The absolute structures of R-(-)-2-methylpiperazine (rmpip), S-(+)-2-methylpiperazine (smpip), R-(-)-2-methylpiperazinediium dibromide (rmpipBr) and S-(+)-2-methylpiperazinediium dibromide (smpipBr) have been determined by anomalous dispersion employing the Parsons' Q and Hooft methods. The studies were undertaken to determine the limitations of the absolute structure determination of light element structures (C, H, N) employing routine single-crystal X-ray diffraction laboratory conditions. The structures of the neutral methylpiperazines were known from a priori non-crystallographic methods and were confirmed by the absolute structure determination of their dibromide salts. By employing the full data collection of Bijvoet pairs and minimizing systematic errors, the absolute structure parameters 0.09 (8) (Hooft) for R-(-)-2-methylpiperazine and 0.05 (8) (Hooft) for S-(+)-2-methylpiperazine were determined.
Supporting information
CCDC references: 950483; 950484; 950485; 950486
For all compounds, data collection: FRAMBO (Bruker, 2002); cell refinement: FRAMBO (Bruker, 2002); data reduction: SAINT (Bruker, 2012b); program(s) used to solve structure: SHELXS (Sheldrick 2008); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2012); molecular graphics: OLEX-2 (Dolomanov, 2009); software used to prepare material for publication: Ciftab (Sheldrick, 2008).
(rmpip)
R-(-)-2-methylpiperazine
top
Crystal data top
C5H12N2 | Dx = 1.084 Mg m−3 |
Mr = 100.17 | Melting point: 363 K |
Monoclinic, P21 | Cu Kα radiation, λ = 1.54178 Å |
a = 5.2130 (4) Å | Cell parameters from 4190 reflections |
b = 8.4710 (7) Å | θ = 6.4–63.7° |
c = 7.2048 (6) Å | µ = 0.52 mm−1 |
β = 105.362 (6)° | T = 110 K |
V = 306.79 (4) Å3 | Plate, colorless |
Z = 2 | 0.16 × 0.13 × 0.04 mm |
F(000) = 112 | |
Data collection top
MWPC area detector diffractometer | 929 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
phi and ω scans | θmax = 63.6°, θmin = 8.3° |
Absorption correction: multi-scan SADABS-2009/1 (Bruker,2009) was employed for absorption correction.
wR2(int) was 0.0000 before and 0.0000 after correction.
The ratio of minimum to maximum transmission factors was -1.#IND.
Additional spherical absorption correction applied with mu*r = 0.0000.
The λ/2 correction was not applied | h = −6→6 |
Tmin = 0.611, Tmax = 0.752 | k = −9→9 |
5807 measured reflections | l = −8→8 |
987 independent reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: mixed |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.035 | w = 1/[σ2(Fo2) + (0.078P)2 + 0.0239P]
where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.104 | (Δ/σ)max < 0.001 |
S = 1.01 | Δρmax = 0.15 e Å−3 |
987 reflections | Δρmin = −0.17 e Å−3 |
71 parameters | Absolute structure: Hooft y determined using 450 Bijvoet Pairs
(Hooft,Straver,& Spek,(2008). J.Appl.Cryst. 41, 96-103)
PLATON (2012,161012) Bijvoet Pairs=450, Coverage=0.97,
Bayesian Statistics=Student_T(Nu=10.0), P2(true)=1.000,
P3(true)=1.000, P3(rac-twin)=0.8E-05, P3(false)=0.2E-25,
G =0.824, G (su)=0.167 |
1 restraint | Absolute structure parameter: 0.09 (8) |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.1053 (4) | 0.65182 (18) | 0.4789 (2) | 0.0271 (5) | |
H1 | −0.045 (6) | 0.605 (4) | 0.473 (4) | 0.041* | |
N4 | 0.3949 (4) | 0.93684 (18) | 0.5173 (3) | 0.0304 (5) | |
H4 | 0.550 (6) | 0.985 (4) | 0.519 (4) | 0.046* | |
C2 | 0.0542 (4) | 0.7647 (3) | 0.3190 (3) | 0.0279 (6) | |
