Adducts of meso and racemic 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane with trigonally trisubstituted benzene carboxylic acids: supramolecular structures in one and two ­dimensions

The meso and racemic forms of 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane, C₁₆H₃₆N₄ (tet-a and tet-b, respectively), form adducts with trigonally trisubstituted benzene carboxylic acids; tet-a–3,5-dinitrobenzoic acid (1/2) (1), tet-a–5-hydroxyisophthalic acid–water (1/1/1) (3) and tet-­b–5-hydroxyisophthalic acid–water (1/1/1) (4) are all salts, [C₁₆H₃₈N₄]²⁺·2[C₇H₃N₂O₆]⁻ (1) and [C₁₆H₃₈N₄]²⁺·[C₈H₄O₅]²⁻·H₂O (3) and (4). The conformations of the [(tet-a)H₂]²⁺ and [(tet-b)H₂]²⁺ cations are entirely different: [(tet-a)H₂]²⁺ is precisely centrosymmetric in (1) and approximately so in (3), while [(tet-b)H₂]²⁺ has approximate C₂ symmetry in (4). In each salt the cation forms two intramolecular N—H...N and four intermolecular N—H...O hydrogen bonds. In (1) the supramolecular structure is one-dimensional, a C₂²(13)[R₂⁴(16)] chain of rings. Compounds (3) and (4) crystallize in space groups P2₁2₁2₁ and P2₁/c, respectively, but the supramolecular structures are very similar: in each, the anions and the water molecules form a C(7)[R₃³(13)] chain of rings, generated in (3) by a 2₁ axis and in (4) by a glide plane. These chains are linked, in both (3) and (4), by cations to form sheets. Adjacent meso cations in (3) are related by a 2₁ axis and adjacent chiral cations in (4) are related by a glide plane.

S1. Comment

In full text version

S2. Experimental

In full text version

S3. Refinement

In full text version

Computing details

For all compounds, data collection: Kappa-CCD server software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: NRCVAX96 and SHELXL97 (Sheldrick, 1997b); molecular graphics: NRCVAX96, ORTEP (Johnson, 1976), PLATON (Spek, 2000); software used to prepare material for publication: NRCVAX96, SHELXL97 and WORDPERFECT macro PRPKAPPA (Ferguson, 1999).

Figures

In full text version

(1) meso-5,5,7,12,12,14-Hexamethyl-1,4,8,11-tetraazacyclotetradecane–3,5- dinitrobenzoic acid(1/2)

Crystal data

C16H38N4·2(C7H3N2O6)	Z = 1
Mr = 708.73	F(000) = 376
Triclinic, P1	Dx = 1.356 Mg m^−3
a = 8.7336 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.9388 (3) Å	Cell parameters from 12749 reflections
c = 11.0284 (3) Å	θ = 3.0–30.0°
α = 114.5800 (17)°	µ = 0.11 mm^−1
β = 91.9660 (18)°	T = 150 K
γ = 111.6740 (18)°	Block, colourless
V = 868.09 (4) Å^3	0.26 × 0.16 × 0.14 mm

Data collection

Kappa-CCD diffractometer	5013 independent reflections
Radiation source: fine-focus sealed X-ray tube	3651 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
ϕ scans and ω scans with κ offsets	θmax = 30.0°, θmin = 3.0°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = 0→12
Tmin = 0.973, Tmax = 0.985	k = −15→14
12749 measured reflections	l = −15→15

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.133	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0542P)^2 + 0.1566P] where P = (Fo^2 + 2Fc^2)/3
5013 reflections	(Δ/σ)max = 0.001
229 parameters	Δρmax = 0.24 e Å^−3
0 restraints	Δρmin = −0.27 e Å^−3

Special details

Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm [Fox, G·C. & Holmes, K·C. (1966). Acta Cryst. 20, 886–891] which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the 'size' command in the SHELXL97 input file.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.38165 (12)	0.63318 (10)	0.55172 (10)	0.0214 (2)
C2	0.23199 (16)	0.54780 (13)	0.58511 (13)	0.0252 (3)
C3	0.27683 (16)	0.47571 (13)	0.66386 (12)	0.0259 (3)
N4	0.35154 (13)	0.37403 (10)	0.58203 (10)	0.0214 (2)
C5	0.39028 (16)	0.28369 (13)	0.64208 (12)	0.0242 (3)
C51	0.22302 (19)	0.17058 (15)	0.64215 (15)	0.0351 (3)
C52	0.4994 (2)	0.38603 (16)	0.78661 (13)	0.0356 (3)
C6	0.48122 (16)	0.20053 (13)	0.54566 (13)	0.0254 (3)
C7	0.64938 (16)	0.28992 (13)	0.52269 (12)	0.0238 (3)
C71	0.73192 (18)	0.18624 (15)	0.44979 (15)	0.0344 (3)
O1	0.12100 (13)	0.17636 (11)	0.34034 (9)	0.0387 (3)
O2	0.30300 (12)	0.31943 (12)	0.26448 (10)	0.0399 (3)
O3	0.06891 (16)	0.39464 (13)	−0.09511 (12)	0.0507 (3)
O4	−0.18082 (19)	0.24172 (18)	−0.22159 (14)	0.0710 (4)
O5	−0.52769 (12)	−0.15405 (11)	−0.12954 (10)	0.0399 (3)
O6	−0.42798 (15)	−0.18797 (13)	0.02998 (12)	0.0545 (3)
N3	−0.06477 (18)	0.28683 (16)	−0.12643 (13)	0.0422 (3)
N5	−0.41460 (15)	−0.12071 (13)	−0.03649 (11)	0.0353 (3)
C11	0.01922 (16)	0.17937 (14)	0.14061 (12)	0.0256 (3)
C12	0.04189 (17)	0.25421 (15)	0.06233 (13)	0.0289 (3)
C13	−0.08773 (18)	0.20456 (15)	−0.04618 (13)	0.0305 (3)
C14	−0.23778 (17)	0.08107 (15)	−0.08256 (12)	0.0310 (3)
C15	−0.25553 (16)	0.00957 (14)	−0.00260 (12)	0.0275 (3)
C16	−0.13147 (16)	0.05700 (14)	0.10921 (12)	0.0261 (3)
C17	0.16098 (16)	0.23011 (14)	0.25890 (12)	0.0286 (3)
H1	0.4610	0.7026	0.6316	0.026*
H2A	0.1470	0.4702	0.4997	0.030*
H2B	0.1816	0.6141	0.6407	0.030*
H3A	0.3587	0.5534	0.7509	0.031*
H3B	0.1739	0.4192	0.6860	0.031*
H4A	0.4503	0.4297	0.5672	0.026*
H4B	0.2785	0.3092	0.4980	0.026*
H51A	0.1631	0.2226	0.7016	0.053*
H51B	0.2452	0.1076	0.6761	0.053*
H51C	0.1534	0.1089	0.5488	0.053*
H52A	0.5929	0.4706	0.7871	0.053*
H52B	0.5447	0.3314	0.8171	0.053*
H52C	0.4306	0.4219	0.8485	0.053*
H6A	0.5014	0.1367	0.5808	0.030*
H6B	0.4021	0.1338	0.4552	0.030*
H7	0.7255	0.3666	0.6141	0.029*
H71A	0.6581	0.1090	0.3606	0.052*
H71B	0.7496	0.1401	0.5053	0.052*
H71C	0.8410	0.2431	0.4368	0.052*
H12	0.1446	0.3380	0.0829	0.035*
H14	−0.3243	0.0471	−0.1587	0.037*
H16	−0.1494	0.0066	0.1634	0.031*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0207 (5)	0.0216 (5)	0.0230 (5)	0.0078 (4)	0.0038 (4)	0.0124 (4)
C2	0.0226 (6)	0.0272 (6)	0.0323 (6)	0.0121 (5)	0.0097 (5)	0.0176 (5)
C3	0.0303 (7)	0.0279 (6)	0.0275 (6)	0.0154 (5)	0.0131 (5)	0.0166 (5)
N4	0.0228 (5)	0.0227 (5)	0.0215 (5)	0.0094 (4)	0.0058 (4)	0.0127 (4)
C5	0.0289 (6)	0.0236 (5)	0.0250 (6)	0.0109 (5)	0.0063 (5)	0.0156 (5)
C51	0.0390 (8)	0.0300 (6)	0.0463 (8)	0.0146 (6)	0.0210 (6)	0.0254 (6)
C52	0.0455 (8)	0.0400 (7)	0.0255 (6)	0.0200 (6)	0.0041 (6)	0.0173 (6)
C6	0.0288 (6)	0.0214 (5)	0.0290 (6)	0.0104 (5)	0.0065 (5)	0.0144 (5)
C7	0.0261 (6)	0.0239 (5)	0.0258 (6)	0.0119 (5)	0.0046 (5)	0.0142 (5)
C71	0.0365 (8)	0.0348 (7)	0.0475 (8)	0.0225 (6)	0.0164 (6)	0.0257 (6)
O1	0.0394 (6)	0.0444 (6)	0.0269 (5)	0.0124 (5)	−0.0022 (4)	0.0169 (4)
O2	0.0255 (5)	0.0521 (6)	0.0335 (5)	0.0097 (4)	0.0007 (4)	0.0184 (5)
O3	0.0584 (8)	0.0582 (7)	0.0545 (7)	0.0272 (6)	0.0268 (6)	0.0394 (6)
O4	0.0688 (9)	0.1056 (11)	0.0595 (8)	0.0336 (8)	0.0036 (7)	0.0601 (8)
O5	0.0273 (5)	0.0414 (5)	0.0315 (5)	0.0130 (4)	−0.0015 (4)	0.0017 (4)
O6	0.0455 (7)	0.0526 (7)	0.0528 (7)	0.0008 (5)	0.0040 (5)	0.0310 (6)
N3	0.0486 (8)	0.0600 (8)	0.0368 (7)	0.0304 (7)	0.0171 (6)	0.0318 (6)
N5	0.0286 (6)	0.0367 (6)	0.0283 (6)	0.0100 (5)	0.0050 (5)	0.0074 (5)
C11	0.0247 (6)	0.0316 (6)	0.0196 (5)	0.0144 (5)	0.0045 (4)	0.0089 (5)
C12	0.0270 (6)	0.0334 (6)	0.0256 (6)	0.0135 (5)	0.0070 (5)	0.0123 (5)
C13	0.0334 (7)	0.0426 (7)	0.0256 (6)	0.0213 (6)	0.0112 (5)	0.0198 (6)
C14	0.0280 (7)	0.0448 (7)	0.0207 (6)	0.0192 (6)	0.0043 (5)	0.0122 (6)
C15	0.0221 (6)	0.0314 (6)	0.0235 (6)	0.0107 (5)	0.0049 (5)	0.0083 (5)
C16	0.0287 (7)	0.0303 (6)	0.0199 (5)	0.0150 (5)	0.0068 (5)	0.0099 (5)
C17	0.0266 (7)	0.0335 (6)	0.0218 (6)	0.0152 (5)	0.0017 (5)	0.0075 (5)

