Two hydro­chlorides of 7-methyl-3,7,11,17-tetra­aza­bi­cyclo­[11.3.1]­heptadeca-1(17),13,15-triene

The X-ray structure determinations of the two title com­pounds, namely 7-methyl-7,17-di­aza-3,11-diazo­niabi­cyclo[11.3.1]­hep­ta­deca-1(17),13,15-triene dichloride monohydrate, C₁₄H₂₆N₄²⁺·2Cl^-·H₂O, (I), and 7-methyl-17-aza-3,7,11-triazo­niabi­cyclo­[11.3.1]­heptadeca-1(17),13,15-triene 2.826-chloride 0.174-nitrate, C₁₄H₂₇N₄³⁺·2.826Cl^-·0.174NO₃^-, (II), are re­ported. Protonation occurs at the secondary amine N atoms in (I) and at all three amine N atoms in (II) to which the Cl^- ions are linked via N-H...Cl hydrogen bonds. The macrocyclic hole is quite different in both structures, as is observed by comparing particularly the N3...N4 distances [2.976 (4) and 4.175 (4) Å for (I) and (II), respectively]. In (II), a Cl^- ion alternates with an NO₃^- ion in a disordered structure.

Computing details

For both compounds, data collection: SMART (Siemens, 1994); cell refinement: SMART; data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97.

(I) 7-Methyl-3,7,11,17-tetraazabicyclo[11.3.1]-heptadeca-1(17),13,15-triene dihydrochloride monohydrate

Crystal data

C14H26N4^2+·2Cl^−·H2O	F(000) = 728
Mr = 339.30	Dx = 1.246 Mg m^−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
a = 16.7683 (3) Å	Cell parameters from 6095 reflections
b = 9.7089 (2) Å	θ = 3–56.6°
c = 11.116 (2) Å	µ = 0.36 mm^−1
β = 90.9963 (11)°	T = 293 K
V = 1809.4 (3) Å^3	Needle, colourless
Z = 4	0.70 × 0.20 × 0.15 mm

Data collection

Siemens CCD SMART diffractometer	2812 independent reflections
Radiation source: fine-focus sealed tube	2656 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
ω scans	θmax = 28.2°, θmin = 2.4°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −16→22
Tmin = 0.785, Tmax = 0.948	k = −12→12
6531 measured reflections	l = −12→14

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) = 0.112	Calculated w = 1/[σ^2(Fo^2) + (0.0749P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max = 0.002
2812 reflections	Δρmax = 0.29 e Å^−3
208 parameters	Δρmin = −0.29 e Å^−3
3 restraints	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.02 (6)

Special details

Experimental. Colourless crystals of C₁₄H₂₆N₄·H₂O. 2 Cl (I) and C₁₄H₂₇N₄.2.826Cl.0.174NO₃ (II) crystallized from ethanol were used for structure determination. The reason for using such a large crystal (0.70 mm) for the structure determination of (I) was that we had few crystals and all attemps to cut them before mounting in the diffractometer leds to the breaking in the longitudinal direction of the needles. The chosen crystals were mounted on a glass fiber using an epoxy resin. Data were collected using a Siemens SMART CCD area detector single-crystal diffractometer with graphite monochromated Mo Kα radiation (λ = 0.71073 Å). Preliminary unit cell constants were determined with a set of 45 narrow frames (0.3 in ω scans. A total of 1420 frames of intensity data were collected with a frame width of 0.3° per frame in ω (and counting time of 10 and 20 s/frame for (I) and (II) respectively at a crystal to detector distance of 4.5 cm. Both series of data were corrected for absorption (Sheldrick, 1996). The structures were solved by direct methods.