H2A | −0.0880 | 0.8399 | 0.3319 | 0.033* | |
C3 | 0.3098 (4) | 0.8566 (2) | 0.3313 (3) | 0.0303 (6) | |
H3A | 0.4510 | 0.7834 | 0.3162 | 0.036* | |
H3B | 0.2790 | 0.9353 | 0.2260 | 0.036* | |
C5 | 0.4444 (4) | 0.8224 (3) | 0.6753 (3) | 0.0312 (6) | |
H5A | 0.5022 | 0.8780 | 0.8003 | 0.037* | |
H5B | 0.5875 | 0.7487 | 0.6650 | 0.037* | |
C6 | 0.1908 (4) | 0.7316 (3) | 0.6642 (3) | 0.0298 (6) | |
H6A | 0.2219 | 0.6529 | 0.7695 | 0.036* | |
H6B | 0.0500 | 0.8050 | 0.6796 | 0.036* | |
C7 | −0.0389 (5) | 0.6767 (3) | 0.1303 (3) | 0.0383 (6) | |
H7A | −0.2030 | 0.6192 | 0.1276 | 0.057* | |
H7B | 0.0988 | 0.6019 | 0.1177 | 0.057* | |
H7C | −0.0729 | 0.7522 | 0.0234 | 0.057* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0273 (10) | 0.0171 (10) | 0.0377 (11) | −0.0026 (8) | 0.0100 (8) | 0.0006 (8) |
N4 | 0.0293 (10) | 0.0178 (11) | 0.0448 (11) | −0.0011 (8) | 0.0108 (8) | 0.0019 (9) |
C2 | 0.0283 (11) | 0.0203 (12) | 0.0361 (14) | 0.0026 (9) | 0.0102 (10) | 0.0015 (9) |
C3 | 0.0312 (12) | 0.0221 (14) | 0.0392 (12) | 0.0015 (10) | 0.0122 (10) | 0.0043 (9) |
C5 | 0.0311 (11) | 0.0229 (13) | 0.0386 (14) | 0.0007 (9) | 0.0076 (11) | −0.0003 (10) |
C6 | 0.0341 (12) | 0.0222 (13) | 0.0346 (13) | 0.0000 (10) | 0.0118 (9) | 0.0025 (10) |
C7 | 0.0412 (12) | 0.0333 (12) | 0.0385 (12) | −0.0018 (11) | 0.0074 (9) | −0.0017 (11) |
Geometric parameters (Å, º) top
N1—C6 | 1.457 (3) | C3—H3B | 0.9900 |
N1—C2 | 1.466 (3) | C5—C6 | 1.514 (3) |
N1—H1 | 0.87 (3) | C5—H5A | 0.9900 |
N4—C3 | 1.463 (3) | C5—H5B | 0.9900 |
N4—C5 | 1.465 (3) | C6—H6A | 0.9900 |
N4—H4 | 0.90 (3) | C6—H6B | 0.9900 |
C2—C7 | 1.513 (3) | C7—H7A | 0.9800 |
C2—C3 | 1.526 (3) | C7—H7B | 0.9800 |
C2—H2A | 1.0000 | C7—H7C | 0.9800 |
C3—H3A | 0.9900 | | |
| | | |
C6—N1—C2 | 111.43 (16) | N4—C5—C6 | 108.90 (19) |
C6—N1—H1 | 108.0 (19) | N4—C5—H5A | 109.9 |
C2—N1—H1 | 106.5 (19) | C6—C5—H5A | 109.9 |
C3—N4—C5 | 110.65 (17) | N4—C5—H5B | 109.9 |
C3—N4—H4 | 105.8 (18) | C6—C5—H5B | 109.9 |
C5—N4—H4 | 108.5 (18) | H5A—C5—H5B | 108.3 |
N1—C2—C7 | 109.46 (18) | N1—C6—C5 | 109.54 (17) |
N1—C2—C3 | 108.26 (17) | N1—C6—H6A | 109.8 |
C7—C2—C3 | 111.75 (16) | C5—C6—H6A | 109.8 |
N1—C2—H2A | 109.1 | N1—C6—H6B | 109.8 |
C7—C2—H2A | 109.1 | C5—C6—H6B | 109.8 |
C3—C2—H2A | 109.1 | H6A—C6—H6B | 108.2 |
N4—C3—C2 | 109.78 (17) | C2—C7—H7A | 109.5 |
N4—C3—H3A | 109.7 | C2—C7—H7B | 109.5 |
C2—C3—H3A | 109.7 | H7A—C7—H7B | 109.5 |
N4—C3—H3B | 109.7 | C2—C7—H7C | 109.5 |
C2—C3—H3B | 109.7 | H7A—C7—H7C | 109.5 |
H3A—C3—H3B | 108.2 | H7B—C7—H7C | 109.5 |
| | | |
C6—N1—C2—C7 | −178.90 (17) | C7—C2—C3—N4 | −178.83 (16) |
C6—N1—C2—C3 | 59.1 (2) | C3—N4—C5—C6 | −59.7 (2) |
C5—N4—C3—C2 | 60.0 (2) | C2—N1—C6—C5 | −60.0 (2) |
N1—C2—C3—N4 | −58.2 (2) | N4—C5—C6—N1 | 58.8 (2) |
(smpip)
S-(+)-2-methylpiperazine
top
Crystal data top
C5H12N2 | Dx = 1.084 Mg m−3 |
Mr = 100.17 | Melting point: 363 K |
Monoclinic, P21 | Cu Kα radiation, λ = 1.54178 Å |
a = 5.2090 (4) Å | Cell parameters from 3197 reflections |
b = 8.4798 (6) Å | θ = 6.4–63.6° |
c = 7.2037 (5) Å | µ = 0.52 mm−1 |
β = 105.254 (5)° | T = 110 K |
V = 306.99 (4) Å3 | Plate, colorless |
Z = 2 | 0.12 × 0.11 × 0.04 mm |
F(000) = 112 | |
Data collection top
MWPC area detector diffractometer | 902 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
phi and ω scans | θmax = 63.7°, θmin = 8.3° |
Absorption correction: multi-scan SADABS-2009/1 (Bruker,2009) was employed for absorption correction.
