Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805029442/jh6018sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805029442/jh6018Isup2.hkl |
CCDC reference: 287616
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.004 Å
- R factor = 0.061
- wR factor = 0.141
- Data-to-parameter ratio = 12.3
checkCIF/PLATON results
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Alert level C PLAT420_ALERT_2_C D-H Without Acceptor N2 - H2B ... ?
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion
checkCIF publication errors
Alert level A PUBL023_ALERT_1_A There is a mismatched ^ on line 280 Refinement of F2^ against ALL reflections. The weighted R-factor wR and If you require a ^ then it should be escaped with a \, i.e. \^ Otherwise there must be a matching closing ~, e.g. ^12^C PUBL023_ALERT_1_A There is a mismatched ^ on line 281 goodness of fit S are based on F2^, conventional R-factors R are based If you require a ^ then it should be escaped with a \, i.e. \^ Otherwise there must be a matching closing ~, e.g. ^12^C PUBL023_ALERT_1_A There is a mismatched ^ on line 282 on F, with F set to zero for negative F2^. The threshold expression of If you require a ^ then it should be escaped with a \, i.e. \^ Otherwise there must be a matching closing ~, e.g. ^12^C PUBL023_ALERT_1_A There is a mismatched ^ on line 285 on F2^ are statistically about twice as large as those based on F, and R- If you require a ^ then it should be escaped with a \, i.e. \^ Otherwise there must be a matching closing ~, e.g. ^12^C PUBL023_ALERT_1_A There is a mismatched ^ on line 293 'calc w = 1/[\s^2^(Fo^2^)+(0.0564P)2^+0.2445P] where P = (Fo^2^+2Fc^2^)/3' If you require a ^ then it should be escaped with a \, i.e. \^ Otherwise there must be a matching closing ~, e.g. ^12^C
5 ALERT level A = Data missing that is essential or data in wrong format 0 ALERT level G = General alerts. Data that may be required is missing
Carbamide (0.12 g, 2 mmol) and 4-nitrophenol (0.28 g, 2 mmol) were dissolved in dimethylformamide (10 ml). The reaction mixture was filtered. Colourless prism-shaped crystals separated from the filtrate after about a month.
The presence of two peaks in the difference Fourier map in two suitable locations showed atoms N2 and N3 to be protonated, and the H atoms attached to N2 and N3 were included in the refinement in calculated positions in the riding-model approximation (N—H = 0.86 Å), with Uiso(H) = 1.2Ueq(N). The other H atoms were positioned geometrically and allowed to ride on their parent atoms at distances of 0.82 (O—H) and 0.93 Å (C—H), and Uiso(H) = 1.2Ueq(parent atom).
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
Fig. 1. The structure of (I) with the atom numbering, showing displacement ellipsoids at the 50% probability level. | |
