Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680704442X/rn2027sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680704442X/rn2027Isup2.hkl |
CCDC reference: 663768
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.004 Å
- R factor = 0.036
- wR factor = 0.097
- Data-to-parameter ratio = 14.0
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT027_ALERT_3_B _diffrn_reflns_theta_full (too) Low ............ 24.99 Deg. PLAT111_ALERT_2_B ADDSYM Detects (Pseudo) Centre of Symmetry ..... 90 PerFi
Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C4
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 24.99 From the CIF: _reflns_number_total 3003 Count of symmetry unique reflns 1662 Completeness (_total/calc) 180.69% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1341 Fraction of Friedel pairs measured 0.807 Are heavy atom types Z>Si present yes PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT791_ALERT_1_G Confirm the Absolute Configuration of C2 = . R PLAT791_ALERT_1_G Confirm the Absolute Configuration of C5 = . S PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 2 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 6 ALERT level G = General alerts; check 5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
Aqueous solutions of tetrahydro-pyrimidin-2-ylidene-amine and camphor-10-sulfonic acid were mixed in stoichiometric quantities leading to a clear solution. Colourless faceted chunks of (I) grew over a few days as the water slowly evaporated.
A PLATON/checkcif analysis of (I) indicated pseudosymmetry at the 90% level. However, a centre of symmetry cannot be compatible with the chiral anion.
The N-bound H atoms were located in a difference map and their positions were freely refined with Uiso(H) = 1.2Ueq(N).
The C-bound H atoms were placed geometrically (C—H = 0.93–0.96 Å) and refined as riding with Uiso(H) = 1.2Ueq(carrier) or 1.5Ueq(methyl C). The methyl groups were allowed to rotate, but not to tip, to best fit the electron density.
The title compound, (I), is a molecular salt (Fig. 1). The C—N bond lengths in the cation [C11—N2 = 1.319 (5) Å, C11—N1 = 1.330 (3) Å, C11—N3 = 1.332 (5) Å] indicate delocalization of the electrons in the nominal C—N single bonds and C═N+ double bond (see scheme) in a similar fashion to that seen in the CN3H6+ guanidinium cation. The bond angle sum at C11 is exactly 360°. The conformation of the six-membered ring of the cation is well described as an envelope, with C13 displaced by 0.632 (4) Å from C11/C12/C14/N2/N3 (r.m.s. deviation for these atoms = 0.002 Å). The configurations of the chiral carbon atoms in the camphor sulfonate anion are: C2 R and C5 S. Otherwise, (I) displays normal geometrical parameters (Allen et al., 1995).
In the crystal of (I), the components interact by way of N—H···O hydrogen bonds (Table 1) leading to infinite chains propagating in [010], with every cation and anion linked by two N—H···O bonds (Fig. 2), resulting in graph-theory (Bernstein et al., 1995) R22(8) loops.
For background, see: Bernstein et al. (1995). For reference structural data, see: Allen et al. (1995).
Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
C4H10N3+·C10H15O4S− | F(000) = 356 |
Mr = 331.43 | Dx = 1.267 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 3004 reflections |
a = 7.4207 (4) Å | θ = 2.8–25.0° |
b = 7.3115 (4) Å | µ = 0.21 mm−1 |
c = 16.421 (1) Å | T = 293 K |
β = 102.899 (1)° | Faceted chunk, colourless |
V = 868.46 (9) Å3 | 0.32 × 0.26 × 0.17 mm |
Z = 2 |
Bruker SMART 1000 CCD diffractometer | 3003 independent reflections |
Radiation source: fine-focus sealed tube | 2630 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
ω scans | θmax = 25.0°, θmin = 1.3° |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | h = −8→8 |
Tmin = 0.860, Tmax = 0.967 | k = −8→8 |
5301 measured reflections | l = −16→19 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difmap and geom |
R[F2 > 2σ(F2)] = 0.036 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.097 | w = 1/[σ2(Fo2) + (0.0532P)2 + 0.0964P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max < 0.001 |
3003 reflections | Δρmax = 0.15 e Å−3 |
214 parameters | Δρmin = −0.30 e Å−3 |
1 restraint | Absolute structure: Flack (1983), with 1341 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.17 (9) |
C4H10N3+·C10H15O4S− | V = 868.46 (9) Å3 |
Mr = 331.43 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 7.4207 (4) Å | µ = 0.21 mm−1 |
b = 7.3115 (4) Å | T = 293 K |
c = 16.421 (1) Å | 0.32 × 0.26 × 0.17 mm |
β = 102.899 (1)° |
Bruker SMART 1000 CCD diffractometer | 3003 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | 2630 reflections with I > 2σ(I) |
Tmin = 0.860, Tmax = 0.967 | Rint = 0.017 |
5301 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.097 | Δρmax = 0.15 e Å−3 |
S = 1.09 | Δρmin = −0.30 e Å−3 |
3003 reflections | Absolute structure: Flack (1983), with 1341 Friedel pairs |
214 parameters | Absolute structure parameter: 0.17 (9) |
1 restraint |
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 | ||
C1 | 0.5794 (3) | 0.3098 (6) | 0.20808 (13) | 0.0443 (5) | |
H1A | 0.4756 | 0.2258 | 0.1970 | 0.053* | |
H1B | 0.5307 | 0.4301 | 0.1904 | 0.053* | |
C2 | 0.7072 (3) | 0.2553 (3) | 0.15159 (16) | 0.0429 (6) | |
C3 | 0.6026 (4) | 0.2795 (4) | 0.06007 (18) | 0.0592 (9) | |
C4 | 0.7455 (5) | 0.2783 (7) | 0.00768 (19) | 0.0804 (13) | |
H41 | 0.7483 | 0.3941 | −0.0209 | 0.096* | |
H42 | 0.7233 | 0.1802 | −0.0331 | 0.096* | |
C5 | 0.9240 (5) | 0.2470 (4) | 0.07361 (19) | 0.0636 (8) | |
H51 | 1.0374 | 0.2795 | 0.0557 | 0.062 (8)* | |
C6 | 0.9151 (5) | 0.0456 (5) | 0.1020 (2) | 0.0736 (10) | |
H61 | 0.8800 | −0.0355 | 0.0543 | 0.088* | |
H62 | 1.0330 | 0.0063 | 0.1359 | 0.088* | |
