Structural phases of hexamethylenetetramine–pimelic acid (1/1): a unified description based on a stacking model

The thermotropic phase diagram of 1:1 co-crystals of hexamethylenetetramine and pimelic acid (heptanedioic acid) is investigated. Three crystalline phases are identified at ambient pressure. Phase I is disordered, as revealed by diffuse rods in its diffraction pattern. When the temperature is lowered the diffuse streaks disappear in Phase II, but superstructure reflections emerge indicating an ordering process of the structure through a non-ferroic, or at least non-ferroelastic, phase transition. Phase II is mainly characterized by an unusual distribution of its reflection intensities. Phase III is reached through a ferroelastic phase transition that induces twinned domains. A model based on the stacking of an elementary layer is proposed with the aim of describing the structures in a unified framework. Depending on the value of the unique stacking parameter η, each of the different structures observed can be reproduced by this model. Its validity is then tested by a series of simulations reproducing the main features of the diffraction patterns such as the diffuse scattering streaks, the occurrence of superstructure peaks at lower temperature and twinning.

Computing details

Data collection: Expose - Oxford-CCD for PhaseI; Expose; Stoe, 1997 for PhaseII. Cell refinement: Cell; Stoe, 1997 for PhaseII. Program(s) used to solve structure: SHELXS97 (Sheldrick, 1990) for PhaseI; SHELXS; Sheldrick and Schneider, 1997 for PhaseII. Program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) for PhaseI; (Jana2000; Petricek and Dusek, 2000) for PhaseIII, PhaseII. Software used to prepare material for publication: (Jana2000; Petricek and Dusek, 2000) for PhaseIII, PhaseII.

Figures

(PhaseI)

Crystal data

C13H24N4O4	Dx = 1.260 Mg m^−3
Mr = 300.36	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Bmmb	Cell parameters from 3043 reflections
a = 9.3962 (19) Å	θ = 3.5–25.0°
b = 22.981 (5) Å	µ = 0.09 mm^−1
c = 7.3338 (15) Å	T = 324 K
V = 1583.6 (6) Å^3	Platelets, colourless
Z = 4	0.40 × 0.40 × 0.10 mm
F(000) = 648

Data collection

Oxford-CCD diffractometer	203 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.118
Graphite monochromator	θmax = 25.0°, θmin = 3.5°
Oscillation scans	h = −11→11
3043 measured reflections	k = −20→27
749 independent reflections	l = −8→7

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.047	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.087	w = 1/[σ^2(Fo^2) + (0.0192P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.71	(Δ/σ)max = 0.001
749 reflections	Δρmax = 0.09 e Å^−3
86 parameters	Δρmin = −0.07 e Å^−3
1 restraint	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0018 (10)

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	Occ. (<1)
C1	0.5000	0.4033 (4)	1.0876 (12)	0.113 (2)
C2	0.4218 (7)	0.4438 (5)	1.2128 (14)	0.142 (3)	0.50
H2b	0.3818	0.4749	1.1396	0.170*	0.50
H2a	0.3428	0.4226	1.2659	0.170*	0.50
C3	0.5000	0.4692 (3)	1.3557 (12)	0.160 (3)
H3b	0.5674	0.4958	1.3007	0.192*	0.50
H3a	0.5553	0.4383	1.4118	0.192*	0.50
C4	0.4303 (9)	0.5000	1.5000	0.167 (6)	0.50
H4a	0.3684	0.5281	1.4411	0.200*	0.25
H4b	0.3684	0.4719	1.5589	0.200*	0.25
O1	0.4135 (9)	0.3945 (5)	0.9431 (10)	0.156 (4)	0.50
HO1	0.4716	0.3689	0.9213	0.235*	0.50
O2a	0.605 (4)	0.396 (3)	1.072 (7)	0.16 (2)	0.21 (3)
O2b	0.571 (3)	0.3633 (14)	1.135 (4)	0.188 (13)	0.29 (3)
N2	0.3707 (3)	0.2500	0.5046 (6)	0.0959 (14)
N1	0.5000	0.30261 (16)	0.7375 (5)	0.0910 (12)
Ca	0.5000	0.2500	0.8448 (8)	0.086 (2)
H9a	0.5833	0.2500	0.9228	0.103*	0.50
H9b	0.4167	0.2500	0.9228	0.103*	0.50
Cb	0.3733 (2)	0.30062 (17)	0.6157 (5)	0.1059 (12)
H7a	0.2877	0.3017	0.6896	0.127*
H7b	0.3732	0.3348	0.5381	0.127*
Cc	0.5000	0.2500	0.3894 (8)	0.118 (2)
H8a	0.5000	0.2842	0.3118	0.141*	0.50
H8b	0.5000	0.2158	0.3118	0.141*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.115 (6)	0.102 (7)	0.122 (8)	0.000	0.000	−0.030 (5)
C2	0.143 (5)	0.130 (9)	0.153 (11)	0.006 (5)	−0.027 (6)	−0.012 (7)
C3	0.178 (6)	0.127 (7)	0.175 (10)	0.000	0.000	−0.017 (6)
C4	0.161 (8)	0.173 (16)	0.167 (17)	0.000	0.000	−0.087 (13)
O1	0.152 (5)	0.174 (8)	0.143 (9)	0.039 (4)	−0.035 (5)	−0.042 (7)
O2a	0.106 (13)	0.18 (4)	0.19 (4)	0.109 (17)	−0.059 (16)	−0.08 (3)
O2b	0.23 (3)	0.120 (14)	0.21 (2)	0.096 (10)	−0.059 (11)	0.013 (12)
N2	0.0641 (18)	0.146 (5)	0.077 (3)	0.000	−0.0107 (18)	0.000
N1	0.0852 (19)	0.101 (3)	0.087 (3)	0.000	0.000	0.003 (2)
Ca	0.070 (3)	0.130 (7)	0.058 (5)	0.000	0.000	0.000
Cb	0.0771 (15)	0.147 (4)	0.094 (3)	0.030 (2)	−0.0041 (16)	0.010 (2)
Cc	0.087 (3)	0.204 (8)	0.062 (5)	0.000	0.000	0.000

