Benzyl N-benzyl-N-(2-formyl­phen­yl)carbamate–benzyl N-benzyl-N-(2-carboxy­phen­yl)carbamate [0.332 (4)/0.668 (4)]

The title compound, 0.332 (4)[C₂₂H₁₉NO₃]·0.668 (4)[C₂₂H₁₉NO₄], is a cocrystal of an aromatic aldehyde and its carboxylic acid, which probably arose via an auto-oxidation reaction. In the crystal structure, inter­molecular O—H...O and C—H...O bonds occur, involving the same O-atom acceptor.

Key indicators

• Single-crystal X-ray study
• T = 120 K
• Mean [sigma](C-C) = 0.002 Å
• Disorder in main residue
• R factor = 0.041
• wR factor = 0.104
• Data-to-parameter ratio = 14.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?
PLAT077_ALERT_4_C Unitcell contains non-integer number of atoms ..          ?
PLAT301_ALERT_3_C Main Residue  Disorder .........................       2.00 Perc.

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

   2 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
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

Computing details

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK, DENZO (Otwinowski & Minor, 1997) and SORTAV (Blessing, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Benzyl N-benzyl-N-(2-formylphenyl)carbamate–benzyl N-benzyl-N-(2-carboxyphenyl)carbamate [0.332 (4)/0.668 (4)]

Crystal data

0.332C22H19NO3·0.668C22H19NO4	F(000) = 750
Mr = 356.14	Dx = 1.324 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4071 reflections
a = 10.1185 (4) Å	θ = 2.9–27.5°
b = 11.1077 (4) Å	µ = 0.09 mm^−1
c = 16.4915 (7) Å	T = 120 K
β = 105.502 (2)°	Block, colourless
V = 1786.10 (12) Å^3	0.50 × 0.38 × 0.10 mm
Z = 4

Data collection

Nonius KappaCCD area-detector diffractometer	3506 independent reflections
Radiation source: fine-focus sealed tube	2721 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
φ and ω scans	θmax = 26.0°, θmin = 3.4°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −12→12
Tmin = 0.956, Tmax = 0.995	k = −13→13
21470 measured reflections	l = −20→20

