Structures of relevant ammonium salts in fertilizers

The crystal structures of two double salts of ammonium nitrate (AN) and ammonium sulfate (AS) are reported. The double salts 2NH₄NO₃·(NH₄)₂SO₄ (2AN·AS) and 3NH₄NO₃·(NH₄)₂SO₄ (3AN·AS) show a very similar crystal structure packing with alternating layers of anions and cations. The solid-state ionic distribution is controlled by an extensive hydrogen-bonding network with ammonium groups as the donors and O atoms acting as the acceptors. Crystallographic studies were conducted at both room temperature (293 K) and 100 K. Increasing the temperature involves shortening the b axis in the case of the 3AN·AS salt. Quantification of fertilizer mixtures using the Rietveld method was also carried out by means of the structural models reported in this paper for both salts.

Computing details

Data collection: CrysAlis PRO for (I), (III); Collect (Bruker AXS BV, 1997-2004) for (II); CrysAlis CCD (Oxford Diffraction Ltd.) for (IV). Cell refinement: CrysAlis PRO for (I), (III); HKL SCALEPACK (Otwinowski & Minor 1997) for (II); CrysAlis RED (Oxford Diffraction Ltd.) for (IV). Data reduction: CrysAlis PRO for (I), (III); HKL DENZO and SCALEPACK (Otwinowski & Minor 1997) for (II); CrysAlis RED (Oxford Diffraction Ltd.) for (IV). Program(s) used to solve structure: Patterson method using DIRDIF99 (P.T. Beurskens et al., 1999) for (I), (II); Direct Methods using SIR2004 (M. C. Burla et al., 2005) for (III); Direct methods using SIR2004 (M.C. Burla et al., 2005) for (IV). For all structures, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (L.J. Farrugia, 1997) Mercury 2.2.

(I)

Crystal data

O4S·4(H4N)·2(NO3)	F(000) = 616
Mr = 292.25	Dx = 1.718 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.2410 (3) Å	Cell parameters from 4153 reflections
b = 11.2160 (2) Å	θ = 3.6–32.6°
c = 10.1672 (2) Å	µ = 0.35 mm^−1
β = 104.594 (3)°	T = 100 K
V = 1130.16 (4) Å^3	Prismatic, colourless
Z = 4	0.22 × 0.14 × 0.06 mm

Data collection

Goniometer Xcalibur, detector: Ruby diffractometer	3808 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2588 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
Detector resolution: 10.2673 pixels mm^-1	θmax = 32.6°, θmin = 3.6°
f\ and ω scans	h = −14→15
Absorption correction: analytical CrysAlispro, Oxford Diffraction Ltd.	k = −16→16
Tmin = 0.943, Tmax = 0.979	l = −15→15
11630 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)] = 0.039	Hydrogen site location: difference Fourier map
wR(F^2) = 0.066	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0344P)^2] where P = (Fo^2 + 2Fc^2)/3
3808 reflections	(Δ/σ)max < 0.001
218 parameters	Δρmax = 0.36 e Å^−3
0 restraints	Δρmin = −0.57 e Å^−3

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	0.20067 (3)	0.12773 (2)	0.31667 (3)	0.00948 (7)
O1	0.12739 (8)	0.12759 (7)	0.17143 (8)	0.01307 (17)
O2	0.16614 (8)	0.23674 (7)	0.38268 (9)	0.01520 (19)
O3	0.15861 (9)	0.02226 (7)	0.38470 (9)	0.01484 (19)
O4	0.34643 (8)	0.12272 (7)	0.32975 (8)	0.01604 (19)
O11	0.83555 (9)	0.27251 (7)	0.63145 (9)	0.0172 (2)
O12	0.83510 (8)	0.46637 (7)	0.63167 (9)	0.01555 (19)
O13	0.83520 (9)	0.36932 (7)	0.81636 (9)	0.01786 (19)
O21	0.59300 (9)	0.13979 (7)	0.90286 (9)	0.0173 (2)
O22	0.52764 (12)	0.17849 (9)	0.68751 (10)	0.0317 (3)
O23	0.41911 (10)	0.04892 (9)	0.77754 (10)	0.0252 (2)
N1	0.83431 (10)	0.36956 (9)	0.69333 (10)	0.0126 (2)
N2	0.51256 (11)	0.12285 (9)	0.78708 (11)	0.0155 (2)
N3	0.08231 (12)	0.11844 (11)	0.62132 (12)	0.0142 (2)
N4	0.62438 (12)	0.10914 (10)	0.45465 (13)	0.0137 (2)
N5	0.36992 (12)	0.12152 (11)	1.04740 (12)	0.0125 (2)
N6	0.92080 (13)	0.37440 (12)	0.38828 (13)	0.0146 (2)
H3A	0.0015 (17)	0.0902 (13)	0.6160 (15)	0.024 (4)*
H3B	0.136 (2)	0.0828 (18)	0.690 (2)	0.054 (6)*
H3C	0.1064 (17)	0.1041 (14)	0.5487 (19)	0.034 (5)*
H3D	0.0834 (15)	0.1947 (16)	0.6370 (16)	0.030 (4)*
H4A	0.6458 (15)	0.1802 (14)	0.4416 (15)	0.022 (4)*
H4B	0.6124 (19)	0.0705 (17)	0.382 (2)	0.053 (6)*
H4C	0.6884 (17)	0.0794 (13)	0.5180 (17)	0.025 (4)*
H4D	0.5536 (19)	0.1113 (14)	0.4782 (18)	0.037 (5)*
H5A	0.3119 (16)	0.1667 (13)	0.9973 (16)	0.021 (4)*
H5B	0.3441 (15)	0.0528 (15)	1.0251 (15)	0.023 (4)*
H5C	0.4499 (16)	0.1320 (11)	1.0329 (15)	0.017 (4)*
H5D	0.3740 (16)	0.1295 (12)	1.1328 (18)	0.023 (4)*
H6A	0.8727 (19)	0.3403 (16)	0.325 (2)	0.040 (6)*
H6B	0.8957 (18)	0.3645 (13)	0.4560 (19)	0.035 (5)*
H6C	0.9197 (14)	0.4506 (14)	0.3665 (15)	0.020 (4)*
H6D	1.0005 (19)	0.3463 (14)	0.3988 (16)	0.032 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.00936 (14)	0.00985 (13)	0.00895 (13)	−0.00003 (11)	0.00179 (10)	0.00024 (12)
O1	0.0138 (4)	0.0152 (4)	0.0089 (4)	0.0000 (3)	0.0005 (3)	−0.0001 (4)
O2	0.0165 (4)	0.0126 (4)	0.0163 (4)	0.0008 (3)	0.0036 (4)	−0.0035 (4)
O3	0.0172 (5)	0.0122 (4)	0.0149 (4)	−0.0013 (3)	0.0038 (4)	0.0040 (4)
O4	0.0109 (4)	0.0233 (5)	0.0137 (4)	0.0007 (4)	0.0026 (3)	0.0001 (4)
O11	0.0176 (5)	0.0130 (4)	0.0204 (5)	−0.0001 (3)	0.0034 (4)	−0.0060 (4)
O12	0.0164 (5)	0.0128 (4)	0.0170 (5)	0.0012 (3)	0.0034 (4)	0.0041 (4)
O13	0.0244 (5)	0.0173 (4)	0.0150 (4)	0.0015 (4)	0.0108 (4)	0.0015 (4)
O21	0.0186 (5)	0.0146 (4)	0.0162 (4)	−0.0010 (4)	−0.0003 (4)	−0.0022 (4)
O22	0.0514 (7)	0.0300 (6)	0.0192 (5)	0.0144 (5)	0.0192 (5)	0.0107 (5)
O23	0.0212 (5)	0.0285 (5)	0.0247 (5)	−0.0068 (4)	0.0036 (4)	−0.0129 (5)
N1	0.0101 (5)	0.0124 (5)	0.0152 (5)	0.0005 (4)	0.0031 (4)	0.0004 (5)
N2	0.0193 (6)	0.0145 (5)	0.0139 (5)	0.0058 (5)	0.0062 (4)	−0.0003 (5)
N3	0.0186 (6)	0.0124 (6)	0.0127 (5)	−0.0022 (5)	0.0061 (5)	−0.0018 (5)
N4	0.0112 (6)	0.0137 (6)	0.0162 (6)	0.0001 (4)	0.0035 (5)	0.0004 (5)
N5	0.0141 (6)	0.0118 (5)	0.0119 (5)	0.0006 (5)	0.0039 (4)	0.0000 (5)
N6	0.0170 (6)	0.0140 (6)	0.0131 (5)	0.0009 (5)	0.0042 (5)	0.0008 (5)

