(−)-N,N′-Bis[(1S,2R,5S)-6,6-dimethyl-bicyclo­[3.1.1]heptan-2-ylmeth­yl]pyridine-2,6-dicarboxamide monohydrate

Bernès, S.; Pérez-Flores, F.J.; Gutiérrez, R.

doi:10.1107/S1600536808013652

organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Pages o1078-o1079

doi:10.1107/S1600536808013652

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(−)-N,N′-Bis[(1S,2R,5S)-6,6-dimethyl-bicyclo[3.1.1]heptan-2-ylmethyl]pyridine-2,6-dicarboxamide monohydrate

Sylvain Bernès,^a ^* Francisco Javier Pérez-Flores ^b and René Gutiérrez ^b

^aDEP Facultad de Ciencias Químicas, UANL, Guerrero y Progreso S/N, Col. Treviño, 64570 Monterrey, NL, Mexico, and ^bLaboratorio de Síntesis de Complejos, Facultad de Ciencias Químicas, Universidad Autónoma de Puebla, A.P. 1067, 72001 Puebla, Pue., Mexico
^*Correspondence e-mail: sylvain_bernes@Hotmail.com

(Received 16 April 2008; accepted 8 May 2008; online 14 May 2008)

The title compound, C₂₇H₃₉N₃O₂·H₂O, is a chiral pyridine-2,6-dicarboxamide derivative including cis-myrtanyl groups as amine substituents. The pyridine-2,6-dicarboxamide core approximates C₂ point symmetry and a solvent water molecule lies on the pseudo-twofold axis. The water molecule serves both as acceptor and donor for efficient hydrogen bonds involving N—H and C=O functional groups as donor and acceptor groups, respectively. As a result, each water molecule in the crystal structure is tetrahedrally bonded to three symmetry-related molecules, forming a three-dimensional supramolecular network. Such an arrangement is a common feature found in the majority of X-ray-characterized symmetrically substituted pyridine-2,6-dicarboxamide derivatives.

Related literature

For background to the solvent–free synthesis used for the preparation of the title compound, see: Tanaka & Toda (2000 ); Vázquez et al. (2004 ); Tovar et al. (2007 ); Pérez-Flores & Gutiérrez (2008 ). For hydrates of pyridine-2,6-dicarboxamide derivatives, see: Yu et al. (1999 ); Qi et al. (2002 ); Jain et al. (2004 ); Odriozola et al. (2004 ).

Experimental

Crystal data

C₂₇H₃₉N₃O₂·H₂O
M_r = 455.63
Monoclinic, P 2₁
a = 6.8476 (11) Å
b = 12.1101 (14) Å
c = 16.012 (2) Å
β = 91.173 (15)°
V = 1327.5 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 298 (1) K
0.6 × 0.6 × 0.2 mm

Data collection

Bruker P4 diffractometer
Absorption correction: none
6391 measured reflections
3180 independent reflections
2580 reflections with I > 2σ(I)
R_int = 0.035
3 standard reflections every 97 reflections intensity decay: 2%

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.107
S = 1.04
3180 reflections
319 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O3	0.82 (2)	2.16 (2)	2.941 (3)	160 (2)
N3—H3⋯O3	0.86 (3)	2.19 (3)	3.017 (3)	159 (2)
O3—H31⋯O2ⁱ	0.87 (5)	1.90 (5)	2.756 (3)	167 (4)
O3—H32⋯O1ⁱⁱ	0.90 (4)	1.86 (5)	2.754 (3)	171 (3)
Symmetry codes: (i) $[-x+2, y+{\script{1\over 2}}, -z+2]$ ; (ii) x+1, y, z.

Data collection: XSCANS (Siemens, 1996 ); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and POV-RAY (Cason, 2004 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808013652/rk2088sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808013652/rk2088Isup2.hkl

checkCIF report

Comment top

Nowadays, reactions conducted in the absence of solvents under mild reaction conditions are becoming an important method in laboratories worldwide as an environment–friendly technique for the efficient syntheses of organic molecules. The main advantages of solvent-free organic synthesis are shorter reaction times, minimum waste and generally higher yields, operational simplicity as well as reduction of thermal degradative byproducts along with cleaner work–up (Tanaka & Toda, 2000). As part of an ongoing program aiming to develop simpler and eco–friendly methods for organic transformations under solvent–free conditions (Tovar et al., 2007; Vázquez et al., 2004), we engaged the preparation of chiral pincer ligands (Pérez-Flores & Gutiérrez, 2008). The title compound resulted from this research, by introducing chiral cis–myrtanyl groups as amine substituents.

