Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807026451/nc2037sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807026451/nc2037Isup2.hkl |
CCDC reference: 654873
NGN-GN formed in a side reaction using 4.00 g (17 mmol) copper(II) nitrate pentahemihydrate, 6.30 g GN (52 mmol) and 4.5 ml of concentrated HNO3 at 373 K. Single crystals of the compound were obtained upon evaporation of HNO3.
Because no strong anomalously scattering atoms are present the absolute structure cannot be determined and therefore, Friedel opposites were merged in the refinement.
H atoms were located in Fourier difference maps and their coordinates were refined with Uiso fixed at 0.03 Å.
Guanidinium and nitroguanidinium compounds are objects of investigation for a possible application as energetic materials (e.g., Hiskey et al., 2005; Pace & Flippen-Anderson, 1984). The crystal structures of guanidinium nitrate (GN) (Katrusiak & Szafrański, 1994, 1996) and nitroguanidinium nitrate (NGN) (Pace & Flippen-Anderson, 1984) have been determined previously. Here, we report the structure of a new nitroguanidinium nitrate-guanidinium nitrate (NGN-GN) double salt.
As for every potential energetic material, a high density is desired. The density of NGN-GN – 1.757 g.cm-3 (100 K) – is comparable to that of NGN (1.80 g.cm-3; Pace & Flippen-Anderson, 1984), and significantly higher than that of the three phases of GN (GN1, GN2 and GN3). The respective densities are for GN1: 1.458 g.cm-3 (153 K), 1.443 g.cm-3 (185 K), 1.421 g.cm-3 (257 K), 1.410 g.cm-3 (291 K), for GN2: 1.444 g.cm-3 (292 K), and for GN3: 1.400 (391 K) (Katrusiak & Szafrański, 1996).
NGN-GN contains one guanidinium and one nitroguanidinium ion and two nitrate counter-ions. The compound consists of alternating, perpendicular layers of guanidinium and nitroguanidinium cations.
The bond lengths in the guanidinium ion are similar to those found in guanidinium chloride (Haas et al., 1965). The geometry of the nitroguanidinium ion is similar to that in Bryden et al. (1956) and Pace & Flippen-Anderson (1984).
H-bonds in NGN-GN are medium to weak according to Jeffrey (1997). The only ring pattern observed is R2,2(8), and a variety of chain patterns are also observed: C2,2(6), C2,2(8) and C1,2(6) (Bernstein et al., 1995). An intramolecular H-bond is also present (N8–H10···O7).
For related literature and structures, see: Bryden et al. (1956); Haas et al. (1965); Hiskey et al. (2005); Katrusiak & Szafrański (1994, 1996); Pace & Flippen-Anderson (1984).
For related literature, see: Bernstein et al. (1995); Jeffrey (1997).
Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg & Putz, 2005) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 and ORTEP-3.
CH5N4O2+·CH6N3+·2NO3− | Z = 4 |
Mr = 289.17 | F(000) = 600 |
Monoclinic, Cc | Dx = 1.756 Mg m−3 |
Hall symbol: C -2yc | Mo Kα radiation, λ = 0.71073 Å |
