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In the title compound, C6H5NO3·CH4N2O, 4-nitro­phenol mol­ecules are linked to urea mol­ecules by O—H...O and N—H...O hydrogen bonds, forming a network structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805029442/jh6018sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805029442/jh6018Isup2.hkl
Contains datablock I

CCDC reference: 287616

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.061
  • wR factor = 0.141
  • Data-to-parameter ratio = 12.3

checkCIF/PLATON results

No syntax errors found



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

Comment top

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).

Experimental top

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.

Refinement top

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).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The structure of (I) with the atom numbering, showing displacement ellipsoids at the 50% probability level.
[Figure 2] Fig. 2. View parallel to the a axis of (I), showing hydrogen bonds as dashed lines.
4-Nitrophenol–carbamide (1/1) top
Crystal data top
C6H5NO3·CH4N2OZ = 2
Mr = 199.17F(000) = 208
Triclinic, P1Dx = 1.495 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 3.7619 (9) ÅCell parameters from 1561 reflections
b = 10.230 (2) Åθ = 1.8–25.1°
c = 11.810 (3) ŵ = 0.12 mm1
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
Data collection top
Bruker APEX area-detector
diffractometer
1561 independent reflections
Radiation source: fine-focus sealed tube1234 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.013
600 frames, δ ω = 0.3° scansθmax = 25.1°, θmin = 1.8°
Absorption correction: integration
(SADABS; Bruker, 2002)
h = 44
Tmin = 0.98, Tmax = 0.99k = 1212
2362 measured reflectionsl = 1014
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.061Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.141H-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 parametersΔρmax = 0.18 e Å3
0 restraintsΔρmin = 0.18 e Å3
Crystal data top
C6H5NO3·CH4N2Oγ = 99.326 (4)°
Mr = 199.17V = 442.38 (18) Å3
Triclinic, P1Z = 2
a = 3.7619 (9) ÅMo Kα radiation
b = 10.230 (2) ŵ = 0.12 mm1
c = 11.810 (3) ÅT = 298 K
α = 98.634 (4)°0.23 × 0.13 × 0.05 mm
β = 92.415 (5)°
Data collection top
Bruker APEX area-detector
diffractometer
1561 independent reflections
Absorption correction: integration
(SADABS; Bruker, 2002)
1234 reflections with I > 2σ(I)
Tmin = 0.98, Tmax = 0.99Rint = 0.013
2362 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0610 restraints
wR(F2) = 0.141H-atom parameters constrained
S = 1.07Δρmax = 0.18 e Å3
1561 reflectionsΔρmin = 0.18 e Å3
127 parameters
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
xyzUiso*/Ueq
O10.4143 (7)0.1179 (2)0.12760 (18)0.0757 (8)
O20.7330 (7)0.3127 (2)0.12460 (18)0.0707 (7)
O30.3260 (6)0.37109 (19)0.38223 (15)0.0505 (6)
H30.20590.30910.40760.061*
N10.5483 (7)0.2295 (3)0.0767 (2)0.0493 (6)
C10.4884 (7)0.2644 (2)0.0432 (2)0.0360 (6)
C20.6306 (7)0.3919 (3)0.1001 (2)0.0388 (6)
H20.76150.45460.06160.047*
C30.5751 (7)0.4240 (3)0.2140 (2)0.0388 (6)
H3A0.67200.50890.25320.047*
C40.3762 (7)0.3316 (3)0.2715 (2)0.0358 (6)
C50.2390 (7)0.2037 (3)0.2130 (2)0.0395 (7)
H50.10800.14090.25140.047*
C60.2952 (7)0.1699 (3)0.0998 (2)0.0392 (7)
H60.20470.08410.06100.047*
O40.9669 (6)0.17135 (19)0.46670 (16)0.0518 (6)
N20.7830 (7)0.3079 (2)0.6120 (2)0.0509 (7)
H2B0.81540.37430.57460.061*
H2C0.70540.31840.67970.061*
N30.8076 (7)0.0900 (2)0.6259 (2)0.0573 (7)
H3B0.85500.01240.59850.069*
H3C0.72970.10340.69340.069*
C70.8543 (7)0.1886 (3)0.5643 (2)0.0380 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.112 (2)0.0670 (16)0.0417 (13)0.0110 (14)0.0081 (13)0.0089 (12)
O20.0967 (19)0.0771 (16)0.0446 (13)0.0157 (14)0.0300 (13)0.0218 (12)
O30.0675 (14)0.0494 (12)0.0339 (11)0.0056 (10)0.0131 (9)0.0059 (9)
N10.0631 (17)0.0554 (16)0.0336 (13)0.0213 (13)0.0081 (12)0.0069 (12)
C10.0389 (15)0.0420 (15)0.0302 (14)0.0143 (12)0.0036 (11)0.0076 (11)
C20.0382 (15)0.0392 (15)0.0425 (16)0.0075 (12)0.0110 (12)0.0149 (12)
C30.0373 (15)0.0343 (14)0.0435 (16)0.0036 (11)0.0038 (12)0.0044 (12)
C40.0355 (15)0.0407 (14)0.0333 (14)0.0101 (11)0.0042 (11)0.0086 (11)
C50.0401 (16)0.0388 (14)0.0401 (16)0.0000 (12)0.0045 (12)0.0145 (12)
C60.0448 (16)0.0327 (14)0.0385 (16)0.0041 (12)0.0001 (12)0.0038 (11)
O40.0741 (15)0.0476 (12)0.0349 (11)0.0090 (10)0.0216 (10)0.0068 (9)
N20.0702 (18)0.0444 (14)0.0405 (14)0.0140 (12)0.0172 (12)0.0062 (11)
N30.092 (2)0.0481 (14)0.0390 (14)0.0217 (14)0.0275 (13)0.0131 (11)
C70.0409 (16)0.0424 (15)0.0290 (14)0.0050 (12)0.0044 (11)0.0023 (12)
Geometric parameters (Å, º) top
O1—N11.225 (3)C4—C51.390 (4)
O2—N11.230 (3)C5—C61.365 (4)
O3—C41.341 (3)C5—H50.9300
O3—H30.8200C6—H60.9300
N1—C11.444 (3)O4—C71.243 (3)
C1—C61.385 (4)N2—C71.339 (3)
C1—C21.386 (4)N2—H2B0.8600
C2—C31.368 (4)N2—H2C0.8600
C2—H20.9300N3—C71.323 (3)
C3—C41.386 (4)N3—H3B0.8600
C3—H3A0.9300N3—H3C0.8601
C4—O3—H3109.4C6—C5—C4120.4 (2)
O1—N1—O2122.0 (2)C6—C5—H5119.8
O1—N1—C1119.0 (2)C4—C5—H5119.8
O2—N1—C1119.0 (3)C5—C6—C1119.4 (2)
C6—C1—C2121.1 (2)C5—C6—H6120.3
C6—C1—N1119.7 (2)C1—C6—H6120.3
C2—C1—N1119.2 (2)C7—N2—H2B119.6
C3—C2—C1118.9 (2)C7—N2—H2C120.4
C3—C2—H2120.5H2B—N2—H2C120.0
C1—C2—H2120.5C7—N3—H3B120.0
C2—C3—C4120.8 (2)C7—N3—H3C120.0
C2—C3—H3A119.6H3B—N3—H3C120.0
C4—C3—H3A119.6O4—C7—N3121.0 (2)
O3—C4—C3117.5 (2)O4—C7—N2121.4 (3)
O3—C4—C5123.1 (2)N3—C7—N2117.6 (2)
C3—C4—C5119.4 (2)
O1—N1—C1—C62.8 (4)C2—C3—C4—O3178.5 (2)
O2—N1—C1—C6177.0 (3)C2—C3—C4—C51.5 (4)
O1—N1—C1—C2178.1 (3)O3—C4—C5—C6179.2 (2)
O2—N1—C1—C22.0 (4)C3—C4—C5—C60.8 (4)
C6—C1—C2—C30.5 (4)C4—C5—C6—C10.5 (4)
N1—C1—C2—C3179.5 (2)C2—C1—C6—C51.1 (4)
C1—C2—C3—C40.8 (4)N1—C1—C6—C5179.8 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3C···O1i0.862.463.316 (3)171
N3—H3B···O4ii0.862.143.000 (3)174
N2—H2C···O2i0.862.323.118 (3)155
O3—H3···O4iii0.821.792.613 (3)177
Symmetry codes: (i) x, y, z+1; (ii) x+2, y, z+1; (iii) x1, y, z.