Geometric parameters (Å, º)

N1—C2	1.461 (2)	C7—C71	1.5288 (18)
N1—C7^i	1.477 (2)	C7—H7	1.00
N1—H1	0.92	C71—H71A	0.98
C2—C3	1.5179 (17)	C71—H71B	0.98
C2—H2A	0.99	C71—H71C	0.98
C2—H2B	0.99	O1—C17	1.258 (2)
C3—N4	1.490 (2)	O2—C17	1.244 (2)
C3—H3A	0.99	O3—N3	1.2204 (18)
C3—H3B	0.99	O4—N3	1.2244 (18)
N4—C5	1.518 (2)	O5—N5	1.2307 (15)
N4—H4A	0.92	O6—N5	1.2179 (17)
N4—H4B	0.92	N3—C13	1.4747 (18)
C5—C52	1.5248 (17)	N5—C15	1.4696 (17)
C5—C51	1.5267 (18)	C11—C12	1.3910 (18)
C5—C6	1.5415 (17)	C11—C16	1.3876 (18)
C51—H51A	0.98	C11—C17	1.5238 (17)
C51—H51B	0.98	C12—C13	1.3859 (18)
C51—H51C	0.98	C12—H12	0.95
C52—H52A	0.98	C13—C14	1.382 (2)
C52—H52B	0.98	C14—C15	1.3809 (19)
C52—H52C	0.98	C14—H14	0.95
C6—C7	1.5324 (17)	C15—C16	1.3873 (17)
C6—H6A	0.99	C16—H16	0.95
C6—H6B	0.99
C2—N1—C7^i	114.71 (9)	C7—C6—H6B	107.5
C2—N1—H1	108.6	C5—C6—H6B	107.5
C7^i—N1—H1	108.6	H6A—C6—H6B	107.0
N1—C2—C3	110.90 (10)	N1^i—C7—C71	114.04 (10)
N1—C2—H2A	109.5	N1^i—C7—C6	108.96 (10)
C3—C2—H2A	109.5	C71—C7—C6	108.99 (10)
N1—C2—H2B	109.5	N1^i—C7—H7	108.2
C3—C2—H2B	109.5	C71—C7—H7	108.2
H2A—C2—H2B	108.0	C6—C7—H7	108.2
N4—C3—C2	110.67 (10)	C7—C71—H71A	109.5
N4—C3—H3A	109.5	C7—C71—H71B	109.5
C2—C3—H3A	109.5	H71A—C71—H71B	109.5
N4—C3—H3B	109.5	C7—C71—H71C	109.5
C2—C3—H3B	109.5	H71A—C71—H71C	109.5
H3A—C3—H3B	108.1	H71B—C71—H71C	109.5
C3—N4—C5	117.10 (9)	O3—N3—O4	123.91 (14)
C3—N4—H4A	108.0	O3—N3—C13	118.27 (12)
C5—N4—H4A	108.0	O4—N3—C13	117.82 (14)
C3—N4—H4B	108.0	O6—N5—O5	123.84 (12)
C5—N4—H4B	108.0	O6—N5—C15	118.41 (11)
H4A—N4—H4B	107.3	O5—N5—C15	117.74 (12)
N4—C5—C52	109.85 (10)	C16—C11—C12	119.86 (11)
N4—C5—C51	108.22 (10)	C16—C11—C17	120.16 (12)
C52—C5—C51	111.06 (11)	C12—C11—C17	119.97 (12)
N4—C5—C6	106.76 (9)	C13—C12—C11	118.96 (12)
C52—C5—C6	111.86 (11)	C13—C12—H12	120.5
C51—C5—C6	108.93 (10)	C11—C12—H12	120.5
C5—C51—H51A	109.5	C14—C13—C12	122.80 (12)
C5—C51—H51B	109.5	C14—C13—N3	118.49 (12)
H51A—C51—H51B	109.5	C12—C13—N3	118.70 (13)
C5—C51—H51C	109.5	C15—C14—C13	116.54 (11)
H51A—C51—H51C	109.5	C15—C14—H14	121.7
H51B—C51—H51C	109.5	C13—C14—H14	121.7
C5—C52—H52A	109.5	C14—C15—C16	122.91 (12)
C5—C52—H52B	109.5	C14—C15—N5	118.19 (11)
H52A—C52—H52B	109.5	C16—C15—N5	118.88 (12)
C5—C52—H52C	109.5	C15—C16—C11	118.88 (12)
H52A—C52—H52C	109.5	C15—C16—H16	120.6
H52B—C52—H52C	109.5	C11—C16—H16	120.6
C7—C6—C5	119.13 (10)	O2—C17—O1	127.1 (2)
C7—C6—H6A	107.5	O2—C17—C11	116.81 (12)
C5—C6—H6A	107.5	O1—C17—C11	116.07 (12)
C7^i—N1—C2—C3	−178.79 (9)	O3—N3—C13—C12	0.97 (19)
N1—C2—C3—N4	−59.6 (2)	O4—N3—C13—C12	−179.73 (14)
C2—C3—N4—C5	−175.2 (2)	C12—C13—C14—C15	1.6 (2)
C3—N4—C5—C52	−53.2 (2)	N3—C13—C14—C15	−178.45 (11)
C3—N4—C5—C51	68.2 (2)	C13—C14—C15—C16	0.15 (19)
C3—N4—C5—C6	−174.6 (2)	C13—C14—C15—N5	178.92 (11)
N4—C5—C6—C7	60.7 (2)	O6—N5—C15—C14	176.83 (13)
C52—C5—C6—C7	−59.54 (14)	O5—N5—C15—C14	−4.22 (18)
C51—C5—C6—C7	177.29 (11)	O6—N5—C15—C16	−4.36 (19)
C5—C6—C7—N1^i	−67.1 (2)	O5—N5—C15—C16	174.60 (11)
C6—C7—N1^i—C2^i	−177.8 (2)	C14—C15—C16—C11	−1.71 (19)
C5—C6—C7—C71	167.88 (11)	N5—C15—C16—C11	179.53 (11)
C16—C11—C12—C13	0.06 (18)	C12—C11—C16—C15	1.57 (18)
C17—C11—C12—C13	178.93 (11)	C17—C11—C16—C15	−177.30 (11)
C11—C12—C13—C14	−1.7 (2)	C16—C11—C17—O2	165.61 (12)
C11—C12—C13—N3	178.33 (11)	C12—C11—C17—O2	−13.25 (18)
O3—N3—C13—C14	−178.99 (13)	C16—C11—C17—O1	−14.25 (18)
O4—N3—C13—C14	0.3 (2)	C12—C11—C17—O1	166.88 (11)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O5^ii	0.92	2.42	3.169 (2)	139
N1—H1···O2^i	0.92	2.46	3.107 (2)	127
N4—H4A···N1^i	0.92	2.12	2.808 (2)	131
N4—H4B···O1	0.92	1.81	2.730 (2)	175