wR2(int) was 0.0000 before and 0.0000 after correction.
The ratio of minimum to maximum transmission factors was -1.#IND.
Additional spherical absorption correction applied with mu*r = 0.0000.
The λ/2 correction was not applied | h = −5→5 |
Tmin = 0.649, Tmax = 0.752 | k = −9→8 |
6541 measured reflections | l = −8→8 |
965 independent reflections | |
Refinement top
Refinement on F2 | H atoms treated by a mixture of independent and constrained refinement |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.1P)2]
where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.038 | (Δ/σ)max < 0.001 |
wR(F2) = 0.115 | Δρmax = 0.18 e Å−3 |
S = 1.03 | Δρmin = −0.21 e Å−3 |
965 reflections | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
72 parameters | Extinction coefficient: 0.118 (19) |
1 restraint | Absolute structure: Hooft y determined using 430 Bijvoet Pairs
(Hooft,Straver,& Spek,(2008). J.Appl.Cryst. 41, 96-103)
PLATON (2012,161012) Bijvoet Pairs=430, Coverage=0.92,
Bayesian Statistics=Student_T (Nu=5.0), P2(true)=1.000,
P3(true)=1.0000, P3(rac-twin)=0.2E-07, P3(false)=0.2E-32,
G= 0.9029, G (su)=0.1504 |
Hydrogen site location: mixed | Absolute structure parameter: 0.05 (8) |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | −0.1048 (4) | −0.64441 (18) | −0.4788 (2) | 0.0212 (6) | |
H1 | 0.043 (6) | −0.591 (4) | −0.472 (4) | 0.032* | |
N4 | −0.3949 (4) | −0.92944 (19) | −0.5176 (2) | 0.0241 (6) | |
H4 | −0.549 (6) | −0.980 (4) | −0.517 (4) | 0.036* | |
C2 | −0.0543 (4) | −0.7573 (3) | −0.3192 (3) | 0.0221 (7) | |
H2B | 0.0880 | −0.8324 | −0.3323 | 0.027* | |
C3 | −0.3098 (4) | −0.8492 (2) | −0.3314 (3) | 0.0236 (7) | |
H3A | −0.2792 | −0.9278 | −0.2262 | 0.028* | |
H3B | −0.4512 | −0.7762 | −0.3163 | 0.028* | |
C5 | −0.4444 (4) | −0.8152 (3) | −0.6755 (3) | 0.0241 (7) | |
H5A | −0.5877 | −0.7417 | −0.6652 | 0.029* | |
H5B | −0.5017 | −0.8707 | −0.8004 | 0.029* | |
C6 | −0.1910 (4) | −0.7243 (3) | −0.6644 (3) | 0.0236 (7) | |
H6A | −0.0501 | −0.7975 | −0.6801 | 0.028* | |
H6B | −0.2222 | −0.6457 | −0.7696 | 0.028* | |
C7 | 0.0394 (4) | −0.6695 (3) | −0.1302 (3) | 0.0318 (6) | |
H7B | 0.2024 | −0.6112 | −0.1284 | 0.048* | |
H7C | 0.0753 | −0.7451 | −0.0235 | 0.048* | |
H7D | −0.0990 | −0.5955 | −0.1166 | 0.048* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0174 (10) | 0.0192 (12) | 0.0273 (11) | −0.0027 (7) | 0.0064 (7) | −0.0006 (8) |
N4 | 0.0188 (10) | 0.0181 (12) | 0.0356 (11) | −0.0015 (7) | 0.0074 (7) | 0.0011 (8) |