Experimental details

Crystal data
Chemical formulaC6H5NO3·CH4N2O
Mr199.17
Crystal system, space groupTriclinic, 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)
V3)442.38 (18)
Z2
Radiation typeMo Kα
µ (mm1)0.12
Crystal size (mm)0.23 × 0.13 × 0.05
Data collection
DiffractometerBruker APEX area-detector
diffractometer
Absorption correctionIntegration
(SADABS; Bruker, 2002)
Tmin, Tmax0.98, 0.99
No. of measured, independent and
observed [I > 2σ(I)] reflections
2362, 1561, 1234
Rint0.013
(sin θ/λ)max1)0.597
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.061, 0.141, 1.07
No. of reflections1561
No. of parameters127
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.18, 0.18

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.

Selected geometric parameters (Å, º) top
O1—N11.225 (3)C3—C41.386 (4)
O2—N11.230 (3)C4—C51.390 (4)
O3—C41.341 (3)C5—C61.365 (4)
N1—C11.444 (3)O4—C71.243 (3)
C1—C61.385 (4)N2—C71.339 (3)
C1—C21.386 (4)N3—C71.323 (3)
C2—C31.368 (4)
C4—O3—H3109.4O3—C4—C3117.5 (2)
O1—N1—O2122.0 (2)O3—C4—C5123.1 (2)
O1—N1—C1119.0 (2)C3—C4—C5119.4 (2)
O2—N1—C1119.0 (3)C6—C5—C4120.4 (2)
C6—C1—C2121.1 (2)C5—C6—C1119.4 (2)
C6—C1—N1119.7 (2)O4—C7—N3121.0 (2)
C2—C1—N1119.2 (2)O4—C7—N2121.4 (3)
C3—C2—C1118.9 (2)N3—C7—N2117.6 (2)
C2—C3—C4120.8 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3C···O1i0.862.463.316 (3)171
N3—H3B···O4ii0.862.143.000 (3)174
N2—H2C···O2i0.862.323.118 (3)155
O3—H3···O4iii0.821.792.613 (3)177
Symmetry codes: (i) x, y, z+1; (ii) x+2, y, z+1; (iii) x1, y, z.
 

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