The title compound, C
16H
19N
2O
5PS, is the first phosphonate sulfonylhydrazone to be structurally characterized. The structure exhibits intermolecular N—H
O hydrogen bonding.
Supporting information
CCDC reference: 618124
Key indicators
- Single-crystal X-ray study
- T = 166 K
- Mean (C-C) = 0.005 Å
- R factor = 0.040
- wR factor = 0.094
- Data-to-parameter ratio = 12.0
checkCIF/PLATON results
No syntax errors found
Alert level C
ABSTM02_ALERT_3_C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
Tmin and Tmax reported: 0.753 0.985
Tmin(prime) and Tmax expected: 0.952 0.985
RR(prime) = 0.791
Please check that your absorption correction is appropriate.
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ............. 0.79
PLAT128_ALERT_4_C Non-standard setting of Space group Pc .... Pn
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 5
PLAT352_ALERT_3_C Short N-H Bond (0.87A) N1 - H1 ... 0.71 Ang.
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 26.44
From the CIF: _reflns_number_total 2788
Count of symmetry unique reflns 1850
Completeness (_total/calc) 150.70%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 938
Fraction of Friedel pairs measured 0.507
Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
5 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
0 ALERT type 2 Indicator that the structure model may be wrong or deficient
4 ALERT type 3 Indicator that the structure quality may be low
2 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXTL.
Crystal data top
C16H19N2O5PS | F(000) = 400 |
Mr = 382.36 | Dx = 1.422 Mg m−3 |
Monoclinic, Pn | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P -2yac | Cell parameters from 1816 reflections |
a = 8.4692 (19) Å | θ = 2.8–21.4° |
b = 10.889 (3) Å | µ = 0.30 mm−1 |
c = 9.690 (2) Å | T = 166 K |
β = 92.514 (4)° | Block, colorless |
V = 892.8 (4) Å3 | 0.16 × 0.15 × 0.05 mm |
Z = 2 | |
Data collection top
Bruker APEX CCD diffractometer | 2788 independent reflections |
Radiation source: fine-focus sealed tube | 2383 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
ω scans | θmax = 26.4°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −10→5 |
Tmin = 0.753, Tmax = 0.985 | k = −13→13 |
4987 measured reflections | l = −11→12 |
Refinement top
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)] = 0.040 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.094 | w = 1/[σ2(Fo2) + (0.0496P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.014 |
2788 reflections | Δρmax = 0.36 e Å−3 |
232 parameters | Δρmin = −0.29 e Å−3 |
2 restraints | Absolute structure: Flack (1983), 971 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.05 (9) |
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. |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.18365 (10) | 0.22114 (8) | 0.30113 (8) | 0.0228 (2) | |
