1,4-Bis(dimorpholinometh­yl)benzene

The title compound, C₂₄H₃₈N₄O₄, was synthesized by the reaction of terephthalaldehyde and morpholine in ethanol. The N atoms of the four morpholine rings are bonded to benzyl C atoms, forming a centrosymmetric 1,4-bis­(di­morpholino­meth­yl)benzene mol­ecule.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.045
• wR factor = 0.132
• Data-to-parameter ratio = 19.0

checkCIF/PLATON results

No syntax errors found



Alert level A
DIFF020_ALERT_1_A  _diffrn_standards_interval_count and
            _diffrn_standards_interval_time are missing. Number of measurements
            between standards or time (min) between standards.
DIFF022_ALERT_1_A  _diffrn_standards_decay_% is missing
            Percentage decrease in standards intensity.

Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.823     0.992
            Tmin(prime) and Tmax expected:      0.983     0.992
            RR(prime) =      0.837
            Please check that your absorption correction is appropriate.
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.84
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O1     -   C1      ..       6.07 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for    N2     -   C8      ..       5.20 su

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

   2 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Recently, much attention has been focused on morpholine-containing compounds due to their biological activity as well as chemical and industrial versatility (Bellon et al., 1996; Goodman & Jacobsen, 2002; Lanman & Myers, 2004). Herein, we report the synthesis and crystal structure of a new morpholine-containing compound, 1,4-bis(dimorpholinomethyl)benzene.

As shown in Fig. 1, the nitrogen atoms of four morpholine molecules are bonded to C9 and C9ⁱ[symmetry code, (i) 1 - x, 1 - y, 1 - z], respectively. The title molecule possesses a centre of symmetry at the centroid of the benzene ring. The bond lengths and bond angles in the title compound are within normal ranges. The dihedral angle between the plane formed by C9, N1, N2 and the benzene ring plane is 78.87 (9)°. The bond angle of N2—C9—N1 is 107.7 (1)° and the bond length of the backbone C9—C10 is 1.520 (2) Å, which are comparable with those reported in the references (Fujihara et al., 2002; Ma et al., 2005). The morpholine rings adopt the usual chair conformation. They are similar to those of 4,4'-di(morpholin-1-yl)azoxyfurazan (Averkiev et al., 2005) and 2,5-bis-(morpholinomethyl)hydroquinone (Ma et al., 2005). There are no significant contacts among the neighboring molecules, therefore, the molecules pack together only through van der Waals forces in the solid state.

Related literature

For related literature, see: Averkiev et al. (2005);Bellon et al. (1996); Fujihara et al. (2002); Goodman & Jacobsen (2002); Lanman & Myers (2004); Ma et al. (2005).

S2. Experimental

All reagents were of AR grade, available commercially and used without further purification. The mixture of terephthalaldehyde (0.67 g, 5 mmol), morpholine (1.74 g, 20 mmol) was heated and refluxed in ethanol (20 ml) for 5 h, and then the resulting solution was cooled to room temperature. After filtration, the filtrate was allowed to stand at room temperature. Upon slow evaporation, colorless block crystals suitable for X-ray diffraction analysis were isolated three days later.

S3. Refinement

All the H atoms on carbon were placed in calculated positions and refined using a riding model with C—H distance in the range 0.93 - 0.98 Å, and U_iso(H)= 1.2U_eq(C).

Computing details

Data collection: TEXRAY (Molecular Structure Corporation, 1985); cell refinement: TEXRAY (Molecular Structure Corporation, 1985); data reduction: TEXSAN (Molecular Structure Corporation, 1985); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX (McArdle, 1995); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

Fig. 1. The molecular structure of (I) with the atom-numbering scheme and 50% probability displacement ellipsoids [symmetry code:(i) 1 - x, 1 - y, 1 - z].

