Structural polymorphism of pyrazinium hydrogen sulfate: extending chemistry of the pyrazinium salts with small anions

Two polymorphs (α, β) of pyrazinium hydrogen sulfate (pyzH⁺HSO, abbreviated as PHS) with distinctly different hydrogen-bond types and topologies but close electronic energies have been synthesized and characterized for the first time. The α-polymorph (P2₁2₁2₁) forms distinct blocks in which the pyzH⁺ and HSO ions are interconnected through a network of NH...O and OH...O hydrogen bonds. The β-form () consists of infinite chains of alternating pyzH⁺ and HSO ions connected by NH...O and OH...N hydrogen bonds. Density functional theory (DFT) calculations indicate the possible existence of a hypothetical polar P1 form of the β-polymorph with an unusually high dipole moment.

Computing details

Data collection: CrysAlis CCD, Oxford Diffraction Ltd., Version 1.171.33.46 (release 27-08-2009 CrysAlis171 .NET) (compiled Aug 27 2009,17:19:36) for PHSa-103K, PHSa-293K; CrysAlis CCD, Oxford Diffraction Ltd., Version 1.171.33.41 (release 06-05-2009 CrysAlis171 .NET) (compiled May 6 2009,17:20:42) for PHSb-100K. Cell refinement: CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.33.46 (release 27-08-2009 CrysAlis171 .NET) (compiled Aug 27 2009,17:19:36) for PHSa-103K, PHSa-293K; CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.33.41 (release 06-05-2009 CrysAlis171 .NET) (compiled May 6 2009,17:20:42) for PHSb-100K. Data reduction: CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.33.46 (release 27-08-2009 CrysAlis171 .NET) (compiled Aug 27 2009,17:19:36) for PHSa-103K, PHSa-293K; CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.33.41 (release 06-05-2009 CrysAlis171 .NET) (compiled May 6 2009,17:20:42) for PHSb-100K. For all structures, program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: Mercury for PHSa-103K, PHSa-293K.

pyrazinium hydrogensulfate (PHSa-103K)

Crystal data

C4H5N2·HO4S	Dx = 1.754 Mg m^−3
Mr = 178.17	Melting point: 411 K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 5055 reflections
a = 5.1744 (6) Å	θ = 2.9–28.3°
b = 9.3697 (13) Å	µ = 0.45 mm^−1
c = 13.919 (3) Å	T = 103 K
V = 674.83 (19) Å^3	Needle, colourless
Z = 4	1.00 × 0.20 × 0.20 mm
F(000) = 368

Data collection

KUMA KM-4CCD, Sapphire2, large Be window diffractometer	1555 independent reflections
Radiation source: fine-focus sealed tube	1488 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
Detector resolution: 8.6479 pixels mm^-1	θmax = 28.1°, θmin = 2.9°
ω scans	h = −6→6
Absorption correction: multi-scan CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.33.46 (release 27-08-2009 CrysAlis171 .NET) (compiled Aug 27 2009,17:19:36) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −12→12
Tmin = 0.665, Tmax = 0.916	l = −18→17
6079 measured reflections