P1 | 0.01807 (11) | 0.42942 (8) | 0.74957 (8) | 0.0216 (2) | |
O1 | 0.2054 (3) | 0.2524 (2) | 0.1594 (2) | 0.0300 (6) | |
O2 | 0.0630 (3) | 0.1369 (2) | 0.3358 (3) | 0.0305 (6) | |
O3 | 0.1586 (3) | 0.4799 (3) | 0.8444 (2) | 0.0304 (6) | |
O4 | −0.0025 (3) | 0.2898 (2) | 0.7806 (2) | 0.0308 (6) | |
O5 | −0.1307 (3) | 0.4935 (2) | 0.7600 (2) | 0.0297 (6) | |
N1 | 0.1435 (4) | 0.3543 (3) | 0.3747 (3) | 0.0222 (7) | |
H1 | 0.195 (5) | 0.403 (4) | 0.357 (4) | 0.027* | |
N2 | 0.1013 (3) | 0.3451 (3) | 0.5098 (3) | 0.0202 (6) | |
C1 | 0.8036 (5) | 0.0572 (4) | 0.5705 (4) | 0.0354 (10) | |
H1A | 0.7938 | 0.0534 | 0.6687 | 0.053* | |
H1B | 0.8840 | 0.1156 | 0.5493 | 0.053* | |
H1C | 0.8321 | −0.0223 | 0.5367 | 0.053* | |
C2 | 0.6498 (5) | 0.0958 (3) | 0.5032 (4) | 0.0261 (8) | |
C3 | 0.5072 (5) | 0.0699 (3) | 0.5630 (4) | 0.0284 (9) | |
H3A | 0.5078 | 0.0273 | 0.6461 | 0.034* | |
C4 | 0.3640 (5) | 0.1065 (3) | 0.5010 (3) | 0.0248 (8) | |
H4A | 0.2693 | 0.0890 | 0.5419 | 0.030* | |
C5 | 0.3650 (4) | 0.1701 (3) | 0.3761 (3) | 0.0235 (8) | |
C6 | 0.5029 (5) | 0.1948 (3) | 0.3141 (3) | 0.0273 (9) | |
H6A | 0.5010 | 0.2357 | 0.2297 | 0.033* | |
C7 | 0.6459 (5) | 0.1589 (4) | 0.3767 (4) | 0.0317 (9) | |
H7A | 0.7399 | 0.1767 | 0.3347 | 0.038* | |
C8 | 0.0977 (4) | 0.4455 (3) | 0.5803 (3) | 0.0209 (8) | |
C9 | 0.1337 (4) | 0.5716 (3) | 0.5305 (3) | 0.0221 (8) | |
C10 | 0.0376 (5) | 0.6228 (3) | 0.4254 (4) | 0.0300 (9) | |
H10A | −0.0456 | 0.5778 | 0.3851 | 0.036* | |
C11 | 0.0667 (5) | 0.7410 (4) | 0.3814 (4) | 0.0389 (11) | |
H11A | 0.0025 | 0.7754 | 0.3113 | 0.047* | |
C12 | 0.1892 (5) | 0.8080 (4) | 0.4399 (4) | 0.0364 (10) | |
H12A | 0.2070 | 0.8879 | 0.4104 | 0.044* | |
C13 | 0.2857 (5) | 0.7570 (4) | 0.5421 (4) | 0.0368 (10) | |
H13A | 0.3703 | 0.8018 | 0.5804 | 0.044* | |
C14 | 0.2577 (5) | 0.6401 (3) | 0.5880 (4) | 0.0274 (8) | |
H14A | 0.3224 | 0.6066 | 0.6582 | 0.033* | |
C15 | 0.1320 (6) | 0.5189 (4) | 0.9853 (4) | 0.0402 (11) | |
H15A | 0.2176 | 0.5706 | 1.0178 | 0.060* | |
H15B | 0.1264 | 0.4481 | 1.0438 | 0.060* | |
H15C | 0.0346 | 0.5638 | 0.9870 | 0.060* | |
C16 | 0.1292 (6) | 0.2089 (4) | 0.8126 (4) | 0.0438 (12) | |
H16A | 0.0982 | 0.1256 | 0.7936 | 0.066* | |
H16B | 0.1609 | 0.2169 | 0.9085 | 0.066* | |
H16C | 0.2160 | 0.2305 | 0.7569 | 0.066* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0262 (5) | 0.0258 (5) | 0.0164 (4) | −0.0018 (4) | 0.0019 (3) | −0.0045 (4) |
P1 | 0.0242 (5) | 0.0292 (5) | 0.0115 (4) | 0.0023 (4) | 0.0016 (3) | 0.0001 (4) |
O1 | 0.0370 (16) | 0.0380 (15) | 0.0149 (11) | 0.0029 (13) | 0.0007 (11) | −0.0030 (10) |
O2 | 0.0338 (17) | 0.0281 (14) | 0.0294 (14) | −0.0050 (12) | −0.0002 (12) | −0.0084 (11) |
O3 | 0.0276 (16) | 0.0477 (16) | 0.0157 (12) | 0.0012 (13) | −0.0020 (11) | −0.0011 (11) |
O4 | 0.0340 (17) | 0.0384 (16) | 0.0203 (13) | 0.0001 (13) | 0.0042 (11) | 0.0016 (11) |
