N,N',N''-Tris(2-nitro-benz-yl)-2,2',2''-nitrilo-triethan-aminium trichloride 1.41-hydrate.

The title compound, C(27)H(36)N(7)O(6) (3+)·3Cl(-)1.41H(2)O, is the hydro-chloride of a tripodal amine, and was structurally characterized because the free base, used as a ligand in podate complexes, is an oily material. In the cation, the secondary amine groups are protonated, and, despite the induced Coulombic repulsions, a claw-like conformation is stabilized, with a cavity approximating C(3) point symmetry. Such a topology, with the lone pair of the tertiary N atom placed inside the cavity, allows the encapsulation of guest species. Indeed, three chloride counter-ions balance the charges, one of which is located inside the cation cavity and is strongly bonded to the NH(2) (+) groups. The asymmetric unit is completed by two water mol-ecules with occupancies 0.793 (11) and 0.621 (9). The crystal structure is formed by a complex network of efficient N-H⋯Cl and O-H⋯Cl hydrogen bonds. One nitro group also forms weak contacts with a water mol-ecule.

Related literature

For related tripodal amine structures, see: Hossain et al. (2004 ▶); Coyle et al. (2006 ▶); McKee et al. (2006 ▶); Lakshminarayanan et al. (2007 ▶); For the role of electron-withdrawing groups in these mol­ecules, see: Bryantsev & Hay (2005 ▶).

Experimental

Crystal data

C27H36N7O6 3+·3Cl−·1.41H2O

M = 686.47

Monoclinic,

a = 9.131 (2) Å

b = 13.009 (4) Å

c = 28.071 (7) Å

β = 94.190 (9)°

V = 3326 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.33 mm−1

T = 298 K

0.50 × 0.42 × 0.24 mm

Data collection

Siemens P4 diffractometer

Absorption correction: ψ scan (XSCANS; Siemens, 1996 ▶) T min = 0.819, T max = 0.924

16115 measured reflections

6712 independent reflections

4181 reflections with I > 2σ(I)

R int = 0.042

3 standard reflections every 97 reflections intensity decay: 3.5%

Refinement

R[F 2 > 2σ(F 2)] = 0.056

wR(F 2) = 0.175

S = 1.03

6712 reflections

438 parameters

12 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.34 e Å−3

Δρmin = −0.34 e Å−3

Data collection: XSCANS (Siemens, 1996 ▶); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809022399/im2103sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809022399/im2103Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C27H36N7O63+·3Cl−·1.41H2O	F(000) = 1441
Mr = 686.47	Dx = 1.371 Mg m−3
Monoclinic, P21/n	Melting point: 503.5–504.5 (dec.) K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 9.131 (2) Å	Cell parameters from 69 reflections
b = 13.009 (4) Å	θ = 4.6–12.5°
c = 28.071 (7) Å	µ = 0.33 mm−1
β = 94.190 (9)°	T = 298 K
V = 3326 (2) Å3	Block, colorless
Z = 4	0.50 × 0.42 × 0.24 mm

Siemens P4 diffractometer	4181 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.042
graphite	θmax = 26.3°, θmin = 2.1°
2θ/ω scans	h = −11→10
Absorption correction: ψ scan (XSCANS; Siemens, 1996)	k = −16→1
Tmin = 0.819, Tmax = 0.924	l = −34→34
16115 measured reflections	3 standard reflections every 97 reflections
6712 independent reflections	intensity decay: 3.5%

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.175	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0754P)2 + 1.5076P] where P = (Fo2 + 2Fc2)/3
6712 reflections	(Δ/σ)max < 0.001
438 parameters	Δρmax = 0.34 e Å−3
12 restraints	Δρmin = −0.34 e Å−3
0 constraints

