Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109006325/fg3078sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109006325/fg3078Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109006325/fg3078IIsup3.hkl |
CCDC references: 728221; 728222
Crystals of (I) and (II) were obtained from 2-imino-4-thiobiuret (purchased from Aldrich, 99% purity) dissolved in 5% aqueous solutions of the respective acids (HNO3 or H3PO3). After several days at room temperature, suitable crystals were formed.
The H atom of the HPO32- anion was located from a difference Fourier map and was refined [P1—H1 = 1.36 (2) Å]. All other H atoms were located from difference Fourier maps and were constrained [N—H = 0.86 Å with Uiso(H) = 1.2Ueq(N), and O—H = 0.82 Å with Uiso(H) = 1.5Ueq(O)].
For both compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2006). Cell refinement: CrysAlis RED (Oxford Diffraction, 2006) for (I); CrysAlis CCD (Oxford Diffraction, 2006) for (II). Data reduction: CrysAlis RED (Oxford Diffraction, 2006) for (I); CrysAlis CCD (Oxford Diffraction, 2006) for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Diamond (Brandenburg & Putz, 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
C2H7N4S+·NO3− | F(000) = 376 |
Mr = 181.19 | Dx = 1.631 Mg m−3 Dm = 1.63 Mg m−3 Dm measured by flotation |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 1307 reflections |
a = 9.776 (2) Å | θ = 3.0–28.3° |
b = 8.3320 (17) Å | µ = 0.41 mm−1 |
c = 10.003 (2) Å | T = 295 K |
β = 115.08 (3)° | Paralellepiped, colourless |
V = 738.0 (3) Å3 | 0.36 × 0.32 × 0.14 mm |
Z = 4 |
Kuma KM-4 with area CCD detector diffractometer | 1915 independent reflections |
Radiation source: fine-focus sealed tube | 1307 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
Detector resolution: 1024x1024 with blocks 2x2 pixels mm-1 | θmax = 29.3°, θmin = 3.3° |
ω–scan | h = −13→13 |
Absorption correction: numerical (CrysAlis RED; Oxford Diffraction, 2006) | k = −10→11 |
Tmin = 0.865, Tmax = 0.942 | l = −13→13 |
8419 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.032 | H-atom parameters constrained |
wR(F2) = 0.087 | w = 1/[σ2(Fo2) + (0.0474P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max < 0.001 |
1915 reflections | Δρmax = 0.18 e Å−3 |
104 parameters | Δρmin = −0.16 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0029 (4) |
C2H7N4S+·NO3− | V = 738.0 (3) Å3 |
Mr = 181.19 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.776 (2) Å | µ = 0.41 mm−1 |
b = 8.3320 (17) Å | T = 295 K |
c = 10.003 (2) Å | 0.36 × 0.32 × 0.14 mm |