Fig. 2. View parallel to the a axis of (I), showing hydrogen bonds as dashed lines. |
C6H5NO3·CH4N2O | Z = 2 |
Mr = 199.17 | F(000) = 208 |
Triclinic, P1 | Dx = 1.495 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 3.7619 (9) Å | Cell parameters from 1561 reflections |
b = 10.230 (2) Å | θ = 1.8–25.1° |
c = 11.810 (3) Å | µ = 0.12 mm−1 |
α = 98.634 (4)° | T = 298 K |
β = 92.415 (5)° | Prism, colorless |
γ = 99.326 (4)° | 0.23 × 0.13 × 0.05 mm |
V = 442.38 (18) Å3 |
Bruker APEX area-detector diffractometer | 1561 independent reflections |
Radiation source: fine-focus sealed tube | 1234 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.013 |
600 frames, δ ω = 0.3° scans | θmax = 25.1°, θmin = 1.8° |
Absorption correction: integration (SADABS; Bruker, 2002) | h = −4→4 |
Tmin = 0.98, Tmax = 0.99 | k = −12→12 |
2362 measured reflections | l = −10→14 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.061 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.141 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0564P)2 + 0.2445P] where P = (Fo2 + 2Fc2)/3 |
1561 reflections | (Δ/σ)max < 0.001 |
127 parameters | Δρmax = 0.18 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
C6H5NO3·CH4N2O | γ = 99.326 (4)° |
Mr = 199.17 | V = 442.38 (18) Å3 |
Triclinic, P1 | Z = 2 |
a = 3.7619 (9) Å | Mo Kα radiation |
b = 10.230 (2) Å | µ = 0.12 mm−1 |
c = 11.810 (3) Å | T = 298 K |
α = 98.634 (4)° | 0.23 × 0.13 × 0.05 mm |
β = 92.415 (5)° |
Bruker APEX area-detector diffractometer | 1561 independent reflections |
Absorption correction: integration (SADABS; Bruker, 2002) | 1234 reflections with I > 2σ(I) |
Tmin = 0.98, Tmax = 0.99 | Rint = 0.013 |
2362 measured reflections |
R[F2 > 2σ(F2)] = 0.061 | 0 restraints |
wR(F2) = 0.141 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.18 e Å−3 |
1561 reflections | Δρmin = −0.18 e Å−3 |
127 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 | 0.4143 (7) | 0.1179 (2) | −0.12760 (18) | 0.0757 (8) | |
O2 | 0.7330 (7) | 0.3127 (2) | −0.12460 (18) | 0.0707 (7) | |
O3 | 0.3260 (6) | 0.37109 (19) | 0.38223 (15) | 0.0505 (6) | |
H3 | 0.2059 | 0.3091 | 0.4076 | 0.061* | |
N1 | 0.5483 (7) | 0.2295 (3) | −0.0767 (2) | 0.0493 (6) | |
C1 | 0.4884 (7) | 0.2644 (2) | 0.0432 (2) | 0.0360 (6) | |
C2 | 0.6306 (7) | 0.3919 (3) | 0.1001 (2) | 0.0388 (6) | |
H2 | 0.7615 | 0.4546 | 0.0616 | 0.047* | |
C3 | 0.5751 (7) | 0.4240 (3) | 0.2140 (2) | 0.0388 (6) | |
H3A | 0.6720 | 0.5089 | 0.2532 | 0.047* | |
C4 | 0.3762 (7) | 0.3316 (3) | 0.2715 (2) | 0.0358 (6) | |
C5 | 0.2390 (7) | 0.2037 (3) | 0.2130 (2) | 0.0395 (7) | |
H5 | 0.1080 | 0.1409 | 0.2514 | 0.047* | |
C6 | 0.2952 (7) | 0.1699 (3) | 0.0998 (2) | 0.0392 (7) | |
H6 | 0.2047 | 0.0841 | 0.0610 | 0.047* | |
O4 | 0.9669 (6) | 0.17135 (19) | 0.46670 (16) | 0.0518 (6) | |
N2 | 0.7830 (7) | 0.3079 (2) | 0.6120 (2) | 0.0509 (7) | |