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.9829 (3)	0.79136 (19)	0.17125 (9)	0.0624 (6)
C1	0.9926 (4)	0.8169 (3)	0.22199 (11)	0.0701 (8)
H1A	0.9977	0.8911	0.2253	0.084*
H1B	1.0831	0.7887	0.2368	0.084*
C2	0.8671 (4)	0.7782 (3)	0.24840 (11)	0.0690 (8)
H2A	0.8467	0.7074	0.2393	0.083*
H2B	0.8945	0.7797	0.2824	0.083*
N2	0.7313 (3)	0.8412 (2)	0.23819 (8)	0.0586 (6)
H2C	0.758 (3)	0.9045 (12)	0.2481 (11)	0.070*
H2D	0.706 (3)	0.844 (2)	0.2064 (4)	0.070*
C3	0.6071 (4)	0.7981 (2)	0.26312 (11)	0.0668 (8)
H3A	0.6416	0.7807	0.2956	0.080*
H3B	0.5740	0.7352	0.2472	0.080*
C4	0.4792 (3)	0.8706 (2)	0.26437 (10)	0.0588 (7)
C5	0.4586 (4)	0.9520 (2)	0.23318 (11)	0.0682 (8)
H5A	0.5256	0.9624	0.2102	0.082*
C6	0.3408 (4)	1.0185 (3)	0.23509 (13)	0.0733 (9)
H6A	0.3284	1.0714	0.2129	0.088*
C7	0.2432 (4)	1.0077 (3)	0.26895 (13)	0.0736 (9)
H7A	0.1651	1.0533	0.2702	0.088*
C8	0.2608 (4)	0.9293 (3)	0.30119 (12)	0.0725 (9)
H8A	0.1957	0.9216	0.3249	0.087*
C9	0.3756 (4)	0.8620 (2)	0.29820 (10)	0.0623 (8)
N3	0.3838 (4)	0.7755 (3)	0.33158 (12)	0.0856 (9)
O1	0.3524 (4)	0.7895 (3)	0.37214 (12)	0.1437 (14)
O2	0.4250 (4)	0.6941 (2)	0.31824 (11)	0.1107 (10)
C11	1.0831 (4)	0.8554 (3)	0.14559 (14)	0.0763 (9)
H11A	1.0975	0.8234	0.1151	0.092*
H11B	1.1777	0.8573	0.1637	0.092*
C12	1.0314 (4)	0.9638 (3)	0.13682 (15)	0.0869 (11)
H12A	1.0114	0.9950	0.1670	0.104*
H12B	1.1091	1.0030	0.1235	0.104*
N12	0.8964 (3)	0.9694 (2)	0.10352 (11)	0.0709 (7)
H12C	0.907 (4)	0.923 (2)	0.0803 (9)	0.085*
H12D	0.825 (3)	0.943 (3)	0.1206 (11)	0.085*
C13	0.8715 (4)	1.0771 (3)	0.08618 (13)	0.0800 (10)
H13A	0.9484	1.0955	0.0657	0.096*
H13B	0.8785	1.1233	0.1134	0.096*
C14	0.7249 (4)	1.0919 (2)	0.05908 (11)	0.0671 (8)
C15	0.7256 (4)	1.0997 (3)	0.01013 (12)	0.0784 (10)
H15A	0.8139	1.0911	−0.0039	0.094*
C16	0.6024 (6)	1.1193 (3)	−0.01819 (15)	0.0926 (12)
H16A	0.6072	1.1236	−0.0511	0.111*
C17	0.4729 (5)	1.1328 (3)	0.00097 (16)	0.0919 (12)