a = 12.7337 (11) Å | θ = 4.1–30.0° |
b = 6.9096 (6) Å | µ = 0.17 mm−1 |
c = 13.7852 (13) Å | T = 100 K |
β = 115.623 (11)° | Block, colorless |
V = 1093.6 (2) Å3 | 0.29 × 0.2 × 0.17 mm |
Oxford Diffraction Xcalibur3 CCD area-detector diffractometer | 1586 independent reflections |
Radiation source: fine-focus sealed tube | 1116 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
ω scan | θmax = 30.0°, θmin = 4.1° |
Absorption correction: multi-scan (ABSPACK; Oxford Diffraction, 2006 or???2005) | h = −17→16 |
Tmin = 0.894, Tmax = 0.970 | k = −9→9 |
4546 measured reflections | l = −19→16 |
Refinement on F2 | 2 restraints |
Least-squares matrix: full | Only H-atom coordinates refined |
R[F2 > 2σ(F2)] = 0.028 | w = 1/[σ2(Fo2) + (0.0275P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.054 | (Δ/σ)max < 0.001 |
S = 0.88 | Δρmax = 0.16 e Å−3 |
1586 reflections | Δρmin = −0.21 e Å−3 |
205 parameters |
CH5N4O2+·CH6N3+·2NO3− | V = 1093.6 (2) Å3 |
Mr = 289.17 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 12.7337 (11) Å | µ = 0.17 mm−1 |
b = 6.9096 (6) Å | T = 100 K |
c = 13.7852 (13) Å | 0.29 × 0.2 × 0.17 mm |
β = 115.623 (11)° |
Oxford Diffraction Xcalibur3 CCD area-detector diffractometer | 1586 independent reflections |
Absorption correction: multi-scan (ABSPACK; Oxford Diffraction, 2006 or???2005) | 1116 reflections with I > 2σ(I) |
Tmin = 0.894, Tmax = 0.970 | Rint = 0.029 |
4546 measured reflections |
R[F2 > 2σ(F2)] = 0.028 | 2 restraints |
wR(F2) = 0.054 | Only H-atom coordinates refined |
S = 0.88 | Δρmax = 0.16 e Å−3 |
1586 reflections | Δρmin = −0.21 e Å−3 |
205 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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.08343 (17) | 0.1042 (3) | 0.20399 (16) | 0.0172 (4) | |
C2 | 0.34933 (15) | 0.2984 (3) | 0.14373 (16) | 0.0161 (4) | |
N1 | 0.18538 (15) | 0.0198 (3) | 0.26283 (17) | 0.0221 (4) | |
N2 | 0.03241 (17) | 0.2099 (3) | 0.25130 (16) | 0.0214 (4) | |
N3 | 0.03384 (16) | 0.0827 (3) | 0.09806 (15) | 0.0188 (4) | |
N4 | 0.24964 (13) | 0.8432 (3) | 0.03346 (13) | 0.0179 (4) | |
N5 | 0.01983 (14) | 0.5459 (3) | −0.02710 (14) | 0.0172 (4) | |
N6 | 0.30525 (15) | 0.2977 (3) | 0.03790 (14) | 0.0185 (4) | |
N7 | 0.28239 (16) | 0.3904 (3) | 0.18546 (14) | 0.0192 (4) | |
N8 | 0.44917 (14) | 0.2152 (3) | 0.20268 (15) | 0.0186 (4) | |
N9 | 0.31847 (14) | 0.4428 (3) | 0.29147 (14) | 0.0196 (4) | |
O1 | 0.06327 (12) | 0.5503 (2) | 0.07493 (11) | 0.0218 (4) | |
O2 | −0.07552 (12) | 0.6259 (2) | −0.08132 (11) | 0.0232 (4) | |
O3 | 0.07414 (12) | 0.4623 (2) | −0.07189 (11) | 0.0228 (4) | |
O4 | 0.14695 (12) | 0.9014 (2) | −0.01956 (12) | 0.0224 (4) | |
O5 | 0.30983 (12) | 0.7982 (2) | −0.01384 (12) | 0.0272 (4) | |
O6 | 0.29080 (12) | 0.8303 (2) | 0.13394 (12) | 0.0250 (4) | |
O7 | 0.41354 (12) | 0.3896 (2) | 0.35785 (12) | 0.0240 (4) | |
O8 | 0.24830 (12) | 0.5406 (2) | 0.30883 (12) | 0.0249 (4) | |