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

(3) meso-5,5,7,12,12,14-Hexamethyl-1,4,8,11-tetraazacyclotetradecane–5- hydroxyisophthalic acid–water (1/1/1)

Crystal data

C16H38N4·C8H4O5·H2O	Dx = 1.235 Mg m^−3
Mr = 484.63	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 4203 reflections
a = 11.8760 (5) Å	θ = 2.6–30.0°
b = 13.8395 (6) Å	µ = 0.09 mm^−1
c = 15.8571 (7) Å	T = 100 K
V = 2606.2 (2) Å^3	Block, colourless
Z = 4	0.24 × 0.24 × 0.16 mm
F(000) = 1056

Data collection

Kappa-CCD diffractometer	4203 independent reflections
Radiation source: fine-focus sealed X-ray tube	3479 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
ϕ scans and ω scans with κ offsets	θmax = 30.0°, θmin = 2.6°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = 0→16
Tmin = 0.979, Tmax = 0.986	k = 0→19
30326 measured reflections	l = 0→22

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) = 0.124	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.048P)^2 + 0.8417P] where P = (Fo^2 + 2Fc^2)/3
4203 reflections	(Δ/σ)max = 0.008
323 parameters	Δρmax = 0.30 e Å^−3
4 restraints	Δρmin = −0.27 e Å^−3