C7 | 0.7654 (5) | 0.0506 (4) | 0.1535 (2) | 0.0567 (7) | |
H71 | 0.8148 | 0.0100 | 0.2104 | 0.068* | |
H72 | 0.6612 | −0.0263 | 0.1285 | 0.068* | |
C8 | 0.8908 (4) | 0.3566 (4) | 0.14960 (17) | 0.0496 (8) | |
C9 | 0.8664 (5) | 0.5612 (4) | 0.1348 (3) | 0.0729 (10) | |
H91 | 0.9728 | 0.6098 | 0.1181 | 0.109* | |
H92 | 0.8529 | 0.6199 | 0.1854 | 0.109* | |
H93 | 0.7581 | 0.5833 | 0.0916 | 0.109* | |
C10 | 1.0493 (3) | 0.3306 (7) | 0.22651 (17) | 0.0639 (7) | |
H101 | 1.1640 | 0.3649 | 0.2130 | 0.096* | |
H102 | 1.0550 | 0.2046 | 0.2434 | 0.096* | |
H103 | 1.0280 | 0.4059 | 0.2713 | 0.096* | |
S1 | 0.66387 (7) | 0.31798 (11) | 0.31831 (3) | 0.03870 (15) | |
O1 | 0.7694 (3) | 0.4848 (3) | 0.33660 (15) | 0.0523 (6) | |
O2 | 0.7726 (3) | 0.1533 (3) | 0.34393 (14) | 0.0505 (6) | |
O3 | 0.4966 (2) | 0.3208 (4) | 0.35201 (10) | 0.0505 (4) | |
O4 | 0.4382 (3) | 0.2951 (6) | 0.03598 (13) | 0.0893 (8) | |
C11 | 0.4246 (3) | 0.8182 (6) | 0.38435 (16) | 0.0498 (5) | |
C12 | 0.1889 (5) | 0.6527 (5) | 0.4365 (2) | 0.0538 (9) | |
H12A | 0.2267 | 0.6427 | 0.4969 | 0.065* | |
H12B | 0.1168 | 0.5452 | 0.4156 | 0.065* | |
C13 | 0.0735 (3) | 0.8206 (6) | 0.41374 (18) | 0.0586 (6) | |
H13A | −0.0258 | 0.8211 | 0.4435 | 0.070* | |
H13B | 0.0185 | 0.8195 | 0.3543 | 0.070* | |
C14 | 0.1890 (4) | 0.9908 (4) | 0.4354 (2) | 0.0505 (8) | |
H14A | 0.1171 | 1.0976 | 0.4131 | 0.061* | |
H14B | 0.2262 | 1.0039 | 0.4956 | 0.061* | |
N1 | 0.5722 (3) | 0.8172 (6) | 0.3510 (2) | 0.0822 (9) | |
H1 | 0.629 (6) | 0.699 (7) | 0.345 (3) | 0.099* | |
H2 | 0.627 (7) | 0.906 (7) | 0.350 (3) | 0.099* | |
N2 | 0.3515 (4) | 0.6619 (4) | 0.4010 (2) | 0.0517 (8) | |
H3 | 0.378 (4) | 0.570 (5) | 0.383 (2) | 0.062* | |
N3 | 0.3521 (4) | 0.9775 (4) | 0.4001 (2) | 0.0527 (8) | |
H4 | 0.408 (5) | 1.070 (5) | 0.394 (2) | 0.063* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0366 (10) | 0.0506 (13) | 0.0443 (11) | 0.0004 (17) | 0.0063 (9) | −0.0012 (17) |
C2 | 0.0437 (13) | 0.0438 (14) | 0.0405 (13) | 0.0009 (10) | 0.0080 (10) | −0.0017 (10) |
C3 | 0.0616 (17) | 0.063 (3) | 0.0484 (15) | −0.0021 (15) | 0.0024 (12) | −0.0016 (14) |
C4 | 0.093 (2) | 0.106 (4) | 0.0437 (15) | −0.007 (2) | 0.0184 (15) | −0.0050 (19) |
C5 | 0.0656 (18) | 0.077 (2) | 0.0562 (17) | −0.0009 (15) | 0.0305 (15) | 0.0032 (15) |
C6 | 0.095 (3) | 0.065 (2) | 0.073 (2) | 0.012 (2) | 0.045 (2) | −0.0148 (18) |
C7 | 0.0696 (19) | 0.0443 (16) | 0.0607 (19) | −0.0002 (15) | 0.0238 (15) | −0.0062 (14) |
C8 | 0.0461 (13) | 0.052 (2) | 0.0529 (14) | 0.0002 (12) | 0.0152 (11) | 0.0028 (12) |
C9 | 0.080 (2) | 0.0486 (19) | 0.093 (3) | −0.0117 (18) | 0.024 (2) | 0.0163 (19) |
