Carboxyl­ate–phenolate tautomerism in 5-[(nitro­phen­yl)diazen­yl]salicylate anions

Aryl­diazenyl derivatives of salicylic acid and their salts are used as dyes. In these structures, the carboxyl­ate groups are engaged in short contacts with the cations and in hydrogen bonds with water mol­ecules, if present. If both O atoms of the carboxyl­ate group take part in such inter­actions, the negative charge is delocalized over the two atoms. In the absence of hydrogen bonds and contacts with cations, the negative charge is localized on one of the O atoms. In the crystal structures of tetra­methyl­ammonium 2-hy­droxy-5-[(E)-(4-nitro­phen­yl)diazen­yl]benzoate and tetra­methyl­ammonium 2-hy­droxy-5-[(E)-(2-nitro­phen­yl)diazen­yl]benzoate, both C₄H₁₂N⁺·C₁₃H₈N₃O₅⁻, all the inter­actions between the cations and anions are weak, and their effect on the geometry of the anions is negligible. Under these conditions, the 2-nitro-substituted anion is an almost pure phenol–carboxyl­ate tautomer, whereas in the 4-nitro-substituted anion, the phenolic H atom is shifted towards the carboxyl­ate group, and thus the structure of this anion is inter­mediate between the phenol–carboxyl­ate and phenolate–carb­oxy­lic acid tautomeric forms. The probable formation of such an inter­mediate form is supported by quantum chemical calculations. Being the characteristic feature of this form, a short distance between the phenolic and carboxyl­ate O atoms is observed in the 4-nitro-substituted anion, as well as in the structures of some 3,5-di­nitro­salicylates reported in the literature.

Computing details

For both compounds, data collection: X-AREA (Stoe & Cie, 2012); cell refinement: X-AREA (Stoe & Cie, 2012); data reduction: X-RED32 (Stoe & Cie, 2012); program(s) used to solve structure: SIR2014 (Burla et al., 2015); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).

(I) Tetramethylammonium 2-hydroxy-5-[(E)-(4-nitrophenyl)diazenyl]benzoate

Crystal data

C4H12N^+·C13H8N3O5^−	F(000) = 1520
Mr = 360.37	Dx = 1.335 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 36.5539 (17) Å	Cell parameters from 6560 reflections
b = 6.0781 (2) Å	θ = 3.0–28.2°
c = 16.5167 (7) Å	µ = 0.10 mm^−1
β = 102.228 (4)°	T = 295 K
V = 3586.4 (3) Å^3	Block, dark red
Z = 8	0.40 × 0.35 × 0.25 mm

Data collection

Stoe STADI VARI diffractometer	3337 independent reflections
Radiation source: fine-focus sealed tube	2015 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.015
Detector resolution: 5.81 pixels mm^-1	θmax = 25.5°, θmin = 2.3°
rotation method scans	h = −43→44
Absorption correction: multi-scan (Blessing, 1995)	k = −5→7
Tmin = 0.928, Tmax = 0.974	l = −17→20
6523 measured reflections

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 0.94	w = 1/[σ^2(Fo^2) + (0.0454P)^2] where P = (Fo^2 + 2Fc^2)/3
3337 reflections	(Δ/σ)max < 0.001
243 parameters	Δρmax = 0.19 e Å^−3
0 restraints	Δρmin = −0.12 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.

