Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807054839/at2464sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807054839/at2464Isup2.hkl |
CCDC reference: 674082
A mixture of C6F5B(NMe2)2 (0.266 g) and [Znpz4(NO3)2] (Vitze et al., 2006) in 6 ml tetrahydrofuran and 6 ml NEt3 was refluxed for 1 h. After removal of the solvent in vacuo the residue was extracted with tetrahydrofuran. Layering with hexane led to the deposition of crystals of H2NMe2NO3 at ambient temperature.
All H atoms could be located by difference Fourier synthesis. They were refined with fixed individual displacement parameters [Uiso(H) = 1.2 Ueq(N) or Uiso(H) = 1.5 Ueq(C)] using a riding model with N—H = 0.92 Å or C—H = 0.98 Å, respectively. In the absence of anomalous scatterers, the Flack (1983) parameter is meaningless and therefore, Friedel pairs had been merged prior to refinement.
Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PLATON (Spek, 2003).
C2H8N+·NO3− | F(000) = 232 |
Mr = 108.10 | Dx = 1.291 Mg m−3 |
Orthorhombic, Pna21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2n | Cell parameters from 3599 reflections |
a = 9.9552 (18) Å | θ = 4.1–25.4° |
b = 9.7684 (12) Å | µ = 0.12 mm−1 |
c = 5.7191 (7) Å | T = 173 K |
V = 556.16 (14) Å3 | Plate, colourless |
Z = 4 | 0.37 × 0.17 × 0.08 mm |
STOE IPDS II two-circle- diffractometer | 492 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.081 |
Graphite monochromator | θmax = 25.3°, θmin = 4.1° |
ω scans | h = −11→10 |
4065 measured reflections | k = −11→10 |
557 independent reflections | l = −6→6 |
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)] = 0.036 | H-atom parameters constrained |
wR(F2) = 0.087 | w = 1/[σ2(Fo2) + (0.0532P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
557 reflections | Δρmax = 0.14 e Å−3 |
65 parameters | Δρmin = −0.12 e Å−3 |
1 restraint | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.042 (13) |
C2H8N+·NO3− | V = 556.16 (14) Å3 |
Mr = 108.10 | Z = 4 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 9.9552 (18) Å | µ = 0.12 mm−1 |
b = 9.7684 (12) Å | T = 173 K |
c = 5.7191 (7) Å | 0.37 × 0.17 × 0.08 mm |
STOE IPDS II two-circle- diffractometer | 492 reflections with I > 2σ(I) |
4065 measured reflections | Rint = 0.081 |
557 independent reflections |
R[F2 > 2σ(F2)] = 0.036 | 1 restraint |
wR(F2) = 0.087 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.14 e Å−3 |
557 reflections | Δρmin = −0.12 e Å−3 |
65 parameters |
Experimental. ; |
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 | ||
N1 | 0.4727 (2) | 0.2067 (2) | 0.4304 (4) | 0.0357 (5) | |
O1 | 0.52001 (19) | 0.1106 (2) | 0.3073 (4) | 0.0427 (6) | |
O2 | 0.5451 (2) | 0.2631 (2) | 0.5812 (4) | 0.0460 (6) | |
O3 | 0.3538 (2) | 0.2435 (2) | 0.3993 (5) | 0.0614 (8) | |
C1 | 0.3170 (4) | 0.5648 (3) | 0.5141 (6) | 0.0487 (8) | |
H1A | 0.2722 | 0.5897 | 0.3676 | 0.073* | |
H1B | 0.3991 | 0.5133 | 0.4793 | 0.073* | |
H1C | 0.3401 | 0.6481 | 0.6007 | 0.073* | |
N2 | 0.2255 (2) | 0.4789 (2) | 0.6577 (4) | 0.0348 (6) | |
H2A | 0.2021 | 0.4022 | 0.5736 | 0.042* | |
H2B | 0.1482 | 0.5274 | 0.6879 | 0.042* | |
C2 | 0.2866 (3) | 0.4355 (3) | 0.8836 (5) | 0.0452 (7) | |
H2C | 0.2221 | 0.3794 | 0.9708 | 0.068* | |
H2D | 0.3099 | 0.5166 | 0.9758 | 0.068* | |
H2E | 0.3679 | 0.3819 | 0.8527 | 0.068* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0295 (11) | 0.0322 (12) | 0.0452 (13) | −0.0013 (9) | −0.0008 (12) | −0.0014 (11) |
O1 | 0.0356 (11) | 0.0484 (13) | 0.0440 (10) | 0.0081 (9) | 0.0035 (9) | −0.0096 (10) |
O2 | 0.0388 (11) | 0.0438 (12) | 0.0556 (14) | −0.0041 (9) | −0.0129 (10) | −0.0129 (10) |