C10 | 0.0382 (12) | 0.089 (2) | 0.0655 (16) | 0.007 (2) | 0.0128 (11) | 0.001 (2) |
S1 | 0.0374 (3) | 0.0358 (3) | 0.0450 (3) | 0.0025 (4) | 0.0135 (2) | −0.0019 (4) |
O1 | 0.0490 (14) | 0.0429 (12) | 0.0678 (16) | −0.0062 (11) | 0.0189 (11) | −0.0168 (11) |
O2 | 0.0507 (14) | 0.0494 (13) | 0.0523 (13) | 0.0151 (11) | 0.0134 (11) | 0.0076 (10) |
O3 | 0.0512 (8) | 0.0438 (8) | 0.0642 (10) | 0.0014 (14) | 0.0293 (7) | −0.0024 (13) |
O4 | 0.0631 (12) | 0.134 (2) | 0.0595 (12) | −0.004 (2) | −0.0109 (10) | −0.0016 (19) |
C11 | 0.0422 (11) | 0.0410 (11) | 0.0669 (14) | −0.003 (2) | 0.0134 (10) | −0.004 (2) |
C12 | 0.054 (2) | 0.053 (2) | 0.057 (2) | −0.0091 (17) | 0.0194 (17) | −0.0034 (17) |
C13 | 0.0465 (12) | 0.0590 (15) | 0.0738 (16) | 0.000 (2) | 0.0210 (11) | −0.002 (2) |
C14 | 0.047 (2) | 0.045 (2) | 0.060 (2) | 0.0069 (15) | 0.0136 (16) | −0.0022 (16) |
N1 | 0.0653 (14) | 0.0459 (13) | 0.153 (3) | −0.001 (2) | 0.0619 (16) | −0.001 (3) |
N2 | 0.0480 (18) | 0.0379 (17) | 0.072 (2) | 0.0020 (14) | 0.0194 (15) | −0.0073 (14) |
N3 | 0.051 (2) | 0.0336 (16) | 0.078 (2) | 0.0030 (14) | 0.0253 (16) | −0.0037 (14) |
C1—C2 | 1.520 (3) | C9—H93 | 0.9600 |
C1—S1 | 1.779 (2) | C10—H101 | 0.9600 |
C1—H1A | 0.9700 | C10—H102 | 0.9600 |
C1—H1B | 0.9700 | C10—H103 | 0.9600 |
C2—C3 | 1.540 (4) | S1—O1 | 1.444 (2) |
C2—C7 | 1.556 (4) | S1—O2 | 1.458 (2) |
C2—C8 | 1.558 (3) | S1—O3 | 1.4678 (14) |
C3—O4 | 1.201 (3) | C11—N2 | 1.319 (5) |
C3—C4 | 1.507 (4) | C11—N1 | 1.330 (3) |
C4—C5 | 1.529 (5) | C11—N3 | 1.332 (5) |
C4—H41 | 0.9700 | C12—N2 | 1.454 (4) |
C4—H42 | 0.9700 | C12—C13 | 1.496 (5) |
C5—C8 | 1.548 (4) | C12—H12A | 0.9700 |
C5—C6 | 1.550 (5) | C12—H12B | 0.9700 |
C5—H51 | 0.9800 | C13—C14 | 1.508 (5) |
C6—C7 | 1.540 (4) | C13—H13A | 0.9700 |
C6—H61 | 0.9700 | C13—H13B | 0.9700 |
C6—H62 | 0.9700 | C14—N3 | 1.458 (4) |
C7—H71 | 0.9700 | C14—H14A | 0.9700 |
C7—H72 | 0.9700 | C14—H14B | 0.9700 |
C8—C9 | 1.520 (4) | N1—H1 | 0.98 (5) |
C8—C10 | 1.533 (4) | N1—H2 | 0.77 (5) |
C9—H91 | 0.9600 | N2—H3 | 0.78 (4) |
C9—H92 | 0.9600 | N3—H4 | 0.81 (4) |
C2—C1—S1 | 120.23 (15) | H91—C9—H92 | 109.5 |
C2—C1—H1A | 107.3 | C8—C9—H93 | 109.5 |
S1—C1—H1A | 107.3 | H91—C9—H93 | 109.5 |
C2—C1—H1B | 107.3 | H92—C9—H93 | 109.5 |
S1—C1—H1B | 107.3 | C8—C10—H101 | 109.5 |
H1A—C1—H1B | 106.9 | C8—C10—H102 | 109.5 |
C1—C2—C3 | 108.6 (2) | H101—C10—H102 | 109.5 |
C1—C2—C7 | 116.6 (2) | C8—C10—H103 | 109.5 |
C3—C2—C7 | 102.0 (2) | H101—C10—H103 | 109.5 |
C1—C2—C8 | 123.8 (2) | H102—C10—H103 | 109.5 |
C3—C2—C8 | 100.2 (2) | O1—S1—O2 | 113.46 (10) |
