The title compound, C
10H
12N
2O
4, crystallizes in the monoclinic non-centrosymmetric space group
Pn with
Z = 2. The two methyl carbamate groups, —N(H)—C(=O)—OCH
3, are twisted away from the aromatic ring mean plane, but form a semiflexible eight-membered cavity involving the atoms of the MeO—C(=O)—N(H)—CH
2—CH
2—N(H)—C(=O)—OMe group. The NH groups act as hydrogen-bond donors and the C=O groups as acceptors to form intermolecular N—H
O hydrogen bonding with an
R21(7) motif, generating extended ribbons along the
b direction.
Supporting information
CCDC reference: 251643
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.003 Å
- R factor = 0.031
- wR factor = 0.081
- Data-to-parameter ratio = 8.3
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT128_ALERT_4_C Non-standard setting of Space group Pc .... Pn
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 27.51
From the CIF: _reflns_number_total 1203
Count of symmetry unique reflns 1210
Completeness (_total/calc) 99.42%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 0
Fraction of Friedel pairs measured 0.000
Are heavy atom types Z>Si present no
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
1 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
0 ALERT type 3 Indicator that the structure quality may be low
2 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXL97 and WinGX2003 (Farrugia, 1999).
Dimethyl
N,
N'-(1,2-phenylene)dicarbamate
top
Crystal data top
C10H12N2O4 | F(000) = 236 |
Mr = 224.22 | Dx = 1.418 Mg m−3 |
Monoclinic, Pn | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P -2yac | Cell parameters from 600 reflections |
a = 9.3056 (19) Å | θ = 20–25° |
b = 4.840 (1) Å | µ = 0.11 mm−1 |
c = 11.843 (2) Å | T = 293 K |
β = 100.181 (3)° | Block, colourless |
V = 525.00 (19) Å3 | 0.52 × 0.42 × 0.36 mm |
Z = 2 | |
Data collection top
Bruker SMART Area-detector diffractometer | 1168 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.024 |
Graphite monochromator | θmax = 27.5°, θmin = 2.6° |
φ and ω scans | h = −11→12 |
4221 measured reflections | k = −6→6 |
1203 independent reflections | l = −15→14 |
Refinement top
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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.081 | H-atom parameters constrained |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0548P)2 + 0.0358P] where P = (Fo2 + 2Fc2)/3 |
1203 reflections | (Δ/σ)max < 0.001 |
145 parameters | Δρmax = 0.25 e Å−3 |
2 restraints | Δρmin = −0.24 e Å−3 |
Special details top
Geometry. Bond distances, angles etc. have been calculated using the rounded
fractional coordinates. All e.s.d.'s are estimated from the variances of the