H1A | 0.217 (2) | 0.040 (4) | 0.332 (2) | 0.030* | |
H1B | 0.221 (2) | −0.049 (4) | 0.237 (2) | 0.030* | |
H2A | −0.026 (2) | 0.251 (4) | 0.217 (2) | 0.030* | |
H2B | 0.064 (2) | 0.216 (4) | 0.322 (2) | 0.030* | |
H3A | −0.031 (2) | 0.144 (3) | 0.065 (2) | 0.030* | |
H3B | 0.071 (2) | 0.029 (4) | 0.067 (2) | 0.030* | |
H7 | 0.347 (2) | 0.241 (4) | 0.010 (2) | 0.030* | |
H8 | 0.247 (2) | 0.366 (4) | 0.002 (2) | 0.030* | |
H9 | 0.486 (2) | 0.162 (4) | 0.170 (2) | 0.030* | |
H10 | 0.472 (2) | 0.206 (4) | 0.262 (2) | 0.030* | |
H11 | 0.219 (2) | 0.450 (4) | 0.143 (2) | 0.030* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0179 (9) | 0.0184 (11) | 0.0169 (11) | −0.0031 (9) | 0.0092 (9) | 0.0016 (9) |
C2 | 0.0173 (10) | 0.0144 (10) | 0.0167 (11) | −0.0025 (8) | 0.0075 (9) | 0.0022 (9) |
N1 | 0.0169 (8) | 0.0331 (12) | 0.0146 (9) | 0.0037 (8) | 0.0053 (7) | 0.0008 (9) |
N2 | 0.0197 (9) | 0.0282 (11) | 0.0141 (9) | 0.0051 (8) | 0.0052 (8) | −0.0002 (9) |
N3 | 0.0182 (9) | 0.0231 (10) | 0.0126 (9) | 0.0049 (8) | 0.0043 (7) | −0.0006 (8) |
N4 | 0.0167 (9) | 0.0192 (9) | 0.0166 (10) | −0.0025 (7) | 0.0061 (8) | −0.0009 (8) |
N5 | 0.0130 (8) | 0.0206 (10) | 0.0163 (10) | −0.0022 (7) | 0.0048 (7) | −0.0008 (8) |
N6 | 0.0187 (9) | 0.0233 (10) | 0.0114 (9) | 0.0021 (7) | 0.0047 (7) | 0.0005 (8) |
N7 | 0.0143 (8) | 0.0281 (10) | 0.0128 (10) | 0.0023 (7) | 0.0036 (7) | −0.0008 (8) |
N8 | 0.0170 (8) | 0.0262 (10) | 0.0131 (8) | 0.0024 (8) | 0.0070 (7) | 0.0017 (9) |
N9 | 0.0213 (10) | 0.0238 (10) | 0.0124 (9) | −0.0043 (7) | 0.0060 (8) | −0.0013 (8) |
O1 | 0.0197 (7) | 0.0304 (9) | 0.0130 (8) | 0.0030 (7) | 0.0050 (6) | 0.0013 (7) |
O2 | 0.0151 (7) | 0.0295 (8) | 0.0205 (8) | 0.0026 (7) | 0.0033 (6) | 0.0028 (7) |
O3 | 0.0194 (7) | 0.0291 (8) | 0.0192 (8) | 0.0030 (7) | 0.0078 (7) | −0.0025 (7) |
O4 | 0.0156 (7) | 0.0307 (9) | 0.0175 (8) | 0.0042 (6) | 0.0041 (6) | −0.0010 (7) |
O5 | 0.0219 (8) | 0.0424 (10) | 0.0206 (9) | 0.0074 (7) | 0.0123 (7) | 0.0028 (8) |
O6 | 0.0189 (7) | 0.0390 (10) | 0.0160 (8) | 0.0042 (7) | 0.0066 (6) | 0.0005 (7) |
O7 | 0.0167 (7) | 0.0375 (9) | 0.0156 (8) | −0.0007 (7) | 0.0049 (6) | 0.0002 (7) |
O8 | 0.0249 (7) | 0.0314 (8) | 0.0218 (8) | 0.0031 (7) | 0.0134 (6) | −0.0031 (8) |
C1—N2 | 1.322 (3) | N4—O6 | 1.254 (2) |
C1—N3 | 1.325 (3) | N4—O4 | 1.257 (2) |
C1—N1 | 1.332 (3) | N5—O2 | 1.246 (2) |
C2—N8 | 1.309 (3) | N5—O3 | 1.250 (2) |
C2—N6 | 1.317 (3) | N5—O1 | 1.270 (2) |
C2—N7 | 1.373 (3) | N6—H7 | 0.87 (3) |
N1—H1A | 0.87 (3) | N6—H8 | 0.84 (3) |
N1—H1B | 0.84 (3) | N7—N9 | 1.377 (2) |
N2—H2A | 0.75 (2) | N7—H11 | 0.87 (3) |
N2—H2B | 0.88 (3) | N8—H9 | 0.87 (3) |
N3—H3A | 0.86 (2) | N8—H10 | 0.74 (3) |
N3—H3B | 0.84 (3) | N9—O7 | 1.216 (2) |
N4—O5 | 1.241 (2) | N9—O8 | 1.224 (2) |
N2—C1—N3 | 120.3 (2) | O6—N4—O4 | 119.86 (18) |
N2—C1—N1 | 120.0 (2) | O2—N5—O3 | 120.81 (18) |