H17A	0.3891	1.1470	−0.0188	0.110*
C18	0.4635 (4)	1.1258 (3)	0.04915 (17)	0.0858 (11)
H18A	0.3737	1.1342	0.0623	0.103*
C19	0.5905 (4)	1.1060 (2)	0.07840 (12)	0.0712 (9)
N13	0.5780 (6)	1.1031 (2)	0.12976 (14)	0.0969 (11)
O3	0.4647 (6)	1.1270 (4)	0.14496 (16)	0.1638 (18)
O4	0.6834 (5)	1.0783 (2)	0.15623 (10)	0.1092 (10)
C21	1.0212 (4)	0.6829 (2)	0.16548 (11)	0.0679 (8)
H21A	0.9807	0.6430	0.1906	0.081*
H21B	1.1272	0.6756	0.1689	0.081*
C22	0.9657 (4)	0.6407 (3)	0.11834 (13)	0.0758 (9)
H22A	0.9985	0.6840	0.0931	0.091*
H22B	1.0057	0.5724	0.1144	0.091*
N22	0.8036 (3)	0.63543 (19)	0.11434 (9)	0.0648 (7)
H22C	0.774 (4)	0.596 (2)	0.1381 (9)	0.078*
H22D	0.756 (3)	0.6949 (15)	0.1190 (12)	0.078*
C23	0.7439 (4)	0.5962 (3)	0.06626 (11)	0.0769 (10)
H23A	0.7383	0.6529	0.0437	0.092*
H23B	0.8114	0.5457	0.0549	0.092*
C24	0.5961 (5)	0.5488 (3)	0.06750 (11)	0.0737 (9)
C25	0.4793 (6)	0.6015 (4)	0.04688 (14)	0.0959 (12)
H25A	0.4936	0.6668	0.0345	0.115*
C26	0.3370 (7)	0.5587 (6)	0.04397 (18)	0.1311 (19)
H26A	0.2571	0.5950	0.0301	0.157*
C27	0.3195 (8)	0.4606 (7)	0.0625 (2)	0.138 (3)
H27A	0.2270	0.4303	0.0608	0.166*
C28	0.4359 (10)	0.4094 (5)	0.0827 (2)	0.140 (3)
H28A	0.4229	0.3436	0.0946	0.168*
C29	0.5702 (6)	0.4512 (3)	0.08602 (12)	0.0939 (13)
N23	0.6930 (7)	0.3884 (2)	0.10924 (12)	0.1083 (15)
O5	0.6572 (7)	0.3081 (3)	0.12602 (13)	0.205 (3)
O6	0.8142 (6)	0.4235 (3)	0.11446 (16)	0.1383 (14)
Cl1	0.61515 (8)	0.83642 (6)	0.12955 (2)	0.0618 (2)
Cl2	0.66871 (10)	0.53719 (6)	0.20643 (3)	0.0696 (2)
Cl3	0.91772 (12)	0.82403 (9)	0.01891 (4)	0.0971 (3)
O7	1.0384 (7)	0.6272 (5)	−0.0268 (2)	0.166 (3)	0.793 (11)
H71	1.046 (14)	0.658 (7)	−0.0533 (19)	0.249*	0.793 (11)
H72	1.006 (12)	0.673 (5)	−0.009 (3)	0.249*	0.793 (11)
O8	0.3919 (5)	0.6773 (5)	0.1646 (2)	0.121 (3)	0.621 (9)
H81	0.426 (9)	0.723 (5)	0.147 (3)	0.182*	0.621 (9)
H82	0.461 (7)	0.633 (6)	0.168 (4)	0.182*	0.621 (9)