C2 | 0.0187 (11) | 0.0226 (14) | 0.0262 (13) | 0.0025 (8) | 0.0080 (9) | 0.0013 (9) |
C3 | 0.0203 (11) | 0.0218 (15) | 0.0298 (12) | 0.0014 (9) | 0.0085 (9) | 0.0044 (9) |
C5 | 0.0195 (11) | 0.0217 (14) | 0.0298 (12) | 0.0008 (8) | 0.0040 (9) | −0.0003 (9) |
C6 | 0.0231 (11) | 0.0233 (14) | 0.0254 (12) | 0.0001 (9) | 0.0081 (9) | 0.0008 (9) |
C7 | 0.0301 (11) | 0.0363 (13) | 0.0267 (11) | −0.0013 (10) | 0.0036 (8) | −0.0019 (10) |
Geometric parameters (Å, º) top
N1—C6 | 1.460 (3) | C3—H3B | 0.9900 |
N1—C2 | 1.466 (3) | C5—C6 | 1.512 (3) |
N1—H1 | 0.88 (3) | C5—H5A | 0.9900 |
N4—C5 | 1.464 (3) | C5—H5B | 0.9900 |
N4—C3 | 1.465 (3) | C6—H6A | 0.9900 |
N4—H4 | 0.91 (3) | C6—H6B | 0.9900 |
C2—C7 | 1.515 (3) | C7—H7B | 0.9800 |
C2—C3 | 1.525 (3) | C7—H7C | 0.9800 |
C2—H2B | 1.0000 | C7—H7D | 0.9800 |
C3—H3A | 0.9900 | | |
| | | |
C6—N1—C2 | 111.34 (16) | N4—C5—C6 | 108.86 (18) |
C6—N1—H1 | 109.9 (18) | N4—C5—H5A | 109.9 |
C2—N1—H1 | 108.5 (18) | C6—C5—H5A | 109.9 |
C5—N4—C3 | 110.65 (16) | N4—C5—H5B | 109.9 |
C5—N4—H4 | 110.1 (17) | C6—C5—H5B | 109.9 |
C3—N4—H4 | 105.4 (17) | H5A—C5—H5B | 108.3 |
N1—C2—C7 | 109.44 (18) | N1—C6—C5 | 109.78 (16) |
N1—C2—C3 | 108.33 (16) | N1—C6—H6A | 109.7 |
C7—C2—C3 | 111.90 (15) | C5—C6—H6A | 109.7 |
N1—C2—H2B | 109.0 | N1—C6—H6B | 109.7 |
C7—C2—H2B | 109.0 | C5—C6—H6B | 109.7 |
C3—C2—H2B | 109.0 | H6A—C6—H6B | 108.2 |
N4—C3—C2 | 109.84 (15) | C2—C7—H7B | 109.5 |
N4—C3—H3A | 109.7 | C2—C7—H7C | 109.5 |
C2—C3—H3A | 109.7 | H7B—C7—H7C | 109.5 |
N4—C3—H3B | 109.7 | C2—C7—H7D | 109.5 |
C2—C3—H3B | 109.7 | H7B—C7—H7D | 109.5 |
H3A—C3—H3B | 108.2 | H7C—C7—H7D | 109.5 |
| | | |
C6—N1—C2—C7 | 178.94 (15) | C7—C2—C3—N4 | 178.95 (17) |
C6—N1—C2—C3 | −58.81 (19) | C3—N4—C5—C6 | 59.6 (2) |
C5—N4—C3—C2 | −60.0 (2) | C2—N1—C6—C5 | 59.8 (2) |
N1—C2—C3—N4 | 58.2 (2) | N4—C5—C6—N1 | −58.7 (2) |
(rmpipbr)
R-(-)-2-methylpiperazinediium dibromide
top
Crystal data top
C5H14.71Br2N2O0.36 | F(000) = 263 |
Mr = 268.40 | Dx = 1.869 Mg m−3 |
Monoclinic, P21 | Cu Kα radiation, λ = 1.54178 Å |
a = 6.0418 (3) Å | Cell parameters from 8198 reflections |
b = 11.5649 (5) Å | θ = 7.5–63.9° |
c = 7.1333 (3) Å | µ = 10.28 mm−1 |
β = 106.911 (2)° | T = 110 K |
V = 476.87 (4) Å3 | Plate, colorless |
Z = 2 | 0.21 × 0.11 × 0.04 mm |
Data collection top
MWPC area detector diffractometer | 1517 reflections with I > 2σ(I) |
phi and ω scans | Rint = 0.034 |
Absorption correction: multi-scan SADABS-2009/1 (Bruker,2009) was employed for absorption correction.
wR2(int) was 0.1305 before and 0.0486 after correction.