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)] = 0.021	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.058	w = 1/[σ^2(Fo^2) + (0.0402P)^2 + 0.0852P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
1555 reflections	Δρmax = 0.24 e Å^−3
119 parameters	Δρmin = −0.35 e Å^−3
0 restraints	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.02 (6)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
S1	0.10694 (6)	0.70328 (4)	0.87318 (2)	0.00967 (10)
O1	0.0002 (2)	0.64870 (12)	0.96368 (8)	0.0149 (2)
O2	0.0579 (2)	0.60731 (12)	0.79239 (8)	0.0141 (2)
O3	0.0308 (2)	0.84800 (12)	0.85354 (8)	0.0169 (3)
O4	0.41274 (19)	0.69847 (13)	0.88315 (7)	0.0158 (2)
C1	0.3722 (3)	0.85442 (17)	0.61731 (11)	0.0158 (3)
H1	0.326 (4)	0.946 (2)	0.6119 (13)	0.019*
C2	0.5958 (3)	0.82062 (17)	0.66758 (11)	0.0154 (3)
H2	0.710 (4)	0.889 (2)	0.6982 (15)	0.018*
N3	0.6626 (2)	0.68349 (15)	0.67412 (9)	0.0139 (3)
H3	0.798 (4)	0.660 (2)	0.7076 (15)	0.017*
C4	0.5200 (3)	0.58257 (17)	0.63291 (12)	0.0149 (3)
H4	0.586 (4)	0.495 (2)	0.6355 (13)	0.018*
C5	0.2975 (3)	0.62152 (17)	0.58260 (11)	0.0142 (3)
H5	0.190 (4)	0.552 (2)	0.5523 (13)	0.017*
N6	0.2213 (3)	0.75599 (15)	0.57541 (10)	0.0147 (3)
H14	0.447 (4)	0.738 (2)	0.9351 (14)	0.018*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.00901 (15)	0.00998 (16)	0.01002 (16)	0.00077 (13)	−0.00063 (13)	−0.00022 (14)
O1	0.0180 (5)	0.0139 (5)	0.0127 (5)	−0.0024 (4)	0.0035 (4)	0.0000 (4)
O2	0.0148 (5)	0.0144 (5)	0.0131 (5)	0.0018 (4)	−0.0036 (4)	−0.0039 (4)
O3	0.0199 (5)	0.0106 (5)	0.0202 (6)	0.0024 (4)	−0.0020 (4)	0.0018 (4)
O4	0.0097 (4)	0.0238 (6)	0.0140 (5)	0.0009 (5)	−0.0018 (4)	−0.0055 (5)
C1	0.0185 (7)	0.0108 (7)	0.0181 (7)	0.0026 (6)	0.0033 (7)	−0.0001 (6)
C2	0.0153 (7)	0.0160 (8)	0.0148 (6)	−0.0031 (6)	0.0024 (6)	−0.0028 (6)
N3	0.0100 (6)	0.0204 (8)	0.0112 (5)	0.0031 (5)	−0.0007 (4)	0.0001 (5)
C4	0.0189 (7)	0.0123 (7)	0.0135 (7)	0.0041 (6)	0.0029 (6)	0.0014 (6)
C5	0.0147 (7)	0.0142 (8)	0.0136 (7)	−0.0046 (6)	0.0000 (6)	−0.0010 (6)
N6	0.0120 (6)	0.0165 (7)	0.0158 (6)	0.0016 (5)	0.0004 (5)	0.0018 (5)

Geometric parameters (Å, º)

S1—O3	1.4382 (11)	C2—N3	1.334 (2)
S1—O2	1.4620 (11)	C2—H2	0.97 (2)
S1—O1	1.4675 (11)	N3—C4	1.329 (2)
S1—O4	1.5891 (11)	N3—H3	0.87 (2)
O4—H14	0.83 (2)	C4—C5	1.396 (2)
C1—N6	1.342 (2)	C4—H4	0.89 (2)
C1—C2	1.389 (2)	C5—N6	1.324 (2)
C1—H1	0.90 (2)	C5—H5	0.95 (2)
O3—S1—O2	112.72 (7)	C1—C2—H2	125.5 (12)
O3—S1—O1	112.87 (7)	C4—N3—C2	120.80 (14)
O2—S1—O1	112.37 (7)	C4—N3—H3	120.0 (14)
O3—S1—O4	108.42 (7)	C2—N3—H3	119.1 (14)
O2—S1—O4	102.86 (6)	N3—C4—C5	119.21 (14)
O1—S1—O4	106.85 (6)	N3—C4—H4	115.1 (13)
S1—O4—H14	106.0 (14)	C5—C4—H4	125.4 (13)
N6—C1—C2	123.17 (15)	N6—C5—C4	122.16 (15)
N6—C1—H1	117.9 (13)	N6—C5—H5	116.1 (12)
C2—C1—H1	118.9 (13)	C4—C5—H5	121.8 (12)
N3—C2—C1	118.03 (14)	C5—N6—C1	116.61 (14)
N3—C2—H2	116.5 (12)

pyrazinium hydrogensulfate (PHSa-293K)

Crystal data

C4H5N2·HO4S	Dx = 1.743 Mg m^−3
Mr = 178.17	Melting point: 411 K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 4223 reflections
a = 5.1748 (5) Å	θ = 2.9–28.3°
b = 9.4290 (11) Å	µ = 0.44 mm^−1
c = 13.9135 (15) Å	T = 293 K
V = 678.88 (13) Å^3	Needle, colourless
Z = 4	1.00 × 0.20 × 0.20 mm
F(000) = 368