Geometric parameters (Å, º)

C1—O2a	1.01 (3)	O2a—O2b	0.94 (6)
C1—O2b	1.19 (2)	O2a—C2^i	1.53 (3)
C1—O1	1.351 (8)	O2b—O2b^i	1.34 (5)
C1—C2	1.499 (9)	O2b—O1^i	1.59 (3)
C2—C3	1.407 (8)	N2—Cb	1.420 (4)
C3—C4	1.432 (6)	N2—Cc	1.480 (5)
O1—O2a^i	0.96 (4)	N1—Ca	1.442 (4)
O1—O2b^i	1.59 (3)	N1—Cb	1.489 (3)
O1—O1^i	1.626 (16)
O2a^i—C1—O2a	156 (4)	O2a^i—O1—O1^i	100 (3)
O2a^i—C1—O2b	117 (6)	C1—O1—O1^i	53.0 (5)
O2a—C1—O2b	50 (4)	O2b^i—O1—O1^i	84.7 (9)
O2b^i—C1—O2b	68 (3)	O1^i—O2a—O2b	114 (5)
O2a^i—C1—O1	45 (3)	O1^i—O2a—C1	87 (2)
O2a—C1—O1	118 (2)	O2b—O2a—C1	75 (5)
O2b^i—C1—O1	77.1 (16)	O1^i—O2a—C2^i	131 (6)
O2b—C1—O1	116.9 (16)	O2b—O2a—C2^i	101 (5)
O1^i—C1—O1	74.0 (9)	C1—O2a—C2^i	69.0 (14)
O2a^i—C1—C2	72.2 (17)	O2a—O2b—C1	55 (2)
O2a—C1—C2	130.9 (17)	O2a—O2b—O2b^i	110 (2)
O2b^i—C1—C2	91.5 (16)	C1—O2b—O2b^i	55.8 (17)
O2b—C1—C2	125.2 (19)	O2a—O2b—O1^i	34 (2)
O1^i—C1—C2	150.2 (11)	C1—O2b—O1^i	56.0 (13)
O1—C1—C2	106.1 (5)	O2b^i—O2b—O1^i	95.2 (9)
C2^i—C1—C2	58.7 (6)	Cb^iii—N2—Cb	110.0 (5)
C3—C2—C1	117.2 (5)	Cb—N2—Cc	108.3 (2)
C2—C3—C4	121.1 (5)	Ca—N1—Cb	107.5 (3)
C3^ii—C4—C3	125.6 (8)	Cb—N1—Cb^i	106.2 (4)
O2a^i—O1—C1	48 (2)	N1^iii—Ca—N1	113.9 (6)
O2a^i—O1—O2b^i	33 (4)	N2—Cb—N1	112.5 (3)
C1—O1—O2b^i	46.9 (8)	N2—Cc—N2^iv	110.4 (5)

Symmetry codes: (i) −x+1, y, z; (ii) x, −y+1, −z+3; (iii) x, −y+1/2, z; (iv) −x+1, −y+1/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—HO1···N1	0.82	2.05	2.720 (10)	139

(PhaseIII)

Crystal data

C13H24N4O4	F(000) = 648
Mr = 300.4	Dx = 1.330 (1) Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71069 Å
a = 5.9088 (7) Å	Cell parameters from 30760 reflections
b = 22.2973 (19) Å	θ = 2.6–28.0°
c = 11.856 (7) Å	µ = 0.10 mm^−1
β = 106.281 (7)°	T = 120 K
V = 1499.4 (9) Å^3	Plate, colourless
Z = 4	0.20 × 0.20 × 0.10 mm

Data collection

Stoe-IPDS diffractometer	12650 reflections with I > 3σ(I)
Radiation source: Sealed tube	Rint = 0.000
Graphite monochromator	θmax = 28.0°, θmin = 2.6°
Oscillation scans	h = −7→7
30760 measured reflections	k = −29→29
20129 independent reflections	l = −15→15

Refinement

Refinement on F^2	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.046	Weighting scheme based on measured s.u.'s w = 1/(σ^2(I) + 0.0016I^2)
wR(F^2) = 0.123	(Δ/σ)max = 0.002
S = 1.53	Δρmax = 0.37 e Å^−3
20129 reflections	Δρmin = −0.30 e Å^−3
265 parameters