(full) variance-covariance matrix. The cell e.s.d.'s are taken into account in
the estimation of distances, angles and torsion angles |
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 | |
O8 | −0.19061 (14) | 0.1083 (3) | 0.10711 (12) | 0.0208 (4) | |
O9 | −0.35873 (14) | 0.4484 (3) | 0.09391 (12) | 0.0209 (4) | |
O12 | 0.27835 (16) | 0.8008 (3) | −0.01981 (13) | 0.0264 (4) | |
O13 | 0.09521 (15) | 1.1075 (3) | −0.06882 (12) | 0.0247 (4) | |
N7 | −0.12992 (17) | 0.5497 (3) | 0.16398 (13) | 0.0185 (4) | |
N11 | 0.08810 (17) | 0.8377 (3) | 0.07911 (14) | 0.0205 (4) | |
C1 | 0.0202 (2) | 0.4979 (4) | 0.20952 (15) | 0.0180 (5) | |
C2 | 0.1292 (2) | 0.6385 (4) | 0.16561 (16) | 0.0191 (5) | |
C3 | 0.2751 (2) | 0.5854 (4) | 0.21131 (19) | 0.0265 (6) | |
C4 | 0.3108 (2) | 0.3919 (5) | 0.2986 (2) | 0.0302 (6) | |
C5 | 0.2023 (3) | 0.2534 (5) | 0.34212 (18) | 0.0274 (6) | |
C6 | 0.0572 (2) | 0.3093 (4) | 0.29873 (16) | 0.0220 (5) | |
C8 | −0.22298 (19) | 0.3497 (4) | 0.12072 (14) | 0.0171 (5) | |
C10 | −0.4680 (2) | 0.2582 (4) | 0.03770 (18) | 0.0251 (6) | |
C12 | 0.1666 (2) | 0.9051 (4) | −0.00369 (15) | 0.0189 (5) | |
C14 | 0.1645 (2) | 1.1978 (5) | −0.16184 (17) | 0.0269 (6) | |
H3 | 0.34861 | 0.67944 | 0.18342 | 0.0318* | |
H4 | 0.40834 | 0.35526 | 0.32795 | 0.0362* | |
H5 | 0.22683 | 0.12353 | 0.40020 | 0.0329* | |
H6 | −0.01593 | 0.22064 | 0.32928 | 0.0264* | |
H7 | −0.16190 | 0.71632 | 0.16437 | 0.0222* | |
H10A | −0.56115 | 0.34899 | 0.02257 | 0.0377* | |
H10B | −0.47330 | 0.10144 | 0.08646 | 0.0377* | |
H10C | −0.44221 | 0.19776 | −0.03330 | 0.0377* | |
H11 | 0.00703 | 0.92341 | 0.07857 | 0.0246* | |
H14A | 0.10743 | 1.34220 | −0.20354 | 0.0404* | |
H14B | 0.17174 | 1.04517 | −0.21230 | 0.0404* | |
H14C | 0.26042 | 1.26619 | −0.13172 | 0.0404* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O8 | 0.0206 (7) | 0.0162 (6) | 0.0251 (7) | 0.0026 (5) | 0.0026 (5) | −0.0001 (5) |
O9 | 0.0185 (7) | 0.0199 (6) | 0.0235 (7) | 0.0020 (5) | 0.0018 (5) | −0.0030 (5) |
O12 | 0.0221 (7) | 0.0304 (7) | 0.0280 (7) | 0.0063 (6) | 0.0083 (5) | 0.0053 (6) |
O13 | 0.0240 (7) | 0.0294 (8) | 0.0215 (7) | 0.0052 (6) | 0.0065 (5) | 0.0090 (6) |
N7 | 0.0183 (8) | 0.0139 (7) | 0.0238 (8) | 0.0013 (6) | 0.0051 (6) | 0.0004 (6) |
N11 | 0.0162 (7) | 0.0247 (8) | 0.0213 (7) | 0.0028 (6) | 0.0053 (5) | 0.0057 (6) |
C1 | 0.0199 (9) | 0.0168 (8) | 0.0170 (8) | −0.0001 (7) | 0.0023 (6) | −0.0027 (7) |
C2 | 0.0199 (9) | 0.0195 (8) | 0.0178 (8) | 0.0004 (7) | 0.0027 (6) | 0.0006 (7) |
C3 | 0.0191 (9) | 0.0305 (10) | 0.0287 (10) | −0.0010 (8) | 0.0008 (7) | 0.0080 (8) |
C4 | 0.0232 (10) | 0.0339 (12) | 0.0297 (10) | 0.0012 (9) | −0.0055 (8) | 0.0080 (9) |
