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Acta Cryst. (2007). E63, o3679    [ doi:10.1107/S1600536807037385 ]

N-[4-(Di-2-pyrrolylmethyl)phenyl]acetamide

M. O. Senge

Abstract top

The crystal structure of the title compound, C17H17N3O, shows the formation of infinite chains of molecules that are linked via hydrogen bonds involving the acetamide group. The carbonyl O atom forms hydrogen bonds with both a pyrrole NH group and another acetamide NH unit. In addition, the carbonyl O atom is involved in a weak intramolecular interaction with the neighboring aryl group, thus connecting different chains.

Comment top

Dipyrromethanes are central synthetic building blocks for porphyrins which exhibit a rich structural chemistry (Senge, 2005a; Shin et al., 2004). In continuation of our studies on the hydrogen bonding pattern in porphyrins and related building blocks (Senge, 2000, 2005b; Senge & Smith, 2005). We report here the structure of a dipyrromethane with an acceptor substituted meso position. Using the criteria defined by Steiner (1997) the title compound was investigated for N–H···O and C–H···O interactions. The compound forms infinite chains through hydrogen bonding of O1 to a neighboring pyrrole NH [N1–H1···O1, 2.891 (2) Å, 171°] and the acetamido NH [N3–H3···O2, 2.894 (2) Å, 169°]. Thus, the acetamido group on the meso substituent functions as the connecting unit in the supramolecular structure, primarily through the 3-center hydrogen bond system involving O1.

The pyrrole N–H unit of ring 2 is not involved in any hydrogen bonding. As can be seen in Fig. 1 the two pyrrole rings point in opposite directions and the two pyrrole planes are tilted by 60.1°. As shown in Fig. 2, the N2 unit is effectively shielded by the backbone of the neighboring chain of molecules and points towards the back of pyrrole ring 1 in the neighboring unit, where no acceptor atoms are present. In addition, the carbonyl oxygen atom is involved in a weak intramolecular interaction with the neighboring aryl group [C55–H55A···O1 = 2.55 (2) Å]. Related structures have been reported (Bonnett et al., 1972; Lin et al., 1996; Bennis & Gallagher, 1998; Gallagher & Moriarty, 1999; Patra et al., 2002).

Related literature top

For related literature, see: Bonnett et al. (1972); Lin et al. (1996); Bennis & Gallagher (1998); Gallagher & Moriarty (1999); Patra et al. (2002); Senge (2000, 2005a,b); Senge & Smith (2005); Shin et al. (2004). The compound was prepared as described by Lazzeri & Durantini (2003); crystals were handled as decribed by Hope (1994). The hydrogen-bonding analysis followed the criteria set out by Steiner (1997).

Experimental top

Crystals were handled as described by Hope (1994). The compound was prepared as described earlier (Lazzeri & Durantini, 2003) and crystallized from CH2Cl2/n-hexane.