Special details

Refinement. The total reflections (20129) includes reflections of all the orientational domains as well as a doubling of the number of common reflections.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.1941 (3)	0.89476 (7)	−0.00458 (14)	0.0281 (3)
Ho1	0.230 (2)	0.8623 (6)	0.0528 (12)	0.052 (4)*
O2	−0.1670 (3)	0.87941 (8)	0.00703 (15)	0.0474 (3)
C1	−0.03468 (19)	0.90516 (4)	−0.03551 (9)	0.0188 (3)
C2	−0.10806 (17)	0.95054 (4)	−0.13273 (8)	0.0190 (3)
H2a	−0.0845 (14)	0.9302 (4)	−0.2035 (8)	0.028225 (2)*
H2b	0.0004 (15)	0.9851 (4)	−0.1143 (7)	0.028225 (2)*
C3	−0.36467 (18)	0.97185 (4)	−0.16110 (9)	0.0201 (3)
H3a	−0.4718 (15)	0.9369 (4)	−0.1604 (7)	0.029701 (2)*
H3b	−0.3831 (15)	0.9994 (4)	−0.1012 (8)	0.029701 (2)*
C4	−0.43737 (19)	1.00238 (5)	−0.28073 (9)	0.0228 (3)
H4a	−0.4312 (15)	0.9727 (4)	−0.3378 (8)	0.034119 (2)*
H4b	−0.3172 (16)	1.0330 (4)	−0.2853 (8)	0.034119 (2)*
C5	−0.68134 (18)	1.03163 (4)	−0.31540 (9)	0.0192 (3)
H5a	−0.8010 (17)	1.0028 (4)	−0.3086 (8)	0.028760 (2)*
H5b	−0.6864 (14)	1.0655 (4)	−0.2636 (7)	0.028760 (2)*
C6	−0.73965 (17)	1.05392 (4)	−0.44154 (8)	0.0186 (3)
H6a	−0.6068 (16)	1.0777 (4)	−0.4542 (7)	0.028242 (2)*
H6b	−0.7668 (14)	1.0189 (4)	−0.4947 (8)	0.028242 (2)*
C7	−0.95298 (18)	1.09384 (3)	−0.48246 (10)	0.0182 (4)
O3	−0.9992 (3)	1.10761 (7)	−0.59500 (13)	0.0262 (2)
Ho3	−1.145 (3)	1.1430 (8)	−0.6160 (14)	0.097 (6)*
O4	−1.0697 (3)	1.11248 (7)	−0.42222 (14)	0.0407 (3)
O1m	0.1982	0.896	−0.0038	0.0358*	0
O2m	−0.1692	0.876	0.0015	0.0358*	0
O3m	−0.9947	1.1061	−0.5962	0.0358*	0
O4m	−1.0658	1.1131	−0.421	0.0358*	0
N1	0.34436 (13)	0.80229 (3)	0.14457 (6)	0.0166 (2)
N2	0.7026 (2)	0.74140 (6)	0.21512 (13)	0.0192 (2)
N3	0.3132 (2)	0.69426 (5)	0.17250 (11)	0.0162 (2)
N4	0.4481 (3)	0.76047 (6)	0.34240 (11)	0.0184 (2)
Cf	0.3133 (3)	0.70629 (6)	0.29555 (12)	0.0174 (2)
Hfa	0.1456 (16)	0.7126 (4)	0.2985 (8)	0.0223 (4)
Hfb	0.3852 (15)	0.6711 (4)	0.3436 (8)	0.0219 (4)
Cd	0.6917 (3)	0.75223 (6)	0.33579 (14)	0.0211 (2)
Hda	0.7843 (17)	0.7890 (4)	0.3653 (8)	0.0280 (4)
Hdb	0.7629 (17)	0.7181 (4)	0.3839 (8)	0.0266 (4)
Ca	0.2098 (3)	0.74706 (5)	0.10057 (14)	0.0171 (2)
Haa	0.0446 (19)	0.7526 (4)	0.1048 (11)	0.0228 (4)
Hab	0.209 (2)	0.7387 (4)	0.0186 (9)	0.0217 (4)
Cc	0.5932 (2)	0.79292 (6)	0.14292 (13)	0.0182 (2)
Hca	0.5943 (17)	0.7847 (4)	0.0596 (8)	0.0221 (4)
Hcb	0.6940 (16)	0.8288 (4)	0.1766 (8)	0.0245 (4)
Cb	0.3419 (3)	0.81141 (6)	0.26740 (12)	0.0198 (3)
Hba	0.4409 (16)	0.8480 (4)	0.2977 (8)	0.0264 (4)
Hbb	0.1725 (17)	0.8164 (4)	0.2678 (9)	0.0255 (4)