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

	x	y	z	Uiso*/Ueq
O1	0.06557 (4)	0.7830 (2)	0.33914 (7)	0.0754 (4)
H1	0.0456 (7)	0.661 (5)	0.3479 (16)	0.159 (10)*
O2	0.02960 (3)	0.4775 (2)	0.37447 (7)	0.0666 (3)
O3	0.05522 (3)	0.2235 (2)	0.46551 (8)	0.0772 (4)
O4	0.33013 (4)	−0.2619 (3)	0.76842 (9)	0.0948 (5)
O5	0.35761 (4)	0.0489 (3)	0.77191 (13)	0.1437 (8)
N1	0.19620 (4)	0.4663 (3)	0.53536 (9)	0.0707 (4)
N2	0.19540 (4)	0.2708 (2)	0.55609 (8)	0.0637 (4)
N3	0.33039 (4)	−0.0679 (3)	0.75103 (10)	0.0775 (5)
C1	0.09442 (4)	0.5020 (2)	0.42998 (8)	0.0447 (3)
C2	0.09601 (5)	0.7030 (3)	0.38885 (9)	0.0544 (4)
C3	0.12944 (5)	0.8188 (3)	0.40191 (11)	0.0761 (5)
H3	0.1303	0.9546	0.3764	0.091*
C4	0.16088 (5)	0.7370 (3)	0.45123 (11)	0.0758 (5)
H4	0.1829	0.8186	0.4605	0.091*
C5	0.16039 (4)	0.5296 (3)	0.48844 (10)	0.0640 (5)
C6	0.12681 (4)	0.4152 (3)	0.47819 (9)	0.0504 (4)
H6	0.1261	0.2796	0.5039	0.060*
C7	0.23139 (5)	0.2075 (3)	0.60282 (10)	0.0686 (5)
C8	0.23265 (5)	−0.0006 (3)	0.63663 (10)	0.0670 (5)
H8	0.2109	−0.0845	0.6266	0.080*
C9	0.26464 (4)	−0.0898 (3)	0.68449 (10)	0.0570 (4)
H9	0.2644	−0.2310	0.7061	0.068*
C10	0.29667 (4)	0.0312 (3)	0.69979 (10)	0.0610 (4)
C11	0.29731 (5)	0.2437 (3)	0.66709 (12)	0.0754 (5)
H11	0.3190	0.3282	0.6772	0.090*
C12	0.26383 (6)	0.3227 (3)	0.61852 (11)	0.0715 (5)
H12	0.2638	0.4626	0.5957	0.086*
C13	0.05769 (4)	0.3875 (3)	0.42416 (9)	0.0490 (4)
N4	0.05441 (3)	0.09897 (19)	0.14545 (7)	0.0441 (3)
C41	0.05286 (4)	0.2389 (3)	0.21893 (9)	0.0595 (4)
H41A	0.0729	0.3437	0.2271	0.089*
H41B	0.0553	0.1476	0.2672	0.089*
H41C	0.0293	0.3152	0.2097	0.089*
C42	0.02309 (4)	−0.0620 (3)	0.13261 (11)	0.0618 (4)
H42A	−0.0003	0.0154	0.1233	0.093*
H42B	0.0253	−0.1532	0.1809	0.093*
H42C	0.0240	−0.1523	0.0854	0.093*
C43	0.05044 (5)	0.2411 (3)	0.07027 (10)	0.0684 (5)
H43A	0.0515	0.1512	0.0230	0.103*
H43B	0.0704	0.3467	0.0784	0.103*
H43C	0.0268	0.3165	0.0611	0.103*
C44	0.09044 (4)	−0.0228 (3)	0.15858 (11)	0.0687 (5)
H44A	0.0905	−0.1172	0.1120	0.103*
