Crystal structure of 2,2,4-trimethyl-2,3,4,5-tetra-hydro-1H-benzo[b][1,4]diazepine hemihydrate.

The title compound, C12H18N2·0.5H2O, crystallizes with two independent organic mol-ecules (A and B) in the asymmetric unit, together with a water mol-ecule of crystallization. The diazepine rings in each mol-ecule have a chair conformation. The dihedral angle between benzene ring and the mean plane of the diazepine ring is 21.15 (12)° in mol-ecule A and 17.42 (11)° in mol-ecule B. In the crystal, mol-ecules are linked by N-H⋯O and O-H⋯N hydrogen bonds, forming zigzag chains propagating along [001].

Related literature

For examples of biological activities of benzodiazepines, see: De Baun et al. (1976 ▸). For the use of benzodiazepine derivatives as dyes for acrylic fibres, see: Harris & Straley (1968 ▸). For related structures, see: Thiruselvam et al. (2013 ▸); Lamkaddem et al. (2015 ▸); Ponnuswamy et al. (2006 ▸).

Experimental

Crystal data

C12H18N2·0.5H2O

M = 199.29

Monoclinic,

a = 9.0548 (10) Å

b = 23.246 (2) Å

c = 11.5613 (14) Å

β = 100.483 (3)°

V = 2392.9 (4) Å3

Z = 8

Mo Kα radiation

μ = 0.07 mm−1

T = 293 K

0.30 × 0.25 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▸) T min = 0.980, T max = 0.986

22443 measured reflections

4161 independent reflections

2416 reflections with I > 2σ(I)

R int = 0.042

Refinement

R[F 2 > 2σ(F 2)] = 0.051

wR(F 2) = 0.154

S = 1.03

4161 reflections

293 parameters

4 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.48 e Å−3

Δρmin = −0.20 e Å−3

Data collection: APEX2 (Bruker, 2008 ▸); cell refinement: SAINT (Bruker, 2008 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014/6 (Sheldrick, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸) and Mercury (Macrae et al., 2008 ▸); software used to prepare material for publication: SHELXL2014/6 and PLATON (Spek, 2009 ▸).

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015013201/su5164sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015013201/su5164Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015013201/su5164Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015013201/su5164fig1.tif

The mol­ecular structure of the two independent mol­ecules (A and B) of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level.

Click here for additional data file.

a . DOI: 10.1107/S2056989015013201/su5164fig2.tif

The crystal packing of the title compound, viewed along the a axis. The dashed lines indicate the hydrogen bonds (see Table 1 for details; mol­ecule A red, mol­ecule B blue).

CCDC reference: 1411680

Additional supporting information: crystallographic information; 3D view; checkCIF report

C12H18N2·0.5H2O	F(000) = 872
Mr = 199.29	Dx = 1.106 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.0548 (10) Å	θ = 1.8–24.9°
b = 23.246 (2) Å	µ = 0.07 mm−1
c = 11.5613 (14) Å	T = 293 K
β = 100.483 (3)°	Block, colorless
V = 2392.9 (4) Å3	0.30 × 0.25 × 0.20 mm
Z = 8

Bruker Kappa APEXII CCD diffractometer	4161 independent reflections
Radiation source: fine-focus sealed tube	2416 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
ω and φ scan	θmax = 24.9°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −10→10
Tmin = 0.980, Tmax = 0.986	k = −27→26
22443 measured reflections	l = −13→13

Refinement on F2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.051	w = 1/[σ2(Fo2) + (0.0621P)2 + 0.8577P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.154	(Δ/σ)max < 0.001
S = 1.02	Δρmax = 0.48 e Å−3
4161 reflections	Δρmin = −0.20 e Å−3
293 parameters	Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
4 restraints	Extinction coefficient: 0.0040 (10)