The X–ray characterized monohydrate has the expected molecular geometry (Fig. 1). The pyridine–2,6–dicarboxamide core approximates a C₂ point symmetry, with the pseudo 2–fold axis passing through N1 and C24. The guest water molecule O3 is placed on the pseudo 2–fold axis and is involved in two N—H···O hydrogen bonds within the asymmetric unit (Fig. 1 and Table 1, lines 1 and 2). The same water molecule is a donor group for two C═O···H intermolecular hydrogen bonds of relatively strong strength (Table 1, lines 3 and 4). As a consequence, a three–dimensional supramolecular structure is formed in the crystal structure, with water molecules being bonded in a tetrahedral arrangement (Fig. 2) to three symmetry–related molecules. Such a feature seems to be common for symmetrically substituted pyridine–2,6–dicarboxamide derivatives. These compounds are generally crystallized as hydrates, and, at least for X–ray characterized compounds, water molecules form hydrogen bonds similar to those observed in the title molecule (e.g. Yu et al., 1999; Qi et al., 2002; Jain et al., 2004; Odriozola et al., 2004).

Related literature top

For background to the solvent–free synthesis used for the preparation of the title compound, see: Tanaka & Toda (2000); Vázquez et al. (2004); Tovar et al. (2007); Pérez-Flores & Gutiérrez (2008). For hydrates of pyridine-2,6-dicarboxamide derivatives, see: Yu et al. (1999); Qi et al. (2002); Jain et al. (2004); Odriozola et al. (2004).

Experimental top

Under solvent–free conditions, (-)-cis–myrtanylamine (0.38 g, 2.5 mmol) and 2,6–pyridinedicarbonyl dichloride (0.30 g, 1.5 mmol) were mixed at room temperature, giving a white solid. The crude was recrystallized from EtOH affording the corresponding dicarboxamide (98% yield).

Computing details top

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS (Siemens, 1996); data reduction: XSCANS (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and POV-RAY (Cason, 2004); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit for the title compound, with the numbering scheme. Displacement ellipsoids for non–H atoms are drawn at the 40% probability level. H atoms are presented as small spheres of arbitrary radius. Dashed bonds are hydrogen bonds involving N—H groups as donor groups.
	Fig. 2. A part of the packing structure for the title compound, showing the four H bonds formed by a water molecule, in a tetrahedral geometry (dashed bonds). Symmetry codes: (i) 1+x, y, z; (ii) 2-x, 1/2+y, 2-z. H atoms not involved in hydrogen bonds have been omitted for clarity.

(-)-N,N'-Bis[(1S,2R,5S)-6,6-dimethyl- bicyclo[3.1.1]heptan-2-ylmethyl]pyridine-2,6-dicarboxamide monohydrate top

Crystal data top

C₂₇H₃₉N₃O₂·H₂O	F(000) = 496
M_r = 455.63	D_x = 1.140 Mg m⁻³
Monoclinic, P2₁	Melting point = 398–401 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 6.8476 (11) Å	Cell parameters from 60 reflections
b = 12.1101 (14) Å	θ = 4.6–12.5°
c = 16.012 (2) Å	µ = 0.07 mm⁻¹
β = 91.173 (15)°	T = 298 K
V = 1327.5 (3) Å³	Plate, colourless
Z = 2	0.6 × 0.6 × 0.2 mm

Data collection top

Bruker P4 diffractometer	R_int = 0.035
Radiation source: fine-focus sealed tube	θ_max = 27.5°, θ_min = 2.1°
Graphite monochromator	h = −8→6
ω scans	k = −1→15
6391 measured reflections	l = −20→20
3180 independent reflections	3 standard reflections every 97 reflections
2580 reflections with I > 2σ(I)	intensity decay: 2%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: Full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.107	w = 1/[σ²(F_o²) + (0.0551P)² + 0.0694P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
3180 reflections	Δρ_max = 0.14 e Å⁻³
319 parameters	Δρ_min = −0.13 e Å⁻³
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 constraints	Extinction coefficient: 0.037 (7)
Primary atom site location: structure-invariant direct methods