Data collection

KUMA KM-4CCD, Sapphire2, large Be window diffractometer	1593 independent reflections
Radiation source: fine-focus sealed tube	1459 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
Detector resolution: 8.6479 pixels mm^-1	θmax = 28.3°, θmin = 2.9°
ω scans	h = −6→6
Absorption correction: multi-scan CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.33.41 (release 06-05-2009 CrysAlis171 .NET) (compiled May 6 2009,17:20:42) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −12→12
Tmin = 0.666, Tmax = 0.917	l = −18→18
6199 measured reflections

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)] = 0.027	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.065	w = 1/[σ^2(Fo^2) + (0.0435P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
1593 reflections	Δρmax = 0.18 e Å^−3
118 parameters	Δρmin = −0.36 e Å^−3
0 restraints	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.01 (7)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
S1	0.10284 (7)	0.70573 (4)	0.87344 (3)	0.02534 (11)
O1	−0.0027 (3)	0.65131 (15)	0.96183 (9)	0.0389 (3)
O2	0.0560 (2)	0.61164 (15)	0.79320 (10)	0.0385 (3)
O3	0.0291 (3)	0.84877 (14)	0.85461 (12)	0.0474 (4)
O4	0.4027 (2)	0.70049 (17)	0.88358 (9)	0.0432 (3)
C1	0.3779 (4)	0.8541 (2)	0.61770 (16)	0.0423 (4)
H1	0.333 (4)	0.942 (3)	0.6082 (16)	0.051*
C2	0.5972 (4)	0.8235 (2)	0.66767 (14)	0.0421 (5)
H2	0.712 (4)	0.893 (2)	0.6972 (19)	0.051*
N3	0.6669 (3)	0.6891 (2)	0.67451 (11)	0.0387 (4)
H3	0.793 (4)	0.669 (2)	0.7093 (18)	0.046*
C4	0.5314 (4)	0.5881 (2)	0.63404 (17)	0.0406 (5)
H4	0.599 (5)	0.503 (2)	0.6362 (15)	0.049*
C5	0.3133 (4)	0.6236 (2)	0.58452 (16)	0.0393 (5)
H5	0.211 (4)	0.554 (3)	0.5548 (16)	0.047*
N6	0.2341 (3)	0.75526 (19)	0.57679 (13)	0.0401 (4)
H14	0.429 (4)	0.736 (3)	0.9306 (17)	0.048*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.02472 (17)	0.02632 (19)	0.02497 (18)	0.00183 (16)	−0.00169 (15)	−0.00073 (18)
O1	0.0457 (7)	0.0396 (8)	0.0315 (7)	−0.0066 (6)	0.0083 (6)	0.0005 (6)
O2	0.0408 (7)	0.0420 (7)	0.0328 (7)	0.0067 (6)	−0.0099 (5)	−0.0127 (6)
O3	0.0558 (9)	0.0281 (7)	0.0583 (10)	0.0053 (6)	−0.0093 (7)	0.0059 (7)
O4	0.0252 (5)	0.0675 (10)	0.0368 (7)	0.0036 (7)	−0.0033 (6)	−0.0151 (8)
C1	0.0466 (11)	0.0289 (9)	0.0514 (12)	0.0084 (9)	0.0059 (11)	0.0011 (9)
C2	0.0403 (9)	0.0460 (12)	0.0400 (10)	−0.0103 (10)	0.0021 (8)	−0.0095 (9)
N3	0.0271 (7)	0.0598 (12)	0.0294 (7)	0.0079 (7)	−0.0016 (5)	0.0037 (8)
C4	0.0514 (11)	0.0323 (10)	0.0380 (10)	0.0125 (8)	0.0063 (9)	0.0041 (9)
C5	0.0401 (10)	0.0372 (11)	0.0407 (10)	−0.0096 (8)	−0.0005 (8)	−0.0031 (9)
N6	0.0312 (7)	0.0449 (10)	0.0443 (9)	0.0035 (7)	−0.0041 (7)	0.0039 (8)

Geometric parameters (Å, º)