Special details

Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm [Fox, G·C. & Holmes, K·C. (1966). Acta Cryst. 20, 886–891] which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the 'size' command in the SHELXL97 input file.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.34185 (16)	0.59626 (15)	0.40203 (12)	0.0254 (4)
C2	0.4132 (2)	0.5455 (2)	0.33948 (16)	0.0336 (6)
C3	0.3886 (2)	0.43810 (19)	0.34068 (15)	0.0334 (6)
N4	0.42921 (16)	0.39450 (14)	0.41955 (12)	0.0260 (4)
C5	0.4173 (2)	0.28717 (19)	0.42516 (16)	0.0337 (6)
C51	0.2922 (3)	0.2597 (3)	0.4211 (2)	0.0473 (9)	0.853 (3)
C52	0.4820 (4)	0.2351 (3)	0.3553 (2)	0.0593 (10)
C6	0.4705 (2)	0.2565 (2)	0.51002 (17)	0.0344 (6)
C7	0.4090 (2)	0.28755 (18)	0.58984 (17)	0.0324 (6)
C71'	0.2824 (5)	0.2699 (16)	0.5801 (15)	0.049 (5)*	0.147 (3)
C71	0.4670 (3)	0.2496 (2)	0.66905 (18)	0.0440 (7)
N8	0.40503 (17)	0.39646 (14)	0.59278 (12)	0.0257 (4)
C10	0.3226 (2)	0.5429 (2)	0.65570 (15)	0.0386 (7)
C9	0.3136 (2)	0.4351 (2)	0.64702 (16)	0.0347 (6)
N11	0.30714 (17)	0.59140 (15)	0.57453 (12)	0.0271 (4)
C12	0.3310 (3)	0.6962 (2)	0.57481 (18)	0.0385 (7)
C121	0.4609 (3)	0.7076 (3)	0.5890 (3)	0.0475 (9)	0.853 (3)
C122	0.2638 (4)	0.7483 (2)	0.6430 (2)	0.0634 (11)
C13	0.2956 (3)	0.73753 (19)	0.48878 (18)	0.0373 (6)
C14	0.3596 (2)	0.70319 (19)	0.41085 (18)	0.0344 (6)
C14'	0.4828 (7)	0.7282 (17)	0.4288 (15)	0.054 (6)*	0.147 (3)
C141	0.3172 (3)	0.7541 (2)	0.3324 (2)	0.0532 (9)
O21	0.08937 (16)	0.5272 (2)	0.47951 (11)	0.0544 (6)
O22	0.13527 (15)	0.56795 (16)	0.34915 (11)	0.0409 (5)
O23	−0.12615 (14)	0.53861 (14)	0.11341 (10)	0.0305 (4)
O24	−0.30472 (15)	0.50267 (15)	0.13734 (11)	0.0379 (5)
O25	−0.33493 (15)	0.45280 (17)	0.44872 (11)	0.0418 (5)
C21	−0.05301 (18)	0.52055 (17)	0.37323 (14)	0.0222 (5)
C22	−0.07526 (19)	0.52725 (16)	0.28719 (14)	0.0223 (4)
C23	−0.18219 (19)	0.50781 (16)	0.25599 (13)	0.0206 (4)
C24	−0.26708 (19)	0.48109 (17)	0.31173 (14)	0.0253 (5)
C25	−0.24583 (19)	0.47660 (18)	0.39838 (14)	0.0258 (5)
C26	−0.13844 (19)	0.49559 (16)	0.42937 (14)	0.0234 (5)
C27	0.06621 (19)	0.53952 (19)	0.40395 (14)	0.0276 (5)
C28	−0.2070 (2)	0.51642 (17)	0.16184 (14)	0.0240 (5)
O1	0.03353 (15)	0.5312 (3)	0.64583 (11)	0.0798 (10)
H1A	0.3537	0.5682	0.4539	0.030*
H1B	0.2677	0.5859	0.3880	0.030*
H2A	0.4936	0.5566	0.3528	0.040*
H2B	0.3982	0.5717	0.2825	0.040*
H3A	0.3064	0.4275	0.3354	0.040*
H3B	0.4260	0.4067	0.2921	0.040*
H4A	0.5040	0.4100	0.4260	0.031*
H51A	0.2493	0.3011	0.4596	0.071*	0.853 (3)
H51B	0.2830	0.1920	0.4377	0.071*	0.853 (3)
H51C	0.2645	0.2686	0.3634	0.071*	0.853 (3)
H52A	0.4499	0.2524	0.3004	0.089*
H52B	0.4763	0.1651	0.3636	0.089*
H52C	0.5614	0.2545	0.3571	0.089*
H6A	0.4768	0.1852	0.5105	0.041*
H6B	0.5480	0.2829	0.5123	0.041*
H71X	0.2472	0.2677	0.6360	0.073*	0.147 (3)
H71Y	0.2700	0.2084	0.5510	0.073*	0.147 (3)
H71Z	0.2490	0.3225	0.5471	0.073*	0.147 (3)
H71A	0.5456	0.2710	0.6696	0.066*
H71B	0.4643	0.1788	0.6693	0.066*
H71C	0.4282	0.2745	0.7191	0.066*
H8A	0.4730	0.4191	0.6124	0.031*
H8B	0.3955	0.4196	0.5389	0.031*
H10A	0.2648	0.5661	0.6959	0.046*
H10B	0.3975	0.5597	0.6788	0.046*
H9A	0.3181	0.4049	0.7035	0.042*
H9B	0.2397	0.4183	0.6221	0.042*
H11A	0.2340	0.5822	0.5572	0.032*
H12A	0.4801	0.6873	0.6464	0.071*	0.853 (3)
H12B	0.4823	0.7754	0.5811	0.071*	0.853 (3)
H12C	0.5015	0.6673	0.5483	0.071*	0.853 (3)
H12D	0.1835	0.7338	0.6361	0.095*
H12E	0.2758	0.8181	0.6381	0.095*
H12F	0.2889	0.7264	0.6987	0.095*
H13A	0.2149	0.7225	0.4803	0.045*
H13B	0.3025	0.8087	0.4917	0.045*
H14X	0.5093	0.6904	0.4772	0.081*	0.147 (3)
H14Y	0.4892	0.7972	0.4416	0.081*	0.147 (3)
H14Z	0.5287	0.7128	0.3793	0.081*	0.147 (3)
H14A	0.3586	0.7303	0.2831	0.080*
H14B	0.3290	0.8238	0.3382	0.080*
H14C	0.2367	0.7409	0.3252	0.080*
H25	−0.3192	0.4656	0.4991	0.063*
H22	−0.0168	0.5453	0.2495	0.027*
H24	−0.3399	0.4658	0.2908	0.030*
H26	−0.1236	0.4916	0.4881	0.028*
H41	0.0383	0.5276	0.5930	0.040*
H42	−0.0371	0.5330	0.6507	0.040*
H35	0.3360	0.2685	0.4236	0.040*	0.147 (3)
H37	0.3303	0.2620	0.5880	0.039*	0.853 (3)
H312	0.4133	0.7073	0.5839	0.046*	0.147 (3)
H314	0.4417	0.7167	0.4182	0.041*	0.853 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0179 (9)	0.0360 (11)	0.0222 (9)	−0.0037 (8)	0.0000 (7)	0.0032 (9)
C2	0.0315 (13)	0.0451 (14)	0.0241 (12)	−0.0020 (12)	0.0044 (10)	0.0021 (11)
C3	0.0359 (14)	0.0436 (15)	0.0208 (11)	−0.0008 (12)	−0.0028 (10)	−0.0013 (11)
N4	0.0205 (9)	0.0341 (10)	0.0234 (10)	−0.0056 (8)	−0.0010 (8)	−0.0027 (8)
C5	0.0385 (14)	0.0329 (13)	0.0297 (13)	−0.0034 (11)	0.0008 (11)	−0.0072 (11)
C51	0.046 (2)	0.053 (2)	0.043 (2)	−0.0258 (17)	−0.0080 (16)	0.0007 (17)
C52	0.084 (3)	0.054 (2)	0.0400 (17)	0.013 (2)	0.0132 (18)	−0.0091 (16)
C6	0.0371 (14)	0.0312 (12)	0.0350 (14)	−0.0015 (11)	−0.0005 (11)	−0.0005 (11)
C7	0.0357 (13)	0.0324 (13)	0.0290 (13)	−0.0069 (11)	−0.0028 (11)	0.0008 (11)
C71	0.064 (2)	0.0316 (14)	0.0364 (15)	0.0003 (14)	−0.0077 (14)	0.0073 (12)
N8	0.0248 (9)	0.0332 (10)	0.0189 (9)	−0.0024 (8)	−0.0019 (8)	0.0021 (8)
C10	0.0419 (15)	0.0559 (17)	0.0181 (11)	0.0188 (14)	0.0003 (11)	−0.0039 (12)
C9	0.0275 (12)	0.0506 (15)	0.0260 (12)	0.0046 (12)	0.0054 (10)	0.0072 (12)
N11	0.0197 (9)	0.0373 (11)	0.0242 (10)	−0.0033 (8)	−0.0032 (8)	−0.0012 (8)
C12	0.0445 (16)	0.0380 (14)	0.0331 (15)	−0.0131 (12)	0.0031 (12)	−0.0087 (12)
C121	0.0389 (18)	0.054 (2)	0.049 (2)	−0.0217 (16)	−0.0056 (17)	−0.0082 (18)
C122	0.102 (3)	0.0410 (17)	0.0471 (19)	−0.0081 (19)	0.024 (2)	−0.0160 (15)
C13	0.0428 (16)	0.0300 (12)	0.0389 (15)	−0.0051 (12)	0.0059 (12)	−0.0016 (12)
C14	0.0324 (13)	0.0360 (13)	0.0348 (14)	−0.0073 (11)	0.0048 (12)	0.0047 (12)
C141	0.075 (2)	0.0423 (16)	0.0424 (17)	0.0013 (17)	0.0045 (17)	0.0116 (14)
O21	0.0247 (9)	0.1147 (19)	0.0238 (9)	−0.0193 (12)	−0.0066 (7)	0.0121 (11)
O22	0.0203 (8)	0.0765 (14)	0.0260 (9)	−0.0126 (9)	0.0001 (7)	0.0068 (9)
O23	0.0262 (8)	0.0482 (10)	0.0172 (7)	−0.0037 (8)	0.0005 (6)	0.0021 (7)
O24	0.0265 (9)	0.0639 (13)	0.0234 (8)	−0.0096 (9)	−0.0068 (7)	0.0043 (9)
O25	0.0241 (9)	0.0830 (15)	0.0182 (8)	−0.0216 (10)	0.0018 (7)	−0.0009 (9)
C21	0.0179 (10)	0.0282 (12)	0.0204 (10)	−0.0017 (9)	−0.0015 (8)	−0.0002 (9)
C22	0.0199 (10)	0.0282 (11)	0.0190 (10)	−0.0018 (9)	0.0007 (8)	0.0011 (9)
C23	0.0208 (10)	0.0245 (10)	0.0165 (9)	0.0012 (9)	−0.0006 (8)	−0.0005 (8)
C24	0.0181 (10)	0.0367 (13)	0.0211 (10)	−0.0062 (10)	−0.0003 (8)	−0.0042 (10)
C25	0.0199 (10)	0.0374 (13)	0.0202 (11)	−0.0061 (10)	0.0021 (8)	−0.0014 (10)
C26	0.0219 (10)	0.0294 (12)	0.0189 (10)	−0.0009 (9)	−0.0004 (8)	−0.0005 (9)
C27	0.0207 (11)	0.0424 (13)	0.0197 (11)	−0.0042 (10)	−0.0007 (9)	0.0004 (11)
C28	0.0241 (11)	0.0289 (11)	0.0188 (10)	−0.0014 (9)	−0.0014 (8)	−0.0005 (9)
O1	0.0356 (12)	0.173 (3)	0.0305 (11)	−0.0270 (17)	−0.0003 (9)	−0.0124 (16)

Geometric parameters (Å, º)