H2B | 0.8154 | 0.3743 | 0.5746 | 0.061* | |
H2C | 0.7054 | 0.3184 | 0.6797 | 0.061* | |
N3 | 0.8076 (7) | 0.0900 (2) | 0.6259 (2) | 0.0573 (7) | |
H3B | 0.8550 | 0.0124 | 0.5985 | 0.069* | |
H3C | 0.7297 | 0.1034 | 0.6934 | 0.069* | |
C7 | 0.8543 (7) | 0.1886 (3) | 0.5643 (2) | 0.0380 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.112 (2) | 0.0670 (16) | 0.0417 (13) | 0.0110 (14) | 0.0081 (13) | −0.0089 (12) |
O2 | 0.0967 (19) | 0.0771 (16) | 0.0446 (13) | 0.0157 (14) | 0.0300 (13) | 0.0218 (12) |
O3 | 0.0675 (14) | 0.0494 (12) | 0.0339 (11) | 0.0056 (10) | 0.0131 (9) | 0.0059 (9) |
N1 | 0.0631 (17) | 0.0554 (16) | 0.0336 (13) | 0.0213 (13) | 0.0081 (12) | 0.0069 (12) |
C1 | 0.0389 (15) | 0.0420 (15) | 0.0302 (14) | 0.0143 (12) | 0.0036 (11) | 0.0076 (11) |
C2 | 0.0382 (15) | 0.0392 (15) | 0.0425 (16) | 0.0075 (12) | 0.0110 (12) | 0.0149 (12) |
C3 | 0.0373 (15) | 0.0343 (14) | 0.0435 (16) | 0.0036 (11) | 0.0038 (12) | 0.0044 (12) |
C4 | 0.0355 (15) | 0.0407 (14) | 0.0333 (14) | 0.0101 (11) | 0.0042 (11) | 0.0086 (11) |
C5 | 0.0401 (16) | 0.0388 (14) | 0.0401 (16) | 0.0000 (12) | 0.0045 (12) | 0.0145 (12) |
C6 | 0.0448 (16) | 0.0327 (14) | 0.0385 (16) | 0.0041 (12) | 0.0001 (12) | 0.0038 (11) |
O4 | 0.0741 (15) | 0.0476 (12) | 0.0349 (11) | 0.0090 (10) | 0.0216 (10) | 0.0068 (9) |
N2 | 0.0702 (18) | 0.0444 (14) | 0.0405 (14) | 0.0140 (12) | 0.0172 (12) | 0.0062 (11) |
N3 | 0.092 (2) | 0.0481 (14) | 0.0390 (14) | 0.0217 (14) | 0.0275 (13) | 0.0131 (11) |
C7 | 0.0409 (16) | 0.0424 (15) | 0.0290 (14) | 0.0050 (12) | 0.0044 (11) | 0.0023 (12) |
O1—N1 | 1.225 (3) | C4—C5 | 1.390 (4) |
O2—N1 | 1.230 (3) | C5—C6 | 1.365 (4) |
O3—C4 | 1.341 (3) | C5—H5 | 0.9300 |
O3—H3 | 0.8200 | C6—H6 | 0.9300 |
N1—C1 | 1.444 (3) | O4—C7 | 1.243 (3) |
C1—C6 | 1.385 (4) | N2—C7 | 1.339 (3) |
C1—C2 | 1.386 (4) | N2—H2B | 0.8600 |
C2—C3 | 1.368 (4) | N2—H2C | 0.8600 |
C2—H2 | 0.9300 | N3—C7 | 1.323 (3) |
C3—C4 | 1.386 (4) | N3—H3B | 0.8600 |
C3—H3A | 0.9300 | N3—H3C | 0.8601 |
C4—O3—H3 | 109.4 | C6—C5—C4 | 120.4 (2) |
O1—N1—O2 | 122.0 (2) | C6—C5—H5 | 119.8 |
O1—N1—C1 | 119.0 (2) | C4—C5—H5 | 119.8 |
O2—N1—C1 | 119.0 (3) | C5—C6—C1 | 119.4 (2) |
C6—C1—C2 | 121.1 (2) | C5—C6—H6 | 120.3 |
C6—C1—N1 | 119.7 (2) | C1—C6—H6 | 120.3 |
C2—C1—N1 | 119.2 (2) | C7—N2—H2B | 119.6 |
C3—C2—C1 | 118.9 (2) | C7—N2—H2C | 120.4 |
C3—C2—H2 | 120.5 | H2B—N2—H2C | 120.0 |
C1—C2—H2 | 120.5 | C7—N3—H3B | 120.0 |
C2—C3—C4 | 120.8 (2) | C7—N3—H3C | 120.0 |
C2—C3—H3A | 119.6 | H3B—N3—H3C | 120.0 |
C4—C3—H3A | 119.6 | O4—C7—N3 | 121.0 (2) |
O3—C4—C3 | 117.5 (2) | O4—C7—N2 | 121.4 (3) |
O3—C4—C5 | 123.1 (2) | N3—C7—N2 | 117.6 (2) |
C3—C4—C5 | 119.4 (2) | ||
O1—N1—C1—C6 | 2.8 (4) | C2—C3—C4—O3 | −178.5 (2) |
O2—N1—C1—C6 | −177.0 (3) | C2—C3—C4—C5 | 1.5 (4) |
O1—N1—C1—C2 | −178.1 (3) | O3—C4—C5—C6 | 179.2 (2) |