Geometric parameters (Å, º)

S1—O4	1.4659 (9)	N3—H3D	0.870 (17)
S1—O1	1.4782 (8)	N4—H4A	0.846 (16)
S1—O2	1.4799 (9)	N4—H4B	0.84 (2)
S1—O3	1.4879 (9)	N4—H4C	0.862 (17)
O11—N1	1.2589 (12)	N4—H4D	0.819 (19)
O12—N1	1.2549 (12)	N5—H5A	0.846 (17)
O13—N1	1.2486 (13)	N5—H5B	0.828 (16)
O21—N2	1.2696 (13)	N5—H5C	0.876 (16)
O22—N2	1.2316 (13)	N5—H5D	0.863 (17)
O23—N2	1.2515 (13)	N6—H6A	0.80 (2)
N3—H3A	0.875 (17)	N6—H6B	0.801 (19)
N3—H3B	0.87 (2)	N6—H6C	0.882 (15)
N3—H3C	0.851 (18)	N6—H6D	0.856 (18)
O4—S1—O1	109.86 (5)	H4A—N4—H4B	109.6 (16)
O4—S1—O2	110.17 (5)	H4A—N4—H4C	107.7 (15)
O1—S1—O2	109.56 (5)	H4B—N4—H4C	111.9 (16)
O4—S1—O3	109.56 (5)	H4A—N4—H4D	107.5 (14)
O1—S1—O3	109.27 (5)	H4B—N4—H4D	109.2 (17)
O2—S1—O3	108.41 (5)	H4C—N4—H4D	110.9 (16)
O13—N1—O12	120.20 (10)	H5A—N5—H5B	105.4 (15)
O13—N1—O11	120.03 (10)	H5A—N5—H5C	111.3 (14)
O12—N1—O11	119.76 (10)	H5B—N5—H5C	109.0 (13)
O22—N2—O23	121.59 (12)	H5A—N5—H5D	113.1 (14)
O22—N2—O21	119.99 (11)	H5B—N5—H5D	107.7 (14)
O23—N2—O21	118.42 (10)	H5C—N5—H5D	110.2 (14)
H3A—N3—H3B	106.0 (16)	H6A—N6—H6B	111.2 (17)
H3A—N3—H3C	110.8 (15)	H6A—N6—H6C	107.0 (15)
H3B—N3—H3C	110.6 (16)	H6B—N6—H6C	111.4 (14)
H3A—N3—H3D	109.6 (13)	H6A—N6—H6D	107.2 (16)
H3B—N3—H3D	109.1 (16)	H6B—N6—H6D	110.1 (16)
H3C—N3—H3D	110.7 (14)	H6C—N6—H6D	109.8 (14)

(II)

Crystal data

O4S·4(H4N)·2(NO3)	F(000) = 616
Mr = 292.25	Dx = 1.673 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.3178 (2) Å	Cell parameters from 2187 reflections
b = 11.4014 (2) Å	θ = 0.4–25.4°
c = 10.2567 (2) Å	µ = 0.34 mm^−1
β = 105.956 (1)°	T = 293 K
V = 1160.09 (4) Å^3	Prismatic, colourless
Z = 4	0.25 × 0.17 × 0.07 mm