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difmap and geom
R[F^2 > 2σ(F^2)] = 0.041	H-atom parameters constrained
wR(F^2) = 0.104	w = 1/[σ^2(Fo^2) + (0.0448P)^2 + 0.4124P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
3506 reflections	Δρmax = 0.17 e Å^−3
246 parameters	Δρmin = −0.20 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.020 (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	Occ. (<1)
C1	0.45639 (15)	0.58128 (12)	0.16385 (8)	0.0383 (3)
C2	0.21933 (14)	0.53110 (13)	0.10093 (9)	0.0430 (4)
H2A	0.1439	0.5786	0.0643	0.052*
H2B	0.2146	0.5425	0.1596	0.052*
C3	0.19372 (14)	0.39997 (13)	0.07858 (8)	0.0408 (3)
C4	0.28636 (16)	0.32590 (14)	0.05520 (10)	0.0499 (4)
H4	0.3715	0.3579	0.0513	0.060*
C5	0.2571 (2)	0.20539 (15)	0.03726 (12)	0.0641 (5)
H5	0.3219	0.1558	0.0208	0.077*
C6	0.1360 (2)	0.15744 (19)	0.04307 (12)	0.0728 (6)
H6	0.1165	0.0747	0.0311	0.087*
C7	0.0424 (2)	0.2302 (2)	0.06642 (12)	0.0732 (6)
H7	−0.0423	0.1974	0.0704	0.088*
C8	0.07055 (16)	0.34995 (17)	0.08400 (10)	0.0574 (4)
H8	0.0049	0.3991	0.1000	0.069*
C9	0.34736 (13)	0.65608 (12)	0.02235 (8)	0.0343 (3)
C10	0.32963 (15)	0.60194 (14)	−0.05559 (9)	0.0450 (4)
H10	0.3192	0.5171	−0.0606	0.054*
C11	0.32704 (17)	0.67039 (16)	−0.12621 (9)	0.0522 (4)
H11	0.3130	0.6325	−0.1795	0.063*
C12	0.34473 (16)	0.79263 (15)	−0.11949 (9)	0.0511 (4)
H12	0.3454	0.8393	−0.1677	0.061*
C13	0.36162 (15)	0.84778 (14)	−0.04207 (9)	0.0449 (4)
H13	0.3742	0.9325	−0.0376	0.054*
C14	0.36051 (13)	0.78123 (12)	0.02948 (8)	0.0359 (3)
C15	0.37080 (15)	0.84552 (13)	0.11002 (9)	0.0422 (3)
H15	0.4146	0.9219	0.1165	0.051*	0.332 (4)
C16	0.67726 (17)	0.65508 (18)	0.22777 (10)	0.0589 (5)
H16A	0.7161	0.5759	0.2494	0.071*
H16B	0.6429	0.6949	0.2718	0.071*
C17	0.78487 (15)	0.73099 (14)	0.20629 (9)	0.0451 (4)
C18	0.77032 (16)	0.85437 (15)	0.19898 (10)	0.0541 (4)
H18	0.6881	0.8909	0.2043	0.065*
C19	0.87244 (18)	0.92497 (16)	0.18424 (11)	0.0621 (5)
H19	0.8601	1.0097	0.1788	0.075*
C20	0.99169 (18)	0.87440 (18)	0.17727 (12)	0.0640 (5)
H20	1.0629	0.9236	0.1677	0.077*
C21	1.00777 (19)	0.75321 (19)	0.18408 (13)	0.0713 (6)
H21	1.0908	0.7177	0.1793	0.086*
C22	0.90520 (18)	0.68097 (16)	0.19791 (12)	0.0621 (5)
H22	0.9175	0.5962	0.2017	0.075*
N1	0.34975 (11)	0.58106 (10)	0.09366 (7)	0.0365 (3)