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

	x	y	z	Uiso*/Ueq
N1	0.7167 (2)	0.31832 (9)	0.7595 (2)	0.0571 (6)
H1N	0.736 (3)	0.3010 (10)	0.7008 (18)	0.057 (8)*
N2	0.7489 (2)	0.37679 (9)	0.97935 (19)	0.0501 (5)
H2N	0.781 (2)	0.3936 (9)	1.0446 (16)	0.045 (7)*
C13	0.8453 (2)	0.38831 (9)	0.8995 (2)	0.0428 (6)
C14	0.8286 (2)	0.36004 (10)	0.7919 (2)	0.0452 (6)
C15	0.9343 (3)	0.36978 (12)	0.7212 (2)	0.0594 (7)
H15	0.9214	0.3525	0.6475	0.071*
C16	1.0578 (3)	0.40420 (12)	0.7569 (3)	0.0630 (7)
H16	1.1290	0.4089	0.7090	0.076*
C17	1.0752 (3)	0.43161 (12)	0.8637 (3)	0.0620 (7)
H17	1.1583	0.4549	0.8891	0.074*
C18	0.9676 (3)	0.42414 (10)	0.9325 (2)	0.0552 (7)
H18	0.9774	0.4438	1.0035	0.066*
C19	0.5856 (3)	0.38711 (10)	0.9469 (2)	0.0545 (7)
C20	0.5126 (3)	0.33939 (11)	0.8667 (2)	0.0594 (7)
H20A	0.5330	0.3032	0.9085	0.071*
H20B	0.4048	0.3453	0.8536	0.071*
C21	0.5583 (3)	0.33282 (12)	0.7482 (2)	0.0614 (7)
H21	0.5391	0.3691	0.7047	0.074*
C22	0.4666 (4)	0.28509 (16)	0.6785 (3)	0.0966 (11)
H22A	0.4946	0.2817	0.6026	0.145*
H22B	0.3617	0.2942	0.6689	0.145*
H22C	0.4858	0.2493	0.7201	0.145*
C23	0.5232 (4)	0.38475 (14)	1.0604 (3)	0.0832 (9)
H23A	0.5673	0.4149	1.1122	0.125*
H23B	0.5467	0.3482	1.0978	0.125*
H23C	0.4162	0.3897	1.0429	0.125*
C24	0.5541 (4)	0.44577 (13)	0.8872 (3)	0.0859 (10)
H24A	0.5998	0.4755	0.9394	0.129*
H24B	0.4477	0.4520	0.8684	0.129*
H24C	0.5952	0.4466	0.8163	0.129*
N3	0.9623 (2)	0.08032 (10)	0.75961 (19)	0.0552 (6)
H3N	0.959 (3)	0.0442 (8)	0.738 (2)	0.060 (8)*
N4	0.9115 (2)	0.19484 (10)	0.8412 (2)	0.0564 (6)
H4N	0.878 (3)	0.2259 (9)	0.867 (2)	0.071 (9)*
C1	0.8201 (3)	0.14813 (10)	0.8611 (2)	0.0485 (6)
C2	0.6969 (3)	0.15719 (13)	0.9136 (2)	0.0608 (7)
H2	0.6789	0.1940	0.9392	0.073*
C3	0.6004 (3)	0.11377 (14)	0.9293 (3)	0.0703 (8)
H3	0.5172	0.1214	0.9636	0.084*
C4	0.6268 (3)	0.05903 (14)	0.8944 (3)	0.0698 (8)
H4	0.5626	0.0291	0.9056	0.084*
C5	0.7493 (3)	0.04893 (11)	0.8427 (2)	0.0600 (7)
H5	0.7674	0.0117	0.8195	0.072*
C6	0.8469 (3)	0.09240 (11)	0.8238 (2)	0.0480 (6)
C7	1.1215 (3)	0.09048 (12)	0.8137 (2)	0.0566 (7)
C8	1.1544 (3)	0.15471 (13)	0.8175 (3)	0.0656 (8)
H8A	1.2614	0.1596	0.8452	0.079*
H8B	1.1324	0.1690	0.7374	0.079*
C9	1.0732 (3)	0.19262 (11)	0.8915 (3)	0.0605 (7)
H9	1.0863	0.1767	0.9713	0.073*
C10	1.2146 (3)	0.06159 (16)	0.7333 (3)	0.0893 (11)
H10A	1.1937	0.0211	0.7296	0.134*
H10B	1.3194	0.0676	0.7636	0.134*
H10C	1.1896	0.0778	0.6558	0.134*
C11	1.1571 (3)	0.06352 (13)	0.9354 (3)	0.0776 (9)
H11A	1.1452	0.0225	0.9288	0.116*
H11B	1.0899	0.0786	0.9833	0.116*
H11C	1.2588	0.0724	0.9710	0.116*
C12	1.1335 (3)	0.25374 (14)	0.8980 (3)	0.0984 (12)
H12A	1.0794	0.2768	0.9452	0.148*
H12B	1.1209	0.2696	0.8201	0.148*
H12C	1.2382	0.2535	0.9327	0.148*
O1	0.8427 (3)	0.26647 (10)	1.0918 (3)	0.0817 (7)
H1W	0.861 (4)	0.2794 (15)	1.161 (3)	0.098 (14)*
H2W	0.809 (4)	0.2957 (17)	1.050 (3)	0.114 (15)*