H44B	0.0933	−0.1100	0.2080	0.103*
H44C	0.1108	0.0800	0.1642	0.103*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0851 (9)	0.0706 (9)	0.0668 (8)	0.0105 (7)	0.0074 (7)	0.0223 (7)
O2	0.0501 (6)	0.0831 (9)	0.0628 (7)	−0.0007 (6)	0.0033 (5)	0.0005 (6)
O3	0.0719 (8)	0.0781 (9)	0.0790 (8)	−0.0247 (7)	0.0100 (6)	0.0177 (7)
O4	0.0667 (9)	0.1093 (12)	0.1050 (11)	0.0258 (9)	0.0105 (7)	0.0230 (10)
O5	0.0561 (9)	0.1506 (16)	0.204 (2)	−0.0213 (10)	−0.0185 (10)	−0.0364 (14)
N1	0.0786 (10)	0.0676 (10)	0.0636 (9)	−0.0036 (8)	0.0099 (7)	0.0041 (8)
N2	0.0652 (9)	0.0644 (10)	0.0607 (8)	−0.0007 (7)	0.0117 (7)	0.0003 (8)
N3	0.0412 (8)	0.0999 (13)	0.0883 (12)	0.0014 (9)	0.0066 (7)	−0.0147 (11)
C1	0.0479 (8)	0.0509 (9)	0.0370 (8)	−0.0005 (7)	0.0130 (6)	−0.0043 (7)
C2	0.0693 (10)	0.0533 (10)	0.0438 (8)	0.0004 (9)	0.0193 (8)	0.0049 (8)
C3	0.0870 (14)	0.0705 (12)	0.0721 (12)	−0.0263 (11)	0.0196 (10)	0.0098 (10)
C4	0.0629 (11)	0.0921 (15)	0.0717 (12)	−0.0345 (11)	0.0124 (9)	−0.0082 (11)
C5	0.0578 (10)	0.0836 (13)	0.0527 (10)	−0.0129 (10)	0.0165 (8)	−0.0172 (9)
C6	0.0545 (9)	0.0536 (9)	0.0436 (8)	−0.0003 (8)	0.0118 (7)	0.0028 (7)
C7	0.0666 (11)	0.0785 (13)	0.0621 (11)	0.0129 (11)	0.0168 (9)	−0.0028 (10)
C8	0.0549 (10)	0.0774 (13)	0.0638 (11)	0.0091 (9)	0.0014 (8)	−0.0093 (10)
C9	0.0566 (10)	0.0515 (9)	0.0611 (10)	0.0014 (8)	0.0087 (8)	−0.0004 (8)
C10	0.0515 (9)	0.0678 (11)	0.0654 (11)	0.0001 (9)	0.0164 (8)	−0.0119 (9)
C11	0.0665 (12)	0.0727 (13)	0.0924 (13)	−0.0256 (10)	0.0291 (10)	−0.0174 (11)
C12	0.0973 (14)	0.0527 (11)	0.0713 (12)	0.0013 (11)	0.0329 (11)	0.0003 (9)
C13	0.0502 (9)	0.0559 (10)	0.0408 (8)	−0.0036 (8)	0.0095 (7)	−0.0034 (8)
N4	0.0409 (6)	0.0495 (7)	0.0409 (6)	0.0016 (6)	0.0061 (5)	0.0000 (6)
C41	0.0657 (10)	0.0623 (10)	0.0511 (9)	0.0084 (8)	0.0135 (7)	−0.0073 (8)
C42	0.0527 (9)	0.0634 (11)	0.0676 (10)	−0.0107 (8)	0.0090 (7)	−0.0024 (9)
C43	0.0824 (11)	0.0712 (12)	0.0533 (9)	0.0038 (9)	0.0182 (8)	0.0141 (9)
C44	0.0491 (9)	0.0803 (12)	0.0740 (11)	0.0150 (9)	0.0066 (8)	−0.0091 (10)

