Bis(1,2-dihydroxy­benzene) hexa­methyl­ene­tetra­mine

The title binary complex, 2C₆H₆O₂·C₆H₁₂N₄, is constructed from hexa­methyl­ene­tetra­mine, positioned about a twofold symmetry operator, and 1,2-dihydroxy­benzene. Each of the four tertiary amine N atoms participates in O—H...N contacts that produce mol­ecular strands that propagate along the c axis.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.051
• wR factor = 0.119
• Data-to-parameter ratio = 12.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) .       1.21 Ratio
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1
              C6 H12 N4

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

   1 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
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: XSCANS (Bruker, 1999); cell refinement: XSCANS; data reduction: XPREP (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: X-SEED.

Bis(1,2-dihydroxybenzene) hexamethylenetetramine

Crystal data

2C6H6O2·C6H12N4	F(000) = 768
Mr = 360.41	Dx = 1.326 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 33 reflections
a = 23.794 (2) Å	θ = 20.4–22.6°
b = 6.8422 (5) Å	µ = 0.10 mm^−1
c = 13.244 (1) Å	T = 298 K
β = 123.135 (6)°	Plate, transparent colorless
V = 1805.5 (3) Å^3	0.41 × 0.41 × 0.20 mm
Z = 4

Data collection

Siemens P4 diffractometer	Rint = 0.022
Radiation source: fine-focus sealed tube	θmax = 25.4°, θmin = 2.0°
Graphite monochromator	h = −1→28
ω/2θ\ scans	k = −1→8
1921 measured reflections	l = −14→13
1626 independent reflections	3 standard reflections every 97 reflections
1054 reflections with I > 2σ(I)	intensity decay: none

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0478P)^2 + 0.6351P] where P = (Fo^2 + 2Fc^2)/3
1626 reflections	(Δ/σ)max < 0.001
127 parameters	Δρmax = 0.15 e Å^−3
0 restraints	Δρmin = −0.25 e Å^−3

Special details

Experimental. 1H NMR (acetone-d6): δ 4.63 (s, 12H, HMTA-CH2), 6.62 (dd, J = 5.8 and 3.5?Hz, 4H, H-2, 5), 6.78 (dd, J = 5.8 and 3.5?Hz, 4H, H-3, 4). 13 C NMR (acetone-d6): δ 145.6 (C7—C10), 119.4 (C3, 4), 115.7 (C2, 5), 74.4 (C1, 6).

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	Occ. (<1)
O1	0.08901 (9)	0.7382 (3)	0.13606 (15)	0.0616 (6)
O2	0.11329 (11)	0.4389 (3)	0.03014 (17)	0.0643 (6)
N1	0.04573 (9)	1.0108 (3)	0.23315 (15)	0.0393 (5)
N2	0.04092 (9)	1.2620 (3)	0.35904 (15)	0.0386 (5)
C1	0.13760 (11)	0.6071 (4)	0.2089 (2)	0.0410 (6)
C2	0.17460 (12)	0.6174 (4)	0.3328 (2)	0.0470 (6)
H2	0.1662	0.7169	0.3707	0.056*
C3	0.22395 (12)	0.4820 (4)	0.4012 (2)	0.0558 (8)
H3	0.2489	0.4903	0.4849	0.067*
C4	0.23609 (13)	0.3361 (4)	0.3459 (2)	0.0613 (8)
H4	0.2696	0.2450	0.3919	0.074*
C5	0.19892 (13)	0.3225 (4)	0.2220 (2)	0.0562 (7)
H5	0.2072	0.2215	0.1849	0.067*
C6	0.14958 (12)	0.4572 (4)	0.1527 (2)	0.0433 (6)
C7	0.08446 (11)	1.1372 (4)	0.3404 (2)	0.0438 (6)
H7A	0.1115	1.0560	0.4111	0.053*
H7B	0.1146	1.2188	0.3309	0.053*
C8	0.0000	1.3817 (5)	0.2500	0.0412 (8)
H8A	−0.0293	1.4652	0.2606	0.049*	0.50
H8B	0.0293	1.4652	0.2394	0.049*	0.50
C9	−0.00435 (12)	1.1370 (3)	0.37265 (19)	0.0419 (6)
H9A	−0.0335	1.2183	0.3849	0.050*
H9B	0.0219	1.0558	0.4437	0.050*
C10	0.0000	0.8920 (5)	0.2500	0.0450 (9)
H10A	−0.0263	0.8085	0.1802	0.054*	0.50
H10B	0.0263	0.8085	0.3198	0.054*	0.50
H1O	0.0839 (15)	0.827 (4)	0.182 (3)	0.086 (10)*
H2O	0.0902 (15)	0.530 (5)	−0.003 (3)	0.077 (11)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0695 (13)	0.0651 (13)	0.0405 (10)	0.0360 (11)	0.0238 (9)	0.0047 (9)
O2	0.0907 (16)	0.0549 (13)	0.0490 (11)	0.0317 (12)	0.0393 (11)	0.0079 (10)
N1	0.0423 (11)	0.0358 (10)	0.0401 (11)	0.0073 (9)	0.0227 (9)	0.0017 (9)
N2	0.0469 (11)	0.0335 (11)	0.0399 (10)	−0.0099 (10)	0.0265 (9)	−0.0072 (9)
C1	0.0390 (13)	0.0429 (14)	0.0456 (13)	0.0089 (12)	0.0260 (12)	0.0081 (12)
C2	0.0466 (15)	0.0498 (16)	0.0451 (14)	0.0014 (13)	0.0255 (12)	0.0011 (12)
C3	0.0444 (15)	0.070 (2)	0.0461 (15)	0.0018 (15)	0.0205 (13)	0.0145 (14)
C4	0.0513 (17)	0.071 (2)	0.0639 (18)	0.0229 (15)	0.0333 (15)	0.0320 (16)
C5	0.0680 (17)	0.0494 (16)	0.0699 (18)	0.0219 (14)	0.0496 (16)	0.0165 (14)
C6	0.0490 (14)	0.0455 (15)	0.0457 (14)	0.0104 (13)	0.0324 (12)	0.0098 (12)
C7	0.0377 (13)	0.0458 (15)	0.0439 (13)	−0.0001 (12)	0.0197 (11)	0.0013 (12)
C8	0.055 (2)	0.0278 (17)	0.0518 (19)	0.000	0.0362 (18)	0.000
C9	0.0535 (14)	0.0384 (13)	0.0392 (12)	−0.0080 (12)	0.0288 (12)	−0.0025 (11)
C10	0.058 (2)	0.0240 (17)	0.0426 (18)	0.000	0.0211 (17)	0.000