Ce	0.5610 (3)	0.68772 (6)	0.16974 (13)	0.0190 (3)
Hea	0.6303 (17)	0.6537 (4)	0.2185 (8)	0.0249 (4)
Heb	0.5625 (17)	0.6813 (4)	0.0874 (8)	0.0242 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0254 (4)	0.0283 (4)	0.0318 (4)	0.0071 (3)	0.0098 (3)	0.0156 (3)
O2	0.0287 (4)	0.0568 (6)	0.0589 (6)	0.0040 (4)	0.0158 (4)	0.0421 (5)
C1	0.0241 (6)	0.0128 (4)	0.0192 (6)	0.0005 (4)	0.0057 (5)	−0.0011 (4)
C2	0.0240 (5)	0.0149 (5)	0.0180 (5)	−0.0002 (4)	0.0058 (4)	0.0014 (4)
C3	0.0253 (6)	0.0150 (4)	0.0198 (5)	0.0018 (4)	0.0060 (4)	0.0026 (4)
C4	0.0280 (5)	0.0204 (4)	0.0206 (5)	0.0039 (4)	0.0078 (4)	0.0042 (4)
C5	0.0244 (6)	0.0151 (4)	0.0186 (5)	0.0007 (4)	0.0067 (4)	0.0006 (4)
C6	0.0231 (5)	0.0160 (5)	0.0180 (5)	0.0015 (4)	0.0078 (4)	−0.0002 (4)
C7	0.0241 (6)	0.0117 (4)	0.0189 (6)	0.0009 (4)	0.0063 (4)	0.0002 (4)
O3	0.0310 (4)	0.0280 (4)	0.0200 (4)	0.0142 (3)	0.0079 (3)	0.0059 (3)
O4	0.0470 (5)	0.0503 (5)	0.0307 (4)	0.0304 (4)	0.0209 (4)	0.0094 (4)
N1	0.0187 (4)	0.0156 (3)	0.0158 (3)	0.0026 (2)	0.0050 (2)	0.0021 (2)
N2	0.0130 (3)	0.0229 (4)	0.0217 (4)	0.00108 (16)	0.0050 (2)	0.0021 (3)
N3	0.0167 (4)	0.0156 (2)	0.0161 (4)	−0.0015 (2)	0.0040 (2)	−0.0008 (2)
N4	0.0223 (4)	0.0200 (3)	0.0128 (2)	−0.0007 (3)	0.0049 (2)	−0.00076 (17)
Cf	0.0179 (4)	0.0190 (3)	0.0159 (4)	−0.0007 (2)	0.0060 (3)	0.0024 (2)
Hfa	0.0199 (5)	0.0276 (6)	0.0224 (7)	−0.0013 (4)	0.0108 (5)	0.0035 (5)
Hfb	0.0253 (9)	0.0208 (4)	0.0195 (6)	−0.0009 (4)	0.0064 (5)	0.0061 (4)
Cd	0.0172 (3)	0.0253 (5)	0.0171 (3)	−0.0026 (2)	−0.0010 (2)	0.0018 (3)
Hda	0.0243 (4)	0.0329 (8)	0.0212 (5)	−0.0098 (4)	−0.0030 (3)	−0.0008 (5)
Hdb	0.0197 (5)	0.0329 (8)	0.0217 (4)	0.0006 (5)	−0.0034 (3)	0.0069 (4)
Ca	0.0147 (3)	0.0208 (5)	0.0143 (3)	0.0003 (2)	0.0016 (2)	0.0011 (3)
Haa	0.0135 (3)	0.0305 (9)	0.0220 (6)	0.0016 (3)	0.0012 (3)	0.0042 (6)
Hab	0.0225 (6)	0.0266 (9)	0.0134 (3)	−0.0022 (6)	0.0008 (3)	−0.0002 (3)
Cc	0.0181 (4)	0.0193 (3)	0.0183 (4)	−0.0024 (2)	0.0069 (3)	0.0015 (2)
Hca	0.0240 (7)	0.0254 (5)	0.0201 (5)	−0.0018 (5)	0.0116 (5)	0.0025 (4)
Hcb	0.0249 (7)	0.0233 (4)	0.0256 (9)	−0.0085 (4)	0.0078 (5)	0.0016 (4)
Cb	0.0259 (5)	0.0166 (2)	0.0186 (5)	0.0031 (2)	0.0090 (3)	−0.0016 (2)
Hba	0.0400 (9)	0.0169 (2)	0.0236 (7)	−0.0009 (3)	0.0112 (5)	−0.0052 (3)
Hbb	0.0299 (6)	0.0238 (5)	0.0272 (8)	0.0095 (4)	0.0152 (5)	0.0002 (4)
Ce	0.0198 (5)	0.0170 (2)	0.0217 (5)	0.0042 (2)	0.0082 (3)	−0.0002 (2)
Hea	0.0260 (7)	0.0190 (3)	0.0310 (9)	0.0086 (4)	0.0101 (5)	0.0031 (3)
Heb	0.0296 (8)	0.0215 (4)	0.0253 (6)	0.0045 (4)	0.0141 (5)	−0.0037 (4)