Data collection

KappaCCD diffractometer	2111 independent reflections
Radiation source: Fine focus sealed tube	1685 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	Rint = 0.025
Detector resolution: 9.0 pixels mm^-1	θmax = 25.3°, θmin = 2.1°
f\ and ω scans	h = 0→12
Absorption correction: multi-scan Sortav (Blessing 19995)	k = −13→0
Tmin = 0.933, Tmax = 0.977	l = −12→11
13722 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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.137	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.1037P)^2 + 0.685P] where P = (Fo^2 + 2Fc^2)/3
2111 reflections	(Δ/σ)max = 0.014
213 parameters	Δρmax = 0.79 e Å^−3
76 restraints	Δρmin = −0.34 e Å^−3

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	0.20065 (5)	0.12186 (5)	0.31600 (6)	0.0265 (3)
O1	0.1397 (2)	0.12012 (15)	0.16841 (18)	0.0426 (5)
O2	0.1550 (2)	0.22706 (17)	0.3737 (2)	0.0490 (5)
O3	0.15696 (19)	0.01720 (16)	0.3767 (2)	0.0457 (5)
O4	0.3468 (2)	0.12247 (19)	0.3441 (2)	0.0597 (7)
O11	0.83826 (19)	0.28064 (16)	0.63786 (18)	0.0420 (5)
O12	0.8361 (2)	0.47028 (17)	0.63493 (19)	0.0464 (5)
O13	0.8349 (2)	0.37754 (15)	0.8186 (2)	0.0457 (5)
O21	0.5798 (3)	0.1199 (2)	0.9003 (3)	0.0728 (8)
O22	0.5687 (3)	0.2048 (3)	0.7165 (3)	0.0846 (9)
O23	0.4164 (4)	0.0799 (4)	0.7335 (6)	0.162 (2)
N1	0.8355 (2)	0.37624 (16)	0.6967 (2)	0.0327 (5)
N2	0.5168 (3)	0.1320 (2)	0.7782 (3)	0.0460 (6)
N3	0.0798 (3)	0.12305 (17)	0.6158 (2)	0.0371 (6)
N4	0.6248 (2)	0.12000 (18)	0.4632 (2)	0.0369 (5)
N5	0.3648 (2)	0.1351 (2)	1.0445 (2)	0.0401 (6)
N6	0.9131 (3)	0.37071 (19)	0.3916 (2)	0.0416 (6)
H3A	−0.013 (4)	0.102 (4)	0.602 (5)	0.136 (6)*
H3B	0.141 (5)	0.062 (4)	0.677 (5)	0.136 (6)*
H3C	0.103 (6)	0.119 (4)	0.532 (4)	0.136 (6)*
H3D	0.098 (5)	0.197 (3)	0.658 (5)	0.136 (6)*
H4A	0.638 (5)	0.198 (3)	0.496 (5)	0.136 (6)*
H4B	0.633 (6)	0.123 (4)	0.373 (4)	0.136 (6)*
H4C	0.672 (5)	0.065 (4)	0.517 (5)	0.136 (6)*
H4D	0.531 (3)	0.108 (4)	0.446 (6)	0.136 (6)*
H5A	0.313 (5)	0.169 (4)	0.977 (4)	0.136 (6)*
H5B	0.405 (5)	0.058 (3)	1.021 (5)	0.136 (6)*
H5C	0.452 (4)	0.179 (4)	1.073 (5)	0.136 (6)*
H5D	0.346 (5)	0.119 (4)	1.124 (4)	0.136 (6)*
H6A	0.855 (5)	0.311 (4)	0.333 (5)	0.136 (6)*
H6B	0.874 (5)	0.365 (4)	0.470 (5)	0.136 (6)*
H6C	0.891 (5)	0.448 (3)	0.357 (5)	0.136 (6)*
H6D	1.000 (4)	0.355 (4)	0.408 (6)	0.136 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0246 (4)	0.0265 (4)	0.0275 (4)	0.0001 (2)	0.0057 (2)	0.0018 (2)
O1	0.0474 (12)	0.0509 (12)	0.0260 (10)	−0.0002 (8)	0.0044 (8)	0.0014 (7)
O2	0.0596 (13)	0.0350 (11)	0.0512 (12)	0.0060 (9)	0.0130 (10)	−0.0112 (8)
O3	0.0516 (12)	0.0353 (11)	0.0494 (11)	−0.0047 (8)	0.0124 (9)	0.0132 (8)
O4	0.0235 (11)	0.0854 (17)	0.0665 (15)	−0.0007 (9)	0.0060 (9)	0.0061 (11)
O11	0.0462 (11)	0.0331 (10)	0.0465 (11)	−0.0024 (8)	0.0124 (9)	−0.0094 (8)
O12	0.0561 (13)	0.0344 (11)	0.0459 (11)	0.0034 (8)	0.0093 (9)	0.0071 (8)
O13	0.0569 (13)	0.0455 (12)	0.0418 (11)	−0.0028 (8)	0.0254 (10)	−0.0036 (8)
O21	0.094 (2)	0.0666 (17)	0.0534 (15)	0.0223 (13)	0.0136 (14)	0.0092 (11)
O22	0.108 (2)	0.089 (2)	0.0736 (17)	0.0188 (16)	0.0538 (17)	0.0221 (15)
O23	0.063 (2)	0.171 (4)	0.244 (6)	−0.045 (2)	0.030 (3)	−0.147 (4)
N1	0.0297 (11)	0.0324 (12)	0.0363 (12)	0.0000 (8)	0.0097 (9)	−0.0014 (8)
N2	0.0467 (15)	0.0483 (16)	0.0462 (14)	0.0071 (11)	0.0181 (12)	−0.0087 (11)
N3	0.0497 (14)	0.0289 (12)	0.0359 (12)	−0.0038 (9)	0.0172 (11)	−0.0037 (8)
N4	0.0305 (12)	0.0399 (13)	0.0389 (12)	0.0015 (9)	0.0074 (10)	0.0019 (9)
N5	0.0387 (13)	0.0431 (14)	0.0404 (13)	0.0020 (9)	0.0140 (11)	0.0036 (9)
N6	0.0545 (15)	0.0346 (13)	0.0373 (13)	0.0060 (10)	0.0152 (11)	0.0050 (9)

Geometric parameters (Å, º)

