N—H...O and O—H...O hydrogen bonds in crystal engineering: trimethoprim hydrogen glutarate

In the title compound, C₁₄H₁₉N₄O₃⁺·C₅H₇O₄⁻, trimethoprim (TMP) is protonated. In the glutarate anion, one of the two carboxyl­ic acid groups is deprotonated while the other exists as —COOH. The carboxyl group of the hydrogen glutarate ion makes a hydrogen-bonding pattern with N—H groups of the trimethoprim cation which is similar to the carboxyl­ate group (of Asp-27 of DHFR)-trimethoprim cation interaction observed in trimethoprim–DHFR complexes. Two TMP cations and two hydrogen glutarate anions are arranged about an inversion center so that complementary DDAA arrays of quadruple hydrogen-bonding patterns are formed. The hydrogen glutarate ion bridges the 2-amino and 4-amino groups of TMP. There are also carboxyl–carboxyl­ate hydrogen-bonding interactions involving a head-to-tail arrangement of hydrogen glutarate ions which leads to hydrogen-bonded supramolecular ribbons.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.048
• wR factor = 0.140
• Data-to-parameter ratio = 8.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level A:



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           70.90
         From the CIF: _reflns_number_total               3203
         TEST2: Reflns within _diffrn_reflns_theta_max
         Count of symmetry unique reflns         3958
         Completeness (_total/calc)             80.92%
          Alert A: < 85% complete (theta max?)

Author response: Due to poor data we couldn't achieve more than 85%

 1 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 0 Alert Level C = Please check

---

Computing details

Data collection: MolEN (Fair, 1990); cell refinement: MolEN; data reduction: MolEN; program(s) used to solve structure: SHELXS86 (Sheldrick, 1985); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1997) and PLATON (Spek, 1997); software used to prepare material for publication: PLATON.

2,4-diamino-5-(3,4,5-trimethoxybenzyl)pyrimidin-1-ium glutarate

Crystal data

C14H19N4O3^+·C5H7O4^−	Z = 2
Mr = 422.44	F(000) = 448
Triclinic, P1	Dx = 1.367 Mg m^−3
a = 12.017 (2) Å	Cu Kα radiation, λ = 1.5418 Å
b = 10.090 (3) Å	Cell parameters from 40 reflections
c = 8.804 (4) Å	θ = 3.8–70.9°
α = 84.430 (3)°	µ = 0.89 mm^−1
β = 94.900 (3)°	T = 293 K
γ = 104.590 (3)°	Thin plate, pale yellow
V = 1026.1 (6) Å^3	0.25 × 0.22 × 0.19 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.000
Radiation source: fine-focus sealed tube	θmax = 70.9°, θmin = 3.8°
Graphite monochromator	h = −14→14
ω–2θ scans	k = −12→12
3203 measured reflections	l = 0→10
3203 independent reflections	1 standard reflections every 100 min
3201 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F^2	H-atom parameters not refined
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0866P)^2 + 0.1793P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.048	(Δ/σ)max < 0.001
wR(F^2) = 0.140	Δρmax = 0.21 e Å^−3
S = 1.11	Δρmin = −0.23 e Å^−3
3203 reflections	Absolute structure: Flack (1983)
363 parameters

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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