Geometric parameters (Å, º)

O1—C2	1.3273 (18)	C8—H8	0.9300
O1—H1	1.07 (3)	C9—C10	1.360 (2)
O2—C13	1.2923 (17)	C9—H9	0.9300
O2—H1	1.37 (3)	C10—C11	1.402 (2)
O3—C13	1.2225 (18)	C11—C12	1.399 (2)
O4—N3	1.2141 (19)	C11—H11	0.9300
O5—N3	1.2118 (19)	C12—H12	0.9300
N1—N2	1.2388 (18)	N4—C44	1.4860 (17)
N1—C5	1.426 (2)	N4—C42	1.4870 (17)
N2—C7	1.430 (2)	N4—C41	1.4929 (18)
N3—C10	1.469 (2)	N4—C43	1.4941 (18)
C1—C6	1.3836 (19)	C41—H41A	0.9600
C1—C2	1.405 (2)	C41—H41B	0.9600
C1—C13	1.4971 (19)	C41—H41C	0.9600
C2—C3	1.387 (2)	C42—H42A	0.9600
C3—C4	1.355 (2)	C42—H42B	0.9600
C3—H3	0.9300	C42—H42C	0.9600
C4—C5	1.404 (2)	C43—H43A	0.9600
C4—H4	0.9300	C43—H43B	0.9600
C5—C6	1.390 (2)	C43—H43C	0.9600
C6—H6	0.9300	C44—H44A	0.9600
C7—C12	1.354 (2)	C44—H44B	0.9600
C7—C8	1.380 (2)	C44—H44C	0.9600
C8—C9	1.376 (2)
C2—O1—H1	99.7 (14)	C12—C11—H11	121.5
C13—O2—H1	102.2 (11)	C10—C11—H11	121.5
N2—N1—C5	109.66 (15)	C7—C12—C11	123.81 (17)
N1—N2—C7	109.54 (15)	C7—C12—H12	118.1
O5—N3—O4	123.30 (18)	C11—C12—H12	118.1
O5—N3—C10	117.5 (2)	O3—C13—O2	123.85 (14)
O4—N3—C10	119.15 (16)	O3—C13—C1	120.96 (14)
C6—C1—C2	119.46 (14)	O2—C13—C1	115.17 (14)
C6—C1—C13	120.41 (14)	C44—N4—C42	108.96 (12)
C2—C1—C13	120.09 (13)	C44—N4—C41	110.51 (11)
O1—C2—C3	120.40 (15)	C42—N4—C41	109.26 (11)
O1—C2—C1	120.17 (14)	C44—N4—C43	109.67 (12)
C3—C2—C1	119.41 (15)	C42—N4—C43	108.99 (12)
C4—C3—C2	120.99 (17)	C41—N4—C43	109.43 (12)
C4—C3—H3	119.5	N4—C41—H41A	109.5
C2—C3—H3	119.5	N4—C41—H41B	109.5
C3—C4—C5	120.31 (16)	H41A—C41—H41B	109.5
C3—C4—H4	119.8	N4—C41—H41C	109.5
C5—C4—H4	119.8	H41A—C41—H41C	109.5
C6—C5—C4	119.27 (16)	H41B—C41—H41C	109.5
C6—C5—N1	128.10 (17)	N4—C42—H42A	109.5
C4—C5—N1	112.62 (15)	N4—C42—H42B	109.5
C1—C6—C5	120.36 (15)	H42A—C42—H42B	109.5
C1—C6—H6	119.8	N4—C42—H42C	109.5
C5—C6—H6	119.8	H42A—C42—H42C	109.5
C12—C7—C8	116.36 (17)	H42B—C42—H42C	109.5
C12—C7—N2	129.24 (18)	N4—C43—H43A	109.5
C8—C7—N2	114.40 (17)	N4—C43—H43B	109.5
C9—C8—C7	123.03 (17)	H43A—C43—H43B	109.5
C9—C8—H8	118.5	N4—C43—H43C	109.5
C7—C8—H8	118.5	H43A—C43—H43C	109.5
C10—C9—C8	119.12 (17)	H43B—C43—H43C	109.5
C10—C9—H9	120.4	N4—C44—H44A	109.5
C8—C9—H9	120.4	N4—C44—H44B	109.5
C9—C10—C11	120.71 (16)	H44A—C44—H44B	109.5
C9—C10—N3	118.01 (16)	N4—C44—H44C	109.5
C11—C10—N3	121.29 (16)	H44A—C44—H44C	109.5
C12—C11—C10	116.96 (16)	H44B—C44—H44C	109.5
C5—N1—N2—C7	179.75 (12)	C12—C7—C8—C9	0.5 (2)
C6—C1—C2—O1	176.67 (13)	N2—C7—C8—C9	−179.13 (14)
C13—C1—C2—O1	−5.7 (2)	C7—C8—C9—C10	0.1 (2)
C6—C1—C2—C3	−4.5 (2)	C8—C9—C10—C11	−0.3 (2)
C13—C1—C2—C3	173.12 (14)	C8—C9—C10—N3	180.00 (14)
O1—C2—C3—C4	−178.72 (16)	O5—N3—C10—C9	−172.07 (17)
C1—C2—C3—C4	2.5 (3)	O4—N3—C10—C9	10.0 (2)
C2—C3—C4—C5	1.7 (3)	O5—N3—C10—C11	8.2 (2)
C3—C4—C5—C6	−3.9 (3)	O4—N3—C10—C11	−169.74 (17)
C3—C4—C5—N1	177.61 (16)	C9—C10—C11—C12	−0.2 (2)
N2—N1—C5—C6	11.7 (2)	N3—C10—C11—C12	179.51 (15)
N2—N1—C5—C4	−169.97 (15)	C8—C7—C12—C11	−1.0 (3)
C2—C1—C6—C5	2.4 (2)	N2—C7—C12—C11	178.54 (16)
C13—C1—C6—C5	−175.25 (13)	C10—C11—C12—C7	0.9 (3)
C4—C5—C6—C1	1.8 (2)	C6—C1—C13—O3	4.5 (2)
N1—C5—C6—C1	−179.97 (14)	C2—C1—C13—O3	−173.19 (14)
N1—N2—C7—C12	−6.1 (2)	C6—C1—C13—O2	−176.96 (13)
N1—N2—C7—C8	173.45 (15)	C2—C1—C13—O2	5.41 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	1.07 (3)	1.37 (3)	2.4170 (17)	162 (2)
C41—H41A···O5^i	0.96	2.62	3.491 (2)	151
C41—H41B···O1^ii	0.96	2.50	3.383 (2)	152
C41—H41C···O2^iii	0.96	2.51	3.4058 (19)	156
C42—H42A···O3^iii	0.96	2.56	3.445 (2)	154
C42—H42C···O3^iv	0.96	2.52	3.367 (2)	147
C43—H43A···O3^iv	0.96	2.48	3.336 (2)	148
C44—H44A···O3^iv	0.96	2.57	3.402 (2)	145
C44—H44B···O1^ii	0.96	2.66	3.502 (2)	147
C44—H44C···O5^i	0.96	2.65	3.507 (2)	149