β = 115.08 (3)° |
Kuma KM-4 with area CCD detector diffractometer | 1915 independent reflections |
Absorption correction: numerical (CrysAlis RED; Oxford Diffraction, 2006) | 1307 reflections with I > 2σ(I) |
Tmin = 0.865, Tmax = 0.942 | Rint = 0.026 |
8419 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.087 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.18 e Å−3 |
1915 reflections | Δρmin = −0.16 e Å−3 |
104 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
N5 | 0.69428 (14) | 0.65872 (13) | 1.07747 (13) | 0.0462 (3) | |
O1 | 0.59382 (13) | 0.69920 (12) | 0.95482 (11) | 0.0506 (3) | |
O2 | 0.72641 (15) | 0.51615 (11) | 1.10551 (11) | 0.0621 (4) | |
O3 | 0.75985 (17) | 0.76409 (11) | 1.17092 (12) | 0.0602 (4) | |
S1 | 0.54164 (6) | 0.23394 (4) | 0.57070 (4) | 0.05162 (16) | |
C1 | 0.56851 (16) | 0.33955 (15) | 0.72214 (14) | 0.0363 (3) | |
N1 | 0.61549 (15) | 0.27710 (14) | 0.86351 (11) | 0.0386 (3) | |
H1 | 0.6390 | 0.3432 | 0.9360 | 0.046* | |
C2 | 0.63273 (16) | 0.12143 (15) | 0.90974 (15) | 0.0363 (3) | |
N2 | 0.54808 (15) | 0.49519 (13) | 0.71795 (13) | 0.0494 (3) | |
H21 | 0.5638 | 0.5468 | 0.7976 | 0.059* | |
H22 | 0.5189 | 0.5458 | 0.6355 | 0.059* | |
N3 | 0.67546 (14) | 0.09650 (15) | 1.05159 (13) | 0.0471 (3) | |
H31 | 0.6875 | 0.0001 | 1.0854 | 0.057* | |
H32 | 0.6914 | 0.1766 | 1.1106 | 0.057* | |
N4 | 0.60813 (17) | 0.00144 (14) | 0.81904 (14) | 0.0546 (4) | |
H41 | 0.6198 | −0.0954 | 0.8517 | 0.066* | |
H42 | 0.5802 | 0.0190 | 0.7264 | 0.066* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N5 | 0.0567 (8) | 0.0397 (6) | 0.0407 (6) | −0.0002 (5) | 0.0177 (6) | 0.0010 (5) |
O1 | 0.0609 (7) | 0.0412 (5) | 0.0375 (6) | 0.0087 (5) | 0.0092 (5) | 0.0013 (5) |
O2 | 0.0718 (9) | 0.0430 (5) | 0.0509 (7) | 0.0028 (5) | 0.0095 (6) | 0.0046 (5) |
O3 | 0.0788 (10) | 0.0402 (6) | 0.0413 (6) | −0.0101 (6) | 0.0102 (6) | −0.0067 (4) |
S1 | 0.0629 (4) | 0.0480 (2) | 0.0454 (2) | 0.00012 (19) | 0.0264 (2) | −0.00206 (15) |
C1 | 0.0409 (8) | 0.0313 (7) | 0.0351 (7) | 0.0004 (6) | 0.0116 (6) | 0.0025 (6) |
N1 | 0.0541 (8) | 0.0292 (6) | 0.0293 (6) | 0.0007 (5) | 0.0146 (6) | −0.0026 (5) |
C2 | 0.0386 (8) | 0.0327 (7) | 0.0373 (7) | 0.0019 (6) | 0.0157 (6) | 0.0024 (6) |
N2 | 0.0755 (10) | 0.0309 (6) | 0.0353 (6) | 0.0046 (6) | 0.0174 (6) | 0.0014 (5) |
N3 | 0.0616 (9) | 0.0364 (6) | 0.0371 (6) | 0.0022 (6) | 0.0150 (6) | 0.0048 (5) |
N4 | 0.0907 (11) | 0.0294 (6) | 0.0423 (7) | 0.0059 (6) | 0.0266 (7) | 0.0030 (5) |
N5—O2 | 1.2303 (15) | C2—N4 | 1.3021 (17) |
N5—O3 | 1.2440 (15) | C2—N3 | 1.3148 (18) |