Geometric parameters (Å, º)

O1—C1	1.361 (3)	C4—C5	1.377 (4)
O1—H1O	0.91 (3)	C4—H4	0.9300
O2—C6	1.365 (3)	C5—C6	1.375 (3)
O2—H2O	0.79 (3)	C5—H5	0.9300
N1—C10	1.470 (3)	C7—H7A	0.9700
N1—C9^i	1.473 (3)	C7—H7B	0.9700
N1—C7	1.478 (3)	C8—N2^i	1.472 (2)
N2—C9	1.462 (3)	C8—H8A	0.9700
N2—C7	1.464 (3)	C8—H8B	0.9700
N2—C8	1.472 (2)	C9—N1^i	1.473 (3)
C1—C2	1.376 (3)	C9—H9A	0.9700
C1—C6	1.386 (3)	C9—H9B	0.9700
C2—C3	1.376 (3)	C10—N1^i	1.470 (3)
C2—H2	0.9300	C10—H10A	0.9700
C3—C4	1.360 (4)	C10—H10B	0.9700
C3—H3	0.9300
C1—O1—H1O	109.7 (18)	C5—C6—C1	119.3 (2)
C6—O2—H2O	112 (2)	N2—C7—N1	112.12 (17)
C10—N1—C9^i	107.64 (16)	N2—C7—H7A	109.2
C10—N1—C7	107.58 (16)	N1—C7—H7A	109.2
C9^i—N1—C7	108.21 (17)	N2—C7—H7B	109.2
C9—N2—C7	108.47 (18)	N1—C7—H7B	109.2
C9—N2—C8	108.04 (16)	H7A—C7—H7B	107.9
C7—N2—C8	107.97 (15)	N2^i—C8—N2	112.4 (2)
O1—C1—C2	123.6 (2)	N2^i—C8—H8A	109.1
O1—C1—C6	116.8 (2)	N2—C8—H8A	109.1
C2—C1—C6	119.6 (2)	N2^i—C8—H8B	109.1
C1—C2—C3	120.6 (3)	N2—C8—H8B	109.1
C1—C2—H2	119.7	H8A—C8—H8B	107.9
C3—C2—H2	119.7	N2—C9—N1^i	112.35 (17)
C4—C3—C2	119.7 (2)	N2—C9—H9A	109.1
C4—C3—H3	120.1	N1^i—C9—H9A	109.1
C2—C3—H3	120.1	N2—C9—H9B	109.1
C3—C4—C5	120.3 (2)	N1^i—C9—H9B	109.1
C3—C4—H4	119.9	H9A—C9—H9B	107.9
C5—C4—H4	119.9	N1^i—C10—N1	112.8 (3)
C6—C5—C4	120.5 (3)	N1^i—C10—H10A	109.0
C6—C5—H5	119.7	N1—C10—H10A	109.0
C4—C5—H5	119.7	N1^i—C10—H10B	109.0
O2—C6—C5	119.1 (2)	N1—C10—H10B	109.0
O2—C6—C1	121.6 (2)	H10A—C10—H10B	107.8
O1—C1—C2—C3	−178.7 (2)	C9—N2—C7—N1	58.6 (2)
C6—C1—C2—C3	0.9 (4)	C8—N2—C7—N1	−58.2 (2)
C1—C2—C3—C4	−0.3 (4)	C10—N1—C7—N2	−58.0 (2)
C2—C3—C4—C5	−0.5 (4)	C9^i—N1—C7—N2	58.0 (2)
C3—C4—C5—C6	0.6 (4)	C9—N2—C8—N2^i	−58.50 (13)
C4—C5—C6—O2	−179.5 (2)	C7—N2—C8—N2^i	58.63 (13)
C4—C5—C6—C1	0.0 (4)	C7—N2—C9—N1^i	−58.7 (2)
O1—C1—C6—O2	−1.6 (4)	C8—N2—C9—N1^i	58.1 (2)
C2—C1—C6—O2	178.8 (2)	C9^i—N1—C10—N1^i	−58.19 (13)
O1—C1—C6—C5	178.9 (2)	C7—N1—C10—N1^i	58.22 (13)
C2—C1—C6—C5	−0.8 (4)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···N1	0.91 (3)	1.89 (3)	2.764 (3)	162 (3)
O2—H2O···O1	0.79 (3)	2.34 (3)	2.717 (3)	111 (2)
O2—H2O···N2^ii	0.79 (3)	2.10 (3)	2.832 (3)	155 (3)

Symmetry code: (ii) x, −y+2, z−1/2.