Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801012648/wn6039sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801012648/wn6039Isup2.hkl |
CCDC reference: 170934
Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1990).
C8H16N2O4 | F(000) = 440 |
Mr = 204.23 | Dx = 1.251 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 8.0299 (16) Å | Cell parameters from 4438 reflections |
b = 12.765 (3) Å | θ = 3.0–25.0° |
c = 10.587 (2) Å | µ = 0.10 mm−1 |
β = 92.11 (3)° | T = 120 K |
V = 1084.4 (4) Å3 | Needle, colourless |
Z = 4 | 0.12 × 0.05 × 0.05 mm |
Nonius KappaCCD area-detector diffractometer | 1890 independent reflections |
Radiation source: Nonius FR591 rotating anode | 1289 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.099 |
ϕ and ω scans to fill Ewald sphere | θmax = 25.0°, θmin = 3.0° |
Absorption correction: multi-scan (Blessing, 1997) | h = −9→9 |
Tmin = 0.988, Tmax = 0.995 | k = −15→15 |
4768 measured reflections | l = −12→12 |
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)] = 0.069 | H-atom parameters constrained |
wR(F2) = 0.143 | w = 1/[σ2(Fo2) + (0.0001P)2 + 1.7P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
1890 reflections | Δρmax = 0.51 e Å−3 |
128 parameters | Δρmin = −0.32 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.014 (3) |
C8H16N2O4 | V = 1084.4 (4) Å3 |
Mr = 204.23 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.0299 (16) Å | µ = 0.10 mm−1 |
b = 12.765 (3) Å | T = 120 K |
c = 10.587 (2) Å | 0.12 × 0.05 × 0.05 mm |
β = 92.11 (3)° |
Nonius KappaCCD area-detector diffractometer | 1890 independent reflections |
Absorption correction: multi-scan (Blessing, 1997) | 1289 reflections with I > 2σ(I) |
Tmin = 0.988, Tmax = 0.995 | Rint = 0.099 |
4768 measured reflections |
R[F2 > 2σ(F2)] = 0.069 | 0 restraints |
wR(F2) = 0.143 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.51 e Å−3 |
1890 reflections | Δρmin = −0.32 e Å−3 |
128 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. |
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 | ||
O1 | 0.2492 (2) | −0.23490 (16) | −0.0148 (2) | 0.0231 (5) | |
O2 | 0.0593 (2) | −0.14300 (17) | 0.0931 (2) | 0.0251 (6) | |
O3 | 0.4424 (2) | 0.04803 (17) | 0.1561 (2) | 0.0250 (6) | |
O4 | 0.2496 (2) | 0.17839 (16) | 0.13712 (19) | 0.0205 (5) | |
N1 | 0.2581 (3) | −0.0624 (2) | −0.0204 (3) | 0.0232 (6) | |
H1 | 0.3353 | −0.0703 | −0.0764 | 0.028* | |
N2 | 0.2159 (3) | 0.03625 (19) | 0.0211 (2) | 0.0234 (7) | |
H2 | 0.1259 | 0.0677 | −0.0102 | 0.028* | |
C1 | 0.2215 (5) | −0.4111 (3) | −0.0826 (4) | 0.0372 (9) | |
H1A | 0.1974 | −0.3852 | −0.1685 | 0.056* | |
H1B | 0.1653 | −0.4784 | −0.0712 | 0.056* | |
H1C | 0.3420 | −0.4203 | −0.0694 | 0.056* | |
C2 | 0.1907 (4) | −0.3649 (3) | 0.1472 (3) | 0.0323 (8) | |
H2A | 0.1492 | −0.3102 | 0.2030 | 0.048* | |
H2B | 0.3107 | −0.3743 | 0.1639 | 0.048* | |
H2C | 0.1327 | −0.4308 | 0.1631 | 0.048* | |
C3 | 0.1595 (4) | −0.3330 (2) | 0.0118 (3) | 0.0248 (8) | |
H3 | 0.0373 | −0.3217 | −0.0042 | 0.030* | |
C4 | 0.1791 (3) | −0.1470 (2) | 0.0263 (3) | 0.0193 (7) | |