Crystal data top

C₂₇H₃₉N₃O₂·H₂O	V = 1327.5 (3) Å³
M_r = 455.63	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 6.8476 (11) Å	µ = 0.07 mm⁻¹
b = 12.1101 (14) Å	T = 298 K
c = 16.012 (2) Å	0.6 × 0.6 × 0.2 mm
β = 91.173 (15)°

Data collection top

Bruker P4 diffractometer	R_int = 0.035
6391 measured reflections	3 standard reflections every 97 reflections
3180 independent reflections	intensity decay: 2%
2580 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.040	1 restraint
wR(F²) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.14 e Å⁻³
3180 reflections	Δρ_min = −0.13 e Å⁻³
319 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.6298 (3)	0.24506 (16)	0.95082 (10)	0.0520 (4)
N2	0.5268 (3)	0.37490 (17)	0.81930 (11)	0.0558 (5)
H2	0.636 (4)	0.374 (2)	0.8414 (14)	0.049 (6)*
N3	0.9690 (3)	0.29137 (18)	1.03447 (12)	0.0576 (5)
H3	0.926 (3)	0.330 (2)	0.9926 (17)	0.058 (7)*
O1	0.2258 (2)	0.29762 (18)	0.81492 (11)	0.0731 (5)
O2	0.9360 (4)	0.13912 (17)	1.11410 (13)	0.0893 (6)
C1	0.4749 (3)	0.30035 (19)	0.63787 (13)	0.0529 (5)
H1A	0.4642	0.2424	0.6803	0.063*
C2	0.5749 (3)	0.4058 (2)	0.66831 (13)	0.0556 (5)
H2A	0.7122	0.3869	0.6793	0.067*
C3	0.5733 (5)	0.4954 (2)	0.59935 (16)	0.0724 (7)
H3A	0.7040	0.5257	0.5955	0.087*
H3B	0.4877	0.5549	0.6162	0.087*
C4	0.5059 (6)	0.4548 (3)	0.51078 (18)	0.0866 (9)
H4A	0.4046	0.5037	0.4893	0.104*
H4B	0.6154	0.4589	0.4734	0.104*
C5	0.4292 (4)	0.3386 (2)	0.51132 (15)	0.0737 (7)
H5A	0.3843	0.3108	0.4567	0.088*
C6	0.2858 (3)	0.3192 (2)	0.58333 (14)	0.0598 (5)
C7	0.5754 (4)	0.2641 (2)	0.55738 (16)	0.0737 (7)
H7A	0.7103	0.2878	0.5536	0.088*
H7B	0.5613	0.1862	0.5445	0.088*
C8	0.1734 (5)	0.2103 (3)	0.5733 (2)	0.0834 (8)
H8A	0.0857	0.2152	0.5259	0.125*
H8B	0.1003	0.1964	0.6227	0.125*
H8C	0.2641	0.1510	0.5650	0.125*
C9	0.1402 (4)	0.4092 (3)	0.6038 (2)	0.0831 (8)
H9A	0.0386	0.4109	0.5617	0.125*
H9B	0.2057	0.4793	0.6057	0.125*
H9C	0.0843	0.3943	0.6572	0.125*
C10	0.4962 (4)	0.45157 (19)	0.74996 (14)	0.0597 (5)
H10A	0.5610	0.5209	0.7630	0.072*
H10B	0.3576	0.4663	0.7430	0.072*
C11	0.9333 (3)	0.3930 (2)	1.20404 (14)	0.0620 (6)
H11A	0.8147	0.3610	1.1788	0.074*
C12	1.0879 (3)	0.4242 (2)	1.14197 (14)	0.0604 (6)
H12A	1.0340	0.4855	1.1088	0.072*
C13	1.2723 (5)	0.4692 (3)	1.18754 (18)	0.0875 (9)
H13A	1.3080	0.5385	1.1616	0.105*
H13B	1.3784	0.4177	1.1788	0.105*
C14	1.2550 (5)	0.4890 (3)	1.28285 (19)	0.0920 (10)
H14A	1.3606	0.4507	1.3119	0.110*
H14B	1.2692	0.5673	1.2942	0.110*
C15	1.0623 (5)	0.4496 (3)	1.31641 (16)	0.0800 (8)
H15A	1.0455	0.4611	1.3764	0.096*
C16	1.0091 (4)	0.3322 (3)	1.28420 (15)	0.0737 (7)
C17	0.8967 (5)	0.4939 (3)	1.26053 (18)	0.0884 (9)
H17A	0.9245	0.5645	1.2346	0.106*
H17B	0.7699	0.4942	1.2865	0.106*
C18	0.8353 (7)	0.2817 (5)	1.3307 (2)	0.1257 (16)
H18A	0.8757	0.2633	1.3868	0.189*
H18B	0.7917	0.2162	1.3022	0.189*
H18C	0.7305	0.3343	1.3322	0.189*
C19	1.1675 (6)	0.2462 (3)	1.2809 (2)	0.0988 (11)
H19A	1.2788	0.2762	1.2533	0.148*
H19B	1.1201	0.1829	1.2505	0.148*
H19C	1.2047	0.2245	1.3366	0.148*
C20	1.1400 (3)	0.3334 (2)	1.08030 (14)	0.0637 (6)
H20A	1.2328	0.3622	1.0409	0.076*
H20B	1.2024	0.2731	1.1104	0.076*
C21	0.3935 (3)	0.3035 (2)	0.84428 (13)	0.0548 (5)