N1—C2	1.481 (3)	N11—C12	1.478 (3)
N1—C14	1.501 (3)	N11—H11A	0.9200
N1—H1A	0.9200	C12—C122	1.525 (4)
N1—H1B	0.9200	C12—C13	1.538 (4)
C2—C3	1.515 (4)	C12—C121	1.567 (5)
C2—H2A	0.9900	C121—H12A	0.9800
C2—H2B	0.9900	C121—H12B	0.9800
C3—N4	1.470 (3)	C121—H12C	0.9800
C3—H3A	0.9900	C122—H12D	0.9800
C3—H3B	0.9900	C122—H12E	0.9800
N4—C5	1.495 (3)	C122—H12F	0.9800
N4—H4A	0.9200	C13—C14	1.526 (4)
C5—C52	1.529 (4)	C13—H13A	0.9900
C5—C51	1.534 (4)	C13—H13B	0.9900
C5—C6	1.546 (4)	C14—C141	1.515 (4)
C51—H51A	0.9800	C14—C14'	1.530 (3)
C51—H51B	0.9800	C14'—H14X	0.9800
C51—H51C	0.9800	C14'—H14Y	0.9800
C52—H52A	0.9800	C14'—H14Z	0.9800
C52—H52B	0.9800	C141—H14A	0.9800
C52—H52C	0.9800	C141—H14B	0.9800
C6—C7	1.523 (4)	C141—H14C	0.9800
C6—H6A	0.9900	O21—C27	1.241 (3)
C6—H6B	0.9900	O22—C27	1.258 (3)
C7—N8	1.509 (3)	O23—C28	1.267 (3)
C7—C71	1.526 (4)	O24—C28	1.238 (3)
C7—C71'	1.531 (3)	O25—C25	1.366 (3)
C71'—H71X	0.9800	O25—H25	0.8400
C71'—H71Y	0.9800	C21—C22	1.393 (3)
C71'—H71Z	0.9800	C21—C26	1.393 (3)
C71—H71A	0.9800	C21—C27	1.520 (3)
C71—H71B	0.9800	C22—C23	1.389 (3)
C71—H71C	0.9800	C22—H22	0.9500
N8—C9	1.485 (3)	C23—C24	1.391 (3)
N8—H8A	0.9200	C23—C28	1.526 (3)
N8—H8B	0.9200	C24—C25	1.398 (3)
C10—N11	1.463 (3)	C24—H24	0.9500
C10—C9	1.502 (4)	C25—C26	1.392 (3)
C10—H10A	0.9900	C26—H26	0.9500
C10—H10B	0.9900	O1—H41	0.8412
C9—H9A	0.9900	O1—H42	0.8427
C9—H9B	0.9900
C2—N1—C14	116.7 (2)	N8—C9—H9A	109.4
C2—N1—H1A	108.1	C10—C9—H9A	109.4
C14—N1—H1A	108.1	N8—C9—H9B	109.4
C2—N1—H1B	108.1	C10—C9—H9B	109.4
C14—N1—H1B	108.1	H9A—C9—H9B	108.0
H1A—N1—H1B	107.3	C10—N11—C12	115.0 (2)
N1—C2—C3	110.3 (2)	C10—N11—H11A	108.5
N1—C2—H2A	109.6	C12—N11—H11A	108.5
C3—C2—H2A	109.6	N11—C12—C122	111.4 (2)
N1—C2—H2B	109.6	N11—C12—C13	108.0 (2)
C3—C2—H2B	109.6	C122—C12—C13	108.1 (3)
H2A—C2—H2B	108.1	N11—C12—C121	106.7 (3)
N4—C3—C2	110.5 (2)	C122—C12—C121	111.5 (3)
N4—C3—H3A	109.6	C13—C12—C121	111.0 (3)
C2—C3—H3A	109.6	C14—C13—C12	117.8 (2)
N4—C3—H3B	109.6	C14—C13—H13A	107.9
C2—C3—H3B	109.6	C12—C13—H13A	107.9
H3A—C3—H3B	108.1	C14—C13—H13B	107.9
C3—N4—C5	115.3 (2)	C12—C13—H13B	107.9
C3—N4—H4A	108.5	H13A—C13—H13B	107.2
C5—N4—H4A	108.5	N1—C14—C141	109.6 (2)
N4—C5—C52	112.2 (2)	N1—C14—C13	108.2 (2)
N4—C5—C51	109.6 (2)	C141—C14—C13	110.8 (2)
C52—C5—C51	109.9 (3)	N1—C14—C14'	112.0 (9)
N4—C5—C6	106.6 (2)	C141—C14—C14'	111.4 (9)
C52—C5—C6	107.2 (2)	C13—C14—C14'	104.7 (9)
C51—C5—C6	111.4 (2)	C14—C14'—H14X	109.5
C7—C6—C5	116.7 (2)	C14—C14'—H14Y	109.5
C7—C6—H6A	108.1	H14X—C14'—H14Y	109.5
C5—C6—H6A	108.1	C14—C14'—H14Z	109.5
C7—C6—H6B	108.1	H14X—C14'—H14Z	109.5
C5—C6—H6B	108.1	C25—O25—H25	109.5
H6A—C6—H6B	107.3	C22—C21—C26	120.3 (2)
N8—C7—C6	108.8 (2)	C22—C21—C27	118.63 (19)
N8—C7—C71	109.5 (2)	C26—C21—C27	121.09 (19)
C6—C7—C71	111.8 (2)	C23—C22—C21	120.6 (2)
N8—C7—C71'	97.5 (9)	C23—C22—H22	119.7
C6—C7—C71'	110.0 (9)	C21—C22—H22	119.7
C71—C7—C71'	118.1 (9)	C22—C23—C24	119.20 (19)
C7—C71'—H71X	109.5	C22—C23—C28	120.64 (19)
C7—C71'—H71Y	109.5	C24—C23—C28	120.2 (2)
H71X—C71'—H71Y	109.5	C23—C24—C25	120.4 (2)
C7—C71'—H71Z	109.5	C23—C24—H24	119.8
H71X—C71'—H71Z	109.5	C25—C24—H24	119.8
H71Y—C71'—H71Z	109.5	O25—C25—C26	123.3 (2)
C9—N8—C7	113.6 (2)	O25—C25—C24	116.4 (2)
C9—N8—H8A	108.8	C26—C25—C24	120.3 (2)
C7—N8—H8A	108.8	C25—C26—C21	119.2 (2)
C9—N8—H8B	108.8	C25—C26—H26	120.4
C7—N8—H8B	108.8	C21—C26—H26	120.4
H8A—N8—H8B	107.7	O21—C27—O22	124.4 (2)
N11—C10—C9	111.5 (2)	O21—C27—C21	119.5 (2)
N11—C10—H10A	109.3	O22—C27—C21	116.1 (2)
C9—C10—H10A	109.3	O23—C28—O24	123.9 (2)
N11—C10—H10B	109.3	O24—C28—C23	118.4 (2)
C9—C10—H10B	109.3	O23—C28—C23	117.7 (2)
H10A—C10—H10B	108.0	H41—O1—H42	99
N8—C9—C10	111.0 (2)
C14—N1—C2—C3	177.7 (2)	C2—N1—C14—C14'	−54.3 (10)
N1—C2—C3—N4	−69.4 (3)	C12—C13—C14—N1	62.2 (3)
C2—C3—N4—C5	−175.6 (2)	C12—C13—C14—C141	−177.6 (2)
C3—N4—C5—C52	59.9 (3)	C12—C13—C14—C14'	−57.3 (10)
C3—N4—C5—C51	−62.4 (3)	C13—C14—N1—C2	−169.3 (2)
C3—N4—C5—C6	177.0 (2)	C26—C21—C22—C23	−1.0 (4)
N4—C5—C6—C7	68.5 (3)	C27—C21—C22—C23	178.1 (2)
C52—C5—C6—C7	−171.2 (3)	C21—C22—C23—C24	−0.3 (3)
C51—C5—C6—C7	−51.0 (3)	C21—C22—C23—C28	179.2 (2)
C5—C6—C7—N8	−61.4 (3)	C22—C23—C24—C25	1.9 (4)
C5—C6—C7—C71	177.6 (2)	C28—C23—C24—C25	−177.6 (2)
C5—C6—C7—C71'	44.4 (10)	C23—C24—C25—O25	177.9 (2)
C6—C7—N8—C9	158.0 (2)	C23—C24—C25—C26	−2.2 (4)
C71—C7—N8—C9	−79.6 (3)	O25—C25—C26—C21	−179.2 (2)
C71'—C7—N8—C9	43.8 (9)	C24—C25—C26—C21	1.0 (4)
C7—N8—C9—C10	173.2 (2)	C22—C21—C26—C25	0.6 (3)
N8—C9—C10—N11	63.8 (3)	C27—C21—C26—C25	−178.5 (2)
C9—C10—N11—C12	−171.5 (2)	C22—C21—C27—O21	−174.9 (3)
C10—N11—C12—C122	−54.0 (3)	C26—C21—C27—O21	4.2 (4)
C10—N11—C12—C13	−172.5 (2)	C22—C21—C27—O22	5.6 (4)
C10—N11—C12—C121	68.0 (3)	C26—C21—C27—O22	−175.3 (2)
N11—C12—C13—C14	−64.9 (3)	C22—C23—C28—O24	−176.8 (2)
C122—C12—C13—C14	174.4 (3)	C24—C23—C28—O24	2.7 (3)
C121—C12—C13—C14	51.9 (3)	C22—C23—C28—O23	2.3 (3)
C2—N1—C14—C141	69.8 (3)	C24—C23—C28—O23	−178.3 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N11	0.92	2.02	2.767 (3)	138
N8—H8B···N4	0.92	1.97	2.762 (3)	144
N1—H1B···O22	0.92	1.71	2.622 (3)	173
N4—H4A···O25^i	0.92	2.03	2.952 (3)	175
N8—H8A···O23^ii	0.92	1.91	2.795 (3)	160
N11—H11A···O21	0.92	2.25	3.122 (3)	159
O1—H41···O21	0.84	1.90	2.720 (2)	165
O1—H42···O24^iii	0.84	1.95	2.761 (3)	160
O25—H25···O23^iii	0.84	1.93	2.655 (2)	144

