Structural, theoretic and spectroscopic analysis of 2-methyl-5-nitro­aniline salts with various inorganic acids

Crystal structures of six new salts of 2-methyl-5-nitro­aniline with inorganic acids [(H2Me5NA)Br, (H2Me5NA)I, (H2Me5NA)NO₃, (H2Me5NA)Cl, (H2Me5NA)HSO₄ and (H2Me5NA)I₃·0.5H₂O] are determined by single-crystal X-ray diffraction. The most important hydrogen-bonding patterns are formed by the ammonio group and respective anions composing 1D or 2D networks. The patterns are analysed using the graph-set approach and mathematical interrelations between graph-set descriptors are shown for comparative purposes. Analysis of IR spectra enables the strength of hydrogen bonds in the crystals to be assessed. The frequency of N—H and O—H stretching vibrations and NH₃ group libration indicates that the strongest hydrogen bonds are present in (H2Me5NA)HSO₄, whereas the weakest ones occur in (H2Me5NA)I₃·0.5H₂O. Hirshfeld surface analysis reveals that apart from obvious N—H...anion hydrogen bonds, the molecules are also connected to each other by exclusive C—H...O_NO2 interactions. The opposite occurs in the crystal structure of 2-methyl-4-nitro­aniline salts, where a variety of O_NO2...π(N)_NO2 non-hydrogen bonding interactions are observed.

Computing details

For all structures, data collection: CrysAlis PRO 1.171.38.43 (Rigaku OD, 2015); cell refinement: CrysAlis PRO 1.171.38.43 (Rigaku OD, 2015); data reduction: CrysAlis PRO 1.171.38.43 (Rigaku OD, 2015). Program(s) used to solve structure: ShelXT (Sheldrick, 2015) for (1), (2), (3), (4), (6); SHELXS (Sheldrick, 2008) for (5). For all structures, program(s) used to refine structure: SHELXL (Sheldrick, 2015); molecular graphics: Olex2 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).

(1)

Crystal data

C7H9N2O2·Br	F(000) = 232
Mr = 233.07	Dx = 1.701 Mg m^−3
Monoclinic, P121/m1	Mo Kα radiation, λ = 0.71073 Å
a = 8.5689 (3) Å	Cell parameters from 5231 reflections
b = 6.4113 (2) Å	θ = 2.7–30.2°
c = 8.8248 (4) Å	µ = 4.48 mm^−1
β = 110.200 (4)°	T = 295 K
V = 455.00 (3) Å^3	Plate, clear light colourless
Z = 2	0.75 × 0.57 × 0.14 mm

Data collection

Xcalibur, Atlas diffractometer	1279 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	1187 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
Detector resolution: 10.6249 pixels mm^-1	θmax = 28.7°, θmin = 4.0°
ω scans	h = −11→11
Absorption correction: gaussian CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Numerical absorption correction based on gaussian integration over a multifaceted crystal model Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −8→8
Tmin = 0.127, Tmax = 0.604	l = −11→11
14243 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.024	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.058	w = 1/[σ^2(Fo^2) + (0.0281P)^2 + 0.1895P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = <0.001
1279 reflections	Δρmax = 0.55 e Å^−3
87 parameters	Δρmin = −0.34 e Å^−3
0 restraints

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
Br1	0.73818 (3)	0.250000	0.53360 (3)	0.04217 (10)
O1	0.3445 (4)	0.250000	−0.2577 (3)	0.0934 (10)
O2	0.5579 (3)	0.250000	−0.0397 (3)	0.0731 (7)
N1	0.3307 (3)	0.250000	0.4115 (2)	0.0339 (4)
H1A	0.449 (5)	0.250000	0.450 (4)	0.059 (10)*
H1B	0.301 (3)	0.362 (4)	0.454 (3)	0.052 (6)*
N2	0.4076 (4)	0.250000	−0.1118 (3)	0.0547 (7)
C1	0.2592 (3)	0.250000	0.2349 (3)	0.0302 (4)
C2	0.0867 (3)	0.250000	0.1626 (3)	0.0361 (5)
C3	0.0232 (3)	0.250000	−0.0051 (4)	0.0442 (6)
H3	−0.091475	0.250000	−0.057333	0.053*
C4	0.1255 (4)	0.250000	−0.0965 (3)	0.0452 (6)
H4	0.081006	0.250000	−0.208640	0.054*
C5	0.2956 (3)	0.250000	−0.0173 (3)	0.0387 (5)
C6	0.3664 (3)	0.250000	0.1493 (3)	0.0352 (5)
H6	0.481098	0.250000	0.201031	0.042*
C7	−0.0241 (4)	0.250000	0.2618 (4)	0.0501 (7)
H7A	−0.001 (3)	0.370 (4)	0.333 (3)	0.067 (7)*
H7B	−0.131 (5)	0.250000	0.198 (5)	0.064 (10)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.03419 (14)	0.03781 (15)	0.04864 (17)	0.000	0.00682 (11)	0.000
O1	0.115 (2)	0.134 (3)	0.0360 (12)	0.000	0.0328 (14)	0.000
O2	0.0635 (15)	0.104 (2)	0.0621 (15)	0.000	0.0345 (13)	0.000
N1	0.0359 (11)	0.0365 (11)	0.0280 (10)	0.000	0.0094 (8)	0.000
N2	0.083 (2)	0.0507 (14)	0.0370 (12)	0.000	0.0297 (13)	0.000
C1	0.0332 (11)	0.0267 (10)	0.0272 (10)	0.000	0.0061 (9)	0.000
C2	0.0326 (11)	0.0282 (11)	0.0425 (13)	0.000	0.0067 (10)	0.000
C3	0.0375 (13)	0.0358 (12)	0.0451 (14)	0.000	−0.0037 (11)	0.000
C4	0.0599 (17)	0.0340 (12)	0.0292 (12)	0.000	−0.0006 (12)	0.000
C5	0.0517 (15)	0.0322 (11)	0.0306 (12)	0.000	0.0121 (11)	0.000
C6	0.0361 (12)	0.0352 (11)	0.0325 (12)	0.000	0.0095 (10)	0.000
C7	0.0347 (14)	0.0519 (17)	0.065 (2)	0.000	0.0181 (14)	0.000

Geometric parameters (Å, º)

O1—N2	1.212 (3)	C2—C7	1.497 (4)
O2—N2	1.223 (4)	C3—H3	0.9300
N1—H1A	0.95 (4)	C3—C4	1.381 (5)
N1—H1B^i	0.89 (2)	C4—H4	0.9300
N1—H1B	0.89 (2)	C4—C5	1.382 (4)
N1—C1	1.464 (3)	C5—C6	1.383 (3)
N2—C5	1.473 (4)	C6—H6	0.9300
C1—C2	1.393 (3)	C7—H7A^i	0.97 (3)
C1—C6	1.377 (3)	C7—H7A	0.97 (3)
C2—C3	1.390 (4)	C7—H7B	0.89 (4)
H1A—N1—H1B^i	105.8 (19)	C4—C3—H3	119.1
H1A—N1—H1B	105.8 (19)	C3—C4—H4	120.8
H1B—N1—H1B^i	108 (3)	C3—C4—C5	118.5 (2)
C1—N1—H1A	113 (2)	C5—C4—H4	120.8
C1—N1—H1B	111.9 (14)	C4—C5—N2	119.6 (2)
C1—N1—H1B^i	111.9 (14)	C4—C5—C6	122.4 (3)
O1—N2—O2	123.8 (3)	C6—C5—N2	118.0 (2)
O1—N2—C5	117.5 (3)	C1—C6—C5	116.9 (2)
O2—N2—C5	118.7 (2)	C1—C6—H6	121.5
C2—C1—N1	118.4 (2)	C5—C6—H6	121.5
C6—C1—N1	118.1 (2)	C2—C7—H7A^i	110.3 (15)
C6—C1—C2	123.5 (2)	C2—C7—H7A	110.3 (15)
C1—C2—C7	121.3 (2)	C2—C7—H7B	110 (2)
C3—C2—C1	116.8 (2)	H7A—C7—H7A^i	105 (3)
C3—C2—C7	121.9 (3)	H7A—C7—H7B	110.3 (19)
C2—C3—H3	119.1	H7B—C7—H7A^i	110.3 (19)
C4—C3—C2	121.8 (2)
O1—N2—C5—C4	0.000 (1)	C2—C1—C6—C5	0.000 (1)
O1—N2—C5—C6	180.000 (1)	C2—C3—C4—C5	0.000 (1)
O2—N2—C5—C4	180.0	C3—C4—C5—N2	180.000 (1)
O2—N2—C5—C6	0.000 (1)	C3—C4—C5—C6	0.000 (1)
N1—C1—C2—C3	180.000 (1)	C4—C5—C6—C1	0.000 (1)
N1—C1—C2—C7	0.000 (1)	C6—C1—C2—C3	0.000 (1)
N1—C1—C6—C5	180.000 (1)	C6—C1—C2—C7	180.000 (1)
N2—C5—C6—C1	180.000 (1)	C7—C2—C3—C4	180.000 (1)
C1—C2—C3—C4	0.000 (1)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Br1	0.95 (4)	2.33 (4)	3.280 (2)	177 (3)
N1—H1B···Br1^ii	0.89 (2)	2.52 (2)	3.3251 (6)	152 (2)

Symmetry code: (ii) −x+1, −y+1, −z+1.

(2)

Crystal data

C7H9N2O2·I	Z = 2
Mr = 280.06	F(000) = 268
Triclinic, P1	Dx = 1.930 Mg m^−3
a = 6.5954 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.7764 (2) Å	Cell parameters from 6516 reflections
c = 8.8564 (3) Å	θ = 3.0–29.8°
α = 72.140 (2)°	µ = 3.29 mm^−1
β = 84.002 (2)°	T = 295 K
γ = 81.830 (2)°	Plate, clear light yellow
V = 481.98 (3) Å^3	0.48 × 0.37 × 0.11 mm

Data collection

Xcalibur, Atlas diffractometer	2472 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	2281 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
Detector resolution: 10.6249 pixels mm^-1	θmax = 28.7°, θmin = 2.9°
ω scans	h = −8→8
Absorption correction: gaussian CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Numerical absorption correction based on gaussian integration over a multifaceted crystal model Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −11→11
Tmin = 0.274, Tmax = 0.719	l = −11→11
14289 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.022	w = 1/[σ^2(Fo^2) + (0.0209P)^2 + 0.2291P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.050	(Δ/σ)max = 0.001
S = 1.08	Δρmax = 0.66 e Å^−3
2472 reflections	Δρmin = −0.79 e Å^−3
112 parameters	Extinction correction: SHELXL-2018/1 (Sheldrick 2018), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0379 (13)
Primary atom site location: dual