C5 | 0.3136 (4) | 0.0842 (2) | 0.1101 (3) | 0.0194 (7) | |
C6 | 0.3539 (4) | 0.2462 (2) | 0.2196 (3) | 0.0213 (7) | |
H6 | 0.4729 | 0.2406 | 0.1957 | 0.026* | |
C7 | 0.3381 (4) | 0.2133 (3) | 0.3553 (3) | 0.0284 (8) | |
H7A | 0.3783 | 0.1413 | 0.3660 | 0.043* | |
H7B | 0.2209 | 0.2171 | 0.3778 | 0.043* | |
H7C | 0.4047 | 0.2602 | 0.4104 | 0.043* | |
C8 | 0.2918 (4) | 0.3558 (3) | 0.1948 (3) | 0.0288 (8) | |
H8A | 0.3049 | 0.3732 | 0.1056 | 0.043* | |
H8B | 0.3562 | 0.4052 | 0.2479 | 0.043* | |
H8C | 0.1738 | 0.3602 | 0.2148 | 0.043* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0275 (12) | 0.0132 (12) | 0.0288 (13) | 0.0017 (9) | 0.0061 (9) | 0.0002 (10) |
O2 | 0.0225 (11) | 0.0290 (13) | 0.0241 (12) | 0.0036 (10) | 0.0052 (9) | 0.0037 (10) |
O3 | 0.0219 (12) | 0.0303 (14) | 0.0231 (12) | 0.0039 (10) | 0.0024 (9) | 0.0009 (10) |
O4 | 0.0260 (11) | 0.0150 (11) | 0.0208 (12) | 0.0023 (9) | 0.0018 (9) | −0.0017 (9) |
N1 | 0.0287 (14) | 0.0149 (14) | 0.0267 (15) | 0.0017 (11) | 0.0090 (12) | −0.0023 (12) |
N2 | 0.0289 (14) | 0.0144 (14) | 0.0266 (15) | 0.0049 (11) | −0.0023 (12) | −0.0063 (12) |
C1 | 0.051 (2) | 0.025 (2) | 0.036 (2) | −0.0006 (17) | 0.0004 (17) | −0.0032 (17) |
C2 | 0.042 (2) | 0.0226 (19) | 0.032 (2) | −0.0037 (15) | −0.0008 (16) | 0.0042 (16) |
C3 | 0.0262 (16) | 0.0147 (17) | 0.0332 (19) | −0.0047 (13) | −0.0007 (14) | −0.0007 (14) |
C4 | 0.0224 (16) | 0.0169 (17) | 0.0184 (16) | 0.0019 (13) | −0.0035 (13) | −0.0010 (13) |
C5 | 0.0227 (16) | 0.0183 (17) | 0.0179 (16) | −0.0008 (13) | 0.0088 (13) | −0.0015 (13) |
C6 | 0.0239 (15) | 0.0212 (17) | 0.0188 (17) | −0.0037 (13) | 0.0021 (13) | −0.0059 (14) |
C7 | 0.0366 (18) | 0.031 (2) | 0.0175 (17) | 0.0023 (15) | 0.0041 (14) | −0.0005 (15) |
C8 | 0.0398 (19) | 0.0225 (18) | 0.0241 (18) | −0.0025 (15) | 0.0030 (14) | −0.0039 (15) |
O1—C4 | 1.336 (3) | C2—C3 | 1.503 (5) |
O1—C3 | 1.476 (4) | C2—H2A | 0.9800 |
O2—C4 | 1.216 (3) | C2—H2B | 0.9800 |
O3—C5 | 1.217 (4) | C2—H2C | 0.9800 |
O4—C5 | 1.342 (4) | C3—H3 | 1.0000 |
O4—C6 | 1.470 (4) | C6—C8 | 1.504 (4) |
N1—C4 | 1.354 (4) | C6—C7 | 1.506 (4) |
N1—N2 | 1.380 (3) | C6—H6 | 1.0000 |
N1—H1 | 0.8800 | C7—H7A | 0.9800 |
N2—C5 | 1.351 (4) | C7—H7B | 0.9800 |
N2—H2 | 0.8800 | C7—H7C | 0.9800 |
C1—C3 | 1.509 (5) | C8—H8A | 0.9800 |
C1—H1A | 0.9800 | C8—H8B | 0.9800 |
C1—H1B | 0.9800 | C8—H8C | 0.9800 |
C1—H1C | 0.9800 | ||
C4—O1—C3 | 115.9 (2) | C1—C3—H3 | 109.2 |
C5—O4—C6 | 116.1 (2) | O2—C4—O1 | 125.2 (3) |
C4—N1—N2 | 119.2 (2) | O2—C4—N1 | 124.7 (3) |
C4—N1—H1 | 120.4 | O1—C4—N1 | 110.0 (2) |
N2—N1—H1 | 120.4 | O3—C5—O4 | 125.5 (3) |
C5—N2—N1 | 119.5 (3) | O3—C5—N2 | 124.7 (3) |
C5—N2—H2 | 120.2 | O4—C5—N2 | 109.7 (3) |
N1—N2—H2 | 120.2 | O4—C6—C8 | 105.4 (2) |
C3—C1—H1A | 109.5 | O4—C6—C7 | 109.6 (2) |
C3—C1—H1B | 109.5 | C8—C6—C7 | 112.8 (3) |
H1A—C1—H1B | 109.5 | O4—C6—H6 | 109.6 |
C3—C1—H1C | 109.5 | C8—C6—H6 | 109.6 |
H1A—C1—H1C | 109.5 | C7—C6—H6 | 109.6 |
H1B—C1—H1C | 109.5 | C6—C7—H7A | 109.5 |
C3—C2—H2A | 109.5 | C6—C7—H7B | 109.5 |
C3—C2—H2B | 109.5 | H7A—C7—H7B | 109.5 |