C22	0.4577 (3)	0.22560 (19)	0.91276 (13)	0.0540 (5)
C23	0.3379 (4)	0.1377 (2)	0.93392 (16)	0.0700 (7)
H23A	0.2180	0.1270	0.9068	0.084*
C24	0.4017 (5)	0.0662 (3)	0.99674 (19)	0.0831 (8)
H24A	0.3253	0.0063	1.0120	0.100*
C25	0.5781 (5)	0.0851 (2)	1.03575 (16)	0.0756 (7)
H25A	0.6238	0.0381	1.0777	0.091*
C26	0.6875 (4)	0.17521 (19)	1.01182 (13)	0.0580 (5)
C27	0.8771 (4)	0.2008 (2)	1.05701 (14)	0.0625 (6)
O3	0.9282 (3)	0.42517 (19)	0.87612 (13)	0.0712 (5)
H31	0.970 (6)	0.493 (4)	0.871 (2)	0.103 (12)*
H32	1.020 (6)	0.384 (4)	0.851 (2)	0.111 (13)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0609 (10)	0.0502 (9)	0.0449 (8)	−0.0055 (8)	0.0042 (7)	−0.0049 (8)
N2	0.0580 (10)	0.0596 (11)	0.0496 (9)	−0.0052 (9)	−0.0080 (8)	−0.0031 (8)
N3	0.0677 (11)	0.0598 (11)	0.0448 (9)	0.0007 (10)	−0.0059 (8)	−0.0011 (9)
O1	0.0527 (8)	0.0858 (12)	0.0805 (11)	−0.0020 (9)	−0.0054 (8)	−0.0119 (10)
O2	0.1293 (17)	0.0611 (11)	0.0760 (12)	0.0033 (12)	−0.0296 (11)	0.0112 (10)
C1	0.0608 (11)	0.0457 (10)	0.0521 (10)	0.0023 (10)	−0.0015 (9)	−0.0007 (9)
C2	0.0563 (11)	0.0551 (12)	0.0553 (11)	−0.0027 (10)	−0.0024 (9)	−0.0011 (10)
C3	0.0943 (18)	0.0577 (14)	0.0651 (14)	−0.0191 (14)	−0.0012 (13)	0.0020 (12)
C4	0.127 (2)	0.0740 (17)	0.0585 (14)	−0.0293 (18)	−0.0019 (15)	0.0070 (13)
C5	0.1024 (19)	0.0689 (16)	0.0497 (12)	−0.0215 (15)	−0.0041 (12)	−0.0041 (12)
C6	0.0670 (13)	0.0535 (12)	0.0584 (12)	−0.0066 (11)	−0.0102 (9)	0.0019 (10)
C7	0.0846 (16)	0.0659 (15)	0.0711 (15)	−0.0043 (13)	0.0138 (13)	−0.0193 (13)
C8	0.0909 (18)	0.0741 (18)	0.0846 (18)	−0.0257 (16)	−0.0117 (15)	−0.0012 (15)
C9	0.0700 (15)	0.0827 (18)	0.096 (2)	0.0101 (15)	−0.0225 (14)	−0.0004 (16)
C10	0.0726 (13)	0.0508 (12)	0.0553 (11)	−0.0009 (11)	−0.0083 (10)	−0.0044 (10)
C11	0.0634 (13)	0.0698 (15)	0.0523 (11)	0.0122 (11)	−0.0061 (9)	−0.0083 (11)
C12	0.0732 (14)	0.0547 (13)	0.0527 (11)	0.0017 (11)	−0.0121 (10)	0.0028 (10)
C13	0.0916 (19)	0.100 (2)	0.0709 (16)	−0.0322 (18)	−0.0087 (14)	−0.0056 (16)
C14	0.118 (2)	0.088 (2)	0.0689 (16)	−0.0129 (19)	−0.0287 (16)	−0.0106 (15)
C15	0.105 (2)	0.0843 (19)	0.0502 (12)	0.0075 (17)	−0.0120 (12)	−0.0118 (13)
C16	0.0944 (17)	0.0774 (18)	0.0491 (12)	−0.0003 (15)	−0.0076 (11)	0.0035 (12)
C17	0.102 (2)	0.092 (2)	0.0702 (16)	0.0267 (18)	−0.0074 (14)	−0.0248 (16)
C18	0.154 (3)	0.151 (4)	0.0734 (19)	−0.040 (3)	0.026 (2)	0.006 (2)
C19	0.145 (3)	0.0752 (19)	0.0743 (17)	0.023 (2)	−0.0426 (19)	0.0044 (16)
C20	0.0604 (12)	0.0768 (17)	0.0539 (11)	0.0021 (12)	−0.0013 (9)	−0.0068 (12)
C21	0.0500 (11)	0.0603 (12)	0.0542 (11)	−0.0010 (10)	0.0036 (8)	−0.0155 (10)
C22	0.0580 (12)	0.0564 (12)	0.0481 (10)	−0.0066 (10)	0.0098 (9)	−0.0131 (9)
C23	0.0706 (15)	0.0743 (16)	0.0654 (14)	−0.0205 (13)	0.0127 (11)	−0.0153 (13)
C24	0.101 (2)	0.0730 (17)	0.0755 (16)	−0.0347 (16)	0.0194 (15)	0.0035 (14)
C25	0.108 (2)	0.0615 (15)	0.0573 (13)	−0.0187 (15)	0.0054 (13)	0.0036 (12)
C26	0.0786 (14)	0.0501 (11)	0.0456 (10)	−0.0036 (11)	0.0059 (10)	−0.0029 (9)
C27	0.0860 (16)	0.0513 (12)	0.0501 (11)	0.0064 (12)	−0.0031 (11)	−0.0034 (10)
O3	0.0613 (10)	0.0674 (12)	0.0853 (12)	−0.0080 (10)	0.0110 (8)	−0.0047 (10)