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
I1	0.78581 (3)	0.51505 (2)	0.24637 (2)	0.04437 (8)
O1	0.7065 (5)	−0.2733 (3)	0.6167 (4)	0.0878 (8)
O2	0.7436 (4)	−0.0582 (3)	0.4189 (3)	0.0755 (7)
N1	0.7421 (3)	0.3843 (2)	0.6660 (2)	0.0376 (4)
H1A	0.843423	0.414094	0.705521	0.045*
H1B	0.622298	0.430639	0.696262	0.045*
H1C	0.758228	0.414880	0.560390	0.045*
N2	0.7327 (4)	−0.1300 (3)	0.5603 (4)	0.0568 (7)
C1	0.7457 (3)	0.2080 (2)	0.7254 (3)	0.0336 (5)
C2	0.7477 (4)	0.1340 (3)	0.8893 (3)	0.0401 (5)
C3	0.7533 (4)	−0.0333 (3)	0.9413 (3)	0.0493 (6)
H3	0.758303	−0.087070	1.049386	0.059*
C4	0.7514 (4)	−0.1210 (3)	0.8360 (4)	0.0523 (7)
H4	0.755373	−0.232634	0.872486	0.063*
C5	0.7437 (4)	−0.0411 (3)	0.6769 (3)	0.0412 (5)
C6	0.7424 (4)	0.1252 (3)	0.6174 (3)	0.0382 (5)
H6	0.739373	0.177943	0.509029	0.046*
C7	0.7410 (5)	0.2297 (4)	1.0044 (3)	0.0520 (6)
H7A	0.617986	0.304073	0.993725	0.078*
H7B	0.858469	0.288173	0.982345	0.078*
H7C	0.742373	0.157925	1.110905	0.078*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.04580 (11)	0.04790 (11)	0.03675 (10)	−0.01056 (7)	−0.00244 (6)	−0.00647 (7)
O1	0.114 (2)	0.0369 (11)	0.122 (2)	−0.0087 (12)	−0.0337 (18)	−0.0285 (13)
O2	0.100 (2)	0.0680 (15)	0.0703 (16)	−0.0196 (13)	−0.0027 (14)	−0.0340 (13)
N1	0.0432 (11)	0.0303 (9)	0.0380 (10)	−0.0081 (8)	−0.0043 (8)	−0.0057 (8)
N2	0.0455 (13)	0.0369 (11)	0.095 (2)	0.0003 (10)	−0.0164 (13)	−0.0285 (13)
C1	0.0308 (11)	0.0276 (10)	0.0396 (12)	−0.0065 (8)	−0.0043 (9)	−0.0038 (9)
C2	0.0348 (12)	0.0409 (12)	0.0397 (13)	−0.0078 (10)	−0.0045 (10)	−0.0025 (10)
C3	0.0474 (15)	0.0420 (13)	0.0457 (14)	−0.0074 (11)	−0.0066 (11)	0.0078 (11)
C4	0.0436 (14)	0.0303 (12)	0.074 (2)	−0.0062 (10)	−0.0100 (13)	0.0002 (12)
C5	0.0332 (12)	0.0307 (11)	0.0597 (16)	−0.0034 (9)	−0.0070 (11)	−0.0121 (10)
C6	0.0350 (12)	0.0334 (11)	0.0441 (13)	−0.0067 (9)	−0.0065 (10)	−0.0059 (9)
C7	0.0552 (17)	0.0608 (17)	0.0387 (14)	−0.0118 (13)	−0.0036 (12)	−0.0104 (12)

Geometric parameters (Å, º)

O1—N2	1.233 (3)	C2—C7	1.501 (4)
O2—N2	1.216 (4)	C3—H3	0.9300
N1—H1A	0.8900	C3—C4	1.382 (4)
N1—H1B	0.8900	C4—H4	0.9300
N1—H1C	0.8900	C4—C5	1.371 (4)
N1—C1	1.471 (3)	C5—C6	1.390 (3)
N2—C5	1.485 (4)	C6—H6	0.9300
C1—C2	1.397 (3)	C7—H7A	0.9600
C1—C6	1.371 (3)	C7—H7B	0.9600
C2—C3	1.394 (3)	C7—H7C	0.9600
H1A—N1—H1B	109.5	C4—C3—H3	119.3
H1A—N1—H1C	109.5	C3—C4—H4	120.5
H1B—N1—H1C	109.5	C5—C4—C3	119.0 (2)
C1—N1—H1A	109.5	C5—C4—H4	120.5
C1—N1—H1B	109.5	C4—C5—N2	120.8 (2)
C1—N1—H1C	109.5	C4—C5—C6	122.2 (2)
O1—N2—C5	116.1 (3)	C6—C5—N2	117.1 (2)
O2—N2—O1	124.6 (3)	C1—C6—C5	117.1 (2)
O2—N2—C5	119.3 (2)	C1—C6—H6	121.4
C2—C1—N1	118.3 (2)	C5—C6—H6	121.4
C6—C1—N1	118.3 (2)	C2—C7—H7A	109.5
C6—C1—C2	123.4 (2)	C2—C7—H7B	109.5
C1—C2—C7	121.8 (2)	C2—C7—H7C	109.5
C3—C2—C1	116.8 (2)	H7A—C7—H7B	109.5
C3—C2—C7	121.4 (2)	H7A—C7—H7C	109.5
C2—C3—H3	119.3	H7B—C7—H7C	109.5
C4—C3—C2	121.5 (2)
O1—N2—C5—C4	8.4 (4)	C2—C1—C6—C5	−0.8 (4)
O1—N2—C5—C6	−170.7 (3)	C2—C3—C4—C5	−0.1 (4)
O2—N2—C5—C4	−173.8 (3)	C3—C4—C5—N2	−177.5 (2)
O2—N2—C5—C6	7.2 (4)	C3—C4—C5—C6	1.5 (4)
N1—C1—C2—C3	−179.4 (2)	C4—C5—C6—C1	−1.1 (4)
N1—C1—C2—C7	1.5 (3)	C6—C1—C2—C3	2.1 (4)
N1—C1—C6—C5	−179.3 (2)	C6—C1—C2—C7	−177.0 (2)
N2—C5—C6—C1	177.9 (2)	C7—C2—C3—C4	177.5 (3)
C1—C2—C3—C4	−1.6 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···I1^i	0.89	2.71	3.576 (2)	164
N1—H1B···I1^ii	0.89	2.69	3.533 (2)	159
N1—H1C···I1	0.89	2.64	3.531 (2)	177

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

(3)

Crystal data

C7H9N2O2·NO3	F(000) = 224
Mr = 215.17	Dx = 1.566 Mg m^−3
Monoclinic, P121/m1	Mo Kα radiation, λ = 0.71073 Å
a = 8.1234 (3) Å	Cell parameters from 6221 reflections
b = 6.6252 (2) Å	θ = 3.2–29.4°
c = 8.5799 (3) Å	µ = 0.14 mm^−1
β = 98.712 (3)°	T = 295 K
V = 456.44 (3) Å^3	Plate, clear light yellow
Z = 2	0.37 × 0.34 × 0.06 mm

Data collection

Xcalibur, Atlas diffractometer	1273 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	1078 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
Detector resolution: 10.6249 pixels mm^-1	θmax = 28.7°, θmin = 2.4°
ω scans	h = −10→10
Absorption correction: multi-scan CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −8→8
Tmin = 0.945, Tmax = 1.000	l = −11→11
16584 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.119	w = 1/[σ^2(Fo^2) + (0.0616P)^2 + 0.1128P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = <0.001
1273 reflections	Δρmax = 0.27 e Å^−3
102 parameters	Δρmin = −0.23 e Å^−3
0 restraints

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	0.5011 (2)	0.250000	−0.28675 (16)	0.0548 (5)
O2	0.67966 (17)	0.250000	−0.07587 (17)	0.0487 (4)
O3	0.70869 (14)	0.08936 (17)	0.45570 (11)	0.0474 (3)
O4	0.8951 (2)	0.250000	0.6140 (2)	0.0651 (5)
N1	0.3572 (2)	0.250000	0.37425 (16)	0.0304 (3)
N2	0.53741 (19)	0.250000	−0.14346 (17)	0.0305 (3)
N3	0.77499 (19)	0.250000	0.51188 (17)	0.0332 (4)
C1	0.3144 (2)	0.250000	0.20218 (17)	0.0249 (3)
C2	0.1474 (2)	0.250000	0.13435 (19)	0.0282 (4)
C3	0.1124 (2)	0.250000	−0.0305 (2)	0.0348 (4)
H3	0.002018	0.250000	−0.079124	0.042*
C4	0.2381 (2)	0.250000	−0.1229 (2)	0.0336 (4)
H4	0.213289	0.250000	−0.232379	0.040*
C5	0.4011 (2)	0.250000	−0.04866 (18)	0.0257 (4)
C6	0.4433 (2)	0.250000	0.11448 (18)	0.0251 (3)
H6	0.553894	0.250000	0.162506	0.030*
C7	0.0109 (2)	0.250000	0.2343 (2)	0.0407 (5)
H1A	0.466 (3)	0.250000	0.400 (3)	0.048 (7)*
H1B	0.321 (2)	0.137 (3)	0.418 (2)	0.054 (5)*
H7A	−0.088 (4)	0.250000	0.182 (4)	0.075 (9)*
H7B	0.018 (3)	0.136 (3)	0.307 (2)	0.067 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0475 (9)	0.0966 (14)	0.0222 (7)	0.000	0.0111 (6)	0.000
O2	0.0267 (7)	0.0804 (12)	0.0399 (8)	0.000	0.0081 (6)	0.000
O3	0.0633 (7)	0.0411 (6)	0.0376 (5)	−0.0070 (5)	0.0069 (5)	−0.0014 (4)
O4	0.0458 (9)	0.0950 (15)	0.0474 (9)	0.000	−0.0154 (7)	0.000
N1	0.0291 (8)	0.0425 (9)	0.0189 (6)	0.000	0.0014 (5)	0.000
N2	0.0319 (8)	0.0352 (8)	0.0254 (7)	0.000	0.0080 (6)	0.000
N3	0.0307 (7)	0.0442 (9)	0.0254 (7)	0.000	0.0063 (6)	0.000
C1	0.0270 (8)	0.0282 (8)	0.0189 (7)	0.000	0.0019 (6)	0.000
C2	0.0241 (8)	0.0350 (9)	0.0254 (8)	0.000	0.0031 (6)	0.000
C3	0.0224 (8)	0.0529 (11)	0.0272 (8)	0.000	−0.0021 (6)	0.000
C4	0.0317 (9)	0.0479 (11)	0.0198 (7)	0.000	−0.0003 (6)	0.000
C5	0.0258 (8)	0.0298 (8)	0.0222 (7)	0.000	0.0054 (6)	0.000
C6	0.0227 (7)	0.0291 (8)	0.0225 (7)	0.000	0.0001 (6)	0.000
C7	0.0257 (9)	0.0643 (14)	0.0332 (9)	0.000	0.0083 (7)	0.000

Geometric parameters (Å, º)