O3 | 0.0350 (12) | 0.0566 (15) | 0.0927 (19) | 0.0132 (9) | −0.0180 (13) | −0.0332 (14) |
C1 | 0.0600 (19) | 0.0417 (16) | 0.0444 (17) | −0.0017 (15) | 0.0152 (15) | −0.0015 (14) |
N2 | 0.0331 (11) | 0.0348 (12) | 0.0364 (12) | −0.0030 (9) | 0.0031 (10) | −0.0093 (10) |
C2 | 0.0510 (17) | 0.0467 (17) | 0.0379 (16) | −0.0021 (14) | 0.0003 (13) | 0.0014 (13) |
N1—O3 | 1.249 (3) | N2—C2 | 1.489 (4) |
N1—O2 | 1.252 (3) | N2—H2A | 0.9200 |
N1—O1 | 1.264 (3) | N2—H2B | 0.9200 |
C1—N2 | 1.487 (4) | C2—H2C | 0.9800 |
C1—H1A | 0.9800 | C2—H2D | 0.9800 |
C1—H1B | 0.9800 | C2—H2E | 0.9800 |
C1—H1C | 0.9800 | ||
O3—N1—O2 | 121.1 (3) | C2—N2—H2A | 109.0 |
O3—N1—O1 | 119.2 (2) | C1—N2—H2B | 109.0 |
O2—N1—O1 | 119.7 (2) | C2—N2—H2B | 109.0 |
N2—C1—H1A | 109.5 | H2A—N2—H2B | 107.8 |
N2—C1—H1B | 109.5 | N2—C2—H2C | 109.5 |
H1A—C1—H1B | 109.5 | N2—C2—H2D | 109.5 |
N2—C1—H1C | 109.5 | H2C—C2—H2D | 109.5 |
H1A—C1—H1C | 109.5 | N2—C2—H2E | 109.5 |
H1B—C1—H1C | 109.5 | H2C—C2—H2E | 109.5 |
C1—N2—C2 | 112.9 (2) | H2D—C2—H2E | 109.5 |
C1—N2—H2A | 109.0 |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O3 | 0.92 | 2.38 | 3.018 (3) | 126 |
N2—H2B···O1i | 0.92 | 1.98 | 2.892 (3) | 169 |
N2—H2B···O3i | 0.92 | 2.43 | 3.035 (3) | 123 |
N2—H2A···O1ii | 0.92 | 2.37 | 2.994 (3) | 125 |
N2—H2A···O2ii | 0.92 | 2.25 | 3.000 (3) | 139 |
Symmetry codes: (i) −x+1/2, y+1/2, z+1/2; (ii) x−1/2, −y+1/2, z. |
Experimental details
Crystal data | |
Chemical formula | C2H8N+·NO3− |
Mr | 108.10 |
Crystal system, space group | Orthorhombic, Pna21 |
Temperature (K) | 173 |
a, b, c (Å) | 9.9552 (18), 9.7684 (12), 5.7191 (7) |
V (Å3) | 556.16 (14) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.37 × 0.17 × 0.08 |
Data collection | |
Diffractometer | STOE IPDS II two-circle- diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4065, 557, 492 |
Rint | 0.081 |
(sin θ/λ)max (Å−1) | 0.601 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.087, 1.07 |
No. of reflections | 557 |
No. of parameters | 65 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.14, −0.12 |
Computer programs: X-AREA (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP in SHELXTL-Plus (Sheldrick, 1991), SHELXL97 (Sheldrick, 1997) and PLATON (Spek, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O3 | 0.92 | 2.38 | 3.018 (3) | 126.0 |
N2—H2B···O1i | 0.92 | 1.98 | 2.892 (3) | 169.2 |
N2—H2B···O3i | 0.92 | 2.43 | 3.035 (3) | 123.2 |
N2—H2A···O1ii | 0.92 | 2.37 | 2.994 (3) | 124.9 |
N2—H2A···O2ii | 0.92 | 2.25 | 3.000 (3) | 138.6 |
Symmetry codes: (i) −x+1/2, y+1/2, z+1/2; (ii) x−1/2, −y+1/2, z. |
Poly(pyrazol-1-yl)borates ("scorpionates") are among the most important ligands in transition metal chemistry and were invented by Trofimenko more than 30 years ago (Trofimenko, 1993). Recently, we have extended our studies to ditopic scorpionates with meta- and para-phenylene backbones. Our studies have shown that the synthesis of scorpionates can conveniently be achieved by reaction of bis(dimethylamino)arylboranes and pyrazole or pyrazole derivatives in the presence of bases (Bieller et al., 2005; Zhang et al., 2004). In attempting to synthesize a zinc complex with the [C6F5Bpz3] ligand (pz = pyrazolyl) from C6F5B(NMe2)2 (Me = CH3) and [Znpz4(NO3)2] (Vitze et al., 2006) we obtained the title compound, H2NMe2NO3, as a by-product. Single crystals of H2NMe2NO3 were obtained from a mixture of tetrahydrofuran/hexane at ambient temperature.
The title compound is composed of discrete cations and anions (Fig. 1) which are connected by classical N—H···O hydrogen bonds. Two of the nitrate O atoms accept two hydrogen bonds, whereas the third one just accepts one (Fig. 2). Geometric parameters are in the usual ranges.