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

(4) racemic-5,5,7,12,12,14-Hexamethyl-1,4,8,11-tetraazacyclotetradecane–5- hydroxyisophthalic acid–water (1/1/1)

Crystal data

C16H38N4·C8H4O5·H2O	F(000) = 1056
Mr = 484.63	Dx = 1.245 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 16.0262 (4) Å	Cell parameters from 5899 reflections
b = 11.6461 (3) Å	θ = 2.6–27.5°
c = 15.7907 (3) Å	µ = 0.09 mm^−1
β = 118.6520 (12)°	T = 100 K
V = 2586.33 (10) Å^3	Block, colourless
Z = 4	0.32 × 0.26 × 0.20 mm

Data collection

Kappa-CCD diffractometer	5899 independent reflections
Radiation source: fine-focus sealed X-ray tube	4676 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
ϕ scans and ω scans with κ offsets	θmax = 27.5°, θmin = 2.6°
Absorption correction: multi-scan DENZO-SMN (Otwinowski & Minor, 1997)	h = −20→18
Tmin = 0.972, Tmax = 0.982	k = −15→0
23221 measured reflections	l = 0→20

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)] = 0.049	H-atom parameters constrained
wR(F^2) = 0.126	w = 1/[σ^2(Fo^2) + (0.0515P)^2 + 1.3466P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
5899 reflections	Δρmax = 0.28 e Å^−3
321 parameters	Δρmin = −0.24 e Å^−3
2 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0051 (10)

Special details

Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm [Fox, G·C. & Holmes, K·C. (1966). Acta Cryst. 20, 886–891] which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the 'size' command in the SHELXL97 input file.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.35926 (9)	0.84725 (11)	0.35845 (9)	0.0200 (3)
C2	0.31516 (11)	0.91385 (13)	0.40710 (11)	0.0230 (3)
C3	0.20995 (11)	0.88704 (14)	0.36339 (11)	0.0233 (3)
N4	0.15907 (9)	0.92016 (11)	0.26131 (9)	0.0200 (3)
C5	0.05475 (11)	0.89519 (14)	0.20911 (11)	0.0238 (3)
C51	0.01036 (13)	0.98121 (16)	0.12642 (13)	0.0355 (4)
C52	0.00739 (13)	0.90913 (17)	0.27324 (14)	0.0363 (4)
C6	0.04043 (11)	0.77038 (14)	0.17185 (12)	0.0262 (3)
C7	0.06873 (11)	0.74529 (14)	0.09403 (11)	0.0253 (3)
C71	0.04701 (14)	0.62234 (16)	0.05796 (14)	0.0384 (4)
N8	0.17377 (9)	0.76942 (11)	0.13576 (9)	0.0198 (3)
C9	0.20578 (11)	0.79709 (14)	0.06392 (11)	0.0239 (3)
C10	0.31246 (11)	0.81417 (13)	0.11267 (11)	0.0233 (3)
N11	0.34067 (9)	0.90996 (11)	0.18152 (9)	0.0217 (3)
C12	0.44486 (11)	0.93542 (14)	0.23666 (12)	0.0269 (3)
C121	0.45304 (14)	1.05967 (15)	0.27200 (14)	0.0380 (4)
C122	0.49412 (14)	0.9260 (2)	0.17389 (15)	0.0449 (5)
C13	0.49262 (12)	0.85147 (15)	0.32156 (12)	0.0298 (4)
C14	0.46520 (11)	0.86210 (14)	0.40126 (11)	0.0261 (3)
C141	0.51695 (13)	0.77857 (19)	0.48305 (13)	0.0415 (5)
O21	0.28021 (9)	0.58533 (9)	0.24440 (8)	0.0281 (3)
O22	0.31083 (10)	0.63637 (10)	0.39172 (9)	0.0378 (3)
O23	0.23050 (10)	0.37353 (10)	0.58891 (8)	0.0349 (3)
O24	0.19062 (10)	0.19354 (10)	0.54074 (9)	0.0353 (3)
O25	0.21227 (11)	0.15342 (9)	0.24045 (9)	0.0362 (3)
C21	0.26545 (10)	0.44329 (12)	0.34551 (10)	0.0183 (3)
C22	0.25704 (10)	0.42315 (12)	0.42832 (10)	0.0189 (3)
C23	0.23106 (10)	0.31493 (12)	0.44489 (10)	0.0181 (3)
C24	0.21613 (11)	0.22665 (12)	0.38011 (10)	0.0199 (3)
C25	0.22660 (11)	0.24538 (12)	0.29835 (10)	0.0215 (3)
C26	0.25003 (11)	0.35447 (12)	0.28028 (10)	0.0198 (3)
C27	0.28762 (11)	0.56353 (12)	0.32615 (11)	0.0216 (3)
C28	0.21697 (11)	0.29156 (13)	0.53189 (10)	0.0213 (3)
O1	0.28442 (11)	0.51328 (12)	0.08053 (9)	0.0404 (3)
H1A	0.3309	0.8687	0.2946	0.024*
H1B	0.3465	0.7706	0.3605	0.024*
H2A	0.3237	0.9970	0.4006	0.028*
H2B	0.3474	0.8948	0.4767	0.028*
H3A	0.2014	0.8038	0.3694	0.028*
H3B	0.1830	0.9290	0.3992	0.028*
H4A	0.1674	0.9977	0.2572	0.024*
H51A	0.0084	1.0572	0.1521	0.053*
H51B	−0.0544	0.9567	0.0808	0.053*