O1—N2	1.220 (2)	C2—C3	1.400 (2)
O2—N2	1.212 (2)	C2—C7	1.501 (2)
O3—N3	1.2556 (13)	C3—H3	0.9300
O4—N3	1.209 (2)	C3—C4	1.385 (3)
N1—C1	1.465 (2)	C4—H4	0.9300
N1—H1A	0.88 (3)	C4—C5	1.380 (2)
N1—H1B^i	0.91 (2)	C5—C6	1.390 (2)
N1—H1B	0.91 (2)	C6—H6	0.9300
N2—C5	1.470 (2)	C7—H7A	0.86 (3)
C1—C2	1.394 (2)	C7—H7B	0.98 (2)
C1—C6	1.379 (2)	C7—H7B^i	0.98 (2)
C1—N1—H1A	109.2 (16)	C2—C3—H3	119.2
C1—N1—H1B	112.1 (11)	C4—C3—C2	121.64 (15)
C1—N1—H1B^i	112.1 (11)	C4—C3—H3	119.2
H1A—N1—H1B	105.8 (14)	C3—C4—H4	120.8
H1A—N1—H1B^i	105.8 (14)	C5—C4—C3	118.34 (15)
H1B—N1—H1B^i	111 (2)	C5—C4—H4	120.8
O1—N2—C5	118.05 (15)	C4—C5—N2	119.67 (14)
O2—N2—O1	123.34 (15)	C4—C5—C6	122.56 (15)
O2—N2—C5	118.61 (14)	C6—C5—N2	117.77 (14)
O3—N3—O3^i	115.91 (15)	C1—C6—C5	117.26 (14)
O4—N3—O3	122.04 (8)	C1—C6—H6	121.4
O4—N3—O3^i	122.04 (8)	C5—C6—H6	121.4
C2—C1—N1	119.23 (14)	C2—C7—H7A	114 (2)
C6—C1—N1	117.80 (14)	C2—C7—H7B	113.1 (12)
C6—C1—C2	122.96 (14)	C2—C7—H7B^i	113.1 (12)
C1—C2—C3	117.23 (15)	H7A—C7—H7B	107.2 (17)
C1—C2—C7	121.24 (15)	H7A—C7—H7B^i	107.2 (17)
C3—C2—C7	121.53 (16)	H7B—C7—H7B^i	101 (2)
O1—N2—C5—C4	0.000 (1)	C2—C1—C6—C5	0.000 (1)
O1—N2—C5—C6	180.000 (1)	C2—C3—C4—C5	0.000 (1)
O2—N2—C5—C4	180.0	C3—C4—C5—N2	180.0
O2—N2—C5—C6	0.000 (1)	C3—C4—C5—C6	0.000 (1)
N1—C1—C2—C3	180.000 (1)	C4—C5—C6—C1	0.0
N1—C1—C2—C7	0.000 (1)	C6—C1—C2—C3	0.000 (1)
N1—C1—C6—C5	180.000 (1)	C6—C1—C2—C7	180.000 (1)
N2—C5—C6—C1	180.000 (1)	C7—C2—C3—C4	180.000 (1)
C1—C2—C3—C4	0.000 (1)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3	0.88 (3)	2.23 (2)	3.0279 (19)	152 (1)
N1—H1A···O3^i	0.88 (3)	2.23 (2)	3.0279 (19)	152 (1)
N1—H1B···O3^ii	0.91 (2)	1.88 (2)	2.7762 (13)	166.5 (17)

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

(4)

Crystal data

C7H9N2O2·Cl	Z = 8
Mr = 188.61	F(000) = 784
Triclinic, P1	Dx = 1.405 Mg m^−3
a = 7.9756 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.9803 (1) Å	Cell parameters from 23182 reflections
c = 28.2986 (3) Å	θ = 2.9–29.6°
α = 84.468 (1)°	µ = 0.39 mm^−1
β = 84.229 (1)°	T = 295 K
γ = 89.897 (1)°	Block, clear light colourless
V = 1783.61 (4) Å^3	0.25 × 0.22 × 0.21 mm

Data collection

Xcalibur, Atlas diffractometer	7878 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	6977 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
Detector resolution: 10.6249 pixels mm^-1	θmax = 27.1°, θmin = 2.6°
ω scans	h = −10→10
Absorption correction: multi-scan CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −10→10
Tmin = 0.983, Tmax = 1.000	l = −36→36
50750 measured reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.052	H-atom parameters constrained
wR(F^2) = 0.138	w = 1/[σ^2(Fo^2) + (0.0451P)^2 + 2.1746P] where P = (Fo^2 + 2Fc^2)/3
S = 1.13	(Δ/σ)max = 0.001
7878 reflections	Δρmax = 0.53 e Å^−3
441 parameters	Δρmin = −0.42 e Å^−3
0 restraints

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
Cl1	0.27234 (8)	0.51707 (8)	−0.02367 (2)	0.03836 (15)
Cl2	0.75538 (8)	0.98275 (8)	0.02191 (2)	0.03798 (15)
Cl3	0.51633 (8)	0.24448 (8)	0.47618 (2)	0.03827 (15)
O1C	0.6228 (6)	−0.2640 (4)	0.74378 (10)	0.1210 (16)
O2C	0.6812 (6)	−0.3930 (3)	0.68174 (10)	0.1154 (15)
N1C	0.7560 (3)	0.0454 (3)	0.54403 (7)	0.0366 (5)
H1CA	0.792880	−0.056267	0.537804	0.044*
H1CB	0.835689	0.121851	0.533631	0.044*
H1CC	0.664042	0.068997	0.529334	0.044*
N2C	0.6522 (5)	−0.2645 (4)	0.70086 (10)	0.0771 (10)
C1C	0.7155 (3)	0.0480 (3)	0.59548 (9)	0.0329 (5)
C2C	0.6882 (3)	0.2004 (3)	0.61522 (9)	0.0368 (5)
C3C	0.6434 (4)	0.1929 (4)	0.66442 (10)	0.0475 (7)
H3C	0.622613	0.292562	0.678466	0.057*
C4C	0.6292 (5)	0.0424 (4)	0.69264 (11)	0.0526 (8)
H4C	0.598875	0.039391	0.725318	0.063*
C5C	0.6610 (4)	−0.1034 (4)	0.67124 (10)	0.0501 (7)
C6C	0.7035 (4)	−0.1046 (3)	0.62279 (10)	0.0425 (6)
H6C	0.723303	−0.205036	0.609066	0.051*
C7C	0.7063 (4)	0.3677 (4)	0.58590 (11)	0.0507 (7)
H7CA	0.669426	0.357591	0.555019	0.076*
H7CB	0.822247	0.402913	0.582310	0.076*
H7CC	0.638630	0.449515	0.601611	0.076*
Cl4	0.98216 (8)	0.72791 (8)	0.52207 (2)	0.03751 (15)
O1D	0.9739 (6)	0.4123 (4)	0.25865 (10)	0.1128 (14)
O2D	0.9109 (7)	0.2371 (4)	0.31919 (12)	0.1363 (19)
N1D	0.7451 (3)	0.5736 (3)	0.45526 (7)	0.0359 (5)
H1DA	0.701711	0.469977	0.460245	0.043*
H1DB	0.668427	0.646774	0.465355	0.043*
H1DC	0.835213	0.579220	0.471221	0.043*
N2D	0.9234 (5)	0.3799 (4)	0.30012 (11)	0.0791 (11)
C1D	0.7940 (3)	0.6143 (3)	0.40444 (8)	0.0313 (5)
C2D	0.8098 (3)	0.7817 (3)	0.38477 (9)	0.0344 (5)
C3D	0.8606 (4)	0.8108 (4)	0.33610 (10)	0.0455 (7)
H3D	0.870610	0.921153	0.322130	0.055*
C4D	0.8963 (4)	0.6815 (4)	0.30821 (10)	0.0489 (7)
H4D	0.930008	0.703355	0.275767	0.059*
C5D	0.8813 (4)	0.5190 (4)	0.32920 (10)	0.0472 (7)
C6D	0.8300 (4)	0.4813 (3)	0.37720 (10)	0.0419 (6)
H6D	0.819943	0.370380	0.390699	0.050*
C7D	0.7715 (4)	0.9276 (3)	0.41376 (11)	0.0501 (7)
H7DA	0.839243	0.920471	0.440051	0.075*
H7DB	0.654397	0.924622	0.425683	0.075*
H7DC	0.796323	1.031134	0.394063	0.075*
O1A	−0.2587 (4)	0.0225 (6)	0.23985 (10)	0.1180 (15)
O2A	−0.3892 (3)	0.0729 (6)	0.17824 (11)	0.1039 (12)
N1A	0.0432 (3)	0.2558 (3)	0.04420 (8)	0.0372 (5)
H1AA	0.065436	0.166933	0.027942	0.045*
H1AB	0.120054	0.335913	0.034645	0.045*
H1AC	−0.058610	0.294734	0.038985	0.045*
N2A	−0.2614 (4)	0.0696 (5)	0.19800 (11)	0.0726 (9)