	x	y	z	Uiso*/Ueq
O1	0.45141 (13)	0.87527 (15)	0.73650 (15)	0.0585 (5)
O2	0.59069 (12)	0.78210 (15)	0.57704 (17)	0.0572 (5)
O3	0.52998 (13)	0.71564 (16)	0.29046 (16)	0.0600 (5)
N1	0.05252 (14)	0.82591 (17)	−0.10391 (17)	0.0491 (5)
N2	0.06864 (17)	0.98838 (19)	−0.31074 (18)	0.0575 (6)
N3	0.15813 (15)	1.05315 (17)	−0.07878 (18)	0.0508 (5)
N4	0.24980 (19)	1.1136 (2)	0.1481 (2)	0.0693 (7)
C2	0.09384 (17)	0.9571 (2)	−0.1627 (2)	0.0461 (6)
C4	0.18378 (17)	1.0157 (2)	0.0689 (2)	0.0490 (6)
C5	0.14042 (16)	0.8791 (2)	0.1401 (2)	0.0471 (6)
C6	0.07496 (17)	0.7889 (2)	0.0470 (2)	0.0481 (6)
C7	0.15670 (17)	0.8417 (3)	0.3090 (2)	0.0568 (7)
C8	0.27701 (15)	0.83263 (19)	0.37225 (19)	0.0438 (5)
C9	0.30932 (16)	0.86674 (19)	0.5205 (2)	0.0452 (6)
C10	0.41372 (16)	0.84784 (18)	0.5896 (2)	0.0442 (5)
C11	0.48561 (15)	0.79685 (18)	0.5096 (2)	0.0447 (5)
C12	0.45284 (16)	0.76436 (19)	0.3595 (2)	0.0445 (6)
C13	0.34798 (16)	0.78229 (19)	0.2912 (2)	0.0450 (6)
C14	0.3789 (2)	0.9274 (3)	0.8200 (2)	0.0637 (8)
C15	0.5871 (3)	0.6471 (3)	0.6435 (4)	0.0887 (11)
C16	0.5029 (2)	0.6836 (3)	0.1364 (3)	0.0718 (9)
O4	0.07782 (16)	0.22219 (17)	0.46913 (16)	0.0730 (6)
O5	0.08143 (15)	0.37575 (17)	0.27020 (15)	0.0680 (6)
O6	0.27767 (17)	0.4052 (2)	1.00442 (19)	0.0808 (7)
O7	0.14593 (17)	0.5178 (2)	1.01426 (18)	0.0769 (7)
C17	0.21973 (17)	0.47756 (18)	0.9423 (2)	0.0467 (6)
C18	0.2212 (2)	0.5289 (2)	0.7757 (2)	0.0599 (7)
C19	0.1775 (2)	0.4110 (2)	0.6763 (2)	0.0597 (7)
C20	0.1615 (2)	0.4566 (2)	0.5084 (2)	0.0579 (7)
C21	0.10397 (17)	0.3416 (2)	0.4102 (2)	0.0514 (6)
H1	0.01188	0.76561	−0.16215	0.0589*
H2A	0.09426	1.07055	−0.35075	0.0690*
H2B	0.02682	0.92626	−0.36587	0.0690*
H4A	0.27354	1.19502	0.10514	0.0831*
H4B	0.26913	1.09607	0.24285	0.0831*
H6	0.04414	0.69920	0.08567	0.0578*
H7A	0.10386	0.75354	0.33305	0.0682*
H7B	0.13408	0.90891	0.36339	0.0682*
H9	0.26158	0.90228	0.57429	0.0542*
H13	0.32619	0.76023	0.19099	0.0540*
H14A	0.36428	1.00926	0.76587	0.0955*
H14B	0.41563	0.94859	0.91885	0.0955*
H14C	0.30728	0.85986	0.83196	0.0955*
H15A	0.53305	0.62400	0.72187	0.1328*
H15B	0.66225	0.64316	0.68745	0.1328*
H15C	0.56371	0.58310	0.56618	0.1328*
H16A	0.43188	0.61417	0.12954	0.1077*
H16B	0.56356	0.65035	0.10126	0.1077*
H16C	0.49499	0.76465	0.07415	0.1077*
H7	0.13895	0.47592	1.09892	0.1155*
H18A	0.17318	0.59359	0.75535	0.0719*
H18B	0.29921	0.57640	0.75171	0.0719*
H19A	0.10431	0.35621	0.71116	0.0717*