S1—O4	1.456 (2)	N3—H3D	0.94 (3)
S1—O1	1.4711 (18)	N4—H4A	0.94 (3)
S1—O2	1.4713 (19)	N4—H4B	0.96 (3)
S1—O3	1.4729 (18)	N4—H4C	0.89 (3)
O11—N1	1.250 (3)	N4—H4D	0.95 (3)
O12—N1	1.246 (3)	N5—H5A	0.84 (3)
O13—N1	1.252 (3)	N5—H5B	1.03 (3)
O21—N2	1.250 (4)	N5—H5C	1.00 (3)
O22—N2	1.250 (3)	N5—H5D	0.90 (3)
O23—N2	1.173 (4)	N6—H6A	1.00 (3)
N3—H3A	0.96 (3)	N6—H6B	1.00 (3)
N3—H3B	1.03 (3)	N6—H6C	0.95 (3)
N3—H3C	0.95 (3)	N6—H6D	0.89 (3)
O4—S1—O1	109.29 (13)	H4A—N4—H4B	105 (3)
O4—S1—O2	110.21 (13)	H4A—N4—H4C	117 (4)
O1—S1—O2	109.35 (11)	H4B—N4—H4C	117 (4)
O4—S1—O3	109.95 (12)	H4A—N4—H4D	104 (3)
O1—S1—O3	109.28 (11)	H4B—N4—H4D	101 (4)
O2—S1—O3	108.73 (13)	H4C—N4—H4D	112 (4)
O12—N1—O11	120.1 (2)	H5A—N5—H5B	114 (4)
O12—N1—O13	119.9 (2)	H5A—N5—H5C	109 (4)
O11—N1—O13	119.9 (2)	H5B—N5—H5C	97 (3)
O23—N2—O21	119.7 (4)	H5A—N5—H5D	126 (4)
O23—N2—O22	126.4 (4)	H5B—N5—H5D	103 (3)
O21—N2—O22	113.8 (3)	H5C—N5—H5D	103 (4)
H3A—N3—H3B	110 (4)	H6A—N6—H6B	98 (3)
H3A—N3—H3C	110 (4)	H6A—N6—H6C	111 (4)
H3B—N3—H3C	105 (3)	H6B—N6—H6C	104 (3)
H3A—N3—H3D	111 (4)	H6A—N6—H6D	112 (4)
H3B—N3—H3D	108 (4)	H6B—N6—H6D	117 (4)
H3C—N3—H3D	113 (4)	H6C—N6—H6D	113 (4)

(III)

Crystal data

3(NO3)·O4S·5(H4N)	F(000) = 392
Mr = 372.30	Dx = 1.711 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 9.8642 (1) Å	Cell parameters from 7014 reflections
b = 5.9636 (1) Å	θ = 3.3–32.6°
c = 12.3046 (2) Å	µ = 0.31 mm^−1
β = 93.115 (1)°	T = 100 K
V = 722.77 (2) Å^3	Prismatic, colourless
Z = 2	0.59 × 0.26 × 0.17 mm

Data collection

Goniometer Xcalibur, detector: Ruby diffractometer	3967 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3883 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.015
Detector resolution: 10.2673 pixels mm^-1	θmax = 32.7°, θmin = 3.3°
f\ and ω scans	h = −14→14
Absorption correction: analytical CrysAlis RED, Oxford Diffraction Ltd.	k = −6→8
Tmin = 0.908, Tmax = 0.950	l = −17→18
7655 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.020	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.050	w = 1/[σ^2(Fo^2) + (0.0373P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.037
3967 reflections	Δρmax = 0.23 e Å^−3
288 parameters	Δρmin = −0.39 e Å^−3
1 restraint	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.25 (3)