N5—O1 | 1.2498 (15) | N2—H21 | 0.8600 |
S1—C1 | 1.6736 (14) | N2—H22 | 0.8600 |
C1—N2 | 1.3100 (17) | N3—H31 | 0.8600 |
C1—N1 | 1.3896 (17) | N3—H32 | 0.8600 |
N1—C2 | 1.3632 (16) | N4—H41 | 0.8600 |
N1—H1 | 0.8600 | N4—H42 | 0.8600 |
O2—N5—O3 | 120.64 (12) | N3—C2—N1 | 116.97 (12) |
O2—N5—O1 | 120.18 (12) | C1—N2—H21 | 120.0 |
O3—N5—O1 | 119.17 (12) | C1—N2—H22 | 120.0 |
N2—C1—N1 | 112.54 (12) | H21—N2—H22 | 120.0 |
N2—C1—S1 | 121.89 (10) | C2—N3—H31 | 120.0 |
N1—C1—S1 | 125.56 (10) | C2—N3—H32 | 120.0 |
C2—N1—C1 | 129.90 (11) | H31—N3—H32 | 120.0 |
C2—N1—H1 | 112 | C2—N4—H41 | 120.0 |
C1—N1—H1 | 118 | C2—N4—H42 | 120.0 |
N4—C2—N3 | 120.73 (13) | H41—N4—H42 | 120.0 |
N4—C2—N1 | 122.31 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2 | 0.86 | 2.11 | 2.9627 (16) | 171 |
N2—H21···O1 | 0.86 | 1.94 | 2.7938 (16) | 169 |
N2—H22···S1i | 0.86 | 2.63 | 3.4717 (14) | 165 |
N3—H31···O3ii | 0.86 | 2.14 | 2.9903 (17) | 169 |
N3—H32···O3iii | 0.86 | 2.16 | 2.9268 (18) | 149 |
N4—H41···O1ii | 0.86 | 2.07 | 2.8927 (16) | 160 |
N4—H42···S1 | 0.86 | 2.30 | 2.9962 (14) | 139 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y−1, z; (iii) −x+3/2, y−1/2, −z+5/2. |
2C2H7N4S+·HPO32−·H2O | Z = 2 |
Mr = 336.35 | F(000) = 352 |
Triclinic, P1 | Dx = 1.600 Mg m−3 Dm = 1.594 Mg m−3 Dm measured by floatation |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.6109 (12) Å | Cell parameters from 852 reflections |
b = 7.8771 (14) Å | θ = 2.9–29.5° |
c = 12.758 (2) Å | µ = 0.52 mm−1 |
α = 72.700 (16)° | T = 295 K |
β = 72.961 (15)° | Paralellepiped, colourless |
γ = 85.842 (14)° | 0.38 × 0.27 × 0.22 mm |
V = 698.1 (2) Å3 |
Kuma KM-4 with area CCD detector diffractometer | 3529 independent reflections |
Radiation source: fine-focus sealed tube | 1950 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
Detector resolution: 1024x1024 with blocks 2x2 pixels mm-1 | θmax = 29.5°, θmin = 2.9° |
ω–scan | h = −10→10 |
Absorption correction: numerical (CrysAlis RED; Oxford Diffraction, 2006) | k = −7→10 |
Tmin = 0.850, Tmax = 0.923 | l = −16→16 |
8542 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.089 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.028P)2] where P = (Fo2 + 2Fc2)/3 |
3529 reflections | (Δ/σ)max = 0.001 |
188 parameters | Δρmax = 0.43 e Å−3 |
0 restraints | Δρmin = −0.35 e Å−3 |
2C2H7N4S+·HPO32−·H2O | γ = 85.842 (14)° |
Mr = 336.35 | V = 698.1 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.6109 (12) Å | Mo Kα radiation |
b = 7.8771 (14) Å | µ = 0.52 mm−1 |
c = 12.758 (2) Å | T = 295 K |
α = 72.700 (16)° | 0.38 × 0.27 × 0.22 mm |