H19B	0.23141	0.35296	0.68798	0.0717*
H20A	0.11585	0.52405	0.49846	0.0695*
H20B	0.23641	0.50118	0.47063	0.0695*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0623 (9)	0.0730 (9)	0.0425 (7)	0.0242 (7)	−0.0178 (6)	−0.0137 (6)
O2	0.0463 (8)	0.0617 (8)	0.0632 (9)	0.0194 (6)	−0.0184 (6)	−0.0057 (7)
O3	0.0579 (8)	0.0791 (10)	0.0521 (8)	0.0335 (7)	−0.0016 (7)	−0.0095 (7)
N1	0.0559 (10)	0.0568 (9)	0.0362 (8)	0.0191 (8)	−0.0087 (7)	−0.0075 (7)
N2	0.0778 (12)	0.0601 (10)	0.0335 (8)	0.0206 (9)	−0.0137 (8)	−0.0041 (7)
N3	0.0618 (10)	0.0559 (9)	0.0368 (8)	0.0224 (8)	−0.0123 (7)	−0.0060 (7)
N4	0.0913 (14)	0.0665 (11)	0.0453 (9)	0.0185 (10)	−0.0269 (9)	−0.0106 (8)
C2	0.0529 (10)	0.0565 (11)	0.0346 (9)	0.0259 (9)	−0.0067 (7)	−0.0062 (8)
C4	0.0531 (10)	0.0624 (11)	0.0363 (9)	0.0256 (9)	−0.0111 (8)	−0.0091 (8)
C5	0.0447 (10)	0.0671 (12)	0.0344 (9)	0.0264 (9)	−0.0048 (7)	−0.0015 (8)
C6	0.0487 (10)	0.0601 (11)	0.0380 (9)	0.0215 (9)	−0.0031 (8)	0.0009 (8)
C7	0.0475 (11)	0.0916 (16)	0.0351 (10)	0.0294 (10)	−0.0042 (8)	0.0037 (9)
C8	0.0441 (9)	0.0540 (10)	0.0318 (8)	0.0150 (8)	−0.0049 (7)	0.0054 (7)
C9	0.0473 (10)	0.0534 (10)	0.0363 (9)	0.0182 (8)	−0.0022 (7)	0.0003 (7)
C10	0.0480 (10)	0.0441 (9)	0.0370 (9)	0.0099 (8)	−0.0096 (7)	−0.0002 (7)
C11	0.0411 (9)	0.0447 (9)	0.0460 (10)	0.0120 (8)	−0.0097 (8)	0.0014 (8)
C12	0.0455 (10)	0.0442 (9)	0.0441 (10)	0.0145 (8)	0.0001 (8)	0.0013 (7)
C13	0.0473 (10)	0.0536 (10)	0.0337 (9)	0.0154 (8)	−0.0054 (7)	−0.0002 (7)
C14	0.0773 (15)	0.0705 (14)	0.0450 (11)	0.0219 (12)	−0.0100 (10)	−0.0156 (10)
C15	0.0932 (19)	0.0690 (16)	0.105 (2)	0.0394 (14)	−0.0495 (17)	−0.0099 (14)
C16	0.0840 (17)	0.0896 (17)	0.0559 (13)	0.0452 (14)	0.0034 (12)	−0.0126 (12)
O4	0.0981 (13)	0.0656 (10)	0.0387 (7)	−0.0026 (9)	−0.0159 (8)	−0.0004 (7)
O5	0.0904 (12)	0.0756 (10)	0.0283 (7)	0.0067 (8)	−0.0054 (7)	−0.0004 (6)
O6	0.0981 (13)	0.1065 (14)	0.0543 (9)	0.0601 (12)	−0.0022 (9)	−0.0001 (9)
O7	0.1041 (13)	0.0958 (13)	0.0474 (9)	0.0590 (11)	0.0186 (9)	0.0171 (8)
C17	0.0562 (11)	0.0426 (9)	0.0386 (9)	0.0085 (8)	−0.0055 (8)	−0.0076 (7)
C18	0.0796 (15)	0.0553 (12)	0.0394 (10)	0.0083 (10)	0.0014 (10)	−0.0017 (8)
C19	0.0742 (14)	0.0598 (12)	0.0357 (10)	0.0023 (10)	−0.0059 (9)	−0.0030 (8)
C20	0.0698 (14)	0.0612 (12)	0.0377 (10)	0.0083 (10)	−0.0001 (9)	−0.0026 (9)
C21	0.0522 (11)	0.0654 (12)	0.0319 (9)	0.0075 (9)	0.0003 (8)	−0.0012 (8)

