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tert-Butyl (5-chloro­penta-2,4-diyn-1-yl)carbamate and tert-butyl (5-iodo­penta-2,4-diyn-1-yl)carbamate are new members of the isostructural family of compounds with the general formula BocNHCH2CCCCX (X = H, Cl, Br, I). In the crystals of all these di­acetyl­enes, mol­ecules are linked via a bifurcated N—H...O hydrogen bond and C—X...O halogen bond involving the same carbonyl group.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989017010155/mw2133sup1.cif
Contains datablocks global, II, IV

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2056989017010155/mw2133IIsup2.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2056989017010155/mw2133IVsup3.hkl
Contains datablock IV

CCDC references: 1551031; 1551032

checkCIF/PLATON results

No syntax errors found



Datablock: II


Alert level C PLAT373_ALERT_2_C Long C(sp)-C(sp) Bond C2 - C3 .. 1.38 Ang. PLAT761_ALERT_1_C CIF Contains no X-H Bonds ...................... Please Check PLAT762_ALERT_1_C CIF Contains no X-Y-H or H-Y-H Angles .......... Please Check PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 9 Report PLAT978_ALERT_2_C Number C-C Bonds with Positive Residual Density. 0 Note
Alert level G PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms .............. 1 Report PLAT230_ALERT_2_G Hirshfeld Test Diff for Cl1 -- C1 .. 10.3 s.u. PLAT431_ALERT_2_G Short Inter HL..A Contact Cl1 .. O1 .. 3.13 Ang. PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L= 0.600 5 Note PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ... 8 Note
0 ALERT level A = Most likely a serious problem - resolve or explain 0 ALERT level B = A potentially serious problem, consider carefully 5 ALERT level C = Check. Ensure it is not caused by an omission or oversight 5 ALERT level G = General information/check it is not something unexpected 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 5 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
Datablock: IV
Alert level C PLAT373_ALERT_2_C Long C(sp)-C(sp) Bond C2 - C3 .. 1.38 Ang.
Alert level G PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms .............. 1 Report PLAT431_ALERT_2_G Short Inter HL..A Contact I1 .. O2 .. 2.94 Ang. PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ... 1 Note PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density. 3 Note
0 ALERT level A = Most likely a serious problem - resolve or explain 0 ALERT level B = A potentially serious problem, consider carefully 1 ALERT level C = Check. Ensure it is not caused by an omission or oversight 4 ALERT level G = General information/check it is not something unexpected 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 4 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 1 ALERT type 5 Informative message, check

Computing details top

For both structures, data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SORTAV (Blessing, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 2012) and publCIF (Westrip, 2010).