C1A	0.0477 (3)	0.2063 (3)	0.09511 (9)	0.0326 (5)
C2A	0.2007 (3)	0.1941 (3)	0.11498 (9)	0.0364 (5)
C3A	0.1951 (4)	0.1427 (4)	0.16340 (10)	0.0482 (7)
H3A	0.295464	0.133792	0.177573	0.058*
C4A	0.0451 (4)	0.1045 (4)	0.19119 (11)	0.0525 (7)
H4A	0.043525	0.072170	0.223702	0.063*
C5A	−0.1014 (4)	0.1154 (4)	0.16954 (10)	0.0478 (7)
C6A	−0.1041 (3)	0.1680 (4)	0.12178 (10)	0.0411 (6)
H6A	−0.205121	0.177468	0.107972	0.049*
C7A	0.3674 (4)	0.2339 (5)	0.08648 (11)	0.0521 (7)
H7AA	0.403824	0.138814	0.069878	0.078*
H7AB	0.449242	0.258697	0.107536	0.078*
H7AC	0.355671	0.329674	0.063815	0.078*
O1B	0.5905 (4)	0.6261 (6)	0.24487 (9)	0.1120 (14)
O2B	0.7651 (3)	0.6667 (7)	0.18239 (11)	0.1316 (18)
N1B	0.4242 (3)	0.7562 (3)	0.04480 (7)	0.0373 (5)
H1BA	0.415415	0.663140	0.030197	0.045*
H1BB	0.528824	0.796803	0.038771	0.045*
H1BC	0.352201	0.832679	0.034117	0.045*
N2B	0.6226 (4)	0.6468 (6)	0.20188 (11)	0.0794 (11)
C1B	0.3852 (3)	0.7166 (3)	0.09616 (9)	0.0327 (5)
C2B	0.2185 (3)	0.6909 (3)	0.11578 (9)	0.0364 (5)
C3B	0.1910 (4)	0.6461 (4)	0.16463 (10)	0.0469 (7)
H3B	0.081333	0.625439	0.178453	0.056*
C4B	0.3220 (4)	0.6313 (4)	0.19335 (11)	0.0509 (7)
H4B	0.301648	0.602606	0.226071	0.061*
C5B	0.4826 (4)	0.6603 (4)	0.17196 (10)	0.0499 (7)
C6B	0.5185 (3)	0.7019 (4)	0.12358 (10)	0.0432 (6)
H6B	0.628828	0.719447	0.109952	0.052*
C7B	0.0722 (3)	0.7092 (5)	0.08622 (11)	0.0517 (7)
H7BA	0.047713	0.826430	0.079539	0.078*
H7BB	−0.024778	0.652678	0.103432	0.078*
H7BC	0.099988	0.660183	0.056778	0.078*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0337 (3)	0.0364 (3)	0.0441 (4)	0.0021 (2)	−0.0024 (2)	−0.0012 (3)
Cl2	0.0347 (3)	0.0361 (3)	0.0426 (3)	−0.0025 (2)	−0.0032 (2)	−0.0018 (2)
Cl3	0.0362 (3)	0.0337 (3)	0.0442 (3)	−0.0021 (2)	−0.0007 (3)	−0.0041 (2)
O1C	0.257 (5)	0.0628 (18)	0.0371 (14)	0.015 (2)	0.005 (2)	0.0066 (12)
O2C	0.247 (5)	0.0365 (13)	0.0562 (17)	−0.001 (2)	0.010 (2)	0.0015 (12)
N1C	0.0422 (12)	0.0327 (11)	0.0343 (11)	0.0004 (9)	−0.0002 (9)	−0.0047 (8)
N2C	0.146 (3)	0.0425 (15)	0.0400 (15)	−0.0006 (18)	0.0001 (18)	0.0001 (12)
C1C	0.0334 (12)	0.0329 (12)	0.0325 (12)	0.0002 (10)	−0.0014 (10)	−0.0057 (10)
C2C	0.0386 (13)	0.0339 (13)	0.0379 (13)	0.0000 (10)	−0.0015 (11)	−0.0060 (10)
C3C	0.0626 (18)	0.0394 (15)	0.0404 (15)	−0.0013 (13)	0.0052 (13)	−0.0135 (12)
C4C	0.077 (2)	0.0472 (16)	0.0328 (14)	−0.0011 (15)	0.0039 (14)	−0.0077 (12)
C5C	0.076 (2)	0.0364 (14)	0.0361 (15)	−0.0047 (14)	−0.0016 (14)	0.0005 (11)
C6C	0.0575 (17)	0.0319 (13)	0.0379 (14)	0.0008 (12)	−0.0018 (12)	−0.0060 (11)
C7C	0.072 (2)	0.0331 (14)	0.0465 (16)	0.0010 (13)	0.0018 (14)	−0.0075 (12)
Cl4	0.0358 (3)	0.0341 (3)	0.0419 (3)	0.0024 (2)	−0.0014 (2)	−0.0030 (2)
O1D	0.211 (4)	0.0737 (19)	0.0464 (16)	0.022 (2)	0.030 (2)	−0.0128 (14)
O2D	0.292 (6)	0.0399 (15)	0.068 (2)	0.004 (2)	0.033 (3)	−0.0127 (14)
N1D	0.0401 (11)	0.0327 (11)	0.0333 (11)	−0.0022 (9)	0.0003 (9)	0.0005 (8)
N2D	0.141 (3)	0.0478 (17)	0.0451 (16)	0.0076 (18)	0.0104 (18)	−0.0095 (13)
C1D	0.0331 (12)	0.0302 (11)	0.0299 (12)	−0.0014 (9)	−0.0034 (9)	0.0005 (9)
C2D	0.0389 (13)	0.0295 (12)	0.0348 (13)	0.0014 (10)	−0.0052 (10)	−0.0010 (10)
C3D	0.0624 (18)	0.0341 (13)	0.0378 (14)	−0.0026 (12)	−0.0025 (13)	0.0062 (11)
C4D	0.068 (2)	0.0454 (16)	0.0306 (13)	−0.0001 (14)	0.0033 (13)	0.0016 (11)
C5D	0.0677 (19)	0.0376 (14)	0.0358 (14)	0.0032 (13)	0.0003 (13)	−0.0057 (11)
C6D	0.0592 (17)	0.0298 (12)	0.0357 (14)	0.0005 (11)	−0.0035 (12)	0.0006 (10)
C7D	0.074 (2)	0.0301 (13)	0.0451 (16)	−0.0002 (13)	0.0006 (14)	−0.0038 (11)
O1A	0.0687 (19)	0.221 (4)	0.0509 (17)	−0.023 (2)	0.0059 (14)	0.042 (2)
O2A	0.0396 (13)	0.200 (4)	0.0652 (18)	−0.0098 (18)	0.0006 (12)	0.019 (2)
N1A	0.0348 (11)	0.0420 (12)	0.0343 (11)	0.0020 (9)	−0.0040 (9)	−0.0011 (9)
N2A	0.0448 (16)	0.122 (3)	0.0460 (16)	−0.0055 (16)	0.0022 (12)	0.0122 (17)
C1A	0.0342 (12)	0.0330 (12)	0.0314 (12)	0.0020 (10)	−0.0055 (10)	−0.0050 (9)
C2A	0.0325 (12)	0.0404 (13)	0.0371 (13)	0.0001 (10)	−0.0051 (10)	−0.0059 (11)
C3A	0.0386 (14)	0.068 (2)	0.0393 (15)	0.0029 (13)	−0.0108 (12)	−0.0027 (13)
C4A	0.0481 (17)	0.073 (2)	0.0351 (15)	−0.0017 (15)	−0.0064 (12)	0.0025 (14)
C5A	0.0392 (14)	0.0656 (19)	0.0366 (14)	−0.0022 (13)	0.0016 (11)	0.0003 (13)
C6A	0.0312 (12)	0.0556 (16)	0.0364 (14)	−0.0010 (11)	−0.0051 (10)	−0.0023 (12)
C7A	0.0329 (14)	0.073 (2)	0.0494 (17)	−0.0021 (13)	−0.0052 (12)	−0.0008 (15)
O1B	0.0693 (18)	0.227 (4)	0.0384 (14)	−0.019 (2)	−0.0161 (13)	0.007 (2)
O2B	0.0376 (14)	0.294 (6)	0.0595 (18)	0.004 (2)	−0.0091 (13)	0.008 (3)
N1B	0.0332 (11)	0.0441 (12)	0.0332 (11)	−0.0024 (9)	0.0004 (9)	−0.0005 (9)
N2B	0.0456 (16)	0.148 (3)	0.0424 (16)	−0.0056 (18)	−0.0089 (13)	0.0055 (18)
C1B	0.0324 (12)	0.0329 (12)	0.0315 (12)	−0.0017 (9)	0.0014 (9)	−0.0018 (9)
C2B	0.0309 (12)	0.0404 (13)	0.0369 (13)	0.0012 (10)	0.0004 (10)	−0.0028 (10)
C3B	0.0340 (13)	0.0624 (18)	0.0406 (15)	−0.0030 (12)	0.0045 (11)	0.0053 (13)
C4B	0.0464 (16)	0.069 (2)	0.0340 (14)	−0.0017 (14)	0.0009 (12)	0.0051 (13)
C5B	0.0387 (15)	0.074 (2)	0.0369 (15)	−0.0008 (14)	−0.0057 (12)	−0.0010 (14)
C6B	0.0305 (13)	0.0611 (18)	0.0367 (14)	−0.0010 (12)	0.0010 (10)	−0.0020 (12)
C7B	0.0311 (13)	0.076 (2)	0.0457 (16)	−0.0011 (13)	−0.0018 (12)	0.0024 (15)