Geometric parameters (Å, º) top

N1—C22	1.337 (3)	C11—C17	1.544 (4)
N1—C26	1.345 (3)	C11—C16	1.559 (3)
N2—C21	1.325 (3)	C11—H11A	0.9800
N2—C10	1.459 (3)	C12—C20	1.525 (4)
N2—H2	0.82 (2)	C12—C13	1.545 (4)
N3—C27	1.318 (3)	C12—H12A	0.9800
N3—C20	1.461 (3)	C13—C14	1.552 (4)
N3—H3	0.86 (3)	C13—H13A	0.9700
O1—C21	1.234 (3)	C13—H13B	0.9700
O2—C27	1.242 (3)	C14—C15	1.512 (5)
C1—C2	1.524 (3)	C14—H14A	0.9700
C1—C7	1.537 (3)	C14—H14B	0.9700
C1—C6	1.564 (3)	C15—C17	1.527 (4)
C1—H1A	0.9800	C15—C16	1.553 (4)
C2—C10	1.528 (3)	C15—H15A	0.9800
C2—C3	1.548 (3)	C16—C19	1.506 (5)
C2—H2A	0.9800	C16—C18	1.543 (5)
C3—C4	1.562 (4)	C17—H17A	0.9700
C3—H3A	0.9700	C17—H17B	0.9700
C3—H3B	0.9700	C18—H18A	0.9600
C4—C5	1.502 (4)	C18—H18B	0.9600
C4—H4A	0.9700	C18—H18C	0.9600
C4—H4B	0.9700	C19—H19A	0.9600
C5—C7	1.526 (4)	C19—H19B	0.9600
C5—C6	1.548 (4)	C19—H19C	0.9600
C5—H5A	0.9800	C20—H20A	0.9700
C6—C9	1.518 (4)	C20—H20B	0.9700
C6—C8	1.534 (4)	C21—C22	1.505 (3)
C7—H7A	0.9700	C22—C23	1.390 (4)
C7—H7B	0.9700	C23—C24	1.391 (4)
C8—H8A	0.9600	C23—H23A	0.9300
C8—H8B	0.9600	C24—C25	1.368 (4)
C8—H8C	0.9600	C24—H24A	0.9300
C9—H9A	0.9600	C25—C26	1.382 (4)
C9—H9B	0.9600	C25—H25A	0.9300
C9—H9C	0.9600	C26—C27	1.506 (3)
C10—H10A	0.9700	O3—H31	0.87 (5)
C10—H10B	0.9700	O3—H32	0.90 (4)
C11—C12	1.514 (4)