	U11	U22	U33	U12	U13	U23
N1	0.0624 (15)	0.0558 (13)	0.0550 (15)	−0.0084 (11)	0.0155 (12)	−0.0159 (11)
N2	0.0565 (13)	0.0543 (13)	0.0407 (13)	−0.0018 (10)	0.0117 (11)	−0.0061 (11)
C13	0.0454 (14)	0.0404 (13)	0.0432 (15)	0.0044 (11)	0.0098 (11)	0.0019 (11)
C14	0.0455 (14)	0.0449 (14)	0.0450 (15)	0.0016 (11)	0.0078 (11)	0.0002 (11)
C15	0.0599 (17)	0.0710 (18)	0.0489 (16)	−0.0039 (14)	0.0142 (13)	−0.0050 (13)
C16	0.0556 (17)	0.0743 (18)	0.0628 (19)	−0.0033 (14)	0.0206 (14)	0.0047 (16)
C17	0.0502 (16)	0.0662 (18)	0.068 (2)	−0.0099 (13)	0.0071 (14)	0.0016 (15)
C18	0.0579 (16)	0.0551 (16)	0.0511 (17)	−0.0044 (13)	0.0058 (13)	−0.0073 (12)
C19	0.0508 (15)	0.0552 (16)	0.0618 (18)	0.0055 (12)	0.0216 (13)	0.0000 (13)
C20	0.0494 (15)	0.0621 (17)	0.0684 (19)	−0.0023 (12)	0.0150 (13)	0.0008 (14)
C21	0.0542 (16)	0.0690 (18)	0.0604 (19)	−0.0100 (13)	0.0086 (13)	−0.0041 (14)
C22	0.080 (2)	0.120 (3)	0.088 (3)	−0.040 (2)	0.0105 (18)	−0.031 (2)
C23	0.082 (2)	0.097 (2)	0.080 (2)	−0.0006 (18)	0.0405 (18)	−0.0111 (18)
C24	0.079 (2)	0.069 (2)	0.113 (3)	0.0140 (16)	0.0257 (19)	0.0008 (18)
N3	0.0463 (13)	0.0679 (16)	0.0517 (14)	0.0055 (11)	0.0100 (10)	−0.0027 (12)
N4	0.0496 (13)	0.0521 (14)	0.0662 (16)	0.0015 (11)	0.0073 (11)	0.0007 (11)
C1	0.0411 (14)	0.0554 (16)	0.0462 (15)	0.0010 (12)	0.0006 (11)	0.0032 (12)
C2	0.0429 (15)	0.0755 (19)	0.0633 (18)	0.0046 (14)	0.0081 (13)	−0.0101 (14)
C3	0.0455 (16)	0.095 (2)	0.073 (2)	0.0023 (16)	0.0178 (14)	−0.0012 (17)
C4	0.0516 (17)	0.080 (2)	0.079 (2)	−0.0084 (15)	0.0143 (15)	0.0148 (17)
C5	0.0556 (16)	0.0565 (16)	0.0675 (19)	0.0021 (13)	0.0100 (14)	0.0074 (13)
C6	0.0399 (14)	0.0614 (16)	0.0418 (15)	0.0022 (12)	0.0052 (11)	0.0058 (12)
C7	0.0438 (15)	0.0738 (19)	0.0522 (17)	0.0099 (13)	0.0087 (12)	0.0064 (14)
C8	0.0404 (14)	0.090 (2)	0.0657 (19)	−0.0016 (14)	0.0076 (13)	0.0205 (16)
C9	0.0480 (15)	0.0640 (18)	0.0665 (19)	−0.0068 (13)	0.0027 (13)	0.0078 (14)
C10	0.0529 (18)	0.131 (3)	0.086 (2)	0.0169 (18)	0.0190 (16)	−0.014 (2)
C11	0.0698 (19)	0.084 (2)	0.075 (2)	0.0150 (15)	0.0010 (16)	0.0181 (17)
C12	0.069 (2)	0.074 (2)	0.145 (3)	−0.0189 (17)	0.001 (2)	0.008 (2)
O1	0.120 (2)	0.0592 (14)	0.0643 (16)	−0.0014 (13)	0.0126 (14)	0.0038 (13)