Geometric parameters (Å, º)

O1—C10	1.364 (2)	C9—C10	1.396 (3)
O1—C14	1.411 (3)	C10—C11	1.380 (3)
O2—C11	1.385 (2)	C11—C12	1.392 (3)
O2—C15	1.421 (3)	C12—C13	1.395 (3)
O3—C12	1.362 (3)	C6—H6	0.9301
O3—C16	1.417 (3)	C7—H7B	0.9702
O4—C21	1.239 (3)	C7—H7A	0.9701
O5—C21	1.272 (2)	C9—H9	0.9301
O6—C17	1.196 (3)	C13—H13	0.9305
O7—C17	1.296 (3)	C14—H14B	0.9596
O7—H7	0.8203	C14—H14A	0.9605
N1—C6	1.368 (2)	C14—H14C	0.9604
N1—C2	1.359 (3)	C15—H15B	0.9603
N2—C2	1.338 (2)	C15—H15C	0.9595
N3—C2	1.321 (3)	C15—H15A	0.9599
N3—C4	1.350 (2)	C16—H16B	0.9600
N4—C4	1.317 (3)	C16—H16A	0.9597
N1—H1	0.8600	C16—H16C	0.9599
N2—H2B	0.8601	C17—C18	1.507 (3)
N2—H2A	0.8599	C18—C19	1.505 (3)
N4—H4B	0.8603	C19—C20	1.516 (3)
N4—H4A	0.8599	C20—C21	1.503 (3)
C4—C5	1.446 (3)	C18—H18A	0.9698
C5—C7	1.507 (3)	C18—H18B	0.9700
C5—C6	1.339 (3)	C19—H19A	0.9704
C7—C8	1.526 (3)	C19—H19B	0.9702
C8—C9	1.381 (3)	C20—H20A	0.9696
C8—C13	1.374 (3)	C20—H20B	0.9702
O1···O2	2.666 (2)	C16···H13	2.5322
O1···C15	3.334 (4)	C17···H16A^vi	3.0116
O2···O1	2.666 (2)	C21···H15B^v	2.9706
O2···O3	2.667 (2)	C21···H7^iv	2.9517
O2···N4^i	3.053 (3)	C21···H1^iii	2.6567
O3···O2	2.667 (2)	C21···H2B^iii	2.8084
O3···C15	3.173 (4)	H1···O4^iii	2.8259
O4···N2^ii	2.890 (3)	H1···O5^iii	1.8633
O4···N2^iii	2.798 (3)	H1···C21^iii	2.6567
O5···N1^iii	2.720 (3)	H1···H2B	2.2849
O5···C17^iv	3.396 (3)	H2A···O4^ix	2.1266
O5···O7^iv	2.616 (3)	H2B···H1	2.2849
O6···C16^v	3.355 (4)	H2B···O4^iii	1.9420
O6···N4^ii	3.037 (3)	H2B···C21^iii	2.8084
O7···O5^vi	2.616 (3)	H4A···H15B^i	2.5098
O7···C6^vi	3.109 (3)	H4A···C15^i	2.9911
O2···H4B^i	2.3962	H4A···O6^ix	2.2081
O3···H15C	2.7056	H4B···C7	2.6171
O3···H14A^i	2.7620	H4B···C8	2.8094
O4···H19B	2.7421	H4B···H7B	2.3848
O4···H19A	2.5879	H4B···O2^i	2.3962
O4···H2B^iii	1.9420	H4B···C15^i	2.9418
O4···H1^iii	2.8259	H6···H7A	2.3077
O4···H2A^ii	2.1266	H6···O7^viii	2.8803
O5···H7^iv	1.8175	H6···O7^iv	2.5931
O5···H1^iii	1.8633	H6···H19A^viii	2.5579
O6···H16A^vi	2.6883	H7···C21^vi	2.9517
O6···H15B^vii	2.7757	H7···O5^vi	1.8175
O6···H19B	2.8673	H7A···H19A^viii	2.4814
O6···H4A^ii	2.2081	H7A···H6	2.3077
O6···H16B^v	2.4007	H7B···N2^x	2.8652
O7···H6^viii	2.8803	H7B···N4	2.8347
O7···H6^vi	2.5931	H7B···H4B	2.3848
N1···O5^iii	2.720 (3)	H7B···H9	2.3111
N2···O4^iii	2.798 (3)	H9···H14A	2.2045
N2···O4^ix	2.890 (3)	H9···C14	2.4773
N3···C14^iv	3.430 (3)	H9···H7B	2.3111
N4···O6^ix	3.037 (3)	H9···H14C	2.3126
N4···C8	3.363 (3)	H13···C5	2.7743
N4···O2^i	3.053 (3)	H13···C16	2.5322
N4···C15^i	3.301 (4)	H13···H16A	2.3006
N2···H7B^x	2.8652	H13···H16C	2.3403
N4···H7B	2.8347	H14A···C9	2.6555
N4···H15B^i	2.8911	H14A···H9	2.2045
C2···C14^iv	3.530 (4)	H14A···O3^i	2.7620
C2···C4^x	3.587 (3)	H14A···C12^i	2.9430
C4···C2^x	3.587 (3)	H14B···H16C^vi	2.5298
C6···O7^iv	3.109 (3)	H14B···H14B^xi	2.4419
C8···N4	3.363 (3)	H14C···C2^vi	2.9734
C10···C11^i	3.531 (3)	H14C···C9	2.7383
C10···C10^i	3.554 (3)	H14C···H9	2.3126
C11···C10^i	3.531 (3)	H15A···C10	3.0577
C12···C14^i	3.561 (4)	H15B···O6^vii	2.7757
C14···C12^i	3.561 (4)	H15B···N4^i	2.8911
C14···C2^vi	3.530 (4)	H15B···C21^v	2.9706
C14···N3^vi	3.430 (3)	H15B···H4A^i	2.5098
C15···O3	3.173 (4)	H15C···O3	2.7056
C15···O1	3.334 (4)	H15C···C12	2.9323
C15···N4^i	3.301 (4)	H15C···H15C^v	2.3012
C16···O6^v	3.355 (4)	H16A···O6^iv	2.6883
C17···O5^vi	3.396 (3)	H16A···C13	2.7377
C2···H14C^iv	2.9734	H16A···C17^iv	3.0116
C5···H13	2.7743	H16A···H13	2.3006
C7···H4B	2.6171	H16B···O6^v	2.4007