β = 72.961 (15)° |
Kuma KM-4 with area CCD detector diffractometer | 3529 independent reflections |
Absorption correction: numerical (CrysAlis RED; Oxford Diffraction, 2006) | 1950 reflections with I > 2σ(I) |
Tmin = 0.850, Tmax = 0.923 | Rint = 0.037 |
8542 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.089 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.43 e Å−3 |
3529 reflections | Δρmin = −0.35 e Å−3 |
188 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
P1 | 0.37123 (9) | 0.14677 (9) | 0.64056 (6) | 0.02563 (18) | |
H1 | 0.430 (3) | 0.146 (3) | 0.5294 (18) | 0.017 (6)* | |
O1 | 0.3364 (2) | 0.3387 (2) | 0.63694 (17) | 0.0362 (5) | |
O2 | 0.1971 (2) | 0.0318 (2) | 0.69163 (16) | 0.0331 (5) | |
O3 | 0.5187 (2) | 0.0705 (2) | 0.69932 (16) | 0.0338 (5) | |
S11 | 0.22758 (10) | −0.45085 (10) | 1.07379 (7) | 0.0407 (2) | |
C11 | 0.2605 (4) | −0.2956 (3) | 0.9465 (2) | 0.0306 (7) | |
N11 | 0.1256 (3) | −0.1898 (3) | 0.90960 (19) | 0.0301 (6) | |
H11 | 0.1540 | −0.1260 | 0.8385 | 0.036* | |
N12 | 0.4235 (3) | −0.2654 (3) | 0.8699 (2) | 0.0410 (7) | |
H121 | 0.4364 | −0.1862 | 0.8049 | 0.049* | |
H122 | 0.5168 | −0.3250 | 0.8850 | 0.049* | |
C12 | −0.0556 (4) | −0.1779 (3) | 0.9673 (2) | 0.0301 (7) | |
N14 | −0.1252 (3) | −0.2582 (3) | 1.0754 (2) | 0.0443 (7) | |
H141 | −0.2384 | −0.2428 | 1.1089 | 0.053* | |
H142 | −0.0581 | −0.3269 | 1.1136 | 0.053* | |
N13 | −0.1568 (3) | −0.0726 (3) | 0.9080 (2) | 0.0442 (7) | |
H131 | −0.2702 | −0.0564 | 0.9408 | 0.053* | |
H132 | −0.1096 | −0.0199 | 0.8364 | 0.053* | |
S21 | −0.15934 (10) | 0.79949 (9) | 0.64775 (7) | 0.0371 (2) | |
C21 | 0.0111 (3) | 0.6542 (3) | 0.6403 (2) | 0.0253 (6) | |
N21 | −0.0014 (3) | 0.4810 (3) | 0.63714 (19) | 0.0243 (5) | |
H21 | 0.1010 | 0.4230 | 0.6310 | 0.029* | |
N22 | 0.1791 (3) | 0.6955 (3) | 0.6381 (2) | 0.0396 (7) | |
H221 | 0.2644 | 0.6178 | 0.6350 | 0.048* | |
H222 | 0.2022 | 0.7998 | 0.6397 | 0.048* | |
C22 | −0.1487 (3) | 0.3912 (3) | 0.6396 (2) | 0.0199 (6) | |
N24 | −0.3072 (3) | 0.4674 (3) | 0.6383 (2) | 0.0347 (6) | |
H241 | −0.3976 | 0.4077 | 0.6385 | 0.042* | |
H242 | −0.3209 | 0.5772 | 0.6372 | 0.042* | |
N23 | −0.1257 (3) | 0.2238 (3) | 0.64123 (18) | 0.0294 (6) | |
H231 | −0.2153 | 0.1629 | 0.6415 | 0.035* | |
H232 | −0.0212 | 0.1750 | 0.6421 | 0.035* | |
O4W | 0.5009 (3) | 0.1613 (3) | 0.89006 (19) | 0.0471 (6) | |
H1W | 0.5500 | 0.2580 | 0.8750 | 0.071* | |
H2W | 0.5070 | 0.1360 | 0.8310 | 0.071* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0176 (4) | 0.0247 (4) | 0.0297 (5) | −0.0002 (3) | −0.0073 (3) | −0.0086 (3) |