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
Cl1	0.81700 (4)	0.83287 (6)	0.55323 (5)	0.04561 (17)
Cl2	0.58601 (5)	0.52347 (8)	0.53363 (7)	0.0614 (2)
O1W	0.9975 (2)	0.7336 (4)	0.5626 (5)	0.1050 (15)
N1	0.82743 (13)	0.7522 (2)	0.26247 (18)	0.0346 (4)
N2	0.68646 (15)	0.6942 (2)	0.3611 (2)	0.0401 (5)
N3	0.69080 (15)	1.0765 (3)	0.36737 (19)	0.0433 (5)
N4	0.85779 (13)	1.0194 (2)	0.2967 (2)	0.0361 (4)
C1	0.89915 (14)	0.7910 (2)	0.2247 (2)	0.0336 (4)
C2	0.94779 (18)	0.7064 (3)	0.1559 (2)	0.0445 (6)
H2	0.9971	0.7366	0.1294	0.053*
C3	0.9195 (2)	0.5747 (3)	0.1285 (3)	0.0534 (7)
H3	0.9502	0.5152	0.0828	0.064*
C4	0.8464 (2)	0.5330 (3)	0.1689 (3)	0.0497 (7)
H4	0.8271	0.4454	0.1512	0.060*
C5	0.80172 (17)	0.6244 (2)	0.2370 (2)	0.0392 (5)
C6	0.7240 (2)	0.5816 (3)	0.2905 (3)	0.0526 (7)
H6A	0.6876	0.5534	0.2264	0.063*
H6B	0.7330	0.5028	0.3427	0.063*
C9	0.6358 (2)	0.9925 (3)	0.4388 (3)	0.0557 (8)
H9A	0.5987	1.0534	0.4786	0.067*
H9B	0.6663	0.9445	0.5008	0.067*
C7	0.6371 (2)	0.7908 (4)	0.2872 (3)	0.0518 (7)
H7A	0.6014	0.7384	0.2350	0.062*
H7B	0.6717	0.8452	0.2367	0.062*
C8	0.5882 (2)	0.8868 (4)	0.3654 (4)	0.0607 (8)
H8A	0.5576	0.8311	0.4204	0.073*
H8B	0.5506	0.9358	0.3139	0.073*
C10	0.7361 (2)	1.1692 (3)	0.4486 (3)	0.0524 (7)
H10A	0.7543	1.1174	0.5185	0.063*
H10B	0.7009	1.2413	0.4764	0.063*
C11	0.8075 (2)	1.2348 (3)	0.3895 (3)	0.0545 (8)
H11A	0.8242	1.3135	0.4374	0.065*
H11B	0.7908	1.2689	0.3110	0.065*
C12	0.8792 (2)	1.1403 (3)	0.3736 (3)	0.0481 (6)
H12A	0.9221	1.1913	0.3368	0.058*
H12B	0.8979	1.1083	0.4518	0.058*
C13	0.92735 (16)	0.9309 (3)	0.2662 (2)	0.0402 (5)
H13A	0.9620	0.9207	0.3365	0.048*
H13B	0.9577	0.9743	0.2032	0.048*
C14	0.6459 (2)	1.1588 (4)	0.2769 (3)	0.0607 (8)
H14A	0.6824	1.2130	0.2312	0.091*
H14B	0.6092	1.2185	0.3169	0.091*
H14C	0.6168	1.0981	0.2238	0.091*
H2NA	0.722 (3)	0.745 (5)	0.398 (4)	0.073*