O1	0.45382 (11)	0.53259 (10)	0.22965 (6)	0.0528 (3)
O2	0.56561 (9)	0.63900 (9)	0.15169 (6)	0.0420 (3)
O3	0.33191 (13)	0.80824 (11)	0.16809 (7)	0.0618 (3)
O4	0.43885 (17)	0.94901 (13)	0.11386 (9)	0.0486 (7)	0.668 (4)
H1	0.4541	0.9801	0.1684	0.058*	0.668 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0487 (8)	0.0341 (7)	0.0316 (7)	0.0019 (6)	0.0098 (6)	0.0004 (6)
C2	0.0421 (8)	0.0457 (8)	0.0441 (8)	0.0029 (6)	0.0163 (6)	0.0066 (6)
C3	0.0388 (8)	0.0472 (8)	0.0329 (7)	−0.0051 (6)	0.0035 (6)	0.0065 (6)
C4	0.0477 (9)	0.0421 (8)	0.0586 (10)	−0.0033 (7)	0.0119 (7)	0.0032 (7)
C5	0.0740 (12)	0.0446 (10)	0.0683 (12)	−0.0023 (9)	0.0099 (9)	−0.0020 (8)
C6	0.0889 (15)	0.0537 (11)	0.0646 (12)	−0.0271 (11)	0.0010 (10)	0.0003 (9)
C7	0.0627 (12)	0.0856 (15)	0.0636 (12)	−0.0412 (11)	0.0032 (9)	0.0027 (10)
C8	0.0429 (9)	0.0752 (12)	0.0515 (9)	−0.0133 (8)	0.0082 (7)	0.0017 (8)
C9	0.0344 (7)	0.0375 (7)	0.0303 (7)	0.0004 (6)	0.0077 (5)	0.0022 (6)
C10	0.0550 (9)	0.0433 (8)	0.0359 (8)	−0.0003 (7)	0.0108 (6)	−0.0042 (6)
C11	0.0635 (10)	0.0625 (11)	0.0303 (8)	0.0040 (8)	0.0123 (7)	−0.0026 (7)
C12	0.0573 (10)	0.0609 (10)	0.0362 (8)	0.0044 (8)	0.0144 (7)	0.0138 (7)
C13	0.0498 (9)	0.0413 (8)	0.0430 (8)	−0.0002 (7)	0.0115 (7)	0.0090 (6)
C14	0.0355 (7)	0.0380 (8)	0.0335 (7)	−0.0001 (6)	0.0081 (5)	0.0016 (6)
C15	0.0497 (9)	0.0358 (8)	0.0405 (8)	−0.0013 (6)	0.0112 (7)	−0.0015 (6)
C16	0.0563 (10)	0.0738 (12)	0.0365 (8)	−0.0102 (8)	−0.0054 (7)	0.0027 (8)
C17	0.0438 (8)	0.0504 (9)	0.0341 (7)	0.0014 (7)	−0.0015 (6)	−0.0060 (6)
C18	0.0427 (9)	0.0558 (10)	0.0591 (10)	0.0095 (7)	0.0053 (7)	−0.0129 (8)
C19	0.0624 (11)	0.0466 (10)	0.0688 (11)	−0.0010 (8)	0.0027 (9)	−0.0050 (8)
C20	0.0540 (10)	0.0720 (13)	0.0654 (11)	−0.0095 (9)	0.0147 (8)	−0.0081 (9)
C21	0.0465 (10)	0.0793 (14)	0.0902 (15)	0.0079 (9)	0.0222 (9)	−0.0170 (11)
C22	0.0608 (11)	0.0480 (10)	0.0709 (12)	0.0132 (8)	0.0063 (9)	−0.0092 (9)
N1	0.0419 (6)	0.0357 (6)	0.0314 (6)	−0.0036 (5)	0.0089 (5)	0.0028 (5)
O1	0.0641 (7)	0.0561 (7)	0.0361 (6)	−0.0028 (5)	0.0096 (5)	0.0126 (5)
O2	0.0414 (6)	0.0512 (6)	0.0303 (5)	−0.0037 (4)	0.0043 (4)	0.0008 (4)
O3	0.0855 (9)	0.0589 (7)	0.0521 (7)	−0.0148 (6)	0.0375 (6)	−0.0135 (6)
O4	0.0738 (12)	0.0333 (9)	0.0380 (9)	−0.0117 (7)	0.0137 (7)	−0.0065 (6)