tert-Butyl (5-chloropenta-2,4-diyn-1-yl)carbamate (II) top
Crystal data top
C10H12ClNO2F(000) = 448
Mr = 213.66Dx = 1.283 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 8841 reflections
a = 10.336 (3) Åθ = 2.8–26.4°
b = 9.171 (3) ŵ = 0.32 mm1
c = 11.870 (3) ÅT = 173 K
β = 100.656 (5)°Plate, orange
V = 1105.8 (5) Å30.34 × 0.22 × 0.02 mm
Z = 4
Data collection top
Bruker APEXII
diffractometer
2249 independent reflections
Radiation source: sealed x-ray tube1755 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.045
φ or ω oscillation scansθmax = 26.4°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
h = 1212
Tmin = 0.66, Tmax = 0.745k = 1111
16132 measured reflectionsl = 914
Refinement top
Refinement on F20 constraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036H-atom parameters constrained
wR(F2) = 0.089 w = 1/[σ2(Fo2) + (0.0397P)2 + 0.2863P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
2249 reflectionsΔρmax = 0.22 e Å3
130 parametersΔρmin = 0.21 e Å3
0 restraints
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.40035 (19)0.0211 (2)0.15762 (16)0.0343 (4)
C20.50716 (18)0.0266 (2)0.15615 (16)0.0336 (4)
C30.63096 (19)0.0798 (2)0.15309 (16)0.0336 (4)
C40.73990 (19)0.1223 (2)0.15037 (16)0.0334 (4)
C50.87519 (17)0.1687 (2)0.14761 (17)0.0339 (4)
H5A0.8829350.2748280.162430.041*
H5B0.8943450.1505690.0701250.041*
C61.04144 (17)0.15939 (19)0.32333 (15)0.0271 (4)
C71.22986 (18)0.11065 (19)0.47967 (15)0.0304 (4)
C81.1748 (2)0.1841 (2)0.57483 (17)0.0439 (5)
H8A1.1063640.1223680.5970470.066*
H8B1.2456440.1989550.6411320.066*
H8C1.1369130.2786180.5479230.066*
C91.32333 (19)0.2075 (2)0.42986 (18)0.0408 (5)
H9A1.2787450.2988150.402990.061*
H9B1.4005770.2289710.4889020.061*
H9C1.3512830.157660.3653710.061*
C101.2953 (2)0.0332 (2)0.52078 (19)0.0449 (5)
H10A1.3241360.0827150.4565270.067*
H10B1.3717350.0144140.5813780.067*
H10C1.2323650.0951150.5509160.067*
Cl10.24981 (4)0.08590 (5)0.15756 (4)0.03061 (14)
N10.97160 (14)0.09282 (16)0.23144 (13)0.0314 (4)
H10.9847660.0007390.2215510.038*
O11.03225 (13)0.28874 (13)0.34594 (11)0.0361 (3)
O21.12149 (12)0.06256 (12)0.38708 (11)0.0311 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0342 (11)0.0349 (11)0.0334 (11)0.0009 (9)0.0055 (8)0.0009 (8)
C20.0337 (11)0.0333 (10)0.0323 (11)0.0036 (8)0.0019 (8)0.0007 (8)
C30.0333 (11)0.0300 (10)0.0346 (11)0.0005 (8)0.0011 (8)0.0016 (8)
C40.0339 (11)0.0279 (10)0.0350 (11)0.0023 (8)0.0028 (8)0.0006 (8)
C50.0309 (10)0.0311 (10)0.0368 (11)0.0013 (8)0.0014 (8)0.0030 (8)
C60.0264 (9)0.0222 (9)0.0323 (10)0.0014 (7)0.0045 (7)0.0023 (7)
C70.0311 (10)0.0269 (10)0.0299 (10)0.0017 (8)0.0026 (8)0.0021 (8)
C80.0524 (13)0.0429 (12)0.0369 (12)0.0014 (10)0.0091 (10)0.0049 (9)
C90.0344 (11)0.0415 (12)0.0451 (13)0.0056 (9)0.0037 (9)0.0019 (9)
C100.0468 (13)0.0339 (11)0.0462 (13)0.0041 (10)0.0121 (10)0.0007 (9)
Cl10.0268 (2)0.0320 (3)0.0337 (3)0.00451 (19)0.00733 (18)0.00090 (19)
N10.0303 (8)0.0220 (8)0.0381 (9)0.0024 (7)0.0036 (7)0.0013 (7)
O10.0409 (8)0.0217 (7)0.0427 (8)0.0034 (6)0.0003 (6)0.0014 (6)
O20.0314 (7)0.0220 (7)0.0358 (8)0.0009 (5)0.0049 (6)0.0006 (5)
Geometric parameters (Å, º) top
C1—C21.191 (3)C6—N11.339 (2)
C1—Cl11.666 (2)C6—O21.347 (2)
C2—C31.376 (3)C7—O21.484 (2)