Refinement top

H atoms were mostly placed in geometrically idealized positions and constrained to ride on their parent atoms with C—H distances in the range of 0.88–1.00 Å and Uiso (H) = 1.2 Ueq (C) for CH and NH groups and Uiso (H) = 1.5 Ueq (C) for methyl groups.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Siemens, 1995); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. A view of (I). Displacement ellipsoids for the non-hydrogen atoms are drawn at the 50% probability level.
[Figure 2] Fig. 2. View of the molecular arrangement of (I) in the crystal. Dashed lines indicate intermolecular hydrogen bonds.
N-[4-(Di-2-pyrrolylmethyl)phenyl]acetamide top
Crystal data top
C17H17N3OF000 = 592
Mr = 279.34Dx = 1.320 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3237 reflections
a = 7.4007 (6) Åθ = 5.6–62.6º
b = 24.858 (2) ŵ = 0.09 mm−1
c = 8.2690 (7) ÅT = 90 (2) K
β = 112.490 (2)ºPlate, yellow
V = 1405.5 (2) Å30.50 × 0.40 × 0.01 mm
Z = 4
Data collection top
Bruker SMART APEX II
diffractometer		4656 independent reflections
Radiation source: sealed tube3167 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.061
Detector resolution: 8.3 pixels mm-1θmax = 31.5º
T = 90(2) Kθmin = 2.8º
φ and ω scansh = −10→10
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		k = −36→36
Tmin = 0.96, Tmax = 0.99l = −12→12
20557 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.051H-atom parameters constrained
wR(F2) = 0.131  w = 1/[σ2(Fo2) + (0.0603P)2 + 0.3541P]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max = 0.001
4656 reflectionsΔρmax = 0.41 e Å−3
191 parametersΔρmin = −0.26 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C17H17N3OV = 1405.5 (2) Å3
Mr = 279.34Z = 4
Monoclinic, P21/cMo Kα
a = 7.4007 (6) ŵ = 0.09 mm−1
b = 24.858 (2) ÅT = 90 (2) K
c = 8.2690 (7) Å0.50 × 0.40 × 0.01 mm
β = 112.490 (2)º
Data collection top
Bruker SMART APEX II
diffractometer		4656 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		3167 reflections with I > 2σ(I)
Tmin = 0.96, Tmax = 0.99Rint = 0.061
20557 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.051191 parameters
wR(F2) = 0.131H-atom parameters constrained
S = 1.01Δρmax = 0.41 e Å−3
4656 reflectionsΔρmin = −0.26 e Å−3
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 > 2sigma(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. All hydrogen atoms were located in difference maps. All hydrogen atoms were located in difference maps. No H-acceptor was found for N2.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.09109 (16)0.41540 (5)0.30239 (15)0.0171 (2)
H1A0.04140.38360.26310.020*
N20.29445 (17)0.43496 (5)0.84943 (16)0.0194 (2)
H2A0.18020.44960.78900.023*
C10.0471 (2)0.46203 (6)0.2072 (2)0.0195 (3)
H1B−0.04070.46550.08870.023*
C20.1523 (2)0.50284 (6)0.31309 (19)0.0189 (3)
H2B0.15090.53960.28170.023*
C30.2638 (2)0.47978 (5)0.47852 (19)0.0181 (3)
H3A0.35030.49840.57840.022*
C40.22382 (18)0.42563 (5)0.46783 (18)0.0154 (3)