The ratio of minimum to maximum transmission factors was 0.5252.
Additional spherical absorption correction applied with mu*r = 0.6000.
The λ/2 correction factor of 0.0015 was applied. | θmax = 63.9°, θmin = 6.5° |
Tmin = 0.244, Tmax = 0.464 | h = −6→6 |
10680 measured reflections | k = −13→13 |
1537 independent reflections | l = −8→8 |
Refinement top
Refinement on F2 | H-atom parameters constrained |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.050P)2 + 0.0247P]
where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.020 | (Δ/σ)max < 0.001 |
wR(F2) = 0.060 | Δρmax = 0.51 e Å−3 |
S = 1.03 | Δρmin = −0.64 e Å−3 |
1537 reflections | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
96 parameters | Extinction coefficient: 0.0158 (10) |
1 restraint | Absolute structure: Flack x determined using 697 quotients [(I+)-(I-)]/[(I+)+(I-)]
(Parsons and Flack (2004), Acta Cryst. A60, s61). |
Hydrogen site location: mixed | Absolute structure parameter: 0.041 (13) |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Br1 | 0.28253 (9) | 0.12496 (5) | 0.11627 (8) | 0.0145 (2) | |
Br2 | 0.89365 (10) | −0.06055 (4) | −0.57535 (8) | 0.0233 (2) | |
O1W | 0.835 (2) | 0.2119 (11) | −0.619 (2) | 0.029 (4) | 0.350 (12) |
H1W | 0.8501 | 0.1389 | −0.6072 | 0.03 (5)* | 0.350 (12) |
H2W | 0.9067 | 0.2725 | −0.5671 | 0.02 (7)* | 0.350 (12) |
N1 | 0.7332 (7) | 0.0748 (4) | −0.0416 (7) | 0.0131 (9) | |
H1A | 0.8763 | 0.0866 | 0.0467 | 0.016* | |
H1B | 0.6234 | 0.0869 | 0.0225 | 0.016* | |
C2 | 0.6980 (9) | 0.1601 (4) | −0.2052 (8) | 0.0147 (12) | |
H2 | 0.8214 | 0.1489 | −0.2713 | 0.018* | |
C3 | 0.4633 (9) | 0.1386 (4) | −0.3525 (8) | 0.0119 (11) | |
H3A | 0.3399 | 0.1545 | −0.2902 | 0.014* | |
H3B | 0.4420 | 0.1921 | −0.4647 | 0.014* | |
C5 | 0.4830 (9) | −0.0680 (5) | −0.2591 (8) | 0.0159 (11) | |
H5A | 0.4767 | −0.1480 | −0.3097 | 0.019* | |
H5B | 0.3600 | −0.0593 | −0.1939 | 0.019* | |
N4 | 0.4427 (8) | 0.0156 (3) | −0.4254 (7) | 0.0141 (10) | |
H4A | 0.2975 | 0.0040 | −0.5104 | 0.017* | |
H4B | 0.5491 | 0.0027 | −0.4927 | 0.017* | |
C6 | 0.7172 (9) | −0.0463 (6) | −0.1122 (7) | 0.0133 (15) | |
H6A | 0.7394 | −0.0998 | 0.0001 | 0.016* | |
H6B | 0.8410 | −0.0614 | −0.1745 | 0.016* | |
C7 | 0.7118 (12) | 0.2822 (6) | −0.1271 (10) | 0.0197 (17) | |
H7A | 0.7113 | 0.3369 | −0.2322 | 0.030* | |
H7B | 0.8548 | 0.2916 | −0.0196 | 0.030* | |
H7C | 0.5784 | 0.2974 | −0.0789 | 0.030* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.0113 (3) | 0.0192 (3) | 0.0135 (3) | 0.0008 (2) | 0.0044 (2) | 0.0016 (2) |
Br2 | 0.0182 (4) | 0.0382 (4) | 0.0150 (4) | −0.0085 (2) | 0.0071 (2) | −0.0052 (2) |
O1W | 0.027 (7) | 0.022 (7) | 0.040 (8) | −0.001 (5) | 0.012 (6) | 0.007 (6) |