Geometric parameters (Å, º)

O1—Ho1	0.975 (14)	O3m—Ho3	1.184 (17)
O1—C1	1.3183 (19)	N1—Ca	1.4794 (15)
O2—C1	1.190 (2)	N1—Cc	1.4908 (17)
C1—C2	1.5034 (13)	N1—Cb	1.4745 (17)
C1—O1m	1.3366 (11)	N2—Cd	1.470 (2)
C1—O2m	1.2010 (11)	N2—Cc	1.4698 (18)
C2—H2a	0.998 (10)	N2—Ce	1.4731 (18)
C2—H2b	0.988 (9)	N3—Ho3^i	1.540 (16)
C2—C3	1.5336 (14)	N3—Cf	1.483 (2)
C3—H3a	1.005 (10)	N3—Ca	1.4813 (17)
C3—H3b	0.968 (10)	N3—Ce	1.481 (2)
C3—C4	1.5225 (15)	N4—Cf	1.4678 (18)
C4—H4a	0.954 (10)	N4—Cd	1.475 (2)
C4—H4b	0.998 (10)	N4—Cb	1.4703 (18)
C4—C5	1.5298 (15)	Cf—Hfa	1.011 (10)
C5—H5a	0.975 (10)	Cf—Hfb	0.993 (9)
C5—H5b	0.979 (9)	Cd—Hda	0.993 (9)
C5—C6	1.5210 (14)	Cd—Hdb	0.973 (9)
C6—H6a	0.993 (10)	Ca—Haa	0.999 (12)
C6—H6b	0.988 (9)	Ca—Hab	0.988 (11)
C6—C7	1.5080 (13)	Cc—Hca	1.007 (10)
C7—O3	1.3209 (19)	Cc—Hcb	1.010 (9)
C7—O4	1.198 (2)	Cb—Hba	1.009 (9)
C7—O3m	1.3294 (11)	Cb—Hbb	1.008 (10)
C7—O4m	1.1967 (12)	Ce—Hea	0.971 (9)
O3—Ho3	1.142 (17)	Ce—Heb	0.989 (10)
O1m—Ho1	0.989 (14)
Ho1—O1—C1	109.3 (8)	Cc—N2—Ce	108.07 (11)
O1—C1—O2	122.79 (13)	Ho3^i—N3—Cf	112.6 (7)
O1—C1—C2	112.61 (12)	Ho3^i—N3—Ca	103.2 (6)
O2—C1—C2	124.54 (12)	Ho3^i—N3—Ce	116.0 (7)
O1m—C1—O2m	123.31 (7)	Cf—N3—Ca	107.99 (11)
C1—C2—H2a	105.1 (5)	Cf—N3—Ce	108.16 (11)
C1—C2—H2b	109.0 (5)	Ca—N3—Ce	108.43 (12)
C1—C2—C3	115.57 (9)	Cf—N4—Cd	108.16 (12)
H2a—C2—H2b	107.9 (8)	Cf—N4—Cb	108.22 (10)
H2a—C2—C3	108.6 (4)	Cd—N4—Cb	108.76 (13)
H2b—C2—C3	110.3 (5)	N3—Cf—N4	111.82 (13)
C2—C3—H3a	110.2 (5)	N3—Cf—Hfa	109.2 (5)
C2—C3—H3b	110.1 (5)	N3—Cf—Hfb	107.7 (6)
C2—C3—C4	110.26 (9)	N4—Cf—Hfa	107.8 (6)
H3a—C3—H3b	106.6 (8)	N4—Cf—Hfb	109.5 (5)
H3a—C3—C4	109.9 (5)	Hfa—Cf—Hfb	110.8 (8)
H3b—C3—C4	109.8 (5)	N2—Cd—N4	112.46 (12)
C3—C4—H4a	107.0 (6)	N2—Cd—Hda	108.0 (6)
C3—C4—H4b	109.7 (5)	N2—Cd—Hdb	108.2 (6)
C3—C4—C5	116.07 (10)	N4—Cd—Hda	109.1 (6)
H4a—C4—H4b	105.5 (8)	N4—Cd—Hdb	109.5 (7)
H4a—C4—C5	109.0 (5)	Hda—Cd—Hdb	109.5 (7)
H4b—C4—C5	109.0 (5)	N1—Ca—N3	111.37 (10)
C4—C5—H5a	110.3 (5)	N1—Ca—Haa	108.3 (5)
C4—C5—H5b	110.6 (4)	N1—Ca—Hab	111.0 (6)
C4—C5—C6	109.88 (9)	N3—Ca—Haa	108.7 (6)
H5a—C5—H5b	107.8 (8)	N3—Ca—Hab	107.7 (6)
H5a—C5—C6	109.1 (5)	Haa—Ca—Hab	109.7 (10)
H5b—C5—C6	109.1 (5)	N1—Cc—N2	112.11 (12)
C5—C6—H6a	110.6 (4)	N1—Cc—Hca	108.4 (5)
C5—C6—H6b	108.7 (5)	N1—Cc—Hcb	111.0 (6)
C5—C6—C7	116.60 (9)	N2—Cc—Hca	107.9 (6)
H6a—C6—H6b	108.6 (8)	N2—Cc—Hcb	105.9 (5)
H6a—C6—C7	105.2 (5)	Hca—Cc—Hcb	111.5 (8)
H6b—C6—C7	106.8 (5)	N1—Cb—N4	111.71 (11)
C6—C7—O3	112.30 (11)	N1—Cb—Hba	107.3 (6)
C6—C7—O4	125.60 (11)	N1—Cb—Hbb	107.7 (6)
O3m—C7—O4m	124.56 (7)	N4—Cb—Hba	107.6 (5)
C7—O3—Ho3	108.1 (9)	N4—Cb—Hbb	109.8 (6)
Ho1—O1m—C1	107.0 (8)	Hba—Cb—Hbb	112.8 (8)
C7—O3m—Ho3	105.0 (9)	N2—Ce—N3	112.09 (12)
Ca—N1—Cc	108.26 (9)	N2—Ce—Hea	108.4 (5)
Ca—N1—Cb	108.06 (10)	N2—Ce—Heb	108.5 (6)
Cc—N1—Cb	108.37 (9)	N3—Ce—Hea	108.6 (6)
Cd—N2—Cc	107.83 (12)	N3—Ce—Heb	108.6 (6)
Cd—N2—Ce	108.26 (13)	Hea—Ce—Heb	110.8 (8)

Symmetry code: (i) −x−1, y−1/2, −z−1/2.

(PhaseII)

Crystal data

C13H24N4O4	Dx = 1.287 (1) Mg m^−3
Mr = 300.4	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pccn	Cell parameters from 31084 reflections
a = 9.5005 (4) Å	θ = 2.3–28.0°
b = 22.6599 (16) Å	µ = 0.10 mm^−1
c = 14.4004 (7) Å	T = 293 K
V = 3100.1 (3) Å^3	Plate, colourless
Z = 8	0.20 × 0.20 × 0.10 mm
F(000) = 1296

Data collection

Stoe-IPDS diffractometer	1509 reflections with I > 3σ(I)
Radiation source: Sealed tube	Rint = 0.061
Graphite monochromator	θmax = 28.0°, θmin = 2.3°
Oscillation scans	h = −11→11
31084 measured reflections	k = −29→29
3074 independent reflections	l = −18→18