Geometric parameters (Å, º)

O1C—N2C	1.214 (4)	O1A—N2A	1.210 (4)
O2C—N2C	1.216 (4)	O2A—N2A	1.210 (4)
N1C—H1CA	0.8900	N1A—H1AA	0.8900
N1C—H1CB	0.8900	N1A—H1AB	0.8900
N1C—H1CC	0.8900	N1A—H1AC	0.8900
N1C—C1C	1.461 (3)	N1A—C1A	1.461 (3)
N2C—C5C	1.463 (4)	N2A—C5A	1.465 (4)
C1C—C2C	1.394 (3)	C1A—C2A	1.393 (3)
C1C—C6C	1.376 (4)	C1A—C6A	1.379 (4)
C2C—C3C	1.398 (4)	C2A—C3A	1.388 (4)
C2C—C7C	1.501 (4)	C2A—C7A	1.502 (4)
C3C—H3C	0.9300	C3A—H3A	0.9300
C3C—C4C	1.375 (4)	C3A—C4A	1.382 (4)
C4C—H4C	0.9300	C4A—H4A	0.9300
C4C—C5C	1.375 (4)	C4A—C5A	1.372 (4)
C5C—C6C	1.380 (4)	C5A—C6A	1.378 (4)
C6C—H6C	0.9300	C6A—H6A	0.9300
C7C—H7CA	0.9600	C7A—H7AA	0.9600
C7C—H7CB	0.9600	C7A—H7AB	0.9600
C7C—H7CC	0.9600	C7A—H7AC	0.9600
O1D—N2D	1.205 (4)	O1B—N2B	1.213 (4)
O2D—N2D	1.213 (4)	O2B—N2B	1.216 (4)
N1D—H1DA	0.8900	N1B—H1BA	0.8900
N1D—H1DB	0.8900	N1B—H1BB	0.8900
N1D—H1DC	0.8900	N1B—H1BC	0.8900
N1D—C1D	1.457 (3)	N1B—C1B	1.459 (3)
N2D—C5D	1.464 (4)	N2B—C5B	1.465 (4)
C1D—C2D	1.398 (3)	C1B—C2B	1.396 (3)
C1D—C6D	1.384 (4)	C1B—C6B	1.376 (4)
C2D—C3D	1.394 (4)	C2B—C3B	1.389 (4)
C2D—C7D	1.502 (4)	C2B—C7B	1.502 (4)
C3D—H3D	0.9300	C3B—H3B	0.9300
C3D—C4D	1.371 (4)	C3B—C4B	1.385 (4)
C4D—H4D	0.9300	C4B—H4B	0.9300
C4D—C5D	1.373 (4)	C4B—C5B	1.371 (4)
C5D—C6D	1.383 (4)	C5B—C6B	1.379 (4)
C6D—H6D	0.9300	C6B—H6B	0.9300
C7D—H7DA	0.9600	C7B—H7BA	0.9600
C7D—H7DB	0.9600	C7B—H7BB	0.9600
C7D—H7DC	0.9600	C7B—H7BC	0.9600
H1CA—N1C—H1CB	109.5	H1AA—N1A—H1AB	109.5
H1CA—N1C—H1CC	109.5	H1AA—N1A—H1AC	109.5
H1CB—N1C—H1CC	109.5	H1AB—N1A—H1AC	109.5
C1C—N1C—H1CA	109.5	C1A—N1A—H1AA	109.5
C1C—N1C—H1CB	109.5	C1A—N1A—H1AB	109.5
C1C—N1C—H1CC	109.5	C1A—N1A—H1AC	109.5
O1C—N2C—O2C	122.6 (3)	O1A—N2A—O2A	122.8 (3)
O1C—N2C—C5C	118.6 (3)	O1A—N2A—C5A	118.4 (3)
O2C—N2C—C5C	118.7 (3)	O2A—N2A—C5A	118.7 (3)
C2C—C1C—N1C	120.4 (2)	C2A—C1A—N1A	120.6 (2)
C6C—C1C—N1C	117.3 (2)	C6A—C1A—N1A	117.2 (2)
C6C—C1C—C2C	122.3 (2)	C6A—C1A—C2A	122.2 (2)
C1C—C2C—C3C	117.2 (2)	C1A—C2A—C7A	123.0 (2)
C1C—C2C—C7C	122.6 (2)	C3A—C2A—C1A	117.3 (2)
C3C—C2C—C7C	120.1 (2)	C3A—C2A—C7A	119.8 (2)
C2C—C3C—H3C	119.1	C2A—C3A—H3A	119.0
C4C—C3C—C2C	121.9 (3)	C4A—C3A—C2A	122.0 (3)
C4C—C3C—H3C	119.1	C4A—C3A—H3A	119.0
C3C—C4C—H4C	120.9	C3A—C4A—H4A	120.9
C5C—C4C—C3C	118.2 (3)	C5A—C4A—C3A	118.2 (3)
C5C—C4C—H4C	120.9	C5A—C4A—H4A	120.9
C4C—C5C—N2C	119.1 (3)	C4A—C5A—N2A	119.1 (3)
C4C—C5C—C6C	122.7 (3)	C4A—C5A—C6A	122.4 (3)
C6C—C5C—N2C	118.2 (3)	C6A—C5A—N2A	118.5 (3)
C1C—C6C—C5C	117.6 (3)	C1A—C6A—H6A	121.0
C1C—C6C—H6C	121.2	C5A—C6A—C1A	117.9 (2)
C5C—C6C—H6C	121.2	C5A—C6A—H6A	121.0
C2C—C7C—H7CA	109.5	C2A—C7A—H7AA	109.5
C2C—C7C—H7CB	109.5	C2A—C7A—H7AB	109.5
C2C—C7C—H7CC	109.5	C2A—C7A—H7AC	109.5
H7CA—C7C—H7CB	109.5	H7AA—C7A—H7AB	109.5
H7CA—C7C—H7CC	109.5	H7AA—C7A—H7AC	109.5
H7CB—C7C—H7CC	109.5	H7AB—C7A—H7AC	109.5
H1DA—N1D—H1DB	109.5	H1BA—N1B—H1BB	109.5
H1DA—N1D—H1DC	109.5	H1BA—N1B—H1BC	109.5
H1DB—N1D—H1DC	109.5	H1BB—N1B—H1BC	109.5
C1D—N1D—H1DA	109.5	C1B—N1B—H1BA	109.5
C1D—N1D—H1DB	109.5	C1B—N1B—H1BB	109.5
C1D—N1D—H1DC	109.5	C1B—N1B—H1BC	109.5
O1D—N2D—O2D	122.8 (3)	O1B—N2B—O2B	123.2 (3)
O1D—N2D—C5D	118.7 (3)	O1B—N2B—C5B	118.6 (3)
O2D—N2D—C5D	118.5 (3)	O2B—N2B—C5B	118.1 (3)
C2D—C1D—N1D	120.7 (2)	C2B—C1B—N1B	120.3 (2)
C6D—C1D—N1D	117.4 (2)	C6B—C1B—N1B	117.4 (2)
C6D—C1D—C2D	121.8 (2)	C6B—C1B—C2B	122.2 (2)
C1D—C2D—C7D	122.6 (2)	C1B—C2B—C7B	122.6 (2)
C3D—C2D—C1D	117.5 (2)	C3B—C2B—C1B	117.3 (2)
C3D—C2D—C7D	119.9 (2)	C3B—C2B—C7B	120.2 (2)
C2D—C3D—H3D	119.0	C2B—C3B—H3B	119.0
C4D—C3D—C2D	121.9 (3)	C4B—C3B—C2B	122.0 (3)
C4D—C3D—H3D	119.0	C4B—C3B—H3B	119.0
C3D—C4D—H4D	120.7	C3B—C4B—H4B	121.1
C3D—C4D—C5D	118.6 (3)	C5B—C4B—C3B	117.8 (3)
C5D—C4D—H4D	120.7	C5B—C4B—H4B	121.1
C4D—C5D—N2D	119.1 (3)	C4B—C5B—N2B	118.5 (3)
C4D—C5D—C6D	122.5 (3)	C4B—C5B—C6B	123.0 (3)
C6D—C5D—N2D	118.4 (3)	C6B—C5B—N2B	118.5 (3)
C1D—C6D—H6D	121.1	C1B—C6B—C5B	117.6 (2)
C5D—C6D—C1D	117.7 (2)	C1B—C6B—H6B	121.2
C5D—C6D—H6D	121.1	C5B—C6B—H6B	121.2
C2D—C7D—H7DA	109.5	C2B—C7B—H7BA	109.5
C2D—C7D—H7DB	109.5	C2B—C7B—H7BB	109.5
C2D—C7D—H7DC	109.5	C2B—C7B—H7BC	109.5
H7DA—C7D—H7DB	109.5	H7BA—C7B—H7BB	109.5
H7DA—C7D—H7DC	109.5	H7BA—C7B—H7BC	109.5
H7DB—C7D—H7DC	109.5	H7BB—C7B—H7BC	109.5
O1C—N2C—C5C—C4C	−2.6 (6)	O1A—N2A—C5A—C4A	−0.4 (6)
O1C—N2C—C5C—C6C	176.5 (4)	O1A—N2A—C5A—C6A	179.6 (4)
O2C—N2C—C5C—C4C	−179.7 (4)	O2A—N2A—C5A—C4A	−177.0 (4)
O2C—N2C—C5C—C6C	−0.5 (6)	O2A—N2A—C5A—C6A	3.0 (6)
N1C—C1C—C2C—C3C	177.5 (2)	N1A—C1A—C2A—C3A	−178.6 (2)
N1C—C1C—C2C—C7C	−2.9 (4)	N1A—C1A—C2A—C7A	1.5 (4)
N1C—C1C—C6C—C5C	−178.3 (3)	N1A—C1A—C6A—C5A	177.8 (3)
N2C—C5C—C6C—C1C	−178.4 (3)	N2A—C5A—C6A—C1A	−178.2 (3)
C1C—C2C—C3C—C4C	1.1 (5)	C1A—C2A—C3A—C4A	0.2 (5)
C2C—C1C—C6C—C5C	0.7 (4)	C2A—C1A—C6A—C5A	−0.3 (4)
C2C—C3C—C4C—C5C	0.2 (5)	C2A—C3A—C4A—C5A	1.2 (5)
C3C—C4C—C5C—N2C	177.9 (3)	C3A—C4A—C5A—N2A	177.8 (3)
C3C—C4C—C5C—C6C	−1.1 (5)	C3A—C4A—C5A—C6A	−2.1 (5)
C4C—C5C—C6C—C1C	0.7 (5)	C4A—C5A—C6A—C1A	1.7 (5)
C6C—C1C—C2C—C3C	−1.5 (4)	C6A—C1A—C2A—C3A	−0.6 (4)
C6C—C1C—C2C—C7C	178.1 (3)	C6A—C1A—C2A—C7A	179.5 (3)
C7C—C2C—C3C—C4C	−178.6 (3)	C7A—C2A—C3A—C4A	−179.9 (3)
O1D—N2D—C5D—C4D	1.7 (6)	O1B—N2B—C5B—C4B	−6.8 (6)
O1D—N2D—C5D—C6D	−177.4 (4)	O1B—N2B—C5B—C6B	173.1 (4)
O2D—N2D—C5D—C4D	179.4 (5)	O2B—N2B—C5B—C4B	177.4 (4)
O2D—N2D—C5D—C6D	0.3 (6)	O2B—N2B—C5B—C6B	−2.8 (6)
N1D—C1D—C2D—C3D	178.6 (2)	N1B—C1B—C2B—C3B	177.1 (2)
N1D—C1D—C2D—C7D	−2.4 (4)	N1B—C1B—C2B—C7B	−2.6 (4)
N1D—C1D—C6D—C5D	−178.1 (3)	N1B—C1B—C6B—C5B	−178.4 (3)
N2D—C5D—C6D—C1D	178.7 (3)	N2B—C5B—C6B—C1B	−179.0 (3)
C1D—C2D—C3D—C4D	−0.8 (4)	C1B—C2B—C3B—C4B	1.6 (5)
C2D—C1D—C6D—C5D	−0.5 (4)	C2B—C1B—C6B—C5B	0.0 (4)
C2D—C3D—C4D—C5D	−0.1 (5)	C2B—C3B—C4B—C5B	−0.8 (5)
C3D—C4D—C5D—N2D	−178.4 (3)	C3B—C4B—C5B—N2B	179.4 (3)
C3D—C4D—C5D—C6D	0.7 (5)	C3B—C4B—C5B—C6B	−0.5 (5)
C4D—C5D—C6D—C1D	−0.4 (5)	C4B—C5B—C6B—C1B	0.9 (5)
C6D—C1D—C2D—C3D	1.1 (4)	C6B—C1B—C2B—C3B	−1.2 (4)
C6D—C1D—C2D—C7D	−180.0 (3)	C6B—C1B—C2B—C7B	179.1 (3)
C7D—C2D—C3D—C4D	−179.8 (3)	C7B—C2B—C3B—C4B	−178.6 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1C—H1CA···Cl4^i	0.89	2.33	3.181 (2)	159
N1C—H1CB···Cl4^ii	0.89	2.28	3.116 (2)	156
N1C—H1CC···Cl3	0.89	2.36	3.163 (2)	151
N1D—H1DA···Cl3	0.89	2.31	3.175 (2)	163
N1D—H1DB···Cl3^iii	0.89	2.33	3.152 (2)	153
N1D—H1DC···Cl4	0.89	2.35	3.137 (2)	147
N1A—H1AA···Cl2^iv	0.89	2.32	3.127 (2)	151
N1A—H1AB···Cl1	0.89	2.33	3.148 (2)	153
N1A—H1AC···Cl1^v	0.89	2.32	3.167 (2)	160
N1B—H1BA···Cl1	0.89	2.38	3.171 (2)	148
N1B—H1BB···Cl2	0.89	2.32	3.180 (2)	162
N1B—H1BC···Cl2^vi	0.89	2.29	3.119 (2)	155

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

(5)

Crystal data

C7H9N2O2·HO4S	Dx = 1.643 Mg m^−3
Mr = 250.23	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna21	Cell parameters from 24691 reflections
a = 12.8927 (2) Å	θ = 3.2–29.8°
b = 4.97471 (10) Å	µ = 0.34 mm^−1
c = 31.5518 (7) Å	T = 295 K
V = 2023.66 (7) Å^3	Plank, clear light colourless
Z = 8	0.46 × 0.21 × 0.06 mm
F(000) = 1040

Data collection

Xcalibur, Atlas diffractometer	5220 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	4577 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.060
Detector resolution: 10.6249 pixels mm^-1	θmax = 28.7°, θmin = 3.2°
ω scans	h = −17→17
Absorption correction: gaussian CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Numerical absorption correction based on gaussian integration over a multifaceted crystal model Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −6→6
Tmin = 0.874, Tmax = 0.980	l = −42→42
84145 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.044	w = 1/[σ^2(Fo^2) + (0.0621P)^2 + 1.5552P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.120	(Δ/σ)max = <0.001
S = 1.06	Δρmax = 0.51 e Å^−3
5220 reflections	Δρmin = −0.35 e Å^−3
295 parameters	Absolute structure: Flack x determined using 2026 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
1 restraint	Absolute structure parameter: 0.15 (4)
Primary atom site location: structure-invariant direct methods

