 (15)	0.0038 (12)	0.0274 (13)	0.0141 (12)
O4	0.0576 (18)	0.077 (2)	0.109 (2)	0.0405 (16)	0.0518 (17)	0.070 (2)
N1	0.044 (2)	0.0372 (18)	0.0471 (17)	0.0098 (14)	0.0177 (15)	0.0169 (15)
N2	0.050 (2)	0.0497 (19)	0.0426 (17)	0.0174 (15)	0.0276 (15)	0.0256 (15)
N3	0.0435 (18)	0.0400 (17)	0.0440 (17)	0.0192 (14)	0.0207 (14)	0.0215 (14)
N4	0.0386 (19)	0.0439 (18)	0.0445 (17)	0.0153 (14)	0.0158 (14)	0.0222 (15)
C1	0.047 (2)	0.040 (2)	0.041 (2)	0.0190 (18)	0.0202 (17)	0.0180 (17)
C2	0.103 (4)	0.081 (3)	0.063 (3)	0.053 (3)	0.046 (3)	0.051 (3)
C3	0.066 (3)	0.076 (3)	0.064 (3)	0.037 (2)	0.038 (2)	0.049 (2)
C4	0.039 (2)	0.0336 (19)	0.0414 (19)	0.0127 (16)	0.0199 (17)	0.0166 (16)
C5	0.040 (2)	0.0283 (18)	0.0389 (19)	0.0114 (16)	0.0189 (16)	0.0135 (15)
C6	0.045 (2)	0.041 (2)	0.052 (2)	0.0135 (17)	0.0249 (18)	0.0236 (18)
C7	0.032 (2)	0.0353 (19)	0.0363 (18)	0.0111 (16)	0.0163 (15)	0.0166 (16)
C8	0.039 (2)	0.036 (2)	0.0353 (18)	0.0122 (16)	0.0153 (16)	0.0149 (16)
C9	0.047 (3)	0.055 (2)	0.064 (3)	0.013 (2)	0.008 (2)	0.025 (2)
C10	0.037 (2)	0.042 (2)	0.0372 (19)	0.0189 (17)	0.0196 (16)	0.0203 (17)
C11	0.042 (2)	0.063 (3)	0.063 (3)	0.019 (2)	0.0154 (19)	0.030 (2)

Geometric parameters (Å, º)