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	Occ. (<1)
S1	0.756747 (16)	0.42911 (3)	0.832981 (14)	0.00773 (4)
O1	0.67407 (6)	0.63248 (12)	0.84700 (6)	0.01472 (13)
O2	0.89899 (5)	0.47602 (12)	0.87306 (5)	0.01225 (13)
O3	0.70166 (6)	0.24160 (11)	0.89494 (5)	0.01153 (12)
O4	0.75701 (6)	0.36581 (13)	0.71685 (5)	0.01544 (13)
O11	0.54124 (6)	−0.13794 (13)	0.45368 (5)	0.01513 (13)
O12	0.65071 (6)	−0.19867 (12)	0.30879 (5)	0.01471 (13)
O13	0.61257 (7)	0.14294 (12)	0.35815 (6)	0.01846 (14)
O21	1.20244 (6)	−0.19160 (13)	0.85515 (6)	0.01666 (14)
O22	1.18262 (6)	0.16646 (12)	0.88266 (6)	0.01463 (13)
O23	1.38302 (6)	0.01531 (13)	0.88108 (5)	0.01401 (12)
O31	0.80712 (10)	−0.0411 (3)	0.55033 (11)	0.0276 (4)	0.825 (5)
O32	0.9682 (2)	−0.0594 (2)	0.67677 (8)	0.0381 (5)	0.825 (5)
O33	0.98698 (12)	0.1584 (2)	0.53772 (12)	0.0183 (3)	0.825 (5)
O331	0.9242 (13)	0.1384 (15)	0.5240 (5)	0.045 (3)	0.175 (5)
O311	0.8398 (6)	−0.1257 (13)	0.6154 (11)	0.053 (4)	0.175 (5)
O321	1.0401 (7)	−0.0142 (10)	0.6560 (5)	0.0236 (15)	0.175 (5)
N1	0.60126 (6)	−0.06248 (15)	0.37380 (5)	0.01010 (12)
N2	1.25540 (7)	−0.00350 (14)	0.87280 (6)	0.01083 (14)
N3	0.92204 (8)	0.01364 (16)	0.59088 (7)	0.01490 (15)
N4	0.92305 (8)	−0.01375 (16)	0.29893 (7)	0.01287 (15)
N5	1.26344 (8)	−0.01418 (15)	0.50060 (7)	0.01222 (14)
N6	0.58666 (7)	−0.02293 (14)	0.69831 (6)	0.01101 (14)
N7	0.92563 (7)	−0.05691 (16)	0.92868 (6)	0.01200 (13)
N8	1.41830 (7)	−0.49573 (16)	0.92421 (7)	0.01287 (14)
H4A	0.9263 (14)	0.126 (3)	0.3124 (13)	0.0242 (8)*
H4B	0.8461 (14)	−0.047 (3)	0.2765 (11)	0.0242 (8)*
H4C	0.9504 (14)	−0.105 (3)	0.3466 (13)	0.0242 (8)*
H4D	0.9743 (14)	−0.026 (3)	0.2456 (12)	0.0242 (8)*
H5A	1.3215 (15)	0.085 (3)	0.5127 (12)	0.0242 (8)*
H5B	1.2936 (14)	−0.131 (3)	0.5329 (12)	0.0242 (8)*
H5C	1.1904 (15)	0.036 (3)	0.5238 (12)	0.0242 (8)*
H5D	1.2545 (13)	−0.034 (3)	0.4318 (12)	0.0242 (8)*
H6A	0.5755 (13)	−0.061 (3)	0.6312 (12)	0.0242 (8)*
H6B	0.5108 (15)	0.023 (3)	0.7230 (12)	0.0242 (8)*
H6C	0.6182 (15)	−0.138 (3)	0.7380 (12)	0.0242 (8)*
H6D	0.6401 (16)	0.088 (3)	0.7047 (12)	0.0242 (8)*
H7A	0.9651 (13)	−0.055 (3)	0.9908 (12)	0.0242 (8)*
H7B	0.8940 (15)	−0.197 (3)	0.9094 (12)	0.0242 (8)*
H7C	0.8508 (15)	0.034 (3)	0.9268 (12)	0.0242 (8)*
H7D	0.9841 (14)	−0.008 (3)	0.8824 (12)	0.0242 (8)*
H8A	1.3984 (15)	−0.641 (3)	0.9060 (13)	0.0242 (8)*
H8B	1.4953 (15)	−0.466 (3)	0.8979 (12)	0.0242 (8)*
H8C	1.3583 (15)	−0.404 (3)	0.8891 (13)	0.0242 (8)*
H8D	1.4150 (14)	−0.462 (3)	0.9917 (12)	0.0242 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.00720 (7)	0.00809 (9)	0.00784 (8)	−0.00057 (6)	−0.00014 (5)	0.00091 (7)
O1	0.0125 (2)	0.0103 (3)	0.0216 (3)	0.0029 (2)	0.0029 (2)	0.0032 (3)
O2	0.0076 (2)	0.0156 (4)	0.0134 (3)	−0.0010 (2)	−0.00093 (18)	−0.0016 (2)
O3	0.0121 (2)	0.0100 (3)	0.0128 (3)	−0.0009 (2)	0.0030 (2)	0.0034 (2)
O4	0.0200 (3)	0.0180 (3)	0.0083 (3)	−0.0062 (2)	0.0001 (2)	−0.0004 (2)
O11	0.0145 (2)	0.0191 (3)	0.0123 (3)	−0.0005 (2)	0.0052 (2)	0.0008 (2)
O12	0.0155 (2)	0.0150 (3)	0.0140 (3)	0.0005 (2)	0.0047 (2)	−0.0050 (3)
O13	0.0263 (3)	0.0091 (3)	0.0196 (3)	0.0006 (3)	−0.0022 (3)	0.0015 (3)
O21	0.0139 (3)	0.0132 (3)	0.0225 (3)	−0.0014 (2)	−0.0027 (2)	−0.0053 (3)
O22	0.0138 (2)	0.0125 (3)	0.0179 (3)	0.0030 (2)	0.0032 (2)	0.0017 (3)
O23	0.0082 (2)	0.0182 (3)	0.0156 (3)	−0.0009 (2)	0.0003 (2)	0.0027 (3)
O31	0.0149 (4)	0.0320 (8)	0.0365 (6)	−0.0099 (4)	0.0066 (4)	−0.0164 (6)
O32	0.0748 (13)	0.0239 (6)	0.0147 (4)	0.0220 (8)	−0.0060 (5)	0.0032 (5)
O33	0.0163 (4)	0.0122 (5)	0.0273 (5)	−0.0035 (4)	0.0093 (4)	−0.0012 (4)
O331	0.082 (7)	0.036 (4)	0.018 (3)	0.042 (5)	0.011 (4)	0.010 (3)
O311	0.017 (2)	0.032 (4)	0.113 (9)	−0.013 (2)	0.028 (4)	−0.036 (5)
O321	0.027 (3)	0.020 (3)	0.022 (2)	0.015 (2)	−0.013 (2)	−0.0095 (19)
N1	0.0094 (2)	0.0109 (3)	0.0099 (3)	0.0006 (3)	−0.0004 (2)	−0.0003 (3)
N2	0.0107 (3)	0.0136 (4)	0.0082 (3)	0.0005 (2)	0.0002 (2)	0.0006 (3)
N3	0.0181 (3)	0.0117 (4)	0.0151 (3)	−0.0012 (3)	0.0030 (3)	−0.0037 (3)
N4	0.0109 (3)	0.0140 (4)	0.0137 (3)	−0.0002 (3)	0.0005 (2)	0.0004 (3)
N5	0.0122 (3)	0.0123 (4)	0.0121 (3)	0.0001 (3)	0.0000 (2)	−0.0015 (3)
N6	0.0106 (3)	0.0103 (4)	0.0121 (3)	−0.0004 (2)	0.0000 (2)	−0.0007 (3)
N7	0.0110 (2)	0.0105 (4)	0.0142 (3)	−0.0016 (3)	−0.0017 (2)	0.0014 (3)
N8	0.0105 (3)	0.0140 (4)	0.0141 (3)	−0.0002 (3)	0.0005 (2)	−0.0029 (3)

Geometric parameters (Å, º)