C22—N1—C26	117.60 (19)	C20—C12—C13	111.1 (2)
C21—N2—C10	123.8 (2)	C11—C12—H12A	106.5
C21—N2—H2	119.2 (17)	C20—C12—H12A	106.5
C10—N2—H2	116.9 (17)	C13—C12—H12A	106.5
C27—N3—C20	122.3 (2)	C12—C13—C14	116.2 (3)
C27—N3—H3	120.2 (17)	C12—C13—H13A	108.2
C20—N3—H3	117.4 (17)	C14—C13—H13A	108.2
C2—C1—C7	107.55 (19)	C12—C13—H13B	108.2
C2—C1—C6	114.69 (18)	C14—C13—H13B	108.2
C7—C1—C6	87.32 (18)	H13A—C13—H13B	107.4
C2—C1—H1A	114.7	C15—C14—C13	112.7 (2)
C7—C1—H1A	114.7	C15—C14—H14A	109.1
C6—C1—H1A	114.7	C13—C14—H14A	109.1
C1—C2—C10	114.43 (19)	C15—C14—H14B	109.1
C1—C2—C3	111.28 (17)	C13—C14—H14B	109.1
C10—C2—C3	111.0 (2)	H14A—C14—H14B	107.8
C1—C2—H2A	106.5	C14—C15—C17	108.9 (3)
C10—C2—H2A	106.5	C14—C15—C16	111.8 (3)
C3—C2—H2A	106.5	C17—C15—C16	87.8 (2)
C2—C3—C4	115.1 (2)	C14—C15—H15A	115.1
C2—C3—H3A	108.5	C17—C15—H15A	115.1
C4—C3—H3A	108.5	C16—C15—H15A	115.1
C2—C3—H3B	108.5	C19—C16—C18	107.8 (3)
C4—C3—H3B	108.5	C19—C16—C15	118.8 (3)
H3A—C3—H3B	107.5	C18—C16—C15	112.3 (3)
C5—C4—C3	112.8 (2)	C19—C16—C11	121.7 (2)
C5—C4—H4A	109.0	C18—C16—C11	109.7 (3)
C3—C4—H4A	109.0	C15—C16—C11	85.0 (2)
C5—C4—H4B	109.0	C15—C17—C11	86.4 (2)
C3—C4—H4B	109.0	C15—C17—H17A	114.3
H4A—C4—H4B	107.8	C11—C17—H17A	114.3
C4—C5—C7	109.3 (2)	C15—C17—H17B	114.3
C4—C5—C6	111.9 (2)	C11—C17—H17B	114.2
C7—C5—C6	88.31 (19)	H17A—C17—H17B	111.4
C4—C5—H5A	114.8	C16—C18—H18A	109.5
C7—C5—H5A	114.8	C16—C18—H18B	109.5
C6—C5—H5A	114.8	H18A—C18—H18B	109.5
C9—C6—C8	108.1 (2)	C16—C18—H18C	109.5
C9—C6—C5	118.8 (2)	H18A—C18—H18C	109.5
C8—C6—C5	112.2 (2)	H18B—C18—H18C	109.5
C9—C6—C1	121.6 (2)	C16—C19—H19A	109.5
C8—C6—C1	109.9 (2)	C16—C19—H19B	109.5
C5—C6—C1	84.67 (18)	H19A—C19—H19B	109.5
C5—C7—C1	86.32 (19)	C16—C19—H19C	109.5
C5—C7—H7A	114.3	H19A—C19—H19C	109.5
C1—C7—H7A	114.3	H19B—C19—H19C	109.5
C5—C7—H7B	114.3	N3—C20—C12	112.38 (19)
C1—C7—H7B	114.3	N3—C20—H20A	109.1
H7A—C7—H7B	111.4	C12—C20—H20A	109.1
C6—C8—H8A	109.5	N3—C20—H20B	109.1
C6—C8—H8B	109.5	C12—C20—H20B	109.1
H8A—C8—H8B	109.5	H20A—C20—H20B	107.9
C6—C8—H8C	109.5	O1—C21—N2	124.4 (2)
H8A—C8—H8C	109.5	O1—C21—C22	119.8 (2)
H8B—C8—H8C	109.5	N2—C21—C22	115.86 (18)
C6—C9—H9A	109.5	N1—C22—C23	122.9 (2)
C6—C9—H9B	109.5	N1—C22—C21	117.59 (19)
H9A—C9—H9B	109.5	C23—C22—C21	119.5 (2)
C6—C9—H9C	109.5	C22—C23—C24	118.4 (2)
H9A—C9—H9C	109.5	C22—C23—H23A	120.8
H9B—C9—H9C	109.5	C24—C23—H23A	120.8
N2—C10—C2	111.88 (19)	C25—C24—C23	119.2 (3)
N2—C10—H10A	109.2	C25—C24—H24A	120.4
C2—C10—H10A	109.2	C23—C24—H24A	120.4
N2—C10—H10B	109.2	C24—C25—C26	118.9 (3)
C2—C10—H10B	109.2	C24—C25—H25A	120.5
H10A—C10—H10B	107.9	C26—C25—H25A	120.5
C12—C11—C17	108.1 (2)	N1—C26—C25	123.0 (2)
C12—C11—C16	115.7 (2)	N1—C26—C27	117.2 (2)
C17—C11—C16	86.95 (19)	C25—C26—C27	119.7 (2)
C12—C11—H11A	114.3	O2—C27—N3	123.5 (2)
C17—C11—H11A	114.3	O2—C27—C26	119.6 (2)
C16—C11—H11A	114.3	N3—C27—C26	116.9 (2)
C11—C12—C20	114.9 (2)	H31—O3—H32	103 (4)
C11—C12—C13	110.7 (2)