H2NB	0.661 (3)	0.662 (5)	0.410 (5)	0.073*
H4NA	0.825 (3)	0.979 (5)	0.339 (4)	0.073*
H4NB	0.832 (3)	1.051 (5)	0.221 (4)	0.073*
H1W	0.963 (3)	0.771 (5)	0.601 (4)	0.073*
H2W	1.025 (3)	0.794 (4)	0.532 (4)	0.073*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0499 (3)	0.0495 (3)	0.0371 (3)	0.0023 (3)	−0.0053 (2)	0.0016 (2)
Cl2	0.0585 (4)	0.0587 (4)	0.0678 (5)	−0.0034 (4)	0.0199 (3)	0.0161 (3)
O1W	0.0577 (18)	0.0572 (17)	0.200 (5)	0.0060 (13)	−0.001 (2)	0.025 (2)
N1	0.0407 (10)	0.0295 (9)	0.0339 (9)	0.0016 (8)	0.0055 (8)	−0.0019 (7)
N2	0.0406 (11)	0.0393 (11)	0.0407 (11)	−0.0079 (9)	0.0088 (9)	−0.0005 (8)
N3	0.0471 (12)	0.0491 (12)	0.0337 (10)	0.0141 (10)	0.0020 (9)	0.0024 (8)
N4	0.0406 (11)	0.0300 (9)	0.0378 (10)	−0.0032 (8)	−0.0008 (9)	−0.0037 (7)
C1	0.0353 (11)	0.0347 (10)	0.0308 (10)	0.0049 (9)	0.0002 (9)	0.0041 (8)
C2	0.0447 (14)	0.0459 (13)	0.0431 (14)	0.0132 (11)	0.0074 (11)	0.0046 (10)
C3	0.0712 (19)	0.0399 (13)	0.0495 (15)	0.0197 (14)	0.0164 (14)	−0.0007 (11)
C4	0.075 (2)	0.0271 (11)	0.0475 (14)	0.0054 (12)	0.0116 (14)	−0.0021 (9)
C5	0.0519 (14)	0.0292 (10)	0.0366 (12)	−0.0010 (10)	0.0040 (10)	0.0009 (8)
C6	0.0627 (18)	0.0345 (12)	0.0610 (17)	−0.0113 (12)	0.0145 (14)	−0.0092 (11)
C9	0.0576 (18)	0.0638 (18)	0.0461 (15)	0.0245 (15)	0.0178 (13)	0.0089 (12)
C7	0.0486 (15)	0.0597 (17)	0.0469 (15)	−0.0011 (13)	−0.0046 (12)	0.0035 (12)
C8	0.0416 (15)	0.068 (2)	0.072 (2)	0.0109 (14)	0.0078 (14)	0.0152 (16)
C10	0.071 (2)	0.0489 (15)	0.0374 (14)	0.0199 (14)	−0.0006 (13)	−0.0081 (10)
C11	0.081 (2)	0.0313 (12)	0.0504 (15)	0.0045 (13)	−0.0126 (15)	−0.0110 (10)
C12	0.0581 (17)	0.0387 (12)	0.0471 (14)	−0.0054 (12)	−0.0091 (12)	−0.0105 (10)
C13	0.0361 (12)	0.0421 (12)	0.0426 (13)	−0.0017 (10)	0.0023 (10)	−0.0017 (9)
C14	0.062 (2)	0.072 (2)	0.0484 (16)	0.0170 (16)	−0.0030 (14)	0.0131 (13)