	U11	U22	U33	U12	U13	U23
N1	0.0575 (14)	0.0559 (14)	0.0721 (15)	0.0051 (12)	−0.0083 (12)	−0.0021 (12)
C1	0.0607 (19)	0.0697 (19)	0.077 (2)	0.0053 (16)	−0.0152 (16)	−0.0118 (16)
C2	0.070 (2)	0.071 (2)	0.0636 (18)	0.0112 (17)	−0.0087 (15)	−0.0050 (15)
N2	0.0642 (15)	0.0621 (14)	0.0480 (12)	0.0035 (12)	−0.0052 (11)	−0.0073 (11)
C3	0.076 (2)	0.0637 (18)	0.0605 (17)	0.0026 (16)	0.0023 (15)	0.0007 (14)
C4	0.0616 (18)	0.0628 (17)	0.0509 (15)	−0.0004 (14)	−0.0026 (13)	−0.0095 (13)
C5	0.072 (2)	0.0675 (19)	0.0659 (18)	0.0044 (17)	0.0064 (15)	0.0024 (15)
C6	0.073 (2)	0.0644 (19)	0.081 (2)	0.0048 (17)	−0.0035 (18)	0.0015 (16)
C7	0.0618 (19)	0.073 (2)	0.084 (2)	0.0042 (17)	−0.0072 (18)	−0.0149 (18)
C8	0.0571 (19)	0.088 (2)	0.073 (2)	−0.0054 (18)	0.0035 (15)	−0.0145 (18)
C9	0.0652 (19)	0.0674 (18)	0.0530 (16)	−0.0069 (16)	−0.0055 (14)	−0.0046 (14)
N3	0.087 (2)	0.096 (2)	0.075 (2)	0.0044 (19)	0.0149 (16)	0.0109 (18)
O1	0.163 (3)	0.182 (4)	0.091 (2)	0.048 (3)	0.042 (2)	0.042 (2)
O2	0.139 (3)	0.0850 (19)	0.109 (2)	0.0062 (19)	0.0188 (19)	0.0254 (17)
C11	0.060 (2)	0.075 (2)	0.092 (2)	−0.0038 (17)	−0.0063 (17)	0.0100 (18)
C12	0.078 (2)	0.072 (2)	0.105 (3)	−0.0145 (18)	−0.030 (2)	0.0173 (19)
N12	0.0734 (18)	0.0586 (16)	0.0781 (19)	−0.0116 (14)	−0.0118 (15)	0.0082 (13)
C13	0.085 (2)	0.066 (2)	0.084 (2)	−0.0186 (18)	−0.0207 (18)	0.0212 (17)
C14	0.077 (2)	0.0526 (17)	0.0688 (19)	−0.0149 (16)	−0.0133 (16)	0.0096 (14)
C15	0.087 (2)	0.076 (2)	0.071 (2)	−0.0080 (19)	−0.0006 (18)	0.0149 (17)
C16	0.115 (4)	0.082 (3)	0.077 (2)	−0.007 (2)	−0.020 (2)	0.0171 (19)
C17	0.099 (3)	0.070 (2)	0.101 (3)	−0.009 (2)	−0.035 (3)	0.016 (2)