S1—O3	1.4259 (14)	C2—N3	1.321 (3)
S1—O1	1.4401 (14)	C2—H2	0.98 (2)
S1—O2	1.4465 (13)	N3—C4	1.310 (3)
S1—O4	1.5587 (13)	N3—H3	0.83 (2)
O4—H14	0.75 (2)	C4—C5	1.364 (3)
C1—N6	1.322 (3)	C4—H4	0.88 (2)
C1—C2	1.362 (3)	C5—N6	1.312 (3)
C1—H1	0.87 (3)	C5—H5	0.94 (2)
O3—S1—O1	113.11 (9)	C1—C2—H2	125.4 (14)
O3—S1—O2	113.17 (9)	C4—N3—C2	121.35 (18)
O1—S1—O2	112.15 (9)	C4—N3—H3	120.0 (16)
O3—S1—O4	108.24 (9)	C2—N3—H3	118.5 (17)
O1—S1—O4	106.79 (8)	N3—C4—C5	118.78 (19)
O2—S1—O4	102.54 (8)	N3—C4—H4	115.8 (16)
S1—O4—H14	104.3 (18)	C5—C4—H4	125.0 (16)
N6—C1—C2	122.64 (19)	N6—C5—C4	122.16 (19)
N6—C1—H1	117.2 (15)	N6—C5—H5	116.8 (14)
C2—C1—H1	120.0 (16)	C4—C5—H5	121.0 (14)
N3—C2—C1	117.90 (19)	C5—N6—C1	117.15 (18)
N3—C2—H2	116.7 (14)

(PHSb-100K)

Crystal data

C4H5N2·HO4S	Z = 4
Mr = 178.17	F(000) = 368
Triclinic, P1	Dx = 1.837 Mg m^−3
Hall symbol: -P1	Mo Kα radiation, λ = 0.71073 Å
a = 5.3552 (7) Å	Cell parameters from 2099 reflections
b = 7.4832 (10) Å	θ = 3.0–28.7°
c = 16.506 (2) Å	µ = 0.47 mm^−1
α = 86.484 (12)°	T = 100 K
β = 88.111 (11)°	Prism, colourless
γ = 77.487 (12)°	0.20 × 0.10 × 0.10 mm
V = 644.38 (15) Å^3

Data collection

KM4CCD diffractometer	3124 independent reflections
Radiation source: fine-focus sealed tube	1242 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.109
Detector resolution: 8.6479 pixels mm^-1	θmax = 28.7°, θmin = 3.0°
ω scans	h = −7→6
Absorption correction: multi-scan CrysAlis RED, Oxford Diffraction Ltd.	k = −9→9
Tmin = 0.910, Tmax = 0.954	l = −22→22
12016 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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.109	H atoms treated by a mixture of independent and constrained refinement
S = 0.82	w = 1/[σ^2(Fo^2) + (0.0334P)^2] where P = (Fo^2 + 2Fc^2)/3
3124 reflections	(Δ/σ)max < 0.001
211 parameters	Δρmax = 0.37 e Å^−3
0 restraints	Δρmin = −0.45 e Å^−3