O2—N1—C1—C2 | 2.0 (4) | C3—C4—C5—C6 | −0.8 (4) |
C6—C1—C2—C3 | −0.5 (4) | C4—C5—C6—C1 | −0.5 (4) |
N1—C1—C2—C3 | −179.5 (2) | C2—C1—C6—C5 | 1.1 (4) |
C1—C2—C3—C4 | −0.8 (4) | N1—C1—C6—C5 | −179.8 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3C···O1i | 0.86 | 2.46 | 3.316 (3) | 171 |
N3—H3B···O4ii | 0.86 | 2.14 | 3.000 (3) | 174 |
N2—H2C···O2i | 0.86 | 2.32 | 3.118 (3) | 155 |
O3—H3···O4iii | 0.82 | 1.79 | 2.613 (3) | 177 |
Symmetry codes: (i) x, y, z+1; (ii) −x+2, −y, −z+1; (iii) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C6H5NO3·CH4N2O |
Mr | 199.17 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 3.7619 (9), 10.230 (2), 11.810 (3) |
α, β, γ (°) | 98.634 (4), 92.415 (5), 99.326 (4) |
V (Å3) | 442.38 (18) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.23 × 0.13 × 0.05 |
Data collection | |
Diffractometer | Bruker APEX area-detector diffractometer |
Absorption correction | Integration (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.98, 0.99 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2362, 1561, 1234 |
Rint | 0.013 |
(sin θ/λ)max (Å−1) | 0.597 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.061, 0.141, 1.07 |
No. of reflections | 1561 |
No. of parameters | 127 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.18, −0.18 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.
O1—N1 | 1.225 (3) | C3—C4 | 1.386 (4) |
O2—N1 | 1.230 (3) | C4—C5 | 1.390 (4) |
O3—C4 | 1.341 (3) | C5—C6 | 1.365 (4) |
N1—C1 | 1.444 (3) | O4—C7 | 1.243 (3) |
C1—C6 | 1.385 (4) | N2—C7 | 1.339 (3) |
C1—C2 | 1.386 (4) | N3—C7 | 1.323 (3) |
C2—C3 | 1.368 (4) | ||
C4—O3—H3 | 109.4 | O3—C4—C3 | 117.5 (2) |
O1—N1—O2 | 122.0 (2) | O3—C4—C5 | 123.1 (2) |
O1—N1—C1 | 119.0 (2) | C3—C4—C5 | 119.4 (2) |
O2—N1—C1 | 119.0 (3) | C6—C5—C4 | 120.4 (2) |
C6—C1—C2 | 121.1 (2) | C5—C6—C1 | 119.4 (2) |
C6—C1—N1 | 119.7 (2) | O4—C7—N3 | 121.0 (2) |
C2—C1—N1 | 119.2 (2) | O4—C7—N2 | 121.4 (3) |
C3—C2—C1 | 118.9 (2) | N3—C7—N2 | 117.6 (2) |
C2—C3—C4 | 120.8 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3C···O1i | 0.86 | 2.46 | 3.316 (3) | 171 |
N3—H3B···O4ii | 0.86 | 2.14 | 3.000 (3) | 174 |
N2—H2C···O2i | 0.86 | 2.32 | 3.118 (3) | 155 |
O3—H3···O4iii | 0.82 | 1.79 | 2.613 (3) | 177 |
Symmetry codes: (i) x, y, z+1; (ii) −x+2, −y, −z+1; (iii) x−1, y, z. |
In the design of crystal structures, the assembly of molecular units in predefined arrangements is a key goal (Desiraju, 1995, 1997; Braga et al., 1998). Directional intermolecular interactions are the primary tools in achieving this goal and hydrogen bonding is currently the best among them (Zaworotko, 1997; Braga & Grepioni, 2000).
The title compound, (I), forms a co-crystal (Fig. 1 and Table 1) in which 4-nitrophenol and carbamide molecules interact through multiple hydrogen bonds (Table 2) generating a three-dimensional network (Fig. 2).