1,4-Bis(dimorpholinomethyl)benzene

Crystal data

C24H38N4O4	F(000) = 484
Mr = 446.58	Dx = 1.217 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2780 reflections
a = 11.5497 (6) Å	θ = 2.4–27.5°
b = 8.6735 (4) Å	µ = 0.08 mm^−1
c = 12.1645 (6) Å	T = 293 K
β = 90.2410 (12)°	Block, colourless
V = 1218.58 (10) Å^3	0.20 × 0.12 × 0.10 mm
Z = 2

Data collection

Rigaku Weissenberg IP diffractometer	2780 independent reflections
Radiation source: fine-focus sealed tube	1609 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
ω scans	θmax = 27.5°, θmin = 2.4°
Absorption correction: multi-scan (TEXRAY; Molecular Structure Corporation, 1985)	h = −14→0
Tmin = 0.823, Tmax = 0.992	k = −11→0
2966 measured reflections	l = −15→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.132	H-atom parameters constrained
S = 0.95	w = 1/[σ^2(Fo^2) + (0.0648P)^2] where P = (Fo^2 + 2Fc^2)/3
2780 reflections	(Δ/σ)max < 0.001
146 parameters	Δρmax = 0.19 e Å^−3
0 restraints	Δρmin = −0.15 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
N1	0.55070 (11)	0.42236 (14)	0.20137 (9)	0.0428 (3)
N2	0.45661 (10)	0.20450 (13)	0.27757 (9)	0.0398 (3)
O1	0.74303 (13)	0.56750 (17)	0.10348 (11)	0.0763 (4)
O2	0.35081 (12)	−0.08940 (14)	0.24153 (11)	0.0708 (4)
C1	0.6295 (2)	0.6191 (2)	0.08464 (15)	0.0702 (6)
H1A	0.5993	0.5696	0.0190	0.084*
H1B	0.6309	0.7294	0.0714	0.084*
C2	0.54923 (17)	0.58595 (18)	0.17956 (13)	0.0551 (5)
H2A	0.5745	0.6421	0.2443	0.066*
H2B	0.4712	0.6188	0.1613	0.066*
C3	0.66818 (15)	0.3723 (2)	0.22554 (14)	0.0576 (5)
H3A	0.6692	0.2625	0.2405	0.069*
H3B	0.6975	0.4259	0.2899	0.069*
C4	0.74258 (17)	0.4077 (2)	0.12769 (16)	0.0731 (6)
H4A	0.8212	0.3737	0.1423	0.088*
H4B	0.7139	0.3512	0.0644	0.088*
C5	0.36981 (15)	0.1420 (2)	0.35187 (13)	0.0523 (4)
H5A	0.2937	0.1787	0.3304	0.063*
H5B	0.3853	0.1771	0.4262	0.063*