C7—C1—C2—C10	−178.2 (2)	C14—C15—C16—C18	168.8 (3)
C6—C1—C2—C10	86.5 (2)	C17—C15—C16—C18	−81.7 (3)
C7—C1—C2—C3	54.9 (3)	C14—C15—C16—C11	−81.9 (2)
C6—C1—C2—C3	−40.3 (3)	C17—C15—C16—C11	27.6 (2)
C1—C2—C3—C4	−10.1 (4)	C12—C11—C16—C19	−39.6 (4)
C10—C2—C3—C4	−138.8 (3)	C17—C11—C16—C19	−148.2 (3)
C2—C3—C4—C5	7.6 (4)	C12—C11—C16—C18	−166.7 (3)
C3—C4—C5—C7	−50.0 (4)	C17—C11—C16—C18	84.7 (3)
C3—C4—C5—C6	46.1 (4)	C12—C11—C16—C15	81.3 (3)
C4—C5—C6—C9	40.2 (3)	C17—C11—C16—C15	−27.3 (2)
C7—C5—C6—C9	150.4 (2)	C14—C15—C17—C11	84.4 (3)
C4—C5—C6—C8	167.5 (3)	C16—C15—C17—C11	−27.8 (2)
C7—C5—C6—C8	−82.3 (2)	C12—C11—C17—C15	−88.3 (2)
C4—C5—C6—C1	−83.1 (2)	C16—C11—C17—C15	27.7 (2)
C7—C5—C6—C1	27.07 (17)	C27—N3—C20—C12	−97.3 (3)
C2—C1—C6—C9	−39.5 (3)	C11—C12—C20—N3	55.0 (3)
C7—C1—C6—C9	−147.6 (3)	C13—C12—C20—N3	−178.4 (2)
C2—C1—C6—C8	−167.1 (2)	C10—N2—C21—O1	−4.0 (3)
C7—C1—C6—C8	84.8 (2)	C10—N2—C21—C22	175.63 (19)
C2—C1—C6—C5	81.2 (2)	C26—N1—C22—C23	0.4 (3)
C7—C1—C6—C5	−26.87 (18)	C26—N1—C22—C21	−179.78 (18)
C4—C5—C7—C1	85.2 (3)	O1—C21—C22—N1	−170.6 (2)
C6—C5—C7—C1	−27.51 (18)	N2—C21—C22—N1	9.8 (3)
C2—C1—C7—C5	−87.9 (2)	O1—C21—C22—C23	9.3 (3)
C6—C1—C7—C5	27.22 (18)	N2—C21—C22—C23	−170.4 (2)
C21—N2—C10—C2	−95.3 (3)	N1—C22—C23—C24	−0.9 (4)
C1—C2—C10—N2	62.7 (2)	C21—C22—C23—C24	179.2 (2)
C3—C2—C10—N2	−170.3 (2)	C22—C23—C24—C25	0.5 (4)
C17—C11—C12—C20	−179.3 (2)	C23—C24—C25—C26	0.3 (4)
C16—C11—C12—C20	85.2 (3)	C22—N1—C26—C25	0.6 (3)
C17—C11—C12—C13	53.8 (3)	C22—N1—C26—C27	−177.24 (19)
C16—C11—C12—C13	−41.6 (3)	C24—C25—C26—N1	−0.9 (4)
C11—C12—C13—C14	−8.2 (4)	C24—C25—C26—C27	176.8 (3)
C20—C12—C13—C14	−137.1 (3)	C20—N3—C27—O2	−6.1 (4)
C12—C13—C14—C15	5.6 (5)	C20—N3—C27—C26	171.8 (2)
C13—C14—C15—C17	−48.7 (4)	N1—C26—C27—O2	179.6 (2)
C13—C14—C15—C16	46.6 (4)	C25—C26—C27—O2	1.8 (3)
C14—C15—C16—C19	41.7 (3)	N1—C26—C27—N3	1.6 (3)
C17—C15—C16—C19	151.2 (3)	C25—C26—C27—N3	−176.2 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O3	0.82 (2)	2.16 (2)	2.941 (3)	160 (2)
N3—H3···O3	0.86 (3)	2.19 (3)	3.017 (3)	159 (2)
O3—H31···O2ⁱ	0.87 (5)	1.90 (5)	2.756 (3)	167 (4)
O3—H32···O1ⁱⁱ	0.90 (4)	1.86 (5)	2.754 (3)	171 (3)