Geometric parameters (Å, º)

N1—C1	1.335 (3)	C1—C13	1.508 (4)
N1—C5	1.342 (3)	C2—C3	1.395 (4)
N2—C7	1.489 (4)	C3—C4	1.375 (5)
N2—C6	1.491 (4)	C4—C5	1.394 (4)
N3—C9	1.474 (4)	C5—C6	1.501 (4)
N3—C10	1.477 (4)	C9—C8	1.527 (6)
N3—C14	1.481 (4)	C7—C8	1.523 (5)
N4—C12	1.492 (3)	C10—C11	1.516 (5)
N4—C13	1.492 (3)	C11—C12	1.525 (5)
C1—C2	1.395 (4)
C1—N1—C5	118.8 (2)	N1—C5—C4	122.0 (3)
C7—N2—C6	114.0 (3)	N1—C5—C6	116.8 (2)
C9—N3—C10	109.1 (2)	C4—C5—C6	121.2 (2)
C9—N3—C14	110.4 (3)	N2—C6—C5	112.5 (2)
C10—N3—C14	109.7 (3)	N3—C9—C8	114.2 (2)
C12—N4—C13	113.7 (2)	N2—C7—C8	111.7 (3)
N1—C1—C2	123.1 (2)	C7—C8—C9	115.8 (3)
N1—C1—C13	115.9 (2)	N3—C10—C11	113.1 (2)
C2—C1—C13	121.0 (2)	C10—C11—C12	115.3 (2)
C1—C2—C3	117.4 (3)	N4—C12—C11	111.0 (3)
C4—C3—C2	120.0 (2)	N4—C13—C1	110.2 (2)
C3—C4—C5	118.8 (2)
C5—N1—C1—C2	2.4 (4)	C10—N3—C9—C8	−177.1 (2)
C5—N1—C1—C13	−174.5 (2)	C14—N3—C9—C8	62.2 (3)
N1—C1—C2—C3	−1.3 (4)	C6—N2—C7—C8	169.4 (3)
C13—C1—C2—C3	175.5 (2)	N2—C7—C8—C9	68.0 (4)
C1—C2—C3—C4	0.0 (4)	N3—C9—C8—C7	52.9 (4)
C2—C3—C4—C5	0.1 (4)	C9—N3—C10—C11	166.2 (2)
C1—N1—C5—C4	−2.3 (4)	C14—N3—C10—C11	−72.7 (3)
C1—N1—C5—C6	174.8 (2)	N3—C10—C11—C12	−75.6 (3)
C3—C4—C5—N1	1.1 (4)	C13—N4—C12—C11	173.6 (2)
C3—C4—C5—C6	−175.9 (3)	C10—C11—C12—N4	60.3 (3)
C7—N2—C6—C5	85.2 (3)	C12—N4—C13—C1	161.7 (2)
N1—C5—C6—N2	2.2 (4)	N1—C1—C13—N4	−23.8 (3)
C4—C5—C6—N2	179.3 (3)	C2—C1—C13—N4	159.2 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4NA···Cl1	0.83 (5)	2.77 (5)	3.456 (2)	140 (4)
N2—H2NA···Cl1	0.87 (5)	2.48 (5)	3.317 (3)	162 (4)
N2—H2NB···Cl2	0.77 (5)	2.31 (5)	3.062 (2)	168 (5)
N4—H4NA···N3	0.83 (5)	2.46 (5)	2.973 (3)	121 (4)
N4—H4NB···Cl1^i	0.99 (5)	2.19 (5)	3.128 (2)	158 (4)
O1W—H1W···Cl1	0.81 (3)	2.57 (5)	3.177 (3)	133 (5)
O1W—H2W···Cl2^ii	0.82 (3)	2.45 (4)	3.200 (4)	152 (4)

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

(II) 7-Methyl-3,7,11,17-tetraazabicyclo[11.3.1]-heptadeca-1(17),13,15-triene trihydrochloride

Crystal data

C14H27N4^3+·2.826Cl^−·0.174NO3^−	F(000) = 770
Mr = 362.37	Dx = 1.329 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.7592 (3) Å	Cell parameters from 4178 reflections
b = 10.8825 (3) Å	θ = 3–56.6°
c = 15.4988 (3) Å	µ = 0.48 mm^−1
β = 93.9033 (13)°	T = 293 K
V = 1810.50 (8) Å^3	Irregular, colourless
Z = 4	0.30 × 0.15 × 0.10 mm

Data collection

Siemens CCD SMART diffractometer	4252 independent reflections
Radiation source: fine-focus sealed tube	2388 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.056
ω scans	θmax = 28.3°, θmin = 2.2°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −11→13
Tmin = 0.868, Tmax = 0.953	k = −14→5
9674 measured reflections	l = −20→20

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	Calculated w = 1/[σ^2(Fo^2) + (0.0457P)^2] where P = (Fo^2 + 2Fc^2)/3
4252 reflections	(Δ/σ)max = 0.053
224 parameters	Δρmax = 0.33 e Å^−3
6 restraints	Δρmin = −0.25 e Å^−3