Refinement

Refinement on F^2	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.039	Weighting scheme based on measured s.u.'s w = 1/(σ^2(I) + 0.0016I^2)
wR(F^2) = 0.105	(Δ/σ)max = 0.001
S = 1.29	Δρmax = 0.26 e Å^−3
3074 reflections	Δρmin = −0.26 e Å^−3
260 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.1555 (4)	0.39155 (13)	0.3397 (2)	0.0720 (6)
Ho1	0.202 (3)	0.3576 (15)	0.291 (2)	0.133 (10)*
O2	0.3484 (4)	0.38268 (19)	0.4147 (3)	0.1230 (10)
C1	0.2384 (3)	0.40388 (10)	0.40812 (15)	0.0488 (9)
C2	0.1756 (2)	0.44637 (8)	0.47673 (12)	0.0530 (7)
H2a	0.0953 (15)	0.4260 (6)	0.5053 (9)	0.078648 (2)*
H2b	0.1399 (14)	0.4801 (6)	0.4418 (9)	0.078648 (2)*
C3	0.2731 (2)	0.46858 (10)	0.55240 (14)	0.0556 (7)
H3a	0.3414 (15)	0.4966 (6)	0.5259 (9)	0.082608 (2)*
H3b	0.3255 (15)	0.4352 (6)	0.5793 (9)	0.082608 (2)*
C4	0.1888 (2)	0.49941 (9)	0.62785 (14)	0.0617 (6)
H4a	0.1320 (15)	0.5301 (6)	0.5976 (9)	0.091585 (2)*
H4b	0.1244 (16)	0.4706 (6)	0.6566 (9)	0.091585 (2)*
C5	0.2733 (2)	0.52857 (10)	0.70471 (14)	0.0539 (7)
H5a	0.3373 (15)	0.4996 (6)	0.7311 (9)	0.080094 (2)*
H5b	0.3291 (15)	0.5607 (6)	0.6779 (8)	0.080094 (2)*
C6	0.1769 (2)	0.55229 (8)	0.77950 (12)	0.0533 (6)
H6a	0.1014 (15)	0.5735 (6)	0.7508 (8)	0.079116 (2)*
H6b	0.1360 (15)	0.5198 (6)	0.8132 (9)	0.079116 (2)*
C7	0.2424 (2)	0.59334 (11)	0.84811 (16)	0.0495 (9)
O3	0.1609 (4)	0.60876 (15)	0.9143 (3)	0.0845 (7)
Ho3	0.203 (4)	0.6426 (19)	0.968 (3)	0.178 (14)*
O4	0.3533 (5)	0.6120 (2)	0.8448 (3)	0.1404 (11)
O1m	0.1514	0.3921	0.3375	0.038*	0
O2m	0.3476	0.3785	0.4185	0.038*	0
O3m	0.1521	0.6059	0.9161	0.038*	0
O4m	0.3598	0.6133	0.8435	0.038*	0
N1a	0.23116 (13)	0.30331 (6)	0.22403 (7)	0.0420 (6)
N2a	0.3768 (2)	0.25818 (10)	0.10499 (13)	0.0472 (9)
Caa	0.250 (2)	0.2500 (12)	0.28157 (14)	0.0417 (11)
Haaa	0.1672 (12)	0.2444 (5)	0.3192 (7)	0.0555 (17)
Cba	0.3563 (2)	0.30958 (9)	0.16443 (13)	0.0495 (6)
Hbaa	0.3428 (11)	0.3454 (5)	0.1247 (8)	0.0689 (10)
Hbba	0.4375 (11)	0.3152 (5)	0.2042 (7)	0.0632 (12)
Cca	0.1072 (2)	0.29380 (10)	0.16384 (13)	0.0469 (7)
Hcaa	0.0239 (11)	0.2885 (5)	0.2034 (7)	0.0598 (13)
Hcba	0.0942 (10)	0.3287 (5)	0.1239 (8)	0.0631 (10)
Cda	0.2500 (17)	0.2500 (9)	0.04827 (15)	0.0540 (11)
Hdaa	0.2649 (13)	0.2140 (6)	0.0066 (7)	0.0726 (19)
N1b	0.23374 (13)	0.69679 (6)	1.02777 (7)	0.0446 (6)
N2b	0.3771 (2)	0.74300 (10)	1.14695 (12)	0.0496 (9)
Cab	0.250 (2)	0.7500 (12)	0.97043 (14)	0.0480 (12)
Haab	0.1668 (12)	0.7552 (5)	0.9329 (7)	0.0659 (18)
Cbb	0.3592 (2)	0.69153 (9)	1.08731 (13)	0.0532 (7)
Hbab	0.3475 (11)	0.6555 (5)	1.1269 (8)	0.0783 (11)
Hbbb	0.4406 (11)	0.6866 (5)	1.0475 (7)	0.0729 (13)
Ccb	0.1094 (2)	0.70513 (10)	1.08802 (13)	0.0502 (7)
Hcab	0.0258 (11)	0.7097 (5)	1.0485 (7)	0.0675 (14)
Hcbb	0.0981 (10)	0.6701 (5)	1.1278 (8)	0.0732 (10)