C8···H4B	2.8094	H16C···C13	2.7578
C9···H14A	2.6555	H16C···C14^iv	3.0914
C9···H14C	2.7383	H16C···H13	2.3403
C10···H18B	3.0182	H16C···H14B^iv	2.5298
C10···H15A	3.0577	H18A···H20A	2.4250
C12···H15C	2.9323	H18B···C10	3.0182
C12···H14A^i	2.9430	H19A···O4	2.5879
C13···H16C	2.7578	H19A···H6^viii	2.5579
C13···H16A	2.7377	H19A···H7A^viii	2.4814
C14···H16C^vi	3.0914	H19B···O4	2.7421
C14···H9	2.4773	H19B···O6	2.8673
C15···H4A^i	2.9911	H20A···H18A	2.4250
C15···H4B^i	2.9418
C10—O1—C14	116.40 (16)	C10—C9—H9	120.02
C11—O2—C15	113.33 (19)	C8—C9—H9	120.05
C12—O3—C16	117.51 (17)	C12—C13—H13	120.08
C17—O7—H7	109.42	C8—C13—H13	120.09
C2—N1—C6	120.61 (16)	O1—C14—H14A	109.48
C2—N3—C4	117.39 (17)	O1—C14—H14B	109.53
C2—N1—H1	119.68	H14A—C14—H14B	109.47
C6—N1—H1	119.71	H14A—C14—H14C	109.40
C2—N2—H2A	120.02	O1—C14—H14C	109.48
H2A—N2—H2B	120.00	H14B—C14—H14C	109.47
C2—N2—H2B	119.97	O2—C15—H15B	109.43
H4A—N4—H4B	119.99	O2—C15—H15C	109.49
C4—N4—H4B	119.98	O2—C15—H15A	109.46
C4—N4—H4A	120.03	H15A—C15—H15C	109.53
N2—C2—N3	119.60 (18)	H15B—C15—H15C	109.48
N1—C2—N3	122.10 (16)	H15A—C15—H15B	109.45
N1—C2—N2	118.30 (17)	O3—C16—H16B	109.43
N3—C4—C5	123.49 (17)	O3—C16—H16C	109.44
N3—C4—N4	115.62 (18)	H16A—C16—H16B	109.51
N4—C4—C5	120.87 (17)	H16A—C16—H16C	109.51
C4—C5—C6	114.99 (16)	H16B—C16—H16C	109.49
C6—C5—C7	121.26 (19)	O3—C16—H16A	109.45
C4—C5—C7	123.50 (18)	O6—C17—O7	121.99 (18)
N1—C6—C5	121.36 (18)	O6—C17—C18	125.14 (19)
C5—C7—C8	117.48 (17)	O7—C17—C18	112.85 (18)
C7—C8—C13	122.08 (16)	C17—C18—C19	110.45 (15)
C9—C8—C13	120.37 (17)	C18—C19—C20	113.27 (16)
C7—C8—C9	117.35 (17)	C19—C20—C21	114.01 (16)
C8—C9—C10	119.93 (17)	O4—C21—C20	119.42 (16)
O1—C10—C11	115.66 (17)	O5—C21—C20	116.42 (17)
C9—C10—C11	120.26 (16)	O4—C21—O5	124.11 (18)
O1—C10—C9	124.08 (17)	C17—C18—H18A	109.55
C10—C11—C12	119.34 (17)	C17—C18—H18B	109.54
O2—C11—C10	120.07 (16)	C19—C18—H18A	109.58
O2—C11—C12	120.57 (17)	C19—C18—H18B	109.57
O3—C12—C11	114.75 (17)	H18A—C18—H18B	108.12
O3—C12—C13	125.00 (16)	C18—C19—H19A	108.93
C11—C12—C13	120.26 (17)	C18—C19—H19B	108.94
C8—C13—C12	119.83 (16)	C20—C19—H19A	108.91
C5—C6—H6	119.36	C20—C19—H19B	108.94
N1—C6—H6	119.28	H19A—C19—H19B	107.70
C5—C7—H7A	107.96	C19—C20—H20A	108.74
C5—C7—H7B	107.95	C19—C20—H20B	108.71
C8—C7—H7B	107.92	C21—C20—H20A	108.79
H7A—C7—H7B	107.19	C21—C20—H20B	108.75
C8—C7—H7A	107.91	H20A—C20—H20B	107.66
C14—O1—C10—C9	−0.8 (3)	C7—C8—C13—C12	−174.13 (19)
C14—O1—C10—C11	−179.96 (18)	C7—C8—C9—C10	173.84 (19)
C15—O2—C11—C10	96.3 (2)	C9—C8—C13—C12	0.6 (3)
C15—O2—C11—C12	−85.6 (2)	C13—C8—C9—C10	−1.1 (3)
C16—O3—C12—C11	−178.61 (19)	C8—C9—C10—C11	0.9 (3)
C16—O3—C12—C13	1.5 (3)	C8—C9—C10—O1	−178.28 (17)
C6—N1—C2—N2	−179.43 (19)	C9—C10—C11—O2	178.08 (16)
C6—N1—C2—N3	1.0 (3)	O1—C10—C11—C12	179.14 (16)
C2—N1—C6—C5	−1.8 (3)	O1—C10—C11—O2	−2.7 (2)
C4—N3—C2—N1	1.3 (3)	C9—C10—C11—C12	−0.1 (3)
C2—N3—C4—C5	−2.9 (3)	O2—C11—C12—O3	1.5 (3)
C4—N3—C2—N2	−178.3 (2)	C10—C11—C12—C13	−0.5 (3)
C2—N3—C4—N4	178.8 (2)	O2—C11—C12—C13	−178.61 (17)
N3—C4—C5—C7	−172.1 (2)	C10—C11—C12—O3	179.63 (16)
N4—C4—C5—C6	−179.6 (2)	O3—C12—C13—C8	−179.88 (18)
N4—C4—C5—C7	6.1 (3)	C11—C12—C13—C8	0.2 (3)
N3—C4—C5—C6	2.2 (3)	O7—C17—C18—C19	−113.2 (2)
C7—C5—C6—N1	174.68 (19)	O6—C17—C18—C19	65.4 (3)
C4—C5—C7—C8	−72.8 (3)	C17—C18—C19—C20	172.29 (19)
C6—C5—C7—C8	113.2 (2)	C18—C19—C20—C21	−172.7 (2)
C4—C5—C6—N1	0.2 (3)	C19—C20—C21—O5	175.3 (2)
C5—C7—C8—C13	−36.7 (3)	C19—C20—C21—O4	−2.1 (3)
C5—C7—C8—C9	148.4 (2)

Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x, y−1, z+1; (iii) −x, −y+1, −z; (iv) x, y, z−1; (v) −x+1, −y+1, −z+1; (vi) x, y, z+1; (vii) −x+1, −y+1, −z+2; (viii) −x, −y+1, −z+1; (ix) x, y+1, z−1; (x) −x, −y+2, −z; (xi) −x+1, −y+2, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O5^iii	0.8600	1.8633	2.720 (3)	174.16
N2—H2A···O4^ix	0.8599	2.1266	2.890 (3)	147.64
N2—H2B···O4^iii	0.8601	1.9420	2.798 (3)	173.23
N4—H4A···O6^ix	0.8599	2.2081	3.037 (3)	161.81
N4—H4B···O2^i	0.8603	2.3962	3.053 (3)	133.56
O7—H7···O5^vi	0.8203	1.8175	2.616 (3)	164.12
C6—H6···O7^iv	0.9301	2.5931	3.109 (3)	115.46
C16—H16B···O6^v	0.9600	2.4007	3.355 (4)	172.79

Symmetry codes: (i) −x+1, −y+2, −z+1; (iii) −x, −y+1, −z; (iv) x, y, z−1; (v) −x+1, −y+1, −z+1; (vi) x, y, z+1; (ix) x, y+1, z−1.