O1 | 0.0377 (11) | 0.0313 (10) | 0.0406 (14) | −0.0011 (8) | −0.0179 (10) | −0.0079 (10) |
O2 | 0.0260 (10) | 0.0266 (10) | 0.0473 (13) | −0.0045 (8) | −0.0128 (9) | −0.0080 (9) |
O3 | 0.0269 (11) | 0.0278 (11) | 0.0478 (13) | 0.0050 (8) | −0.0151 (9) | −0.0092 (9) |
S11 | 0.0374 (5) | 0.0398 (5) | 0.0362 (5) | 0.0022 (4) | −0.0089 (4) | −0.0002 (4) |
C11 | 0.0293 (16) | 0.0264 (15) | 0.0378 (18) | 0.0037 (12) | −0.0090 (13) | −0.0131 (13) |
N11 | 0.0265 (13) | 0.0305 (14) | 0.0274 (14) | 0.0032 (10) | −0.0059 (11) | −0.0022 (11) |
N12 | 0.0298 (14) | 0.0381 (15) | 0.0395 (16) | 0.0082 (11) | −0.0016 (11) | 0.0019 (12) |
C12 | 0.0285 (16) | 0.0276 (16) | 0.0360 (19) | 0.0018 (13) | −0.0081 (13) | −0.0135 (14) |
N14 | 0.0265 (14) | 0.0615 (18) | 0.0384 (16) | 0.0067 (12) | −0.0032 (12) | −0.0121 (14) |
N13 | 0.0320 (15) | 0.0496 (16) | 0.0461 (17) | 0.0107 (12) | −0.0118 (12) | −0.0081 (13) |
S21 | 0.0376 (4) | 0.0349 (4) | 0.0413 (6) | 0.0037 (3) | −0.0117 (4) | −0.0182 (4) |
C21 | 0.0238 (14) | 0.0238 (15) | 0.0271 (16) | −0.0008 (11) | −0.0062 (11) | −0.0062 (12) |
N21 | 0.0210 (12) | 0.0226 (12) | 0.0301 (14) | 0.0002 (9) | −0.0074 (10) | −0.0099 (10) |
N22 | 0.0233 (13) | 0.0278 (13) | 0.074 (2) | 0.0013 (10) | −0.0162 (12) | −0.0220 (13) |
C22 | 0.0169 (13) | 0.0227 (14) | 0.0183 (14) | −0.0008 (11) | −0.0052 (10) | −0.0028 (11) |
N24 | 0.0265 (13) | 0.0236 (12) | 0.0607 (18) | 0.0004 (10) | −0.0195 (12) | −0.0149 (12) |
N23 | 0.0253 (12) | 0.0231 (12) | 0.0441 (16) | −0.0004 (9) | −0.0115 (11) | −0.0151 (11) |
O4W | 0.0381 (13) | 0.0594 (15) | 0.0428 (15) | −0.0057 (11) | −0.0082 (11) | −0.0152 (13) |
P1—O1 | 1.5051 (18) | N13—H132 | 0.8600 |
P1—O3 | 1.5195 (19) | S21—C21 | 1.667 (3) |
P1—O2 | 1.5226 (18) | C21—N22 | 1.332 (3) |
P1—H1 | 1.36 (2) | C21—N21 | 1.388 (3) |
S11—C11 | 1.679 (3) | N21—C22 | 1.357 (3) |
C11—N12 | 1.321 (3) | N21—H21 | 0.8700 |
C11—N11 | 1.376 (3) | N22—H221 | 0.8600 |
N11—C12 | 1.372 (3) | N22—H222 | 0.8600 |
N11—H11 | 0.8700 | C22—N24 | 1.311 (3) |
N12—H121 | 0.8600 | C22—N23 | 1.312 (3) |
N12—H122 | 0.8600 | N24—H241 | 0.8600 |
C12—N14 | 1.298 (3) | N24—H242 | 0.8600 |
C12—N13 | 1.315 (3) | N23—H231 | 0.8600 |
N14—H141 | 0.8600 | N23—H232 | 0.8600 |
N14—H142 | 0.8600 | O4W—H1W | 0.8200 |
N13—H131 | 0.8600 | O4W—H2W | 0.8200 |
O1—P1—O3 | 111.38 (11) | C12—N13—H132 | 120.0 |
O1—P1—O2 | 113.20 (10) | H131—N13—H132 | 120.0 |
O3—P1—O2 | 111.99 (10) | N22—C21—N21 | 112.2 (2) |
O1—P1—H1 | 105.4 (8) | N22—C21—S21 | 121.7 (2) |
O3—P1—H1 | 109.6 (9) | N21—C21—S21 | 126.02 (19) |