O5 | 0.0317 (16) | 0.0410 (15) | 0.0165 (12) | 0.0076 (12) | 0.0034 (10) | −0.0020 (11) |
N1 | 0.0282 (19) | 0.0253 (17) | 0.0139 (14) | −0.0053 (13) | 0.0078 (12) | 0.0001 (12) |
N2 | 0.0197 (16) | 0.0278 (17) | 0.0135 (13) | −0.0011 (13) | 0.0025 (11) | 0.0007 (13) |
C1 | 0.033 (3) | 0.040 (2) | 0.033 (2) | −0.0016 (19) | −0.0030 (18) | 0.0126 (18) |
C2 | 0.031 (2) | 0.0246 (19) | 0.0222 (17) | −0.0006 (16) | −0.0023 (16) | −0.0002 (14) |
C3 | 0.040 (3) | 0.0235 (19) | 0.0216 (17) | −0.0034 (18) | 0.0043 (17) | 0.0026 (15) |
C4 | 0.032 (2) | 0.0266 (19) | 0.0157 (16) | −0.0036 (17) | 0.0049 (15) | −0.0014 (14) |
C5 | 0.030 (2) | 0.0216 (18) | 0.0186 (18) | 0.0007 (16) | 0.0000 (15) | −0.0051 (14) |
C6 | 0.032 (2) | 0.031 (2) | 0.0188 (17) | −0.0019 (17) | 0.0067 (16) | 0.0092 (15) |
C7 | 0.031 (2) | 0.035 (2) | 0.0285 (19) | −0.0027 (18) | 0.0017 (17) | 0.0077 (16) |
C8 | 0.0195 (19) | 0.030 (2) | 0.0129 (15) | 0.0031 (15) | 0.0001 (14) | 0.0008 (13) |
C9 | 0.023 (2) | 0.0276 (19) | 0.0160 (16) | 0.0000 (16) | 0.0060 (15) | −0.0034 (14) |
C10 | 0.026 (2) | 0.036 (2) | 0.0275 (19) | −0.0034 (19) | −0.0016 (16) | 0.0064 (16) |
C11 | 0.038 (3) | 0.036 (2) | 0.042 (2) | 0.000 (2) | −0.001 (2) | 0.0138 (18) |
C12 | 0.046 (3) | 0.023 (2) | 0.041 (2) | −0.0037 (19) | 0.017 (2) | 0.0027 (17) |
C13 | 0.039 (3) | 0.044 (3) | 0.027 (2) | −0.014 (2) | 0.0090 (19) | −0.0053 (18) |
C14 | 0.024 (2) | 0.037 (2) | 0.0206 (18) | −0.0052 (18) | −0.0010 (15) | −0.0015 (16) |
C15 | 0.055 (3) | 0.051 (3) | 0.0135 (17) | 0.006 (2) | −0.0064 (18) | −0.0061 (17) |
C16 | 0.064 (3) | 0.043 (2) | 0.024 (2) | 0.017 (2) | −0.002 (2) | 0.0016 (18) |
Geometric parameters (Å, º) top
S1—O2 | 1.424 (3) | C5—C6 | 1.363 (5) |
S1—O1 | 1.435 (2) | C6—C7 | 1.388 (6) |
S1—N1 | 1.658 (3) | C6—H6A | 0.930 |
S1—C5 | 1.760 (4) | C7—H7A | 0.930 |
P1—O5 | 1.448 (3) | C8—C9 | 1.491 (5) |
P1—O4 | 1.561 (3) | C9—C14 | 1.384 (5) |
P1—O3 | 1.571 (3) | C9—C10 | 1.393 (5) |
P1—C8 | 1.809 (3) | C10—C11 | 1.381 (5) |
O3—C15 | 1.457 (4) | C10—H10A | 0.930 |
O4—C16 | 1.444 (5) | C11—C12 | 1.371 (6) |
N1—N2 | 1.376 (4) | C11—H11A | 0.930 |
N1—H1 | 0.71 (4) | C12—C13 | 1.373 (6) |
N2—C8 | 1.290 (4) | C12—H12A | 0.930 |
C1—C2 | 1.492 (5) | C13—C14 | 1.372 (5) |
C1—H1A | 0.960 | C13—H13A | 0.930 |
C1—H1B | 0.960 | C14—H14A | 0.930 |
C1—H1C | 0.960 | C15—H15A | 0.960 |
C2—C3 | 1.391 (5) | C15—H15B | 0.960 |
C2—C7 | 1.404 (5) | C15—H15C | 0.960 |
C3—C4 | 1.388 (6) | C16—H16A | 0.960 |
C3—H3A | 0.930 | C16—H16B | 0.960 |
C4—C5 | 1.395 (5) | C16—H16C | 0.960 |
C4—H4A | 0.930 | | |
| | | |
O2—S1—O1 | 120.14 (16) | C7—C6—H6A | 120.0 |
O2—S1—N1 | 107.38 (16) | C6—C7—C2 | 120.4 (4) |
O1—S1—N1 | 103.99 (15) | C6—C7—H7A | 119.8 |
O2—S1—C5 | 108.77 (17) | C2—C7—H7A | 119.8 |
O1—S1—C5 | 108.88 (16) | N2—C8—C9 | 126.8 (3) |