C50.30492 (19)0.38041 (5)0.59659 (18)0.0163 (3)
H5A0.19320.35620.58680.020*
C60.39253 (19)0.40006 (5)0.78285 (18)0.0165 (3)
C70.5625 (2)0.38611 (6)0.9176 (2)0.0205 (3)
H7A0.65980.36240.91050.025*
C80.5673 (2)0.41349 (6)1.0705 (2)0.0226 (3)
H8A0.66770.41131.18400.027*
C90.4008 (2)0.44351 (6)1.0236 (2)0.0217 (3)
H9A0.36510.46631.09860.026*
C510.45508 (19)0.34645 (5)0.55772 (18)0.0155 (3)
C520.5895 (2)0.37005 (6)0.4991 (2)0.0202 (3)
H52A0.58210.40750.47520.024*
C530.7340 (2)0.33949 (6)0.4753 (2)0.0202 (3)
H53A0.82630.35630.43750.024*
C540.74457 (19)0.28430 (5)0.50661 (17)0.0159 (3)
C550.6086 (2)0.25983 (5)0.56148 (19)0.0176 (3)
H55A0.61230.22210.58020.021*
C560.46718 (19)0.29128 (5)0.58853 (19)0.0177 (3)
H56A0.37670.27470.62900.021*
C570.98507 (19)0.21091 (5)0.55646 (18)0.0158 (3)
C581.1101 (2)0.18235 (6)0.4755 (2)0.0226 (3)
H58A1.23430.17170.56770.034*
H58B1.13580.20660.39320.034*
H58C1.04140.15030.41300.034*
N30.88981 (17)0.25458 (5)0.47060 (15)0.0174 (2)
H3B0.91990.26610.38330.021*
O10.97034 (14)0.19367 (4)0.69187 (13)0.0187 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0165 (5)0.0150 (5)0.0188 (6)−0.0017 (4)0.0058 (5)−0.0015 (4)
N20.0149 (5)0.0209 (6)0.0222 (6)0.0029 (4)0.0070 (5)−0.0013 (5)
C10.0168 (6)0.0206 (7)0.0200 (7)0.0026 (5)0.0060 (6)0.0030 (5)
C20.0171 (6)0.0155 (6)0.0242 (8)0.0025 (5)0.0080 (6)0.0032 (5)
C30.0158 (6)0.0144 (6)0.0221 (7)−0.0003 (5)0.0051 (5)−0.0009 (5)
C40.0131 (6)0.0143 (6)0.0191 (7)0.0016 (5)0.0063 (5)0.0007 (5)
C50.0138 (6)0.0140 (6)0.0211 (7)0.0012 (5)0.0066 (5)0.0008 (5)
C60.0158 (6)0.0155 (6)0.0206 (7)0.0014 (5)0.0095 (5)0.0023 (5)
C70.0174 (6)0.0234 (7)0.0213 (7)0.0050 (5)0.0082 (6)0.0049 (6)
C80.0205 (7)0.0282 (8)0.0182 (7)0.0013 (6)0.0065 (6)0.0037 (6)
C90.0224 (7)0.0240 (7)0.0210 (7)−0.0018 (5)0.0107 (6)−0.0029 (6)
C510.0144 (6)0.0148 (6)0.0161 (6)0.0020 (5)0.0047 (5)−0.0003 (5)
C520.0210 (6)0.0138 (6)0.0278 (8)0.0032 (5)0.0117 (6)0.0051 (6)
C530.0206 (6)0.0178 (7)0.0265 (8)0.0037 (5)0.0140 (6)0.0065 (6)
C540.0165 (6)0.0163 (6)0.0151 (6)0.0038 (5)0.0063 (5)0.0010 (5)
C550.0188 (6)0.0122 (6)0.0220 (7)0.0014 (5)0.0080 (6)0.0009 (5)
C560.0157 (6)0.0148 (6)0.0236 (7)−0.0005 (5)0.0086 (6)0.0013 (5)
C570.0153 (6)0.0141 (6)0.0184 (7)0.0005 (5)0.0068 (5)−0.0019 (5)
C580.0239 (7)0.0201 (7)0.0281 (8)0.0057 (6)0.0147 (6)−0.0004 (6)
N30.0193 (5)0.0183 (6)0.0173 (6)0.0049 (4)0.0101 (5)0.0030 (4)
O10.0218 (5)0.0170 (5)0.0185 (5)0.0042 (4)0.0090 (4)0.0026 (4)
Geometric parameters (Å, °) top
N1—C41.3686 (18)C8—H8A0.9500
N1—C11.3685 (18)C9—H9A0.9500
N1—H1A0.8800C51—C561.3914 (18)
N2—C91.368 (2)C51—C521.3917 (18)
N2—C61.3741 (17)C52—C531.3859 (19)
N2—H2A0.8800C52—H52A0.9500
C1—C21.371 (2)C53—C541.3926 (19)
C1—H1B0.9500C53—H53A0.9500
C2—C31.420 (2)C54—C551.3921 (18)
C2—H2B0.9500C54—N31.4265 (16)
C3—C41.3737 (19)C55—C561.3913 (18)
C3—H3A0.9500C55—H55A0.9500
C4—C51.5061 (19)C56—H56A0.9500
C5—C61.506 (2)C57—O11.2421 (16)