S1—O3	1.4738 (6)	N4—H4A	0.852 (18)
S1—O1	1.4769 (7)	N4—H4B	0.818 (14)
S1—O4	1.4781 (6)	N4—H4C	0.834 (18)
S1—O2	1.4883 (6)	N4—H4D	0.852 (15)
O11—N1	1.2580 (9)	N5—H5A	0.833 (16)
O12—N1	1.2569 (10)	N5—H5B	0.849 (18)
O13—N1	1.2461 (11)	N5—H5C	0.845 (15)
O21—N2	1.2514 (11)	N5—H5D	0.855 (15)
O22—N2	1.2518 (10)	N6—H6A	0.858 (14)
O23—N2	1.2624 (8)	N6—H6B	0.866 (15)
O31—O311	0.986 (13)	N6—H6C	0.887 (18)
O31—N3	1.2566 (13)	N6—H6D	0.848 (17)
O31—O331	1.620 (14)	N7—H7A	0.839 (15)
O32—O321	0.813 (7)	N7—H7B	0.917 (17)
O32—N3	1.2089 (14)	N7—H7C	0.914 (16)
O32—O311	1.492 (8)	N7—H7D	0.882 (15)
O33—O331	0.644 (13)	N8—H8A	0.914 (19)
O33—N3	1.2764 (14)	N8—H8B	0.860 (15)
O331—N3	1.110 (7)	N8—H8C	0.898 (16)
O311—N3	1.211 (7)	N8—H8D	0.856 (15)
O321—N3	1.388 (4)
O3—S1—O1	109.95 (4)	O331—N3—O321	117.3 (6)
O3—S1—O4	109.05 (4)	O32—N3—O321	35.7 (3)
O1—S1—O4	110.65 (4)	O311—N3—O321	109.1 (6)
O3—S1—O2	109.80 (4)	O31—N3—O321	155.4 (3)
O1—S1—O2	108.88 (4)	O33—N3—O321	87.0 (3)
O4—S1—O2	108.49 (3)	H4A—N4—H4B	109.3 (15)
O311—O31—N3	64.0 (3)	H4A—N4—H4C	119.6 (16)
O311—O31—O331	107.2 (4)	H4B—N4—H4C	109.6 (15)
N3—O31—O331	43.1 (3)	H4A—N4—H4D	102.5 (15)
O321—O32—N3	84.2 (3)	H4B—N4—H4D	107.3 (13)
O321—O32—O311	131.3 (5)	H4C—N4—H4D	107.6 (14)
N3—O32—O311	52.0 (5)	H5A—N5—H5B	106.5 (14)
O331—O33—N3	60.4 (7)	H5A—N5—H5C	106.1 (15)
O33—O331—N3	89.3 (7)	H5B—N5—H5C	114.7 (14)
O33—O331—O31	139.1 (8)	H5A—N5—H5D	107.8 (14)
N3—O331—O31	50.7 (5)	H5B—N5—H5D	111.6 (15)
O31—O311—N3	68.9 (7)	H5C—N5—H5D	109.8 (14)
O31—O311—O32	120.5 (6)	H6A—N6—H6B	110.7 (13)
N3—O311—O32	51.9 (3)	H6A—N6—H6C	110.3 (15)
O32—O321—N3	60.1 (3)	H6B—N6—H6C	109.3 (14)
O13—N1—O12	119.73 (7)	H6A—N6—H6D	110.1 (14)
O13—N1—O11	121.49 (8)	H6B—N6—H6D	105.5 (16)
O12—N1—O11	118.78 (9)	H6C—N6—H6D	110.8 (14)
O21—N2—O22	120.42 (6)	H7A—N7—H7B	112.5 (15)
O21—N2—O23	119.91 (7)	H7A—N7—H7C	110.5 (13)
O22—N2—O23	119.66 (8)	H7B—N7—H7C	105.5 (13)
O331—N3—O32	150.2 (7)	H7A—N7—H7D	107.3 (13)
O331—N3—O311	133.2 (7)	H7B—N7—H7D	111.0 (14)
O32—N3—O311	76.1 (6)	H7C—N7—H7D	110.1 (14)
O331—N3—O31	86.2 (7)	H8A—N8—H8B	106.6 (15)
O32—N3—O31	122.83 (13)	H8A—N8—H8C	109.3 (14)
O311—N3—O31	47.0 (6)	H8B—N8—H8C	105.5 (15)
O331—N3—O33	30.3 (7)	H8A—N8—H8D	116.1 (15)
O32—N3—O33	121.08 (13)	H8B—N8—H8D	113.4 (14)
O311—N3—O33	162.5 (6)	H8C—N8—H8D	105.4 (14)
O31—N3—O33	116.06 (11)

(IV)

Crystal data

3(NO3)·O4S·5(H4N)	F(000) = 392
Mr = 372.30	Dx = 1.688 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 9.9566 (3) Å	Cell parameters from 3044 reflections
b = 5.9332 (2) Å	θ = 2.6–32.7°
c = 12.4161 (3) Å	µ = 0.31 mm^−1
β = 92.817 (2)°	T = 293 K
V = 732.59 (4) Å^3	Prismatic, colourless
Z = 2	0.33 × 0.12 × 0.10 mm

Data collection

Goniometer Xcalibur, detector: Ruby diffractometer	4389 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3191 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
Detector resolution: 10.2673 pixels mm^-1	θmax = 32.8°, θmin = 2.6°
f\ and ω scans	h = −14→14
Absorption correction: empirical (using intensity measurements) CrysAlis RED (SCALE3 ABSPACK)	k = −9→8
Tmin = 0.957, Tmax = 0.970	l = −17→17
7869 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.045	w = 1/[σ^2(Fo^2) + (0.0511P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.078	(Δ/σ)max = 0.012
S = 1.02	Δρmax = 0.33 e Å^−3
4389 reflections	Δρmin = −0.40 e Å^−3
289 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
57 restraints	Extinction coefficient: 0.039 (3)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.01 (8)