N1 | 0.010 (2) | 0.0177 (19) | 0.012 (2) | −0.0005 (17) | 0.0047 (18) | −0.0018 (19) |
C2 | 0.013 (3) | 0.017 (3) | 0.016 (3) | −0.0011 (19) | 0.007 (2) | 0.003 (2) |
C3 | 0.016 (2) | 0.007 (2) | 0.011 (3) | 0.003 (2) | 0.002 (2) | 0.002 (2) |
C5 | 0.021 (3) | 0.012 (2) | 0.017 (3) | −0.005 (2) | 0.009 (2) | −0.002 (2) |
N4 | 0.021 (2) | 0.012 (2) | 0.008 (2) | −0.0012 (17) | 0.0034 (19) | −0.0022 (17) |
C6 | 0.016 (4) | 0.013 (3) | 0.010 (3) | −0.001 (2) | 0.003 (2) | 0.004 (2) |
C7 | 0.023 (4) | 0.016 (3) | 0.019 (4) | −0.0047 (19) | 0.005 (3) | −0.007 (2) |
Geometric parameters (Å, º) top
O1W—H1W | 0.8500 | C5—N4 | 1.494 (7) |
O1W—H2W | 0.8500 | C5—C6 | 1.517 (7) |
N1—C6 | 1.482 (8) | C5—H5A | 0.9900 |
N1—C2 | 1.495 (7) | C5—H5B | 0.9900 |
N1—H1A | 0.9200 | N4—H4A | 0.9200 |
N1—H1B | 0.9200 | N4—H4B | 0.9200 |
C2—C7 | 1.512 (9) | C6—H6A | 0.9900 |
C2—C3 | 1.520 (7) | C6—H6B | 0.9900 |
C2—H2 | 1.0000 | C7—H7A | 0.9800 |
C3—N4 | 1.507 (7) | C7—H7B | 0.9800 |
C3—H3A | 0.9900 | C7—H7C | 0.9800 |
C3—H3B | 0.9900 | | |
| | | |
H1W—O1W—H2W | 138.5 | N4—C5—H5B | 109.6 |
C6—N1—C2 | 112.2 (4) | C6—C5—H5B | 109.6 |
C6—N1—H1A | 109.2 | H5A—C5—H5B | 108.1 |
C2—N1—H1A | 109.2 | C5—N4—C3 | 111.0 (4) |
C6—N1—H1B | 109.2 | C5—N4—H4A | 109.4 |
C2—N1—H1B | 109.2 | C3—N4—H4A | 109.4 |
H1A—N1—H1B | 107.9 | C5—N4—H4B | 109.4 |
N1—C2—C7 | 110.4 (5) | C3—N4—H4B | 109.4 |
N1—C2—C3 | 108.9 (4) | H4A—N4—H4B | 108.0 |
C7—C2—C3 | 110.4 (5) | N1—C6—C5 | 110.3 (4) |
N1—C2—H2 | 109.0 | N1—C6—H6A | 109.6 |
C7—C2—H2 | 109.0 | C5—C6—H6A | 109.6 |
C3—C2—H2 | 109.0 | N1—C6—H6B | 109.6 |
N4—C3—C2 | 111.1 (4) | C5—C6—H6B | 109.6 |
N4—C3—H3A | 109.4 | H6A—C6—H6B | 108.1 |
C2—C3—H3A | 109.4 | C2—C7—H7A | 109.5 |
N4—C3—H3B | 109.4 | C2—C7—H7B | 109.5 |
C2—C3—H3B | 109.4 | H7A—C7—H7B | 109.5 |
H3A—C3—H3B | 108.0 | C2—C7—H7C | 109.5 |
N4—C5—C6 | 110.2 (4) | H7A—C7—H7C | 109.5 |
N4—C5—H5A | 109.6 | H7B—C7—H7C | 109.5 |
C6—C5—H5A | 109.6 | | |
(smpipbr)
S-(+)-2-methylpiperazinediium dibromide
top
Crystal data top
2(Br)·0.25(H2O)·C5H14N2 | F(000) = 261 |
Mr = 266.51 | Dx = 1.862 Mg m−3 |
Monoclinic, P21 | Cu Kα radiation, λ = 1.54178 Å |
a = 6.0262 (3) Å | Cell parameters from 7786 reflections |
b = 11.5550 (6) Å | θ = 3.8–63.6° |
c = 7.1392 (4) Å | µ = 10.30 mm−1 |
β = 107.018 (3)° | T = 110 K |
V = 475.35 (4) Å3 | Plate, colorless |
Z = 2 | 0.20 × 0.10 × 0.01 mm |
Data collection top
MWPC area detector diffractometer | 1499 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
phi and ω scans | θmax = 63.7°, θmin = 6.5° |
Absorption correction: multi-scan SADABS-2009/1 (Bruker,2009) was employed for absorption correction.
wR2(int) was 0.0000 before and 0.0000 after correction.