Special details

Experimental. CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.33.41 (release 06–05-2009 CrysAlis171. NET) (compiled May 6 2009,17:20:42) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
S11	0.0458 (2)	0.23348 (17)	0.64386 (7)	0.0209 (3)
O11	0.3323 (5)	0.2577 (4)	0.63754 (18)	0.0238 (8)
H11	0.404 (8)	0.243 (5)	0.584 (3)	0.029*
O12	0.0226 (6)	0.0994 (4)	0.58689 (18)	0.0255 (8)
O13	−0.1161 (6)	0.4132 (4)	0.62680 (19)	0.0331 (9)
O14	0.0270 (6)	0.1655 (4)	0.72778 (17)	0.0296 (8)
S21	0.9535 (2)	0.22672 (17)	0.13654 (7)	0.0206 (3)
H21	0.869 (8)	0.374 (6)	0.027 (2)	0.025*
O21	0.9252 (6)	0.3966 (4)	0.07399 (18)	0.0224 (8)
O22	1.1014 (5)	0.0712 (4)	0.09721 (18)	0.0240 (8)
O23	1.0736 (5)	0.2853 (4)	0.20453 (17)	0.0232 (8)
O24	0.6914 (5)	0.2046 (4)	0.15722 (17)	0.0213 (8)
N11	0.4781 (7)	0.2481 (5)	0.4772 (2)	0.0202 (9)
C12	0.6576 (8)	0.3229 (6)	0.4411 (3)	0.0228 (12)
H12	0.7546	0.3838	0.4729	0.027*
C13	0.7089 (8)	0.3154 (6)	0.3587 (3)	0.0212 (11)
H13	0.8389	0.3699	0.3339	0.025*
N14	0.5713 (7)	0.2297 (5)	0.3148 (2)	0.0205 (9)
H14	0.615 (7)	0.235 (6)	0.261 (2)	0.025*
C15	0.3892 (8)	0.1534 (6)	0.3487 (3)	0.0190 (11)
H15	0.2920	0.0931	0.3167	0.023*
C16	0.3434 (8)	0.1628 (6)	0.4307 (3)	0.0204 (11)
H16	0.2135	0.1079	0.4553	0.025*
N21	0.6452 (6)	0.3303 (5)	0.9478 (2)	0.0196 (9)
C22	0.6661 (8)	0.3724 (6)	0.8689 (3)	0.0204 (11)
H22	0.7872	0.4426	0.8506	0.024*
C23	0.5179 (8)	0.3176 (6)	0.8129 (3)	0.0207 (11)
H23	0.5363	0.3474	0.7566	0.025*
N24	0.3476 (7)	0.2211 (5)	0.8403 (2)	0.0213 (10)
H24	0.241 (8)	0.199 (6)	0.811 (3)	0.026*
C25	0.3169 (8)	0.1786 (6)	0.9186 (3)	0.0205 (11)
H25	0.1922	0.1115	0.9369	0.025*
C26	0.4702 (8)	0.2343 (6)	0.9727 (3)	0.0184 (11)
H26	0.4517	0.2040	1.0290	0.022*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S11	0.0174 (7)	0.0240 (8)	0.0222 (8)	−0.0051 (6)	−0.0054 (5)	−0.0025 (6)
O11	0.0170 (17)	0.035 (2)	0.0220 (19)	−0.0085 (15)	−0.0013 (14)	−0.0073 (16)
O12	0.0281 (19)	0.027 (2)	0.0251 (19)	−0.0106 (15)	−0.0043 (15)	−0.0103 (15)
O13	0.028 (2)	0.018 (2)	0.051 (2)	0.0020 (15)	−0.0171 (17)	−0.0034 (16)
O14	0.0255 (19)	0.050 (2)	0.0167 (18)	−0.0154 (16)	−0.0061 (14)	−0.0003 (16)
S21	0.0179 (7)	0.0262 (8)	0.0189 (7)	−0.0068 (6)	−0.0047 (5)	−0.0014 (6)
O21	0.0266 (18)	0.025 (2)	0.0182 (18)	−0.0119 (15)	−0.0085 (14)	0.0012 (15)
O22	0.0189 (17)	0.026 (2)	0.0273 (19)	−0.0039 (15)	0.0001 (14)	−0.0079 (15)
O23	0.0234 (18)	0.032 (2)	0.0170 (18)	−0.0109 (15)	−0.0102 (14)	−0.0048 (14)
O24	0.0159 (17)	0.030 (2)	0.0203 (18)	−0.0081 (14)	−0.0026 (13)	−0.0049 (15)
N11	0.019 (2)	0.022 (2)	0.019 (2)	−0.0035 (18)	−0.0054 (17)	−0.0030 (18)
C12	0.023 (3)	0.021 (3)	0.024 (3)	−0.004 (2)	−0.002 (2)	−0.004 (2)
C13	0.016 (3)	0.019 (3)	0.030 (3)	−0.007 (2)	−0.005 (2)	0.003 (2)
N14	0.022 (2)	0.023 (2)	0.016 (2)	−0.0015 (18)	−0.0056 (18)	−0.0009 (19)
C15	0.018 (3)	0.025 (3)	0.016 (3)	−0.007 (2)	−0.007 (2)	−0.001 (2)
C16	0.018 (3)	0.017 (3)	0.025 (3)	0.001 (2)	−0.007 (2)	−0.001 (2)
N21	0.018 (2)	0.021 (2)	0.020 (2)	−0.0035 (17)	−0.0007 (16)	−0.0036 (18)
C22	0.017 (3)	0.018 (3)	0.027 (3)	−0.008 (2)	−0.005 (2)	0.002 (2)
C23	0.019 (3)	0.023 (3)	0.019 (3)	−0.002 (2)	0.000 (2)	−0.002 (2)
N24	0.015 (2)	0.026 (3)	0.024 (3)	−0.0054 (19)	−0.0110 (17)	−0.003 (2)
C25	0.015 (2)	0.017 (3)	0.029 (3)	−0.001 (2)	−0.006 (2)	0.001 (2)
C26	0.023 (3)	0.017 (3)	0.016 (3)	−0.005 (2)	−0.002 (2)	0.001 (2)