Special details

Experimental. Colourless crystals of C₁₄H₂₆N₄·H₂O. 2 Cl (I) and C₁₄H₂₇N₄.2.826Cl.0.174NO₃ (II) crystallized from ethanol were used for structure determination. The reason for using such a large crystal (0.70 mm) for the structure determination of (I) was that we had few crystals and all attemps to cut them before mounting in the diffractometer leds to the breaking in the longitudinal direction of the needles. The chosen crystals were mounted on a glass fiber using an epoxy resin. Data were collected using a Siemens SMART CCD area detector single-crystal diffractometer with graphite monochromated Mo Kα radiation (λ = 0.71073 Å). Preliminary unit cell constants were determined with a set of 45 narrow frames (0.3 in ω scans. A total of 1420 frames of intensity data were collected with a frame width of 0.3° per frame in ω (and counting time of 10 and 20 s/frame for (I) and (II) respectively at a crystal to detector distance of 4.5 cm. Both series of data were corrected for absorption (Sheldrick, 1996). The structures were solved by direct methods.

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)
Cl1	0.76168 (7)	0.91368 (6)	0.08908 (4)	0.0433 (2)
Cl2	0.71122 (7)	0.96745 (7)	0.40628 (4)	0.0471 (2)
Cl3	0.71992 (11)	0.98723 (15)	0.76760 (8)	0.0465 (5)	0.826 (4)
N5	0.717 (2)	0.973 (4)	0.7695 (17)	0.099 (4)	0.174 (4)
O1	0.7333 (14)	0.9219 (16)	0.7047 (10)	0.099 (4)	0.174 (4)
O2	0.8004 (15)	0.9904 (15)	0.8194 (11)	0.099 (4)	0.174 (4)
O3	0.6269 (16)	1.0291 (16)	0.7770 (10)	0.099 (4)	0.174 (4)
N1	0.5643 (2)	0.1747 (2)	0.08888 (14)	0.0414 (6)
N2	0.7029 (2)	0.1116 (2)	0.23680 (15)	0.0412 (6)
N3	0.9915 (2)	0.2649 (2)	0.09213 (15)	0.0373 (6)
N4	0.6914 (2)	0.1191 (2)	−0.05944 (16)	0.0417 (6)
C1	0.5224 (3)	0.2226 (3)	0.01315 (19)	0.0424 (7)
C2	0.4484 (3)	0.3264 (3)	0.0066 (2)	0.0497 (8)
H2	0.4210	0.3578	−0.0472	0.060*
C3	0.4162 (3)	0.3824 (3)	0.0817 (2)	0.0534 (9)
H3	0.3662	0.4521	0.0791	0.064*
C4	0.4584 (3)	0.3347 (3)	0.1601 (2)	0.0494 (8)
H4	0.4375	0.3711	0.2115	0.059*
C5	0.5328 (3)	0.2310 (3)	0.16112 (18)	0.0403 (7)
C6	0.5798 (3)	0.1710 (3)	0.24411 (18)	0.0500 (8)
H6A	0.5868	0.2323	0.2896	0.060*
H6B	0.5201	0.1097	0.2602	0.060*
C7	0.8040 (3)	0.2022 (3)	0.22812 (18)	0.0424 (7)
H7A	0.8078	0.2569	0.2777	0.051*
H7B	0.7852	0.2514	0.1767	0.051*
C8	0.9294 (3)	0.1415 (3)	0.22205 (18)	0.0424 (7)
H8A	0.9189	0.0682	0.1867	0.051*
H8B	0.9609	0.1161	0.2795	0.051*
C9	1.0251 (3)	0.2244 (3)	0.18372 (18)	0.0471 (8)
H9A	1.0365	0.2969	0.2199	0.056*
H9B	1.1042	0.1814	0.1853	0.056*
C10	0.9667 (3)	0.1594 (3)	0.03129 (18)	0.0428 (7)
H10A	0.9103	0.1027	0.0570	0.051*