O2—P1—H1 | 104.7 (9) | C22—N21—C21 | 129.4 (2) |
N12—C11—N11 | 113.0 (2) | C22—N21—H21 | 115.7 |
N12—C11—S11 | 121.8 (2) | C21—N21—H21 | 114.9 |
N11—C11—S11 | 125.2 (2) | C21—N22—H221 | 120.0 |
C12—N11—C11 | 129.3 (2) | C21—N22—H222 | 120.0 |
C12—N11—H11 | 113.4 | H221—N22—H222 | 120.0 |
C11—N11—H11 | 117.2 | N24—C22—N23 | 120.7 (2) |
C11—N12—H121 | 120.0 | N24—C22—N21 | 122.1 (2) |
C11—N12—H122 | 120.0 | N23—C22—N21 | 117.2 (2) |
H121—N12—H122 | 120.0 | C22—N24—H241 | 120.0 |
N14—C12—N13 | 120.6 (3) | C22—N24—H242 | 120.0 |
N14—C12—N11 | 123.2 (3) | H241—N24—H242 | 120.0 |
N13—C12—N11 | 116.2 (3) | C22—N23—H231 | 120.0 |
C12—N14—H141 | 120.0 | C22—N23—H232 | 120.0 |
C12—N14—H142 | 120.0 | H231—N23—H232 | 120.0 |
H141—N14—H142 | 120.0 | H1W—O4W—H2W | 111 |
C12—N13—H131 | 120.0 |
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11···O2 | 0.87 | 1.87 | 2.728 (3) | 173 |
N12—H121···O3 | 0.86 | 2.09 | 2.862 (3) | 149 |
N12—H122···S11i | 0.86 | 2.59 | 3.444 (2) | 170 |
N14—H141···O4Wii | 0.86 | 2.05 | 2.846 (3) | 153 |
N14—H142···S11 | 0.86 | 2.30 | 2.984 (3) | 137 |
N13—H131···O4Wii | 0.86 | 2.31 | 3.037 (3) | 142 |
N13—H131···O4Wiii | 0.86 | 2.44 | 3.104 (3) | 134 |
N13—H132···O2 | 0.86 | 2.49 | 3.188 (3) | 139 |
N21—H21···O1 | 0.87 | 1.88 | 2.729 (3) | 165 |
N22—H221···O1 | 0.86 | 2.22 | 2.976 (3) | 146 |
N22—H222···O2iv | 0.86 | 2.12 | 2.948 (3) | 163 |
N24—H241···O1iii | 0.86 | 2.14 | 2.970 (3) | 162 |
N24—H242···S21 | 0.86 | 2.27 | 2.969 (2) | 139 |
N23—H231···O3iii | 0.86 | 2.05 | 2.846 (3) | 154 |
N23—H231···S21v | 0.86 | 2.84 | 3.345 (2) | 119 |
N23—H232···O2 | 0.86 | 2.09 | 2.923 (3) | 164 |
O4W—H1W···S11vi | 0.82 | 2.68 | 3.399 (2) | 147 |
O4W—H2W···O3 | 0.82 | 1.88 | 2.698 (3) | 178 |
Symmetry codes: (i) −x+1, −y−1, −z+2; (ii) −x, −y, −z+2; (iii) x−1, y, z; (iv) x, y+1, z; (v) x, y−1, z; (vi) −x+1, −y, −z+2. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C2H7N4S+·NO3− | 2C2H7N4S+·HPO32−·H2O |
Mr | 181.19 | 336.35 |
Crystal system, space group | Monoclinic, P21/n | Triclinic, P1 |
Temperature (K) | 295 | 295 |
a, b, c (Å) | 9.776 (2), 8.3320 (17), 10.003 (2) | 7.6109 (12), 7.8771 (14), 12.758 (2) |
α, β, γ (°) | 90, 115.08 (3), 90 | 72.700 (16), 72.961 (15), 85.842 (14) |
V (Å3) | 738.0 (3) | 698.1 (2) |
Z | 4 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.41 | 0.52 |
Crystal size (mm) | 0.36 × 0.32 × 0.14 | 0.38 × 0.27 × 0.22 |
Data collection | ||
Diffractometer | Kuma KM-4 with area CCD detector diffractometer | Kuma KM-4 with area CCD detector diffractometer |