N3—C1—N1 | 119.8 (2) | O2—N5—O1 | 119.89 (19) |
N8—C2—N6 | 121.4 (2) | O3—N5—O1 | 119.30 (17) |
N8—C2—N7 | 123.7 (2) | C2—N6—H7 | 116.1 (16) |
N6—C2—N7 | 114.90 (18) | C2—N6—H8 | 119.8 (19) |
C1—N1—H1A | 117.5 (17) | H7—N6—H8 | 123 (3) |
C1—N1—H1B | 123.9 (17) | C2—N7—N9 | 125.70 (17) |
H1A—N1—H1B | 119 (2) | C2—N7—H11 | 120.4 (18) |
C1—N2—H2A | 118 (2) | N9—N7—H11 | 111.8 (18) |
C1—N2—H2B | 119.0 (17) | C2—N8—H9 | 117.6 (16) |
H2A—N2—H2B | 122 (3) | C2—N8—H10 | 123 (2) |
C1—N3—H3A | 114.5 (17) | H9—N8—H10 | 119 (3) |
C1—N3—H3B | 120.1 (18) | O7—N9—O8 | 126.37 (18) |
H3A—N3—H3B | 125 (3) | O7—N9—N7 | 119.05 (18) |
O5—N4—O6 | 120.27 (16) | O8—N9—N7 | 114.58 (16) |
O5—N4—O4 | 119.87 (17) | ||
N8—C2—N7—N9 | 13.7 (3) | C2—N7—N9—O7 | −7.4 (3) |
N6—C2—N7—N9 | −166.8 (2) | C2—N7—N9—O8 | 172.97 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O4i | 0.87 (3) | 2.59 (3) | 3.287 (3) | 138 (2) |
N1—H1A···O5i | 0.87 (3) | 2.23 (3) | 3.058 (3) | 157 (2) |
N1—H1B···O6ii | 0.84 (3) | 2.14 (3) | 2.956 (3) | 164 (2) |
N2—H2B···O3i | 0.88 (3) | 2.63 (3) | 3.199 (3) | 123 (2) |
N2—H2B···O4i | 0.88 (3) | 2.13 (3) | 2.952 (2) | 155 (2) |
N2—H2A···O6iii | 0.75 (2) | 2.17 (3) | 2.910 (2) | 169 (3) |
N3—H3B···O4ii | 0.84 (3) | 2.04 (3) | 2.880 (3) | 175 (3) |
N3—H3A···O5iii | 0.86 (2) | 2.13 (2) | 2.988 (2) | 179 (2) |
N6—H7···O2iv | 0.87 (3) | 2.07 (3) | 2.928 (3) | 170 (2) |
N6—H8···O3 | 0.84 (3) | 2.09 (3) | 2.897 (2) | 161 (2) |
N7—H11···O1 | 0.87 (3) | 1.92 (3) | 2.766 (2) | 165 (3) |
N8—H9···O1iv | 0.87 (3) | 2.09 (3) | 2.954 (3) | 174 (2) |
N8—H10···O3v | 0.74 (3) | 2.39 (3) | 3.069 (2) | 153 (3) |
N8—H10···O7 | 0.74 (3) | 2.19 (3) | 2.660 (3) | 122 (3) |
Symmetry codes: (i) x, −y+1, z+1/2; (ii) x, y−1, z; (iii) x−1/2, y−1/2, z; (iv) x+1/2, y−1/2, z; (v) x+1/2, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | CH5N4O2+·CH6N3+·2NO3− |
Mr | 289.17 |
Crystal system, space group | Monoclinic, Cc |
Temperature (K) | 100 |
a, b, c (Å) | 12.7337 (11), 6.9096 (6), 13.7852 (13) |
β (°) | 115.623 (11) |
V (Å3) | 1093.6 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.17 |
Crystal size (mm) | 0.29 × 0.2 × 0.17 |
Data collection | |
Diffractometer | Oxford Diffraction Xcalibur3 CCD area-detector |
Absorption correction | Multi-scan (ABSPACK; Oxford Diffraction, 2006 or???2005) |
Tmin, Tmax | 0.894, 0.970 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4546, 1586, 1116 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.703 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.054, 0.88 |
No. of reflections | 1586 |
No. of parameters | 205 |
No. of restraints | 2 |
H-atom treatment | Only H-atom coordinates refined |
Δρmax, Δρmin (e Å−3) | 0.16, −0.21 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), CrysAlis RED, SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg & Putz, 2005) and ORTEP-3 (Farrugia, 1997), SHELXL97 and ORTEP-3.