C6	0.37208 (18)	−0.0308 (2)	0.34842 (14)	0.0629 (5)
H6A	0.4471	−0.0667	0.3737	0.075*
H6B	0.3140	−0.0708	0.3982	0.075*
C7	0.43089 (19)	−0.0256 (2)	0.16656 (16)	0.0711 (6)
H7A	0.4122	−0.0614	0.0931	0.085*
H7B	0.5079	−0.0623	0.1848	0.085*
C8	0.43114 (16)	0.14682 (19)	0.16718 (13)	0.0550 (5)
H8A	0.4890	0.1845	0.1162	0.066*
H8B	0.3561	0.1847	0.1433	0.066*
C9	0.46178 (13)	0.37317 (16)	0.28013 (11)	0.0404 (4)
H9	0.3870	0.4125	0.2540	0.048*
C10	0.48108 (13)	0.43400 (17)	0.39599 (11)	0.0396 (4)
C11	0.56048 (13)	0.37049 (17)	0.46801 (11)	0.0454 (4)
H11	0.6019	0.2832	0.4475	0.054*
C12	0.42098 (13)	0.56446 (17)	0.42950 (12)	0.0445 (4)
H12A	0.3672	0.6090	0.3821	0.053*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0500 (8)	0.0404 (7)	0.0380 (6)	−0.0053 (6)	0.0085 (6)	0.0027 (5)
N2	0.0494 (8)	0.0355 (7)	0.0345 (6)	−0.0040 (6)	0.0089 (5)	0.0005 (5)
O1	0.0728 (9)	0.0909 (11)	0.0652 (8)	−0.0337 (8)	0.0154 (7)	0.0087 (7)
O2	0.0860 (10)	0.0511 (8)	0.0754 (9)	−0.0234 (7)	0.0067 (7)	−0.0023 (6)
C1	0.1010 (16)	0.0583 (12)	0.0514 (10)	−0.0190 (11)	0.0081 (10)	0.0114 (8)
C2	0.0721 (12)	0.0468 (10)	0.0465 (9)	−0.0085 (8)	0.0056 (8)	0.0059 (7)
C3	0.0559 (11)	0.0661 (12)	0.0507 (9)	0.0006 (9)	0.0107 (8)	0.0101 (8)
C4	0.0574 (12)	0.0940 (17)	0.0679 (12)	−0.0048 (11)	0.0199 (9)	0.0106 (11)
C5	0.0597 (11)	0.0496 (10)	0.0476 (9)	−0.0087 (8)	0.0126 (8)	0.0042 (7)
C6	0.0757 (13)	0.0508 (11)	0.0622 (11)	−0.0130 (9)	0.0138 (10)	0.0092 (9)
C7	0.0981 (16)	0.0513 (11)	0.0640 (11)	−0.0132 (11)	0.0128 (11)	−0.0129 (9)
C8	0.0746 (12)	0.0470 (10)	0.0436 (9)	−0.0097 (9)	0.0057 (8)	−0.0024 (7)
C9	0.0439 (9)	0.0395 (9)	0.0378 (7)	0.0025 (7)	0.0059 (6)	0.0010 (6)
C10	0.0477 (8)	0.0379 (8)	0.0333 (7)	−0.0018 (7)	0.0076 (6)	0.0011 (6)
C11	0.0536 (10)	0.0401 (8)	0.0425 (8)	0.0129 (7)	0.0083 (7)	−0.0008 (7)
C12	0.0468 (9)	0.0477 (9)	0.0390 (7)	0.0098 (8)	0.0019 (6)	0.0019 (7)