Absorption correction | Numerical (CrysAlis RED; Oxford Diffraction, 2006) | Numerical (CrysAlis RED; Oxford Diffraction, 2006) |
Tmin, Tmax | 0.865, 0.942 | 0.850, 0.923 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8419, 1915, 1307 | 8542, 3529, 1950 |
Rint | 0.026 | 0.037 |
(sin θ/λ)max (Å−1) | 0.689 | 0.693 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.087, 1.00 | 0.047, 0.089, 1.00 |
No. of reflections | 1915 | 3529 |
No. of parameters | 104 | 188 |
H-atom treatment | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.18, −0.16 | 0.43, −0.35 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Diamond (Brandenburg & Putz, 2006).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2 | 0.86 | 2.11 | 2.9627 (16) | 171 |
N2—H21···O1 | 0.86 | 1.94 | 2.7938 (16) | 169 |
N2—H22···S1i | 0.86 | 2.63 | 3.4717 (14) | 165 |
N3—H31···O3ii | 0.86 | 2.14 | 2.9903 (17) | 169 |
N3—H32···O3iii | 0.86 | 2.16 | 2.9268 (18) | 149 |
N4—H41···O1ii | 0.86 | 2.07 | 2.8927 (16) | 160 |
N4—H42···S1 | 0.86 | 2.30 | 2.9962 (14) | 139 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y−1, z; (iii) −x+3/2, y−1/2, −z+5/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11···O2 | 0.87 | 1.87 | 2.728 (3) | 173 |
N12—H121···O3 | 0.86 | 2.09 | 2.862 (3) | 149 |
N12—H122···S11i | 0.86 | 2.59 | 3.444 (2) | 170 |
N14—H141···O4Wii | 0.86 | 2.05 | 2.846 (3) | 153 |
N14—H142···S11 | 0.86 | 2.30 | 2.984 (3) | 137 |
N13—H131···O4Wii | 0.86 | 2.31 | 3.037 (3) | 142 |
N13—H131···O4Wiii | 0.86 | 2.44 | 3.104 (3) | 134 |
N13—H132···O2 | 0.86 | 2.49 | 3.188 (3) | 139 |
N21—H21···O1 | 0.87 | 1.88 | 2.729 (3) | 165 |
N22—H221···O1 | 0.86 | 2.22 | 2.976 (3) | 146 |
N22—H222···O2iv | 0.86 | 2.12 | 2.948 (3) | 163 |
N24—H241···O1iii | 0.86 | 2.14 | 2.970 (3) | 162 |
N24—H242···S21 | 0.86 | 2.27 | 2.969 (2) | 139 |
N23—H231···O3iii | 0.86 | 2.05 | 2.846 (3) | 154 |
N23—H231···S21v | 0.86 | 2.84 | 3.345 (2) | 119 |
N23—H232···O2 | 0.86 | 2.09 | 2.923 (3) | 164 |
O4W—H1W···S11vi | 0.82 | 2.68 | 3.399 (2) | 147 |
O4W—H2W···O3 | 0.82 | 1.88 | 2.698 (3) | 178 |
Symmetry codes: (i) −x+1, −y−1, −z+2; (ii) −x, −y, −z+2; (iii) x−1, y, z; (iv) x, y+1, z; (v) x, y−1, z; (vi) −x+1, −y, −z+2. |
As a continuation of our studies on 1-(diaminomethylene)thiourea and its imino tautomer, i.e. 2-imino-4-thiobiuret, whose utility has been described previously (Janczak & Perpétuo, 2008a,b; Perpétuo & Janczak, 2008), we have investigated the crystal structure of 1-(diaminomethylene)thiouron-1-ium nitrate, (I), and bis[1-(diaminomethylene)thiouron-1-ium] phosphonate monohydrate, (II).