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

(II) Tetramethylammonium 2-hydroxy-5-[(E)-(2-nitrophenyl)diazenyl]benzoate

Crystal data

C4H12N^+·C13H8N3O5^−	F(000) = 760
Mr = 360.37	Dx = 1.353 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.4305 (7) Å	Cell parameters from 5134 reflections
b = 6.7820 (4) Å	θ = 3.0–27.7°
c = 19.4498 (11) Å	µ = 0.10 mm^−1
β = 92.935 (4)°	T = 295 K
V = 1769.27 (17) Å^3	Irregular block, red
Z = 4	0.35 × 0.30 × 0.25 mm

Data collection

Stoe STADI VARI diffractometer	3294 independent reflections
Radiation source: fine-focus sealed tube	1831 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
Detector resolution: 5.81 pixels mm^-1	θmax = 25.5°, θmin = 1.5°
rotation method scans	h = −16→16
Absorption correction: multi-scan (Blessing, 1995)	k = −7→8
Tmin = 0.931, Tmax = 0.975	l = −23→23
6430 measured reflections

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0282P)^2 + 0.165P] where P = (Fo^2 + 2Fc^2)/3
3294 reflections	(Δ/σ)max < 0.001
243 parameters	Δρmax = 0.12 e Å^−3
0 restraints	Δρmin = −0.11 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.