H10B	1.0444	0.1162	0.0248	0.051*
C11	0.9112 (3)	0.1955 (3)	−0.05761 (18)	0.0503 (8)
H11A	0.9239	0.1280	−0.0969	0.060*
H11B	0.9574	0.2654	−0.0774	0.060*
C12	0.7736 (3)	0.2282 (3)	−0.06457 (19)	0.0474 (8)
H12A	0.7568	0.2847	−0.0184	0.057*
H12B	0.7539	0.2700	−0.1191	0.057*
C13	0.5572 (3)	0.1510 (3)	−0.06484 (18)	0.0497 (8)
H13A	0.5082	0.0761	−0.0695	0.060*
H13B	0.5376	0.1993	−0.1166	0.060*
C14	1.0954 (3)	0.3446 (3)	0.0638 (2)	0.0641 (10)
H14A	1.1081	0.4122	0.1032	0.096*
H14B	1.0739	0.3754	0.0067	0.096*
H14C	1.1705	0.2970	0.0635	0.096*
H2NA	0.719 (3)	0.064 (3)	0.289 (2)	0.077*
H2NB	0.700 (3)	0.060 (3)	0.186 (2)	0.077*
H3N	0.923 (3)	0.315 (3)	0.097 (2)	0.077*
H4NA	0.705 (3)	0.061 (3)	−0.111 (2)	0.077*
H4NB	0.714 (3)	0.078 (3)	−0.008 (2)	0.077*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0421 (5)	0.0365 (4)	0.0523 (4)	−0.0002 (3)	0.0098 (3)	−0.0019 (3)
Cl2	0.0627 (6)	0.0369 (4)	0.0423 (4)	−0.0108 (4)	0.0081 (3)	0.0011 (3)
Cl3	0.0474 (9)	0.0487 (7)	0.0441 (6)	0.0019 (5)	0.0085 (5)	−0.0043 (5)
N5	0.110 (10)	0.092 (8)	0.094 (8)	0.021 (6)	0.002 (6)	−0.035 (6)
O1	0.110 (10)	0.092 (8)	0.094 (8)	0.021 (6)	0.002 (6)	−0.035 (6)
O2	0.110 (10)	0.092 (8)	0.094 (8)	0.021 (6)	0.002 (6)	−0.035 (6)
O3	0.110 (10)	0.092 (8)	0.094 (8)	0.021 (6)	0.002 (6)	−0.035 (6)
N1	0.0369 (15)	0.0451 (15)	0.0429 (13)	0.0059 (12)	0.0072 (11)	0.0002 (11)
N2	0.0467 (17)	0.0404 (15)	0.0374 (13)	−0.0034 (13)	0.0095 (12)	0.0044 (11)
N3	0.0327 (15)	0.0346 (13)	0.0458 (13)	−0.0031 (11)	0.0114 (11)	−0.0026 (11)
N4	0.0377 (17)	0.0477 (16)	0.0401 (13)	0.0038 (13)	0.0048 (11)	−0.0016 (12)
C1	0.0293 (18)	0.0470 (18)	0.0509 (18)	0.0041 (14)	0.0021 (14)	−0.0005 (14)
C2	0.039 (2)	0.0478 (19)	0.062 (2)	0.0056 (16)	−0.0025 (15)	0.0057 (16)
C3	0.038 (2)	0.0385 (18)	0.083 (3)	0.0084 (15)	0.0039 (17)	−0.0028 (17)
C4	0.0371 (19)	0.0482 (19)	0.065 (2)	0.0018 (16)	0.0171 (16)	−0.0122 (16)
C5	0.0297 (18)	0.0422 (17)	0.0501 (17)	−0.0028 (14)	0.0110 (14)	−0.0041 (14)
C6	0.049 (2)	0.057 (2)	0.0463 (17)	0.0003 (17)	0.0225 (15)	−0.0001 (15)
C7	0.051 (2)	0.0334 (16)	0.0445 (16)	−0.0022 (15)	0.0126 (14)	0.0006 (13)
C8	0.043 (2)	0.0398 (16)	0.0435 (16)	−0.0005 (15)	−0.0014 (14)	0.0029 (13)
C9	0.0381 (19)	0.0493 (19)	0.0532 (18)	0.0016 (15)	−0.0018 (15)	0.0003 (15)
C10	0.0385 (19)	0.0349 (16)	0.0564 (18)	−0.0006 (14)	0.0134 (14)	−0.0064 (14)
C11	0.048 (2)	0.058 (2)	0.0464 (17)	−0.0024 (17)	0.0161 (15)	−0.0050 (15)
C12	0.052 (2)	0.0457 (18)	0.0440 (16)	0.0042 (17)	0.0033 (15)	0.0009 (14)
C13	0.039 (2)	0.064 (2)	0.0446 (17)	0.0060 (17)	−0.0035 (14)	−0.0027 (15)
C14	0.055 (2)	0.061 (2)	0.079 (2)	−0.0228 (19)	0.0219 (18)	−0.0026 (19)