C5 | 0.0315 (11) | 0.0275 (10) | 0.0203 (9) | −0.0004 (8) | −0.0036 (7) | 0.0077 (8) |
C6 | 0.0245 (9) | 0.0201 (9) | 0.0212 (9) | −0.0041 (7) | 0.0035 (7) | 0.0010 (7) |
C8 | 0.0185 (9) | 0.0200 (9) | 0.0138 (8) | 0.0007 (7) | 0.0056 (6) | 0.0021 (6) |
C10 | 0.0174 (9) | 0.0247 (10) | 0.0313 (11) | −0.0013 (7) | −0.0009 (7) | −0.0043 (8) |
C12 | 0.0180 (9) | 0.0201 (9) | 0.0179 (8) | −0.0022 (7) | 0.0016 (6) | −0.0008 (7) |
C14 | 0.0273 (10) | 0.0337 (10) | 0.0204 (9) | 0.0010 (9) | 0.0062 (7) | 0.0061 (8) |
Geometric parameters (Å, º) top
O8—C8 | 1.224 (2) | C2—C3 | 1.394 (3) |
O9—C8 | 1.335 (2) | C3—C4 | 1.391 (3) |
O9—C10 | 1.444 (2) | C4—C5 | 1.385 (3) |
O12—C12 | 1.201 (2) | C5—C6 | 1.384 (3) |
O13—C12 | 1.347 (2) | C3—H3 | 0.9296 |
O13—C14 | 1.439 (2) | C4—H4 | 0.9298 |
N7—C1 | 1.428 (2) | C5—H5 | 0.9300 |
N7—C8 | 1.339 (2) | C6—H6 | 0.9302 |
N11—C2 | 1.410 (2) | C10—H10A | 0.9600 |
N11—C12 | 1.362 (2) | C10—H10B | 0.9600 |
N7—H7 | 0.8599 | C10—H10C | 0.9600 |
N11—H11 | 0.8600 | C14—H14A | 0.9600 |
C1—C6 | 1.393 (3) | C14—H14B | 0.9600 |
C1—C2 | 1.396 (3) | C14—H14C | 0.9597 |
| | | |
O8···N7i | 2.819 (2) | C10···H14Cx | 2.9362 |
O8···N11i | 2.976 (2) | C12···H3 | 2.7650 |
O8···C6 | 3.093 (2) | C14···H7xii | 2.8625 |
O9···C14ii | 3.335 (3) | H3···O12 | 2.4514 |
O12···C3 | 2.934 (3) | H3···C12 | 2.7650 |
O12···C10iii | 3.220 (3) | H3···H14Axiii | 2.5425 |
O8···H7i | 2.0166 | H4···H14Axiii | 2.4413 |
O8···H11i | 2.1254 | H5···O8xiv | 2.6811 |
O8···H5iv | 2.6811 | H5···H10Cxiv | 2.4394 |
O8···H14Bv | 2.7812 | H6···O8 | 2.8894 |
O8···H6 | 2.8894 | H6···C8 | 2.9191 |
O8···H10B | 2.5988 | H6···O12v | 2.8424 |
O8···H10C | 2.6567 | H7···O8viii | 2.0166 |
O9···H14Aii | 2.6735 | H7···N11 | 2.7581 |
O12···H3 | 2.4514 | H7···H11 | 2.2523 |
O12···H10Avi | 2.6457 | H7···C14ii | 2.8625 |
O12···H10Biii | 2.8309 | H7···H14Bii | 2.5811 |
O12···H14B | 2.6039 | H10A···O12xv | 2.6457 |
O12···H14Ci | 2.8985 | H10A···H14Cx | 2.2768 |
O12···H14C | 2.6038 | H10B···O8 | 2.5988 |
O12···H6vii | 2.8424 | H10B···O12x | 2.8309 |
N7···O8viii | 2.819 (2) | H10C···O8 | 2.6567 |
N7···N11 | 2.791 (2) | H10C···C5iv | 3.0749 |
N7···C14ii | 3.287 (3) | H10C···H5iv | 2.4394 |
N11···O8viii | 2.976 (2) | H11···O8viii | 2.1254 |
N11···N7 | 2.791 (2) | H11···N7 | 2.5248 |
N7···H14Cii | 2.9261 | H11···C8viii | 3.0765 |
N7···H11 | 2.5248 | H11···H7 | 2.2523 |
N11···H7 | 2.7581 | H14A···O9xii | 2.6735 |
C3···O12 | 2.934 (3) | H14A···C3xvi | 3.0985 |
C6···O8 | 3.093 (2) | H14A···C4xvi | 3.0498 |
C6···C10ix | 3.561 (3) | H14A···H3xvi | 2.5425 |
C10···O12x | 3.220 (3) | H14A···H4xvi | 2.4413 |
C10···C6xi | 3.561 (3) | H14B···O12 | 2.6039 |