C7—C2—C8 | 102.6 (2) | O1—S1—O3 | 112.00 (13) |
O4—C3—C4 | 127.2 (3) | O2—S1—O3 | 111.28 (14) |
O4—C3—C2 | 125.9 (3) | O1—S1—C1 | 106.94 (16) |
C4—C3—C2 | 106.9 (2) | O2—S1—C1 | 108.20 (15) |
C3—C4—C5 | 101.8 (2) | O3—S1—C1 | 104.38 (10) |
C3—C4—H41 | 111.4 | N2—C11—N1 | 119.7 (4) |
C5—C4—H41 | 111.4 | N2—C11—N3 | 120.9 (2) |
C3—C4—H42 | 111.4 | N1—C11—N3 | 119.4 (4) |
C5—C4—H42 | 111.4 | N2—C12—C13 | 110.0 (3) |
H41—C4—H42 | 109.3 | N2—C12—H12A | 109.7 |
C4—C5—C8 | 103.0 (3) | C13—C12—H12A | 109.7 |
C4—C5—C6 | 105.5 (3) | N2—C12—H12B | 109.7 |
C8—C5—C6 | 103.0 (2) | C13—C12—H12B | 109.7 |
C4—C5—H51 | 114.7 | H12A—C12—H12B | 108.2 |
C8—C5—H51 | 114.7 | C12—C13—C14 | 110.76 (19) |
C6—C5—H51 | 114.7 | C12—C13—H13A | 109.5 |
C7—C6—C5 | 103.1 (2) | C14—C13—H13A | 109.5 |
C7—C6—H61 | 111.1 | C12—C13—H13B | 109.5 |
C5—C6—H61 | 111.1 | C14—C13—H13B | 109.5 |
C7—C6—H62 | 111.1 | H13A—C13—H13B | 108.1 |
C5—C6—H62 | 111.1 | N3—C14—C13 | 109.3 (2) |
H61—C6—H62 | 109.1 | N3—C14—H14A | 109.8 |
C6—C7—C2 | 104.0 (2) | C13—C14—H14A | 109.8 |
C6—C7—H71 | 111.0 | N3—C14—H14B | 109.8 |
C2—C7—H71 | 111.0 | C13—C14—H14B | 109.8 |
C6—C7—H72 | 111.0 | H14A—C14—H14B | 108.3 |
C2—C7—H72 | 111.0 | C11—N1—H1 | 118 (3) |
H71—C7—H72 | 109.0 | C11—N1—H2 | 120 (4) |
C9—C8—C10 | 107.2 (3) | H1—N1—H2 | 120 (3) |
C9—C8—C5 | 114.6 (3) | C11—N2—C12 | 122.7 (3) |
C10—C8—C5 | 111.6 (3) | C11—N2—H3 | 121 (3) |
C9—C8—C2 | 113.4 (2) | C12—N2—H3 | 114 (3) |
C10—C8—C2 | 115.9 (2) | C11—N3—C14 | 122.9 (3) |
C5—C8—C2 | 93.9 (2) | C11—N3—H4 | 118 (3) |
C8—C9—H91 | 109.5 | C14—N3—H4 | 119 (3) |
C8—C9—H92 | 109.5 | ||
S1—C1—C2—C3 | −174.3 (2) | C4—C5—C8—C2 | 55.4 (3) |
S1—C1—C2—C7 | 71.4 (3) | C6—C5—C8—C2 | −54.1 (3) |
S1—C1—C2—C8 | −57.5 (4) | C1—C2—C8—C9 | −53.8 (3) |
C1—C2—C3—O4 | −16.5 (5) | C3—C2—C8—C9 | 66.8 (3) |
C7—C2—C3—O4 | 107.2 (4) | C7—C2—C8—C9 | 171.7 (3) |
C8—C2—C3—O4 | −147.5 (4) | C1—C2—C8—C10 | 70.9 (3) |
C1—C2—C3—C4 | 163.9 (3) | C3—C2—C8—C10 | −168.5 (3) |
C7—C2—C3—C4 | −72.5 (3) | C7—C2—C8—C10 | −63.6 (3) |
C8—C2—C3—C4 | 32.8 (3) | C1—C2—C8—C5 | −172.8 (2) |
O4—C3—C4—C5 | −177.9 (4) | C3—C2—C8—C5 | −52.1 (2) |
C2—C3—C4—C5 | 1.8 (4) | C7—C2—C8—C5 | 52.7 (2) |
C3—C4—C5—C8 | −36.4 (3) | C2—C1—S1—O1 | 77.3 (3) |
C3—C4—C5—C6 | 71.2 (3) | C2—C1—S1—O2 | −45.2 (3) |
C4—C5—C6—C7 | −71.9 (3) | C2—C1—S1—O3 | −163.9 (3) |
C8—C5—C6—C7 | 35.8 (3) | N2—C12—C13—C14 | −51.8 (3) |
C5—C6—C7—C2 | −1.5 (3) | C12—C13—C14—N3 | 51.3 (3) |
C1—C2—C7—C6 | −171.4 (2) | N1—C11—N2—C12 | −179.2 (3) |
C3—C2—C7—C6 | 70.6 (3) | N3—C11—N2—C12 | 0.4 (4) |
C8—C2—C7—C6 | −32.9 (3) | C13—C12—N2—C11 | 26.5 (4) |
C4—C5—C8—C9 | −62.6 (3) | N2—C11—N3—C14 | −0.6 (4) |