The asymmetric unit of (I) consists of a 1-(diaminomethylene)thiouron-1-ium cation and a nitrate anion (Fig. 1a), while the asymmetric unit of (II) consists of two 1-(diaminomethylene)thiouron-1-ium cations, one phosphonate dianion and a water molecule (Fig.1b). The cations in these crystals are not strictly planar but are twisted. Both arms of each cation are rotated relative to the central N atom. The dihedral angle between the planes defined by the N1/C2/N3/N4 and N1/C1/N2/S1 atoms is 7.2 (1)° in (I), while the eqivalent angles in (II) are 9.1 (1) and 3.7 (1)° in (II) for the independent M1 and M2 units, respectively (for the M1 unit the planes are N11/C12/N13/N14 and N11/C11/N12/S11, and for M2 the planes are N21/C22/N23/N24 and N21/C21/N22/S21). For comparison, the neutral molecule of 1-(diaminomethylene)thiourea also has a twisted conformation, with a dihedral angle of 2.1 (1)° (Janczak & Perpétuo, 2008a).
The respective C—N and C═S bond lengths in (I) and in both independent cations in (II) are very similar. The average distance of the C—N bonds involving the central N atom [1.374 (12) Å] is significantly longer than the average distance of the other C—N bonds linking the amine groups [1.313 (9) Å]. The values of the C═S bonds in these salts are intermediate between the pure double C═S bond [1.6109 (8) Å; Johnson et al., 1971] and the distance of ca. 1.74 Å which represents 50% double-bond character (Abrahams, 1956; Allen et al. 1987). The elongation of the C═S bond and the shortening of the C—NH2 bonds indicate partial delocalization of the π bonds (C═S and C═N) over the whole 1-(diaminomethylene)thiouron-1-ium cation. The anionic species of the (I) and (II) crystals exhibit a slightly distorted C3h geometry for the NO3- anion and C3v geometry for the HPO32- anion, with N—O and P—O values typical for bond lengths and angles found in several crystals of this type (Allen, 2002).
In the crystal structures of (I) and (II), the oppositely charged units are linked through hydrogen bonds. In both crystals, 1-(diaminomethylene)thiouron-1-ium cations, related by inversion, are linked via a pair of N—H···S hydrogen bonds (Tables 1 and 2) forming R22(8) dimeric structures. In (I), these dimers are linked by NO3- anions via N—H···O hydrogen bonds into layers that lie parallel to the (301) plane (Fig. 2). The layers are separated by a distance of ~3.37 Å. In (II), the dimers of the independent M1 and M2 units are located essentially perpendicular, (M1)2, and parallel, (M2)2, to the (001) plane (Fig. 3). Within one layer the M2 dimeric cations are interconnected by HPO32- anions via N—H···O hydrogen bonds, while in the second layer M1 dimers are linked via N—H···O interactions with water molecules as well as with HPO32- anions. The dimeric units of M1 and M2 are arranged into layers located parallel to the (001) crystallographic plane at z = 0 (M1 layer) and at z = 0.50 (15) (M2 layer) (Fig. 3). The layer of M1 units is surrounded by two layers of M2 units, forming a sheet parallel to the (001) plane (Fig. 3). The adjacent M2 sheets are separated by a distance of ~3.27 Å. Owing to the partial delocalization of the π electrons of the double C═S and N21═C22 bonds of the M2 cation over the whole cation, the π–π interaction between the M2 units stabilizes the structure and makes it more planar than the M1 unit [the greatest deviations of the non-H atoms observed in the M2 cation are 0.042 (2) Å, while in the M1 cation they are 0.122 (2) Å]. The distance of 3.27 Å between the layers of M2 units is nearly intermediate between the sum of the van der Waals radii for C atoms of π-interacting aromatic rings (~3.4 Å) and the distance of 3.08 Å at which the steric interactions between the π systems become predominantly repulsive (Pauling, 1960; Scheidt & Lee, 1987).
This study illustrates the usefulness of 1-(diaminomethylene)thiourea in crystal engineering for developing supramolecular structures. Protonation of the molecule at the central N atom offers seven active donor sites for hydrogen bonds. Depending on the form of the anion, hydrogen-bonding interactions lead to the formation of layers in nitrate salts or double layers in phosphonate salts.