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	Occ. (<1)
S1	0.75020 (5)	0.44112 (12)	0.83572 (4)	0.02570 (13)
O1	0.6804 (2)	0.6482 (4)	0.8645 (2)	0.0549 (7)
O2	0.89160 (14)	0.4571 (5)	0.87367 (12)	0.0435 (4)
O3	0.6883 (2)	0.2480 (3)	0.88685 (18)	0.0407 (5)
O4	0.7435 (2)	0.4058 (5)	0.71960 (13)	0.0673 (7)
O11	0.5444 (2)	−0.0845 (11)	0.45023 (18)	0.1265 (15)
O12	0.6446 (2)	−0.2054 (4)	0.3195 (2)	0.0646 (7)
O13	0.6330 (3)	0.1423 (4)	0.3369 (3)	0.0766 (9)
O21	1.1882 (2)	−0.2118 (4)	0.86873 (17)	0.0412 (5)
O22	1.1842 (2)	0.1525 (4)	0.87861 (19)	0.0447 (6)
O23	1.37493 (15)	−0.0217 (4)	0.87862 (13)	0.0429 (5)
O31	0.8064 (4)	−0.0379 (12)	0.5487 (3)	0.0555 (15)	0.662 (15)
O32	0.9528 (11)	−0.0595 (12)	0.6791 (3)	0.085 (3)	0.662 (15)
O33	0.9885 (5)	0.1345 (11)	0.5386 (7)	0.0564 (19)	0.662 (15)
O321	1.0400 (15)	−0.025 (2)	0.6572 (10)	0.075 (4)	0.338 (15)
O311	0.8422 (16)	−0.126 (2)	0.617 (2)	0.132 (11)	0.338 (15)
O331	0.945 (3)	0.125 (3)	0.5233 (12)	0.124 (8)	0.338 (15)
N1	0.60525 (17)	−0.0463 (6)	0.37013 (14)	0.0371 (4)
N2	1.24935 (19)	−0.0279 (4)	0.87510 (14)	0.0341 (5)
N3	0.9231 (3)	0.0053 (4)	0.59241 (19)	0.0409 (6)
N4	0.9265 (2)	−0.0237 (5)	0.29596 (17)	0.0357 (5)
N5	1.2661 (2)	−0.0228 (5)	0.49938 (16)	0.0347 (5)
N6	0.58925 (19)	−0.0357 (5)	0.70375 (16)	0.0363 (5)
N7	0.92003 (18)	−0.0534 (6)	0.93366 (16)	0.0353 (4)
N8	1.4145 (2)	−0.5277 (5)	0.93046 (18)	0.0387 (5)
H7A	0.954 (3)	−0.074 (7)	1.007 (2)	0.078 (3)*
H7B	0.863 (3)	−0.192 (6)	0.915 (3)	0.078 (3)*
H7C	0.871 (4)	0.062 (6)	0.929 (3)	0.078 (3)*
H7D	0.982 (3)	−0.049 (8)	0.888 (2)	0.078 (3)*
H8D	1.404 (3)	−0.502 (6)	1.001 (2)	0.078 (3)*
H8B	1.504 (3)	−0.500 (6)	0.917 (2)	0.078 (3)*
H8A	1.391 (3)	−0.675 (5)	0.920 (3)	0.078 (3)*
H8C	1.351 (3)	−0.442 (6)	0.888 (3)	0.078 (3)*
H5D	1.271 (3)	−0.025 (7)	0.424 (2)	0.078 (3)*
H5A	1.338 (3)	0.080 (6)	0.520 (3)	0.078 (3)*
H5B	1.282 (3)	−0.164 (5)	0.524 (3)	0.078 (3)*
H5C	1.181 (3)	0.039 (6)	0.508 (3)	0.078 (3)*
H4D	0.994 (3)	−0.016 (6)	0.246 (2)	0.078 (3)*
H4C	0.958 (3)	0.051 (6)	0.351 (2)	0.078 (3)*
H4A	0.856 (3)	0.069 (6)	0.264 (3)	0.078 (3)*
H4B	0.896 (4)	−0.150 (5)	0.288 (3)	0.078 (3)*
H6C	0.604 (3)	−0.153 (5)	0.757 (2)	0.078 (3)*
H6B	0.503 (3)	0.016 (6)	0.712 (3)	0.078 (3)*
H6A	0.601 (3)	−0.075 (7)	0.646 (2)	0.078 (3)*
H6D	0.647 (3)	0.088 (5)	0.720 (3)	0.078 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0260 (2)	0.0269 (2)	0.0241 (2)	−0.0017 (3)	−0.00049 (15)	0.0034 (3)
O1	0.0509 (15)	0.0354 (11)	0.0788 (18)	0.0153 (10)	0.0056 (12)	0.0070 (11)
O2	0.0238 (7)	0.0600 (11)	0.0463 (8)	−0.0025 (12)	−0.0023 (6)	−0.0004 (12)
O3	0.0422 (13)	0.0348 (11)	0.0457 (12)	−0.0118 (9)	0.0091 (9)	0.0063 (8)
O4	0.0867 (14)	0.0930 (19)	0.0214 (8)	−0.0283 (15)	−0.0048 (8)	0.0046 (11)
O11	0.0563 (14)	0.273 (5)	0.0527 (13)	0.012 (3)	0.0261 (11)	0.006 (3)
O12	0.0607 (17)	0.0468 (13)	0.0865 (19)	0.0014 (11)	0.0070 (13)	−0.0217 (12)
O13	0.087 (2)	0.0348 (13)	0.104 (2)	0.0052 (13)	−0.0366 (17)	0.0088 (13)
O21	0.0360 (12)	0.0383 (11)	0.0487 (13)	−0.0041 (9)	−0.0047 (9)	−0.0089 (9)
O22	0.0452 (14)	0.0360 (11)	0.0533 (14)	0.0078 (9)	0.0061 (10)	0.0036 (9)
O23	0.0257 (7)	0.0557 (14)	0.0473 (9)	0.0011 (9)	0.0021 (6)	0.0053 (10)
O31	0.0373 (17)	0.057 (3)	0.071 (3)	−0.006 (2)	−0.0023 (16)	−0.018 (2)
O32	0.134 (7)	0.075 (3)	0.0435 (19)	0.032 (5)	−0.018 (3)	0.011 (3)
O33	0.052 (3)	0.042 (3)	0.077 (5)	−0.017 (2)	0.027 (2)	−0.008 (3)
O321	0.077 (7)	0.055 (6)	0.089 (6)	0.009 (6)	−0.033 (5)	−0.017 (5)
O311	0.064 (8)	0.066 (7)	0.27 (3)	−0.029 (6)	0.088 (13)	−0.053 (11)
O331	0.27 (2)	0.071 (10)	0.031 (5)	0.087 (12)	0.007 (10)	0.027 (5)
N1	0.0275 (8)	0.0527 (13)	0.0307 (9)	0.0063 (17)	−0.0006 (7)	0.0026 (15)
N2	0.0307 (9)	0.0445 (15)	0.0270 (8)	0.0004 (12)	0.0004 (6)	−0.0001 (12)
N3	0.0480 (14)	0.0323 (14)	0.0428 (13)	−0.0009 (10)	0.0073 (11)	−0.0069 (10)
N4	0.0340 (10)	0.0380 (16)	0.0351 (10)	0.0004 (11)	0.0019 (8)	0.0032 (12)
N5	0.0354 (10)	0.0349 (15)	0.0336 (10)	0.0018 (10)	0.0004 (7)	−0.0005 (10)
N6	0.0337 (10)	0.0390 (13)	0.0359 (10)	−0.0038 (12)	−0.0006 (8)	−0.0046 (14)
N7	0.0307 (9)	0.0289 (10)	0.0459 (10)	0.0014 (14)	−0.0016 (7)	−0.0009 (15)
N8	0.0308 (10)	0.0421 (17)	0.0432 (10)	0.0007 (12)	0.0012 (8)	−0.0033 (13)