C6—C5—C8—C9 | −172.1 (3) | N1—C11—N3—C14 | 179.0 (3) |
C4—C5—C8—C10 | 175.3 (3) | C13—C14—N3—C11 | −25.8 (4) |
C6—C5—C8—C10 | 65.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1 | 0.98 (5) | 1.90 (5) | 2.873 (5) | 173 (4) |
N1—H2···O2i | 0.77 (5) | 2.12 (5) | 2.888 (5) | 178 (6) |
N2—H3···O3 | 0.78 (4) | 2.13 (4) | 2.900 (4) | 169 (3) |
N3—H4···O3i | 0.81 (4) | 2.11 (4) | 2.908 (4) | 165 (3) |
Symmetry code: (i) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | C4H10N3+·C10H15O4S− |
Mr | 331.43 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 293 |
a, b, c (Å) | 7.4207 (4), 7.3115 (4), 16.421 (1) |
β (°) | 102.899 (1) |
V (Å3) | 868.46 (9) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.21 |
Crystal size (mm) | 0.32 × 0.26 × 0.17 |
Data collection | |
Diffractometer | Bruker SMART 1000 CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 1999) |
Tmin, Tmax | 0.860, 0.967 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5301, 3003, 2630 |
Rint | 0.017 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.097, 1.09 |
No. of reflections | 3003 |
No. of parameters | 214 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.15, −0.30 |
Absolute structure | Flack (1983), with 1341 Friedel pairs |
Absolute structure parameter | 0.17 (9) |
Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1 | 0.98 (5) | 1.90 (5) | 2.873 (5) | 173 (4) |
N1—H2···O2i | 0.77 (5) | 2.12 (5) | 2.888 (5) | 178 (6) |
N2—H3···O3 | 0.78 (4) | 2.13 (4) | 2.900 (4) | 169 (3) |
N3—H4···O3i | 0.81 (4) | 2.11 (4) | 2.908 (4) | 165 (3) |
Symmetry code: (i) x, y+1, z. |
The title compound, (I), is a molecular salt (Fig. 1). The C—N bond lengths in the cation [C11—N2 = 1.319 (5) Å, C11—N1 = 1.330 (3) Å, C11—N3 = 1.332 (5) Å] indicate delocalization of the electrons in the nominal C—N single bonds and C═N+ double bond (see scheme) in a similar fashion to that seen in the CN3H6+ guanidinium cation. The bond angle sum at C11 is exactly 360°. The conformation of the six-membered ring of the cation is well described as an envelope, with C13 displaced by 0.632 (4) Å from C11/C12/C14/N2/N3 (r.m.s. deviation for these atoms = 0.002 Å). The configurations of the chiral carbon atoms in the camphor sulfonate anion are: C2 R and C5 S. Otherwise, (I) displays normal geometrical parameters (Allen et al., 1995).
In the crystal of (I), the components interact by way of N—H···O hydrogen bonds (Table 1) leading to infinite chains propagating in [010], with every cation and anion linked by two N—H···O bonds (Fig. 2), resulting in graph-theory (Bernstein et al., 1995) R22(8) loops.