C18	0.078 (2)	0.0571 (19)	0.123 (3)	−0.0040 (18)	0.007 (2)	0.013 (2)
C19	0.095 (3)	0.0479 (16)	0.0705 (19)	−0.0080 (16)	0.0032 (18)	0.0081 (14)
N13	0.143 (4)	0.0622 (18)	0.088 (2)	−0.004 (2)	0.030 (3)	0.0144 (17)
O3	0.183 (4)	0.170 (4)	0.150 (3)	0.037 (3)	0.090 (3)	0.048 (3)
O4	0.182 (3)	0.0783 (18)	0.0662 (16)	−0.005 (2)	−0.0007 (18)	0.0081 (13)
C21	0.0662 (19)	0.0653 (19)	0.0718 (19)	0.0132 (16)	0.0023 (15)	0.0041 (15)
C22	0.080 (2)	0.067 (2)	0.082 (2)	0.0100 (17)	0.0165 (18)	−0.0071 (17)
N22	0.088 (2)	0.0529 (14)	0.0541 (14)	0.0044 (13)	0.0074 (13)	−0.0057 (11)
C23	0.110 (3)	0.066 (2)	0.0553 (17)	−0.0139 (19)	0.0089 (17)	−0.0046 (15)
C24	0.110 (3)	0.0599 (18)	0.0524 (17)	−0.0175 (19)	0.0113 (18)	−0.0092 (14)
C25	0.123 (4)	0.096 (3)	0.068 (2)	−0.014 (3)	0.001 (2)	−0.013 (2)
C26	0.125 (5)	0.181 (6)	0.086 (3)	−0.011 (4)	−0.003 (3)	−0.042 (4)
C27	0.138 (5)	0.185 (7)	0.098 (4)	−0.088 (5)	0.044 (4)	−0.053 (4)
C28	0.207 (7)	0.133 (5)	0.087 (3)	−0.087 (5)	0.055 (4)	−0.043 (3)
C29	0.152 (4)	0.077 (2)	0.0545 (19)	−0.039 (3)	0.022 (2)	−0.0207 (18)
N23	0.213 (5)	0.0461 (18)	0.0650 (18)	−0.013 (3)	0.006 (3)	−0.0040 (14)
O5	0.416 (8)	0.075 (2)	0.113 (3)	−0.073 (3)	−0.056 (4)	0.0271 (19)
O6	0.187 (4)	0.079 (2)	0.151 (3)	0.034 (3)	0.029 (3)	0.007 (2)
Cl1	0.0686 (5)	0.0594 (4)	0.0555 (4)	0.0021 (4)	−0.0085 (3)	0.0005 (3)
Cl2	0.0815 (5)	0.0606 (4)	0.0665 (5)	0.0027 (4)	0.0050 (4)	0.0078 (3)
Cl3	0.1002 (7)	0.1081 (8)	0.0858 (6)	−0.0133 (6)	0.0264 (5)	0.0007 (5)
O7	0.139 (5)	0.212 (6)	0.145 (5)	0.047 (4)	0.003 (4)	−0.046 (4)
O8	0.077 (3)	0.125 (5)	0.163 (5)	−0.006 (3)	0.025 (3)	0.052 (4)