The ratio of minimum to maximum transmission factors was -1.#IND.
Additional spherical absorption correction applied with mu*r = 0.0000.
The λ/2 correction was not applied | h = −6→6 |
Tmin = 0.383, Tmax = 0.752 | k = −13→13 |
8987 measured reflections | l = −6→7 |
1507 independent reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: mixed |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.019 | w = 1/[σ2(Fo2) + (0.032P)2 + 0.1521P]
where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.050 | (Δ/σ)max < 0.001 |
S = 1.09 | Δρmax = 0.37 e Å−3 |
1507 reflections | Δρmin = −0.60 e Å−3 |
92 parameters | Absolute structure: Flack x determined using 699 quotients [(I+)-(I-)]/[(I+)+(I-)]
(Parsons and Flack (2004), Acta Cryst. A60, s61). |
1 restraint | Absolute structure parameter: 0.038 (13) |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Br1 | 0.28497 (8) | 0.81549 (4) | 0.61690 (7) | 0.01346 (16) | |
Br2 | 0.89230 (8) | 1.00194 (4) | −0.07683 (7) | 0.02154 (17) | |
O1W | 0.833 (3) | 0.7318 (14) | −0.122 (3) | 0.033 (4) | 0.25 |
H1W | 0.9097 | 0.6675 | −0.0678 | 0.050* | 0.25 |
H2W | 0.8495 | 0.8091 | −0.1106 | 0.050* | 0.25 |
N1 | 0.7346 (6) | 0.8674 (3) | 0.4576 (6) | 0.0115 (8) | |
H1N1 | 0.6254 | 0.8552 | 0.5226 | 0.014* | |
H2N1 | 0.8787 | 0.8556 | 0.5453 | 0.014* | |
C2 | 0.6978 (8) | 0.7813 (4) | 0.2944 (7) | 0.0132 (10) | |
H2 | 0.8212 | 0.7923 | 0.2280 | 0.016* | |
C3 | 0.4606 (8) | 0.8026 (4) | 0.1456 (7) | 0.0121 (9) | |
H3A | 0.4394 | 0.7492 | 0.0333 | 0.015* | |
H3B | 0.3366 | 0.7868 | 0.2074 | 0.015* | |
N4 | 0.4418 (7) | 0.9256 (3) | 0.0738 (6) | 0.0132 (9) | |
H1N4 | 0.5488 | 0.9381 | 0.0068 | 0.016* | |
H2N4 | 0.2963 | 0.9377 | −0.0115 | 0.016* | |
C5 | 0.4830 (8) | 1.0098 (4) | 0.2399 (6) | 0.0131 (9) | |
H5A | 0.3591 | 1.0018 | 0.3045 | 0.016* | |
H5B | 0.4776 | 1.0897 | 0.1889 | 0.016* | |
C6 | 0.7180 (8) | 0.9880 (5) | 0.3884 (7) | 0.0143 (13) | |
H6A | 0.8428 | 1.0036 | 0.3274 | 0.017* | |
H6B | 0.7391 | 1.0411 | 0.5010 | 0.017* | |
C7 | 0.7125 (11) | 0.6578 (5) | 0.3739 (9) | 0.0206 (13) | |
H7A | 0.7072 | 0.6028 | 0.2682 | 0.031* | |
H7B | 0.5814 | 0.6434 | 0.4258 | 0.031* | |
H7C | 0.8583 | 0.6480 | 0.4788 | 0.031* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.0110 (3) | 0.0179 (2) | 0.0117 (3) | −0.0008 (2) | 0.00384 (18) | −0.0013 (2) |