N1—C14	1.404 (3)	N3—C7	1.482 (3)
N1—C21	1.455 (3)	N3—H3N	0.874 (16)
N1—H1N	0.835 (16)	N4—C1	1.410 (3)
N2—C13	1.406 (3)	N4—C9	1.475 (3)
N2—C19	1.477 (3)	N4—H4N	0.856 (17)
N2—H2N	0.852 (16)	C1—C2	1.380 (3)
C13—C18	1.382 (3)	C1—C6	1.400 (3)
C13—C14	1.391 (3)	C2—C3	1.368 (4)
C14—C15	1.386 (3)	C2—H2	0.9300
C15—C16	1.376 (4)	C3—C4	1.369 (4)
C15—H15	0.9300	C3—H3	0.9300
C16—C17	1.372 (4)	C4—C5	1.373 (4)
C16—H16	0.9300	C4—H4	0.9300
C17—C18	1.377 (4)	C5—C6	1.386 (3)
C17—H17	0.9300	C5—H5	0.9300
C18—H18	0.9300	C7—C10	1.520 (4)
C19—C20	1.518 (4)	C7—C11	1.520 (4)
C19—C23	1.521 (4)	C7—C8	1.522 (4)
C19—C24	1.532 (4)	C8—C9	1.510 (4)
C20—C21	1.510 (4)	C8—H8A	0.9700
C20—H20A	0.9700	C8—H8B	0.9700
C20—H20B	0.9700	C9—C12	1.519 (4)
C21—C22	1.525 (4)	C9—H9	0.9800
C21—H21	0.9800	C10—H10A	0.9600
C22—H22A	0.9600	C10—H10B	0.9600
C22—H22B	0.9600	C10—H10C	0.9600
C22—H22C	0.9600	C11—H11A	0.9600
C23—H23A	0.9600	C11—H11B	0.9600
C23—H23B	0.9600	C11—H11C	0.9600
C23—H23C	0.9600	C12—H12A	0.9600
C24—H24A	0.9600	C12—H12B	0.9600
C24—H24B	0.9600	C12—H12C	0.9600
C24—H24C	0.9600	O1—H1W	0.84 (4)
N3—C6	1.415 (3)	O1—H2W	0.86 (4)
C14—N1—C21	121.0 (2)	C6—N3—H3N	110.3 (17)
C14—N1—H1N	107.4 (18)	C7—N3—H3N	104.9 (17)
C21—N1—H1N	113.0 (18)	C1—N4—C9	118.6 (2)
C13—N2—C19	121.0 (2)	C1—N4—H4N	109.9 (18)
C13—N2—H2N	109.9 (16)	C9—N4—H4N	106.1 (19)
C19—N2—H2N	108.4 (15)	C2—C1—C6	118.4 (2)
C18—C13—C14	118.9 (2)	C2—C1—N4	120.0 (2)
C18—C13—N2	119.7 (2)	C6—C1—N4	121.5 (2)
C14—C13—N2	121.2 (2)	C3—C2—C1	122.2 (3)
C15—C14—C13	118.4 (2)	C3—C2—H2	118.9
C15—C14—N1	119.9 (2)	C1—C2—H2	118.9
C13—C14—N1	121.4 (2)	C2—C3—C4	119.8 (3)
C16—C15—C14	121.9 (3)	C2—C3—H3	120.1
C16—C15—H15	119.0	C4—C3—H3	120.1