N1—C1	1.459 (4)	C14—C19	1.389 (5)
N1—C11	1.465 (4)	C15—C16	1.354 (5)
N1—C21	1.466 (4)	C15—H15A	0.9300
C1—C2	1.497 (5)	C16—C17	1.346 (6)
C1—H1A	0.9700	C16—H16A	0.9300
C1—H1B	0.9700	C17—C18	1.364 (6)
C2—N2	1.497 (4)	C17—H17A	0.9300
C2—H2A	0.9700	C18—C19	1.396 (5)
C2—H2B	0.9700	C18—H18A	0.9300
N2—C3	1.485 (4)	C19—N13	1.455 (5)
N2—H2C	0.897 (10)	N13—O3	1.190 (5)
N2—H2D	0.906 (10)	N13—O4	1.216 (5)
C3—C4	1.504 (4)	C21—C22	1.487 (5)
C3—H3A	0.9700	C21—H21A	0.9700
C3—H3B	0.9700	C21—H21B	0.9700
C4—C5	1.378 (4)	C22—N22	1.478 (5)
C4—C9	1.393 (4)	C22—H22A	0.9700
C5—C6	1.385 (5)	C22—H22B	0.9700
C5—H5A	0.9300	N22—C23	1.507 (4)
C6—C7	1.357 (5)	N22—H22C	0.899 (10)
C6—H6A	0.9300	N22—H22D	0.900 (10)
C7—C8	1.365 (5)	C23—C24	1.487 (5)
C7—H7A	0.9300	C23—H23A	0.9700
C8—C9	1.372 (5)	C23—H23B	0.9700
C8—H8A	0.9300	C24—C25	1.361 (6)
C9—N3	1.463 (4)	C24—C29	1.398 (5)
N3—O2	1.193 (4)	C25—C26	1.411 (7)
N3—O1	1.208 (4)	C25—H25A	0.9300
C11—C12	1.501 (5)	C26—C27	1.391 (9)
C11—H11A	0.9700	C26—H26A	0.9300
C11—H11B	0.9700	C27—C28	1.345 (9)
C12—N12	1.493 (4)	C27—H27A	0.9300
C12—H12A	0.9700	C28—C29	1.338 (8)
C12—H12B	0.9700	C28—H28A	0.9300
N12—C13	1.495 (4)	C29—N23	1.498 (7)
N12—H12C	0.897 (10)	N23—O6	1.196 (6)
N12—H12D	0.902 (10)	N23—O5	1.202 (5)
C13—C14	1.503 (5)	O7—H71	0.851 (10)
C13—H13A	0.9700	O7—H72	0.851 (10)
C13—H13B	0.9700	O8—H81	0.850 (10)
C14—C15	1.378 (5)	O8—H82	0.850 (10)
C1—N1—C11	110.8 (3)	C14—C13—H13B	108.9
C1—N1—C21	109.2 (2)	H13A—C13—H13B	107.8
C11—N1—C21	109.3 (3)	C15—C14—C19	116.6 (3)
N1—C1—C2	114.4 (3)	C15—C14—C13	116.4 (3)
N1—C1—H1A	108.7	C19—C14—C13	126.8 (3)
C2—C1—H1A	108.7	C16—C15—C14	122.3 (4)
N1—C1—H1B	108.7	C16—C15—H15A	118.8
C2—C1—H1B	108.7	C14—C15—H15A	118.8
H1A—C1—H1B	107.6	C17—C16—C15	120.5 (4)
N2—C2—C1	112.0 (3)	C17—C16—H16A	119.8
N2—C2—H2A	109.2	C15—C16—H16A	119.8
C1—C2—H2A	109.2	C16—C17—C18	120.5 (4)
N2—C2—H2B	109.2	C16—C17—H17A	119.7
C1—C2—H2B	109.2	C18—C17—H17A	119.7
H2A—C2—H2B	107.9	C17—C18—C19	119.1 (4)
C3—N2—C2	110.7 (2)	C17—C18—H18A	120.5
C3—N2—H2C	114 (2)	C19—C18—H18A	120.5
C2—N2—H2C	104 (2)	C14—C19—C18	121.0 (3)
C3—N2—H2D	109 (2)	C14—C19—N13	121.3 (4)
C2—N2—H2D	111 (2)	C18—C19—N13	117.8 (4)
H2C—N2—H2D	109 (3)	O3—N13—O4	121.4 (4)
N2—C3—C4	113.3 (3)	O3—N13—C19	118.8 (5)
N2—C3—H3A	108.9	O4—N13—C19	119.8 (4)
C4—C3—H3A	108.9	N1—C21—C22	112.6 (3)