Geometric parameters (Å, º)

S11—O12	1.444 (3)	N14—C15	1.326 (6)
S11—O13	1.451 (3)	N14—H14	0.92 (4)
S11—O14	1.454 (3)	C15—C16	1.371 (6)
S11—O11	1.582 (3)	C15—H15	0.9500
O11—H11	0.96 (4)	C16—H16	0.9500
S21—O22	1.436 (3)	N21—C22	1.329 (5)
S21—O23	1.447 (3)	N21—C26	1.339 (5)
S21—O24	1.475 (3)	C22—C23	1.374 (6)
S21—O21	1.572 (3)	C22—H22	0.9500
O21—H21	0.89 (4)	C23—N24	1.332 (6)
N11—C12	1.322 (5)	C23—H23	0.9500
N11—C16	1.346 (5)	N24—C25	1.326 (6)
C12—C13	1.381 (6)	N24—H24	0.81 (4)
C12—H12	0.9500	C25—C26	1.374 (5)
C13—N14	1.332 (5)	C25—H25	0.9500
C13—H13	0.9500	C26—H26	0.9500
O12—S11—O13	114.17 (19)	C13—N14—H14	112 (3)
O12—S11—O14	112.5 (2)	N14—C15—C16	118.9 (4)
O13—S11—O14	113.35 (19)	N14—C15—H15	120.6
O12—S11—O11	106.88 (18)	C16—C15—H15	120.6
O13—S11—O11	106.89 (18)	N11—C16—C15	121.6 (4)
O14—S11—O11	101.91 (17)	N11—C16—H16	119.2
S11—O11—H11	113 (2)	C15—C16—H16	119.2
O22—S21—O23	115.61 (18)	C22—N21—C26	118.2 (4)
O22—S21—O24	112.00 (18)	N21—C22—C23	122.0 (4)
O23—S21—O24	111.87 (18)	N21—C22—H22	119.0
O22—S21—O21	107.36 (18)	C23—C22—H22	119.0
O23—S21—O21	102.80 (17)	N24—C23—C22	117.8 (4)
O24—S21—O21	106.23 (18)	N24—C23—H23	121.1
S21—O21—H21	112 (3)	C22—C23—H23	121.1
C12—N11—C16	117.7 (4)	C25—N24—C23	122.3 (4)
N11—C12—C13	122.2 (4)	C25—N24—H24	115 (3)
N11—C12—H12	118.9	C23—N24—H24	122 (3)
C13—C12—H12	118.9	N24—C25—C26	118.2 (4)
N14—C13—C12	118.3 (4)	N24—C25—H25	120.9
N14—C13—H13	120.9	C26—C25—H25	120.9
C12—C13—H13	120.9	N21—C26—C25	121.4 (4)
C15—N14—C13	121.4 (4)	N21—C26—H26	119.3
C15—N14—H14	126 (3)	C25—C26—H26	119.3
C16—N11—C12—C13	−0.1 (6)	C26—N21—C22—C23	−1.2 (6)
N11—C12—C13—N14	0.1 (6)	N21—C22—C23—N24	0.7 (7)
C12—C13—N14—C15	0.1 (6)	C22—C23—N24—C25	0.5 (7)
C13—N14—C15—C16	−0.2 (6)	C23—N24—C25—C26	−1.1 (7)
C12—N11—C16—C15	−0.1 (6)	C22—N21—C26—C25	0.6 (6)
N14—C15—C16—N11	0.2 (6)	N24—C25—C26—N21	0.6 (7)