Geometric parameters (Å, º)

C1—O1	1.2191 (16)	C12—C13	1.385 (2)
C1—O2	1.3383 (17)	C12—H12	0.9500
C1—N1	1.3552 (18)	C13—C14	1.3950 (19)
C2—N1	1.4657 (17)	C13—H13	0.9500
C2—C3	1.508 (2)	C14—C15	1.4870 (19)
C2—H2A	0.9900	C15—O3	1.2019 (17)
C2—H2B	0.9900	C15—O4	1.333 (2)
C3—C4	1.377 (2)	C15—H15	0.9500
C3—C8	1.389 (2)	C16—O2	1.4576 (17)
C4—C5	1.386 (2)	C16—C17	1.493 (2)
C4—H4	0.9500	C16—H16A	0.9900
C5—C6	1.362 (3)	C16—H16B	0.9900
C5—H5	0.9500	C17—C22	1.378 (2)
C6—C7	1.376 (3)	C17—C18	1.380 (2)
C6—H6	0.9500	C18—C19	1.370 (2)
C7—C8	1.375 (3)	C18—H18	0.9500
C7—H7	0.9500	C19—C20	1.363 (2)
C8—H8	0.9500	C19—H19	0.9500
C9—C10	1.3866 (19)	C20—C21	1.357 (3)
C9—C14	1.3984 (19)	C20—H20	0.9500
C9—N1	1.4362 (16)	C21—C22	1.378 (3)
C10—C11	1.385 (2)	C21—H21	0.9500
C10—H10	0.9500	C22—H22	0.9500
C11—C12	1.370 (2)	O4—H1	0.9375
C11—H11	0.9500
O1—C1—O2	124.12 (13)	C12—C13—H13	119.4
O1—C1—N1	123.92 (13)	C14—C13—H13	119.4
O2—C1—N1	111.95 (11)	C13—C14—C9	118.54 (12)
N1—C2—C3	116.45 (12)	C13—C14—C15	119.12 (13)
N1—C2—H2A	108.2	C9—C14—C15	122.34 (12)
C3—C2—H2A	108.2	O3—C15—O4	122.30 (14)
N1—C2—H2B	108.2	O3—C15—C14	125.91 (13)
C3—C2—H2B	108.2	O4—C15—C14	111.63 (13)
H2A—C2—H2B	107.3	O3—C15—H15	117.4
C4—C3—C8	117.93 (15)	C14—C15—H15	116.7
C4—C3—C2	124.06 (13)	O2—C16—C17	108.16 (12)
C8—C3—C2	117.99 (14)	O2—C16—H16A	110.1
C3—C4—C5	120.94 (15)	C17—C16—H16A	110.1
C3—C4—H4	119.5	O2—C16—H16B	110.1
C5—C4—H4	119.5	C17—C16—H16B	110.1
C6—C5—C4	120.51 (18)	H16A—C16—H16B	108.4
C6—C5—H5	119.7	C22—C17—C18	117.90 (15)
C4—C5—H5	119.7	C22—C17—C16	121.07 (16)
C5—C6—C7	119.29 (18)	C18—C17—C16	120.93 (15)
C5—C6—H6	120.4	C19—C18—C17	121.07 (15)
C7—C6—H6	120.4	C19—C18—H18	119.5
C8—C7—C6	120.53 (17)	C17—C18—H18	119.5
C8—C7—H7	119.7	C20—C19—C18	120.38 (17)
C6—C7—H7	119.7	C20—C19—H19	119.8
C7—C8—C3	120.80 (18)	C18—C19—H19	119.8
C7—C8—H8	119.6	C21—C20—C19	119.40 (18)
C3—C8—H8	119.6	C21—C20—H20	120.3
C10—C9—C14	119.67 (12)	C19—C20—H20	120.3
C10—C9—N1	118.49 (12)	C20—C21—C22	120.82 (17)
C14—C9—N1	121.83 (11)	C20—C21—H21	119.6
C11—C10—C9	120.66 (14)	C22—C21—H21	119.6
C11—C10—H10	119.7	C21—C22—C17	120.42 (17)
C9—C10—H10	119.7	C21—C22—H22	119.8
C12—C11—C10	120.21 (14)	C17—C22—H22	119.8
C12—C11—H11	119.9	C1—N1—C9	122.25 (11)
C10—C11—H11	119.9	C1—N1—C2	117.36 (11)
C11—C12—C13	119.61 (14)	C9—N1—C2	117.91 (11)
C11—C12—H12	120.2	C1—O2—C16	114.26 (11)
C13—C12—H12	120.2	C15—O4—H1	108.3
C12—C13—C14	121.23 (14)
N1—C2—C3—C4	2.3 (2)	C9—C14—C15—O4	153.13 (14)
N1—C2—C3—C8	−179.40 (12)	O2—C16—C17—C22	−104.63 (17)
C8—C3—C4—C5	0.3 (2)	O2—C16—C17—C18	79.13 (18)
C2—C3—C4—C5	178.58 (15)	C22—C17—C18—C19	−0.3 (2)
C3—C4—C5—C6	−0.5 (3)	C16—C17—C18—C19	176.08 (15)
C4—C5—C6—C7	0.5 (3)	C17—C18—C19—C20	−0.6 (3)
C5—C6—C7—C8	−0.2 (3)	C18—C19—C20—C21	0.8 (3)
C6—C7—C8—C3	0.0 (3)	C19—C20—C21—C22	0.0 (3)
C4—C3—C8—C7	−0.1 (2)	C20—C21—C22—C17	−1.0 (3)
C2—C3—C8—C7	−178.43 (15)	C18—C17—C22—C21	1.1 (2)
C14—C9—C10—C11	1.0 (2)	C16—C17—C22—C21	−175.29 (16)
N1—C9—C10—C11	−179.79 (13)	O1—C1—N1—C9	168.99 (13)
C9—C10—C11—C12	1.3 (2)	O2—C1—N1—C9	−12.36 (18)
C10—C11—C12—C13	−1.7 (2)	O1—C1—N1—C2	7.2 (2)
C11—C12—C13—C14	−0.2 (2)	O2—C1—N1—C2	−174.13 (11)
C12—C13—C14—C9	2.5 (2)	C10—C9—N1—C1	123.86 (15)
C12—C13—C14—C15	−176.41 (13)	C14—C9—N1—C1	−57.00 (18)
C10—C9—C14—C13	−2.9 (2)	C10—C9—N1—C2	−74.47 (16)
N1—C9—C14—C13	177.98 (12)	C14—C9—N1—C2	104.67 (15)
C10—C9—C14—C15	176.00 (13)	C3—C2—N1—C1	−93.70 (15)
N1—C9—C14—C15	−3.1 (2)	C3—C2—N1—C9	103.72 (14)
C13—C14—C15—O3	156.60 (16)	O1—C1—O2—C16	−8.6 (2)
C9—C14—C15—O3	−22.3 (2)	N1—C1—O2—C16	172.75 (13)
C13—C14—C15—O4	−27.99 (19)	C17—C16—O2—C1	−174.33 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H1···O1^i	0.94	1.79	2.6838 (17)	159
C18—H18···O1^i	0.95	2.56	3.4460 (19)	155

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