C3—C41.198 (3)C7—C91.511 (3)
C4—C51.468 (3)C7—C81.513 (3)
C5—N11.449 (2)C7—C101.521 (3)
C6—O11.224 (2)
C2—C1—Cl1178.9 (2)O2—C7—C9109.55 (15)
C1—C2—C3179.0 (2)O2—C7—C8110.41 (15)
C4—C3—C2178.2 (2)C9—C7—C8112.70 (16)
C3—C4—C5177.8 (2)O2—C7—C10102.12 (14)
N1—C5—C4112.49 (16)C9—C7—C10110.89 (17)
O1—C6—N1124.66 (17)C8—C7—C10110.67 (17)
O1—C6—O2125.48 (17)C6—N1—C5122.64 (16)
N1—C6—O2109.86 (15)C6—O2—C7121.42 (13)
O1—C6—N1—C50.3 (3)N1—C6—O2—C7166.78 (14)
O2—C6—N1—C5178.98 (15)C9—C7—O2—C659.3 (2)
C4—C5—N1—C6111.1 (2)C8—C7—O2—C665.4 (2)
O1—C6—O2—C713.9 (3)C10—C7—O2—C6176.85 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.882.092.935162
C1—Cl1···O1ii1.673.134.793179
Symmetry codes: (i) x+2, y+1/2, z+1/2; (ii) x+1, y+1/2, z+1/2.
tert-Butyl (5-iodopenta-2,4-diyn-1-yl)carbamate (IV) top
Crystal data top
C10H12INO2F(000) = 592
Mr = 305.11Dx = 1.635 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 9940 reflections
a = 11.1587 (16) Åθ = 2.3–26.4°
b = 9.0288 (13) ŵ = 2.56 mm1
c = 12.9899 (18) ÅT = 173 K
β = 108.731 (2)°Prism, yellow
V = 1239.4 (3) Å30.36 × 0.3 × 0.28 mm
Z = 4
Data collection top
Bruker APEXII
diffractometer
2532 independent reflections
Radiation source: sealed x-ray tube2342 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.02
φ or ω oscillation scansθmax = 26.4°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
h = 1213
Tmin = 0.675, Tmax = 0.745k = 1111
17970 measured reflectionsl = 1516
Refinement top
Refinement on F20 constraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.022H-atom parameters constrained
wR(F2) = 0.054 w = 1/[σ2(Fo2) + (0.0203P)2 + 1.7447P]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max = 0.001
2532 reflectionsΔρmax = 1.32 e Å3
130 parametersΔρmin = 0.69 e Å3
0 restraints
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.2157 (2)1.0340 (3)0.3437 (2)0.0328 (6)
C20.3210 (2)1.0012 (3)0.34873 (19)0.0304 (5)
C30.4425 (2)0.9623 (3)0.35280 (19)0.0279 (5)
C40.5465 (2)0.9286 (3)0.35525 (19)0.0275 (5)
C50.6760 (2)0.8938 (3)0.35692 (19)0.0282 (5)
H5A0.7367040.9270890.426910.034*
H5B0.6848330.7850760.3521720.034*
C60.7111 (2)0.8882 (2)0.18051 (19)0.0219 (4)
C70.7579 (3)0.9226 (3)0.0094 (2)0.0344 (6)
C80.7976 (4)1.0622 (3)0.0367 (3)0.0511 (8)
H8A0.7304691.1366250.0498320.077*
H8B0.8123861.0386090.1053070.077*
H8C0.8756161.1012120.0152780.077*
C90.6338 (4)0.8624 (4)0.0654 (3)0.0559 (9)
H9A0.6112520.7723680.0336980.084*
H9B0.6425080.8391130.1363370.084*
H9C0.5671950.9368320.0745870.084*
C100.8637 (3)0.8100 (4)0.0377 (3)0.0506 (8)
H10A0.9364430.8492220.0958070.076*
H10B0.8887030.7894970.026660.076*
H10C0.8346260.7182480.0622970.076*
N10.7077 (2)0.9636 (2)0.26832 (16)0.0263 (4)
H10.7252561.0589130.2724550.032*
O10.73962 (17)0.97953 (18)0.11063 (13)0.0272 (4)
O20.69111 (17)0.75519 (18)0.16743 (14)0.0289 (4)
I10.04221 (2)1.09875 (2)0.33737 (2)0.03907 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0294 (14)0.0398 (14)0.0301 (13)0.0020 (11)0.0106 (10)0.0027 (11)
C20.0333 (14)0.0328 (13)0.0263 (12)0.0012 (11)0.0110 (10)0.0031 (10)
C30.0312 (14)0.0309 (13)0.0250 (11)0.0015 (10)0.0139 (10)0.0011 (10)
C40.0337 (14)0.0284 (12)0.0236 (11)0.0036 (10)0.0135 (10)0.0005 (9)