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
S1A	0.76667 (6)	0.50110 (18)	0.23895 (3)	0.0213 (2)
S1B	0.55265 (7)	1.00247 (18)	0.30729 (3)	0.0215 (2)
O1B	0.5304 (5)	0.1877 (13)	0.50800 (16)	0.0867 (17)
O2B	0.5676 (4)	0.0425 (12)	0.44610 (17)	0.0744 (16)
O3A	0.7695 (2)	0.1872 (5)	0.24244 (13)	0.0330 (7)
H3AA	0.711125	0.130872	0.247637	0.049*
O3B	0.5495 (2)	0.6886 (6)	0.30379 (13)	0.0352 (7)
H3BA	0.607377	0.632213	0.297754	0.053*
O4A	0.8713 (2)	0.5631 (6)	0.22501 (10)	0.0303 (6)
O4B	0.4481 (2)	1.0670 (6)	0.32144 (10)	0.0291 (6)
O5A	0.6876 (2)	0.5729 (7)	0.20828 (11)	0.0360 (7)
O5B	0.6322 (2)	1.0721 (7)	0.33754 (11)	0.0357 (7)
O6A	0.7430 (2)	0.6045 (8)	0.28084 (10)	0.0339 (7)
O6B	0.5753 (2)	1.1059 (7)	0.26530 (11)	0.0332 (7)
N1B	0.3455 (3)	0.5558 (8)	0.34486 (11)	0.0259 (7)
H1BA	0.387642	0.434695	0.333248	0.031*
H1BB	0.358939	0.717179	0.333975	0.031*
H1BC	0.279958	0.511636	0.339447	0.031*
N2B	0.5211 (4)	0.1915 (11)	0.46967 (15)	0.0503 (12)
C1B	0.3620 (3)	0.5623 (9)	0.39071 (14)	0.0264 (8)
C2B	0.3029 (3)	0.7370 (10)	0.41586 (16)	0.0323 (9)
C3B	0.3184 (4)	0.7247 (12)	0.45947 (17)	0.0471 (12)
H3B	0.280357	0.838394	0.476953	0.056*
C4B	0.3885 (5)	0.5490 (13)	0.47764 (16)	0.0482 (13)
H4B	0.396818	0.541568	0.506896	0.058*
C5B	0.4461 (4)	0.3845 (11)	0.45129 (17)	0.0377 (11)
C6B	0.4351 (3)	0.3892 (10)	0.40817 (14)	0.0301 (9)
H6B	0.475573	0.279336	0.390965	0.036*
C7B	0.2240 (4)	0.9241 (13)	0.3970 (2)	0.0426 (12)
H7BA	0.248308	0.987339	0.370000	0.064*
H7BB	0.213615	1.074240	0.415607	0.064*
H7BC	0.159560	0.830219	0.393235	0.064*
O1A	0.2341 (5)	0.6202 (15)	0.04289 (18)	0.104 (2)
O2A	0.2341 (3)	0.8860 (11)	0.09563 (16)	0.0590 (12)
N1A	0.4738 (3)	0.4574 (7)	0.20183 (11)	0.0259 (7)
H1AA	0.541510	0.486730	0.204869	0.031*
H1AB	0.456004	0.310204	0.216110	0.031*
H1AC	0.438620	0.597590	0.211844	0.031*
N2A	0.2666 (4)	0.6882 (11)	0.07691 (16)	0.0507 (12)
C1A	0.4496 (3)	0.4207 (10)	0.15679 (15)	0.0250 (9)
C2A	0.5048 (3)	0.2286 (10)	0.13396 (15)	0.0318 (9)
C3A	0.4790 (4)	0.1948 (11)	0.09153 (16)	0.0424 (12)
H3A	0.515258	0.069633	0.075422	0.051*
C4A	0.4009 (4)	0.3423 (12)	0.07268 (16)	0.0464 (13)
H4A	0.383218	0.313767	0.044454	0.056*
C5A	0.3498 (4)	0.5316 (11)	0.09641 (15)	0.0376 (11)
C6A	0.3718 (3)	0.5757 (10)	0.13891 (15)	0.0318 (9)
H6A	0.336034	0.703614	0.154663	0.038*
C7A	0.5893 (4)	0.0634 (11)	0.15390 (17)	0.0383 (11)
H7AA	0.654501	0.154614	0.150816	0.058*
H7AB	0.592915	−0.108568	0.140162	0.058*
H7AC	0.574542	0.038466	0.183462	0.058*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1A	0.0141 (4)	0.0199 (4)	0.0301 (5)	0.0002 (3)	0.0014 (3)	0.0006 (4)
S1B	0.0146 (4)	0.0210 (4)	0.0290 (4)	−0.0001 (3)	0.0014 (3)	−0.0005 (4)
O1B	0.108 (4)	0.103 (5)	0.048 (3)	0.018 (4)	−0.027 (3)	0.021 (3)
O2B	0.067 (3)	0.089 (4)	0.066 (3)	0.041 (3)	−0.006 (2)	0.014 (3)
O3A	0.0229 (14)	0.0212 (13)	0.0549 (19)	0.0005 (11)	0.0099 (13)	0.0027 (15)
O3B	0.0225 (14)	0.0213 (14)	0.062 (2)	−0.0008 (11)	0.0115 (14)	−0.0012 (15)
O4A	0.0167 (13)	0.0310 (15)	0.0431 (17)	−0.0019 (12)	0.0050 (12)	0.0044 (13)
O4B	0.0199 (13)	0.0277 (15)	0.0398 (16)	0.0011 (12)	0.0064 (12)	−0.0022 (12)
O5A	0.0221 (14)	0.0443 (18)	0.0416 (17)	0.0000 (14)	−0.0063 (13)	0.0075 (16)
O5B	0.0229 (15)	0.0433 (18)	0.0409 (17)	−0.0002 (14)	−0.0063 (13)	−0.0038 (15)
O6A	0.0227 (15)	0.0414 (19)	0.0375 (17)	0.0006 (14)	0.0022 (13)	−0.0068 (14)
O6B	0.0230 (14)	0.0407 (18)	0.0358 (16)	−0.0004 (13)	0.0018 (13)	0.0053 (14)
N1B	0.0178 (16)	0.0297 (17)	0.0303 (18)	0.0019 (13)	0.0002 (13)	0.0036 (14)
N2B	0.048 (3)	0.057 (3)	0.046 (3)	−0.004 (2)	−0.015 (2)	0.017 (2)
C1B	0.0207 (18)	0.026 (2)	0.032 (2)	0.0004 (16)	0.0024 (16)	0.0011 (16)
C2B	0.026 (2)	0.032 (2)	0.039 (2)	−0.0028 (18)	0.0052 (17)	−0.0048 (18)
C3B	0.046 (3)	0.055 (3)	0.040 (3)	0.004 (3)	0.005 (2)	−0.013 (2)
C4B	0.051 (3)	0.066 (4)	0.027 (2)	−0.008 (3)	0.002 (2)	−0.001 (2)
C5B	0.033 (3)	0.043 (3)	0.037 (3)	−0.005 (2)	−0.0035 (19)	0.006 (2)
C6B	0.026 (2)	0.032 (2)	0.032 (2)	0.0010 (17)	−0.0013 (16)	0.0001 (17)
C7B	0.035 (3)	0.036 (3)	0.057 (3)	0.005 (2)	−0.003 (2)	−0.008 (3)
O1A	0.107 (5)	0.141 (6)	0.065 (3)	0.049 (4)	−0.055 (3)	−0.023 (4)
O2A	0.050 (3)	0.065 (3)	0.062 (3)	0.016 (2)	−0.007 (2)	0.013 (2)
N1A	0.0210 (15)	0.0280 (18)	0.0286 (18)	0.0034 (13)	0.0003 (13)	−0.0020 (14)
N2A	0.041 (2)	0.064 (3)	0.048 (3)	0.005 (2)	−0.012 (2)	0.012 (2)
C1A	0.0194 (19)	0.028 (2)	0.027 (2)	0.0007 (16)	0.0007 (15)	0.0008 (17)
C2A	0.029 (2)	0.030 (2)	0.036 (2)	0.0023 (18)	0.0029 (17)	−0.0027 (17)
C3A	0.042 (3)	0.048 (3)	0.037 (2)	0.007 (2)	0.004 (2)	−0.007 (2)
C4A	0.048 (3)	0.060 (4)	0.031 (2)	0.001 (3)	−0.003 (2)	−0.006 (2)
C5A	0.034 (2)	0.047 (3)	0.032 (2)	0.001 (2)	−0.0062 (19)	0.0041 (19)
C6A	0.027 (2)	0.033 (2)	0.036 (2)	0.0044 (18)	0.0025 (17)	0.0031 (18)
C7A	0.032 (2)	0.037 (2)	0.045 (3)	0.009 (2)	−0.001 (2)	−0.009 (2)

Geometric parameters (Å, º)