Geometric parameters (Å, º)

N1—C2	1.4435 (18)	C4—H4B	0.9700
N1—C3	1.453 (2)	C5—C6	1.500 (2)
N1—C9	1.4707 (18)	C5—H5A	0.9700
N2—C5	1.4571 (18)	C5—H5B	0.9700
N2—C8	1.4618 (18)	C6—H6A	0.9700
N2—C9	1.4645 (17)	C6—H6B	0.9700
O1—C1	1.403 (2)	C7—C8	1.495 (2)
O1—C4	1.417 (2)	C7—H7A	0.9700
O2—C7	1.415 (2)	C7—H7B	0.9700
O2—C6	1.417 (2)	C8—H8A	0.9700
C1—C2	1.512 (2)	C8—H8B	0.9700
C1—H1A	0.9700	C9—C10	1.5204 (19)
C1—H1B	0.9700	C9—H9	0.9800
C2—H2A	0.9700	C10—C11	1.380 (2)
C2—H2B	0.9700	C10—C12	1.3895 (19)
C3—C4	1.502 (2)	C11—C12^i	1.384 (2)
C3—H3A	0.9700	C11—H11	0.9300
C3—H3B	0.9700	C12—C11^i	1.384 (2)
C4—H4A	0.9700	C12—H12A	0.9300
C2—N1—C3	109.93 (13)	C6—C5—H5B	109.7
C2—N1—C9	113.40 (12)	H5A—C5—H5B	108.2
C3—N1—C9	115.81 (12)	O2—C6—C5	112.41 (15)
C5—N2—C8	107.84 (12)	O2—C6—H6A	109.1
C5—N2—C9	112.73 (12)	C5—C6—H6A	109.1
C8—N2—C9	111.68 (12)	O2—C6—H6B	109.1
C1—O1—C4	109.98 (14)	C5—C6—H6B	109.1
C7—O2—C6	109.88 (13)	H6A—C6—H6B	107.9
O1—C1—C2	112.97 (15)	O2—C7—C8	112.92 (16)
O1—C1—H1A	109.0	O2—C7—H7A	109.0
C2—C1—H1A	109.0	C8—C7—H7A	109.0
O1—C1—H1B	109.0	O2—C7—H7B	109.0
C2—C1—H1B	109.0	C8—C7—H7B	109.0
H1A—C1—H1B	107.8	H7A—C7—H7B	107.8
N1—C2—C1	108.70 (15)	N2—C8—C7	110.32 (14)
N1—C2—H2A	109.9	N2—C8—H8A	109.6
C1—C2—H2A	109.9	C7—C8—H8A	109.6
N1—C2—H2B	109.9	N2—C8—H8B	109.6
C1—C2—H2B	109.9	C7—C8—H8B	109.6
H2A—C2—H2B	108.3	H8A—C8—H8B	108.1
N1—C3—C4	108.38 (14)	N2—C9—N1	107.73 (11)
N1—C3—H3A	110.0	N2—C9—C10	111.85 (12)
C4—C3—H3A	110.0	N1—C9—C10	113.78 (12)
N1—C3—H3B	110.0	N2—C9—H9	107.8
C4—C3—H3B	110.0	N1—C9—H9	107.8
H3A—C3—H3B	108.4	C10—C9—H9	107.8
O1—C4—C3	111.52 (16)	C11—C10—C12	118.04 (13)
O1—C4—H4A	109.3	C11—C10—C9	122.97 (14)
C3—C4—H4A	109.3	C12—C10—C9	118.89 (13)
O1—C4—H4B	109.3	C10—C11—C12^i	120.58 (14)
C3—C4—H4B	109.3	C10—C11—H11	119.7
H4A—C4—H4B	108.0	C12^i—C11—H11	119.7
N2—C5—C6	110.00 (14)	C11^i—C12—C10	121.37 (14)
N2—C5—H5A	109.7	C11^i—C12—H12A	119.3
C6—C5—H5A	109.7	C10—C12—H12A	119.3
N2—C5—H5B	109.7
C4—O1—C1—C2	56.2 (2)	C5—N2—C9—N1	−179.27 (12)
C3—N1—C2—C1	57.91 (17)	C8—N2—C9—N1	−57.68 (16)
C9—N1—C2—C1	−170.66 (14)	C5—N2—C9—C10	54.98 (17)
O1—C1—C2—N1	−56.7 (2)	C8—N2—C9—C10	176.58 (12)
C2—N1—C3—C4	−59.91 (18)	C2—N1—C9—N2	168.49 (12)
C9—N1—C3—C4	169.95 (14)	C3—N1—C9—N2	−63.05 (16)
C1—O1—C4—C3	−57.6 (2)	C2—N1—C9—C10	−66.91 (17)
N1—C3—C4—O1	59.7 (2)	C3—N1—C9—C10	61.55 (17)
C8—N2—C5—C6	58.37 (18)	N2—C9—C10—C11	43.93 (19)
C9—N2—C5—C6	−177.88 (14)	N1—C9—C10—C11	−78.42 (18)
C7—O2—C6—C5	55.6 (2)	N2—C9—C10—C12	−139.67 (14)
N2—C5—C6—O2	−58.9 (2)	N1—C9—C10—C12	97.98 (16)
C6—O2—C7—C8	−55.1 (2)	C12—C10—C11—C12^i	0.1 (2)
C5—N2—C8—C7	−57.8 (2)	C9—C10—C11—C12^i	176.50 (14)
C9—N2—C8—C7	177.87 (15)	C11—C10—C12—C11^i	−0.1 (2)
O2—C7—C8—N2	57.5 (2)	C9—C10—C12—C11^i	−176.65 (14)

Symmetry code: (i) −x+1, −y+1, −z+1.