Cdb	0.2500 (17)	0.7500 (9)	1.20373 (15)	0.0565 (12)
Hdab	0.2632 (13)	0.7861 (6)	1.2455 (7)	0.080 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0681 (12)	0.0779 (9)	0.0699 (9)	0.0204 (8)	−0.0125 (8)	−0.0310 (8)
O2	0.0909 (16)	0.1573 (19)	0.1207 (15)	0.0761 (14)	−0.0448 (13)	−0.0801 (14)
C1	0.0544 (19)	0.0424 (13)	0.0496 (11)	0.0114 (8)	−0.0028 (9)	−0.0022 (10)
C2	0.0592 (14)	0.0491 (10)	0.0506 (10)	0.0126 (9)	−0.0024 (8)	−0.0070 (8)
C3	0.0618 (13)	0.0509 (13)	0.0541 (11)	0.0092 (9)	−0.0025 (9)	−0.0107 (10)
C4	0.0611 (12)	0.0615 (10)	0.0625 (10)	0.0051 (12)	−0.0038 (11)	−0.0189 (8)
C5	0.0557 (12)	0.0500 (12)	0.0561 (11)	0.0008 (9)	−0.0008 (9)	−0.0068 (10)
C6	0.0530 (13)	0.0525 (10)	0.0543 (10)	−0.0010 (8)	−0.0032 (8)	−0.0092 (8)
C7	0.053 (2)	0.0411 (13)	0.0548 (12)	−0.0031 (8)	−0.0014 (10)	−0.0053 (10)
O3	0.0690 (13)	0.0968 (12)	0.0878 (11)	−0.0160 (9)	0.0117 (10)	−0.0489 (10)
O4	0.0845 (17)	0.187 (2)	0.1494 (18)	−0.0712 (15)	0.0446 (14)	−0.1077 (17)
N1a	0.0404 (10)	0.0454 (13)	0.0403 (7)	0.0000 (6)	0.0009 (4)	−0.0056 (8)
N2a	0.0384 (10)	0.066 (2)	0.0374 (13)	−0.0015 (9)	0.0100 (8)	0.0029 (11)
Caa	0.040 (2)	0.059 (2)	0.0266 (9)	0.0004 (13)	−0.0004 (7)	−0.0007 (12)
Haaa	0.053 (3)	0.081 (4)	0.0326 (11)	0.003 (2)	0.0110 (12)	0.0060 (17)
Cba	0.0421 (8)	0.0504 (13)	0.0559 (11)	−0.0130 (7)	0.0046 (6)	0.0029 (9)
Hbaa	0.0695 (18)	0.0550 (14)	0.0822 (19)	−0.0158 (11)	0.0114 (12)	0.0177 (12)
Hbba	0.0445 (10)	0.066 (3)	0.079 (2)	−0.0229 (12)	−0.0023 (10)	−0.0068 (17)
Cca	0.0356 (7)	0.0590 (15)	0.0463 (11)	0.0081 (6)	−0.0023 (5)	0.0050 (9)
Hcaa	0.0332 (8)	0.082 (3)	0.064 (2)	0.0124 (9)	0.0037 (9)	0.0041 (18)
Hcba	0.0581 (13)	0.0673 (19)	0.0639 (18)	0.0195 (12)	−0.0055 (10)	0.0145 (14)
Cda	0.058 (2)	0.077 (2)	0.0266 (9)	0.0052 (13)	−0.0029 (7)	0.0002 (12)
Hdaa	0.086 (4)	0.101 (4)	0.0311 (19)	0.012 (2)	−0.0065 (17)	−0.017 (2)
N1b	0.0437 (11)	0.0458 (14)	0.0443 (7)	−0.0025 (6)	0.0000 (5)	−0.0087 (8)
N2b	0.0394 (11)	0.067 (2)	0.0420 (13)	−0.0023 (10)	−0.0122 (8)	0.0045 (12)
Cab	0.047 (2)	0.069 (3)	0.0280 (9)	−0.0030 (14)	0.0005 (8)	0.0030 (13)
Haab	0.065 (3)	0.098 (4)	0.0346 (12)	−0.002 (2)	−0.0146 (13)	0.0067 (18)
Cbb	0.0459 (9)	0.0524 (14)	0.0614 (12)	0.0134 (7)	−0.0044 (6)	0.0032 (10)
Hbab	0.0851 (19)	0.0549 (15)	0.095 (2)	0.0194 (12)	−0.0129 (12)	0.0195 (13)
Hbbb	0.0482 (11)	0.082 (3)	0.089 (2)	0.0270 (13)	0.0032 (10)	−0.0094 (18)
Ccb	0.0382 (8)	0.0590 (17)	0.0533 (12)	−0.0162 (6)	0.0043 (5)	0.0009 (10)
Hcab	0.0354 (8)	0.091 (3)	0.076 (2)	−0.0205 (10)	−0.0039 (9)	−0.007 (2)
Hcbb	0.0706 (14)	0.069 (2)	0.0798 (19)	−0.0330 (13)	0.0107 (10)	0.0139 (15)
Cdb	0.063 (2)	0.079 (3)	0.0280 (10)	−0.0081 (13)	0.0013 (8)	−0.0002 (13)
Hdab	0.094 (4)	0.110 (4)	0.037 (2)	−0.012 (3)	0.0005 (18)	−0.023 (3)