Geometric parameters (Å, º)

S1—O4	1.4552 (17)	N4—H4D	0.94 (3)
S1—O3	1.461 (2)	N4—H4C	0.86 (3)
S1—O1	1.465 (2)	N4—H4A	0.96 (3)
S1—O2	1.4655 (15)	N4—H4B	0.81 (3)
O11—N1	1.211 (3)	N5—H5D	0.93 (2)
O12—N1	1.210 (4)	N5—H5A	0.97 (3)
O13—N1	1.229 (4)	N5—H5B	0.91 (3)
O21—N2	1.250 (3)	N5—H5C	0.94 (3)
O22—N2	1.254 (3)	N6—H6C	0.97 (3)
O23—N2	1.249 (2)	N6—H6B	0.92 (3)
O31—O311	1.04 (3)	N6—H6A	0.77 (3)
O31—N3	1.284 (4)	N6—H6D	0.95 (3)
O31—O331	1.72 (2)	N7—H7A	0.97 (2)
O32—O321	0.945 (10)	N7—H7B	1.02 (3)
O32—N3	1.167 (4)	N7—H7C	0.84 (3)
O32—O311	1.373 (19)	N7—H7D	0.86 (2)
O33—N3	1.225 (6)	N8—H8D	0.90 (3)
O33—O321	1.802 (13)	N8—H8B	0.93 (3)
O321—N3	1.393 (10)	N8—H8A	0.91 (3)
O311—N3	1.172 (11)	N8—H8C	0.95 (3)
O331—N3	1.141 (16)
O4—S1—O3	108.53 (15)	O331—N3—O321	109.2 (11)
O4—S1—O1	111.29 (16)	O32—N3—O321	42.2 (4)
O3—S1—O1	109.69 (10)	O311—N3—O321	109.4 (13)
O4—S1—O2	108.94 (11)	O33—N3—O321	86.8 (7)
O3—S1—O2	109.27 (14)	O31—N3—O321	158.7 (6)
O1—S1—O2	109.09 (16)	H4D—N4—H4C	105 (3)
O311—O31—N3	59.4 (6)	H4D—N4—H4A	103 (3)
O311—O31—O331	100.7 (8)	H4C—N4—H4A	105 (3)
N3—O31—O331	41.4 (5)	H4D—N4—H4B	104 (3)
O321—O32—N3	81.8 (7)	H4C—N4—H4B	134 (3)
O321—O32—O311	128.6 (11)	H4A—N4—H4B	103 (3)
N3—O32—O311	54.2 (9)	H5D—N5—H5A	101 (3)
N3—O33—O321	50.5 (5)	H5D—N5—H5B	108 (3)
O32—O321—N3	56.0 (6)	H5A—N5—H5B	112 (3)
O32—O321—O33	97.0 (8)	H5D—N5—H5C	102 (2)
N3—O321—O33	42.7 (3)	H5A—N5—H5C	113 (3)
O31—O311—N3	70.6 (13)	H5B—N5—H5C	118 (3)
O31—O311—O32	123.0 (11)	H6C—N6—H6B	106 (2)
N3—O311—O32	53.9 (6)	H6C—N6—H6A	113 (3)
N3—O331—O31	48.1 (9)	H6B—N6—H6A	113 (3)
O12—N1—O11	118.0 (5)	H6C—N6—H6D	110 (3)
O12—N1—O13	116.9 (2)	H6B—N6—H6D	106 (3)
O11—N1—O13	125.1 (4)	H6A—N6—H6D	108 (3)
O23—N2—O21	120.8 (3)	H7A—N7—H7B	106 (3)
O23—N2—O22	119.5 (3)	H7A—N7—H7C	110 (3)
O21—N2—O22	119.71 (18)	H7B—N7—H7C	109 (3)
O331—N3—O32	148.1 (11)	H7A—N7—H7D	114 (3)
O331—N3—O311	139.9 (14)	H7B—N7—H7D	107 (3)
O32—N3—O311	71.9 (13)	H7C—N7—H7D	111 (3)
O331—N3—O33	22.5 (13)	H8D—N8—H8B	108 (3)
O32—N3—O33	126.3 (6)	H8D—N8—H8A	105 (3)
O311—N3—O33	161.5 (16)	H8B—N8—H8A	113 (3)
O331—N3—O31	90.4 (12)	H8D—N8—H8C	110 (3)
O32—N3—O31	120.5 (5)	H8B—N8—H8C	115 (3)
O311—N3—O31	50.0 (14)	H8A—N8—H8C	106 (3)
O33—N3—O31	112.8 (5)