N2—C3—H3B	108.9	N1—C21—H21A	109.1
C4—C3—H3B	108.9	C22—C21—H21A	109.1
H3A—C3—H3B	107.7	N1—C21—H21B	109.1
C5—C4—C9	115.3 (3)	C22—C21—H21B	109.1
C5—C4—C3	122.5 (3)	H21A—C21—H21B	107.8
C9—C4—C3	122.2 (3)	N22—C22—C21	111.1 (3)
C4—C5—C6	121.7 (3)	N22—C22—H22A	109.4
C4—C5—H5A	119.1	C21—C22—H22A	109.4
C6—C5—H5A	119.1	N22—C22—H22B	109.4
C7—C6—C5	120.9 (3)	C21—C22—H22B	109.4
C7—C6—H6A	119.5	H22A—C22—H22B	108.0
C5—C6—H6A	119.5	C22—N22—C23	112.2 (3)
C6—C7—C8	119.4 (3)	C22—N22—H22C	109 (2)
C6—C7—H7A	120.3	C23—N22—H22C	111 (2)
C8—C7—H7A	120.3	C22—N22—H22D	116 (2)
C7—C8—C9	119.3 (3)	C23—N22—H22D	106 (2)
C7—C8—H8A	120.4	H22C—N22—H22D	102 (3)
C9—C8—H8A	120.4	C24—C23—N22	112.9 (3)
C8—C9—C4	123.4 (3)	C24—C23—H23A	109.0
C8—C9—N3	117.1 (3)	N22—C23—H23A	109.0
C4—C9—N3	119.5 (3)	C24—C23—H23B	109.0
O2—N3—O1	122.1 (4)	N22—C23—H23B	109.0
O2—N3—C9	119.0 (3)	H23A—C23—H23B	107.8
O1—N3—C9	118.9 (4)	C25—C24—C29	117.9 (4)
N1—C11—C12	114.5 (3)	C25—C24—C23	117.7 (3)
N1—C11—H11A	108.6	C29—C24—C23	124.4 (4)
C12—C11—H11A	108.6	C24—C25—C26	121.0 (5)
N1—C11—H11B	108.6	C24—C25—H25A	119.5
C12—C11—H11B	108.6	C26—C25—H25A	119.5
H11A—C11—H11B	107.6	C27—C26—C25	118.1 (6)
N12—C12—C11	112.6 (3)	C27—C26—H26A	121.0
N12—C12—H12A	109.1	C25—C26—H26A	121.0
C11—C12—H12A	109.1	C28—C27—C26	120.2 (6)
N12—C12—H12B	109.1	C28—C27—H27A	119.9
C11—C12—H12B	109.1	C26—C27—H27A	119.9
H12A—C12—H12B	107.8	C29—C28—C27	121.3 (6)
C12—N12—C13	110.5 (2)	C29—C28—H28A	119.4
C12—N12—H12C	107 (2)	C27—C28—H28A	119.4
C13—N12—H12C	114 (2)	C28—C29—C24	121.5 (6)
C12—N12—H12D	104 (2)	C28—C29—N23	117.5 (5)
C13—N12—H12D	115 (2)	C24—C29—N23	121.0 (4)
H12C—N12—H12D	104 (3)	O6—N23—O5	124.0 (6)
N12—C13—C14	113.2 (3)	O6—N23—C29	120.1 (4)
N12—C13—H13A	108.9	O5—N23—C29	115.4 (6)
C14—C13—H13A	108.9	H71—O7—H72	104 (3)
N12—C13—H13B	108.9	H81—O8—H82	104 (3)
C11—N1—C1—C2	163.5 (3)	C16—C17—C18—C19	0.9 (6)
C21—N1—C1—C2	−76.1 (3)	C15—C14—C19—C18	0.7 (5)
N1—C1—C2—N2	−75.8 (3)	C13—C14—C19—C18	175.6 (3)
C1—C2—N2—C3	177.4 (2)	C15—C14—C19—N13	−177.8 (3)
C2—N2—C3—C4	165.9 (2)	C13—C14—C19—N13	−2.9 (5)
N2—C3—C4—C5	19.9 (4)	C17—C18—C19—C14	−1.0 (5)
N2—C3—C4—C9	−158.0 (3)	C17—C18—C19—N13	177.6 (3)
C9—C4—C5—C6	−1.4 (4)	C14—C19—N13—O3	171.6 (4)
C3—C4—C5—C6	−179.5 (3)	C18—C19—N13—O3	−6.9 (5)
C4—C5—C6—C7	2.0 (5)	C14—C19—N13—O4	−7.1 (5)