C14···O9xii | 3.335 (3) | H14B···O8vii | 2.7812 |
C14···N7xii | 3.287 (3) | H14B···C8vii | 3.0345 |
C3···H14Axiii | 3.0985 | H14B···H7xii | 2.5811 |
C4···H14Axiii | 3.0498 | H14C···O12 | 2.6038 |
C5···H10Cxiv | 3.0749 | H14C···O12viii | 2.8985 |
C8···H6 | 2.9191 | H14C···C10iii | 2.9362 |
C8···H14Bv | 3.0345 | H14C···H10Aiii | 2.2768 |
C8···H11i | 3.0765 | H14C···N7xii | 2.9261 |
| | | |
C8—O9—C10 | 116.17 (15) | O13—C12—N11 | 108.27 (16) |
C12—O13—C14 | 114.63 (15) | O12—C12—O13 | 124.59 (17) |
C1—N7—C8 | 122.75 (15) | C2—C3—H3 | 119.95 |
C2—N11—C12 | 125.17 (16) | C4—C3—H3 | 119.98 |
C1—N7—H7 | 118.62 | C3—C4—H4 | 119.69 |
C8—N7—H7 | 118.62 | C5—C4—H4 | 119.75 |
C2—N11—H11 | 117.41 | C4—C5—H5 | 120.17 |
C12—N11—H11 | 117.42 | C6—C5—H5 | 120.17 |
N7—C1—C2 | 120.03 (16) | C1—C6—H6 | 119.85 |
N7—C1—C6 | 119.72 (16) | C5—C6—H6 | 119.89 |
C2—C1—C6 | 120.24 (17) | O9—C10—H10A | 109.46 |
C1—C2—C3 | 119.18 (18) | O9—C10—H10B | 109.47 |
N11—C2—C1 | 118.85 (17) | O9—C10—H10C | 109.47 |
N11—C2—C3 | 121.93 (17) | H10A—C10—H10B | 109.47 |
C2—C3—C4 | 120.07 (18) | H10A—C10—H10C | 109.47 |
C3—C4—C5 | 120.56 (19) | H10B—C10—H10C | 109.48 |
C4—C5—C6 | 119.7 (2) | O13—C14—H14A | 109.44 |
C1—C6—C5 | 120.27 (18) | O13—C14—H14B | 109.45 |
O8—C8—O9 | 123.68 (17) | O13—C14—H14C | 109.47 |
O8—C8—N7 | 125.65 (17) | H14A—C14—H14B | 109.47 |
O9—C8—N7 | 110.67 (16) | H14A—C14—H14C | 109.49 |
O12—C12—N11 | 127.11 (18) | H14B—C14—H14C | 109.50 |
| | | |
C10—O9—C8—O8 | −5.0 (3) | C6—C1—C2—N11 | −176.99 (17) |
C10—O9—C8—N7 | 175.17 (15) | N7—C1—C2—N11 | 2.2 (3) |
C14—O13—C12—O12 | −0.8 (3) | N7—C1—C2—C3 | 179.91 (17) |
C14—O13—C12—N11 | −179.04 (16) | C2—C1—C6—C5 | −2.0 (3) |
C1—N7—C8—O9 | 174.24 (15) | C6—C1—C2—C3 | 0.7 (3) |
C8—N7—C1—C2 | 123.6 (2) | N7—C1—C6—C5 | 178.76 (18) |
C8—N7—C1—C6 | −57.2 (2) | N11—C2—C3—C4 | 178.40 (19) |
C1—N7—C8—O8 | −5.6 (3) | C1—C2—C3—C4 | 0.8 (3) |
C12—N11—C2—C3 | 31.7 (3) | C2—C3—C4—C5 | −1.0 (3) |
C2—N11—C12—O12 | 3.4 (3) | C3—C4—C5—C6 | −0.3 (3) |
C12—N11—C2—C1 | −150.73 (18) | C4—C5—C6—C1 | 1.8 (3) |
C2—N11—C12—O13 | −178.46 (16) | | |
Symmetry codes: (i) x, y−1, z; (ii) x−1/2, −y+2, z+1/2; (iii) x+1, y+1, z; (iv) x−1/2, −y, z−1/2; (v) x−1/2, −y+1, z+1/2; (vi) x+1, y, z; (vii) x+1/2, −y+1, z−1/2; (viii) x, y+1, z; (ix) x+1/2, −y+1, z+1/2; (x) x−1, y−1, z; (xi) x−1/2, −y+1, z−1/2; (xii) x+1/2, −y+2, z−1/2; (xiii) x+1/2, −y+2, z+1/2; (xiv) x+1/2, −y, z+1/2; (xv) x−1, y, z; (xvi) x−1/2, −y+2, z−1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N7—H7···O8viii | 0.86 | 2.02 | 2.819 (2) | 155 |
N11—H11···O8viii | 0.86 | 2.13 | 2.976 (2) | 170 |
C3—H3···O12 | 0.93 | 2.45 | 2.934 (3) | 112 |
Symmetry code: (viii) x, y+1, z. |