C50.0298 (13)0.0321 (13)0.0259 (12)0.0007 (10)0.0132 (10)0.0032 (10)
C60.0180 (11)0.0216 (11)0.0271 (11)0.0013 (8)0.0087 (9)0.0020 (9)
C70.0490 (17)0.0323 (13)0.0293 (13)0.0017 (12)0.0229 (12)0.0034 (10)
C80.085 (3)0.0407 (17)0.0437 (17)0.0055 (16)0.0430 (18)0.0016 (13)
C90.067 (2)0.065 (2)0.0325 (15)0.0141 (18)0.0106 (15)0.0046 (15)
C100.065 (2)0.0415 (17)0.063 (2)0.0074 (15)0.0446 (18)0.0051 (15)
N10.0334 (11)0.0215 (10)0.0304 (10)0.0039 (8)0.0191 (9)0.0015 (8)
O10.0396 (10)0.0196 (8)0.0293 (9)0.0004 (7)0.0209 (7)0.0004 (7)
O20.0348 (10)0.0197 (8)0.0352 (9)0.0030 (7)0.0157 (8)0.0001 (7)
I10.02499 (10)0.04928 (12)0.04157 (11)0.00657 (8)0.00878 (7)0.00614 (8)
Geometric parameters (Å, º) top
C1—C21.193 (4)C7—C91.514 (4)
C1—I11.999 (3)C7—C81.521 (4)
C2—C31.385 (4)C8—H8A0.98
C3—C41.191 (4)C8—H8B0.98
C4—C51.472 (3)C8—H8C0.98
C5—N11.452 (3)C9—H9A0.98
C5—H5A0.99C9—H9B0.98
C5—H5B0.99C9—H9C0.98
C6—O21.223 (3)C10—H10A0.98
C6—O11.338 (3)C10—H10B0.98
C6—N11.340 (3)C10—H10C0.98
C7—O11.486 (3)N1—H10.88
C7—C101.512 (4)
C2—C1—I1177.3 (3)H8A—C8—H8B109.5
C1—C2—C3179.1 (3)C7—C8—H8C109.5
C4—C3—C2179.4 (3)H8A—C8—H8C109.5
C3—C4—C5177.4 (3)H8B—C8—H8C109.5
N1—C5—C4112.5 (2)C7—C9—H9A109.5
N1—C5—H5A109.1C7—C9—H9B109.5
C4—C5—H5A109.1H9A—C9—H9B109.5
N1—C5—H5B109.1C7—C9—H9C109.5
C4—C5—H5B109.1H9A—C9—H9C109.5
H5A—C5—H5B107.8H9B—C9—H9C109.5
O2—C6—O1125.7 (2)C7—C10—H10A109.5
O2—C6—N1124.3 (2)C7—C10—H10B109.5
O1—C6—N1110.00 (19)H10A—C10—H10B109.5
O1—C7—C10109.6 (2)C7—C10—H10C109.5
O1—C7—C9109.6 (2)H10A—C10—H10C109.5
C10—C7—C9113.4 (3)H10B—C10—H10C109.5
O1—C7—C8101.7 (2)C6—N1—C5122.3 (2)
C10—C7—C8110.5 (3)C6—N1—H1118.8
C9—C7—C8111.5 (3)C5—N1—H1118.8
C7—C8—H8A109.5C6—O1—C7121.17 (18)
C7—C8—H8B109.5
O2—C6—N1—C51.7 (4)N1—C6—O1—C7175.9 (2)
O1—C6—N1—C5178.5 (2)C10—C7—O1—C658.9 (3)
C4—C5—N1—C6103.9 (3)C9—C7—O1—C666.1 (3)
O2—C6—O1—C73.9 (4)C8—C7—O1—C6175.8 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O2i0.882.042.881160
C1—I1···O2ii2.002.954.919168
Symmetry codes: (i) x+3/2, y+3/2, z+3/2; (ii) x+1/2, y+3/2, z+3/2.
CSD data retrieved for the CC—X···OC contacts shorter than the sum of their van der Waals radii top
CC—X···OC contactsCrystal structureSpace groupX···O distance (Å)C—X···O angle (°)Reference
CC—Cl···OCNIDWAAP13.111; 3.241152.59; 158.76Kawai et al. (2013)
CC—Br···OCHEVWAIC22.959158.12Hoheisel et al. (2013)
CC—Br···OCHEVWAI01P2121212.966166.70Hoheisel et al. (2013)
CC—Br···OCNIDWIIP21/n2.867171.11Kawai et al. (2013)
CC—Br···OCKAMXIIP21/c3.060178.26Baillargeon et al. (2016)
CC—I···OCCOHYUUP13.096164.55Luo et al. (2008)
CC—I···OCIYAYUCPca212.861170.36Hou et al. (2004)
CC—I···OCMASVUZP21/n2.834; 2.887170.72; 172.97Perkins et al. (2012)
CC—I···OCTOYPUSP21/c2.933175.36Avtomonov et al. (1997)
CC—I···OCHOWXICP21/c2.887169.51Dumele et al. (2014)
CC—I···OCLUNKOWP2/c2.791174.12Kratzer et al. (2015)
CC—I···OCLUNKUCP21/c2.754172.63Kratzer et al. (2015)
CC—I···OCLUNLAJP21/c2.773173.70Kratzer et al. (2015)
CC—I···OCLUNLIRPca212.858170.94Kratzer et al. (2015)
CC—I···OCLUNLOXC2/c2.763175.58Kratzer et al. (2015)
CC—I···OCIBUYAIP21/m2.856177.96Dumele et al. (2017)
CC—I···OCIBUYOWP21/c2.830176.52Dumele et al. (2017)
CC—I···OCIBUYUCP12.878177.89Dumele et al. (2017)
 

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