N1—S1—C5 | 106.90 (16) | N2—C8—P1 | 114.6 (3) |
O5—P1—O4 | 110.56 (16) | C9—C8—P1 | 118.2 (2) |
O5—P1—O3 | 115.45 (15) | C14—C9—C10 | 119.2 (3) |
O4—P1—O3 | 108.46 (15) | C14—C9—C8 | 121.9 (3) |
O5—P1—C8 | 112.15 (15) | C10—C9—C8 | 118.9 (3) |
O4—P1—C8 | 108.56 (15) | C11—C10—C9 | 119.5 (4) |
O3—P1—C8 | 101.13 (15) | C11—C10—H10A | 120.3 |
C15—O3—P1 | 120.4 (3) | C9—C10—H10A | 120.3 |
C16—O4—P1 | 122.9 (3) | C12—C11—C10 | 120.7 (4) |
N2—N1—S1 | 114.3 (2) | C12—C11—H11A | 119.7 |
N2—N1—H1 | 118 (3) | C10—C11—H11A | 119.7 |
S1—N1—H1 | 114 (3) | C11—C12—C13 | 119.9 (4) |
C8—N2—N1 | 117.1 (3) | C11—C12—H12A | 120.0 |
C2—C1—H1A | 109.5 | C13—C12—H12A | 120.0 |
C2—C1—H1B | 109.5 | C14—C13—C12 | 120.2 (4) |
H1A—C1—H1B | 109.5 | C14—C13—H13A | 119.9 |
C2—C1—H1C | 109.5 | C12—C13—H13A | 119.9 |
H1A—C1—H1C | 109.5 | C13—C14—C9 | 120.5 (4) |
H1B—C1—H1C | 109.5 | C13—C14—H14A | 119.7 |
C3—C2—C7 | 118.4 (4) | C9—C14—H14A | 119.7 |
C3—C2—C1 | 121.3 (3) | O3—C15—H15A | 109.5 |
C7—C2—C1 | 120.4 (4) | O3—C15—H15B | 109.5 |
C4—C3—C2 | 121.3 (3) | H15A—C15—H15B | 109.5 |
C4—C3—H3A | 119.3 | O3—C15—H15C | 109.5 |
C2—C3—H3A | 119.3 | H15A—C15—H15C | 109.5 |
C3—C4—C5 | 118.7 (4) | H15B—C15—H15C | 109.5 |
C3—C4—H4A | 120.7 | O4—C16—H16A | 109.5 |
C5—C4—H4A | 120.7 | O4—C16—H16B | 109.5 |
C6—C5—C4 | 121.2 (4) | H16A—C16—H16B | 109.5 |
C6—C5—S1 | 120.3 (3) | O4—C16—H16C | 109.5 |
C4—C5—S1 | 118.5 (3) | H16A—C16—H16C | 109.5 |
C5—C6—C7 | 120.0 (3) | H16B—C16—H16C | 109.5 |
C5—C6—H6A | 120.0 | | |
| | | |
O5—P1—O3—C15 | 40.3 (3) | C5—C6—C7—C2 | 0.8 (6) |
O4—P1—O3—C15 | −84.4 (3) | C3—C2—C7—C6 | 0.3 (6) |
C8—P1—O3—C15 | 161.6 (3) | C1—C2—C7—C6 | 180.0 (3) |
O5—P1—O4—C16 | −163.7 (2) | N1—N2—C8—C9 | 0.4 (5) |
O3—P1—O4—C16 | −36.2 (3) | N1—N2—C8—P1 | 172.7 (2) |
C8—P1—O4—C16 | 72.9 (3) | O5—P1—C8—N2 | −113.0 (3) |
O2—S1—N1—N2 | 45.1 (3) | O4—P1—C8—N2 | 9.4 (3) |
O1—S1—N1—N2 | 173.4 (3) | O3—P1—C8—N2 | 123.4 (3) |
C5—S1—N1—N2 | −71.5 (3) | O5—P1—C8—C9 | 60.0 (3) |
S1—N1—N2—C8 | 167.3 (3) | O4—P1—C8—C9 | −177.5 (3) |
C7—C2—C3—C4 | −0.8 (5) | O3—P1—C8—C9 | −63.6 (3) |
C1—C2—C3—C4 | 179.6 (4) | N2—C8—C9—C14 | −117.9 (4) |
C2—C3—C4—C5 | 0.2 (5) | P1—C8—C9—C14 | 70.0 (4) |
C3—C4—C5—C6 | 1.0 (5) | N2—C8—C9—C10 | 63.6 (5) |
C3—C4—C5—S1 | −177.7 (3) | P1—C8—C9—C10 | −108.5 (3) |
O2—S1—C5—C6 | 149.7 (3) | C14—C9—C10—C11 | −0.6 (5) |
O1—S1—C5—C6 | 17.1 (3) | C8—C9—C10—C11 | 178.0 (3) |
N1—S1—C5—C6 | −94.6 (3) | C9—C10—C11—C12 | 0.1 (6) |
O2—S1—C5—C4 | −31.5 (3) | C10—C11—C12—C13 | 0.9 (6) |
O1—S1—C5—C4 | −164.1 (3) | C11—C12—C13—C14 | −1.4 (6) |
N1—S1—C5—C4 | 84.1 (3) | C12—C13—C14—C9 | 1.0 (6) |
C4—C5—C6—C7 | −1.5 (5) | C10—C9—C14—C13 | 0.0 (5) |
S1—C5—C6—C7 | 177.2 (3) | C8—C9—C14—C13 | −178.5 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O5i | 0.71 (4) | 2.11 (4) | 2.797 (4) | 162 (4) |
Symmetry code: (i) x+1/2, −y+1, z−1/2. |