H51C	0.0486	0.9850	0.0932	0.053*
H52A	0.0298	0.8484	0.3222	0.054*
H52B	−0.0618	0.9036	0.2334	0.054*
H52C	0.0240	0.9843	0.3050	0.054*
H6A	0.0776	0.7191	0.2274	0.031*
H6B	−0.0275	0.7503	0.1459	0.031*
H7	0.0328	0.7983	0.0384	0.030*
H71A	0.0706	0.6084	0.0120	0.058*
H71B	−0.0219	0.6097	0.0260	0.058*
H71C	0.0783	0.5695	0.1126	0.058*
H8A	0.1893	0.8299	0.1781	0.024*
H8B	0.2070	0.7062	0.1706	0.024*
H9A	0.1736	0.8679	0.0287	0.029*
H9B	0.1876	0.7338	0.0165	0.029*
H10A	0.3448	0.7430	0.1471	0.028*
H10B	0.3323	0.8305	0.0634	0.028*
H11A	0.3098	0.9751	0.1482	0.026*
H12A	0.4308	1.1121	0.2169	0.057*
H12B	0.5196	1.0768	0.3178	0.057*
H12C	0.4140	1.0695	0.3039	0.057*
H12D	0.4959	0.8454	0.1571	0.067*
H12E	0.5592	0.9557	0.2098	0.067*
H12F	0.4587	0.9710	0.1148	0.067*
H13A	0.4778	0.7724	0.2956	0.036*
H13B	0.5623	0.8616	0.3509	0.036*
H14	0.4816	0.9416	0.4283	0.031*
H14A	0.4962	0.7895	0.5317	0.062*
H14B	0.5856	0.7921	0.5124	0.062*
H14C	0.5027	0.6999	0.4582	0.062*
H25	0.2206	0.1728	0.1938	0.054*
H22	0.2691	0.4834	0.4733	0.023*
H24	0.1986	0.1527	0.3915	0.024*
H26	0.2555	0.3684	0.2239	0.024*
H41	0.2841 (18)	0.529 (2)	0.1323 (10)	0.060*
H42	0.2555 (16)	0.4503 (11)	0.0629 (17)	0.060*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0218 (6)	0.0196 (6)	0.0177 (6)	−0.0010 (5)	0.0088 (5)	−0.0007 (5)
C2	0.0245 (8)	0.0247 (7)	0.0207 (7)	−0.0016 (6)	0.0115 (6)	−0.0042 (6)
C3	0.0245 (8)	0.0273 (8)	0.0204 (7)	−0.0024 (6)	0.0126 (6)	−0.0013 (6)
N4	0.0209 (6)	0.0183 (6)	0.0209 (6)	−0.0019 (5)	0.0100 (5)	−0.0005 (5)
C5	0.0201 (7)	0.0266 (8)	0.0245 (7)	−0.0013 (6)	0.0106 (6)	−0.0039 (6)
C51	0.0315 (9)	0.0322 (9)	0.0326 (9)	0.0031 (7)	0.0072 (7)	−0.0007 (7)
C52	0.0291 (9)	0.0466 (10)	0.0384 (10)	−0.0034 (8)	0.0202 (8)	−0.0119 (8)
C6	0.0236 (8)	0.0279 (8)	0.0277 (8)	−0.0063 (6)	0.0125 (6)	−0.0047 (7)
C7	0.0223 (8)	0.0265 (8)	0.0252 (8)	−0.0053 (6)	0.0099 (6)	−0.0059 (6)
C71	0.0369 (10)	0.0354 (10)	0.0458 (11)	−0.0146 (8)	0.0222 (9)	−0.0193 (8)
N8	0.0226 (6)	0.0179 (6)	0.0197 (6)	−0.0022 (5)	0.0109 (5)	−0.0012 (5)
C9	0.0316 (8)	0.0246 (7)	0.0180 (7)	−0.0039 (6)	0.0139 (6)	−0.0016 (6)
C10	0.0284 (8)	0.0229 (7)	0.0236 (7)	−0.0013 (6)	0.0165 (7)	−0.0004 (6)
N11	0.0234 (6)	0.0200 (6)	0.0240 (6)	−0.0023 (5)	0.0133 (5)	0.0001 (5)
C12	0.0245 (8)	0.0313 (8)	0.0293 (8)	−0.0067 (7)	0.0164 (7)	−0.0033 (7)
C121	0.0386 (10)	0.0304 (9)	0.0416 (10)	−0.0129 (8)	0.0164 (8)	−0.0019 (8)
C122	0.0358 (10)	0.0669 (14)	0.0433 (11)	−0.0119 (10)	0.0280 (9)	−0.0037 (10)
C13	0.0241 (8)	0.0328 (9)	0.0334 (9)	0.0003 (7)	0.0145 (7)	−0.0038 (7)
C14	0.0200 (8)	0.0303 (8)	0.0251 (8)	−0.0017 (6)	0.0086 (6)	−0.0031 (7)
C141	0.0303 (9)	0.0524 (12)	0.0328 (10)	0.0082 (9)	0.0079 (8)	0.0088 (9)
O21	0.0460 (7)	0.0196 (5)	0.0257 (6)	0.0012 (5)	0.0228 (5)	0.0043 (4)
O22	0.0695 (9)	0.0204 (6)	0.0314 (6)	−0.0122 (6)	0.0306 (7)	−0.0062 (5)
O23	0.0593 (8)	0.0301 (6)	0.0270 (6)	−0.0119 (6)	0.0302 (6)	−0.0079 (5)
O24	0.0600 (9)	0.0264 (6)	0.0314 (6)	−0.0063 (6)	0.0315 (6)	0.0014 (5)
O25	0.0751 (10)	0.0191 (5)	0.0323 (6)	−0.0134 (6)	0.0402 (7)	−0.0089 (5)
C21	0.0223 (7)	0.0159 (7)	0.0174 (7)	0.0003 (5)	0.0102 (6)	0.0011 (5)
C22	0.0232 (7)	0.0182 (7)	0.0164 (7)	0.0005 (6)	0.0104 (6)	−0.0018 (5)
C23	0.0200 (7)	0.0200 (7)	0.0152 (6)	0.0016 (5)	0.0093 (6)	0.0022 (5)
C24	0.0258 (7)	0.0165 (7)	0.0207 (7)	−0.0008 (6)	0.0136 (6)	0.0014 (6)
C25	0.0299 (8)	0.0180 (7)	0.0196 (7)	−0.0009 (6)	0.0141 (6)	−0.0033 (6)
C26	0.0253 (7)	0.0203 (7)	0.0174 (7)	0.0000 (6)	0.0131 (6)	0.0001 (6)
C27	0.0264 (8)	0.0177 (7)	0.0240 (7)	−0.0001 (6)	0.0147 (6)	0.0004 (6)
C28	0.0257 (8)	0.0226 (7)	0.0178 (7)	0.0007 (6)	0.0121 (6)	0.0014 (6)
O1	0.0604 (9)	0.0388 (7)	0.0308 (7)	−0.0065 (6)	0.0291 (7)	−0.0008 (6)