Symmetry codes: (i) −x+2, y+1/2, −z+2; (ii) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₂₇H₃₉N₃O₂·H₂O
M_r	455.63
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	298
a, b, c (Å)	6.8476 (11), 12.1101 (14), 16.012 (2)
β (°)	91.173 (15)
V (Å³)	1327.5 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.6 × 0.6 × 0.2

Data collection
Diffractometer	Bruker P4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6391, 3180, 2580
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.107, 1.04
No. of reflections	3180
No. of parameters	319
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.13

Computer programs: XSCANS (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and POV-RAY (Cason, 2004).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O3	0.82 (2)	2.16 (2)	2.941 (3)	160 (2)
N3—H3···O3	0.86 (3)	2.19 (3)	3.017 (3)	159 (2)
O3—H31···O2ⁱ	0.87 (5)	1.90 (5)	2.756 (3)	167 (4)
O3—H32···O1ⁱⁱ	0.90 (4)	1.86 (5)	2.754 (3)	171 (3)

Symmetry codes: (i) −x+2, y+1/2, −z+2; (ii) x+1, y, z.

Acknowledgements

Partial support from VIEP–UAP (14/G/NAT/05) is acknowledged.

References

Cason, C. J. (2004). POV-RAY for Windows. Persistence of Vision Raytracer Pty Ltd, Victoria, Australia. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
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Tovar, A., Peña, U., Hernández, G., Portillo, R. & Gutiérrez, R. (2007). Synthesis, pp. 22–24. Google Scholar
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Volume 64| Part 6| June 2008| Pages o1078-o1079

doi:10.1107/S1600536808013652

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

(−)-N,N′-Bis[(1S,2R,5S)-6,6-di­methyl-bi­cyclo­[3.1.1]heptan-2-ylmeth­yl]pyridine-2,6-dicarboxamide monohydrate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

(−)-N,N′-Bis[(1S,2R,5S)-6,6-dimethyl-bicyclo[3.1.1]heptan-2-ylmethyl]pyridine-2,6-dicarboxamide monohydrate