C5—C6—C7—C8	−0.8 (5)	C18—C19—N13—O4	174.3 (3)
C6—C7—C8—C9	−1.0 (5)	C1—N1—C21—C22	159.9 (3)
C7—C8—C9—C4	1.7 (5)	C11—N1—C21—C22	−78.8 (3)
C7—C8—C9—N3	−176.1 (3)	N1—C21—C22—N22	−67.4 (4)
C5—C4—C9—C8	−0.5 (4)	C21—C22—N22—C23	178.1 (3)
C3—C4—C9—C8	177.6 (3)	C22—N22—C23—C24	155.5 (3)
C5—C4—C9—N3	177.2 (3)	N22—C23—C24—C25	107.9 (4)
C3—C4—C9—N3	−4.7 (4)	N22—C23—C24—C29	−75.9 (4)
C8—C9—N3—O2	143.3 (4)	C29—C24—C25—C26	−0.5 (5)
C4—C9—N3—O2	−34.6 (5)	C23—C24—C25—C26	176.0 (3)
C8—C9—N3—O1	−38.7 (5)	C24—C25—C26—C27	−0.5 (6)
C4—C9—N3—O1	143.5 (4)	C25—C26—C27—C28	0.4 (8)
C1—N1—C11—C12	−76.1 (3)	C26—C27—C28—C29	0.6 (8)
C21—N1—C11—C12	163.6 (3)	C27—C28—C29—C24	−1.7 (7)
N1—C11—C12—N12	−66.1 (4)	C27—C28—C29—N23	179.9 (5)
C11—C12—N12—C13	−165.5 (3)	C25—C24—C29—C28	1.6 (5)
C12—N12—C13—C14	−170.5 (3)	C23—C24—C29—C28	−174.6 (4)
N12—C13—C14—C15	−104.5 (4)	C25—C24—C29—N23	180.0 (3)
N12—C13—C14—C19	80.5 (4)	C23—C24—C29—N23	3.8 (5)
C19—C14—C15—C16	−0.4 (5)	C28—C29—N23—O6	−177.6 (4)
C13—C14—C15—C16	−175.9 (3)	C24—C29—N23—O6	3.9 (6)
C14—C15—C16—C17	0.4 (6)	C28—C29—N23—O5	−5.1 (5)
C15—C16—C17—C18	−0.6 (6)	C24—C29—N23—O5	176.4 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2D···Cl1	0.91 (1)	2.26 (1)	3.155 (2)	172 (3)
N12—H12D···Cl1	0.90 (1)	2.40 (2)	3.225 (3)	153 (3)
N22—H22D···Cl1	0.90 (1)	2.28 (1)	3.176 (3)	174 (3)
N12—H12C···Cl3	0.90 (1)	2.16 (1)	3.054 (3)	174 (3)
N22—H22C···Cl2	0.90 (1)	2.34 (1)	3.209 (3)	164 (3)
O8—H81···Cl1	0.85 (1)	2.35 (5)	3.115 (5)	150 (9)
O8—H82···Cl2	0.85 (1)	2.46 (4)	3.265 (5)	159 (10)
O7—H72···Cl3	0.85 (1)	2.28 (3)	3.102 (6)	163 (9)
N2—H2C···Cl2i	0.90 (1)	2.22 (1)	3.089 (3)	163 (3)
O7—H71···O6ii	0.85 (1)	2.45 (8)	2.965 (7)	119 (8)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2D⋯Cl1	0.906 (10)	2.255 (11)	3.155 (2)	172 (3)
N12—H12D⋯Cl1	0.902 (10)	2.396 (19)	3.225 (3)	153 (3)
N22—H22D⋯Cl1	0.900 (10)	2.279 (11)	3.176 (3)	174 (3)
N12—H12C⋯Cl3	0.897 (10)	2.161 (11)	3.054 (3)	174 (3)
N22—H22C⋯Cl2	0.899 (10)	2.335 (14)	3.209 (3)	164 (3)
O8—H81⋯Cl1	0.850 (10)	2.35 (5)	3.115 (5)	150 (9)
O8—H82⋯Cl2	0.850 (10)	2.46 (4)	3.265 (5)	159 (10)
O7—H72⋯Cl3	0.851 (10)	2.28 (3)	3.102 (6)	163 (9)
N2—H2C⋯Cl2i	0.897 (10)	2.221 (14)	3.089 (3)	163 (3)
O7—H71⋯O6ii	0.851 (10)	2.45 (8)	2.965 (7)	119 (8)

Symmetry codes: (i) ; (ii) .