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

	x	y	z	Uiso*/Ueq
O1	0.33438 (12)	0.4885 (3)	0.51425 (8)	0.0620 (5)
H1	0.391 (2)	0.473 (4)	0.4911 (14)	0.108 (11)*
O2	0.45032 (12)	0.4248 (3)	0.42289 (9)	0.0846 (6)
O3	0.40133 (12)	0.4292 (3)	0.31267 (8)	0.0807 (6)
O4	0.10733 (12)	0.6880 (3)	0.14040 (9)	0.0750 (5)
O5	0.06993 (13)	0.4564 (3)	0.06850 (9)	0.0888 (6)
N1	0.02075 (11)	0.5636 (2)	0.32067 (8)	0.0420 (4)
N2	0.03466 (11)	0.5247 (2)	0.25841 (8)	0.0422 (4)
N3	0.04997 (13)	0.5637 (3)	0.11612 (9)	0.0519 (5)
C1	0.28106 (14)	0.4898 (3)	0.39495 (10)	0.0400 (5)
C2	0.26088 (15)	0.5068 (3)	0.46500 (10)	0.0436 (5)
C3	0.16524 (15)	0.5435 (3)	0.48431 (10)	0.0522 (6)
H3	0.1525	0.5548	0.5307	0.063*
C4	0.08906 (15)	0.5633 (3)	0.43534 (10)	0.0481 (5)
H4	0.0250	0.5907	0.4487	0.058*
C5	0.10645 (15)	0.5428 (3)	0.36564 (10)	0.0405 (5)
C6	0.20263 (14)	0.5081 (3)	0.34630 (9)	0.0388 (5)
H6	0.2148	0.4969	0.2998	0.047*
C7	−0.05544 (14)	0.5363 (3)	0.21610 (9)	0.0398 (5)
C8	−0.04811 (15)	0.5440 (3)	0.14504 (10)	0.0415 (5)
C9	−0.13029 (16)	0.5332 (3)	0.09981 (10)	0.0477 (5)
H9	−0.1229	0.5371	0.0525	0.057*
C10	−0.22288 (16)	0.5166 (3)	0.12545 (10)	0.0496 (6)
H10	−0.2793	0.5099	0.0957	0.059*
C11	−0.23201 (16)	0.5098 (3)	0.19601 (11)	0.0502 (6)
H11	−0.2951	0.4993	0.2133	0.060*
C12	−0.14965 (15)	0.5184 (3)	0.24100 (10)	0.0465 (5)
H12	−0.1573	0.5122	0.2882	0.056*
C13	0.38500 (16)	0.4464 (4)	0.37393 (12)	0.0560 (6)
N4	0.38289 (14)	0.4930 (3)	0.13083 (9)	0.0573 (5)
C41	0.3152 (2)	0.3330 (4)	0.15256 (13)	0.0852 (9)
H41A	0.3236	0.3147	0.2015	0.128*
H41B	0.3312	0.2126	0.1296	0.128*
H41C	0.2474	0.3685	0.1406	0.128*
C42	0.36231 (19)	0.6799 (4)	0.16767 (12)	0.0732 (8)
H42A	0.4074	0.7804	0.1538	0.110*
H42B	0.3713	0.6591	0.2164	0.110*
H42C	0.2949	0.7207	0.1566	0.110*
C43	0.48775 (19)	0.4341 (5)	0.14858 (17)	0.1053 (11)
H43A	0.5321	0.5347	0.1337	0.158*
H43B	0.5020	0.3122	0.1260	0.158*
H43C	0.4969	0.4174	0.1975	0.158*
C44	0.3678 (3)	0.5272 (5)	0.05562 (13)	0.1033 (11)
H44A	0.2996	0.5632	0.0449	0.155*
H44B	0.3832	0.4088	0.0313	0.155*