H2A—C2—H2B | 109.5 | C6—C7—H7C | 109.5 |
C3—C2—H2C | 109.5 | H7A—C7—H7C | 109.5 |
H2A—C2—H2C | 109.5 | H7B—C7—H7C | 109.5 |
H2B—C2—H2C | 109.5 | C6—C8—H8A | 109.5 |
O1—C3—C2 | 110.2 (3) | C6—C8—H8B | 109.5 |
O1—C3—C1 | 105.0 (2) | H8A—C8—H8B | 109.5 |
C2—C3—C1 | 113.9 (3) | C6—C8—H8C | 109.5 |
O1—C3—H3 | 109.2 | H8A—C8—H8C | 109.5 |
C2—C3—H3 | 109.2 | H8B—C8—H8C | 109.5 |
C4—N1—N2—C5 | 100.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O3i | 0.88 | 2.02 | 2.853 (3) | 157 |
N2—H2···O2ii | 0.88 | 1.95 | 2.829 (3) | 174 |
Symmetry codes: (i) −x+1, −y, −z; (ii) −x, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | C8H16N2O4 |
Mr | 204.23 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 120 |
a, b, c (Å) | 8.0299 (16), 12.765 (3), 10.587 (2) |
β (°) | 92.11 (3) |
V (Å3) | 1084.4 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.12 × 0.05 × 0.05 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (Blessing, 1997) |
Tmin, Tmax | 0.988, 0.995 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4768, 1890, 1289 |
Rint | 0.099 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.069, 0.143, 1.06 |
No. of reflections | 1890 |
No. of parameters | 128 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.51, −0.32 |
Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), DENZO and COLLECT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 1990).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O3i | 0.88 | 2.02 | 2.853 (3) | 157.0 |
N2—H2···O2ii | 0.88 | 1.95 | 2.829 (3) | 174.1 |
Symmetry codes: (i) −x+1, −y, −z; (ii) −x, −y, −z. |
The title compound, (I), was obtained as a byproduct of a Mitsunobu coupling reaction using triphenylphosphine and diisopropylazodicarboxylate as reagents. The N1—N2 bond is 1.380 (3) %A, and the two C═O bond distances are 1.216 (3) and 1.217 (4) Å. These values are in agreement with the parameters of 1.381 and 1.202/1.206 Å, respectively, reported for the 1:1 adduct of (I) with triphenylphosphine oxide (Héroux & Brisse, 1997). The torsion angle around the central N—N bond is 73.2° in the latter structure, compared with 100.4° in the title compound.
Each molecule of (I) is connected to two adjacent molecules by four N—H···O hydrogen bonds (Fig. 2 and Table 1). The hydrogen-bond linkage between two neighbouring molecules A and B involves one H-atom donor site and one acceptor site in each of them, N—H(A)···O(B) and N—H(B)···O(A). The hydrogen-bonded chains propagate parallel to [100], with N···O distances of 2.853 (3) and 2.829 (3) Å and N—H···O bond angles of 157 and 174°. A similar hydrogen-bonded one-dimensional network occurs in the diethyl analogue of (I) (Linke & Kalker, 1977).
In contrast, in the 1:1 adduct of diisopropyl hydrazocarboxylate, (I), with triphenylphosphine oxide, (II), the carbonyl O atoms do not participate in hydrogen bonding. Instead, each phosphoryl O atom of (II) is a bifurcated acceptor to the NH groups of two molecules of (I). The result is a cyclic arrangement of four molecules, two (I) + two (II) (Héroux & Brisse, 1997).