C14—C15—H15	119.0	C3—C4—C5	119.0 (3)
C17—C16—C15	119.6 (3)	C3—C4—H4	120.5
C17—C16—H16	120.2	C5—C4—H4	120.5
C15—C16—H16	120.2	C4—C5—C6	122.2 (3)
C16—C17—C18	118.9 (3)	C4—C5—H5	118.9
C16—C17—H17	120.5	C6—C5—H5	118.9
C18—C17—H17	120.5	C5—C6—C1	118.3 (2)
C17—C18—C13	122.1 (2)	C5—C6—N3	119.4 (2)
C17—C18—H18	118.9	C1—C6—N3	122.1 (2)
C13—C18—H18	118.9	N3—C7—C10	106.1 (2)
N2—C19—C20	109.9 (2)	N3—C7—C11	110.6 (2)
N2—C19—C23	106.7 (2)	C10—C7—C11	109.6 (2)
C20—C19—C23	108.2 (2)	N3—C7—C8	109.8 (2)
N2—C19—C24	110.8 (2)	C10—C7—C8	108.9 (2)
C20—C19—C24	110.5 (2)	C11—C7—C8	111.7 (2)
C23—C19—C24	110.7 (2)	C9—C8—C7	118.4 (2)
C21—C20—C19	117.9 (2)	C9—C8—H8A	107.7
C21—C20—H20A	107.8	C7—C8—H8A	107.7
C19—C20—H20A	107.8	C9—C8—H8B	107.7
C21—C20—H20B	107.8	C7—C8—H8B	107.7
C19—C20—H20B	107.8	H8A—C8—H8B	107.1
H20A—C20—H20B	107.2	N4—C9—C8	110.3 (2)
N1—C21—C20	111.7 (2)	N4—C9—C12	108.0 (2)
N1—C21—C22	108.2 (2)	C8—C9—C12	111.5 (2)
C20—C21—C22	109.9 (2)	N4—C9—H9	109.0
N1—C21—H21	109.0	C8—C9—H9	109.0
C20—C21—H21	109.0	C12—C9—H9	109.0
C22—C21—H21	109.0	C7—C10—H10A	109.5
C21—C22—H22A	109.5	C7—C10—H10B	109.5
C21—C22—H22B	109.5	H10A—C10—H10B	109.5
H22A—C22—H22B	109.5	C7—C10—H10C	109.5
C21—C22—H22C	109.5	H10A—C10—H10C	109.5
H22A—C22—H22C	109.5	H10B—C10—H10C	109.5
H22B—C22—H22C	109.5	C7—C11—H11A	109.5
C19—C23—H23A	109.5	C7—C11—H11B	109.5
C19—C23—H23B	109.5	H11A—C11—H11B	109.5
H23A—C23—H23B	109.5	C7—C11—H11C	109.5
C19—C23—H23C	109.5	H11A—C11—H11C	109.5
H23A—C23—H23C	109.5	H11B—C11—H11C	109.5
H23B—C23—H23C	109.5	C9—C12—H12A	109.5
C19—C24—H24A	109.5	C9—C12—H12B	109.5
C19—C24—H24B	109.5	H12A—C12—H12B	109.5
H24A—C24—H24B	109.5	C9—C12—H12C	109.5
C19—C24—H24C	109.5	H12A—C12—H12C	109.5