S1A—O3A	1.566 (3)	C5B—C6B	1.368 (7)
S1A—O4A	1.452 (3)	C6B—H6B	0.9300
S1A—O5A	1.450 (3)	C7B—H7BA	0.9600
S1A—O6A	1.451 (3)	C7B—H7BB	0.9600
S1B—O3B	1.566 (3)	C7B—H7BC	0.9600
S1B—O4B	1.456 (3)	O1A—N2A	1.201 (7)
S1B—O5B	1.443 (3)	O2A—N2A	1.222 (7)
S1B—O6B	1.451 (4)	N1A—H1AA	0.8900
O1B—N2B	1.215 (7)	N1A—H1AB	0.8900
O2B—N2B	1.209 (7)	N1A—H1AC	0.8900
O3A—H3AA	0.8200	N1A—C1A	1.466 (6)
O3B—H3BA	0.8200	N2A—C5A	1.461 (7)
N1B—H1BA	0.8900	C1A—C2A	1.392 (6)
N1B—H1BB	0.8900	C1A—C6A	1.385 (6)
N1B—H1BC	0.8900	C2A—C3A	1.390 (7)
N1B—C1B	1.463 (6)	C2A—C7A	1.503 (7)
N2B—C5B	1.481 (7)	C3A—H3A	0.9300
C1B—C2B	1.402 (6)	C3A—C4A	1.381 (8)
C1B—C6B	1.391 (6)	C4A—H4A	0.9300
C2B—C3B	1.392 (7)	C4A—C5A	1.372 (8)
C2B—C7B	1.503 (7)	C5A—C6A	1.388 (7)
C3B—H3B	0.9300	C6A—H6A	0.9300
C3B—C4B	1.382 (9)	C7A—H7AA	0.9600
C4B—H4B	0.9300	C7A—H7AB	0.9600
C4B—C5B	1.382 (8)	C7A—H7AC	0.9600
O4A—S1A—O3A	102.20 (17)	C5B—C6B—H6B	120.8
O5A—S1A—O3A	108.0 (2)	C2B—C7B—H7BA	109.5
O5A—S1A—O4A	113.5 (2)	C2B—C7B—H7BB	109.5
O5A—S1A—O6A	111.9 (2)	C2B—C7B—H7BC	109.5
O6A—S1A—O3A	107.1 (2)	H7BA—C7B—H7BB	109.5
O6A—S1A—O4A	113.3 (2)	H7BA—C7B—H7BC	109.5
O4B—S1B—O3B	102.54 (17)	H7BB—C7B—H7BC	109.5
O5B—S1B—O3B	107.7 (2)	H1AA—N1A—H1AB	109.5
O5B—S1B—O4B	113.7 (2)	H1AA—N1A—H1AC	109.5
O5B—S1B—O6B	112.1 (2)	H1AB—N1A—H1AC	109.5
O6B—S1B—O3B	107.1 (2)	C1A—N1A—H1AA	109.5
O6B—S1B—O4B	112.86 (19)	C1A—N1A—H1AB	109.5
S1A—O3A—H3AA	109.5	C1A—N1A—H1AC	109.5
S1B—O3B—H3BA	109.5	O1A—N2A—O2A	122.6 (5)
H1BA—N1B—H1BB	109.5	O1A—N2A—C5A	118.8 (6)
H1BA—N1B—H1BC	109.5	O2A—N2A—C5A	118.5 (5)
H1BB—N1B—H1BC	109.5	C2A—C1A—N1A	118.6 (4)
C1B—N1B—H1BA	109.5	C6A—C1A—N1A	118.6 (4)
C1B—N1B—H1BB	109.5	C6A—C1A—C2A	122.8 (4)
C1B—N1B—H1BC	109.5	C1A—C2A—C7A	122.0 (4)
O1B—N2B—C5B	117.6 (6)	C3A—C2A—C1A	117.3 (4)
O2B—N2B—O1B	123.6 (6)	C3A—C2A—C7A	120.7 (4)
O2B—N2B—C5B	118.7 (5)	C2A—C3A—H3A	119.1
C2B—C1B—N1B	119.6 (4)	C4A—C3A—C2A	121.7 (5)
C6B—C1B—N1B	118.5 (4)	C4A—C3A—H3A	119.1
C6B—C1B—C2B	121.9 (4)	C3A—C4A—H4A	120.7
C1B—C2B—C7B	121.8 (5)	C5A—C4A—C3A	118.7 (5)
C3B—C2B—C1B	117.0 (5)	C5A—C4A—H4A	120.7
C3B—C2B—C7B	121.1 (5)	C4A—C5A—N2A	119.2 (5)
C2B—C3B—H3B	118.9	C4A—C5A—C6A	122.5 (5)
C4B—C3B—C2B	122.1 (5)	C6A—C5A—N2A	118.2 (5)
C4B—C3B—H3B	118.9	C1A—C6A—C5A	117.0 (4)
C3B—C4B—H4B	120.8	C1A—C6A—H6A	121.5
C3B—C4B—C5B	118.4 (5)	C5A—C6A—H6A	121.5
C5B—C4B—H4B	120.8	C2A—C7A—H7AA	109.5
C4B—C5B—N2B	119.9 (5)	C2A—C7A—H7AB	109.5
C6B—C5B—N2B	117.9 (5)	C2A—C7A—H7AC	109.5
C6B—C5B—C4B	122.2 (5)	H7AA—C7A—H7AB	109.5
C1B—C6B—H6B	120.8	H7AA—C7A—H7AC	109.5
C5B—C6B—C1B	118.3 (4)	H7AB—C7A—H7AC	109.5
O1B—N2B—C5B—C4B	−1.0 (8)	O1A—N2A—C5A—C4A	11.4 (9)
O1B—N2B—C5B—C6B	−179.8 (6)	O1A—N2A—C5A—C6A	−166.8 (6)
O2B—N2B—C5B—C4B	177.2 (6)	O2A—N2A—C5A—C4A	−167.4 (5)
O2B—N2B—C5B—C6B	−1.6 (8)	O2A—N2A—C5A—C6A	14.4 (8)
N1B—C1B—C2B—C3B	176.9 (4)	N1A—C1A—C2A—C3A	178.9 (4)
N1B—C1B—C2B—C7B	−1.4 (7)	N1A—C1A—C2A—C7A	−1.3 (7)
N1B—C1B—C6B—C5B	−176.2 (4)	N1A—C1A—C6A—C5A	−178.8 (4)
N2B—C5B—C6B—C1B	177.5 (4)	N2A—C5A—C6A—C1A	178.8 (5)
C1B—C2B—C3B—C4B	−0.1 (8)	C1A—C2A—C3A—C4A	−0.9 (8)
C2B—C1B—C6B—C5B	2.4 (7)	C2A—C1A—C6A—C5A	0.3 (7)
C2B—C3B—C4B—C5B	1.2 (9)	C2A—C3A—C4A—C5A	1.8 (9)
C3B—C4B—C5B—N2B	−179.3 (5)	C3A—C4A—C5A—N2A	−179.7 (5)
C3B—C4B—C5B—C6B	−0.5 (9)	C3A—C4A—C5A—C6A	−1.7 (9)
C4B—C5B—C6B—C1B	−1.3 (8)	C4A—C5A—C6A—C1A	0.7 (8)
C6B—C1B—C2B—C3B	−1.7 (7)	C6A—C1A—C2A—C3A	−0.2 (7)
C6B—C1B—C2B—C7B	180.0 (5)	C6A—C1A—C2A—C7A	179.7 (5)
C7B—C2B—C3B—C4B	178.2 (5)	C7A—C2A—C3A—C4A	179.3 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3A—H3AA···O6B^i	0.82	1.84	2.637 (4)	163
O3B—H3BA···O6A	0.82	1.83	2.632 (4)	164
N1B—H1BB···O4B	0.89	2.12	2.960 (5)	156
N1B—H1BB···O6A^ii	0.89	2.41	2.947 (5)	119
N1B—H1BC···O5B^ii	0.89	1.95	2.833 (5)	170
C6B—H6B···O4B^i	0.93	2.46	3.176 (6)	134
N1A—H1AA···O5A	0.89	1.93	2.823 (5)	176
N1A—H1AB···O3A^iii	0.89	2.54	3.016 (5)	114
N1A—H1AB···O4A^iii	0.89	2.17	2.998 (5)	154
N1A—H1AB···O6B^i	0.89	2.41	2.963 (5)	121
N1A—H1AC···O4A^ii	0.89	1.94	2.824 (5)	170
C6A—H6A···O4A^ii	0.93	2.55	3.257 (6)	134

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

(6)

Crystal data

2(C7H9N2O2)·2(I3)·H2O	F(000) = 1960
Mr = 1085.74	Dx = 2.631 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.2876 (3) Å	Cell parameters from 12710 reflections
b = 13.9536 (3) Å	θ = 2.8–26.2°
c = 17.5279 (5) Å	µ = 6.83 mm^−1
β = 96.808 (3)°	T = 295 K
V = 2741.24 (13) Å^3	Prism, metallic dark black
Z = 4	0.36 × 0.3 × 0.25 mm

Data collection

Xcalibur, Atlas diffractometer	5817 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	3896 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.054
Detector resolution: 10.6249 pixels mm^-1	θmax = 26.7°, θmin = 2.9°
ω scans	h = −14→14
Absorption correction: gaussian CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Numerical absorption correction based on gaussian integration over a multifaceted crystal model Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −17→17
Tmin = 0.186, Tmax = 0.307	l = −22→22
68555 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.038	w = 1/[σ^2(Fo^2) + (0.0151P)^2 + 3.8369P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.070	(Δ/σ)max = 0.001
S = 1.04	Δρmax = 1.12 e Å^−3
5817 reflections	Δρmin = −0.89 e Å^−3
270 parameters	Extinction correction: SHELXL-2018/1 (Sheldrick 2018), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00079 (2)
Primary atom site location: dual

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
I1A	0.64624 (4)	0.50637 (3)	0.08214 (2)	0.06385 (14)
I2A	0.57755 (3)	0.50647 (2)	0.23304 (2)	0.04762 (11)
I3A	0.52222 (3)	0.50555 (3)	0.39667 (2)	0.05488 (12)
I1B	0.22121 (5)	0.50120 (3)	0.09683 (3)	0.07356 (15)
I2B	0.16741 (3)	0.50837 (2)	0.25145 (2)	0.04951 (12)
I3B	0.10195 (4)	0.52686 (3)	0.41361 (3)	0.06239 (14)
O1A	0.7170 (4)	0.2251 (3)	0.9670 (2)	0.0740 (13)
O2A	0.5583 (4)	0.2735 (3)	0.8977 (2)	0.0696 (13)
O1W	0.4585 (5)	0.2074 (3)	0.5506 (3)	0.0697 (13)
H1W	0.482453	0.167765	0.518828	0.105*
H2W	0.426080	0.177022	0.584686	0.105*
N1A	0.6729 (4)	0.2899 (3)	0.6304 (3)	0.0544 (13)
H1AA	0.640382	0.346116	0.639990	0.065*
H1AB	0.617091	0.251430	0.607041	0.065*
H1AC	0.730037	0.298795	0.600255	0.065*
N2A	0.6596 (5)	0.2417 (3)	0.9049 (3)	0.0526 (13)
C1A	0.7246 (5)	0.2458 (3)	0.7034 (3)	0.0379 (13)
C2A	0.8283 (5)	0.1927 (4)	0.7055 (3)	0.0431 (14)
C3A	0.8716 (5)	0.1521 (4)	0.7754 (4)	0.0519 (15)
H3A	0.939535	0.113851	0.778380	0.062*
C4A	0.8173 (5)	0.1667 (4)	0.8405 (3)	0.0507 (15)
H4A	0.847865	0.139195	0.887016	0.061*
C5A	0.7163 (5)	0.2229 (4)	0.8353 (3)	0.0400 (13)
C6A	0.6672 (4)	0.2618 (3)	0.7669 (3)	0.0378 (13)
H6A	0.597345	0.297653	0.763703	0.045*
C7A	0.8947 (5)	0.1802 (4)	0.6362 (4)	0.0634 (18)
H7AA	0.924146	0.241163	0.621553	0.095*
H7AB	0.841782	0.154214	0.594425	0.095*
H7AC	0.960518	0.137110	0.648759	0.095*
O1B	0.2295 (5)	0.1950 (4)	0.1429 (3)	0.0898 (16)
O2B	0.3816 (5)	0.2714 (4)	0.1983 (3)	0.0882 (16)
N1B	0.3023 (4)	0.3318 (3)	0.4657 (3)	0.0643 (15)
H1BA	0.341580	0.290610	0.498145	0.077*
H1BB	0.249335	0.363791	0.489673	0.077*
H1BC	0.353595	0.372956	0.448874	0.077*
N2B	0.2842 (5)	0.2323 (4)	0.1994 (4)	0.0667 (15)
C1B	0.2397 (5)	0.2790 (4)	0.3999 (3)	0.0477 (15)
C2B	0.1350 (5)	0.2317 (4)	0.4083 (3)	0.0474 (15)
C3B	0.0815 (5)	0.1813 (4)	0.3450 (4)	0.0538 (16)
H3B	0.011241	0.147824	0.348980	0.065*
C4B	0.1300 (5)	0.1798 (4)	0.2767 (4)	0.0532 (16)
H4B	0.093703	0.145519	0.234835	0.064*
C5B	0.2331 (5)	0.2301 (4)	0.2717 (4)	0.0496 (15)
C6B	0.2899 (5)	0.2795 (4)	0.3337 (4)	0.0513 (16)
H6B	0.360762	0.312140	0.330047	0.062*
C7B	0.0773 (6)	0.2335 (5)	0.4809 (4)	0.0711 (19)
H7BA	0.004759	0.197019	0.474007	0.107*
H7BB	0.059636	0.298576	0.493417	0.107*
H7BC	0.130604	0.206222	0.521956	0.107*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1A	0.0834 (3)	0.0601 (3)	0.0469 (3)	−0.0021 (2)	0.0028 (2)	0.0022 (2)
I2A	0.0511 (2)	0.0373 (2)	0.0534 (3)	0.00123 (16)	0.00153 (18)	0.00136 (17)
I3A	0.0603 (2)	0.0514 (2)	0.0539 (3)	−0.00282 (18)	0.0110 (2)	−0.00344 (19)
I1B	0.0925 (3)	0.0704 (3)	0.0593 (3)	−0.0053 (2)	0.0153 (3)	−0.0071 (2)
I2B	0.0469 (2)	0.0401 (2)	0.0602 (3)	−0.00399 (16)	0.00068 (19)	0.00317 (17)
I3B	0.0719 (3)	0.0581 (3)	0.0586 (3)	0.0007 (2)	0.0137 (2)	−0.0001 (2)
O1A	0.097 (4)	0.096 (4)	0.029 (3)	0.006 (3)	0.007 (3)	0.003 (2)
O2A	0.070 (3)	0.089 (3)	0.055 (3)	0.008 (3)	0.028 (2)	−0.008 (2)
O1W	0.085 (3)	0.062 (3)	0.061 (3)	0.005 (2)	0.005 (3)	−0.006 (2)
N1A	0.060 (3)	0.065 (3)	0.038 (3)	0.005 (2)	0.007 (2)	0.011 (2)
N2A	0.065 (4)	0.051 (3)	0.044 (4)	−0.008 (3)	0.014 (3)	−0.002 (2)
C1A	0.045 (3)	0.033 (3)	0.034 (3)	−0.005 (2)	−0.001 (3)	0.002 (2)
C2A	0.046 (3)	0.038 (3)	0.046 (4)	−0.006 (2)	0.009 (3)	−0.005 (3)
C3A	0.045 (3)	0.055 (4)	0.056 (4)	0.011 (3)	0.007 (3)	0.008 (3)
C4A	0.056 (4)	0.052 (4)	0.041 (4)	0.005 (3)	−0.005 (3)	0.010 (3)
C5A	0.045 (3)	0.040 (3)	0.036 (3)	−0.006 (2)	0.008 (3)	−0.005 (2)
C6A	0.040 (3)	0.035 (3)	0.038 (4)	0.001 (2)	0.000 (3)	0.004 (2)
C7A	0.062 (4)	0.070 (4)	0.063 (5)	0.002 (3)	0.024 (3)	−0.004 (3)
O1B	0.100 (4)	0.119 (4)	0.050 (3)	0.014 (3)	0.004 (3)	0.004 (3)
O2B	0.085 (4)	0.105 (4)	0.079 (4)	−0.004 (3)	0.030 (3)	0.020 (3)
N1B	0.066 (3)	0.058 (3)	0.064 (4)	−0.003 (3)	−0.014 (3)	−0.006 (3)
N2B	0.065 (4)	0.068 (4)	0.068 (5)	0.011 (3)	0.010 (4)	0.014 (3)
C1B	0.052 (4)	0.038 (3)	0.049 (4)	0.005 (3)	−0.012 (3)	−0.001 (3)
C2B	0.052 (4)	0.046 (3)	0.043 (4)	0.007 (3)	0.000 (3)	0.000 (3)
C3B	0.045 (3)	0.060 (4)	0.055 (4)	−0.004 (3)	0.005 (3)	−0.001 (3)
C4B	0.052 (4)	0.055 (4)	0.050 (4)	0.002 (3)	−0.003 (3)	−0.008 (3)
C5B	0.054 (4)	0.047 (3)	0.048 (4)	0.009 (3)	0.005 (3)	0.007 (3)
C6B	0.042 (3)	0.044 (3)	0.066 (5)	0.000 (3)	−0.001 (3)	0.007 (3)
C7B	0.082 (5)	0.071 (5)	0.060 (5)	0.002 (4)	0.008 (4)	−0.003 (4)