H44C	0.4108	0.6316	0.0420	0.155*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0534 (11)	0.0871 (14)	0.0440 (9)	0.0041 (10)	−0.0124 (8)	0.0016 (9)
O2	0.0491 (10)	0.1366 (18)	0.0665 (11)	0.0210 (11)	−0.0116 (9)	−0.0138 (12)
O3	0.0533 (10)	0.1354 (17)	0.0541 (11)	0.0126 (11)	0.0095 (8)	−0.0038 (11)
O4	0.0585 (11)	0.0849 (13)	0.0820 (12)	−0.0216 (10)	0.0061 (9)	−0.0070 (10)
O5	0.0820 (13)	0.1237 (17)	0.0627 (11)	−0.0099 (12)	0.0245 (9)	−0.0344 (12)
N1	0.0421 (10)	0.0450 (11)	0.0382 (9)	−0.0014 (8)	−0.0026 (8)	0.0008 (8)
N2	0.0446 (10)	0.0432 (11)	0.0381 (10)	0.0006 (8)	−0.0059 (7)	−0.0019 (8)
N3	0.0476 (12)	0.0657 (14)	0.0425 (10)	−0.0013 (10)	0.0027 (8)	−0.0020 (10)
C1	0.0422 (12)	0.0339 (12)	0.0433 (11)	−0.0035 (9)	−0.0020 (9)	0.0011 (9)
C2	0.0489 (13)	0.0414 (13)	0.0398 (11)	−0.0026 (11)	−0.0049 (10)	0.0003 (10)
C3	0.0546 (14)	0.0660 (16)	0.0357 (11)	−0.0008 (12)	0.0007 (10)	0.0016 (11)
C4	0.0417 (12)	0.0609 (15)	0.0418 (12)	0.0016 (11)	0.0042 (9)	0.0011 (11)
C5	0.0442 (12)	0.0376 (13)	0.0392 (11)	−0.0030 (10)	−0.0044 (9)	0.0015 (10)
C6	0.0461 (12)	0.0355 (12)	0.0344 (10)	0.0006 (9)	−0.0016 (9)	0.0026 (9)
C7	0.0426 (12)	0.0361 (12)	0.0399 (11)	0.0033 (9)	−0.0053 (9)	−0.0010 (9)
C8	0.0457 (12)	0.0373 (12)	0.0412 (11)	0.0045 (10)	−0.0016 (9)	−0.0013 (10)
C9	0.0543 (14)	0.0467 (14)	0.0412 (11)	0.0034 (11)	−0.0057 (10)	−0.0012 (10)
C10	0.0480 (13)	0.0489 (14)	0.0500 (13)	0.0045 (11)	−0.0157 (10)	−0.0026 (11)
C11	0.0435 (12)	0.0500 (15)	0.0566 (14)	0.0045 (11)	−0.0028 (10)	0.0014 (11)
C12	0.0468 (13)	0.0488 (14)	0.0436 (11)	0.0020 (11)	0.0012 (9)	0.0030 (10)
C13	0.0395 (13)	0.0742 (18)	0.0537 (14)	0.0027 (12)	−0.0021 (11)	−0.0023 (13)
N4	0.0576 (12)	0.0619 (13)	0.0527 (11)	−0.0023 (10)	0.0053 (9)	0.0002 (10)
C41	0.102 (2)	0.075 (2)	0.0782 (19)	−0.0297 (17)	0.0046 (16)	0.0032 (15)
C42	0.0696 (18)	0.0688 (18)	0.0814 (18)	−0.0017 (15)	0.0061 (14)	−0.0160 (15)
C43	0.067 (2)	0.110 (3)	0.140 (3)	0.0313 (18)	0.0169 (19)	0.025 (2)
C44	0.162 (3)	0.094 (2)	0.0539 (16)	−0.008 (2)	0.0070 (18)	0.0043 (16)