C5—C511.5245 (18)C57—N31.3402 (17)
C5—H5A1.0000C57—C581.5110 (18)
C6—C71.368 (2)C58—H58A0.9800
C7—C81.424 (2)C58—H58B0.9800
C7—H7A0.9500C58—H58C0.9800
C8—C91.364 (2)N3—H3B0.8800
C4—N1—C1109.84 (12)C8—C9—N2107.93 (13)
C4—N1—H1A125.1C8—C9—H9A126.0
C1—N1—H1A125.1N2—C9—H9A126.0
C9—N2—C6109.90 (12)C56—C51—C52118.34 (12)
C9—N2—H2A125.1C56—C51—C5120.55 (12)
C6—N2—H2A125.1C52—C51—C5121.04 (12)
N1—C1—C2107.90 (13)C53—C52—C51120.76 (13)
N1—C1—H1B126.0C53—C52—H52A119.6
C2—C1—H1B126.0C51—C52—H52A119.6
C1—C2—C3107.16 (13)C52—C53—C54120.35 (12)
C1—C2—H2B126.4C52—C53—H53A119.8
C3—C2—H2B126.4C54—C53—H53A119.8
C4—C3—C2107.58 (13)C55—C54—C53119.65 (12)
C4—C3—H3A126.2C55—C54—N3122.55 (12)
C2—C3—H3A126.2C53—C54—N3117.70 (12)
N1—C4—C3107.51 (12)C54—C55—C56119.26 (12)
N1—C4—C5120.50 (12)C54—C55—H55A120.4
C3—C4—C5131.91 (13)C56—C55—H55A120.4
C4—C5—C6112.35 (11)C51—C56—C55121.61 (12)
C4—C5—C51112.94 (11)C51—C56—H56A119.2
C6—C5—C51109.38 (11)C55—C56—H56A119.2
C4—C5—H5A107.3O1—C57—N3123.18 (12)
C6—C5—H5A107.3O1—C57—C58121.15 (12)
C51—C5—H5A107.3N3—C57—C58115.66 (12)
C7—C6—N2107.19 (13)C57—C58—H58A109.5
C7—C6—C5130.77 (12)C57—C58—H58B109.5
N2—C6—C5121.86 (12)H58A—C58—H58B109.5
C6—C7—C8107.76 (12)C57—C58—H58C109.5
C6—C7—H7A126.1H58A—C58—H58C109.5
C8—C7—H7A126.1H58B—C58—H58C109.5
C9—C8—C7107.22 (13)C57—N3—C54126.48 (11)
C9—C8—H8A126.4C57—N3—H3B116.8
C7—C8—H8A126.4C54—N3—H3B116.8
C4—N1—C1—C2−0.28 (15)C7—C8—C9—N20.71 (17)
N1—C1—C2—C3−0.04 (15)C6—N2—C9—C8−0.77 (16)
C1—C2—C3—C40.34 (15)C4—C5—C51—C56−144.69 (13)
C1—N1—C4—C30.49 (15)C6—C5—C51—C5689.39 (15)
C1—N1—C4—C5−176.75 (11)C4—C5—C51—C5238.56 (18)
C2—C3—C4—N1−0.50 (15)C6—C5—C51—C52−87.36 (15)
C2—C3—C4—C5176.30 (13)C56—C51—C52—C53−1.2 (2)
N1—C4—C5—C6−160.97 (11)C5—C51—C52—C53175.61 (14)
C3—C4—C5—C622.6 (2)C51—C52—C53—C541.2 (2)
N1—C4—C5—C5174.73 (15)C52—C53—C54—C550.2 (2)
C3—C4—C5—C51−101.74 (17)C52—C53—C54—N3176.64 (13)
C9—N2—C6—C70.50 (16)C53—C54—C55—C56−1.7 (2)
C9—N2—C6—C5176.08 (12)N3—C54—C55—C56−177.90 (13)
C4—C5—C6—C7−136.77 (15)C52—C51—C56—C55−0.3 (2)
C51—C5—C6—C7−10.5 (2)C5—C51—C56—C55−177.10 (13)
C4—C5—C6—N248.81 (16)C54—C55—C56—C511.7 (2)
C51—C5—C6—N2175.06 (12)O1—C57—N3—C54−7.1 (2)
N2—C6—C7—C8−0.05 (16)C58—C57—N3—C54171.41 (13)
C5—C6—C7—C8−175.09 (14)C55—C54—N3—C57−36.2 (2)
C6—C7—C8—C9−0.41 (17)C53—C54—N3—C57147.52 (14)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O1i0.882.022.8914 (15)171
N3—H3B···O1ii0.882.032.8936 (15)169
C55—H55A···O10.952.552.9708 (17)107
Symmetry codes: (i) x−1, −y+1/2, z−1/2; (ii) x, −y+1/2, z−1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O1i0.882.022.8914 (15)171
N3—H3B···O1ii0.882.032.8936 (15)169
C55—H55A···O10.952.552.9708 (17)107
Symmetry codes: (i) x−1, −y+1/2, z−1/2; (ii) x, −y+1/2, z−1/2.
Acknowledgements top

This work was supported by grants from the Science Foundation Ireland (SFI Fellow – Research Professorship, 04/RP1/B482).

references
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