Geometric parameters (Å, º)

N1—C2	1.487 (2)	N11—C12	1.497 (2)
N1—C14	1.506 (2)	N11—H11A	0.9200
N1—H1A	0.9200	C12—C121	1.534 (2)
N1—H1B	0.9200	C12—C13	1.535 (2)
C2—C3	1.517 (2)	C12—C122	1.539 (2)
C2—H2A	0.9900	C121—H12A	0.9800
C2—H2B	0.9900	C121—H12B	0.9800
C3—N4	1.467 (2)	C121—H12C	0.9800
C3—H3A	0.9900	C122—H12D	0.9800
C3—H3B	0.9900	C122—H12E	0.9800
N4—C5	1.496 (2)	C122—H12F	0.9800
N4—H4A	0.9200	C13—C14	1.524 (2)
C5—C51	1.524 (2)	C13—H13A	0.9900
C5—C52	1.538 (2)	C13—H13B	0.9900
C5—C6	1.543 (2)	C14—C141	1.508 (2)
C51—H51A	0.9800	C14—H14	1.0000
C51—H51B	0.9800	C141—H14A	0.9800
C51—H51C	0.9800	C141—H14B	0.9800
C52—H52A	0.9800	C141—H14C	0.9800
C52—H52B	0.9800	O21—C27	1.264 (2)
C52—H52C	0.9800	O22—C27	1.249 (2)
C6—C7	1.528 (2)	O23—C28	1.258 (2)
C6—H6A	0.9900	O24—C28	1.248 (2)
C6—H6B	0.9900	O25—C25	1.3544 (18)
C7—N8	1.511 (2)	O25—H25	0.8400
C7—C71	1.518 (2)	C21—C26	1.396 (2)
C7—H7	1.0000	C21—C22	1.3971 (19)
C71—H71A	0.9800	C21—C27	1.511 (2)
C71—H71B	0.9800	C22—C23	1.391 (2)
C71—H71C	0.9800	C22—H22	0.9500
N8—C9	1.487 (2)	C23—C24	1.388 (2)
N8—H8A	0.9200	C23—C28	1.5198 (19)
N8—H8B	0.9200	C24—C25	1.396 (2)
C9—C10	1.514 (2)	C24—H24	0.9500
C9—H9A	0.9900	C25—C26	1.393 (2)
C9—H9B	0.9900	C26—H26	0.9500
C10—N11	1.470 (12)	O1—H41	0.841
C10—H10A	0.9900	O1—H42	0.841
C10—H10B	0.9900
C2—N1—C14	114.9 (2)	N11—C10—H10A	109.6
C2—N1—H1A	108.5	C9—C10—H10A	109.6
C14—N1—H1A	108.5	N11—C10—H10B	109.6
C2—N1—H1B	108.5	C9—C10—H10B	109.6
C14—N1—H1B	108.5	H10A—C10—H10B	108.1
H1A—N1—H1B	107.5	C10—N11—C12	116.3 (2)
N1—C2—C3	110.94 (12)	C10—N11—H11A	108.2
N1—C2—H2A	109.5	C12—N11—H11A	108.2
C3—C2—H2A	109.5	N11—C12—C121	106.00 (13)
N1—C2—H2B	109.5	N11—C12—C13	109.39 (13)
C3—C2—H2B	109.5	C121—C12—C13	111.31 (14)
H2A—C2—H2B	108.0	N11—C12—C122	112.64 (14)
N4—C3—C2	110.91 (12)	C121—C12—C122	108.70 (15)
N4—C3—H3A	109.5	C13—C12—C122	108.80 (15)
C2—C3—H3A	109.5	C12—C121—H12A	109.5
N4—C3—H3B	109.5	C12—C121—H12B	109.5
C2—C3—H3B	109.5	H12A—C121—H12B	109.5
H3A—C3—H3B	108.0	C12—C121—H12C	109.5
C3—N4—C5	116.1 (2)	H12A—C121—H12C	109.5
C3—N4—H4A	108.3	H12B—C121—H12C	109.5
C5—N4—H4A	108.3	C12—C122—H12D	109.5
N4—C5—C51	106.46 (13)	C12—C122—H12E	109.5
N4—C5—C52	112.99 (13)	H12D—C122—H12E	109.5
C51—C5—C52	108.65 (14)	C12—C122—H12F	109.5
N4—C5—C6	108.41 (12)	H12D—C122—H12F	109.5
C51—C5—C6	111.68 (13)	H12E—C122—H12F	109.5
C52—C5—C6	108.69 (14)	C14—C13—C12	116.69 (14)
C5—C51—H51A	109.5	C14—C13—H13A	108.1
C5—C51—H51B	109.5	C12—C13—H13A	108.1
H51A—C51—H51B	109.5	C14—C13—H13B	108.1
C5—C51—H51C	109.5	C12—C13—H13B	108.1
H51A—C51—H51C	109.5	H13A—C13—H13B	107.3
H51B—C51—H51C	109.5	N1—C14—C141	110.42 (14)
C5—C52—H52A	109.5	N1—C14—C13	109.23 (12)
C5—C52—H52B	109.5	C141—C14—C13	113.38 (15)
H52A—C52—H52B	109.5	N1—C14—H14	107.9
C5—C52—H52C	109.5	C141—C14—H14	107.9
H52A—C52—H52C	109.5	C13—C14—H14	107.9
H52B—C52—H52C	109.5	C14—C141—H14A	109.5
C7—C6—C5	116.07 (13)	C14—C141—H14B	109.5
C7—C6—H6A	108.3	H14A—C141—H14B	109.5
C5—C6—H6A	108.3	C14—C141—H14C	109.5
C7—C6—H6B	108.3	H14A—C141—H14C	109.5
C5—C6—H6B	108.3	H14B—C141—H14C	109.5
H6A—C6—H6B	107.4	C25—O25—H25	109.5
N8—C7—C71	110.24 (13)	C26—C21—C22	120.26 (13)
N8—C7—C6	108.17 (12)	C26—C21—C27	120.86 (12)
C71—C7—C6	112.27 (14)	C22—C21—C27	118.84 (13)
N8—C7—H7	108.7	C23—C22—C21	120.01 (13)
C71—C7—H7	108.7	C23—C22—H22	120.0
C6—C7—H7	108.7	C21—C22—H22	120.0
C7—C71—H71A	109.5	C24—C23—C22	119.60 (13)
C7—C71—H71B	109.5	C24—C23—C28	119.07 (13)
H71A—C71—H71B	109.5	C22—C23—C28	121.33 (13)
C7—C71—H71C	109.5	C23—C24—C25	120.74 (13)
H71A—C71—H71C	109.5	C23—C24—H24	119.6
H71B—C71—H71C	109.5	C25—C24—H24	119.6
C9—N8—C7	115.3 (2)	O25—C25—C26	123.93 (13)
C9—N8—H8A	108.4	O25—C25—C24	116.36 (13)
C7—N8—H8A	108.4	C26—C25—C24	119.71 (13)
C9—N8—H8B	108.4	C25—C26—C21	119.65 (13)
C7—N8—H8B	108.4	C25—C26—H26	120.2
H8A—N8—H8B	107.5	C21—C26—H26	120.2
N8—C9—C10	111.04 (12)	O22—C27—O21	123.7 (2)
N8—C9—H9A	109.4	O22—C27—C21	117.83 (13)
C10—C9—H9A	109.4	O21—C27—C21	118.47 (13)
N8—C9—H9B	109.4	O24—C28—O23	124.4 (2)
C10—C9—H9B	109.4	O24—C28—C23	118.02 (13)
H9A—C9—H9B	108.0	O23—C28—C23	117.51 (13)
N11—C10—C9	110.35 (12)	H41—O1—H42	105
C14—N1—C2—C3	−176.1 (2)	C2—N1—C14—C13	−148.1 (2)
N1—C2—C3—N4	−62.2 (2)	C12—C13—C14—N1	57.8 (2)
C2—C3—N4—C5	178.5 (2)	C12—C13—C14—C141	−178.60 (15)
C3—N4—C5—C51	154.09 (13)	C26—C21—C22—C23	−1.5 (2)
C3—N4—C5—C52	34.91 (19)	C27—C21—C22—C23	176.13 (13)
C3—N4—C5—C6	−85.6 (2)	C21—C22—C23—C24	1.7 (2)
N4—C5—C6—C7	−66.3 (2)	C21—C22—C23—C28	−177.23 (13)
C51—C5—C6—C7	50.68 (19)	C22—C23—C24—C25	−0.2 (2)
C52—C5—C6—C7	170.53 (14)	C28—C23—C24—C25	178.78 (14)
C5—C6—C7—N8	61.3 (2)	C23—C24—C25—O25	178.80 (14)
C5—C6—C7—C71	−176.79 (14)	C23—C24—C25—C26	−1.6 (2)
C71—C7—N8—C9	81.27 (17)	O25—C25—C26—C21	−178.59 (15)
C6—C7—N8—C9	−155.6 (2)	C24—C25—C26—C21	1.8 (2)
C7—N8—C9—C10	−177.3 (2)	C22—C21—C26—C25	−0.3 (2)
N8—C9—C10—N11	−60.7 (2)	C27—C21—C26—C25	−177.87 (14)
C9—C10—N11—C12	178.9 (2)	C26—C21—C27—O22	−172.39 (15)
C10—N11—C12—C121	159.18 (13)	C22—C21—C27—O22	10.0 (2)
C10—N11—C12—C13	−80.7 (2)	C26—C21—C27—O21	8.7 (2)
C10—N11—C12—C122	40.43 (19)	C22—C21—C27—O21	−168.87 (14)
N11—C12—C13—C14	−66.5 (2)	C24—C23—C28—O24	−1.3 (2)
C121—C12—C13—C14	50.26 (19)	C22—C23—C28—O24	177.68 (15)
C122—C12—C13—C14	170.03 (15)	C24—C23—C28—O23	−179.58 (14)
C2—N1—C14—C141	86.60 (17)	C22—C23—C28—O23	−0.6 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N11	0.92	1.93	2.762 (2)	150
N8—H8A···N4	0.92	1.92	2.742 (2)	148
N1—H1B···O22	0.92	1.81	2.702 (2)	162
N4—H4A···O25^i	0.92	2.01	2.913 (2)	165
N8—H8B···O21	0.92	1.85	2.765 (2)	176
N11—H11A···O23^ii	0.92	2.11	3.023 (2)	170
O1—H41···O21	0.84	1.92 (2)	2.752 (2)	172 (2)
O1—H42···O24^iii	0.84	1.91 (2)	2.748 (2)	172 (2)
O25—H25···O23^iii	0.84	1.82	2.565 (2)	147

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