P1—O1	1.496 (2)	C3—C4	1.485 (5)
P1—O2	1.523 (2)	C3—H3B	0.9600
P1—O3	1.565 (2)	C3—H3C	0.9600
P1—O4	1.535 (3)	C3—H3D	0.9600
O3—H3A	0.8200	C4—C5	1.390 (5)
O4—H4	0.8200	C5—C6	1.502 (5)
N1—N4	1.349 (4)	C6—C7	1.503 (5)
N1—C10	1.350 (4)	C6—H6A	0.9700
N1—H1	0.8600	C6—H6B	0.9700
N2—C1	1.341 (4)	C7—C10	1.373 (4)
N2—N3	1.346 (4)	C7—C8	1.392 (5)
N2—H2	0.8600	C8—C9	1.500 (5)
N3—C4	1.344 (4)	C9—H9A	0.9600
N3—H3	0.8600	C9—H9B	0.9600
N4—C8	1.341 (4)	C9—H9C	0.9600
C1—C5	1.377 (5)	C10—C11	1.493 (5)
C1—C2	1.489 (5)	C11—H11A	0.9600
C2—H2A	0.9600	C11—H11B	0.9600
C2—H2B	0.9600	C11—H11C	0.9600
C2—H2C	0.9600
O1—P1—O2	114.01 (15)	N3—C4—C5	107.9 (3)
O1—P1—O4	111.46 (17)	N3—C4—C3	122.0 (3)
O2—P1—O4	105.64 (15)	C5—C4—C3	130.1 (3)
O1—P1—O3	109.37 (13)	C1—C5—C4	106.5 (3)
O2—P1—O3	108.22 (15)	C1—C5—C6	126.8 (3)
O4—P1—O3	107.89 (16)	C4—C5—C6	126.6 (3)
P1—O3—H3A	109.5	C5—C6—C7	114.5 (3)
P1—O4—H4	109.5	C5—C6—H6A	108.6
N4—N1—C10	111.6 (3)	C7—C6—H6A	108.6
N4—N1—H1	124.2	C5—C6—H6B	108.6
C10—N1—H1	124.2	C7—C6—H6B	108.6
C1—N2—N3	109.5 (3)	H6A—C6—H6B	107.6
C1—N2—H2	125.2	C10—C7—C8	105.4 (3)
N3—N2—H2	125.2	C10—C7—C6	127.9 (3)
C4—N3—N2	108.3 (3)	C8—C7—C6	126.6 (3)
C4—N3—H3	125.8	N4—C8—C7	110.7 (3)
N2—N3—H3	125.8	N4—C8—C9	119.5 (3)
C8—N4—N1	105.2 (3)	C7—C8—C9	129.8 (3)
N2—C1—C5	107.7 (3)	C8—C9—H9A	109.5
N2—C1—C2	123.4 (3)	C8—C9—H9B	109.5
C5—C1—C2	128.9 (3)	H9A—C9—H9B	109.5
C1—C2—H2A	109.5	C8—C9—H9C	109.5
C1—C2—H2B	109.5	H9A—C9—H9C	109.5
H2A—C2—H2B	109.5	H9B—C9—H9C	109.5
C1—C2—H2C	109.5	N1—C10—C7	107.0 (3)
H2A—C2—H2C	109.5	N1—C10—C11	120.7 (3)
H2B—C2—H2C	109.5	C7—C10—C11	132.3 (3)
C4—C3—H3B	109.5	C10—C11—H11A	109.5
C4—C3—H3C	109.5	C10—C11—H11B	109.5
H3B—C3—H3C	109.5	H11A—C11—H11B	109.5
C4—C3—H3D	109.5	C10—C11—H11C	109.5
H3B—C3—H3D	109.5	H11A—C11—H11C	109.5
H3C—C3—H3D	109.5	H11B—C11—H11C	109.5
C1—N2—N3—C4	0.7 (4)	C4—C5—C6—C7	121.5 (4)
C10—N1—N4—C8	−0.3 (4)	C5—C6—C7—C10	−44.3 (5)
N3—N2—C1—C5	−0.7 (4)	C5—C6—C7—C8	134.6 (4)
N3—N2—C1—C2	177.6 (3)	N1—N4—C8—C7	0.2 (4)
N2—N3—C4—C5	−0.3 (4)	N1—N4—C8—C9	−179.4 (3)
N2—N3—C4—C3	−178.3 (3)	C10—C7—C8—N4	−0.1 (4)
N2—C1—C5—C4	0.5 (4)	C6—C7—C8—N4	−179.2 (3)
C2—C1—C5—C4	−177.7 (4)	C10—C7—C8—C9	179.5 (3)
N2—C1—C5—C6	179.9 (3)	C6—C7—C8—C9	0.4 (6)
C2—C1—C5—C6	1.7 (6)	N4—N1—C10—C7	0.2 (4)
N3—C4—C5—C1	−0.1 (4)	N4—N1—C10—C11	−179.9 (3)
C3—C4—C5—C1	177.7 (4)	C8—C7—C10—N1	0.0 (4)
N3—C4—C5—C6	−179.5 (3)	C6—C7—C10—N1	179.1 (3)
C3—C4—C5—C6	−1.8 (6)	C8—C7—C10—C11	−180.0 (4)
C1—C5—C6—C7	−57.8 (5)	C6—C7—C10—C11	−0.9 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^i	0.86	1.89	2.726 (4)	164
N2—H2···O2	0.86	1.96	2.789 (4)	161
N3—H3···O2^ii	0.86	1.79	2.649 (4)	178
O3—H3A···O1^iii	0.82	1.83	2.639 (3)	169
O4—H4···N4^iv	0.82	1.85	2.571 (4)	146

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