H24A—C24—H24C	109.5	H12B—C12—H12C	109.5
H24B—C24—H24C	109.5	H1W—O1—H2W	104 (3)
C6—N3—C7	120.1 (2)
C19—N2—C13—C18	125.4 (2)	C9—N4—C1—C2	123.2 (3)
C19—N2—C13—C14	−60.9 (3)	C9—N4—C1—C6	−59.8 (3)
C18—C13—C14—C15	−1.1 (3)	C6—C1—C2—C3	−0.5 (4)
N2—C13—C14—C15	−174.8 (2)	N4—C1—C2—C3	176.6 (2)
C18—C13—C14—N1	172.8 (2)	C1—C2—C3—C4	1.3 (4)
N2—C13—C14—N1	−1.0 (3)	C2—C3—C4—C5	−0.8 (4)
C21—N1—C14—C15	−125.1 (3)	C3—C4—C5—C6	−0.4 (4)
C21—N1—C14—C13	61.1 (3)	C4—C5—C6—C1	1.2 (4)
C13—C14—C15—C16	3.1 (4)	C4—C5—C6—N3	−173.7 (2)
N1—C14—C15—C16	−170.8 (2)	C2—C1—C6—C5	−0.7 (3)
C14—C15—C16—C17	−2.4 (4)	N4—C1—C6—C5	−177.8 (2)
C15—C16—C17—C18	−0.3 (4)	C2—C1—C6—N3	174.1 (2)
C16—C17—C18—C13	2.3 (4)	N4—C1—C6—N3	−3.0 (4)
C14—C13—C18—C17	−1.6 (4)	C7—N3—C6—C5	−122.3 (3)
N2—C13—C18—C17	172.2 (2)	C7—N3—C6—C1	63.0 (3)
C13—N2—C19—C20	76.8 (3)	C6—N3—C7—C10	168.2 (2)
C13—N2—C19—C23	−166.1 (2)	C6—N3—C7—C11	49.4 (3)
C13—N2—C19—C24	−45.6 (3)	C6—N3—C7—C8	−74.3 (3)
N2—C19—C20—C21	−63.4 (3)	N3—C7—C8—C9	63.8 (3)
C23—C19—C20—C21	−179.5 (2)	C10—C7—C8—C9	179.5 (2)
C24—C19—C20—C21	59.2 (3)	C11—C7—C8—C9	−59.3 (3)
C14—N1—C21—C20	−75.5 (3)	C1—N4—C9—C8	78.6 (3)
C14—N1—C21—C22	163.4 (2)	C1—N4—C9—C12	−159.3 (3)
C19—C20—C21—N1	63.1 (3)	C7—C8—C9—N4	−67.3 (3)
C19—C20—C21—C22	−176.8 (2)	C7—C8—C9—C12	172.7 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1i	0.84 (2)	2.33 (2)	3.122 (3)	159 (2)
O1—H1W···N4ii	0.84 (4)	2.14 (4)	2.976 (4)	175 (3)
O1—H2W···N2	0.86 (4)	2.09 (4)	2.930 (3)	167 (4)

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N1H1NO1i	0.84(2)	2.33(2)	3.122(3)	159(2)
O1H1WN4ii	0.84(4)	2.14(4)	2.976(4)	175(3)
O1H2WN2	0.86(4)	2.09(4)	2.930(3)	167(4)

Symmetry codes: (i) ; (ii) .