Geometric parameters (Å, º)

O1—C2	1.346 (2)	C9—C10	1.368 (3)
O1—H1	0.91 (3)	C9—H9	0.9300
O2—C13	1.270 (2)	C10—C11	1.385 (3)
O3—C13	1.228 (2)	C10—H10	0.9300
O4—N3	1.221 (2)	C11—C12	1.376 (3)
O5—N3	1.219 (2)	C11—H11	0.9300
N1—N2	1.263 (2)	C12—H12	0.9300
N1—C5	1.417 (2)	N4—C44	1.485 (3)
N2—C7	1.430 (2)	N4—C43	1.487 (3)
N3—C8	1.465 (2)	N4—C42	1.489 (3)
C1—C6	1.385 (2)	N4—C41	1.491 (3)
C1—C2	1.407 (2)	C41—H41A	0.9600
C1—C13	1.504 (3)	C41—H41B	0.9600
C2—C3	1.379 (3)	C41—H41C	0.9600
C3—C4	1.368 (3)	C42—H42A	0.9600
C3—H3	0.9300	C42—H42B	0.9600
C4—C5	1.394 (3)	C42—H42C	0.9600
C4—H4	0.9300	C43—H43A	0.9600
C5—C6	1.384 (3)	C43—H43B	0.9600
C6—H6	0.9300	C43—H43C	0.9600
C7—C12	1.383 (3)	C44—H44A	0.9600
C7—C8	1.392 (3)	C44—H44B	0.9600
C8—C9	1.378 (3)	C44—H44C	0.9600
C2—O1—H1	105.1 (17)	C10—C11—H11	119.3
N2—N1—C5	114.57 (16)	C11—C12—C7	120.1 (2)
N1—N2—C7	112.20 (16)	C11—C12—H12	120.0
O5—N3—O4	123.20 (19)	C7—C12—H12	120.0
O5—N3—C8	118.33 (19)	O3—C13—O2	124.5 (2)
O4—N3—C8	118.47 (18)	O3—C13—C1	119.79 (19)
C6—C1—C2	118.47 (18)	O2—C13—C1	115.7 (2)
C6—C1—C13	121.06 (18)	C44—N4—C43	110.5 (2)
C2—C1—C13	120.44 (18)	C44—N4—C42	108.8 (2)
O1—C2—C3	118.83 (18)	C43—N4—C42	108.3 (2)
O1—C2—C1	120.73 (19)	C44—N4—C41	109.8 (2)
C3—C2—C1	120.44 (18)	C43—N4—C41	108.8 (2)
C4—C3—C2	120.12 (19)	C42—N4—C41	110.65 (19)
C4—C3—H3	119.9	N4—C41—H41A	109.5
C2—C3—H3	119.9	N4—C41—H41B	109.5
C3—C4—C5	120.7 (2)	H41A—C41—H41B	109.5
C3—C4—H4	119.7	N4—C41—H41C	109.5
C5—C4—H4	119.7	H41A—C41—H41C	109.5
C6—C5—C4	119.10 (18)	H41B—C41—H41C	109.5
C6—C5—N1	126.11 (18)	N4—C42—H42A	109.5
C4—C5—N1	114.78 (18)	N4—C42—H42B	109.5
C5—C6—C1	121.16 (18)	H42A—C42—H42B	109.5
C5—C6—H6	119.4	N4—C42—H42C	109.5
C1—C6—H6	119.4	H42A—C42—H42C	109.5
C12—C7—C8	117.62 (18)	H42B—C42—H42C	109.5
C12—C7—N2	123.77 (18)	N4—C43—H43A	109.5
C8—C7—N2	118.21 (18)	N4—C43—H43B	109.5
C9—C8—C7	122.48 (19)	H43A—C43—H43B	109.5
C9—C8—N3	117.81 (18)	N4—C43—H43C	109.5
C7—C8—N3	119.71 (18)	H43A—C43—H43C	109.5
C10—C9—C8	119.03 (19)	H43B—C43—H43C	109.5
C10—C9—H9	120.5	N4—C44—H44A	109.5
C8—C9—H9	120.5	N4—C44—H44B	109.5
C9—C10—C11	119.49 (19)	H44A—C44—H44B	109.5
C9—C10—H10	120.3	N4—C44—H44C	109.5
C11—C10—H10	120.3	H44A—C44—H44C	109.5
C12—C11—C10	121.3 (2)	H44B—C44—H44C	109.5
C12—C11—H11	119.3
C5—N1—N2—C7	176.40 (16)	N2—C7—C8—C9	172.57 (19)
C6—C1—C2—O1	179.4 (2)	C12—C7—C8—N3	179.74 (19)
C13—C1—C2—O1	1.3 (3)	N2—C7—C8—N3	−7.2 (3)
C6—C1—C2—C3	−0.9 (3)	O5—N3—C8—C9	−46.3 (3)
C13—C1—C2—C3	−179.0 (2)	O4—N3—C8—C9	133.0 (2)
O1—C2—C3—C4	179.8 (2)	O5—N3—C8—C7	133.6 (2)
C1—C2—C3—C4	0.1 (3)	O4—N3—C8—C7	−47.2 (3)
C2—C3—C4—C5	1.3 (3)	C7—C8—C9—C10	0.8 (3)
C3—C4—C5—C6	−2.0 (3)	N3—C8—C9—C10	−179.39 (19)
C3—C4—C5—N1	179.0 (2)	C8—C9—C10—C11	−0.4 (3)
N2—N1—C5—C6	8.2 (3)	C9—C10—C11—C12	−0.3 (3)
N2—N1—C5—C4	−172.94 (18)	C10—C11—C12—C7	0.7 (3)
C4—C5—C6—C1	1.3 (3)	C8—C7—C12—C11	−0.3 (3)
N1—C5—C6—C1	−179.88 (19)	N2—C7—C12—C11	−172.89 (19)
C2—C1—C6—C5	0.2 (3)	C6—C1—C13—O3	0.9 (4)
C13—C1—C6—C5	178.2 (2)	C2—C1—C13—O3	179.0 (2)
N1—N2—C7—C12	−22.6 (3)	C6—C1—C13—O2	−177.2 (2)
N1—N2—C7—C8	164.85 (18)	C2—C1—C13—O2	0.8 (3)
C12—C7—C8—C9	−0.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.91 (3)	1.61 (3)	2.460 (2)	153 (3)
C9—H9···O5^i	0.93	2.49	3.413 (3)	170
C41—H41A···O3	0.96	2.48	3.331 (3)	148
C41—H41B···O1^ii	0.96	2.63	3.482 (3)	148
C42—H42B···O3	0.96	2.45	3.312 (3)	149
C42—H42C···O4	0.96	2.53	3.439 (3)	157
C43—H43C···O3	0.96	2.64	3.452 (3)	143

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