Geometric parameters (Å, º)

I1A—I2A	2.8432 (6)	C7A—H7AA	0.9600
I2A—I3A	3.0067 (6)	C7A—H7AB	0.9600
I1B—I2B	2.8485 (6)	C7A—H7AC	0.9600
I2B—I3B	3.0314 (6)	O1B—N2B	1.220 (7)
O1A—N2A	1.221 (6)	O2B—N2B	1.229 (7)
O2A—N2A	1.219 (6)	N1B—H1BA	0.8900
O1W—H1W	0.8508	N1B—H1BB	0.8900
O1W—H2W	0.8503	N1B—H1BC	0.8900
N1A—H1AA	0.8900	N1B—C1B	1.476 (6)
N1A—H1AB	0.8900	N2B—C5B	1.454 (8)
N1A—H1AC	0.8900	C1B—C2B	1.377 (8)
N1A—C1A	1.476 (6)	C1B—C6B	1.350 (8)
N2A—C5A	1.466 (7)	C2B—C3B	1.388 (7)
C1A—C2A	1.382 (7)	C2B—C7B	1.498 (8)
C1A—C6A	1.370 (7)	C3B—H3B	0.9300
C2A—C3A	1.387 (7)	C3B—C4B	1.375 (8)
C2A—C7A	1.510 (8)	C4B—H4B	0.9300
C3A—H3A	0.9300	C4B—C5B	1.370 (8)
C3A—C4A	1.373 (8)	C5B—C6B	1.379 (8)
C4A—H4A	0.9300	C6B—H6B	0.9300
C4A—C5A	1.378 (7)	C7B—H7BA	0.9600
C5A—C6A	1.372 (7)	C7B—H7BB	0.9600
C6A—H6A	0.9300	C7B—H7BC	0.9600
I1A—I2A—I3A	176.179 (17)	H7AB—C7A—H7AC	109.5
I1B—I2B—I3B	176.600 (18)	H1BA—N1B—H1BB	109.5
H1W—O1W—H2W	109.4	H1BA—N1B—H1BC	109.5
H1AA—N1A—H1AB	109.5	H1BB—N1B—H1BC	109.5
H1AA—N1A—H1AC	109.5	C1B—N1B—H1BA	109.5
H1AB—N1A—H1AC	109.5	C1B—N1B—H1BB	109.5
C1A—N1A—H1AA	109.5	C1B—N1B—H1BC	109.5
C1A—N1A—H1AB	109.5	O1B—N2B—O2B	123.0 (7)
C1A—N1A—H1AC	109.5	O1B—N2B—C5B	118.9 (6)
O1A—N2A—C5A	118.0 (5)	O2B—N2B—C5B	118.1 (6)
O2A—N2A—O1A	123.6 (6)	C2B—C1B—N1B	119.6 (6)
O2A—N2A—C5A	118.3 (5)	C6B—C1B—N1B	117.3 (5)
C2A—C1A—N1A	119.5 (5)	C6B—C1B—C2B	123.1 (5)
C6A—C1A—N1A	117.4 (5)	C1B—C2B—C3B	117.1 (6)
C6A—C1A—C2A	123.1 (5)	C1B—C2B—C7B	123.2 (6)
C1A—C2A—C3A	116.8 (5)	C3B—C2B—C7B	119.7 (6)
C1A—C2A—C7A	122.8 (5)	C2B—C3B—H3B	119.3
C3A—C2A—C7A	120.4 (5)	C4B—C3B—C2B	121.5 (6)
C2A—C3A—H3A	119.1	C4B—C3B—H3B	119.3
C4A—C3A—C2A	121.9 (5)	C3B—C4B—H4B	120.7
C4A—C3A—H3A	119.1	C5B—C4B—C3B	118.5 (6)
C3A—C4A—H4A	120.7	C5B—C4B—H4B	120.7
C3A—C4A—C5A	118.5 (5)	C4B—C5B—N2B	119.7 (6)
C5A—C4A—H4A	120.7	C4B—C5B—C6B	121.6 (6)
C4A—C5A—N2A	119.1 (5)	C6B—C5B—N2B	118.8 (6)
C6A—C5A—N2A	119.1 (5)	C1B—C6B—C5B	118.2 (6)
C6A—C5A—C4A	121.9 (5)	C1B—C6B—H6B	120.9
C1A—C6A—C5A	117.7 (5)	C5B—C6B—H6B	120.9
C1A—C6A—H6A	121.2	C2B—C7B—H7BA	109.5
C5A—C6A—H6A	121.2	C2B—C7B—H7BB	109.5
C2A—C7A—H7AA	109.5	C2B—C7B—H7BC	109.5
C2A—C7A—H7AB	109.5	H7BA—C7B—H7BB	109.5
C2A—C7A—H7AC	109.5	H7BA—C7B—H7BC	109.5
H7AA—C7A—H7AB	109.5	H7BB—C7B—H7BC	109.5
H7AA—C7A—H7AC	109.5
O1A—N2A—C5A—C4A	15.8 (7)	O1B—N2B—C5B—C4B	5.2 (8)
O1A—N2A—C5A—C6A	−164.3 (5)	O1B—N2B—C5B—C6B	−174.4 (5)
O2A—N2A—C5A—C4A	−164.7 (5)	O2B—N2B—C5B—C4B	−174.3 (5)
O2A—N2A—C5A—C6A	15.2 (7)	O2B—N2B—C5B—C6B	6.1 (8)
N1A—C1A—C2A—C3A	−179.2 (5)	N1B—C1B—C2B—C3B	−178.5 (5)
N1A—C1A—C2A—C7A	2.3 (7)	N1B—C1B—C2B—C7B	2.3 (8)
N1A—C1A—C6A—C5A	−178.5 (4)	N1B—C1B—C6B—C5B	179.6 (5)
N2A—C5A—C6A—C1A	177.7 (4)	N2B—C5B—C6B—C1B	178.1 (5)
C1A—C2A—C3A—C4A	−2.4 (8)	C1B—C2B—C3B—C4B	−0.8 (8)
C2A—C1A—C6A—C5A	0.3 (8)	C2B—C1B—C6B—C5B	0.1 (8)
C2A—C3A—C4A—C5A	0.4 (8)	C2B—C3B—C4B—C5B	−0.4 (8)
C3A—C4A—C5A—N2A	−178.0 (5)	C3B—C4B—C5B—N2B	−178.0 (5)
C3A—C4A—C5A—C6A	2.1 (8)	C3B—C4B—C5B—C6B	1.6 (8)
C4A—C5A—C6A—C1A	−2.4 (8)	C4B—C5B—C6B—C1B	−1.5 (8)
C6A—C1A—C2A—C3A	2.1 (8)	C6B—C1B—C2B—C3B	1.0 (8)
C6A—C1A—C2A—C7A	−176.4 (5)	C6B—C1B—C2B—C7B	−178.2 (5)
C7A—C2A—C3A—C4A	176.2 (5)	C7B—C2B—C3B—C4B	178.4 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1AA···I3A^i	0.89	2.79	3.602 (4)	152
N1A—H1AB···O1W	0.89	2.03	2.887 (7)	160
N1B—H1BA···O1W	0.89	1.91	2.778 (7)	165
N1B—H1BB···I3B	0.89	3.03	3.586 (5)	122
N1B—H1BC···I3A	0.89	2.88	3.770 (5)	179

Symmetry code: (i) −x+1, −y+1, −z+1.