Geometric parameters (Å, º)

N5—O2	1.155 (16)	N4—C12	1.486 (4)
N5—O3	1.160 (16)	C1—C2	1.381 (4)
N5—O1	1.172 (16)	C1—C13	1.507 (4)
N1—C1	1.335 (3)	C2—C3	1.379 (4)
N1—C5	1.340 (3)	C3—C4	1.370 (4)
N2—C7	1.481 (4)	C4—C5	1.383 (4)
N2—C6	1.485 (4)	C5—C6	1.499 (4)
N3—C10	1.498 (3)	C7—C8	1.511 (4)
N3—C14	1.503 (4)	C8—C9	1.520 (4)
N3—C9	1.507 (3)	C10—C11	1.516 (4)
N4—C13	1.482 (4)	C11—C12	1.519 (4)
O2—N5—O3	117.6 (16)	C4—C3—C2	119.7 (3)
O2—N5—O1	120.0 (16)	C3—C4—C5	118.4 (3)
O3—N5—O1	120.5 (16)	N1—C5—C4	122.9 (3)
C1—N1—C5	117.8 (3)	N1—C5—C6	115.3 (3)
C7—N2—C6	112.4 (2)	C4—C5—C6	121.7 (3)
C10—N3—C14	111.3 (2)	N2—C6—C5	112.0 (2)
C10—N3—C9	113.0 (2)	N2—C7—C8	112.3 (2)
C14—N3—C9	107.9 (2)	C7—C8—C9	113.3 (2)
C13—N4—C12	113.0 (2)	N3—C9—C8	114.6 (2)
N1—C1—C2	122.9 (3)	N3—C10—C11	114.6 (2)
N1—C1—C13	114.6 (3)	C10—C11—C12	116.5 (2)
C2—C1—C13	122.5 (3)	N4—C12—C11	112.9 (3)
C3—C2—C1	118.4 (3)	N4—C13—C1	111.7 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4NB···Cl1^i	0.92 (3)	2.38 (4)	3.260 (3)	160 (3)
N2—H2NB···Cl1^i	0.96 (3)	2.32 (3)	3.237 (3)	159 (3)
N2—H2NA···Cl2^i	0.96 (3)	2.11 (3)	3.056 (2)	167 (3)
N4—H4NA···Cl3^ii	1.03 (3)	2.07 (3)	3.074 (3)	164 (3)
N4—H4NA···O2^ii	1.03 (3)	1.72 (4)	2.676 (14)	152 (3)
N4—H4NA···O3^ii	1.03 (3)	1.91 (3)	2.761 (14)	137 (3)
N3—H3N···Cl2^iii	0.93 (3)	2.20 (3)	3.102 (3)	166 (3)

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