C1—N2 | 1.322 (3) | N4—O6 | 1.254 (2) |
C1—N3 | 1.325 (3) | N4—O4 | 1.257 (2) |
C1—N1 | 1.332 (3) | N7—N9 | 1.377 (2) |
C2—N8 | 1.309 (3) | N9—O7 | 1.216 (2) |
C2—N6 | 1.317 (3) | N9—O8 | 1.224 (2) |
N4—O5 | 1.241 (2) | ||
N2—C1—N3 | 120.3 (2) | O5—N4—O4 | 119.87 (17) |
N2—C1—N1 | 120.0 (2) | O6—N4—O4 | 119.86 (18) |
N3—C1—N1 | 119.8 (2) | C2—N7—N9 | 125.70 (17) |
N8—C2—N6 | 121.4 (2) | O7—N9—O8 | 126.37 (18) |
N8—C2—N7 | 123.7 (2) | O7—N9—N7 | 119.05 (18) |
N6—C2—N7 | 114.90 (18) | O8—N9—N7 | 114.58 (16) |
O5—N4—O6 | 120.27 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O4i | 0.87 (3) | 2.59 (3) | 3.287 (3) | 138 (2) |
N1—H1A···O5i | 0.87 (3) | 2.23 (3) | 3.058 (3) | 157 (2) |
N1—H1B···O6ii | 0.84 (3) | 2.14 (3) | 2.956 (3) | 164 (2) |
N2—H2B···O3i | 0.88 (3) | 2.63 (3) | 3.199 (3) | 123 (2) |
N2—H2B···O4i | 0.88 (3) | 2.13 (3) | 2.952 (2) | 155 (2) |
N2—H2A···O6iii | 0.75 (2) | 2.17 (3) | 2.910 (2) | 169 (3) |
N3—H3B···O4ii | 0.84 (3) | 2.04 (3) | 2.880 (3) | 175 (3) |
N3—H3A···O5iii | 0.86 (2) | 2.13 (2) | 2.988 (2) | 179 (2) |
N6—H7···O2iv | 0.87 (3) | 2.07 (3) | 2.928 (3) | 170 (2) |
N6—H8···O3 | 0.84 (3) | 2.09 (3) | 2.897 (2) | 161 (2) |
N7—H11···O1 | 0.87 (3) | 1.92 (3) | 2.766 (2) | 165 (3) |
N8—H9···O1iv | 0.87 (3) | 2.09 (3) | 2.954 (3) | 174 (2) |
N8—H10···O3v | 0.74 (3) | 2.39 (3) | 3.069 (2) | 153 (3) |
N8—H10···O7 | 0.74 (3) | 2.19 (3) | 2.660 (3) | 122 (3) |
Symmetry codes: (i) x, −y+1, z+1/2; (ii) x, y−1, z; (iii) x−1/2, y−1/2, z; (iv) x+1/2, y−1/2, z; (v) x+1/2, −y+1/2, z+1/2. |
Guanidinium and nitroguanidinium compounds are objects of investigation for a possible application as energetic materials (e.g., Hiskey et al., 2005; Pace & Flippen-Anderson, 1984). The crystal structures of guanidinium nitrate (GN) (Katrusiak & Szafrański, 1994, 1996) and nitroguanidinium nitrate (NGN) (Pace & Flippen-Anderson, 1984) have been determined previously. Here, we report the structure of a new nitroguanidinium nitrate-guanidinium nitrate (NGN-GN) double salt.
As for every potential energetic material, a high density is desired. The density of NGN-GN – 1.757 g.cm-3 (100 K) – is comparable to that of NGN (1.80 g.cm-3; Pace & Flippen-Anderson, 1984), and significantly higher than that of the three phases of GN (GN1, GN2 and GN3). The respective densities are for GN1: 1.458 g.cm-3 (153 K), 1.443 g.cm-3 (185 K), 1.421 g.cm-3 (257 K), 1.410 g.cm-3 (291 K), for GN2: 1.444 g.cm-3 (292 K), and for GN3: 1.400 (391 K) (Katrusiak & Szafrański, 1996).
NGN-GN contains one guanidinium and one nitroguanidinium ion and two nitrate counter-ions. The compound consists of alternating, perpendicular layers of guanidinium and nitroguanidinium cations.
The bond lengths in the guanidinium ion are similar to those found in guanidinium chloride (Haas et al., 1965). The geometry of the nitroguanidinium ion is similar to that in Bryden et al. (1956) and Pace & Flippen-Anderson (1984).
H-bonds in NGN-GN are medium to weak according to Jeffrey (1997). The only ring pattern observed is R2,2(8), and a variety of chain patterns are also observed: C2,2(6), C2,2(8) and C1,2(6) (Bernstein et al., 1995). An intramolecular H-bond is also present (N8–H10···O7).