Br2 | 0.0161 (3) | 0.0359 (3) | 0.0137 (3) | 0.0065 (2) | 0.0061 (2) | 0.0041 (2) |
O1W | 0.030 (9) | 0.025 (8) | 0.046 (10) | 0.013 (7) | 0.011 (8) | 0.005 (7) |
N1 | 0.007 (2) | 0.0171 (17) | 0.009 (2) | 0.0000 (16) | 0.0009 (15) | 0.0005 (16) |
C2 | 0.015 (3) | 0.012 (2) | 0.012 (2) | 0.0007 (17) | 0.0037 (19) | −0.0029 (17) |
C3 | 0.015 (2) | 0.010 (2) | 0.009 (2) | −0.0018 (19) | −0.0002 (18) | 0.000 (2) |
N4 | 0.016 (2) | 0.015 (2) | 0.007 (2) | 0.0019 (16) | 0.0014 (16) | 0.0016 (15) |
C5 | 0.017 (3) | 0.012 (2) | 0.011 (2) | 0.0036 (19) | 0.0045 (18) | 0.0015 (17) |
C6 | 0.015 (3) | 0.017 (3) | 0.010 (3) | 0.001 (2) | 0.002 (2) | −0.003 (2) |
C7 | 0.023 (3) | 0.016 (3) | 0.023 (4) | 0.0038 (18) | 0.006 (3) | 0.004 (2) |
Geometric parameters (Å, º) top
O1W—H1W | 0.9000 | N4—C5 | 1.497 (6) |
O1W—H2W | 0.8999 | N4—H1N4 | 0.9200 |
N1—C6 | 1.472 (7) | N4—H2N4 | 0.9200 |
N1—C2 | 1.498 (6) | C5—C6 | 1.521 (6) |
N1—H1N1 | 0.9200 | C5—H5A | 0.9900 |
N1—H2N1 | 0.9200 | C5—H5B | 0.9900 |
C2—C3 | 1.531 (6) | C6—H6A | 0.9900 |
C2—C7 | 1.529 (7) | C6—H6B | 0.9900 |
C2—H2 | 1.0000 | C7—H7A | 0.9800 |
C3—N4 | 1.504 (6) | C7—H7B | 0.9800 |
C3—H3A | 0.9900 | C7—H7C | 0.9800 |
C3—H3B | 0.9900 | | |
| | | |
H1W—O1W—H2W | 138.8 | C5—N4—H2N4 | 109.3 |
C6—N1—C2 | 112.8 (4) | C3—N4—H2N4 | 109.3 |
C6—N1—H1N1 | 109.0 | H1N4—N4—H2N4 | 108.0 |
C2—N1—H1N1 | 109.0 | N4—C5—C6 | 110.4 (4) |
C6—N1—H2N1 | 109.0 | N4—C5—H5A | 109.6 |
C2—N1—H2N1 | 109.0 | C6—C5—H5A | 109.6 |
H1N1—N1—H2N1 | 107.8 | N4—C5—H5B | 109.6 |
N1—C2—C3 | 109.2 (4) | C6—C5—H5B | 109.6 |
N1—C2—C7 | 110.6 (4) | H5A—C5—H5B | 108.1 |
C3—C2—C7 | 110.4 (4) | N1—C6—C5 | 110.4 (4) |
N1—C2—H2 | 108.9 | N1—C6—H6A | 109.6 |
C3—C2—H2 | 108.9 | C5—C6—H6A | 109.6 |
C7—C2—H2 | 108.9 | N1—C6—H6B | 109.6 |
N4—C3—C2 | 110.5 (4) | C5—C6—H6B | 109.6 |
N4—C3—H3A | 109.6 | H6A—C6—H6B | 108.1 |
C2—C3—H3A | 109.6 | C2—C7—H7A | 109.5 |
N4—C3—H3B | 109.6 | C2—C7—H7B | 109.5 |
C2—C3—H3B | 109.6 | H7A—C7—H7B | 109.5 |
H3A—C3—H3B | 108.1 | C2—C7—H7C | 109.5 |
C5—N4—C3 | 111.5 (4) | H7A—C7—H7C | 109.5 |
C5—N4—H1N4 | 109.3 | H7B—C7—H7C | 109.5 |
C3—N4—H1N4 | 109.3 | | |
| | | |
C6—N1—C2—C3 | −57.4 (5) | C2—C3—N4—C5 | −56.7 (5) |
C6—N1—C2—C7 | −179.0 (4) | C3—N4—C5—C6 | 56.3 (5) |
N1—C2—C3—N4 | 55.7 (5) | C2—N1—C6—C5 | 57.7 (5) |
C7—C2—C3—N4 | 177.5 (4) | N4—C5—C6—N1 | −55.9 (5) |