Geometric parameters (Å, º)

O1—Ho1	1.13 (3)	N1a—Caa	1.48 (2)
O1—C1	1.292 (4)	N1a—Cba	1.473 (2)
O2—C1	1.155 (5)	N1a—Cca	1.478 (2)
C1—C2	1.503 (3)	N2a—Cba	1.459 (3)
C1—O1m	1.337 (2)	N2a—Cca^i	1.459 (3)
C1—O2m	1.196 (2)	N2a—Cda	1.484 (14)
C2—H2a	0.982 (14)	Caa—Haaa	0.96 (2)
C2—H2b	0.977 (14)	Cba—Hbaa	1.001 (11)
C2—C3	1.516 (3)	Cba—Hbba	0.969 (10)
C3—H3a	0.984 (14)	Cca—Hcaa	0.983 (10)
C3—H3b	0.985 (14)	Cca—Hcba	0.985 (11)
C3—C4	1.520 (3)	Cda—Hdaa	0.99 (2)
C4—H4a	0.982 (14)	Cda—Hdaa^i	1.05 (2)
C4—H4b	0.986 (14)	N1b—Ho3	1.53 (4)
C4—C5	1.518 (3)	N1b—Cab	1.48 (2)
C5—H5a	0.972 (14)	N1b—Cbb	1.473 (2)
C5—H5b	0.980 (14)	N1b—Ccb	1.478 (2)
C5—C6	1.513 (3)	N2b—Cbb	1.459 (3)
C6—H6a	0.957 (14)	N2b—Ccb^ii	1.455 (3)
C6—H6b	0.964 (14)	N2b—Cdb	1.484 (14)
C6—C7	1.493 (3)	Cab—Haab	0.96 (2)
C7—O3	1.276 (4)	Cab—Haab^ii	0.97 (2)
C7—O4	1.137 (5)	Cbb—Hbab	1.001 (11)
C7—O3m	1.332 (2)	Cbb—Hbbb	0.969 (10)
C7—O4m	1.206 (2)	Ccb—Hcab	0.983 (10)
O3—Ho3	1.16 (4)	Ccb—Hcbb	0.985 (11)
O1m—Ho1	1.13 (3)	Cdb—Hdab	0.99 (2)
O3m—Ho3	1.22 (4)	Cdb—Hdab^ii	1.05 (2)
N1a—Ho1	1.59 (3)
Ho1—O1—C1	112.3 (17)	C7—O3—Ho3	118 (2)
O1—C1—O2	121.6 (3)	Ho1—O1m—C1	108.8 (16)
O1—C1—C2	113.5 (2)	C7—O3m—Ho3	109.8 (18)
O2—C1—C2	124.9 (3)	Ho1—N1a—Caa	108.3 (13)
O1m—C1—O2m	122.36 (18)	Ho1—N1a—Cba	115.0 (12)
C1—C2—H2a	106.4 (8)	Ho1—N1a—Cca	109.4 (12)
C1—C2—H2b	107.5 (8)	Caa—N1a—Cba	107.9 (8)
C1—C2—C3	116.27 (18)	Caa—N1a—Cca	107.7 (8)
H2a—C2—H2b	108.3 (11)	Cba—N1a—Cca	108.38 (12)
H2a—C2—C3	109.2 (8)	Cba—N2a—Cda	109.6 (7)
H2b—C2—C3	108.8 (8)	N1a—Caa—Haaa	108 (2)
C2—C3—H3a	109.7 (8)	N1a—Cba—N2a	111.87 (16)
C2—C3—H3b	109.6 (8)	N1a—Cba—Hbaa	107.9 (6)
C2—C3—C4	110.14 (17)	N1a—Cba—Hbba	108.1 (6)
H3a—C3—H3b	108.4 (12)	N2a—Cba—Hbaa	109.2 (7)
H3a—C3—C4	109.2 (8)	N2a—Cba—Hbba	110.2 (7)
H3b—C3—C4	109.8 (8)	Hbaa—Cba—Hbba	109.4 (9)
C3—C4—H4a	107.3 (8)	N1a—Cca—Hcaa	108.6 (6)
C3—C4—H4b	108.9 (8)	N1a—Cca—Hcba	109.0 (6)
C3—C4—C5	116.27 (17)	Hcaa—Cca—Hcba	109.5 (9)
H4a—C4—H4b	108.2 (12)	N2a—Cda—Hdaa	108.9 (15)
H4a—C4—C5	107.8 (8)	Ho3—N1b—Cab	111.6 (16)
H4b—C4—C5	108.0 (8)	Ho3—N1b—Cbb	114.6 (15)
C4—C5—H5a	108.7 (8)	Ho3—N1b—Ccb	106.4 (15)
C4—C5—H5b	108.8 (8)	Cab—N1b—Cbb	107.9 (8)
C4—C5—C6	110.71 (17)	Cab—N1b—Ccb	107.7 (8)
H5a—C5—H5b	108.4 (12)	Cbb—N1b—Ccb	108.38 (12)
H5a—C5—C6	110.0 (8)	Cbb—N2b—Cdb	109.6 (7)
H5b—C5—C6	110.2 (8)	N1b—Cab—Haab	108 (2)
C5—C6—H6a	109.0 (8)	N1b—Cbb—N2b	111.87 (16)
C5—C6—H6b	109.3 (8)	N1b—Cbb—Hbab	107.9 (6)
C5—C6—C7	116.12 (17)	N1b—Cbb—Hbbb	108.1 (6)
H6a—C6—H6b	107.4 (12)	N2b—Cbb—Hbab	109.2 (7)
H6a—C6—C7	106.6 (8)	N2b—Cbb—Hbbb	110.2 (7)
H6b—C6—C7	108.1 (8)	Hbab—Cbb—Hbbb	109.4 (9)
C6—C7—O3	114.3 (2)	N1b—Ccb—Hcab	108.6 (6)
C6—C7—O4	126.2 (3)	N1b—Ccb—Hcbb	109.0 (6)
O3—C7—O4	119.4 (3)	Hcab—Ccb—Hcbb	109.5 (9)
O3m—C7—O4m	123.77 (19)	N2b—Cdb—Hdab	108.9 (16)

Symmetry codes: (i) x+1/2, y+1/2, −z; (ii) x+1/2, y+3/2, −z.